JP2012025941A - Thermoplastic resin composition for lamp housings, and molded article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition for lamp housings which gives a molded article excellent in impact resistance, heat resistance, molded appearance nature, and oscillating welding nature, in which outstanding welding nature with other resin molded articles and glossy brightness appearance after direct vapor deposition are acquired, and to provide a molded article.SOLUTION: The thermoplastic resin composition for lamp housings comprises: an acrylic-rubber-reinforced graft resin obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an acrylic rubber that has a gel content of 70 mass% or more, a toluene swelling degree of 5.5 to 30 times, a volume-mean particle diameter of 100 to 200 nm, and a (volume-mean particle diameter)/(number-mean particle diameter) ratio of less than 1.1; a composite-rubber-reinforced graft resin obtained by polymerizing methyl methacrylate, styrene, acrylonitrile and so on in the presence of a composite rubber that comprises both an organosiloxane-based rubber and a (meth)acrylic (co)polymer rubber; and a maleimide copolymer that comprises 10 to 70 mass% of structural units derived from a maleimide compound.

Description

  The present invention provides a molded article excellent in impact resistance, heat resistance, molded appearance and weldability, excellent weldability with other resin molded articles, and a beautiful bright appearance after direct vapor deposition. The present invention relates to a thermoplastic resin composition for a housing.

  Vehicle lamps such as headlamps, tail lamps, stop lamps and the like are generally composed of a resin lens part (hereinafter also referred to as “lamp lens”) and a resin housing part (hereinafter also referred to as “lamp housing”). ing. As a constituent material of these members, transparent resin such as polymethyl methacrylate (PMMA) and polycarbonate (PC) is used for the resin lens portion and ABS resin is used for the resin housing portion from the viewpoint of weight reduction and productivity. For example, a resin composition in which a colorant is blended is used.

  As a method of joining the lamp lens and the lamp housing, there are methods such as a vibration welding method, a hot plate welding method, and a laser welding method. Among these, the vibration welding method is a method in which vibrations caused by pressure and reciprocating motion are applied to the surfaces to be joined of two resin members, and the resin component of the bonding part is melted by the frictional heat to join the two. There is no need to heat the resin members, and this is an excellent method capable of joining the resin members in a very short time. However, in this method, a phenomenon in which the molten resin protrudes into a thread shape (hereinafter referred to as “thread burr”) may occur outside the joint portion. If this thread burr becomes prominent, it will be visible from the outside through the lamp lens, resulting in poor appearance. In addition, the yarn burr has a problem that it cannot be removed by post-processing.

In the vibration welding method, in order to make thread burrs inconspicuous, a method of making the joint part concealed (see Patent Document 1), a method of making the joint part invisible using refraction of light (see Patent Document 2) ) Etc. are known. However, both methods define the shape of the resin member, and there are restrictions on the design.
On the other hand, as a vibration welding resin composition for suppressing the generation of yarn burrs, a composition containing a rubber-reinforced styrene resin using a rubber having a special structure with a butadiene rubber as a core (Patent Document 3), butadiene A composition containing a rubber-reinforced styrene-based resin using a rubber made of acrylate and alkyl acrylate (Patent Document 4), a composition using a butadiene rubber-reinforced resin and a silicone-based rubber reinforced resin (Patent Document 5), etc. are known. ing. However, these documents do not mention direct vapor deposition.

  The lamp housing is usually subjected to secondary processing such as painting, metal deposition, and plating in order to increase the brightness of the vehicular lamp. In order to obtain a beautiful appearance by painting, metal deposition, plating, or the like after the secondary processing, the surface of the molded product before the secondary processing needs to have excellent smoothness. In order to smooth the surface of a molded product to be subjected to secondary processing, an undercoat treatment is usually performed. If the molded product has smoothness, a metal layer or the like can be directly formed without forming an undercoat layer (hereinafter also referred to as “undercoatless”), leading to a reduction in product cost. it can. As a method for forming a metal layer without forming an undercoat layer, a so-called “direct vapor deposition method” is known and has been generally used in recent years. Therefore, a resin composition used for forming a lamp housing or the like is required not only to suppress yarn burrs but also to provide a molded product having excellent smoothness.

  On the other hand, as a resin composition suitable for direct vapor deposition, a composition containing a rubber-containing graft copolymer grafted with a rubbery polymer having a specific particle size distribution is disclosed (see Patent Document 6). However, this composition cannot fully satisfy the recent required level for high glitter, and nothing is mentioned regarding the thread burr appearance of the vibration weld joint.

  As a composition for improving the direct vapor deposition property after improving the appearance by yarn burr in the vibration welding method, a rubber containing a specific gel amount is used, and the rubber content in the composition is in a specific range. A composition containing a graft copolymer (see Patent Document 7), a composition containing a butadiene rubber reinforced resin having a specific gel content and a silicone rubber reinforced resin (see Patent Document 8), and a silicone rubber reinforced resin containing silicone rubber. A method for controlling the structure in detail (see Patent Documents 9 to 11) and the like are disclosed. Furthermore, a composition is disclosed that uses a small amount of a copolymer obtained by grafting a methacrylic acid alkyl ester to a silicone rubber to a normal acrylic rubber-reinforced styrene resin in order to impart impact resistance (Patent Document). 12).

Japanese Patent Laid-Open No. 9-63307 JP-A-10-308104 JP 11-199727 A Japanese Patent Laid-Open No. 2000-302824 JP 2002-322340 A JP 2001-002869 A JP 2004-182835 A JP 2004-346189 A JP 2005-139331 A JP 2005-139332 A JP 2006-028393 A JP 2007-217488 A

As a resin composition for forming a lamp housing, a composition excellent in balance of impact resistance, glitter after metallization by direct vapor deposition, and suppression of yarn burr generation in vibration welding is strongly desired. In spite of this, there is still not enough.
An object of the present invention is to provide a lamp housing which gives a molded article excellent in impact resistance, heat resistance and molded appearance, has excellent weldability with other resin molded articles, and a beautiful brilliant appearance after direct vapor deposition. It is providing the thermoplastic resin composition for use, and a molded article containing the same.

The present invention is as follows.
1. [A] The gel content is 70% by mass or more, the degree of swelling with toluene is 5.5 to 30 times, the volume average particle size is 100 to 200 nm, and the volume average particle size and number average particle size Acrylic rubber obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an acrylic rubber polymer (a1) having a ratio less than 1.1 In the presence of a composite polymer reinforced graft resin, [B] an organosiloxane rubber, and a composite rubber (b1) containing a (co) polymer rubber having a structural unit derived from an alkyl (meth) acrylate Composite rubber obtained by polymerizing a vinyl monomer containing a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyanide compound having a glass transition temperature exceeding 0 ° C. Graft resin, a maleimide copolymer containing 10 to 70% by mass of the structural unit derived from the [C] maleimide compound, and [D] an aromatic vinyl compound, if necessary. Includes structural units derived from, and structural units derived from vinyl cyanide compounds and / or structural units derived from (meth) acrylic acid alkyl ester compounds, and does not include structural units derived from maleimide compounds. A thermoplastic resin composition for a lamp housing, wherein the total content of the acrylic rubbery polymer (a1) and the content of the composite rubber (b1) is the acrylic rubber. Polymer resin reinforced graft resin [A], composite rubber reinforced graft resin [B], maleimide copolymer [C], and polymer [D] total 100 quality. %, The content of the structural unit derived from the maleimide compound is the structural unit constituting the acrylic rubbery polymer reinforced graft resin [A], the composite When the total of the structural unit constituting the rubber-reinforced graft resin [B], the structural unit constituting the maleimide copolymer [C], and the structural unit constituting the polymer [D] is 100% by mass And a thermoplastic resin composition for a lamp housing, characterized by being 5 to 30% by mass.
2. The content ratios of the acrylic rubbery polymer (a1) and the composite rubber (b1) are 10 to 95% by mass and 5 to 90% by mass, respectively, when the total of both is 100% by mass. 2. The thermoplastic resin composition for a lamp housing according to 1.
3. In the presence of the alkyl sulfonate and / or alkyl sulfate ester salt, the acrylic rubbery polymer (a1) is (meth) acrylic acid alkyl ester compound (m1-1) 50 to 100% by mass, 0-50 mass% of other compounds (m1-2) copolymerizable with the (meth) acrylic acid alkyl ester compound (m1-1) (however, the total of (m1-1) and (m1-2) is 100 mass%) A monomer (m1) consisting of a first polymerization step of polymerizing in an aqueous medium to form a first polymer, and in the presence of the first polymer, an alkyl sulfonate and Polymerization having 50 to 99.99% by mass of (meth) acrylic acid alkyl ester compound (m2-1) and two or more carbon-carbon double bonds in the presence or absence of alkyl sulfate ester salt Unsaturated compounds ( 2-2) 0.01 to 5% by mass and other compounds (m2−) copolymerizable with the (meth) acrylic acid alkyl ester compound (m2-1) and the polymerizable unsaturated compound (m2-2) 3) A monomer (m2) consisting of 0 to 49.99% by mass (provided that the total of (m2-1), (m2-2) and (m2-3) is 100% by mass), A second polymerization step of polymerizing in an aqueous medium, a polymer obtained by sequentially proceeding,
In the above 1 or 2, the proportions of the monomers (m1) and (m2) used are 1 to 50% by mass and 50 to 99% by mass, respectively, when the total of both is 100% by mass. The thermoplastic resin composition for a lamp housing as described.
4). [S] An acrylic rubber obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound without a maleimide compound in the presence of the acrylic rubbery polymer (a1). (T) polymerizing a (meth) acrylic acid alkyl ester compound in which the glass transition temperature of the homopolymer exceeds 0 ° C. in the presence of the composite rubber (b1); Next, a rubber reinforced resin containing a composite rubber reinforced graft resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound without containing a maleimide compound, and [U] maleimide (1) to (3) obtained by mixing a raw material containing a maleimide copolymer containing 10 to 70% by mass of a structural unit derived from a compound based on the total structural unit. The thermoplastic resin composition for the lamp housing according to Re or claim.
5. In any one of 1 to 4 above, the intrinsic viscosity of an acetone-soluble polymer obtained by immersing the thermoplastic resin composition for lamp housing in acetone is 0.2 to 1.0 dl / g. The thermoplastic resin composition for a lamp housing as described.
6). The thermoplastic resin composition for a lamp housing according to any one of 1 to 5 above, which is a molding material for a molded product in which a vapor deposition layer is formed on the surface thereof by direct vapor deposition.
7). The thermoplastic resin composition for a lamp housing according to any one of the above 1 to 6, which is a molding material for a molded product to which the vibration welding method is applied.
8). A molded article comprising the thermoplastic resin composition for a lamp housing according to any one of 1 to 7 above.

  According to the thermoplastic resin composition for a lamp housing of the present invention, a molded product excellent in impact resistance, heat resistance, molded appearance and weldability (particularly vibration welding) can be obtained. In addition, excellent weldability with other resin molded products and a beautiful glitter appearance after direct vapor deposition can be obtained.

It is a schematic perspective view which shows the resin lens part (lamp lens) used for evaluation of the vibration weldability in an Example. It is a schematic perspective view which shows the resin housing part (lamp housing) used for evaluation of the vibration weldability in an Example. It is a schematic sectional drawing which shows the welding part of the resin lens part (lamp lens) and resin housing part (lamp housing) used for evaluation of the vibration welding property in an Example.

The present invention will be described in detail below.
In the present specification, “(meth) acryl” means acryl and methacryl, and “(co) polymer” means a homopolymer and a copolymer.

  The thermoplastic resin composition for a lamp housing of the present invention has [A] a gel content of 70% by mass or more and a swelling degree with toluene (hereinafter referred to as “toluene swelling degree”) of 5.5 to 30 times. In the presence of the acrylic rubbery polymer (a1) having a volume average particle diameter of 100 to 200 nm and a ratio of the volume average particle diameter to the number average particle diameter of less than 1.1, aromatic vinyl is used. Acrylic rubbery polymer reinforced graft resin (hereinafter, referred to as “vinyl monomer (a2)”) obtained by polymerizing a vinyl monomer containing a compound and a vinyl cyanide compound (hereinafter also referred to as “vinyl monomer (a2)”). "Component [A]"), and (B) an organosiloxane rubber and a composite rubber (b1) including a (co) polymer rubber having a structural unit derived from an alkyl (meth) acrylate. Homopolymerization in the presence A composite rubber reinforced graft resin (hereinafter referred to as “polymer rubber reinforced graft resin”) obtained by polymerizing a vinyl monomer containing a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyanide compound having a glass transition temperature exceeding 0 ° C. "Component [B]") and a maleimide copolymer (hereinafter referred to as "Component [C]") containing 10 to 70% by mass of structural units derived from [C] maleimide compounds with respect to all structural units. And [D] a structural unit derived from an aromatic vinyl compound, a structural unit derived from a vinyl cyanide compound, and a structural unit derived from a (meth) acrylic acid alkyl ester compound, if necessary. A polymer (hereinafter also referred to as “component [D]”) containing at least one structural unit selected from the above and not containing a structural unit derived from a maleimide compound. The total content of the acrylic rubbery polymer (a1) and the content of the composite rubber (b1) is the above component [A], the component [B], the component [C], and the component [ D] is 8 to 35% by mass when the total of D is 100% by mass, and the content of the structural unit derived from the maleimide compound is the structural unit constituting the component [A], the component [A] B], the structural unit constituting the component [C], and the total of the structural unit constituting the component [D] are 100% by mass, and 5 to 30% by mass. It is characterized by.

The component [A] is a resin composition obtained by polymerizing the vinyl monomer (a2) in the presence of the acrylic rubbery polymer (a1) (hereinafter referred to as “graft polymerization”). (Hereinafter referred to as “rubber reinforced resin”), an acrylic rubbery polymer reinforced graft resin. This acrylic rubber polymer reinforced graft resin is a resin in which a copolymer of a vinyl monomer (a2) is grafted to an acrylic rubber polymer (a1), and the acrylic rubber polymer Part and a copolymer part containing a structural unit derived from the vinyl monomer (a2).
The rubber-reinforced resin obtained by graft polymerization is usually a (co) polymer not grafted to a rubbery polymer (hereinafter referred to as “ungrafted polymer”) in addition to the rubbery polymer-reinforced graft resin. .)including. The composition of this ungrafted polymer depends on the type of vinyl monomer (a2) used, and when the vinyl monomer (a2) contains a maleimide compound, the ungrafted polymer obtained is Usually, in the composition of this invention, it is contained in component [C]. In addition, when the vinyl monomer (a2) contains another aromatic vinyl compound excluding the maleimide compound, and a vinyl cyanide compound and / or a (meth) acrylic acid alkyl ester compound, an ungrafted product is obtained. The polymer is usually contained in component [D] in the composition of the present invention.

The acrylic rubbery polymer (a1) has a gel content of 70% by mass or more, a toluene swelling degree of 5.5 to 30 times, a volume average particle diameter of 100 to 200 nm, and a volume average. A polymer (acrylic rubber) having a ratio of particle diameter to number average particle diameter of less than 1.1. The acrylic rubbery polymer (a1) usually has a polymer part containing a structural unit derived from a (meth) acrylic acid alkyl ester compound, and is a rubbery (co) polymer at 25 ° C. is there.
The acrylic rubbery polymer (a1) may be a homopolymer containing a structural unit derived from a (meth) acrylic acid alkyl ester compound, or a copolymer containing this structural unit. The copolymer may be a copolymer containing two or more structural units derived from a (meth) acrylic acid alkyl ester compound, a structural unit derived from a (meth) acrylic acid alkyl ester compound, and other structural units. It may be a copolymer containing a structural unit derived from a vinyl monomer. Further, the acrylic rubbery polymer (a1) may be a crosslinked polymer or a non-crosslinked polymer.

  As the (meth) acrylic acid alkyl ester compound used for forming the structural unit derived from the (meth) acrylic acid alkyl ester compound, which constitutes the acrylic rubbery polymer (a1), methyl (meth) acrylate, Ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, (meta ) Pentyl acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, ( Examples thereof include dodecyl (meth) acrylate and cyclohexyl (meth) acrylate. These compounds can be used alone or in combination of two or more. Of these, compounds having 1 to 14 carbon atoms in the alkyl group in the ester moiety are preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.

  When the acrylic rubbery polymer (a1) is a copolymer, the compound (vinyl monomer) used for forming other structural units excludes (meth) acrylic acid alkyl ester compounds. It can be set as the compound which has one or more carbon-carbon double bonds, and / or the compound which has two or more carbon-carbon double bonds.

  Examples of the compound having one carbon-carbon double bond include aromatic vinyl compounds, vinyl cyanide compounds, amide group-containing unsaturated compounds, alkyl vinyl ethers, and vinylidene chloride. In addition, these compounds may be used independently and may be used in combination of 2 or more type.

Examples of the aromatic vinyl compound include styrene, p-methylstyrene, o-methylstyrene, m-methylstyrene, ethylstyrene, tert-butylstyrene, α-methylstyrene, 1,1-diphenylstyrene, N, N-diethyl. -P-aminostyrene, N, N-diethyl-p-aminomethylstyrene, vinylpyridine, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, vinylnaphthalene and the like. .
Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile.
Examples of the amide group-containing unsaturated compound include acrylamide and methacrylamide.
Examples of the alkyl vinyl ether include compounds having 1 to 6 carbon atoms in the alkyl group constituting the alkyl portion.

  In addition, as a compound having two or more carbon-carbon double bonds, a bifunctional aromatic vinyl compound, a bifunctional (meth) acrylic ester, a trifunctional (meth) acrylic ester, a tetrafunctional (meta ) Acrylic acid ester, pentafunctional (meth) acrylic acid ester, hexafunctional (meth) acrylic acid ester, polyhydric alcohol (meth) acrylic acid ester, and the like. In addition, these compounds may be used independently and may be used in combination of 2 or more type.

