JP2019019264A - Thermoplastic resin composition, molded article, and coated molded article - Google Patents

Abstract

To provide a thermoplastic resin composition which can improve impact resistance, tapping strength and coating properties of a thick part of a molded article in a well balanced manner.SOLUTION: A thermoplastic resin composition contains 5-30 pts.mass of a graft copolymer (I) obtained by graft copolymerization of a rubbery polymer with at least an unsaturated nitrile monomer and an aromatic vinyl monomer, 5-85 pts.mass of a styrenic copolymer (II) containing at least an unsaturated nitrile monomer unit and an aromatic vinyl monomer unit, 5-40 pts.mass of polyamide (III) and 0.1-40 pts.mass of a modified styrenic copolymer (IV) containing at least a maleic acid anhydride monomer unit and an aromatic vinyl monomer unit so that the total amount of (I), (II), (III) and (IV) is 100 pts.mass, where IZOD impact strength in a 1/4 inch thickness molded article according to ASTM D 256 is 90 J/m or more.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition, a molded product, and a coated molded product.

  As measures against environmental problems, attempts have been made to reduce the weight of automobile parts for a long time in order to improve the fuel efficiency of automobiles. As one of the means, it is possible to use a member in which a metal has been conventionally used, in particular, a resin instead of the material of the exterior member (for example, Patent Documents 1 to 3).

  In automobile exterior members, various chemicals such as gasoline, various oils, and car shampoos may adhere, so chemical resistance against these is required. As the resin having high chemical resistance, a crystalline resin or a polymer alloy having a crystalline resin as a continuous phase is usually used. However, the crystalline resin has a problem that it is difficult to control the dimensions because of large molding shrinkage, and the same applies to a polymer alloy having the crystalline resin as a continuous phase. In addition, since the crystalline resin has too high chemical resistance, there is also a problem that adhesion during coating is low. In particular, polyamide (PA) is a continuous phase PA / polyphenylene ether (PPE), PA / acrylonitrile-butadiene-styrene copolymer (ABS) not only has the problem of insufficient mold shrinkage and paint adhesion, but also in the usage environment. There is also a problem that dimensional change during water absorption is likely to occur.

  On the other hand, a polymer alloy material having an amorphous resin as a continuous phase has been proposed for the above-described problem (for example, Patent Document 4).

Japanese Patent No. 5629477 Japanese Patent No. 5363253 JP 2000-178389 A Japanese Patent No. 4250220

  However, the present inventor shows that when the amorphous resin is used as a continuous phase, the strength changes greatly depending on the thickness. More specifically, the strength decreases in a thick molded product or a thick portion such as a rib or a tapping boss. Found a tendency to become prominent.

  Then, an object of this invention is to provide the thermoplastic resin composition which can improve the impact resistance of the thick part of a molded article, tapping strength, and paintability with sufficient balance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the graft copolymer (I), the styrene copolymer (II), the polyamide (III), and the modified styrene copolymer (IV ) In a specific proportion, the molded article of the obtained thermoplastic resin composition is found to be able to improve the impact resistance, tapping strength, and paintability of the thick-walled portion in a balanced manner, and the present invention has been completed. It was.

