JP6853471B2 - Thermoplastic resin composition and molded products using it - Google Patents

Description

The present invention relates to a thermoplastic resin composition and a molded product using the same.

The applicant has an excellent balance of paintability, impact resistance, moldability and chemical resistance, and as a coating resin composition capable of obtaining a good coating appearance even when a large molded product is coated, for example. We have proposed a coating resin composition composed of a rubber-reinforced vinyl resin [A], a polyester resin [B], and an ethylene / (meth) acrylic acid ester / carbon monoxide copolymer [C] (Patent Document 1). ..

Japanese Patent No. 5862039

The present invention is an improved invention of the above invention, and an object of the present invention is to provide a thermoplastic resin composition having further improved heat resistance and impact resistance, and a molded product using the same.

That is, the present invention is as follows.

(1) Rubber-reinforced vinyl resin [A] 10.0 to 78.9 parts by mass, polyester resin [B] 1.0 to 30.0 parts by mass, ethylene / (meth) acrylic acid ester / carbon monoxide copolymer weight Combined [C] 0.1 to 10.0 parts by mass and polycarbonate resin [D] 20.0 to 80.0 parts by mass (however, [A] + [B] + [C] + [D] = 100.0 parts by weight) containing the component (B) and the mass ratio of component [D] ([B] / [D]) is a thermoplastic resin composition characterized .050 to .200 der Rukoto.

(2) The thermoplastic resin composition according to (1) above, further containing 1 to 50 parts by mass of talc [E] with respect to a total of 100 parts by mass of the above [A] to [D].

(3) The rubber-reinforced vinyl-based resin [A] is a rubber-reinforced copolymer resin [A1] having a rubbery polymer portion and a vinyl-based resin portion, or the rubber-reinforced copolymer resin [A1] and a vinyl-based simple resin. The above-mentioned (1) or (2), which is a copolymer [A2] of a weight, and the content of the rubbery polymer portion is 5 to 40% by mass with respect to 100% by mass of the rubber-reinforced vinyl resin [A]. ). The thermoplastic resin composition.

(4) The rubber-reinforced vinyl resin [A] contains a structural unit derived from α-methylstyrene and / or a structural unit derived from a maleimide compound, and is a structural unit derived from α-methylstyrene. And / Or, the total amount of structural units derived from the maleimide-based compound is 1 to 50% by mass with respect to 100% by mass of the rubber-reinforced vinyl-based resin, according to any one of (1) to (3) above. Thermoplastic resin composition.

(5) The thermoplastic resin composition according to any one of (1) to (4) above, wherein the polyester resin [B] is polybutylene terephthalate.

(6) A molded product comprising the thermoplastic resin composition according to any one of (1) to (5) above.

(7) The molded product according to (6) above, which is obtained by injection molding.

(8) An automobile exterior part comprising the thermoplastic resin composition according to any one of (1) to (5) above.

(9) The automobile exterior part according to (8) above, which is obtained by injection molding.

(10) A spoiler comprising the thermoplastic resin composition according to any one of (1) to (5) above.

(11) The spoiler according to (10) above, which is obtained by injection molding.

According to the present invention, the above-mentioned problems are achieved.

FIG. 1A is a bottom view of the test piece used in the peeling test described in the examples, and FIG. 1B is a sectional view taken along the line AA of FIG. 1A.

Hereinafter, the present invention will be described in detail. In the present invention, "(co) polymerization" means homopolymerization and copolymerization, and "(meth) acrylic" means acrylic and methacrylic.

[1] Thermoplastic resin composition:
The thermoplastic resin composition of the present invention contains a rubber-reinforced vinyl resin [A], a polyester resin [B], an ethylene / (meth) acrylic acid ester / carbon monoxide copolymer [C], and a polycarbonate resin [D]. contains.

Hereinafter, each of the above components may be abbreviated as component [A], component [B], component [C], and component [D], respectively.

(1-1) Rubber-reinforced vinyl resin [A]:
In the present invention, the rubber-reinforced vinyl-based resin [A] is a rubber-reinforced copolymer resin [A1] having a rubbery polymer portion and a vinyl-based resin portion, or the rubber-reinforced copolymer resin [A1] and a vinyl-based resin. A monomer copolymer [A2] is used. The content of the rubbery polymer portion is usually 5 to 40% by mass with respect to 100% by mass of the rubber-reinforced vinyl-based resin [A], as will be described later.
The rubber-reinforced copolymer resin [A1] is obtained by polymerizing a vinyl-based monomer [b1] in the presence of the rubber-based polymer [a] as described below, and the rubber-based polymer portion and the vinyl-based resin are obtained. Has a part.

In the rubber-reinforced copolymer resin [A1] obtained by polymerizing the vinyl-based monomer [b1] in the presence of the rubber-based polymer [a], the vinyl-based monomer is usually grafted onto the rubber-based polymer. (Co) between the graft copolymer and the ungrafted component in which the vinyl-based monomer component is not grafted on the rubbery polymer (that is, the vinyl-based monomer [b1] similar to the above component [A2]). Polymer) is included. Further, the graft copolymer may contain a rubbery polymer [a] to which the (co) polymer of the vinyl-based monomer [b1] is not grafted. Of these, the preferred rubber-reinforced vinyl-based resin [A] is the rubber-reinforced copolymer resin [A1] obtained by polymerizing the vinyl-based monomer [b1] in the presence of the rubbery polymer [a]. It is a rubber-reinforced vinyl-based resin containing a (co) polymer [A2] of a vinyl-based monomer [b2].

The rubbery polymer [a] may be a homopolymer or a copolymer as long as it is rubbery at room temperature. Further, the rubbery polymer [a] may be a non-crosslinked polymer or a crosslinked polymer. Specific examples of the rubbery polymer [a] include a diene-based polymer (diene-based rubbery polymer) and a non-diene-based polymer (non-diene-based rubbery polymer). These may be used alone or in combination.

Examples of the diene polymer include homopolymers such as polybutadiene, polyisoprene, and polychloroprene; styrene such as styrene / butadiene copolymer, styrene / butadiene / styrene copolymer, and acrylonitrile / styrene / butadiene copolymer. Butadiene-based copolymer rubber; styrene / isoprene-based copolymer rubber such as styrene / isoprene copolymer, styrene / isoprene / styrene copolymer, acrylonitrile / styrene / isoprene copolymer; natural rubber and the like can be mentioned. Each of the above copolymers may be a block copolymer or a random copolymer. The above diene-based polymer can also be used in combination of two or more.

Examples of the non-diene polymer include composite rubbers such as ethylene / α-olefin copolymer rubber, acrylic rubber, urethane rubber, silicone rubber, silicone / acrylic IPN rubber, and conjugated diene compounds. Examples thereof include a polymer obtained by hydrogenating a (co) polymer containing a unit composed of. Each of the above copolymers may be a block copolymer or a random copolymer. The above non-diene polymer can also be used in combination of two or more. As the above-mentioned non-diene polymer, ethylene / α-olefin copolymer rubber and acrylic rubber are preferable.

The above ethylene / α-olefin copolymer rubber contains an ethylene unit and a unit composed of an α-olefin having 3 or more carbon atoms, and is an ethylene / α-olefin copolymer rubber or an ethylene / α-. Examples thereof include olefin / non-conjugated diene copolymer rubber.

Examples of the α-olefin having 3 or more carbon atoms include propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 3-methyl-1-pentene, and 4-methyl-1-pentene. , 3,3-Dimethyl-1-butene, 1-hexene, methyl-1-hexene, dimethyl-1-pentene, trimethyl-1-butene, ethyl-1-pentene, 1-octene, propyl-1-pentene, etc. Can be mentioned.