Examples of the bifunctional aromatic vinyl compound include divinylbenzene and divinyltoluene.
Examples of the bifunctional (meth) acrylic acid ester include 1,6-hexanediol diacrylate, ethylene glycol dimethacrylate, neopentyl glycol diacrylate, allyl (meth) acrylate, neopentyl glycol dimethacrylate, and triethylene glycol diacrylate. Examples include acrylate and triethylene glycol dimethacrylate.
Examples of the trifunctional (meth) acrylic acid ester include trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, and the like.
Examples of the tetrafunctional (meth) acrylic acid ester include pentaerythritol tetraacrylate and pentaerythritol tetramethacrylate.
Examples of the pentafunctional (meth) acrylic acid ester include pentaerythritol pentaacrylate and pentaerythritol pentamethacrylate.
Examples of the hexafunctional (meth) acrylic acid ester include dipentaerythritol hexaacrylate and dipentaerythritol hexamethacrylate.
Examples of the (meth) acrylic acid ester of the polyhydric alcohol include (poly) ethylene glycol dimethacrylate.
In addition, diallyl malate, diallyl fumarate, triallyl cyanurate, triallyl isocyanurate, diallyl phthalate, bis (acryloyloxyethyl) ether of bisphenol A, and the like can be used.
Of these, allyl methacrylate and triallyl cyanurate are preferred.

  The acrylic rubbery polymer (a1) is preferably a copolymer containing a structural unit derived from a (meth) acrylic acid alkyl ester compound. In this case, when the total amount of all the structural units constituting the copolymer is 100% by mass, the content of the structural unit derived from the (meth) acrylic acid alkyl ester compound is preferably 50 to 100% by mass, more Preferably it is 70-100 mass%, More preferably, it is 80-100 mass%.

  The gel content of the acrylic rubbery polymer (a1) is 70% by mass or more, preferably 75% by mass or more, more preferably 80% by mass or more, regardless of the type of structural unit. When the acrylic rubbery polymer (a1) having a high gel content is used, excellent glitter can be obtained when a metal layer or the like is provided on the surface of the obtained molded product.

  The toluene swelling degree of the acrylic rubbery polymer (a1) is 5.5 to 30 times, preferably 6 to 25 times, more preferably 10 to 23 times, regardless of the type of structural unit. is there. When the acrylic rubbery polymer (a1) in the above range is used, a molded article having excellent impact resistance can be obtained, and excellent glitter when a metal layer or the like is disposed on the surface of the obtained molded article. Can be obtained.

In addition, the said gel content and toluene swelling degree can be calculated | required with the following method, for example.
First, about 0.2 gram of the acrylic rubbery polymer (a1) is weighed (mass is Wr), put into 25 ml of toluene, and lightly stirred. Then, it is allowed to stand at 25 ° C. for 48 hours, and is filtered using a 200-mesh wire mesh (mass is Wm gram) weighed in advance to separate into insoluble and soluble components. Immediately after the separation, the insoluble matter is weighed together with the filtered wire mesh (mass is W1 gram), and the weight value (Wm) of the wire mesh is subtracted from the weight value (W1), and the insoluble matter swollen with toluene. Is obtained (the mass is defined as Ws gram). Next, since the insoluble matter swollen with toluene contains toluene, it is air-dried at 25 ° C. for 12 hours, and subsequently dried at 60 ° C. for 12 hours using a vacuum dryer. Toluene contained in the minute is removed by drying. The insoluble matter after drying is weighed together with the wire mesh (the mass is W2 grams), and the weight value (Wm) of the wire mesh is subtracted from the weight value (W2) to obtain the dry weight of the insoluble matter (the mass is Wd grams). And). From these weighed values, the gel content and the toluene swelling degree are calculated by the following equations.
Gel content (mass%) = [Wd (g) / Wr (g)] × 100
= [{W2 (g) -Wm (g)} / Wr (g)] × 100
Toluene swelling degree (times) = Ws (g) / Wd (g)
= [W1 (g) -Wm (g)] / [W2 (g) -Wm (g)]

  The gel content and the degree of toluene swelling are the types and amounts of monomers used in producing the acrylic rubbery polymer (a1), the types and amounts of chain transfer agents (molecular weight regulators), and polymerization. The time, polymerization temperature, polymerization conversion rate, and the like are adjusted by appropriately selecting.

The volume average particle diameter (hereinafter also referred to as “Mv”) of the acrylic rubbery polymer (a1) is from 100 to 200 nm, preferably from 105 to 200 nm, from the viewpoint of impact resistance and glitter of the molded product. It is 180 nm, more preferably 110 to 170 nm.
Further, a particle size distribution (Mv / Mn) represented by a ratio between the volume average particle size (Mv) of the acrylic rubbery polymer (a1) and the number average particle size (hereinafter also referred to as “Mn”). ) Is less than 1.1, preferably less than 1.07.
When the Mv and / or particle size distribution (Mv / Mn) is outside the above range, the impact resistance, glossiness, and yarn burr during vibration welding are insufficiently suppressed. There is.

  Mv and Mn of the acrylic rubbery polymer (a1) can be measured, for example, by “Microtrack UPA150” (trade name) manufactured by HONEYWELL.

The acrylic rubbery polymer (a1) can be obtained by a known production method, but the following copolymer obtained by a production method comprising a first polymerization step and a second polymerization step It is particularly preferable that it is a polymer (hereinafter referred to as “copolymer (a11)”).
(1) 1st superposition | polymerization process (meth) acrylic-acid alkylester compound (m1-1) in presence of alkyl sulfonate and / or alkyl sulfate ester salt (henceforth "emulsifier (e)"). ) 50-100% by mass and other compounds (m1-2) copolymerizable with the (meth) acrylic acid alkyl ester compound (m1-1) 0-50% by mass (however, (m1-1) and (m1) -2) is a polymerization step of polymerizing a monomer (m1) consisting of 100% by mass in an aqueous medium to form a first polymer.
(2) Second polymerization step (meth) acrylic acid alkyl ester compound in the presence or absence of alkyl sulfonate and / or alkyl sulfate ester salt (emulsifier (e)) in the presence of the first polymer. (M2-1) 50 to 99.99 mass%, polymerizable unsaturated compound (m2-2) having 2 or more carbon-carbon double bonds, 0.01 to 5 mass%, and alkyl (meth) acrylate 0 to 49.99 mass% of other compounds (m2-3) copolymerizable with the ester compound (m2-1) and the polymerizable unsaturated compound (m2-2) (however, (m2-1), (m2- 2) and the sum of (m2-3) is 100% by mass.) And a monomer (m2) is polymerized in an aqueous medium to obtain a copolymer (a11).
And when the ratio of the usage-amount of the monomer (m1) and (m2) used at the said superposition | polymerization process makes both the sum total 100 mass%, 1-50 mass% and 50-99 mass%, respectively. To do.

  In the presence of the emulsifier (e), the first polymerization step includes (meth) acrylic acid alkyl ester compound (m1-1) 50 to 100% by mass, (meth) acrylic acid alkyl ester compound (m1-1), Monomer (m1) comprising 0-50% by mass of another copolymerizable compound (m1-2) (provided that the total of (m1-1) and (m1-2) is 100% by mass) Is an emulsion polymerization in an aqueous medium to form a first polymer. In the polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an electrolyte and the like can be used as necessary. A known method is applied as a specific method of emulsion polymerization.

  As the (meth) acrylic acid alkyl ester compound (m1-1) constituting the monomer (m1), a compound having 1 to 14 carbon atoms in the alkyl group of the ester part is preferably used. N-butyl acrylate and 2-ethylhexyl acrylate are preferably used. In addition, the said (meth) acrylic-acid alkylester compound (m1-1) may be used independently, and may use 2 or more types.

  In addition, as the other compound (m1-2) copolymerizable with the above (meth) acrylic acid alkyl ester compound (m1-1), a compound having one carbon-carbon double bond is usually used. A group vinyl compound, a vinyl cyanide compound and the like are preferably used. In addition, these compounds may be used independently and can be used in combination of 2 or more type.

  The ratio of the (meth) acrylic acid alkyl ester compound (m1-1) and the other compound (m1-2) used in the first polymerization step is as follows when the total of both is 100% by mass: Preferably they are 50-100 mass% and 0-50 mass%, More preferably, they are 70-100 mass% and 0-30 mass%, More preferably, they are 90-100 mass% and 0-10 mass%. By setting it as the above ratio, the molded article is excellent in impact resistance and glitter, and the occurrence of yarn burrs during vibration welding is suppressed.

  In the first polymerization step, the monomer is polymerized in the reaction system in the presence of the emulsifier (e). By using the emulsifier (e), the gel content is 70% by mass or more, the degree of swelling with toluene is 5.5 to 30 times, the volume average particle diameter is 100 to 200 nm, and the volume average particle The 1st polymer for setting it as the acrylic rubber-like polymer (a1) whose ratio of a diameter and a number average particle diameter is less than 1.1 can be manufactured efficiently.

  Examples of the alkyl sulfonate include alkane sulfonate, alkyl benzene sulfonate, and alkyl naphthalene sulfonate. These compounds may be used alone or in combination of two or more.

As the alkane sulfonate, a compound represented by the following general formula (1) can be used.
R ¹ —SO ₃ M (1)
(In the formula, R ¹ is a hydrocarbon group having 8 to 20 carbon atoms, and M is Na or K.)

（式中、Ｒ^２は、炭素原子数１０〜１８の炭化水素基であり、Ｍは、Ｎａ又はＫである。） As the alkylbenzene sulfonate, a compound represented by the following general formula (2) can be used.

(In the formula, R ² is a hydrocarbon group having 10 to 18 carbon atoms, and M is Na or K.)

（式中、Ｒ^３は、炭素原子数３〜８の炭化水素基であり、Ｍは、Ｎａ又はＫである。） Moreover, the said alkyl naphthalene sulfonate can use the compound represented by following General formula (3).

(In the formula, R ³ is a hydrocarbon group having 3 to 8 carbon atoms, and M is Na or K.)

  As the alkyl sulfonate, alkane sulfonate and alkyl benzene sulfonate are preferable, and alkyl benzene sulfonate is more preferable. As the alkylbenzene sulfonate, sodium dodecylbenzenesulfonate is particularly preferable.

Examples of the alkyl sulfate ester salt include higher alcohol sulfate ester salt, higher alkyl ether sulfate ester salt, sulfated oil, sulfated fatty acid ester, sulfated olefin and the like. These compounds may be used alone or in combination of two or more.
Examples of the alkyl sulfate ester salt include sodium octyl sulfate, sodium 2-ethylhexyl sulfate, sodium decyl sulfate, sodium lauryl sulfate, potassium lauryl sulfate, ammonium lauryl sulfate, triethanolamine lauryl sulfate, sodium myristyl sulfate, sodium stearyl sulfate, sodium cetyl sulfate. And sodium polyoxyethylene lauryl ether sulfate.

  The amount of the emulsifier (e) used is preferably 0.01 to 4.0 parts by mass, more preferably 0.02 to 3.0 parts by mass, when the monomer (m1) is 100 parts by mass. Part, more preferably 0.04 to 2.5 parts by mass. When the amount of the emulsifier (e) is in the above range, the first polymer for making the acrylic rubbery polymer (a1) having the above properties can be efficiently produced, and the resulting molding is obtained. The product can be excellent in impact resistance and glitter.

  In addition, when using together the said alkyl sulfonate and alkyl sulfate ester salt, when the sum total of both is 100 mass%, Preferably it is 1-99 mass% and 1-99 mass, respectively. %, More preferably 5 to 95 mass% and 5 to 95 mass%, particularly preferably 10 to 90 mass% and 10 to 90 mass%.

  As a method of using the emulsifier (e) in the first polymerization step, a method in which the whole amount is charged all at once into the reaction system before the polymerization, and a part of the emulsifier is added to the reaction system before the polymerization is started. Then, the remainder can be divided or continuously added, or after polymerization has begun, divided or continuously.

  In the first polymerization step, when a polymerization initiator is used, an organic peroxide, an azo compound, an inorganic peroxide, a redox polymerization initiator, or the like can be used.

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

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

Examples of the inorganic peroxide include potassium persulfate, sodium persulfate, and ammonium persulfate.
Redox polymerization initiators include sodium sulfite, sodium thiosulfate, sodium formaldehyde sulfoxylate, ascorbic acid, ferrous sulfate, etc. as reducing agents, potassium peroxodisulfate, hydrogen peroxide, tert-butyl hydroper What used an oxide etc. as an oxidizing agent can be used.

  As the polymerization initiator, an inorganic peroxide is preferable.

  The amount of the polymerization initiator used is preferably 0.01 to 3.0 parts by mass, more preferably 0.03 to 2.0 parts by mass when the monomer (m1) is 100 parts by mass. More preferably, it is 0.05-1.0 mass part, Most preferably, it is 0.1-0.8 mass part. When the amount of the polymerization initiator used is in the above range, the first polymer for making the acrylic rubbery polymer (a1) having the above properties can be efficiently produced, and the obtained molded product Can be made excellent in impact resistance and glitter.

  As a method of using the polymerization initiator in the first polymerization step, a method in which the whole amount is charged all at once into the reaction system before the polymerization, a part of the polymerization initiator is added to the reaction system before the polymerization, and the polymerization starts. The remainder can be divided or continuously added, or the like.

  In the first polymerization step, when a chain transfer agent (molecular weight regulator) is used, halogenated hydrocarbons such as chloroform and carbon tetrabromide; n-hexyl mercaptan, n-octyl mercaptan, n-dodecyl mercaptan, Conventionally known compounds such as mercaptans such as tert-dodecyl mercaptan and thioglycolic acid; xanthogens such as dimethylxanthogen disulfide and diisopropylxanthogen disulfide; terpinolene and α-methylstyrene dimer can be used. Of the chain transfer agents, tert-dodecyl mercaptan is preferred.

  The amount of the chain transfer agent used is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, when the monomer (m1) is 100 parts by mass. If the amount of the chain transfer agent used is too large, the impact resistance of the molded product may be insufficient.

  As a method of using the chain transfer agent in the first polymerization step, a method in which the whole amount is charged all at once into the reaction system before polymerization, a part of the chain transfer agent is added to the reaction system before polymerization, and the polymerization starts. The remainder can be divided or continuously added, or the like.

  In the first polymerization step, when an electrolyte is used, conventionally known compounds such as potassium sulfate, potassium carbonate, sodium carbonate, potassium hydroxide, sodium hydrogen carbonate, sodium pyrophosphate, potassium phosphate, sodium dithionite, etc. Can be used. These compounds may be used alone or in combination of two or more. Of the above compounds, potassium carbonate, sodium carbonate, sodium bicarbonate and sodium dithionite are preferred.

  The amount of the electrolyte used is preferably 0.01 to 1.5 parts by mass, more preferably 0.03 to 1.3 parts by mass, further preferably 100 parts by mass of the monomer (m1). Is 0.05 to 1.0 part by mass. When the usage-amount of the said electrolyte exists in the said range, the 1st polymer for setting it as the copolymer (a11) which is the acrylic rubber-like polymer (a1) which has the said property can be manufactured efficiently.

  As a method of using the electrolyte in the first polymerization step, a method in which the whole amount is charged all at once into the reaction system before the polymerization, a part is added to the reaction system before the polymerization, and the polymerization is started. The remainder may be divided or continuously added, or after polymerization has started, divided or continuously.

The polymerization temperature in the first polymerization step is usually from 65 ° C to 98 ° C, preferably from 70 ° C to 95 ° C. The polymerization time is usually 0.5 to 2.0 hours.
The pH of the reaction system in the first polymerization step is not particularly limited, but is usually in the range of 2-12. By maintaining the pH of the reaction system in the above range and proceeding with polymerization, the first polymer for making the copolymer (a11), which is the acrylic rubbery polymer (a1) having the above properties, can be efficiently obtained. Can be manufactured.

The first polymerization step is completed when the polymerization conversion rate is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more. When the polymerization conversion is low, the acrylic rubber polymer (a1) having the above properties can be obtained even if it is supplied to the second polymerization step using the obtained first polymer. It may not be possible.
In addition, when the said 1st polymerization process is complete | finished by 85% or more of polymerization conversion, the volume average particle diameter of the 1st polymer obtained is 40-120 nm normally.

  In the second polymerization step, the (meth) acrylic acid alkyl ester compound is present in the presence of the first polymer, in the presence or absence of an alkyl sulfonate and / or an alkyl sulfate ester salt (emulsifier (e)). (M2-1) 50 to 99.99 mass%, polymerizable unsaturated compound (m2-2) having 2 or more carbon-carbon double bonds, 0.01 to 5 mass%, and alkyl (meth) acrylate 0 to 49.99 mass% of other compounds (m2-3) copolymerizable with the ester compound (m2-1) and the polymerizable unsaturated compound (m2-2) (however, (m2-1), (m2- 2) and the sum of (m2-3) is 100% by mass.) And the monomer (m2) is polymerized in an aqueous medium to obtain a copolymer.

The second polymerization step may be performed in the same reaction system as the first polymerization step, or may be performed in a different reaction system. When the reaction is performed in a different reaction system, the polymerization may be performed in the presence of the emulsifier (e) or may be performed in the absence of the emulsifier (e). In the latter case, other emulsifiers may be used.
In the second polymerization step, when an emulsifier is used, a polymerization initiator, a chain transfer agent (molecular weight regulator), an electrolyte, and the like can be used as necessary. As these components, any of the compounds exemplified above can be used.