That is, the present invention is as follows.
[1]
5-30 parts by mass of a graft copolymer (I) obtained by graft copolymerizing at least an unsaturated nitrile monomer and an aromatic vinyl monomer to a rubber polymer,
5 to 85 parts by mass of a styrene copolymer (II) containing at least an unsaturated nitrile monomer unit and an aromatic vinyl monomer unit,
0.1 to 40 parts by mass of a modified styrene copolymer (IV) containing 5 to 40 parts by mass of polyamide (III) and at least a maleic anhydride monomer unit and an aromatic vinyl monomer unit, The total amount of I), (II), (III), and (IV) is 100 parts by mass,
IZOD impact strength in a 1/4 inch-thick molded product in accordance with ASTM D256 is 90 J / m or more,
Thermoplastic resin composition.
[2]
The thermoplastic resin composition according to [1], wherein the mass ratio of the modified styrene copolymer (IV) to the polyamide (III) is (IV) / (III) = 0.16 to 1.00.
[3]
In the styrene copolymer (II), the ratio of the unsaturated nitrile monomer unit to the total amount of the unsaturated nitrile monomer unit and the aromatic vinyl monomer unit is 25 to 50% by mass. 1] or the thermoplastic resin composition according to [2].
[4]
The thermoplastic resin composition according to any one of [1] to [3], wherein the modified styrene copolymer (IV) does not contain an unsaturated nitrile monomer unit.
[5]
The thermoplastic resin composition according to any one of [1] to [4], wherein the modified styrenic copolymer (IV) includes a maleimide monomer unit.
[6]
A molded article of the thermoplastic resin composition according to any one of [1] to [5] above.
[7]
The molded product according to [6], wherein the thickness is 1.0 mm or more.
[8]
The molded product according to [6] or [7], which is a painted molded product.
[9]
The coated molded article according to [8], wherein the coated molded article is for automobile exterior use.

  According to the present invention, it is possible to provide a thermoplastic resin composition that can improve the impact resistance, tapping strength, and paintability of a thick-walled part of a molded product in a well-balanced manner.

  DESCRIPTION OF EMBODIMENTS Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail. However, the present invention is not limited to this, and various modifications can be made without departing from the gist thereof. Is possible.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present embodiment is a graft copolymer (I) obtained by graft copolymerizing at least an unsaturated nitrile monomer and an aromatic vinyl monomer to a rubbery polymer. Styrene copolymer (II) containing at least an unsaturated nitrile monomer unit and an aromatic vinyl monomer unit, 5 to 85 parts by mass, polyamide (III) 5 to 40 parts by mass, and at least maleic anhydride 0.1 to 40 parts by mass of a modified styrenic copolymer (IV) containing a monomer unit and an aromatic vinyl monomer unit, (I), (II), (III), and (IV) The IZOD impact strength of a molded article having a thickness of 1/4 inch conforming to ASTM D256 is 90 J / m or more. As a result, the thermoplastic resin composition of the present embodiment tends to improve the impact resistance, tapping strength, and paintability of the thick part of the molded product in a well-balanced manner and improve the chemical resistance and moldability. .

  In the thermoplastic resin composition of the present embodiment, for example, the continuous phase is styrene copolymer (II), and the dispersed phase is graft copolymer (I) and polyamide (III).

  Hereinafter, each (co) polymer (I), (II), (III), and (IV) constituting the thermoplastic resin composition of the present embodiment will be described.

(I) Graft copolymer Graft copolymer (I) is a copolymer obtained by graft-polymerizing at least an unsaturated nitrile monomer and an aromatic vinyl monomer to a rubber polymer.

  Although it does not specifically limit as a rubbery polymer, For example, the rubbery polymer whose glass transition temperature (Tg) is 0 degrees C or less is mentioned. Specific examples of the rubbery polymer include, but are not limited to, polybutadiene, styrene-butadiene copolymer rubber, acrylonitrile-butadiene copolymer rubber, polyisoprene, polychloroprene, styrene-butadiene block copolymer rubber, styrene- Isoprene block copolymer rubber, conjugated diene rubber such as ethylene-propylene-diene terpolymer rubber, acrylic rubber such as polybutyl acrylate, ethylene-propylene rubber, silicon rubber, silicon-acrylic composite rubber, and these Examples thereof include hydrogenated products. These rubbery polymers can be used alone or in combination of two or more.

  Among these, from the viewpoint of impact resistance, conjugated diene rubber is preferable, and polybutadiene, styrene-butadiene copolymer rubber, and acrylonitrile-butadiene copolymer rubber are more preferable.

  The rubbery polymer contained in the graft copolymer (I) is preferably in the form of particles, and more preferably present in a finely dispersed state in the thermoplastic resin composition.