Examples of the non-conjugated diene include linear acyclic diene compounds such as 1,4-pentadiene, 1,4-hexadiene and 1,5-hexadiene; 5-methyl-1,4-hexadiene and 3,7. Branch chain of −dimethyl-1,6-octadene, 5,7-dimethyl-1,6-octadene, 3,7-dimethyl-1,7-octadene, 7-methyl-1,6-octadiene, dihydromilsen, etc. Acyclic diene compounds; 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexalidene-2-norbornene, 5 -Vinyl-2-norbornene, dicyclopentadiene, 1,4-cyclohexadiene, 1,4-cyclooctadiene, 1,5-cyclooctadiene, tetrahydroinden, methyltetrahydroinden, dicyclopentadiene, bicyclo [2.2] .1] -Alicyclic diene compounds such as hepta-2,5-diene and the like can be mentioned.

Specific examples of the above ethylene / α-olefin copolymer rubber include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-pentene copolymer, and ethylene / 3-methyl-1-. Butene copolymer, ethylene / 1-hexene copolymer, ethylene / 3-methyl-1-pentene copolymer, ethylene / 4-methyl-1-pentene copolymer, ethylene / 3-ethyl-1-pentene Examples thereof include a polymer, an ethylene / 1-octene copolymer, an ethylene / 1-decene copolymer, and an ethylene / 1-undecene copolymer.

Specific examples of the above-mentioned ethylene / α-olefin / non-conjugated diene copolymer rubber include ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / dicyclopentadiene copolymer, and ethylene.・ Propropylene ・ 5-ethylidene-2-norbornene ・ dicyclopentadiene copolymer, ethylene ・ propylene ・ 5-ethylidene-2-norbornene ・ 5-vinyl-2-norbornene copolymer, ethylene ・ 1-butene ・ 5-ethylidene -2-Norbornene copolymer and the like can be mentioned.

The content of ethylene units constituting the above-mentioned ethylene / α-olefin copolymer rubber is usually 10 to 90% by mass, preferably 20 to 80% by mass, more preferably 30 to 30 to the total amount of all units. It is 70% by mass. The weight average molecular weight (Mw) of the ethylene / α-olefin copolymer rubber is usually 5,000 to 1,000,000, preferably 30,000 to 300,000. If this Mw is too large, the processability when the obtained non-diene rubber reinforced resin is used may be deteriorated. Further, the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 10 or less.

The acrylic rubber (acrylic rubber polymer) is not particularly limited as long as it is a (co) polymer composed of a monomer containing an acrylic acid alkyl ester and / or a methacrylic acid alkyl ester.

The above monomer preferably contains an acrylic acid alkyl ester, and more preferably contains an acrylic acid alkyl ester having an alkyl group having 1 to 12 carbon atoms. Examples of this acrylic acid alkyl ester include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, amyl acrylate, and n-acrylic acid. Examples thereof include hexyl, n-octyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, cyclohexyl acrylate, phenyl acrylate, and benzyl acrylate. Of these compounds, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred. Further, these acrylic acid alkyl esters can also be used in combination of two or more kinds.

The acrylic rubber polymer may be a homopolymer made by using one kind of the above acrylic acid alkyl ester, or may be a copolymer made by using two or more kinds. Further, it may be a copolymer made by using one or more kinds of acrylic acid alkyl esters and one or more kinds of compounds copolymerizable with the acrylic acid alkyl esters.

The compound that can be copolymerized with the above acrylic acid alkyl ester is not particularly limited, and is not particularly limited, such as a methacrylic acid alkyl ester, a monofunctional aromatic vinyl compound, a monofunctional vinyl cyanide compound, a diene compound, and a polyfunctional vinyl compound. Can be mentioned. These can also be used in combination of two or more.

The shape of the rubbery polymer [a] used for forming the rubber-reinforced copolymer resin [A1] is not particularly limited, but when it is in the form of particles, its volume average particle size is usually 30 to 2,000 nm, preferably 30 to 2,000 nm. Is 50 to 1,500 nm, more preferably 100 to 1,000 nm. If the volume average particle size is too small, the impact resistance of the composition of the present invention tends to be inferior. On the other hand, if it is too large, the surface appearance of the molded product tends to be inferior. The volume average particle diameter can be measured by a laser diffraction method, a light scattering method, or the like.

When the rubbery polymer [a] is in the form of particles obtained by emulsion polymerization, if the volume average particle size is within the above range, for example, JP-A-61-23310 and JP-A-59. It is also possible to use those enlarged by a known method described in Japanese Patent Application Laid-Open No. -93701, Japanese Patent Application Laid-Open No. 56-167704, and the like.

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

Examples of the vinyl-based monomer [b1] used for forming the rubber-reinforced copolymer resin [A1] include aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide-based compounds, and acid anhydrides. Can be mentioned. These can also be used in combination of two or more.

The above aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring, and specific examples thereof include styrene, α-methylstyrene, and o-. Methylstyrene, p-methylstyrene, vinyltoluene, β-methylstyrene, ethylstyrene, p-tert-butylstyrene, vinylxylene, vinylnaphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, etc. Be done. These can also be used in combination of two or more. Of these, styrene and α-methylstyrene are particularly preferable.

Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. These can also be used in combination of two or more. Of these, acrylonitrile is particularly preferable.

Examples of the above (meth) acrylic acid ester compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate and the like. These can also be used in combination of two or more. Of these, methyl methacrylate is particularly preferable.

Examples of the maleimide-based compound include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like. Can be mentioned. These can also be used in combination of two or more. Of these, N-phenylmaleimide is particularly preferable. As another method for introducing a unit composed of a maleimide-based compound, for example, a method of copolymerizing maleic anhydride and then imidizing may be used.

Examples of the acid anhydride include maleic anhydride, itaconic anhydride, and citraconic anhydride. These can also be used in combination of two or more.

In addition to the above compounds, vinyl compounds having a functional group such as a hydroxyl group, an amino group, an epoxy group, an amide group, a carboxyl group and an oxazoline group can be used, if necessary. Specific examples of the above vinyl compounds include 2-hydroxyethyl (meth) acrylate, hydroxystyrene, N, N-dimethylaminomethyl (meth) acrylate, N, N-diethyl-p-aminomethylstyrene, and (. Examples thereof include glycidyl acrylate, 3,4-oxycyclohexyl (meth) acrylic acid, vinyl glycidyl ether, metallicyl glycidyl ether, allyl glycidyl ether, methacrylicamide, acrylamide, (meth) acrylic acid and vinyl oxazoline. These can also be used in combination of two or more.

As the vinyl-based monomer [b1] used for forming the rubber-reinforced copolymer resin [A1], it is preferable to mainly use a compound having the following combination.

(1) Aromatic vinyl compound and vinyl cyanide compound.
(2) Aromatic vinyl compounds, vinyl cyanide compounds and maleimide compounds.

In the above aspect (1), the ratio of the aromatic vinyl compound and the vinyl cyanide compound used is usually 50 to 97% by mass and 3 to 50% by mass, preferably 50% by mass, when the total amount thereof is 100% by mass. Is 55 to 95% by mass and 5 to 45% by mass. Further, in the above aspect (2), the ratio of the aromatic vinyl compound, the vinyl cyanide compound and the maleimide compound to be used is usually 50 to 96% by mass and 3 to 49 when the total amount thereof is 100% by mass. It is mass% and 1 to 47 mass%, preferably 50 to 90 mass%, 5 to 45 mass% and 5 to 45 mass%.

When α-methylstyrene is used as the aromatic vinyl compound in the above aspects (1) and (2), the content of α-methylstyrene in the aromatic vinyl compound is usually 10 to 100% by mass, preferably 10 to 100% by mass. Is 20 to 90% by mass. In addition, in the above-mentioned aspects (1) and (2), another monomer may be used in combination. In addition, these can also be used in combination.