  As the (meth) acrylic acid alkyl ester compound (m2-1) constituting the monomer (m2), a compound having 1 to 14 carbon atoms of the alkyl group in the ester part is preferably used. N-butyl acrylate and 2-ethylhexyl acrylate are preferably used. In addition, the said (meth) acrylic-acid alkylester compound (m2-1) may be used independently and may use 2 or more types.

  The polymerizable unsaturated compound (m2-2) having two or more carbon-carbon double bonds is preferably a bifunctional aromatic vinyl compound, a bifunctional (meth) acrylic acid ester, a trifunctional ( (Meth) acrylic acid ester, tetrafunctional (meth) acrylic acid ester, pentafunctional (meth) acrylic acid ester, hexafunctional (meth) acrylic acid ester, polyhydric alcohol (meth) acrylic acid ester, etc. are used. In particular, allyl methacrylate and triallyl cyanurate are preferably used. In addition, the said polymerizable unsaturated compound (m2-2) may be used independently and may use 2 or more types.

  Moreover, as said (meth) acrylic-acid alkylester compound (m2-1) and the said other compound (m2-3) copolymerizable with the said polymerizable unsaturated compound (m2-2), carbon-carbon two is normally used. A compound having one heavy bond is used, and an aromatic vinyl compound, a vinyl cyanide compound and the like are preferably used. In addition, these compounds may be used independently and can be used in combination of 2 or more type.

  The ratio of the (meth) acrylic acid alkyl ester compound (m2-1), the polymerizable unsaturated compound (m2-2), and the other compound (m2-3) used in the second polymerization step is the sum of these. When the content is 100% by mass, preferably 50 to 99.99% by mass, 0.01 to 5.0% by mass and 0 to 49.99% by mass, more preferably 70 to 99.99% by mass, They are 0.01-3.0 mass% and 0-29.99 mass%, More preferably, it is 90-99.99 mass%, 0.01-2.0 mass%, and 0-9.99 mass%. By setting it as the above ratio, the molded article is excellent in impact resistance and glitter, and the occurrence of yarn burrs during vibration welding is suppressed.

  In addition, the ratio of the usage-amount of the monomer (m1) used at the said 1st superposition | polymerization process and the monomer (m2) used at the said 2nd superposition | polymerization process is when the sum total of both is 100 mass%, Preferably they are 1-50 mass% and 50-99 mass%, respectively, More preferably, they are 3-40 mass% and 60-97 mass%, Most preferably, they are 5-35 mass% and 65-95 mass%. By setting it as the above ratio, the molded article is excellent in impact resistance and glitter, and the occurrence of yarn burrs during vibration welding is suppressed.

  The second polymerization step is a step of polymerizing the monomer (m2) in the presence of the first polymer obtained in the first polymerization step, and the entire amount of the monomer (m2) is reacted with the reaction system. The polymerization may be carried out by adding them all at once, or the polymerization may be carried out while adding the monomer (m2) separately or continuously. About the usage method of an emulsifier, a polymerization initiator, a chain transfer agent (molecular weight regulator), it can be made to be the same as that of the method in the said 1st polymerization process.

As described above, the second polymerization step may proceed in the same reaction system as the first polymerization step, or may proceed in a different reaction system.
When the second polymerization step proceeds in the same reaction system as the first polymerization step, the monomer (m2) is added to the latex containing the first polymer obtained in the first polymerization step, and polymerization is performed. If necessary, an aqueous medium or the like may be newly added.
Further, when the second polymerization step proceeds in a new reaction system, the latex containing the first polymer obtained in the first polymerization step may be used as it is. A suspension suspended in an aqueous medium may be used.

When the second polymerization step proceeds in the presence of the emulsifier (e), a preferred type of the emulsifier (e), a preferred combination of an alkyl sulfonate and an alkyl sulfate ester salt, and a method of using the emulsifier (e) are: These are the same as those in the first polymerization step.
Moreover, the usage-amount of the said emulsifier (e) becomes like this. Preferably the said monomer (m2) is 100 mass parts, 0.01-4.0 mass parts, More preferably, 0.02-3. It is 0 mass part, More preferably, it is 0.04-2.5 mass part. When the amount of the emulsifier (e) is in the above range, the copolymer (a11) which is the acrylic rubbery polymer (a1) having the above properties can be efficiently produced, and the obtained molding is obtained. The product can be excellent in impact resistance and glitter.

  Further, when a polymerization initiator, a chain transfer agent (molecular weight regulator), an electrolyte, or the like is used in the second polymerization step, the same compounds and methods of use as those used in the first polymerization step are preferably used. It is done. About the usage-amount of each component, the same quantity can be used as what replaced the monomer (m1) with the monomer (m2).

The polymerization temperature in the second polymerization step is usually 65 ° C to 98 ° C, preferably 70 ° C to 95 ° C. The polymerization time is usually 2.0 to 8.0 hours.
The pH of the reaction system in the second polymerization step is not particularly limited, but is usually in the range of 2-12. By proceeding the polymerization while maintaining the pH of the reaction system in the above range, the copolymer (a11) which is the acrylic rubbery polymer (a1) having the above properties can be produced efficiently.

  The second polymerization step ends when the polymerization conversion rate is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more. When the second polymerization step is completed at a polymerization conversion rate of 85% or more, a copolymer (a11) that is an acrylic rubbery polymer (a1) having the above properties can be produced efficiently. In addition, when the polymerization conversion rate is lowered and the polymerization is terminated, the resulting acrylic rubbery polymer has a small particle diameter and may have insufficient impact resistance.

Examples of the acrylic rubbery polymer (a1) include the copolymer (a11) obtained as described above and the conventional acrylic rubbery polymer obtained by a known method. Can be used.
Examples of the method for the enlargement treatment include a method in which an acid such as acetic anhydride, acetic acid, nitric acid, phosphoric acid is added to the latex containing the polymer for enlargement. Among these, acetic anhydride is preferable, and thereby an acrylic rubber polymer (a1) having no variation in particle diameter after enlargement can be obtained.

  As the acrylic rubbery polymer (a1), any of a polymer that is not enlarged and a polymer that is enlarged may be used, or a combination thereof may be used.

  In the presence of the acrylic rubbery polymer (a1), the vinyl monomer (a2) subjected to polymerization is a monomer containing an aromatic vinyl compound and a vinyl cyanide compound, and if necessary , (Meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, amino group-containing unsaturated compounds, amide group-containing unsaturated compounds, epoxy group-containing An unsaturated compound, an oxazoline group-containing unsaturated compound, and the like may be included. In addition, the ratio of the total amount of the aromatic vinyl compound and the vinyl cyanide compound in the vinyl monomer (a2) is preferably 50 to 100% by mass, more preferably 70 to 100% by mass, and still more preferably 80. ˜100 mass%.

  The aromatic vinyl compound is not particularly limited, but has no substituent such as a functional group. Examples thereof include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinyltoluene, vinylxylene, vinylnaphthalene and the like. These compounds can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferable, and styrene is particularly preferable.

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

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

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-methyl). Phenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N-naphthylmaleimide, N- Examples thereof include cyclohexylmaleimide. Of these, N-phenylmaleimide is preferred. Moreover, these compounds can be used individually or in combination of 2 or more. In addition, as another method for introducing a structural unit derived from a maleimide compound into the component [A], for example, a method of copolymerizing an unsaturated dicarboxylic anhydride of maleic anhydride and then imidizing it may be used. .

Examples of the unsaturated acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These compounds can be used alone or in combination of two or more.
Examples of the carboxyl group-containing unsaturated compound include (meth) acrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid and the like. These compounds can be used alone or in combination of two or more.

  Examples of the hydroxyl group-containing unsaturated compound include hydroxymethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, (meth ) 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, (meth) acrylic acid 2 (Meth) acrylic acid ester having a hydroxyl group such as a compound obtained by adding ε-caprolactone to hydroxyethyl; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methyl Styrene, m -Hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, 2-hydroxymethyl-α-methylstyrene, 3-hydroxymethyl-α-methylstyrene, 4-hydroxymethyl-α-methylstyrene, 4-hydroxy Methyl-1-vinylnaphthalene, 7-hydroxymethyl-1-vinylnaphthalene, 8-hydroxymethyl-1-vinylnaphthalene, 4-hydroxymethyl-1-isopropenylnaphthalene, 7-hydroxymethyl-1-isopropenylnaphthalene, 8 -Hydroxymethyl-1-isopropenylnaphthalene, N- (4-hydroxyphenyl) maleimide, p-vinylbenzyl alcohol, 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2- Butene, trans-4-hydroxy Ci-2-butene, 3-hydroxy-2-methyl-1-propene and the like can be mentioned. These compounds can be used alone or in combination of two or more.

  Examples of the amino group-containing unsaturated compound include aminoethyl (meth) acrylate, propylaminoethyl (meth) acrylate, dimethylaminomethyl (meth) acrylate, diethylaminomethyl (meth) acrylate, (meth) acrylic acid 2 -Dimethylaminoethyl, 2-diethylaminoethyl (meth) acrylate, 2- (di-n-propylamino) ethyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 2- (meth) acrylic acid 2- Diethylaminopropyl, 2- (di-n-propylamino) propyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 3-diethylaminopropyl (meth) acrylate, 3- (di) (meth) acrylate -N-propylamino) propyl, (meth) acrylic acid 2-tert- Tylaminoethyl, phenylaminoethyl (meth) acrylate, (meth) acrylic acid amino ether, 4-aminostyrene, 4-dimethylaminostyrene, N-vinyldiethylamine, N-acetylvinylamine, (meth) acrylamine, N -Methyl (meth) acrylamine etc. are mentioned. These compounds can be used alone or in combination of two or more.

  Examples of the amide group-containing unsaturated compound include (meth) acrylamide, N-methylol (meth) acrylamide, 3-dimethylaminopropyl (meth) acrylamide and the like. These compounds can be used alone or in combination of two or more.

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

As the component [A], preferred graft resins are as follows.
(1) Resin (2) Acrylic obtained by polymerizing vinyl monomer (a2-1) composed of aromatic vinyl compound and vinyl cyanide compound in the presence of acrylic rubbery polymer (a1) Obtained by polymerizing a vinyl monomer (a2-2) comprising an aromatic vinyl compound, a vinyl cyanide compound and a (meth) acrylic acid ester compound in the presence of the rubber-based polymer (a1)

  The component [A] is composed of an acrylic rubbery polymer part and a copolymer part containing a structural unit derived from the vinyl monomer (a2) as described above. The content of the acrylic rubbery polymer part constituting this component [A] is 100 parts by mass in total of the acrylic rubbery polymer part and the copolymer part from the viewpoint of impact resistance and glitter of the molded product. The amount is preferably 5 to 80 parts by mass, more preferably 10 to 70 parts by mass, and still more preferably 10 to 65 parts by mass. In addition, when there is too much content of the said acrylic rubber-like polymer part, the productivity, heat resistance, and glitter of acrylic rubber-like polymer reinforcement | strengthening graft resin may fall. On the other hand, if the content of the acrylic rubbery polymer part is too small, the impact resistance may not be sufficient.

  The method for producing the component [A] is not particularly limited, and a known method can be applied. The graft polymerization method may be emulsion polymerization, suspension polymerization, solution polymerization, bulk polymerization, or a polymerization method combining these. Of these, emulsion polymerization is preferred. In the above polymerization method, an ungrafted polymer is by-produced in addition to the component [A].

  When the component [A] is produced, the amount of the acrylic rubbery polymer (a1) and the vinyl monomer (a2) used is 100% in total from the viewpoint of impact resistance and glitter. %, Preferably 5 to 90% by mass and 10 to 95% by mass, more preferably 10 to 80% by mass and 20 to 90% by mass, still more preferably 30 to 70% by mass and 30 to 70% by mass, respectively. %.

  When the component [A] is produced, in the reaction system, the vinyl monomer (a2) is added all at once in the presence of the total amount of the acrylic rubber polymer (a1), and polymerization is started. Alternatively, the polymerization may be carried out in portions or continuously. Further, in the presence or absence of a part of the acrylic rubbery polymer (a1), the vinyl monomer (a2) may be added all at once to initiate polymerization, or may be divided or continuously. May be added. At this time, you may add the remainder of the said acrylic rubber-like polymer (a1) collectively, in the middle of reaction, dividing | segmenting or continuously.

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

As the polymerization initiator, a redox polymerization initiator is preferable. Moreover, the usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (a2) whole quantity.
The polymerization initiator can be added to the reaction system all at once or continuously.

As the chain transfer agent, mercaptans are preferable, and tert-dodecyl mercaptan is particularly preferable. Moreover, the usage-amount of the said chain transfer agent is 5 mass% or less normally with respect to the said vinylic monomer (a2) whole quantity.
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 0.01-5 mass% normally with respect to the said vinylic monomer (a2) whole quantity.

Emulsion polymerization can be carried out under known conditions depending on the type and formulation of the vinyl monomer (a2), the polymerization initiator and the like.
The polymerization temperature for polymerizing the vinyl monomer (a2) is usually 40 ° C to 80 ° C, preferably 50 ° C to 75 ° C. The polymerization time is usually 4 to 8 hours.

  Although the pH of the reaction system in emulsion polymerization is not specifically limited, Usually, it is the range of 8-12, Preferably it is 9-12. Formation of component [A] can be efficiently advanced by advancing polymerization while maintaining the pH of the reaction system in the above range.

  The emulsion polymerization is terminated when the polymerization conversion rate is preferably 85% or more, more preferably 90% or more, and particularly preferably 95% or more. When this emulsion polymerization is completed at a polymerization conversion rate of 85% or more, a molded article excellent in impact resistance and glitter can be obtained using the composition containing the obtained component [A].

  After the completion of the emulsion polymerization, the latex containing the component [A] is usually subjected to coagulation of the resin component with a coagulant to form a powder or the like. Thereafter, it is purified by washing with water, etc., dried and collected. For coagulation, conventionally known coagulants are used, and inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and calcium acetate; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid are used.

  When the component [A] is produced by solution polymerization, bulk polymerization, and bulk-suspension polymerization, known methods can be applied.

The rubber reinforced resin obtained as described above usually contains the component [A] and the ungrafted polymer. Therefore, when separating the component [A] and the ungrafted polymer, for example, 1 g of the rubber reinforced resin. Is added to 20 to 30 ml of acetone, followed by stirring at 25 ° C. for 2 to 6 hours, and a method for separating and recovering the generated insoluble matter and soluble matter (acetone soluble polymer) is applied.
The acetone-soluble polymer corresponds to an ungrafted polymer, and as described above, is included in the component [C] and / or the component [D] depending on the type of the vinyl monomer (a2) used. There is something to be done.

  The graft ratio in the component [A], that is, the proportion of the copolymer containing a structural unit derived from the vinyl monomer (a2) grafted to the acrylic rubber polymer (a1) is moldability, From the viewpoints of impact resistance, glitter and the like, it is preferably 5 to 200% by mass, more preferably 10 to 150% by mass, and still more preferably 20 to 120% by mass. If the graft ratio is too low, the impact resistance of the molded product may not be sufficient. On the other hand, if the graft ratio is too high, moldability may not be sufficient.

The graft ratio can be determined by the following formula.
Graft rate (%) = {(S−T) / T} × 100
In the formula, S is a rubber-reinforced resin obtained by graft polymerization, put into acetone, shaken using a shaker (temperature 23 ° C., 2 hours), and then centrifuged using a centrifuge. The mass (g) of insoluble matter (temperature 60 ° C., dried for 12 hours) obtained by separation (temperature 0 ° C., rotation speed 28,000 rpm, 1 hour) and separation of insoluble matter and soluble matter, T Is the mass (g) of the acrylic rubbery polymer (a1) contained in the rubber-reinforced resin. The mass of the acrylic rubbery polymer (a1) can be obtained by a method of calculating from a polymerization prescription and a polymerization conversion rate, a method of obtaining from an infrared absorption spectrum (IR), and the like.

  The graft ratio is, for example, the type and amount of polymerization initiator used in the production of component [A], the type and amount of chain transfer agent, the vinyl monomer (a2) supply method and supply time, The polymerization temperature and the like can be adjusted by appropriately selecting.

  The component [B] is a homopolymer glass in the presence of an organosiloxane rubber and a composite rubber (b1) containing a (co) polymer rubber having a structural unit derived from a (meth) acrylic acid alkyl ester. A vinyl monomer containing a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyanide compound having a transition temperature exceeding 0 ° C. (hereinafter also referred to as “vinyl monomer (b2)”). This is a composite rubber reinforced graft resin obtained by polymerization (graft polymerization).

  The component [B] is a resin in which the copolymer of the vinyl monomer (b2) is grafted to the composite rubber (b1), like the component [A], and the composite rubber portion; It is a resin comprising a copolymer part containing a structural unit derived from the vinyl monomer (b2).

  The composite rubber (b1) used for forming the component [B] is composed of an organosiloxane rubber and a (co) polymer rubber having a structural unit derived from a (meth) acrylic acid alkyl ester, It is a compounded rubber that is not independent of each other due to entanglement of the two. Examples of the organosiloxane rubber include polyorganosiloxane (b1-1) described later and a (co) polymer rubber containing a structural unit derived from (meth) acrylic acid alkyl ester. (B1-2) is preferred.

  The composite rubber (b1) containing the polyorganosiloxane (b1-1) and the poly (meth) acrylate (b1-2) is an alkyl (meth) acrylate in the presence of the polyorganosiloxane (b1-1). In the presence of rubber obtained by a method of polymerizing a monomer containing an ester compound (hereinafter referred to as “monomer (mm)”) or poly (meth) acrylate (b1-2), organo A rubber obtained by a method of polymerizing siloxane can be used. Among these, from the viewpoint of impact resistance, glitter and productivity of the molded product, the former method is preferable, and the method will be described in detail below.