  Examples of the unsaturated nitrile monomer that can be graft copolymerized with the rubbery polymer of the present embodiment include acrylonitrile, methacrylonitrile, and ethacrylonitrile. These unsaturated nitrile monomers can be used individually by 1 type or in combination of 2 or more types.

  Examples of the aromatic vinyl monomer that can be graft-copolymerized with the rubbery polymer of the present embodiment include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, Examples include p-ethyl styrene and pt-butyl styrene, and vinyl naphthalene. These aromatic vinyl monomers can be used individually by 1 type or in combination of 2 or more types.

  Monomers to be graft copolymerized with the rubbery polymer include monomers other than the unsaturated nitrile monomer and aromatic vinyl monomer that can be graft copolymerized with the rubbery polymer (hereinafter referred to as “other monomers”). Monomer ")) may be graft copolymerized.

  Other monomers include, but are not limited to, for example, unsaturated carboxylic acid alkyl ester monomers, maleic anhydride, N-phenylmaleimide, N-substituted maleimide monomers such as N-methylmaleimide, And glycidyl group-containing monomers such as glycidyl methacrylate. These other monomers can be used individually by 1 type or in combination of 2 or more types.

  The method for producing the rubbery polymer constituting the graft copolymer (I) is not particularly limited, and examples thereof include a bulk polymerization method, a solution polymerization method, a suspension polymerization method, a bulk suspension polymerization method, and an emulsion polymerization method. Is mentioned. Among these, the emulsion polymerization method, the suspension polymerization method, or the bulk suspension polymerization method is preferable from the viewpoint that a particulate rubber component is obtained and the particle diameter can be easily controlled.

  When a polymer having a plurality of Tg is used as the rubber polymer, those having different monomer compositions can be polymerized in multiple stages to produce a rubber polymer. In this case, it is preferable to produce by multistage polymerization using an emulsion polymerization method.

  Further, when the rubbery polymer is a polymer having a composition gradient, the polymerization can be performed by continuously changing the monomer composition. For example, in emulsion polymerization, a rubbery polymer can be produced using a so-called power feed method.

  When the rubbery polymer is a block copolymer of an aromatic vinyl monomer and a diene vinyl monomer (for example, a styrene-butadiene block copolymer), the rubbery polymer is obtained by living anion polymerization in a solution. A polymer can be produced.

  Further, the method for producing the graft copolymer (I) containing a graft component (for example, a method for graft polymerization of a monomer mixture to a rubbery polymer) is not particularly limited, and examples thereof include a bulk polymerization method and a solution. Examples of the polymerization method include suspension polymerization, bulk suspension polymerization, and emulsion polymerization. In addition, after producing the particulate rubbery polymer, the graft polymerization may be continuously performed in the same reactor, or after the rubbery polymer particles are once isolated as a latex, the graft polymerization may be performed. Good. When a radical initiator is used, an initiator such as peroxodisulfate or t-butylperoxy-2-ethylhexanoate can be used as the radical initiator. Among these, when producing a rubbery polymer by an emulsion polymerization method, a thermal decomposition type initiator that generates radicals by heat or a redox type initiator can be used. In the emulsion polymerization method, for example, a rubbery polymer obtained separately by emulsion polymerization is used, and a method of emulsion polymerization of a monomer mixture containing an unsaturated nitrile monomer and an aromatic vinyl monomer is used. Can do.

  When using the solution polymerization method, a diene monomer is subjected to living anion polymerization to obtain an uncrosslinked rubber polymer, and then the obtained uncrosslinked rubber polymer and aromatic vinyl monomer are obtained. For example, a method obtained by precipitating a composite of a rubber component and a high Tg resin component by dissolving the nitrile monomer and the unsaturated nitrile monomer together for polymerization can be used.