As described above, the component [A] may be only the rubber-reinforced copolymer resin [A1], and was obtained by polymerizing the rubber-reinforced copolymer resin [A1] and the vinyl-based monomer (b2). It may be a mixture composed of a (co) polymer [A2]. As the vinyl-based monomer [b2], one or more selected from the vinyl-based monomer [b1] used for forming the rubber-reinforced copolymer resin [A1] can be used. Therefore, in the (co) polymer [A2], a compound having exactly the same composition as the vinyl-based monomer [b1] used for forming the rubber-reinforced copolymer resin [A1] is polymerized as the vinyl-based monomer [b2]. It may be a polymer obtained by polymerizing the same type of monomer with different compositions, or it may be a polymer obtained by polymerizing different types of monomers with different compositions. It may be a polymer obtained by polymerizing a body. Two or more of each of these polymers may be contained.

The (co) polymer [A2] is a homopolymer or a copolymer obtained by polymerizing a vinyl-based monomer [b2], and preferred embodiments are exemplified in the following (3) to (9). ..

(3) One or more (co) polymers obtained by polymerizing only an aromatic vinyl compound.
(4) One or more (co) polymers obtained by polymerizing only a (meth) acrylic acid ester compound.
(5) One or more copolymers obtained by polymerizing an aromatic vinyl compound and a vinyl cyanide compound.
(6) One or more copolymers obtained by polymerizing an aromatic vinyl compound and a (meth) acrylic acid ester compound.
(7) One or more of copolymers obtained by polymerizing an aromatic vinyl compound, a vinyl cyanide compound, and a (meth) acrylic acid ester compound.
(8) One or more copolymers obtained by polymerizing an aromatic vinyl compound and a maleimide compound.
(9) One or more of copolymers obtained by polymerizing an aromatic vinyl compound, a vinyl cyanide compound and a maleimide compound.

In the above aspects (3) to (9), two or more types can be used in combination. When α-methylstyrene is used as the aromatic vinyl compound in the above aspects (3) to (9), the content of α-methylstyrene in the aromatic vinyl compound is usually 10 to 100% by mass. , Preferably 20 to 90% by mass.

As each of the above-mentioned monomers, a compound used for forming the rubber-reinforced copolymer resin [A1] can be applied, and the same applies to preferable compounds. When the (co) polymer [A2] is a copolymer, the proportion of each monomer used is not particularly limited.

Therefore, specific examples of the (co) copolymer [A2] include acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / α-methylstyrene copolymer, and acrylonitrile / styrene / methacryl. Methyl acid acid copolymer, styrene / methyl methacrylate copolymer, styrene / N-phenylmaleimide copolymer, acrylonitrile / styrene / N-phenylmaleimide copolymer, styrene / N-phenylmaleimide / maleic anhydride copolymer And so on.

In the present invention, in particular, in order to obtain excellent chemical resistance and heat resistance, the component [A] is composed of only the rubber-reinforced copolymer resin [A1], and the rubber-reinforced copolymer resin [A1]. And, in any case of the (co) polymer [A2], it is preferable to contain a structural unit derived from α-methylstyrene and / or a structural unit derived from a maleimide-based compound. The total amount of these structural units is usually 1 to 50% by mass, preferably 2 to 45% by mass, and more preferably 3 to 40% by mass with respect to 100% by mass of the rubber-reinforced vinyl resin [A1]. The content of the structural unit derived from α-methylstyrene is usually 10 to 50% by mass, preferably 15 to 45% by mass, and more preferably 20 to 20 to 100% by mass with respect to 100% by mass of the rubber reinforced vinyl resin [A1]. The content of the structural unit derived from the maleimide-based compound is 40% by mass, and is usually 1 to 25% by mass, preferably 2 to 20% by mass, more preferably 2 to 20% by mass, based on 100% by mass of the rubber-reinforced vinyl resin [A1]. Is 3 to 15% by mass. Within the above range, heat resistance and surface hardness are high, scratch resistance is excellent, absorption of the solvent into the resin is suppressed, and chemical resistance is highly exhibited.

Therefore, when the component [A] is composed of only the rubber-reinforced copolymer resin [A1], the vinyl-based monomer [b1] preferably contains at least one of α-methylstyrene and a maleimide-based compound. When the component [A] is composed of the rubber-reinforced copolymer resin [A1] and the (co) polymer [A2], α- is added to at least one of the vinyl-based monomers [b1] and [b2]. It preferably contains at least one of methylstyrene and a maleimide-based compound.

The graft ratio of the rubber-reinforced copolymer resin [A1] is usually 10 to 200% by mass, preferably 15 to 150% by mass, and more preferably 20 to 150% by mass. If the graft ratio of the rubber-reinforced copolymer resin [A1] is less than 10% by mass, the surface appearance and impact resistance of the composition of the present invention may be insufficient. Further, if it exceeds 200% by mass, the molding processability may be insufficient.

The above graft ratio refers to x grams of the rubber component in 1 gram of the rubber reinforced copolymer resin [A1] and acetone for 1 gram of the rubber reinforced copolymer resin [A1] (however, the rubber polymer [a] is acrylic. In the case of rubber, it is a value obtained by the following formula when the insoluble content when dissolved in acetonitrile is y grams.
[Number 1]
Graft ratio (mass%) = {(y-x) / x} x 100

Further, the ultimate viscosity [η] of the soluble component of the rubber-reinforced copolymer resin [A1] due to acetone (however, if the rubbery polymer [a] is an acrylic rubber, acetonitrile is used) (30 in methyl ethyl ketone). (Measured at ° C.) is usually 0.1 to 1.0 dl / g, preferably 0.1 to 0.9 dl / g, and more preferably 0.1 to 0.7 dl / g. Within this range, the composition of the present invention is excellent in molding processability and impact resistance.

The above-mentioned graft ratio and ultimate viscosity [η] are the types and amounts of the polymerization initiator, chain transfer agent, emulsifier, solvent, etc. used in producing the rubber-reinforced copolymer resin [A1], and further. It can be easily controlled by changing the polymerization time, polymerization temperature, and the like.

Next, a method for producing the rubber-reinforced copolymer resin [A1] and the (co) polymer [A2] will be described.

The rubber-reinforced copolymer resin [A1] can be produced by polymerizing a vinyl-based monomer [b1] in the presence of a rubbery polymer [a]. Examples of the polymerization method include emulsion polymerization, solution polymerization and bulk polymerization.

When producing the rubber-reinforced copolymer resin [A1], the vinyl-based monomer [b1] should be added to the reaction system collectively or continuously in the presence of the entire amount of the rubbery polymer [a]. Can be done. Further, the rubbery polymer [a] may be added in whole or in part during the polymerization to polymerize.

When 100 parts by mass of the rubber-reinforced copolymer resin [A1] is produced, the amount of the rubbery polymer [a] used is usually 5 to 80 parts by mass, preferably 10 to 70 parts by mass, and more preferably 15 to 65 parts by mass. It is a department. The amount of the vinyl-based monomer [b1] used is usually 20 to 95 parts by mass, preferably 30 to 90 parts by mass, and more preferably 35 to 85 parts by mass.

When a rubber-reinforced copolymer resin [A1] is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight modifier), an emulsifier, water, or the like is used.

As the above-mentioned polymerization initiator, an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentan hydroperoxide and a reducing agent such as a sugar-containing pyrophosphate formulation and a sulfoxylate formulation are combined. Redox-based initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butylperoxylaurate, tert-butylperoxymonocarbonate and the like can be mentioned. These can also be used in combination of two or more. Further, the above-mentioned polymerization initiator can be added to the reaction system collectively or continuously. The amount of the above-mentioned polymerization initiator used is usually 0.1 to 1.5% by mass, preferably 0.2 to 0.7% by mass, based on the total amount of the vinyl-based monomer [b1].