  The polyorganosiloxane (b1-1) is preferably one in which cyclic organosiloxanes are linked via a graft crossing agent, and a cyclic organosiloxane having three or more members and a graft crossing agent for polyorganosiloxane (hereinafter, “ A product obtained by emulsion polymerization of an organosiloxane mixture containing a “siloxane cross-linking agent”) is preferred. The organosiloxane mixture may contain a polyorganosiloxane crosslinking agent (hereinafter referred to as “siloxane crosslinking agent”) as necessary.

  As said 3 or more-membered cyclic organosiloxane, the compound of 3-6 membered ring is preferable. Cyclic organosiloxanes include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane Etc. These may be used alone or in combination of two or more.

As said siloxane crossing agent, it couple | bonds with said cyclic organosiloxane through a siloxane bond, and forms a bond with poly (meth) acrylic acid ester (b1-2) and vinyl monomer (b2) described later. What can be done is preferred. From the viewpoint of reactivity with the cyclic organosiloxane, an alkoxysilane compound having a vinyl group is preferred.
Examples of the alkoxysilane compound include β-methacryloyloxyethyldimethoxymethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyltrimethoxysilane, and γ-methacryloyloxypropylethoxydiethyl. Methacryloyloxysilane such as silane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane; vinylsiloxane such as tetramethyltetravinylcyclotetrasiloxane; vinylphenyl such as p-vinylphenyldimethoxymethylsilane Silane; γ-mercaptopropyldimethoxymethylsilane, γ-mercaptopropyltrimethoxysilane, etc. It includes mercaptosilane. These compounds may be used alone or in combination of two or more.

  As said siloxane crosslinking agent, the compound which has 3 or 4 functional groups which can couple | bond with the said cyclic organosiloxane is preferable. Examples of such compounds include trialkoxyalkylsilanes such as trimethoxymethylsilane; trialkoxyarylsilanes such as triethoxyphenylsilane; tetraalkoxys such as tetramethoxysilane, tetraethoxysilane, tetra n-propoxysilane, and tetrabutoxysilane. Silane etc. are mentioned. These may be used alone or in combination of two or more. Of these, tetraalkoxysilane is preferable, and tetraethoxysilane is particularly preferable.

  When the organosiloxane mixture is composed of a cyclic organosiloxane, a siloxane crossing agent, and a siloxane cross-linking agent, the ratio of the amounts used of these components is preferably 60 to 99, respectively, when the total of these components is 100% by mass. 0.9 mass%, 0.1-10 mass%, and 0-30 mass%. In addition, the especially preferable usage-amount of the said cyclic organosiloxane is 70-99.9 mass%.

The emulsion polymerization of the organosiloxane mixture includes the following methods.
(1) A method in which an emulsifier and water are added to an organosiloxane mixture to obtain a latex, and the latex is microparticulated.
(2) A method in which an acid catalyst is added to an organosiloxane mixture together with an emulsifier and water to form a latex, and the reaction is performed by making the latex fine particles.

  Examples of the emulsifier include anionic emulsifiers such as sodium alkylbenzene sulfonate, sodium alkyl sulfonate, and sodium polyoxyethylene alkyl sulfate. These compounds may be used alone or in combination of two or more. Of these, sulfonate emulsifiers such as sodium alkylbenzene sulfonate and sodium alkyl sulfonate are preferred.

  The amount of the emulsifier used is preferably 0.05 parts by mass or more with respect to 100 parts by mass of the organosiloxane mixture in order to maintain a stable dispersion state of the latex. Further, the upper limit is preferably 15 parts by mass in order to avoid coloration caused by the emulsifier itself and coloration due to deterioration of the thermoplastic resin composition.

Examples of the acid catalyst include sulfonic acids such as alkylsulfonic acid, alkylbenzenesulfonic acid, and alkylnaphthalenesulfonic acid; and mineral acids such as sulfuric acid, hydrochloric acid, and nitric acid. These may be used alone or in combination of two or more. Of these, alkylbenzene sulfonic acid is preferable because n-dodecylbenzene sulfonic acid is more preferable because it is excellent in stabilizing action of the latex containing polyorganosiloxane.
The amount of the acid catalyst used is preferably 0.1 to 15 parts by mass with respect to 100 parts by mass of the organosiloxane mixture.

As a method for using the acid catalyst in the method (1), it is preferable to use an acid catalyst aqueous solution dissolved in water. It is preferable that the acid catalyst aqueous solution is heated to a high temperature, and then the finely divided latex is dropped into the aqueous solution at a constant rate to advance the polymerization reaction. This method (1) is preferable because the particle diameter of the resulting polyorganosiloxane can be easily controlled.
In the method (2), the acid catalyst may be used as it is, or an acid catalyst aqueous solution obtained by dissolving in water may be used. Then, the acid catalyst or the acid catalyst aqueous solution can be added to and mixed with the organosiloxane mixture, the emulsifier and the water.

  In the emulsion polymerization of the above-mentioned organosiloxane mixture, the latex is made into fine particles by a homomixer that makes the hydrophobic substance in the latex fine particles by shearing force by high-speed rotation, a homogenizer that makes fine particles by jetting power from a high-pressure generator, etc. Can be mentioned. Among these, a high-pressure emulsification apparatus such as a homogenizer is preferable because a latex having a small particle size distribution width of the organosiloxane mixture can be obtained.

In the method (1), the polymerization time for forming the polyorganosiloxane (b1-1) is preferably about 1 hour after the end of dropping of the latex. On the other hand, in the above method (2), the polymerization time is preferably 2 hours or more, more preferably 5 hours or more.
In any case, the polymerization temperature is preferably 50 ° C. or higher, more preferably 80 ° C. or higher.

The emulsion polymerization can be stopped by cooling the reaction solution and further neutralizing with an alkaline substance such as sodium hydroxide, potassium hydroxide, sodium carbonate or the like.
The volume average particle diameter of the polyorganosiloxane (b1-1) obtained by the above operation is preferably 120 nm or less, more preferably 100 nm or less. However, the lower limit is usually 60 nm.

Thereafter, in the presence of the obtained polyorganosiloxane (b1-1), a monomer (mm) containing a (meth) acrylic acid alkyl ester compound is polymerized to obtain polyorganosiloxane (b1-1) and poly ( A composite rubber (b1) containing a (meth) acrylic acid ester (b1-2) can be obtained.
The monomer (mm) may be only a (meth) acrylic acid alkyl ester compound, or may be composed of a (meth) acrylic acid alkyl ester compound and another compound.

The (meth) acrylic acid alkyl ester compound is preferably a compound having 1 to 14 carbon atoms in the ester group alkyl group. Specific examples are methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate. , Tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, (meth) Nonyl acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, and the like. These compounds may be used alone or in combination of two or more.
Examples of the (meth) acrylic acid alkyl ester compound include methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, hexyl methacrylate, 2-ethylhexyl (meth) acrylate, dodecyl methacrylate and methacrylic acid. Tridecyl acid is preferred, and n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.

  The other compound is not particularly limited as long as it is a compound copolymerizable with the (meth) acrylic acid alkyl ester compound, and has one carbon-carbon double bond excluding the (meth) acrylic acid alkyl ester compound. Examples thereof include compounds and compounds having two or more carbon-carbon double bonds.

  As the other compound, a compound having two or more carbon-carbon double bonds is preferable, and a graft cross-linking agent for poly (meth) acrylate (hereinafter referred to as “acrylic cross-linking agent”) and poly (meth). A crosslinking agent for acrylic esters (hereinafter referred to as “acrylic crosslinking agent”) is preferably used.

The acrylic crossover agent is preferably a compound having a different reactivity with the (meth) acrylic acid ester compound at a plurality of carbon-carbon double bonds contained in the molecule.
Examples of the acrylic crossing agent include allyl (meth) acrylate, triallyl cyanurate, triallyl isocyanurate and the like. These may be used alone or in combination of two or more.

  The acrylic crosslinking agent is preferably a compound that forms a crosslinked structure in the poly (meth) acrylic acid ester (b1-2).

  Examples of the acrylic crosslinking agent include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, and neopentyl. Examples include glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tetramethyloltetra (meth) acrylate, and divinylbenzene. These may be used alone or in combination of two or more.

The monomer (mm) may be composed of a (meth) acrylic acid alkyl ester compound and an acrylic crosslinking agent, or a (meth) acrylic acid alkyl ester compound, an acrylic crosslinking agent, and an acrylic crosslinking agent. It may consist of:
The use ratio of the above-mentioned (meth) acrylic acid alkyl ester compound, acrylic cross-linking agent and acrylic cross-linking agent is preferably 80 to 99.99% by mass, and 0.0. It is 01-10 mass% and 0-10 mass%. In addition, the especially preferable usage-amount of a (meth) acrylic-acid alkylester compound is 90-99.99 mass%.

If the amount of the acrylic crossing agent used in the monomer (mm) is 0.01% by mass or more, the poly (meth) acrylic acid ester (b1-2) has a sufficient graft polymerization starting point. If it is at most mass%, the rubber elasticity of the poly (meth) acrylic acid ester (b1-2) can be maintained.
Moreover, if the usage-amount of the acrylic crosslinking agent in the said monomer (mm) is 10 mass% or less, the rubber elasticity of poly (meth) acrylic acid ester (b1-2) can be maintained.

  The amount of the monomer (mm) used for polymerization in the presence of the polyorganosiloxane (b1-1) is preferably 400 when the polyorganosiloxane (b1-1) is 100 parts by mass. It is -9,900 mass parts, More preferably, it is 900-1,900 mass parts. When the usage-amount of the said monomer (mm) exists in the said range, the composite rubber (b1) which gives the molded article excellent in impact resistance and luster can be obtained efficiently.

When producing the composite rubber (b1) using the polyorganosiloxane (b1-1) and the monomer (mm), for example, it is necessary for the latex containing the polyorganosiloxane (b1-1). Depending on the method, after adding water, a polymerization initiator, an emulsifier, a chain transfer agent (molecular weight regulator), etc., polymerization is performed while supplying a monomer (mm). In this case, the monomer (mm) may be supplied all at once or divided, or may be continuously provided.
At this time, the monomer (mm) to be supplied may be as it is, or an emulsion prepared in advance using a mixture containing the monomer (mm), an emulsifier and water is used. May be. In the latter case, an emulsion obtained by micronizing the monomer (mm) may be used.

  Examples of the polymerization initiator include organic peroxides, azo compounds, inorganic peroxides, and redox polymerization initiators. Of these, redox type polymerization initiators are preferred, and in particular, a combination of ferrous sulfate, sodium pyrophosphate, glucose, hydroperoxide, a combination of ferrous sulfate, disodium ethylenediaminetetraacetate, longalite, hydroperoxide. Etc. are preferred.

  When the said monomer (mm) is 100 mass parts, the usage-amount of the said polymerization initiator becomes like this. Preferably it is 0.01-5 mass parts, More preferably, it is 0.05-3 mass parts. When the amount of the polymerization initiator used is in the above range, the composite rubber (b1) can be produced efficiently, and the resulting molded article is excellent in impact resistance and glitter. it can.

Examples of the emulsifier include carboxylates such as sodium sarcosine, fatty acid potassium, fatty acid sodium, dipotassium alkenyl succinate, and rosin acid soap; alkyl sulfate ester; sodium alkylbenzene sulfonate; sodium alkyl sulfonate; polyoxyethylene alkyl sodium sulfate, etc. Anionic emulsifiers are mentioned. These compounds may be used alone or in combination of two or more.
By using the above-mentioned emulsifier, the latex at the time of emulsion polymerization can be stably maintained and the polymerization conversion rate can be increased. Moreover, you may use the same thing as the emulsifier used for manufacture of the said polyorganosiloxane (b1-1) as said emulsifier.

  The polymerization temperature at the time of polymerizing the monomer (mm) is usually 65 ° C to 98 ° C, preferably 70 ° C to 95 ° C. The polymerization time is usually 0.5 to 6 hours.

  The volume average particle diameter of the composite rubber (b1) obtained by the above steps is preferably 50 to 150 nm, more preferably 60 to 120 nm. The ratio of the volume average particle diameter to the number average particle diameter is preferably 2 or less, more preferably 1.5 or less, and particularly preferably 1.1 or less. The gel content is preferably 70% by mass or more, more preferably 90% by mass or more, particularly preferably 95% by mass or more, and the toluene swelling degree is preferably 2 to 30 times, more preferably 6 to 25 times. It is.

  The composite rubber (b1) obtained as described above is a poly (meth) acrylic acid ester (b1-2) containing a structural unit derived from the monomer (mm) in the polyorganosiloxane (b1-1). ) Grafted product form or polyorganosiloxane (b1-1) and poly (meth) acrylate ester (b1-2) containing a structural unit derived from the monomer (mm). An intertwined cross-linked network is formed, and is substantially in a form that cannot be separated from each other. The latex containing the composite rubber (b1) includes a poly (meth) acrylic acid ester (b1-2) containing a structural unit derived from the monomer (mm) and a polyorganosiloxane (b1-1). Independently, it may be contained while liberated.

  If necessary, the composite rubber (b1) can be further subjected to an enlargement treatment in the same manner as in the case of the acrylic rubbery polymer (a1).

The vinyl monomer (b2) used for forming the component [B] is a (meth) acrylic acid alkyl ester compound, aromatic vinyl compound and vinyl cyanide compound whose homopolymer has a glass transition temperature exceeding 0 ° C. including.
Examples of the (meth) acrylic acid alkyl ester compound in which the glass transition temperature of the homopolymer exceeds 0 ° C. include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, methyl acrylate and the like.
Regarding the aromatic vinyl compound and the vinyl cyanide compound, the aromatic vinyl compound and the cyanidated vinyl compound that can be used in the vinyl monomer (a2) can be applied.

The proportion of the (meth) acrylic acid alkyl ester compound in which the glass transition temperature of the homopolymer exceeds 0 ° C. contained in the vinyl monomer (b2) is in view of the balance between impact resistance and glitter of the molded product. Therefore, when the total of the (meth) acrylic acid alkyl ester compound, the aromatic vinyl compound and the vinyl cyanide compound is 100% by mass, it is preferably 40 to 60% by mass.
In addition, the ratio of the usage-amount of an aromatic vinyl compound and a vinyl cyanide compound contained in the said vinyl-type monomer (b2), when the sum total of both is 100 mass%, respectively, Preferably it is 10-90, respectively. It is 10 mass% and 10-90 mass%.

  The ratio of the total amount of the (meth) acrylic acid alkyl ester compound, aromatic vinyl compound and vinyl cyanide compound in which the glass transition temperature of the homopolymer exceeds 0 ° C. contained in the vinyl monomer (b2) is as follows: Preferably it is 70-100 mass% with respect to the whole quantity of the said vinylic monomer (b2), More preferably, it is 85-100 mass%.

  The vinyl monomer (b2) may be composed of a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and a vinyl cyanide compound having a glass transition temperature of a homopolymer exceeding 0 ° C., Furthermore, other monomers ((meth) acrylic acid ester compounds, maleimide compounds, unsaturated acid anhydrides, carboxyl group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds whose homopolymer has a glass transition temperature of 0 ° C. or lower , An amino group-containing unsaturated compound, an amide group-containing unsaturated compound, an epoxy group-containing unsaturated compound, an oxazoline group-containing unsaturated compound, etc.). Further, when a maleimide compound is included as another monomer, a structural unit derived from the maleimide compound is added as in the case of producing the component [A] using the acrylic rubbery polymer (a1). Since the containing copolymer may be formed as an ungrafted polymer, when a copolymer containing a structural unit derived from a maleimide compound is produced, this copolymer is included in the component [C]. .

  The proportion of the composite rubber (b1) and the vinyl monomer (b2) used in the production of the component [B] is 100% from the viewpoint of the balance between the impact resistance and the glitter of the molded product. When it is defined as mass%, it is preferably 30 to 90 mass% and 10 to 70 mass%, more preferably 50 to 85 mass% and 15 to 50 mass%, still more preferably 70 to 80 mass% and 20 to 30 mass, respectively. % By mass.

  The production method of the component [B] is not particularly limited, and in the presence of the composite rubber (b1), a part of the vinyl monomer (b2) is supplied for polymerization, and then the remainder is supplied. For example, a method of proceeding the polymerization, a method of proceeding the polymerization by supplying the whole amount of the vinyl monomer (b2) in the presence of the composite rubber (b1), or the like can be used. In the present invention, the former method is preferable. Specifically, in the presence of the composite rubber (b1), a (meth) acrylic acid alkyl ester compound having a glass transition temperature of higher than 0 ° C. is graft-polymerized. Thereafter, a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound can be added and polymerized without a maleimide compound. When the component [B] obtained by using the vinyl monomer (b2) in this way is used, a molded product particularly excellent in impact resistance and glitter can be obtained.

  Graft polymerization can be carried out in the same manner as in the production method of component [A]. If necessary, water, an emulsifier, a polymerization initiator, a chain transfer agent and the like can be added to the reaction system. As these emulsifiers, polymerization initiators, chain transfer agents and the like, the compounds exemplified in the production method of the component [A] can be used.

  The graft ratio in the component [B], that is, the ratio of the copolymer grafted on the composite rubber (b1) and containing the structural unit derived from the vinyl monomer (b2) is determined by molding processability, impact resistance, From the standpoint of glitter and the like, it is preferably 5 to 200% by mass, more preferably 10 to 150% by mass, and still more preferably 20 to 120% by mass. If the graft ratio is too low, the impact resistance of the molded product may not be sufficient. On the other hand, if the graft ratio is too high, moldability may not be sufficient.