  In the graft copolymer (I), the ratio of graft copolymerized monomer to the rubbery polymer (graft ratio) is preferably 20 to 150%, more preferably 25 to 100%, more preferably 30 to 30%. 70% is more preferable. The graft ratio is obtained by removing solvent-soluble components from the thermoplastic resin composition with a solvent (such as acetone), taking out the graft copolymer (I) as a solvent-insoluble component, and using a Fourier transform infrared spectrophotometer (FT-IR). The mass of the rubber polymer and the graft component (that is, the graft polymerized monomer) is measured, and the ratio of the mass of the graft polymerized monomer to the mass of the rubber polymer is obtained from these values. be able to.

  In the graft copolymer (I), the ratio of the unsaturated nitrile monomer unit to the total amount of 100% by mass of the unsaturated nitrile monomer unit and aromatic vinyl monomer unit graft-copolymerized is 25 to 25%. It is preferably 50% by mass, more preferably 27-45% by mass, and further preferably 30-40% by mass.

  As an example of the most preferable embodiment as the graft copolymer (I), polybutadiene is used as a rubber polymer, and acrylonitrile is used as an unsaturated nitrile monomer and styrene is used as an aromatic vinyl monomer. The graft copolymer made is mentioned.

  In the present embodiment, the content of the graft copolymer (I) contained in 100 parts by mass of the thermoplastic resin composition is 5 parts by mass or more, preferably 10 parts by mass or more, more preferably from the viewpoint of impact resistance. Is 15 parts by mass or more, and is 30 parts by mass or less, preferably 28 parts by mass or less, more preferably 25 parts by mass or less from the viewpoint of fluidity.

(II) Styrene copolymer The styrene copolymer (II) is a styrene copolymer having at least an unsaturated nitrile monomer unit and an aromatic vinyl monomer unit as constituent units.

  The unsaturated nitrile monomer corresponding to the unsaturated nitrile monomer unit constituting the styrene copolymer (II) and the aromatic vinyl monomer corresponding to the aromatic vinyl monomer unit include graft copolymer What was illustrated as a specific example of the unsaturated nitrile monomer and aromatic vinyl monomer contained in unification (I) is mentioned.

  The styrenic copolymer (II) may contain monomer units corresponding to the unsaturated nitrile monomer and other monomers copolymerizable with the aromatic vinyl monomer. Other monomers include, but are not limited to, for example, unsaturated carboxylic acid alkyl ester monomers, maleic anhydride, N-phenylmaleimide, N-substituted maleimide monomers such as N-methylmaleimide, And glycidyl group-containing monomers such as glycidyl methacrylate. These may be used alone or in combination of two or more.

  The ratio of the unsaturated nitrile monomer unit to the total amount (100% by mass) of the unsaturated nitrile monomer unit and the aromatic vinyl monomer unit constituting the styrene copolymer (II) is 25 to 50 mass. %, More preferably 27 to 45% by mass, and further preferably 30 to 40% by mass. When the ratio of the unsaturated nitrile monomer unit is 25% by mass or more, the compatibility with the polyamide (III) is excellent, the chemical resistance is excellent, and the sharpness after coating is also high. When the ratio of the unsaturated nitrile monomer unit is 50% by mass or less, the difference in melt viscosity from polyamide (III) is reduced, and a stable extrudability at the time of production is obtained.

  In the present embodiment, the content of the styrene copolymer (II) contained in 100 parts by mass of the thermoplastic resin composition is 5 parts by mass or more, preferably 10 parts by mass or more, more preferably from the viewpoint of rigidity. It is 20 parts by mass or more, more preferably 30 parts by mass or more, and from the viewpoint of fluidity, it is 85 parts by mass or less, preferably 80 parts by mass or less, more preferably 60 parts by mass or less.

(III) Polyamide As the type of polyamide (III) that can be used in the present embodiment, any polymer having an amide bond in the polymer main chain may be used. For example, ring-opening polymerization of lactams, diamine and dicarboxylic acid Examples thereof include those obtained by polycondensation, aminocarboxylic acid polycondensation, and the like.

  Examples of the lactams include, but are not limited to, ε-caprolactam, enantolactam, and ω-laurolactam.