Examples of the chain transfer agent include octyl mercaptans, n-dodecyl mercaptans, tert-dodecyl mercaptans, n-hexyl mercaptans, n-hexadecyl mercaptans, n-tetradecyl mercaptans, tert-tetradecyl mercaptans and other mercaptans, turpinolene, and the like. Examples include α-methylstyrene dimers. These can also be used in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0% by mass with respect to the total amount of the vinyl-based monomer [b1].

Examples of the above emulsifier include sulfate esters of higher alcohols, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, higher aliphatic carboxylates, and anionic surfactants such as phosphates. Activator: Nonionic surfactants such as alkyl ester type and alkyl ether type of polyethylene glycol can be mentioned. These can also be used in combination of two or more. The amount of the above emulsifier used is usually 0.3 to 5.0% by mass with respect to the total amount of the vinyl-based monomer [b1].

The latex obtained by emulsion polymerization is usually coagulated with a coagulant to make the polymer component into a powder, which is then washed with water and dried to purify the latex. As the coagulant, inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; and organic acids such as acetic acid and lactic acid are used.

When a plurality of rubber-reinforced copolymer resins [A1] are used in combination, each resin may be mixed after being produced, but as another method, latex containing each resin is mixed, and then each resin is mixed. A mixed rubber-reinforced copolymer resin [A1] can be obtained by solidifying or the like.

A known method can be applied to the method for producing the rubber-reinforced copolymer resin [A1] by solution polymerization and bulk polymerization.

The (co) polymer [A2] uses a polymerization initiator or the like applied to the production of the rubber-reinforced copolymer resin [A1], and the vinyl-based monomer [b2] is subjected to solution polymerization, bulk polymerization, emulsion polymerization, etc. It can be produced by polymerization by suspension polymerization or the like, or by thermal polymerization without using a polymerization initiator. Moreover, you may combine these polymerization methods.

The ultimate viscosity [η] (measured at 30 ° C. in methyl ethyl ketone) of the (co) polymer [A2] is usually 0.1 to 1.0 dl / g, preferably 0.15 to 0.7 dl / g. When the ultimate viscosity [η] is within the above range, the composition of the present invention has an excellent balance of physical properties between molding processability and impact resistance. The ultimate viscosity [η] of the (co) polymer [A2] can be controlled by adjusting the production conditions as in the case of the rubber-reinforced copolymer resin [A1].

The ultimate viscosity [η] (measured at 30 ° C. in methyl ethyl ketone) of the soluble component due to the acetone of the component [A] (however, acetonitrile is used when the rubbery polymer (a) is an acrylic rubber) is determined. It is usually 0.1 to 0.8 dl / g, preferably 0.15 to 0.7 dl / g. When the ultimate viscosity [η] is within the above range, the composition of the present invention has an excellent balance of physical properties between molding processability and impact resistance.

In either case where the component [A] is a rubber-reinforced copolymer resin [A1] or a mixture of a rubber-reinforced copolymer resin [A1] and a (co) polymer [A2], the above The content of the rubbery polymer [a] in the rubber reinforced resin is usually 5 to 40% by mass, preferably 8 to 30% by mass, and more preferably 10 to 25% by mass. When the content of the rubbery polymer [a] is within the above range, the composition of the present invention is excellent in molding processability, impact resistance and heat resistance. If the content of the rubbery polymer [a] is less than 5% by mass, the impact resistance may be insufficient, while if the content exceeds 40% by mass, the appearance, heat resistance and heat resistance of the molded product may be insufficient. Moldability may be inadequate.

(1-2) Polyester resin [B]:
The polyester resin [B] used in the present invention is not particularly limited as long as it has an ester bond in the main chain of the molecule, and may be a saturated polyester resin or an unsaturated polyester resin. .. Of these, saturated polyester resin is particularly preferable. Further, it may be a homozygous polyester or a copolymerized polyester. Further, it may be a crystalline resin or an amorphous resin.

As the polyester resin [B], for example, a polyester resin obtained by polycondensation of a dicarboxylic acid component and a dihydroxy component, polycondensation of an oxycarboxylic acid component or a lactone component, or the like can be used.

Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid (2,6-naphthalenedicarboxylic acid, etc.), diphenyldicarboxylic acid, diphenyletherdicarboxylic acid, diphenylmethanedicarboxylic acid, diphenylethanedicarboxylic acid, and diphenylketone. Aromatic dicarboxylic acid having about 8 to 16 carbon atoms such as dicarboxylic acid and 4,4'-diphenylsulfonedicarboxylic acid or a derivative thereof; cyclohexanedicarboxylic acid (1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1) , 4-Cyclohexanedicarboxylic acid, etc.), Hexahydrophthalic acid, Hexahydroisophthalic acid, Hexahydroterephthalic acid, Hymic acid, etc. Examples thereof include aliphatic dicarboxylic acids having about 2 to 40 carbon atoms such as suberic acid, azelaic acid, sebacic acid, dodecanedicarboxylic acid, hexadecanedicarboxylic acid and dimer acid, or derivatives thereof. Two or more of these dicarboxylic acid components can be used in combination. The above derivatives include derivatives capable of forming an ester, for example, lower alkyl esters such as dimethyl ester, acid anhydrides, acid halides such as acid chloride, and the like.

Examples of the dihydroxy component include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, neopentyl glycol, 1 , 6-Hexanediol, 1,8-octanediol, decanediol and other linear or branched chain-like aliphatic alkylene glycols such as alkylene glycol having about 2 to 12 carbon atoms; 1,2-cyclohexanediol, 1, Alicyclic diols such as 4-cyclohexanediol, 1,1-cyclohexanedimethylol, 1,4-cyclohexanedimethylol, hydride bisphenol A; hydroquinone, resorcin, dihydroxybiphenyl, naphthala gekito Wol, dihydroxydiphenyl ether, bisphenol A , Aromatic diols such as adducts (diethoxylated bisphenol A, etc.) in which alkylene oxides such as ethylene oxide and propylene oxide are added to bisphenol A; diethylene glycol, triethylene glycol, polyoxyethylene glycol, ditetramethylene glycol, poly Examples thereof include polyoxyalkylene glycols such as tetramethylene glycol, dipropylene glycol, tripropylene glycol, polyoxypropylene glycol and polytetramethylene ether glycol. The above dihydroxy components can be used in combination of two or more. The dihydroxy component may have a substituent such as an alkyl group, an alkoxy group, or a halogen.

Examples of the oxycarboxylic acid component include oxycarboxylic acids such as oxybenzoic acid, oxynaphthoic acid, and diphenylene oxycarboxylic acid, and derivatives thereof. These can also be used in combination of two or more.

In addition, examples of the above-mentioned lactone component include propiolactone, butyrolactone, valerolactone, ε-caprolactone and the like. These can also be used in combination of two or more.

When the polyester resin [B] is a homotype polyester, specific examples thereof include polyethylene terephthalate (PET), polypropylene terephthalate (PPT), polybutylene terephthalate (PBT), polyhexamethylene terephthalate, and polycyclohexane-1,4-. Examples thereof include polyalkylene terephthalates such as dimethyl terephthalate and polyneopentyl terephthalate, and polyalkylene naphthalates such as polyethylene isophthalate, polyethylene naphthalate, polybutylene terephthalate and polyhexamethylene naphthalate. These can also be used in combination of two or more. Of these, polybutylene terephthalate (PBT) is particularly preferable.