Component [C] is a structural unit derived from a maleimide compound (hereinafter referred to as “structural unit (c1)”) in an amount of 10 to 70% by mass, preferably 20 to 70% by mass, based on the total structural unit. More preferred is a maleimide copolymer containing 25 to 65% by mass. When the content of the structural unit (c1) is in the above range, a molded product having excellent heat resistance and impact resistance can be obtained.
In addition, when the said component [A] is a graft resin which consists of an acrylic rubber-like polymer part and a copolymer part containing the structural unit (c1) derived from a maleimide-type compound, and the said component [B ] Is a graft resin comprising a composite rubber part and a copolymer part containing a structural unit (c1) derived from a maleimide compound, these graft resins are included in component [C]. Make it not exist. That is, the component [C] is structurally independent from the components [A] and [B].
The component [C] may be a copolymer containing only one type of structural unit (c1) or a copolymer containing two or more types of structural units (c1).

  The component [C] is a copolymer including the structural unit (c1), and further includes another structural unit (hereinafter referred to as “structural unit (c2)”). This structural unit (c2) is a structural unit derived from a vinyl monomer copolymerizable with the maleimide compound.

  Examples of vinyl monomers copolymerizable with maleimide compounds include aromatic vinyl compounds, vinyl cyanide compounds, unsaturated acid anhydrides, (meth) acrylic acid ester compounds, carboxyl group-containing unsaturated compounds, and hydroxyl group-containing compounds. Examples include unsaturated compounds, amino group-containing unsaturated compounds, amide group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, and oxazoline group-containing unsaturated compounds. The compound illustrated as a vinyl-type monomer (a2) which can be used for formation of the said component [A] is applied to these compounds. And these compounds may be used independently and may be used in combination of 2 or more type.

  In the present invention, the vinyl monomer copolymerizable with the maleimide compound preferably includes an aromatic vinyl compound.

As said component [C], a preferable maleimide-type copolymer is as follows.
(C1) A copolymer of a maleimide compound and an aromatic vinyl compound.
(C2) A copolymer of a maleimide compound, an aromatic vinyl compound, and an unsaturated acid anhydride.
(C3) A copolymer of a maleimide compound, an aromatic vinyl compound, and a vinyl cyanide compound.
(C4) A copolymer of a maleimide compound, an aromatic vinyl compound, a vinyl cyanide compound, and an unsaturated acid anhydride.
(C5) A copolymer of a maleimide compound, an aromatic vinyl compound, and a (meth) acrylic ester compound.
(C6) A copolymer of a maleimide compound, an aromatic vinyl compound, a (meth) acrylic acid ester compound, and an unsaturated acid anhydride.
(C7) A copolymer of a maleimide compound, an aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic acid ester compound.
(C8) A copolymer of a maleimide compound, an aromatic vinyl compound, a vinyl cyanide compound, a (meth) acrylic acid ester compound, and an unsaturated acid anhydride.

  In the above embodiment, N-phenylmaleimide is preferable as the maleimide compound, styrene is preferable as the aromatic vinyl compound, acrylonitrile is preferable as the vinyl cyanide compound, and maleic anhydride as the unsaturated acid anhydride. Is preferred.

  In the present invention, the glass transition temperature of the component [C] measured according to ASTM D3418 is preferably 100 ° C. to 250 ° C., more preferably 120 ° C. to 120 ° C. from the viewpoint of molding processability, heat resistance and molding appearance. 230 ° C. If this glass transition temperature is too high, moldability and impact resistance may be insufficient, and if it is too low, the effect of improving heat resistance may not be sufficiently obtained.

The intrinsic viscosity (in methyl ethyl ketone, 30 ° C.) of the component [C] is preferably 0.1 to 1.5 dl / g, more preferably 0.15 to 1.0 dl / g from the viewpoint of moldability and glitter. g.
The intrinsic viscosity is determined by dissolving the component [C] in methyl ethyl ketone, adjusting five different concentrations, and measuring the reduced viscosity at each concentration at 30 ° C. using an Ubbelohde viscosity tube.

  The intrinsic viscosity is adjusted by adjusting the type and amount of polymerization initiator, chain transfer agent, emulsifier, solvent, etc., polymerization time, polymerization temperature, etc., used when component [C] is produced by the method described below. Can be controlled.

  In the present invention, the component [C] may be derived from an ungrafted polymer formed when the component [A] or the component [B] is produced, or may be prepared separately. A polymer may be blended. In the latter case, it should be formed by a known emulsion polymerization, solution polymerization, bulk polymerization, etc. using a maleimide compound and a vinyl monomer copolymerizable with the maleimide compound. it can.

  As another production method of the component [C], a maleimide compound is not contained, a vinyl monomer containing an unsaturated acid anhydride and an aromatic vinyl compound is copolymerized, and then the obtained copolymer And ammonia and / or a primary amine (hereinafter referred to as “imidation reaction”) to produce a copolymer containing the structural unit (c1).

  The primary amines used in the imidization reaction include methylamine, ethylamine, propylamine, butylamine, hexylamine, cyclohexylamine, decylamine, aniline, toluidine, naphthylamine, chlorophenylamine, dichlorophenylamine, bromophenylamine, dibromophenyl. An amine etc. are mentioned. Of these, aniline is particularly preferred.

  The imidization reaction can be performed in a solution state, a bulk state or a suspension state using an autoclave. It is also possible to carry out the reaction in a molten state using a melt kneader such as a screw extruder.

  When the imidization reaction is performed in a solution state, the solvent to be used is not particularly limited, and ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethers such as tetrahydrofuran and 1,4-dioxane; toluene, Aromatic hydrocarbons such as xylene; dimethylformamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone and the like.

  The imidation reaction temperature is preferably 50 ° C to 350 ° C, more preferably 100 ° C to 300 ° C.

  The imidation reaction does not necessarily require the presence of a catalyst. When a catalyst is used, a tertiary amine such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-diethylaniline is preferable.

  The said component [C] may be used individually by 1 type, and may be used in combination of 2 or more type.

Next, in the composition of the present invention, a structural unit derived from an aromatic vinyl compound (hereinafter also referred to as “structural unit (d1)”), a structural unit derived from a vinyl cyanide compound (hereinafter referred to as “optional component”). , Also referred to as “structural unit (d2)”), and a structural unit derived from a (meth) acrylic acid alkyl ester compound (hereinafter also referred to as “structural unit (d3)”). The component [D], which is a polymer containing a structural unit and not containing a structural unit derived from a maleimide compound, will be described.
In addition, this component [D] is an unsaturated acid anhydride, a carboxyl group-containing unsaturated compound, a hydroxyl group-containing unsaturated compound, an amino group-containing unsaturated compound, an amide group-containing unsaturated compound, an epoxy group-containing unsaturated compound, A structural unit derived from an oxazoline group-containing unsaturated compound or the like may be included.
Aromatic vinyl compound, vinyl cyanide compound, (meth) acrylic acid ester compound, unsaturated acid anhydride, carboxyl group-containing unsaturated compound, hydroxyl group-containing unsaturated compound, amino group-containing unsaturated compound, amide group-containing As the unsaturated compound, the epoxy group-containing unsaturated compound, and the oxazoline group-containing unsaturated compound, the compounds exemplified as the vinyl monomer (a2) that can be used for forming the component [A] are applied. And these compounds may be used independently and may be used in combination of 2 or more type.

  The component [A] does not include the structural unit (c1) derived from the acrylic rubbery polymer part and the maleimide compound, but includes the structural units (d1), (d2), (d3), etc. ) When the graft resin is composed of a polymer part, and the component [B] does not include the composite rubber part and the structural unit (c1) derived from the maleimide compound, the structural unit (d1), ( In the case of a graft resin comprising a (co) polymer part including d2), (d3), etc., these graft resins are not included in component [D]. That is, the component [D] is structurally independent from the components [A] and [B].

  When the composition of this invention contains component [D], it can be excellent in molding processability, and can be excellent in the surface appearance property and impact resistance of the molded product obtained.

The component [D] is exemplified below.
(D1) A copolymer composed of structural units (d1) and (d2) (a copolymer of an aromatic vinyl compound and a vinyl cyanide compound).
(D2) A copolymer composed of structural units (d1) and (d3) (a copolymer of an aromatic vinyl compound and a (meth) acrylic acid ester compound).
(D3) A copolymer (copolymer of an aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic acid ester compound) comprising the structural units (d1), (d2), and (d3).
(D4) (Co) polymer ((co) polymer of (meth) acrylic acid ester compound) composed of structural unit (d3).

  Among these, from the viewpoints of moldability, surface appearance, and impact resistance, the copolymers of the embodiments (D1) and (D3) are particularly preferable.

  In addition, when the said component [D] is a copolymer of the said aspect (D1), the content rate of structural unit (d1) and (d2) is respectively preferable when the sum total of both is 100 mass%. Is 50 to 95 mass% and 5 to 50 mass%, more preferably 60 to 95 mass% and 5 to 40 mass%.

  When the component [D] is the copolymer of the above embodiment (D3), the content ratio of the structural units (d1), (d2), and (d3) Preferably, they are 5-45 mass%, 5-45 mass%, and 10-80 mass%, More preferably, they are 10-30 mass%, 10-30 mass%, and 40-80 mass%.

The intrinsic viscosity of component [D] (in methyl ethyl ketone, at 30 ° C.) is preferably 0.1 to 1.5 dl / g, more preferably from the viewpoints of moldability, heat resistance and surface appearance of the resulting molded product. Is 0.15 to 1.0 dl / g.
The intrinsic viscosity of the component [D] can be determined in the same manner as the intrinsic viscosity of the component [C].

  The above intrinsic viscosity is adjusted by adjusting the type and amount of polymerization initiator, chain transfer agent, emulsifier, solvent, etc., polymerization time, polymerization temperature, etc. used when component [D] is produced by the method described below. Can be controlled.

  In the present invention, the component [D] may be derived from the ungrafted polymer formed when the component [A] or the component [B] is produced, or a separately prepared co-polymer. A polymer may be blended. In the latter case, a known emulsion polymerization or solution polymerization is performed using a vinyl monomer containing at least one selected from an aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic acid alkyl ester compound. Or formed by bulk polymerization or the like.

  The said component [D] may be used individually by 1 type, and may be used in combination of 2 or more type.

As described above, since the composition of the present invention can be a composition that does not contain the component [D], preferred compositions include the components [A], [B], [C], and [D]. And a composition containing components [A] [B] and [C]. These compositions may further contain other thermoplastic resins and additives, which will be described later.
When the composition of the present invention contains other thermoplastic resin, the upper limit of the content is 100 parts by mass of the total amount of the components [A], [B], [C] and [D]. In some cases, the amount is preferably 30 parts by mass, more preferably 20 parts by mass, and still more preferably 10 parts by mass.

  In the composition of the present invention, the total content of the acrylic rubbery polymer (a1) and the content of the composite rubber (b1) is the above components [A], [B], [C] and [D ] Is 8 to 35% by mass, preferably 12 to 32% by mass, and more preferably 15 to 28% by mass. When the ratio of the total amount is in the above range, a molded product having excellent heat resistance, impact resistance, molded appearance, and the like can be obtained.

In the composition of the present invention, the content of the structural unit derived from the maleimide compound includes the structural unit constituting the component [A], the structural unit constituting the component [B], and the component [C]. When the total of the structural unit which comprises and the structural unit which comprises the said component [D] is 100 mass%, it is 5-30 mass%, Preferably it is 5-25 mass%, More preferably, it is 8-25. % By mass, particularly preferably 8 to 20% by mass. When the content of the structural unit is in the above range, a molded product excellent in heat resistance, molding appearance, glitter and the like can be obtained.
The content of 5 to 30% by mass is preferably derived only from the component [C], but is derived from the component [C] and the component [A] and / or the component [B]. Also good. As an example of the latter, component [A] polymerizes a vinyl monomer (a2) containing an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound in the presence of an acrylic rubber polymer (a1). And the copolymer part in the graft resin contains a structural unit derived from a maleimide compound, and the component [B] is present in the presence of the composite rubber (b1). A graft resin obtained by polymerizing a vinyl monomer (b2) containing an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound, and the copolymer part in the graft resin is converted into a maleimide compound. This is the case when the derived structural unit is included.

  Furthermore, in the composition of the present invention, the content of the acrylic rubber polymer (a1) constituting the component [A] and the content ratio of the composite rubber (b1) constituting the component [B] are as follows: When the total of both is 100% by mass, it is preferably 10 to 95% by mass and 5 to 90% by mass, more preferably 20 to 90% by mass and 10 to 80% by mass, respectively. By setting it as the above ratio, the molded article is excellent in impact resistance and glitter, and the occurrence of yarn burrs during vibration welding is suppressed.

  In the composition of the present invention, the sum of the content of the component [A] and the content of the component [B] is the molding processability of the composition, and the impact resistance, heat resistance, and molding of the molded product. From the viewpoint of appearance and glitter, when the total of the above components [A], [B], [C] and [D] is 100% by mass, preferably 10 to 90% by mass, more preferably 15 to It is 70 mass%, Most preferably, it is 20-60 mass%.

  In the composition of the present invention, the ratio of the content of the component [C] is determined from the viewpoints of the impact resistance, heat resistance, molded appearance, and glitter of the molded product, and the components [A], [B], [ When the total of C] and [D] is 100% by mass, it is preferably 10 to 90% by mass, more preferably 15 to 70% by mass, and particularly preferably 15 to 60% by mass.

  When the thermoplastic resin composition for a lamp housing of the present invention contains the component [D], the proportion of the content of the component [D] is the components [A], [B], [C] and [C]. D] is preferably 80% by mass or less, more preferably 15 to 70% by mass, and particularly preferably 20 to 65% by mass when the total of D] is 100% by mass. When content of the said component [D] exceeds 80 mass%, heat resistance and impact resistance may become inadequate.

  When the composition of the present invention contains the component [D], the intrinsic viscosity (in methyl ethyl ketone, 30 ° C.) of the mixture of the components [C] and [D] is the molding processability of the composition and the molding From the viewpoint of the heat resistance, impact resistance and appearance of the product, it is preferably 0.2 to 1.2 dl / g, more preferably 0.25 to 1.0 dl / g, still more preferably 0.3 to 0.8 dl. / G.

The mixture of the above components [C] and [D] is a component corresponding to the ungrafted polymer in the composition of the present invention. When recovering these components, the composition of the present invention is added to acetone, shaken using a shaker (23 ° C., 2 hours), and then centrifuged using a centrifuge. (Temperature 0 ° C., rotational speed 28,000 rpm, 1 hour), and then a method of removing acetone from the recovered acetone-soluble component is applied. The recovered product after removing acetone is referred to as “acetone-soluble polymer”.
The intrinsic viscosity of the acetone-soluble polymer can be determined in the same manner as the intrinsic viscosity of the component [C].

  In the present invention, a preferred composition includes [S] a vinyl monomer that does not contain a maleimide compound and contains an aromatic vinyl compound and a vinyl cyanide compound in the presence of the acrylic rubber polymer (a1). In the presence of a rubber reinforced resin (hereinafter also referred to as “raw material [S]”) containing an acrylic rubbery polymer reinforced graft resin obtained by polymerization, and [T] the composite rubber (b1) alone Polymerize (meth) acrylic acid alkyl ester compounds whose glass transition temperature exceeds 0 ° C, and then polymerize vinyl monomers that do not contain maleimide compounds and contain aromatic vinyl compounds and vinyl cyanide compounds A structural unit derived from a rubber-reinforced resin (hereinafter, also referred to as “raw material [T]”) containing the composite rubber-reinforced graft resin obtained as described above and a [U] maleimide compound It is obtained by mixing a raw material (hereinafter also referred to as “raw material [R]”) containing 10 to 70% by mass of a maleimide copolymer (hereinafter also referred to as “raw material [U]”). Composition (hereinafter referred to as “composition [X]”).

  The raw material [R] and the composition [X] may contain other thermoplastic resins and additives.

  In the raw material [R], the raw material [S] does not contain a maleimide compound in the presence of the acrylic rubber polymer (a1), but contains a vinyl monomer (including an aromatic vinyl compound and a vinyl cyanide compound). An acrylic rubbery polymer reinforced graft resin (hereinafter also referred to as “graft resin (Ar)”) obtained by polymerizing (meth) acrylic acid alkyl ester compound), and aromatic vinyl A copolymer containing a structural unit derived from a compound and a structural unit derived from a vinyl cyanide compound (may include a structural unit derived from a (meth) acrylic acid alkyl ester compound. Hereinafter, “copolymer (Dr1 It is also a rubber-reinforced aromatic vinyl resin containing “)”. Of these, the graft resin (Ar) corresponds to the component [A], and the copolymer (Dr1) corresponds to the component [D].

In the presence of the composite rubber (b1), the raw material [T] polymerizes a (meth) acrylic acid alkyl ester compound whose homopolymer has a glass transition temperature exceeding 0 ° C. It is a rubber reinforced resin containing a composite rubber reinforced graft resin obtained by polymerizing a vinyl monomer containing a group vinyl compound and a vinyl cyanide compound. Composite rubber reinforced graft resin grafted on the composite rubber (b1) (hereinafter also referred to as “graft resin (Br)”), a structural unit derived from an aromatic vinyl compound, and a vinyl cyanide compound A copolymer containing a structural unit (which may contain a structural unit derived from a (meth) acrylic acid alkyl ester compound; hereinafter also referred to as “copolymer (Dr2)”). That. Of these, the graft resin (Br) corresponds to the component [B], and the copolymer (Dr2) corresponds to the component [D].
The raw material [U] is a maleimide copolymer contained in the component [C], and a maleimide copolymer prepared in advance can be used as it is.