  Examples of diamines include aliphatic diamines, alicyclic diamines, and aromatic diamines. Examples of the aliphatic diamine include, but are not limited to, for example, tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2,4. , 4-trimethylhexamethylenediamine, and 5-methylnanomethylenediamine. Examples of the alicyclic diamine include, but are not limited to, 1,3-bisaminomethylcyclohexane and 1,4-bisaminomethylcyclohexane. Examples of the aromatic diamine include, but are not limited to, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine.

  Examples of dicarboxylic acids include aliphatic dicarboxylic acids, alicyclic dicarboxylic aromatic dicarboxylic acids, and dimer acids. Aliphatic dicarboxylic acids include, but are not limited to, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid, and 1,1,3-tridecanedioic acid. Examples of the alicyclic dicarboxylic acid include, but are not limited to, 1,3-cyclohexanedicarboxylic acid. Examples of the aromatic dicarboxylic acid include, but are not limited to, terephthalic acid, isophthalic acid, and naphthalenedicarboxylic acid.

  Examples of aminocarboxylic acids include, but are not limited to, for example, ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13 -Aminotridecanoic acid.

  The above lactams, diamines, dicarboxylic acids, and aminocarboxylic acids may be used as copolymerized polyamides obtained by polycondensation of one kind alone or by polycondensation of a mixture of two or more kinds. In addition, a polymer obtained by polymerizing the above lactams, diamine, dicarboxylic acid, and aminocarboxylic acid up to a low molecular weight oligomer stage in a polymerization reactor and increasing the molecular weight with an extruder or the like can also be suitably used. .

  The polyamide (III) that can be suitably used in the present embodiment is not limited to the following, and examples thereof include polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, and polyamide 6/66. , Polyamide 6/612, polyamide MXD6 (MXD: m-xylylenediamine), polyamide 6 / MXD6, polyamide 66 / MXD6, polyamide 6T, polyamide 6I, polyamide 6 / 6T, polyamide 6 / 6I, polyamide 66 / 6T, polyamide 66 / 6I, polyamide 6 / 6T / 6I, polyamide 66 / 6T / 6I, polyamide 6/12 / 6T, polyamide 66/12 / 6T, polyamide 6/12 / 6I, and polyamide 66/12 / 6I. Multiple polyamides In extruder or the like may be copolymerized with the polyamides. These polyamides can be used singly or in combination of two or more. Among these, polyamide 6, polyamide 66, and polyamide (66 / 6I) copolymer are preferable from the viewpoint of ease of processing.

  The number average molecular weight of the polyamide used in the present embodiment is preferably 5,000 to 100,000, more preferably 10,000 to 30,000. The polyamide may be a mixture of a plurality of polyamides having different molecular weights. For example, a mixture of a low molecular weight polyamide having a number average molecular weight of 10,000 or less and a high molecular weight polyamide having a molecular weight of 30,000 or more, a low molecular weight polyamide having a number average molecular weight of 10,000 or less, and a general polyamide having about 15,000 However, it is not limited to these. Further, different polyamides having different molecular weights may be mixed. The number average molecular weight can be calculated by creating a calibration curve using standard polystyrene by gel permeation chromatography (GPC).

  The end group of the polyamide is involved in the reaction of the modified styrene copolymer (IV) described later with the maleic anhydride monomer. Polyamide generally has an amino group, a carboxyl group or the like as a terminal group. Of these, the amino group concentration is preferably 10 meq / kg to 150 meq / kg, more preferably 20 meq / kg to 100 meq / kg, and even more preferably 30 meq / kg. ~ 90 milliequivalents / kg. When the amino group concentration is 10 milliequivalents / kg or more, the reaction with the modified styrene copolymer proceeds sufficiently to improve impact resistance, and the amino group concentration is 100. By being the milliequivalent / kg or less, excessive reaction with the modified styrenic copolymer is suppressed, gelation is difficult, and sufficient fluidity and impact resistance can be maintained.