When the polyester resin [B] is a copolymerized polyester, the general dicarboxylic acid components used for its formation include aromatic dicarboxylic acids such as terephthalic acid and isophthalic acid; adipic acid, pimelic acid, and suberic acid. Examples thereof include aliphatic dicarboxylic acids such as azelaic acid and suberic acid. The dihydroxy component contains an aliphatic alkylene glycol such as linear alkylene glycol such as ethylene glycol, propylene glycol and 1,4-butanediol; and a poly (oxy-alkylene) unit such as diethylene glycol and polytetramethylene glycol. Examples thereof include polyoxyalkylene glycol having an oxyalkylene unit having a number of repetitions of about 2 to 4.

Further, in addition to the above compounds, if necessary, hydroxycarboxylic acids such as glycolic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthalenecarboxylic acid, p-β-hydroxyethoxybenzoic acid and the like. And alkoxycarboxylic acids, and monofunctional components such as stearyl alcohol, benzyl alcohol, stearic acid, benzoic acid, tert-butyl benzoic acid, benzoyl benzoic acid, or ester derivatives thereof; tricarbaryl acid, trimellitic acid, trimesic acid, pyro. Polycarboxylic acids such as merit acids; Polyvalent alcohols such as glycerin, trimethylolethane, trimethylolpropane, glycerol, pentaerythritol; Trifunctional or higher functional components such as gallic acid or one or two ester derivatives thereof The above may be used as a component for polycondensation.

In the present invention, the preferred copolymerized polyester is a dicarboxylic acid component mainly containing terephthalic acid and / or a derivative thereof (lower alkyl ester such as dimethyl ester, acid anhydride, acid halide such as acid chloride), and 1,4-. A copolymer obtained by polycondensation with a dihydroxy component containing butanediol and having a glass transition temperature in the range of 0 to 75 ° C .; a copolymerized polybutylene terephthalate; terephthalic acid and / or a derivative thereof (dimethyl ester). Such as a copolymerized polyethylene terephthalate obtained by polycondensation of a dicarboxylic acid component mainly containing a lower alkyl ester such as, acid anhydride, acid halide such as acid chloride) and a dihydroxy component containing ethylene glycol. Of these, copolymerized polybutylene terephthalate is particularly preferable. The copolymerized polybutylene terephthalate is known to be substantially more flexible than the above-mentioned polybutylene terephthalate (PBT), and is also called "soft PBT".

The above-mentioned polybutylene terephthalate is a polymer containing a butylene terephthalate unit obtained by polycondensing 1,4-butanediol and terephthalic acid or a derivative thereof, but each of terephthalic acid or 1,4-butanediol It may be a copolymer obtained by substituting a part with another copolymerizable monomer component. Examples of the copolymerizable acid component include dicarboxylic acids such as isophthalic acid, naphthalenedicarboxylic acid, 4,4'-diphenoxyetanedicarboxylic acid, adipic acid, sebacic acid, and cyclohexanedicarboxylic acid. Examples of the glycol component include ethylene glycol, trimethylene glycol, hexamethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and copolyglycol of polyethylene glycol and polypropylene glycol. However, the proportion of the monomer unit composed of such a copolymerizable monomer component is preferably less than 30 mol% with respect to the entire polymer.

The polybutylene terephthalate used in the present invention preferably has an intrinsic viscosity of 0.5 to 1.3 dl / g measured at 30 ° C. in a mixed solvent of 1/1 (mass ratio) of phenol / tetrachloroethane. It is more preferably 0.6 to 0.8 dl / g.

The method for producing the polyester resin [B] is not particularly limited, and a known method can be adopted. For example, as a method for producing a polybutylene terephthalate resin, a single or a plurality of a dicarboxylic acid component containing terephthalic acid and / or an ester derivative thereof as a main component and a diol component containing 1,4-butanediol as a main component are used. In the esterification reaction tank of the above, in the presence of an esterification reaction catalyst, a temperature of usually 150 to 280 ° C., preferably 180 to 265 ° C., and usually 50 to 1000 Torr (6666-133222Pa), preferably 70 to 760 Torr ( The esterification reaction was carried out for 2 to 5 hours with stirring under the condition of a pressure of 9333-101325 Pa), and the obtained esterification reaction product (oligoene) was transferred to a polycondensation reaction tank, and one or more polycondensation reaction tanks. In the presence of a polycondensation reaction catalyst, the temperature is usually 210 to 280 ° C., preferably 220 to 265 ° C., and the pressure is usually 200 Torr (26664 Pa) or less, preferably 150 Torr (19998 Pa) or less. Polycondensation reaction is carried out for 2 to 5 hours with stirring. The reaction form may be a continuous type, a semi-continuous type, or a batch type.

Further, the resin obtained by the polycondensation reaction is usually transferred from the bottom of the polycondensation reaction tank to a polymer extraction die and extracted in a strand shape, and is cut with a cutter while being water-cooled or after water-cooling to pellet. It is a granular material such as a shape or a chip.

Examples of the esterification reaction catalyst include titanium compounds, tin compounds, magnesium compounds, calcium compounds, zirconium compounds and the like. Of these, titanium compounds are preferable, and specific examples thereof include titanium alcoholates such as tetramethyl titanate, tetraisopropyl titanate, and tetrabutyl titanate; and titanium phenolates such as tetraphenyl titanate. In the case of tetrabutyl titanate, for example, the amount of the esterification reaction catalyst used is usually 30 to 300 ppm, preferably 50 to 200 ppm as a titanium atom with respect to the theoretical yield of the polybutylene terephthalate resin.

Further, as the above-mentioned polycondensation reaction catalyst, it is not necessary to add a new catalyst by continuously using the esterification reaction catalyst added at the time of the esterification reaction as the polycondensation reaction catalyst, but at the time of the esterification reaction. The same catalyst as the added esterification reaction catalyst may be further added, and the amount used at that time is usually 300 ppm or less as a titanium atom with respect to the theoretical yield of the polybutylene terephthalate resin in the case of tetrabutyl titanate, for example. , Preferably 150 ppm or less. Further, an antimony compound such as diantimony trioxide, a germanium compound such as germanium dioxide or germanium tetroxide, which is different from the esterification reaction catalyst added at the time of the esterification reaction, may be newly added.

In the above esterification reaction and / or polycondensation reaction, in addition to the above catalyst, in addition to the above catalyst, phosphoric acid, phosphite, hypophosphoric acid, polyphosphoric acid and phosphorus compounds such as these esters and metal salts, sodium hydroxide, benzo Reaction aids such as alkali metals such as sodium acetate, magnesium acetate, calcium acetate or alkaline earth metal compounds; 2,6-di-tert-butyl-4-octylphenol, pentaerythrityl-tetrakis [3- (3', 3', 5'-tert-butyl-4'-hydroxyphenyl) propionate] and other phenolic compounds, dilauryl-3,3'-thiodipropionate, pentaerythrityl-tetrakis (3-laurylthiodipropionate) and other thioether compounds. , Antioxidants such as phosphoric acids such as triphenyl phosphite, tris (nonylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite; paraffin wax, microcrystallin wax, polyethylene wax, montanic acid. Other additives such as long-chain fatty acids typified by acids and montanic acid esters and their esters, and mold release agents such as silicone oil may be present.

The esterification reaction tank may be of any type, for example, a vertical stirring complete mixing tank, a vertical heat convection mixing tank, a column continuous reaction tank, or the like. Further, a single tank may be used, or a plurality of tanks of the same type or different types may be connected in series. Further, the polycondensation reaction tank may be of any type, for example, a vertical stirring polymerization tank, a horizontal stirring polymerization tank, a thin film evaporation type polymerization tank, or a single tank of the same type or a different type. May be a plurality of tanks in series.