  When the composition [X] is obtained using the raw materials [S], [T] and [U] as the polymer or resin contained in the raw material [R], the raw material The ratio of these contents in [R] is preferably 1 to 89% by mass, 1 to 89% by mass, and 10 to 90% by mass, more preferably, when the total of the three members is 100% by mass. They are 8-50 mass%, 2-40 mass%, and 10-90 mass%, Most preferably, they are 8-42 mass%, 2-30 mass%, and 28-90 mass%. By using each component in the above range, a molded product excellent in heat resistance, impact resistance, molded appearance, vibration weldability and glitter can be obtained.

  The raw material [R] is obtained by separately blending a (co) polymer corresponding to the component [D] (hereinafter referred to as “(co) polymer [V]”). You can also. As this (co) polymer [V], the (co) polymer illustrated as said component [D] can be used. These may be used alone or in combination of two or more.

  The composition [X] is obtained using the raw materials [S], [T] and [U] and the (co) polymer [V] as the polymer or resin contained in the raw material [R]. When the total amount of the four components is 100% by mass, 1 to 88% by mass, 1 to 88% by mass, 10 to 89% by mass and 1% are preferable. To 80% by mass, more preferably 8 to 50% by mass, 2 to 40% by mass, 10 to 40% by mass and 5 to 60% by mass, particularly preferably 8 to 42% by mass, 2 to 30% by mass, 10 to 10% by mass. 40 mass% and 20-50 mass%. By using each component in the above range, a molded product excellent in heat resistance, impact resistance, molded appearance, vibration weldability and glitter can be obtained.

  The composition [X] is obtained by mixing the raw material [R], but the raw materials [S], [T] and [U] (and (co) polymer [V]) are subjected to the same polymerization. When obtained by the method, in the latex or resin solution, graft resin (Ar), graft resin (Br), raw material [U], copolymers (Dr1) and (Dr2) (and (co) polymer [V ]), And a composition obtained by collecting the resin mixture.

  The form of the composition of the present invention is not particularly limited, but is preferably a melt-kneaded product. Therefore, when the composition [X] is a melt-kneaded product, the raw material [R] is kneaded such as a single screw extruder, a twin screw extruder, a Banbury mixer, a pressure kneader, and a (two) roll. A method using a machine or the like is applied. In kneading, the components constituting the raw material [R] may be kneaded in a lump or may be kneaded while being divided and blended. In addition, after knead | mixing with a Banbury mixer, a kneader, etc., it can also pelletize with an extruder. The kneading temperature is preferably 200 ° C to 300 ° C, more preferably 220 ° C to 280 ° C.

  In the composition of the present invention, other thermoplastic resins that can be blended include vinyl monomers in the presence of other rubbery polymers excluding the acrylic rubbery polymer (a1) and the composite rubber (b1). And rubber reinforced resins such as ABS resin and AES resin obtained by polymerizing styrene, polyamide resin, polycarbonate resin, polyester resin, polyphenylene oxide resin and the like. These may be contained independently and 2 or more types may be contained.

  In the composition of the present invention, additives that can be blended include fillers, metal powders, reinforcing agents, plasticizers, compatibilizers, thermal stabilizers, light stabilizers, antioxidants, ultraviolet absorbers, pigments, electrification Examples thereof include an inhibitor, a lubricant, a flame retardant, and an antibacterial agent.

The thermoplastic resin composition for a lamp housing of the present invention is preferably a molding material for a molded product in which a vapor deposition layer is formed on the surface thereof by direct vapor deposition. Direct vapor deposition is a method in which a vapor deposition layer of metal or the like is formed directly on the surface of a molded product by a vacuum vapor deposition method, a sputtering method or the like without providing an undercoat layer.
As a specific method of direct vapor deposition, for example, a molded product is placed in a container whose pressure is reduced to about 10 ⁻³ to 10 ⁻⁴ Pa, and a vapor deposition material vaporized or sublimated in the container is used for the molded product. It adheres to the surface and forms a vapor deposition layer. When vapor deposition material is vaporized or sublimated, known means such as resistance heating and high frequency induction are appropriately selected. In addition, as a vapor deposition material, metal oxide etc. other than metals, such as aluminum, chromium, zinc, gold | metal | money, silver, platinum, nickel, can be used. In addition, the molded product before vapor deposition may be subjected to a treatment for improving adhesion by RF plasma, ion gun irradiation or the like in advance, but according to the composition of the present invention, That process can be omitted.

The thermoplastic resin composition for a lamp housing of the present invention is preferably a molding material for a molded product to which the vibration welding method is applied.
In the vibration welding method, one resin member is formed using the composition of the present invention, and the other resin member such as a lamp lens is formed using the composition of the present invention or the other composition. This is a method in which vibrations due to pressure and reciprocating motion are applied to the surfaces of two resin members to be joined, and the resin component at the site for adhesion is melted by the frictional heat to join them together.
As another composition, it can be set as the thermoplastic resin composition containing a polycarbonate resin, polymethyl methacrylate, etc.

  According to the composition of the present invention, when the molded products are vibration welded to each other, the occurrence of yarn burrs is suppressed, so that the appearance of the bonded product is not impaired.

The molded product of the present invention is a molded product (lamp housing or the like) obtained using the composition of the present invention. That is, the molded article of the present invention contains the composition of the present invention.
Since the composition is excellent in molding processability, injection molding method, sheet extrusion molding method, vacuum molding method, profile extrusion molding method, compression molding method, hollow molding method, differential pressure molding method, blow molding method, foam molding method, gas Suitable for injection molding method and the like.
Further, the molded product of the present invention can be subjected to metallization treatment using a direct vapor deposition method such as a vacuum vapor deposition method or a sputtering method without forming an undercoat layer.
The metallized molded article is excellent in glitter. This surface may be left as it is, but for example, a top coat layer can be formed by painting, plasma polymerization or the like in order to protect it from the occurrence of scratches due to dust or the like, oxidation degradation, and the like.

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

1. Evaluation Method The physical properties and the measurement methods related to the evaluation are as follows.
(1) Particle size of acrylic rubber polymer and particle size distribution The volume average particle size (Mv) and number average particle size (Mn) of the acrylic rubber polymer in the latex are “Microtrack” manufactured by HONEYWELL. It was measured at 25 ° C. using “UPA150”. The unit is nm. From this measured value, the particle size distribution Mv / Mn was calculated.
(2) Toluene swelling degree and gel content of acrylic rubbery polymer The toluene swelling degree and gel content were determined by the following methods.
About 0.2 gram of the acrylic rubbery polymer was weighed (mass was set to Wr), charged into 25 ml of toluene, and lightly stirred. Then, it was left to stand at 25 degreeC for 48 hours, and it filtered using the 200-mesh metal-mesh (mass shall be Wm gram) weighed previously, and isolate | separated into the insoluble part and the soluble part. Immediately after the separation, the insoluble matter is weighed together with the filtered wire mesh (mass is W1 gram), and the weight value (Wm) of the wire mesh is subtracted from the weight value (W1), and the insoluble matter swollen with toluene. Was obtained (the mass is defined as Ws gram). Next, since the insoluble matter swollen with toluene contains toluene, it is air-dried at 25 ° C. for 12 hours, and subsequently dried at 60 ° C. for 12 hours using a vacuum dryer. The toluene contained in the minutes was removed by drying. The insoluble matter after drying was weighed together with the wire mesh (mass is W2 grams), and the weighed value (Wm) of the wire mesh was subtracted from the weighed value (W2) to obtain the dry weight of the insoluble matter (mass was Wd). Gram.) From these weighed values, the gel content and the toluene swelling degree were calculated by the following formula.
Gel content (mass%) = [Wd (g) / Wr (g)] × 100
= [{W2 (g) -Wm (g)} / Wr (g)] × 100
Toluene swelling degree (times) = Ws (g) / Wd (g)
= [W1 (g) -Wm (g)] / [W2 (g) -Wm (g)]
The acrylic rubbery polymer used for the measurement was obtained by adding a latex containing the above polymer dropwise while stirring a 15% calcium chloride aqueous solution to solidify the polymer, washing with water and drying. Solid rubber.

(3) Graft rate A certain amount (x grams) of rubber-reinforced resin (S) obtained using an acrylic rubbery polymer is put into acetone, shaken for 2 hours using a shaker, and released. (Co) polymer (ungrafted polymer = acetone soluble polymer) was dissolved. Thereafter, this liquid was centrifuged at 28,000 rpm for 1 hour using a centrifuge. The obtained insoluble precipitate was dried at 120 ° C. for 2 hours using a vacuum dryer, and the insoluble matter (graft resin) was weighed (y gram). When the amount of the acrylic rubbery polymer contained in x gram of the rubber reinforced resin (S) is xr gram, the graft ratio is calculated by the following formula. In the case of a rubber reinforced resin (T) obtained using a composite rubber instead of the acrylic rubbery polymer, the same calculation is performed.
Graft ratio (%) = [(y−xr) ÷ xr] × 100

(4) Intrinsic viscosity The rubber-reinforced resin (S) obtained in Synthesis Examples 2-1 to 2-11 and the rubber-reinforced resin (T) obtained in Synthesis Example 2-12 are ungrafted polymers. The intrinsic viscosity of the (acetone soluble polymer) was measured. Moreover, the intrinsic viscosity of the acetone-soluble polymer obtained from the composition obtained by kneading the raw material components was also measured. The unit is dl / g.

(5) Charpy impact strength Measured according to ISO 179. Load 2J, the unit is kJ / ^{m 2.}
(6) Deflection temperature under load Measured according to ISO 75. The unit is ° C.

(7) Surface appearance (flow mark, color separation, gloss)
When evaluating the surface appearance, as a colorant, 0.2 parts of calcium stearate “SC-100” (trade name) manufactured by Sakai Chemical Co., Ltd. and carbon black “ A composition obtained by blending 0.5 part of “RCF- # 45” (trade name) was used.
This composition is supplied to an electric injection molding machine “Erject NEX30” (trade name) manufactured by Nissei Plastic Industry Co., Ltd., and injection molding (resin temperature 220 ° C. to 260 ° C., mold temperature 50 ° C.) is performed. A flat black molded product of 55 mm × 2.4 mm (equipped with a side gate of 4 mm × 1 mm at the center of one side of 55 mm) was obtained.
The surface of this molded product was visually observed, and the appearance was determined according to the following criteria.
A: Excellent gloss and no flow mark or color separation was observed.
◯: Gloss was good, and flow marks and color separation were hardly recognized.
Δ: Slightly inferior in gloss, and some flow marks and color separation were observed.
X: The gloss was insufficient, and flow marks and color separation were recognized.

(8) Vibration weldability (powder and thread burr)
The black composition used for the evaluation of the surface appearance in (7) above is supplied to an injection molding machine “IS-170FA” (model name) manufactured by Toshiba Machine Co., Ltd., and injection molding (resin temperature 220 ° C. to 260 ° C. The lamp housing 12 having an opening on a curved surface was formed (see FIG. 2). The unit of dimension in the drawing is “mm”.
On the other hand, a methacrylic resin “Acrypet VH-4” (trade name) manufactured by Mitsubishi Rayon Co., Ltd. is supplied as an adherend to an injection molding machine, and injection molding (resin temperature 220 ° C. to 270 ° C.) is performed. Lamp lens 11 was obtained (see FIG. 1).
Thereafter, the lamp lens 11 and the lamp housing 12 were vibration welded according to FIG. 3 using a vibration welding machine “BURANSON 2407” (model name) manufactured by Emerson Japan. FIG. 3 is a drawing showing the welding locations of the two members. Under the following conditions, the downward projection of the lamp lens 11a showing the AA ′ line cross section in FIG. 1 and the BB ′ line cross section in FIG. The peripheral edge of the opening of the lamp housing 12a was welded. At the time of this vibration welding, the number of resin powders (the number of resin powders that are generated in the lamp housing and can be visually confirmed is several tens of microns to 2 mm) and the number of yarn burrs (the number of resin burrs generated in the lamp housing) The number of thread-like burrs of 2 mm or more) was counted. Based on the number of resin powders and the number of yarn burrs, “vibration weldability” was determined based on the following criteria.
A: The number of resin powders was 5 or less. The number of thread burrs was 5 or less.
Δ: The number of resin powders was 6-10. The number of thread burrs was 6 to 10.
X: The number of resin powders was 11 or more. The number of thread burrs was 11 or more.

<Vibration welding conditions>
(I) Welding conditions for powder quantity evaluation Single amplitude 0.5 mm
Initial pressure 2.0 bar
Initial vibration time 4.0 seconds Second stage pressure 4.0 bar
Second stage vibration time 2.0 seconds (ii) Welding conditions for yarn burr quantity evaluation Single amplitude 0.5 mm
Initial pressure 5.0 bar
Initial vibration time 0.5 seconds Second stage pressure 5.0 bar
Second stage vibration time 2.0 seconds.

(9) Luminous property The black composition used for the evaluation of surface appearance in (7) above is supplied to an injection molding machine “IS-170FA” (model name) manufactured by Toshiba Machine Co., Ltd., and injection molding ( (Resin temperature 220 ° C. to 260 ° C.) to obtain a lamp housing having a predetermined shape. Next, an aluminum deposited film having a film thickness of 120 nm was formed on the surface of the lamp housing by sputtering. Thereafter, a plasma polymerized film of HMDS (1,1,1,3,3,3-hexamethyldisilazane) was formed on the surface of the vapor-deposited film to obtain a molded article for evaluation of glitter. The sputtering conditions and plasma polymerization conditions are as follows.
<Sputtering conditions>
Equipment Vacuum deposition system “VRSP350MD” (model name) manufactured by Shin Meiwa Kogyo Co., Ltd.
Pressure after roughing 5.0 Pa
Pressure after completion of main pulling 5.0 × 10 ⁻³ Pa
Introducing gas Argon 100 sccm
Degree of vacuum during film formation 0.7 Pa
<Plasma polymerization conditions>
Introduction gas HMDS 30sccm
Degree of vacuum during polymerization 1.5 Pa

  A diffuse reflectance was measured with respect to the obtained molded article for evaluation of glitter using a digital reflectometer “TR-1100AD” (model name) manufactured by Tokyo Denshoku Co., Ltd. The unit is%.

2. Production raw materials 2-1. Synthesis of Acrylic Rubber Polymer First, a synthesis method of an acrylic rubber polymer for producing an acrylic rubber polymer reinforced graft resin will be described.

Synthesis Example 1-1
(1) Preparation of chemical solution 91.3 parts of n-butyl acrylate (hereinafter abbreviated as “BA”) and 0.7 part of allyl methacrylate (hereinafter abbreviated as “AMA”) were mixed, Monomer mixture (I) was prepared.
Further, 1 part of potassium persulfate (hereinafter abbreviated as “KPS”) was dissolved in 99 parts of water to prepare a polymerization initiator aqueous solution (hereinafter abbreviated as “OXI aqueous solution (I)”). .

(2) First polymerization step In a glass reactor equipped with a stirrer, raw material and auxiliary agent addition device, thermometer, heating device, etc., 150 parts of water and sodium dodecylbenzenesulfonate (hereinafter referred to as “SDBS”) as an emulsifier. Abbreviated.) 0.5 parts and 8 parts BA were charged. Thereafter, the reaction system was heated under a nitrogen stream while stirring the system. When the internal temperature reached 65 ° C., 0.03 part of sodium dithionite (hereinafter abbreviated as “PHS”) as an electrolyte was added to the reactor, and then the reaction system was heated.
When the internal temperature reached 75 ° C., 7 parts of OXI aqueous solution (I) was charged, and polymerization was started at the same temperature. When 1 hour had passed since the start of polymerization, the reaction in the first polymerization step was completed. The polymerization conversion rate at the end of the first polymerization step was 96.2%, and the volume average particle size (Mv) of the rubber-like polymer particles in the obtained latex was 61 nm.

(3) Second polymerization step A reactor containing the latex was charged with one third of the monomer mixture (I) and 7 parts of an OXI aqueous solution (I), and polymerization was started at 75 ° C. One hour after the start of the polymerization, when the internal temperature of the reactor reached 75 ° C., one third of the monomer mixture (I) and 7 parts of the OXI aqueous solution (I) were further fed to conduct the polymerization. Continued. After 1 hour, when the internal temperature of the reactor reached 75 ° C., the remaining one third of the monomer mixture (I) and 7 parts of OXI aqueous solution (I) were supplied, and polymerization was continued. After 1 hour, the polymerization reaction was terminated, and a latex containing an acrylic rubber polymer (a1-1) was obtained.
The polymerization conversion rate at the end of the reaction in the second polymerization step was 99.6%, the volume average particle size (Mv) of the acrylic rubber polymer (a1-1) in the obtained latex was 133 nm, and the particle size distribution Mv. / Mn was 1.03. The toluene swelling degree was 15 and the gel content was 90.0%. The results are shown in Table 1.

Synthesis Example 1-2
A latex containing an acrylic rubbery polymer (a1-2) was obtained in the same manner as in Synthesis Example 1-1 except that 0.5 part of sodium hydrogen carbonate was added in the first polymerization step.
The polymerization conversion rate at the end of the first polymerization step was 97.1%, the volume average particle diameter (Mv) of the rubbery polymer particles in the obtained latex was 75 nm, and the volume average particle at the end of the second polymerization step The diameter (Mv) was 157 m, and the particle size distribution Mv / Mn was 1.04. The toluene swelling degree was 21 and the gel content was 82.0%. The results are shown in Table 1.