  As a method for adjusting the terminal group of the polyamide, a known method can be used, and examples thereof include a method of adding diamines, dicarboxylic acids, monocarboxylic acids and the like at the time of polymerization of the polyamide.

  When an amino group and a carboxyl group are included as terminal groups of the polyamide, the ratio (molar ratio) is not particularly limited, but is preferably amino group / carboxyl group = 0.1 to 10.0, more preferably amino. Group / carboxyl group = 0.15 to 5.0, more preferably 0.2 to 2.0. When the molar ratio is 0.1 or more, the impact resistance tends to be further improved, and when the molar ratio is 10.0 or less, the fluidity tends to be further improved.

  In the present embodiment, the content of polyamide (III) contained in 100 parts by mass of the thermoplastic resin composition is 5 parts by mass or more, preferably 10 parts by mass or more, more preferably 15 parts by mass from the viewpoint of chemical resistance. It is 40 parts by mass or less from the viewpoint of paintability, preferably 35 parts by mass or less, more preferably 30 parts by mass or less. Moreover, in this embodiment, also from a viewpoint which makes a continuous phase a styrene-type copolymer (II), content of polyamide (III) is 40 mass parts or less.

(IV) Modified Styrene Copolymer The modified styrene copolymer (IV) that can be used in the present embodiment contains at least a maleic anhydride monomer unit and an aromatic vinyl monomer unit. The modified styrene copolymer (IV) functions as a compatibilizer between the polyamide (III) and the styrene copolymer (II) because the maleic anhydride and the terminal amino group of the polyamide (III) react with each other.

  The content of the maleic anhydride monomer unit contained in 100% by mass of the modified styrene copolymer (IV) is preferably 2.5% by mass or more from the viewpoint of further improving the compatibility. It is more preferably 8% by mass or more, further preferably 3.0% by mass or more, and from the viewpoint of suppressing gelation due to excessive reaction, it is preferably 15% by mass or less, and 12% by mass or less. More preferably, it is more preferably 10% by mass or less.

  Examples of the aromatic vinyl monomer corresponding to the aromatic vinyl monomer unit include, but are not limited to, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, o-ethylstyrene, p -Ethyl styrene, pt-butyl styrene, and vinyl naphthalene. These aromatic vinyl monomers can be used individually by 1 type or in combination of 2 or more types.

  The modified styrenic copolymer (IV) may contain a monomer unit corresponding to another copolymerizable monomer. Examples of other monomers include, but are not limited to, maleimide monomers, unsaturated carboxylic acid alkyl ester monomers, unsaturated nitrile monomers, and glycidyl group-containing monomers. These modified styrenic copolymers (IV) can be used singly or in combination of two or more. Among these, a maleimide monomer is preferable from the viewpoint of improving heat resistance.

  Examples of the maleimide monomer include, but are not limited to, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-propylmaleimide, N-isopropylmaleimide, N-cyclohexylmaleimide, and N- Examples thereof include lauryl maleimide, and N-phenylmaleimide is preferable from the viewpoint of compatibility with the styrene copolymer (II).

  Further, the modified styrene copolymer (IV) preferably contains no unsaturated nitrile monomer unit from the viewpoint of fluidity and tapping strength.

  In the present embodiment, the content of the modified styrene copolymer (IV) contained in 100 parts by mass of the thermoplastic resin composition is 0.1 parts by mass or more, preferably 1.8 from the viewpoint of impact resistance. From the viewpoint of fluidity, it is 40 parts by mass or less, preferably 35 parts by mass or less, more preferably 25 parts by mass or less.

  In the present embodiment, the IZOD impact strength of the thermoplastic resin composition in a 1/4 inch-thick molded product based on ASTM 256 is 90 J / m or more (for example, 90 to 400 J / m). The IZOD impact strength is 90 J / m or more from the viewpoint of tapping strength, more preferably 140 J / m or more, and still more preferably 160 J / m or more.