(1-3) Ethylene, (meth) acrylic acid ester, carbon monoxide copolymer [C]:
The ethylene / (meth) acrylic acid ester / carbon monoxide copolymer [C] used in the present invention is a unit composed of an ethylene unit (hereinafter referred to as “unit [t1]”) and a (meth) acrylic acid ester (meth). Hereinafter, it is a copolymer containing a unit (hereinafter referred to as "unit [t2]") and a unit composed of carbon monoxide (hereinafter referred to as "unit [t3]").

The content of the unit [t1] is usually 30 to 90% by mass, preferably 40 to 80% by mass, based on 100% by mass of the component [C]. The content of the unit [t2] is usually 5 to 60% by mass, preferably 20 to 50% by mass, based on 100% by mass of the component [C]. Further, the content of the unit [t3] is usually 1 to 40% by mass, preferably 5 to 30% by mass with respect to 100% by mass of the component [C].

The (meth) acrylic acid ester forming the unit [t2] has a linear or branched alkyl group in the (meth) acrylic acid alkyl ester, and has 1 to 18 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an isobutyl group, a hexyl group, a 2-ethylhexyl group and an octyl group. Of these, compounds having 1 to 8 carbon atoms are preferable, and two or more kinds of compounds can be used in combination. Of these, methyl methacrylate and n-butyl acrylate are particularly preferred.

The above ethylene / (meth) acrylic acid alkyl ester / carbon monoxide copolymer [C] can be produced by the methods disclosed in JP-A-9-87484, Japanese Patent No. 2884180 and the like.

That is, ethylene, acrylic acid ester and carbon monoxide are used as the monomer, and first, carbon monoxide and carbon monoxide are press-fitted into the ethylene supply system at the pressure of the reactor, and then the monomer mixture is reacted. It can be manufactured by press-fitting into the reactor together or separately at the pressure of the vessel. The above reactor is capable of withstanding high pressure and high temperature, and preferably has a stirrer and a pressure release valve driven by a high-speed motor, and a wall surface with a jacket for heating or cooling fluid circulation for temperature control. At this time, if necessary, a radical polymerization catalyst (peroxide, perester, azo compound, percarbonate, etc.) may be press-fitted into the reactor through another supply line. The mixture of copolymer and monomer then exits the reactor and its pressure decreases as the mixture flows into the separator. The monomer is either decomposed out of the separator or press-fitted and circulated into the reactor with the formulation monomer. The melted copolymer leaves the separator, is cooled and cut to size. Here, the temperature of the reactor is usually 140 ° C. or higher, preferably 155 to 300 ° C., and more preferably 155 to 225 ° C. The pressure of the reactor is usually 3.45 × 10 ^{7 to} 4.14 × 10 ⁸ Pa, preferably 1.38 × 10 ^{8 to} 2.41 × 10 ⁸ Pa.

The MFR of component [C] (according to JIS K7210, temperature; 200 ° C., weight; 19.6 N) is usually 1 to 500 g / 10 minutes, preferably 1 to 150 g / 10 minutes, and more preferably 3 to 130 g / 10. Minutes, particularly preferably 5-50 g / 10 minutes. By using the component [C] in this range, the chemical resistance of the composition of the present invention can be further enhanced, and defective phenomena such as layered peeling can be suppressed.

Further, the component [C] is preferably uniformly dispersed in the composition of the present invention. The particle size of the component [C] is usually 0.001 to 10 μm, preferably 0.01 to 5 μm. If the dispersed particle size is less than 0.001 μm, the mechanical strength of the obtained composition may be insufficient, while if it exceeds 10 μm, the appearance (glossiness) of the molded product may be insufficient. There is sex.

As the component [C], a commercially available product can be used, and for example, "Elvaloi HP4051", "Elvaloi HP771" (all manufactured by Mitsui-DuPont Chemical Co., Ltd.) and the like can be used.

(1-4) Polycarbonate resin [D]:
The polycarbonate [D] used in the present invention can be obtained by various methods such as a reaction between dihydroxyaryl and phosgene (phosgene method) and a transesterification reaction between dihydroxyaryl and diphenyl carbonate (transesterification method). Typical polycarbonate [D] includes aromatic polycarbonate obtained by reacting 2,2'-bis (4-hydroxyphenyl) propane with phosgene.

Examples of the dihydroxyaryl include bis (4-hydroxyphenyl) methane, 1,1'-bis (4-hydroxyphenyl) ethane, 2,2'-bis (4-hydroxyphenyl) propane, and 2,2'-bis. (4-Hydroxyphenyl) butane, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3, Examples thereof include 3'-dimethyldiphenyl sulfone, hydroquinone, and resorcin. Further, the aromatic ring of such a dihydroxyaryl may be substituted with an organic substituent such as a halogen (preferably bromine), a methyl group or an ethyl group.

The viscosity average molecular weight of the polycarbonate [D] is usually 15,000 to 40,000, preferably 17,000 to 30,000, and more preferably 18,000 to 28,000. When the viscosity average molecular weight of the polycarbonate [D] is in the above range, the thermoplastic resin composition of the present invention having particularly excellent molding processability can be obtained.

(1-5) Additives:
The coating resin composition of the present invention is a refractory agent, a filler, a colorant, a metal powder, a reinforcing agent, a plasticizer, a compatibilizer, a heat stabilizer, and a light stabilizer, as long as the object of the present invention is not impaired. , Antioxidants, UV absorbers, Antistatic agents, Lubricants, Weatherproofing agents, Antioxidants, Antifogging agents, Antibacterial agents, Antifungal agents, Tackling agents, Plasticizers and other additives can be added as appropriate. .. Examples of the colorant include organic pigments, organic dyes, and inorganic pigments.

Examples of the above-mentioned difficult-to-twist agent include phosphoric acid compounds such as ammonium polyphosphate, triethyl phosphate, and tricresyl phosphate. The amount added is usually 1 to 20% by mass when the thermoplastic resin composition is 100% by mass.

Examples of the above-mentioned filler include glass fiber, carbon fiber, wallastnite, talc, mica, kaolin, glass beads, glass flakes, milled fiber, zinc oxide whiskers, potassium titanate whiskers and the like. The amount of the filler added is usually 1 to 50 parts by mass with respect to 100 parts by mass in total of the above components [A] to [D].

Further, the thermoplastic resin composition of the present invention can contain other resins such as polyethylene, polypropylene, polycarbonate, polyphenylene sulfide, polyamide and the like, if necessary, within a range that does not impair the object of the present invention.

[2] Method for producing thermoplastic resin composition:
In the thermoplastic resin composition of the present invention, the blending amount of the component [A] / component [B] / component [C] / component [D] is the above-mentioned components [A], [B], [C] and [D]. ] To 100 parts by mass, 10.0 to 78.9 / 1 to 30 / 0.1 to 10.0 / 20 to 80 parts by mass, preferably 15 to 70/2 to 20 / 0.3 to 8 .0 / 25-75 parts by mass, more preferably 20-65 / 3-10 / 0.5-6.0 / 28-70 parts by mass, particularly preferably 25-45 / 3.5-8.0 / 1. ~ 4/40 ~ 70 parts by mass.