Synthesis Example 1-3
(1) Preparation of chemical solution 79 parts of BA and 1 part of AMA were mixed to prepare monomer mixture (II).
Further, in 10 parts of water, 0.01 parts of disodium ethylenediaminetetraacetate (hereinafter abbreviated as “EDTA”), 0.002 parts of ferrous sulfate (hereinafter abbreviated as “FES”), and Sodium formaldehyde sulfoxylate (hereinafter abbreviated as “NFS”) (0.3 parts) was dissolved to prepare a sulfoxylate-based reducing agent aqueous solution (hereinafter abbreviated as “SFS aqueous solution (I)”). .
Furthermore, 0.025 part of cumene hydride peroxide (hereinafter abbreviated as “CHP”) is dissolved in 30 parts of water, and an aqueous polymerization initiator solution (hereinafter abbreviated as “CAT aqueous solution (I)”). Was prepared.

(2) 1st polymerization process 300 parts of water, 2.0 parts of SDBS, and 20 parts of BA were prepared to the glass reactor provided with the stirring apparatus, the raw material and auxiliary agent addition apparatus, the thermometer, the heating apparatus, etc. Thereafter, the reaction system was heated under a nitrogen stream while stirring the system. When the internal temperature reached 60 ° C., 85% of the SFS aqueous solution (I) and 30% of the CAT aqueous solution (I) were added to the reactor, and polymerization was started at the same temperature. When 1 hour had passed since the start of polymerization, the reaction in the first polymerization step was completed. The polymerization conversion rate at the end of the first polymerization step was 98.5%, and the volume average particle size (Mv) of the rubber-like polymer particles in the obtained latex was 51 nm.

(3) Second polymerization step The reactor containing the latex is charged with the remaining 15% of the SFS aqueous solution (I), and immediately thereafter, 70% of the monomer mixture (II) and the CAT aqueous solution (I). 40% of each was continuously added over 1 hour and 30 minutes to initiate the polymerization. During this time, the internal temperature of the reactor was maintained at 60 ° C. After completion of the addition, the mixture was aged at the same temperature for 30 minutes. Thereafter (2 hours after the start of polymerization), the remaining 30% of the monomer mixture (II) and the remaining 30% of the CAT aqueous solution (I) were continuously added over 1 hour, and the polymerization was continued. . After completion of the addition (3 hours after the start of polymerization), the mixture was aged at the same temperature for 1 hour, and then the polymerization reaction was terminated to obtain a latex containing an acrylic rubbery polymer (a1-3).
The polymerization conversion rate at the end of the second polymerization step was 96.7%, the volume average particle size (Mv) of the acrylic rubber polymer (a1-3) in the obtained latex was 93 nm, and the particle size distribution Mv. / Mn was 1.06. The toluene swelling degree was 7, and the gel content was 98.5%. The results are shown in Table 1.

Synthesis Example 1-4
(1) Preparation of chemical solution 99.8 parts of BA and 0.2 part of AMA were mixed to prepare monomer mixture (III).
Further, as the polymerization initiator aqueous solution, the same OXI aqueous solution (I) as used in Synthesis Example 1-1 was used.
Furthermore, 1 part of disproportionated potassium rosinate soap and 1 part of KPS were dissolved in 99 parts of water to prepare a polymerization initiator aqueous solution (hereinafter abbreviated as “OXI aqueous solution (II)”).

(2) First polymerization step In a glass reactor equipped with a stirrer, raw material and auxiliary agent addition device, thermometer, heating device and the like, 170 parts of water, semi-cured tallow fatty acid sodium soap (hereinafter abbreviated as “SSF”) 0.03 part, β-naphthalenesulfonic acid formalin polycondensate sodium salt (hereinafter abbreviated as “PNF salt”) 1.0 part, electrolyte sodium bicarbonate 1.0 part and single amount 10% of the body mixture (III) was charged. Thereafter, the internal temperature was raised to 65 ° C. under a nitrogen stream while stirring the system. When the temperature reached 65 ° C., 0.005 part of PHS was added, and then the reaction system was heated.
When the internal temperature reached 75 ° C., 7 parts of OXI aqueous solution (I) was charged, and polymerization was started at the same temperature. When 1 hour had passed since the start of polymerization, the reaction in the first polymerization step was completed. The polymerization conversion rate at the end of the first polymerization step was 96.8%, and the volume average particle size (Mv) of the rubber-like polymer particles in the obtained latex was 112 nm.

(3) Second polymerization step In the reactor containing the latex, the remaining 90% of the monomer mixture (III) and 10 parts of OXI aqueous solution (II) were continuously added over 4 hours to polymerize. Started. During this time, the temperature of the reaction system was maintained at 75 ° C. After the addition was completed, the temperature of the reaction system was raised to 80 ° C. over 30 minutes. And it age | cure | ripened at this temperature for 1 hour, the polymerization reaction was complete | finished, and the latex containing an acryl-type rubber-like polymer (a1-4) was obtained.
The polymerization conversion rate at the end of the second polymerization step was 97.7%, the volume average particle size (Mv) of the acrylic rubber polymer (a1-4) in the obtained latex was 192 nm, and the particle size distribution Mv. / Mn was 1.09. The toluene swelling degree was 32 and the gel content was 41%. The results are shown in Table 1.

Synthesis Example 1-5
In the first polymerization step, the amount of SDBS charged into the reactor was 0.1 part, and the same procedure as in Synthesis Example 1-1 except that 0.03 part of PHS and 1.5 part of sodium carbonate were used in combination. A latex containing an acrylic rubbery polymer (a1-5) was obtained. The polymerization conversion rate at the end of the first polymerization step was 96.8%, and the volume average particle size (Mv) of the acrylic rubber-like polymer (a1-5) in the obtained latex was 146 nm, and the second polymerization step The volume average particle size (Mv) at the end was 222 m, and the particle size distribution Mv / Mn was 1.09. Further, the degree of toluene swelling was 18, and the gel content was 89.6%. The results are shown in Table 1.

Synthesis Example 1-6
(1) Preparation of chemical solution 100 parts of BA and 0.3 part of triallyl cyanurate were mixed to prepare a monomer mixture (IV).
Further, the OXI aqueous solution (I) prepared in Synthesis Example 1-1 was used as the polymerization initiator aqueous solution.
(2) Production of acrylic rubbery polymer In a glass reactor equipped with a stirrer, raw material and auxiliary agent addition device, thermometer, heating device, etc., 200 parts of water, 1.5 parts of SSF, and sodium pyrophosphate (hereinafter referred to as "thereof") , Abbreviated as “SPP”.) 0.3 parts was charged. Thereafter, the reaction system was heated under a nitrogen stream while stirring the system. When the internal temperature reached 80 ° C., 100.3 parts of the monomer mixture (IV) and 30 parts of the OXI aqueous solution (I) were continuously supplied to the reactor for 4 hours for polymerization. During this time, the internal temperature of the reactor was maintained at 80 ° C. After the addition of all the chemicals was completed, the mixture was further aged at 80 ° C. for 1 hour, and then the polymerization reaction was completed. The polymerization conversion rate at this time was 97.8%, and the volume average particle size (Mv) of the acrylic rubbery polymer contained in the obtained latex was 87 nm. The toluene swelling degree was 8 and the gel content was 89%.
Next, the particle diameter enlargement process of the said acrylic rubber-like polymer was performed by the method of Unexamined-Japanese-Patent No. 2003-138089.
0.15 parts of SDSB was added to a reactor containing a latex containing 100 parts of the acrylic rubbery polymer. Thereafter, 60 parts of a 5% aqueous acetic acid solution was continuously added over 30 minutes with stirring while maintaining the internal temperature of the reactor at 25 ° C. to 30 ° C. (particle diameter enlargement treatment). Subsequently, 20 parts of 10% sodium hydroxide aqueous solution was continuously added over 10 minutes after the addition of the acetic acid aqueous solution. This obtained the latex containing the acrylic rubber-like polymer (a1-6) with which the particle diameter enlarged. The volume average particle diameter (Mv) of the acrylic rubber polymer in the obtained latex was 157 nm, and the particle diameter distribution Mv / Mn was 1.15. The results are shown in Table 1.

Synthesis Example 1-7
In the first polymerization step, an acrylic rubber polymer (a1-7) was prepared in the same manner as in Synthesis Example 1-1 except that the amounts of water and SDBS charged into the reactor were 200 parts and 2 parts, respectively. Got. The volume average particle diameter (Mv) of the rubber-like polymer particles in the latex at the end of the first polymerization step was 51 nm.
The polymerization conversion rate at the end of the second polymerization step was 99.4%, the volume average particle size (Mv) of the acrylic rubber polymer (a1-7) in the obtained latex was 81 nm, and the particle size distribution Mv. / Mn was 1.04. The toluene swelling degree was 15 and the gel content was 90.7%. The results are shown in Table 1.

Synthesis Example 1-8
In the first polymerization step, the amount of SDBS charged into the reactor is 0.05 parts, and in the second polymerization step, the latex obtained in the first step is added to one third of the monomer mixture (I). An acrylic rubber polymer (a1-8) was obtained in the same manner as in Synthesis Example 1-1 except that the amount of SDBS charged was 0.45 part. The volume average particle diameter (Mv) of the rubber-like polymer particles in the latex at the end of the first polymerization step was 117 nm.
The polymerization conversion rate at the end of the second polymerization step was 98.7%, and the volume average particle size (Mv) of the acrylic rubber polymer (a1-8) in the obtained latex was 278 nm, and the particle size distribution Mv. / Mn was 1.04. The toluene swelling degree was 14 and the gel content was 91.4%. The results are shown in Table 1.

Synthesis Example 1-9
An acrylic rubber-like polymer was prepared in the same manner as in Synthesis Example 1-1 except that a monomer mixture consisting of 90 parts BA and 2 parts AMA was used instead of the monomer mixture (I). (A1-9) was obtained. The volume average particle diameter (Mv) of the rubber-like polymer particles in the latex at the end of the first polymerization step was 54 nm.
The polymerization conversion rate at the end of the second polymerization step was 99.3%, the volume average particle size (Mv) of the acrylic rubber polymer (a1-9) in the obtained latex was 116 nm, and the particle size distribution Mv. / Mn was 1.03. The toluene swelling degree was 5 and the gel content was 91%. The results are shown in Table 1.

Synthesis Example 1-10
In the state in which the first polymerization step in Synthesis Example 1-1 was performed and latex was contained in the reactor, the second polymerization step was performed as a single unit consisting of 91.7 parts BA and 0.3 parts AMA. The total amount of the body mixture and 21 parts of the OXI aqueous solution (I) shown in Synthesis Example 1-1 were charged together and polymerization was started at 75 ° C. Thereafter, the polymerization reaction was carried out for 3 hours while maintaining the internal temperature of the reactor at 75 ° C. to obtain an acrylic rubbery polymer (a1-10).
The polymerization conversion rate at the end of the second polymerization step was 99.2%, the volume average particle size (Mv) of the acrylic rubber polymer (a1-10) in the obtained latex was 121 nm, and the particle size distribution Mv. / Mn was 1.03. The toluene swelling degree was 42 and the gel content was 81.9%. The results are shown in Table 1.

Synthesis Example 1-11
Instead of the monomer mixture (I), an acrylic system was used in the same manner as in Synthesis Example 1-1 except that a monomer mixture consisting of 91.95 parts BA and 0.05 parts AMA was used. A rubbery polymer (a1-11) was obtained.
The volume average particle diameter (Mv) of the rubber-like polymer particles in the latex at the end of the first polymerization step is 72 nm, the polymerization conversion rate at the end of the reaction in the second polymerization step is 98.3%, The acrylic rubbery polymer (a1-11) had a volume average particle size (Mv) of 118 nm and a particle size distribution Mv / Mn of 1.03. The toluene swelling degree was 23 and the gel content was 64.7%. The results are shown in Table 1.

2-2. Synthesis of Composite Rubber Synthesis Example 1-12
1.96 parts of γ-methacryloyloxypropyldimethoxymethylsilane and 98.04 parts of organosiloxane were mixed to obtain 100 parts of an organosiloxane mixture.
To 100 parts of this organosiloxane mixture, 313 parts of a solution prepared by dissolving 0.68 parts of sodium dodecylbenzenesulfonate in deionized water was added, and stirred at 10,000 rpm for 5 minutes using a homomixer. Thereafter, the organosiloxane latex was micronized by passing twice through a homogenizer at a pressure of 300 kg / cm 2.
Next, 13 parts of dodecylbenzenesulfonic acid and 92 parts of deionized water were charged into a separable flask equipped with a thermometer, a cooling pipe and a stirring device to prepare a 12.4% aqueous solution of dodecylbenzenesulfonic acid. The aqueous solution was brought to 85 ° C., and the finely divided organosiloxane latex obtained above was added dropwise over 8 hours with stirring. Thereafter, the temperature was maintained at 85 ° C. for 2 hours and then cooled.
Thereafter, this reaction product was neutralized with an aqueous sodium hydroxide solution to complete the polymerization, and a latex containing polyorganosiloxane was obtained. The volume average particle diameter of the polyorganosiloxane was 60 nm.
The obtained latex was dried at 170 ° C. for 30 minutes and the solid content was determined to be 18.7%.

Next, 28.1 parts of latex containing polyorganosiloxane (5.2 parts of polyorganosiloxane) obtained above was placed in a separable flask equipped with a thermometer, a nitrogen introduction tube, a cooling tube, and a stirring device. I put it in. To this was added 206 parts deionized water, followed by 0.4 parts sodium polyoxyethylene lauryl sulfate, 67.7 parts n-butyl acrylate, 2.1 parts allyl methacrylate and tert-butyl hydroperoxide. A monomer mixed solution consisting of 28 parts was charged and stirred for 30 minutes to be absorbed by the polyorganosiloxane rubber.
Then, nitrogen substitution was performed through a nitrogen stream in the separable flask, and the reaction system was heated to 55 ° C. When the liquid temperature reached 55 ° C, an aqueous solution in which 0.0001 part of ferrous sulfate, 0.0003 part of ethylenediaminetetraacetic acid disodium salt and 0.3 part of Rongalite were dissolved in 3.3 parts of deionized water was added. Then, radical polymerization was started. The liquid temperature rose to 92 ° C. by polymerization of the monomer mixture. This state was maintained for 1 hour, and the polymerization of the monomer was completed to obtain a latex containing the composite rubber (b1-1). The obtained composite rubber (b1-1) had a volume average particle size of 84 nm.

2-3. Synthesis of Rubber Reinforced Resin Containing Acrylic Rubber Polymer Reinforced Graft Resin A method for producing rubber reinforced resin [S] using the acrylic rubbery polymer obtained in Synthesis Examples 1-1 to 1-11 is shown. .

Synthesis Example 2-1
(1) Preparation of chemical solution 73 parts of styrene (hereinafter abbreviated as “ST”), 27 parts of acrylonitrile (hereinafter abbreviated as “AN”), and tert-dodecyl mercaptan (hereinafter referred to as “chain transfer agent”). (Abbreviated as “TDM”) 0.3 parts were mixed to prepare a monomer mixture (V).
Further, 0.05 part of EDTA, 0.005 part of FES and 0.25 part of NFS are dissolved in 100 parts of water to prepare a sulfoxylate-based reducing agent aqueous solution (hereinafter abbreviated as “SFS aqueous solution (II)”). did.
Further, 0.25 part of tert-butylhydroxide (hereinafter abbreviated as “BHP”) is dissolved in 50 parts of water, and a polymerization initiator aqueous solution (hereinafter “CAT aqueous solution (II)”). .) Was prepared.

(2) Graft polymerization In a glass reactor equipped with a stirrer, raw material and auxiliary agent addition device, thermometer, heating device, etc., 100 parts of water, 100 parts of acrylic rubber polymer (a1-1), hydroxylation 0.4 parts of potassium (hereinafter abbreviated as “KOH”), 3 parts of SDBS, and 25% of the monomer mixture (V) were charged. Thereafter, the reaction system was heated under a nitrogen stream while stirring the system. When the internal temperature reached 65 ° C., 50% of the SFS aqueous solution (II) and 30% of the CAT aqueous solution (II) were supplied to the reactor to initiate polymerization. The polymerization reaction was advanced while raising the temperature to 75 ° C. over 1 hour from the start of the polymerization.
One hour after the start of polymerization, when the internal temperature reached 75 ° C., the remaining 75% of the monomer mixture (V), the remaining 50% of the SFS aqueous solution (II), and the remaining CAT aqueous solution (II) Polymerization was continued by continuously supplying 70% for 4 hours. During this time, the temperature of the reaction system was maintained at 75 ° C. After the addition of all the chemicals was completed, the mixture was further aged for 1 hour at 75 ° C., and then the polymerization reaction was completed. As a result, a latex containing a rubber-reinforced resin (S-1) composed of an acrylic rubbery polymer-reinforced graft resin and an ungrafted polymer was obtained.
Next, magnesium sulfate (coagulant) was added to the latex to coagulate the rubber reinforced resin (S-1). Then, it washed with water and dried and collect | recovered rubber-reinforced resin (S-1). Table 2 shows the graft ratio and the intrinsic viscosity of the ungrafted polymer.

Synthesis Examples 2-2 to 2-5
The rubber-reinforced resin (S-2) to (S-2) are the same as in Synthesis Example 2-1, except that the type of acrylic rubber polymer and the amount used thereof and the composition of the monomer mixture are those shown in Table 2. S-5) was obtained. Table 2 shows the graft ratio and the intrinsic viscosity of the ungrafted polymer.

Synthesis Example 2-6
(1) Preparation of chemical solution 28 parts of ST and 12 parts of AN were mixed to prepare a monomer mixture (VI).
Further, 0.02 part of SPP, 0.004 part of FES and 0.2 part of crystalline glucose (hereinafter abbreviated as “CDX”) are dissolved in 10 parts of water to prepare a sugar-containing pyrophosphate-based reducing agent aqueous solution (hereinafter, referred to as “CDX”). (Abbreviated as “DX aqueous solution (I)”).

(2) Graft polymerization In a glass reactor equipped with a stirrer, raw materials and auxiliary agent addition device, thermometer, heating device, etc., 240 parts of water, 60 parts of acrylic rubber polymer (a1-6), KOH 0. 05 parts and 1.5 parts of SSF were charged. Thereafter, the reaction system was heated under a nitrogen stream while stirring the system. When the internal temperature reached 60 ° C., the entire amount of DX aqueous solution (I) was supplied to the reactor. Immediately thereafter, monomer mixture (VI) and 0.25 parts of CHP were continuously added over 2 hours to initiate polymerization. During this time, the temperature of the reaction system was maintained at 60 ° C. After the addition of all the chemicals was completed, the internal temperature was raised to 70 ° C., and further aged for 1 hour at the same temperature, and then the polymerization reaction was completed. As a result, a latex containing a rubber-reinforced resin (S-6) composed of an acrylic rubbery polymer-reinforced graft resin and an ungrafted polymer was obtained.
Next, a coagulant was added to the latex to coagulate the rubber reinforced resin (S-6). Then, it washed with water and dried and collect | recovered rubber reinforced resin (S-6). Table 2 shows the graft ratio and the intrinsic viscosity of the ungrafted polymer.

Synthesis Examples 2-7 to 2-11
Instead of the acrylic rubber polymer (a1-1), the acrylic rubber polymers (a1-7) to (a1-11) shown in Table 2 were used, and instead of the monomer mixture, Table 2 Rubber reinforced resins (S-7) to (S-11) were obtained in the same manner as in Synthesis Example 2-1, except that a monomer mixture having the composition shown was used. Table 2 shows the graft ratio of each resin and the intrinsic viscosity of the ungrafted polymer.

2-4. Synthesis of Rubber Reinforced Resin Containing Composite Rubber Reinforced Graft Resin Next, a method for producing rubber reinforced resin [T] using the composite rubber (b1-1) obtained in Synthesis Example 2-1 will be described.

Synthesis Example 2-12
The latex containing 75 parts of the composite rubber (b1-1) obtained in Synthesis Example 1-12 was set to 75 ° C. Thereafter, while stirring the latex, polymerization was performed while dripping a mixed liquid consisting of 0.07 part of BHP and 12.5 parts of MMA over 20 minutes, and this state was maintained for 30 minutes after completion of the dropwise addition.
Next, while maintaining the reaction system at 75 ° C., polymerization was carried out while dropping a mixed liquid consisting of 0.07 parts of BHP, 9.5 parts of styrene and 3.0 parts of acrylonitrile over 25 minutes. After completion of the dropping, the reaction system was maintained at 75 ° C. for 1 hour with stirring to complete the polymerization. As a result, a latex containing a rubber-reinforced resin (T-1) composed of a composite rubber-reinforced graft resin and an ungrafted polymer was obtained.
Next, a coagulant was added to the latex to coagulate the rubber reinforced resin (T-1). Then, it washed with water and dried and collect | recovered rubber-reinforced resin (T-1). The graft ratio was 28%, and the intrinsic viscosity of the ungrafted polymer (in methyl ethyl ketone, 30 ° C.) was 0.35 dl / g.
In addition, the form of the rubber reinforced resin (T-1) used when manufacturing the composition is as follows. That is, while the latex is sprayed in the form of fine droplets with a pressure nozzle type using a spray dryer, hydrophobic silica “R-972” (trade name) manufactured by Nippon Aerosil Co., Ltd. It is dried (hot air inlet temperature 180 ° C.) while being supplied at a ratio of 0.05 part to 100 parts of the reinforced resin (T-1), and consists of a rubber reinforced resin (T-1) and silica. A powder was obtained. In the following examples, this powder was used when producing the composition.

2-5. Copolymer The polymer (maleimide copolymer etc.) mix | blended with a thermoplastic resin is as follows.
(I) Styrene / N-phenylmaleimide / acrylonitrile copolymer (U-1)
“Denka IP MS-NC” (trade name) manufactured by Denki Kagaku Kogyo Co., Ltd. was used. The content of structural units derived from N-phenylmaleimide was 44%, the intrinsic viscosity (in methyl ethyl ketone, 30 ° C.) was 0.26 dl / g, and the glass transition temperature was 170 ° C.
(Ii) Styrene / N-phenylmaleimide / acrylonitrile copolymer (U-2)
“Polyimilex PAS1460” (trade name) manufactured by Nippon Shokubai Co., Ltd. was used. The content of structural units derived from N-phenylmaleimide was 40%, the intrinsic viscosity (in methyl ethyl ketone, 30 ° C.) was 0.27 dl / g, and the glass transition temperature was 167 ° C.
(Iii) Styrene / N-phenylmaleimide / acrylonitrile copolymer (U-3)
“DENKA IP MS-NI” (trade name) manufactured by Denki Kagaku Kogyo Co., Ltd. was used. The content of structural units derived from N-phenylmaleimide was 50%, and the glass transition temperature was 185 ° C.
(Iv) Styrene / acrylonitrile copolymer (V-1)
It is a polymer obtained by the following synthesis example 3-1.

Synthesis Example 3-1
(1) Preparation of chemical solution 74 parts of ST, 26 parts of AN and 0.5 part of TDM were mixed to prepare a monomer mixture (VIII).
Further, 0.1 part of EDTA, 0.005 part of FES and 0.2 part of NFS were dissolved in 10 parts of water to prepare an aqueous reducing agent solution (hereinafter abbreviated as “SFS aqueous solution (IV)”).
Further, 0.25 part of diisopropylbenzene hydroperoxide (hereinafter abbreviated as “IHP”) is dissolved in 100 parts of water and abbreviated as a polymerization initiator aqueous solution (hereinafter “CAT aqueous solution (IV)”). ) Was prepared.

(2) Polymerization 200 parts of water and 2 parts of SDBS were charged into a glass reactor equipped with a stirrer, raw material and auxiliary agent addition device, thermometer, heating device and the like. Thereafter, the reaction system was heated under a nitrogen stream while stirring the system. When the internal temperature reached 60 ° C., the whole amount of the monomer mixture (VIII), the whole amount of the SFS aqueous solution (IV), and 80% of the CAT aqueous solution (IV) were continuously added over 4 hours. Polymerization was started. The temperature of the reaction system was raised to 70 ° C. at the start of polymerization, and then maintained at the same temperature.
After 4 hours from the start of polymerization, the remaining 20% of the aqueous CAT solution (IV) was fed to the reactor. Then, after maintaining the reaction system at 70 ° C. for 1 hour, the polymerization reaction was completed. Thereby, a latex containing a styrene / acrylonitrile copolymer (V-1) was obtained.
Thereafter, magnesium sulfate (coagulant) was added to the latex to coagulate the styrene / acrylonitrile copolymer (V-1). Next, washing with water and drying were carried out to recover a powder made of styrene / acrylonitrile copolymer (V-1). The intrinsic viscosity (in methyl ethyl ketone, 30 ° C.) was 0.42 dl / g.

2-6. Additives The following antioxidants were used.
(1) F-1
Octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate “Adekastab AO-50” (trade name) manufactured by Adeka Corporation was used.
(2) F-2
Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite “ADEKA STAB PEP-36” (trade name) manufactured by Adeka Corporation was used.

3. Production and Evaluation of Thermoplastic Resin Composition for Lamp Housing Examples 1-8 and Comparative Examples 1-15
Raw materials [S], [T], [U] and [V] and antioxidants were added to a Henschel mixer at the blending ratios shown in Tables 3 to 7, and mixed. Thereafter, using a twin-screw extruder “TEM-50A” (model name) manufactured by Toshiba Machine Co., Ltd., melt-kneading was performed at a temperature of 220 ° C. to 280 ° C. to obtain pellets. Each of the above items was evaluated using this pellet, and the results are also shown in Tables 3 to 7. In Tables 3 to 7, the ratios of the components [A], [B], [C] and [D] according to the present invention calculated from the raw material components are described.

From the results shown in Tables 3 to 7, the following is clear.
Comparative Example 1 is an example that does not contain the component [B] according to the present invention, and was inferior in impact resistance and vibration weldability.
The comparative example 2 is an example which does not contain the component [C] concerning this invention, and was inferior in heat resistance and vibration welding property.
Comparative Example 3 is difficult to knead with a twin-screw extruder, and a large amount of irregularities (dispersion failure) that may have been caused by kneading failure occurred on the surface of the injection molded product. There wasn't.
Comparative Example 4 was an example in which the total content of the acrylic rubber polymer (a1) and the composite rubber (b1) was small, and was inferior in impact resistance and vibration weldability.
In Comparative Example 5, as in Comparative Example 3, it was difficult to knead by the twin-screw extruder, and the surface of the injection molded product had a large amount of irregularities (dispersion failure) that was thought to be caused by the kneading failure. , Did not evaluate.
Comparative Example 6 is an example not containing the component [A] according to the present invention, and the surface appearance and vibration weldability were inferior.
Comparative Example 7 is an example of a composition containing an acrylic rubbery polymer reinforced graft resin obtained by using an acrylic rubbery polymer having a small volume average particle diameter, and is inferior in impact resistance and vibration weldability. It was.
Comparative Example 8 is an example of a composition containing an acrylic rubbery polymer reinforced graft resin obtained by using an acrylic rubbery polymer having a high degree of toluene swelling, and has a surface appearance, vibration weldability, and glitter. Was inferior.
Comparative Example 9 is an example of a composition containing an acrylic rubber polymer reinforced graft resin obtained by using an acrylic rubber polymer having a large volume average particle diameter, and has a surface appearance, vibration weldability, and brightness. The sex was inferior.
Comparative Example 10 is an example of a composition containing an acrylic rubbery polymer reinforced graft resin obtained using an acrylic rubbery polymer having a large particle size distribution (Mv / Mn). The weldability and glossiness were inferior.
Comparative Example 11 is an example of a composition containing an acrylic rubber polymer reinforced graft resin obtained by using an acrylic rubber polymer having a small volume average particle diameter, and is inferior in impact resistance and vibration weldability. It was.
Comparative Example 12 is an example of a composition containing an acrylic rubbery polymer reinforced graft resin obtained using an acrylic rubbery polymer having a large volume average particle size, and has a surface appearance, vibration weldability, and brightness. The sex was inferior.
Comparative Example 13 is an example of a composition containing an acrylic rubbery polymer reinforced graft resin obtained using an acrylic rubbery polymer having a low toluene swelling degree, and was inferior in impact resistance.
Comparative Example 14 is an example of a composition containing an acrylic rubbery polymer reinforced graft resin obtained using an acrylic rubbery polymer having a high toluene swelling degree, and has a surface appearance, vibration weldability, and glitter. Was inferior.
Comparative Example 15 is an example of a composition containing an acrylic rubber polymer reinforced graft resin obtained by using an acrylic rubber polymer having a low gel content, and has a surface appearance, vibration weldability, and glitter. Was inferior.
On the other hand, Examples 1 to 8 are examples of compositions included in the present invention, and were excellent in the balance of impact resistance, heat resistance, surface appearance, vibration weldability and glitter.

Using the compositions of Examples 1, 2, and 5, the hot plate weldability (threading) was evaluated.
The black composition used for the evaluation of the surface appearance in the above (7) is supplied to an electric injection molding machine “Erject NEX30” (trade name) manufactured by Nissei Plastic Industry Co., Ltd., and injection molding (resin temperature 220 ° C. To 260 ° C.) to obtain a plate-shaped test piece of 60 mm × 30 mm × 3 mm.
The test piece was conditioned for 3 hours under conditions of a temperature of 23 ° C. and a relative humidity of 50%, and then tested on a hot plate under the following conditions using a hot plate test piece welding tester (manufactured by Ida Seisakusho). When the piece was pressed and the string was visually observed when the test piece was separated from the hot plate, no string was generated.
<Test conditions>
Surface treatment of hot plate Metal plate processed with fluororesin Temperature of hot plate 240 ℃
Welding surface of test piece 30mm x 3mm
Servo motor moving speed 200mm / sec Time for test piece to contact with hot plate 15sec Melting amount of test piece 0.5mm

  The thermoplastic resin composition for a lamp housing of the present invention is suitable for forming a lamp housing constituting a vehicular lamp such as a head lamp, a tail lamp, and a stop lamp.

11: Resin lens part (lamp lens)
12: Resin housing (lamp housing)

Claims (8)

[A] The gel content is 70% by mass or more, the degree of swelling with toluene is 5.5 to 30 times, the volume average particle size is 100 to 200 nm, and the volume average particle size and number average particle size Acrylic rubber obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an acrylic rubber polymer (a1) having a ratio less than 1.1 A polymer reinforced graft resin,
[B] The glass transition temperature of the homopolymer is 0 in the presence of the composite rubber (b1) containing an organosiloxane rubber and a (co) polymer rubber having a structural unit derived from an alkyl (meth) acrylate. A composite rubber reinforced graft resin obtained by polymerizing a vinyl-based monomer containing a (meth) acrylic acid alkyl ester compound, an aromatic vinyl compound and a cyanidated vinyl compound exceeding ° C;
[C] a maleimide copolymer containing 10 to 70% by mass of a structural unit derived from a maleimide compound with respect to the total structural unit;
If necessary,
[D] including at least one structural unit selected from a structural unit derived from an aromatic vinyl compound, a structural unit derived from a vinyl cyanide compound, and a structural unit derived from a (meth) acrylic acid alkyl ester compound And a polymer containing no structural unit derived from a maleimide compound,
A thermoplastic resin composition for a lamp housing, comprising:
The total content of the acrylic rubbery polymer (a1) and the content of the composite rubber (b1) is the acrylic rubbery polymer reinforced graft resin [A] and the composite rubber reinforced graft resin [B]. , When the total of the maleimide copolymer [C] and the polymer [D] is 100% by mass, it is 8 to 35% by mass, and
The content of the structural unit derived from the maleimide compound includes the structural unit constituting the acrylic rubbery polymer reinforced graft resin [A], the structural unit constituting the composite rubber reinforced graft resin [B], and the maleimide type. The lamp housing, wherein the total of the structural unit constituting the copolymer [C] and the structural unit constituting the polymer [D] is 100% by mass, and is 5 to 30% by mass. Thermoplastic resin composition.   The content ratios of the acrylic rubbery polymer (a1) and the composite rubber (b1) are 10 to 95% by mass and 5 to 90% by mass, respectively, when the total of both is 100% by mass. Item 2. The thermoplastic resin composition for a lamp housing according to Item 1. In the presence of the alkyl sulfonate and / or alkyl sulfate ester salt, the acrylic rubbery polymer (a1) is (meth) acrylic acid alkyl ester compound (m1-1) 50 to 100% by mass, 0-50 mass% of other compounds (m1-2) copolymerizable with the (meth) acrylic acid alkyl ester compound (m1-1) (however, the total of (m1-1) and (m1-2) is 100 mass%) A first polymerization step of polymerizing a monomer (m1) consisting of: in an aqueous medium to form a first polymer, and
In the presence of the first polymer, in the presence or absence of alkyl sulfonate and / or alkyl sulfate ester salt, (meth) acrylic acid alkyl ester compound (m2-1) 50-99.99 mass% 0.01 to 5% by mass of a polymerizable unsaturated compound (m2-2) having two or more carbon-carbon double bonds, the (meth) acrylic acid alkyl ester compound (m2-1) and the polymerizable unsaturated compound. 0 to 49.99 mass% of other compounds (m2-3) copolymerizable with the saturated compound (m2-2) (however, the sum of (m2-1), (m2-2) and (m2-3) is A second polymerization step of polymerizing a monomer (m2) consisting of 100% by mass in an aqueous medium,
Is a polymer obtained by proceeding sequentially,
The ratio of the usage-amount of the said monomer (m1) and (m2) is 1-50 mass% and 50-99 mass%, respectively when the sum total of both is 100 mass%, 1 or 2 A thermoplastic resin composition for a lamp housing as described in 1. [S] An acrylic rubber obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound without a maleimide compound in the presence of the acrylic rubbery polymer (a1). Rubber reinforced resin containing a polymer-reinforced reinforced graft resin,
[T] In the presence of the composite rubber (b1), a (meth) acrylic acid alkyl ester compound in which the glass transition temperature of the homopolymer exceeds 0 ° C. is polymerized, and then contains no maleimide compound and is an aromatic vinyl compound. And a rubber reinforced resin containing a composite rubber reinforced graft resin obtained by polymerizing a vinyl monomer containing a vinyl cyanide compound, and
[U] a maleimide copolymer containing 10 to 70% by mass of a structural unit derived from a maleimide compound,
The thermoplastic resin composition for a lamp housing according to any one of claims 1 to 3, obtained by mixing raw materials containing   The intrinsic viscosity of the acetone-soluble polymer obtained by immersing the thermoplastic resin composition for lamp housing in acetone is 0.2 to 1.0 dl / g. A thermoplastic resin composition for a lamp housing as described in 1.   The thermoplastic resin composition for a lamp housing according to any one of claims 1 to 5, wherein the thermoplastic resin composition is a molding material for a molded article on which a vapor deposition layer is formed by direct vapor deposition.   The thermoplastic resin composition for a lamp housing according to any one of claims 1 to 6, which is a molding material for a molded product to which the vibration welding method is applied.   A molded article comprising the thermoplastic resin composition for a lamp housing according to any one of claims 1 to 7.

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