If the content of the component [B] is less than 1.0 part by mass, the chemical resistance of the composition of the present invention becomes insufficient, and coating defects (armpits) occur due to the suction of an organic solvent such as thinner. On the other hand, when the content of the component [B] exceeds 30.0 parts by mass, the compatibility of the composition of the present invention is lowered, and peeling is likely to occur. In addition, since the paint is easily repelled, the appearance of the paint is deteriorated. If the content of the component [C] is less than 0.1 parts by mass, the compatibility between the component [A] and the component [B] is lowered, the chemical resistance of the composition of the present invention is insufficient, and the coating is poor (armpit). ), The appearance of the paint is deteriorated. On the other hand, when the content of the component [C] exceeds 10.0 parts by mass, the compatibility between the component [A] and the component [B] is lowered, and peeling is likely to occur. In addition, heat resistance is also reduced. If the content of the component [D] is less than 20.0 parts by mass, the effect of sufficiently improving the heat resistance and impact resistance of the composition of the present invention is not exhibited. On the other hand, if the content of the component [D] exceeds 80.0 parts by mass, the chemical resistance of the composition of the present invention becomes insufficient, and coating defects (armpits) and coating appearance deteriorate. In addition, the MFR is lowered and the moldability is lowered. The component [B] and the component [D] ([B] / [D]: mass ratio) are preferably 0.07 to 0.15. If the mass ratio is less than 0.07, coating defects (armpits) may occur, and if it exceeds 0.15, peeling may occur. Further, the component [C] and the component [D] ([C] / [D]: mass ratio) are preferably 0.02 to 0.13. If the mass ratio is less than 0.02, the appearance of the coating may be deteriorated, and if it exceeds 0.13, peeling may occur.

In a preferred embodiment of the present invention, talc [E] is contained as a filler. The content of talc [E] is 1 to 50 parts by mass, preferably 5 to 30 parts by mass, and more preferably 8 to 25 parts by mass with respect to 100 parts by mass of the total of the above components [A] to [D]. Particularly preferably, it is 10 to 20 parts by mass. If the talc [E] content is less than the above range, the coefficient of linear expansion of the composition of the present invention is not improved. On the other hand, when the talc [E] content exceeds the above range, the molding processability of the composition of the present invention is lowered, and the surface appearance of the molded product is lowered.

The thermoplastic resin composition of the present invention can be prepared by kneading the raw material components with various extruders, Banbury mixers, kneaders, rolls, feeder ruders, etc., and can be made into pellets having a predetermined shape or the like. The kneading temperature is selected depending on the type and amount of each raw material component, but is usually 180 to 300 ° C, preferably 200 to 280 ° C. The method of using the raw material components is not particularly limited, and each component may be mixed and kneaded all at once, or may be divided and kneaded in multiple stages.

[3] Molded product:
The thermoplastic resin composition of the present invention includes injection molding, injection compression molding, press molding, extrusion molding, co-extrusion molding, sheet extrusion molding, deformed extrusion molding, foam molding, vacuum molding, blow molding, compression molding, cast molding, A molded product having a predetermined shape can be obtained by a known molding method such as roll molding. In particular, the thermoplastic resin composition of the present invention is suitable for injection molding a large molded product such as a spoiler which has been conventionally manufactured by blow molding.

The coating method for the molded product of the present invention is not particularly limited, and examples thereof include conventionally known coating methods such as electrostatic coating, powder coating, electrodeposition coating, air spray coating, and airless spray coating. The paints used for painting include acrylic resin paints, phenol resin paints, alkyd resin paints, aminoalkide resin paints, vinyl chloride resin paints, silicone resin paints, fluororesin paints, unsaturated resin paints, epoxy resin paints, and polyurethane resin paints. , Melamine resin paint, oil paint, powder paint, enamel paint, water-soluble resin paint, epoxy resin paint, acrylic urethane resin paint, acrylic melamine resin paint, polyester melamine resin paint, etc. Of these, enamel coating, acrylic coating, urethane coating and melamine coating are particularly preferable.

The thermoplastic resin composition of the present invention has an excellent balance of coatability, impact resistance, moldability and chemical resistance, and for example, a good coating appearance can be obtained even when a large molded product is coated. , Used in a wide range of fields such as vehicles, home appliances, and building materials. In particular, it is suitably used in the vehicle field, and can be suitably used for large parts such as front grills, hubcaps, bumpers, fenders, spoilers, and garnishes that require painting.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following 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. The evaluation methods adopted in the following examples are as follows.

(1) Evaluation method

(1-1) Charpy impact strength (C-IMP):
The Charpy impact strength (Edgewise Impact, notched) at room temperature was measured according to ISO179. The measurement conditions are as follows.
Specimen type: Type 1
Notch type: Type A
Load: 2J

(1-2) Mass Melt Flow Rate (MFR):
The measurement was performed under the conditions of a measurement temperature of 240 ° C. and a load of 98 N according to ISO1133.

(1-3) Thermal deformation temperature (HDT):
The measurement was performed under the condition of a load of 1.80 MPa according to ISO75.

(1-4) Poor painting (armpit):
Using an injection molding machine "α-150" (model name) manufactured by FANUC Corporation, a 150 mm × 70 mm × 3 mm test piece made of the thermoplastic resin composition shown in Table 1 was injection molded. The resin temperature at the time of injection molding was 260 ° C., the mold temperature was 5 ° C., and the injection speed was 5 mm / s. The obtained test piece was painted according to the following procedures (i) to (vi), and the determination was made.

<(I) Condition adjustment>
The injection-molded test piece was left in a constant temperature layer controlled at 0 ° C. for 12 hours or more to adjust the state.
<(Ii) Base painting>
A base coating paint consisting of 53 parts of synthetic resin enamel paint and 47 parts of thinner for synthetic resin paint (however, the total of these components was 100 parts) was prepared and spray-painted. The coating film thickness was 20 to 30 μm.
<(Iii) Leave for 1 minute>
The test piece of (ii) was left for 1 minute.
<(Iv) Clear painting>
A clear coating paint consisting of 56 parts of synthetic resin clear paint, 22 parts of thinner for synthetic resin paint, and 22 parts of a curing agent (however, the total of these components is 100 parts) was prepared and spray-painted. The coating film thickness was 30 to 40 μm.
<(V) Leave for 10 minutes>
The test piece after clear coating was left for 10 minutes.
<(Vi) Drying>
The test piece of (v) was dried under the conditions of a temperature of 80 ° C. for 30 minutes.
The coated surface of the test piece after drying was observed, and the occurrence of coating defects (armpits) was determined based on the following evaluation criteria.

<Evaluation of poor painting (armpit)>
◯: No armpit defect occurred on the surface of the test piece.
Δ: 1 to 10 armpit defects occurred on the surface of the test piece.
X: 11 or more armpit defects occurred on the surface of the test piece.

(1-5) Paint appearance:
With respect to the test pieces prepared in the evaluation of coating evaluation (armpit), the occurrence of coating defects other than armpit was judged based on the following criteria.

<Evaluation criteria for poor painting (other than armpits)>
◯: No coating defects occurred on the entire test piece, and a beautiful coating appearance was obtained.
Δ: A coating defect (crack, etc.) occurred on a part of the test piece.
X: Painting defects (cracks, etc.) occurred over the entire test piece, and the beautiful appearance could not be obtained.

(1-6) Peeling test:
A test piece made of the resin composition for coating shown in Table 1 was injection-molded using an injection molding machine "α-150" (model name) manufactured by FANUC Corporation. The resin temperature at the time of injection molding was 260 ° C., the mold temperature was 50 ° C., and the injection speed was 80 mm / s.

1 (a) is a bottom view of the above test piece, and FIG. 1 (b) is a sectional view taken along the line AA of FIG. 1 (a). The dimensions in each figure are as follows. That is, L = 150 mm, W = 70 mm, T = 3 mm, L1 = 45 mm, L0 = 6 mm, W1 = 3 mm, T0 = 2 mm.

In the peeling test, cuts (3) are made in two places on the left and right of the gate (2) of the test piece (1) (the length of the cut is 2 mm), the gate (2) is sandwiched with pliers, and the arrow in FIG. 1 (b). It was pulled in the direction shown, and at that time, it was observed whether or not the surface of the test piece (1) was peeled off, and the judgment was made based on the following evaluation criteria.

<Evaluation criteria for peeling>
◯: No peeling occurred near the gate.
Δ: Peeling occurred from the gate toward the molded product. The length of peeling was 5 mm or less from the gate.
X: Peeling occurred from the gate toward the molded product. The length of peeling exceeded 5 mm from the gate.

(1-7) Coefficient of linear expansion:
A 50 mm × 10 mm × 4 mm test piece obtained by injection molding was annealed at 80 ° C. for 2 hours, and then the reference molded product length was measured in an atmosphere of 23 ° C. After that, the length of the molded product at each temperature of 30 ° C., 50 ° C., and 70 ° C. was measured, and the average rate of change of the length per 1 ° C. from 23 ° C. to 70 ° C. was the coefficient of linear expansion (unit: × 10 ^{−). 5} / ° C). The length of the molded product was measured with a LASERSCAN MICROMETER 1000 manufactured by Mitutoyo.

(2) Raw material component of resin composition for coating

(2-1) Ingredient [A]:

(2-1-1) Rubber reinforced copolymer resin (A1-1):
A diene rubber polymer reinforced vinyl resin with a graft ratio of 53%, obtained by emulsion polymerization of styrene and acrylonitrile in the presence of polybutadiene rubber having a gel content of 86% and an average particle size of 290 nm, was 91.8%. , A rubber reinforced resin composed of 8.2% of ungrafted acrylonitrile / styrene copolymer resin. The graft ratio of the diene-based rubber polymer reinforced vinyl resin was 53%, the content of polybutadiene rubber contained in the rubber reinforced resin was 60.0%, the acrylonitrile unit amount was 10%, and the styrene unit amount was 30%. It was. The intrinsic viscosity [η] (measured at 30 ° C. in methyl ethyl ketone) of the ungrafted acrylonitrile-styrene copolymer resin (acetone-soluble component) was 0.45 dl / g.

(2-1-2) Copolymer (A2-1):
It was an acrylonitrile-styrene copolymer having a styrene unit amount of 76% and an acrylonitrile unit amount of 24%, and had an intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of 0.42 dl / g.

(2-1-3) Copolymer (A2-2):
"Denka IP MS-NIP (trade name)" manufactured by Denki Kagaku Kogyo Co., Ltd. (styrene / N-phenylmaleimide / maleic anhydride copolymer, N-phenylmaleimide unit content 38.5%)

(2-2) Component [B]:

(2-2-1) Polyester resin (B-1):
Wintech Polymer Ltd. "Juranex 200FP (trade name)" (PBT)

(2-3) Component [C]:

(2-3-1) Ethylene, (meth) acrylic acid ester, carbon monoxide copolymer (C-1):
An ethylene / (meth) acrylic acid ester / carbon monoxide copolymer (trade name “Elvalois HP-4051”, manufactured by Mitsui / DuPont Polychemical Co., Ltd.) was used. The MFR (temperature; 200 ° C., load; 19.6 N) according to JIS K7210 is 12 g / 10 minutes.

(2-4) Component [D]:

(D-1) PC
Polycarbonate "NOVAREX 7022PJ" (trade name) manufactured by Mitsubishi Engineering Plastics Co., Ltd. was used. The viscosity average molecular weight (Mv) is 22,000, and the MFR (temperature 240 ° C., load 98N) is 9 g / 10 minutes.

(2-5) Ingredient [E]:

(2-5-1) Talc particles (E-1):
"Micro Ace P-3RC" (trade name) manufactured by Nippon Talc Co., Ltd. was used. The average particle size is 5.0 μm.

Ethylene bisstearic acid amide (trade name "Kaowax EB-P", manufactured by Kao Corporation) was used.

(2-6) Component [F]:

(2-6-1) Lubricants (F-1):
Hardened castor oil (trade name "Kaowax 85P", manufactured by Kao Corporation) was used.

(2-6-2) Antioxidant (F-2):
3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) -N-octadecyl propionate (trade name "ADEKA STAB AO-50", manufactured by ADEKA CORPORATION) was used.

(2-6-3) Antioxidant (D-3):
Bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite (trade name "ADEKA STAB PEP-36", manufactured by ADEKA CORPORATION) was used.

Examples 1-14 and Comparative Examples 1-5:
The above components [A] to [F] are mixed by a Henschel mixer at the blending ratios shown in Tables 1 to 3, and then kneaded with a twin-screw extruder (manufactured by Japan Steel Works, TEX44, barrel set temperature 240 ° C.). , The resin composition for coating was pelletized. Each test piece for evaluation was molded from the obtained pellets, the above evaluation was performed, and the results are shown in Tables 1 and 2.

The following is clear from Tables 1 to 3.

Comparative Example 1 is an example in which the content of the component [A] is high outside the range of the present invention and the content of the component [D] is low outside the range of the present invention, but the heat resistance and impact resistance are poor. ..
Comparative Example 2 is an example in which the content of the component [C] is large outside the range of the present invention, but the heat resistance is poor and the molded product is peeled off.
Comparative Example 3 is an example in which the content of the component [D] is large outside the range of the present invention, but the MFR is poor, coating defects (armpits) occur, and the coating appearance is poor.
Comparative Example 4 is an example in which the content of the component [B] is small outside the range of the present invention, but coating defects (armpits) have occurred.
Comparative Example 5 is an example in which the content of the component [C] is small outside the range of the present invention, but coating defects (armpits) occur and the coating appearance is poor.

1: Test piece 2: Gate 3: Notch

Claims (11)

Rubber reinforced vinyl resin [A] 10.0 to 78.9 parts by mass, polyester resin [B] 1.0 to 30.0 parts by mass, ethylene / (meth) acrylic acid ester / carbon monoxide copolymer [C ] 0.1 to 10.0 parts by mass and polycarbonate resin [D] 20.0 to 80.0 parts by mass (however, [A] + [B] + [C] + [D] = 100.0 parts by mass) containing component (B) and the mass ratio of component [D] ([B] / [D]) is a thermoplastic resin composition characterized .050 to .200 der Rukoto. The thermoplastic resin composition according to claim 1, further containing 1 to 50 parts by mass of talc [E] with respect to a total of 100 parts by mass of the above [A] to [D]. The rubber-reinforced vinyl-based resin [A] is a rubber-reinforced copolymer resin [A1] having a rubbery polymer portion and a vinyl-based resin portion, or a rubber-reinforced copolymer resin [A1] and a vinyl-based monomer. The thermoplastic according to claim 1 or 2, which is a copolymer [A2] and the content of the rubbery polymer portion is 5 to 40% by mass with respect to 100% by mass of the rubber-reinforced vinyl resin [A]. Resin composition. The rubber-reinforced vinyl resin [A] contains a structural unit derived from α-methylstyrene and / or a structural unit derived from a maleimide compound, and a structural unit derived from α-methylstyrene and /. Alternatively, the thermoplastic resin composition according to any one of claims 1 to 3, wherein the total amount of the structural units derived from the maleimide-based compound is 1 to 50% by mass with respect to 100% by mass of the rubber-reinforced vinyl-based resin. .. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the polyester resin [B] is polybutylene terephthalate. A molded product comprising the thermoplastic resin composition according to any one of claims 1 to 5. The molded product according to claim 6, which is obtained by injection molding. An automobile exterior part comprising the thermoplastic resin composition according to any one of claims 1 to 5. The automobile exterior part according to claim 8, which is obtained by injection molding. A spoiler comprising the thermoplastic resin composition according to any one of claims 1 to 5. The spoiler according to claim 10, which is obtained by injection molding.

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