  In the composition containing both the graft copolymer (I) and the styrenic copolymer (II), a method of increasing the content of the graft copolymer is generally used as a method for improving the impact resistance. . However, in a polymer alloy having polyamide (III) as a dispersed phase, a Charpy impact strength of 4 mm thick is improved even if the amount of the graft copolymer (I) is increased, but an IZOD impact strength of 1/4 inch thick. The strength at the time of thick wall is not much changed.

  In order to make the IZOD impact strength within the above-mentioned range, it is not limited to the following, but examples include a method of adjusting the mass ratio of the modified styrene copolymer (IV) to the polyamide (III), and the like (IV) /(III)=0.16 to 1.00 is preferable, and in order to make the IZOD impact strength 90 J / m or more, 0.16 or more is preferable, and 0.17 or more is more preferable. Preferably, it is 0.20 or more, most preferably 0.25 or more, from the viewpoint of fluidity, preferably 1.00 or less, more preferably 0.90 or less, 0 Is more preferably 80 or less, and most preferably 0.75 or less.

(Additive)
In this embodiment, you may mix | blend and use an additive for a thermoplastic resin composition as needed. Examples of the additive include, but are not limited to, for example, phosphite, hindered phenol, benzotriazole, benzophenone, benzoate, and cyanoacrylate UV absorbers and antioxidants; higher fatty acids, acids Lubricants and plasticizers such as ester and acid amides, and higher alcohols; release agents such as montanic acid and salts thereof, esters thereof, half esters thereof, stearyl alcohol, stellar amide and ethylene wax; phosphites, Anti-coloring agents such as hypophosphites; Nucleating agents; Antistatic agents such as amines, sulfonic acids, and polyethers; 1,3-phenylenebis (2,6-dimethylphenyl phosphate), tetraphenyl- m-phenylenebisphosphate, phenoxyphosphoryl, phenoxyphosphazene Include halogen-based flame retardant; phosphorus-based flame retardants.

  Examples of the lubricant include, but are not limited to, aliphatic metal salts, polyolefins, polyester elastomers, and polyamide elastomers.

  When these lubricants are blended and used, the preferred amount is 0.1 parts by mass or more and 10 parts by mass or less when the thermoplastic resin composition is 100 parts by mass.

  Examples of the fatty acid metal salt include, but are not limited to, salts of metals and fatty acids containing at least one selected from sodium, magnesium, calcium, aluminum, and zinc. Examples of the fatty acid metal salt include, but are not limited to, for example, sodium stearate, magnesium stearate, calcium stearate, aluminum stearate (mono, di, tri), zinc stearate, sodium montanate, calcium montanate, ricinol And calcium laurate. Among these, stearic acid-based metal salts such as sodium stearate, magnesium stearate, calcium stearate, and zinc stearate are preferable. Among the stearic acid-based metal salts, calcium stearate is more preferable.

  When these are blended and used, the preferable amount is 0.1 parts by mass or more and 5 parts by mass or less when the thermoplastic resin composition is 100 parts by mass.

  Examples of the polyolefins include, but are not limited to, for example, compositions formed from at least one of ethylene, propylene, α-olefin, and the like, and these are compositions derived from the composition as a raw material. Including. Specific examples include, but are not limited to, polypropylene, ethylene-propylene copolymer, polyethylene (high density, low density, linear low density), oxidized polyolefin, and graft-polymerized polyolefin. Among these, oxidized polyolefin wax and polyolefin grafted with styrene resin are preferred, polypropylene wax, polyethylene wax, oxidized polypropylene wax, oxidized polyethylene wax, acrylonitrile-styrene copolymer grafted polypropylene, acrylonitrile-styrene copolymer. More preferred are graft polyethylene, styrene polymer grafted polypropylene, and styrene polymer grafted polyethylene.

  When these are blended and used, the preferable amount is 0.1 parts by mass or more and 10 parts by mass or less when the thermoplastic resin composition is 100 parts by mass.

  Examples of the polyester elastomer include, but are not limited to, for example, polycondensation of a dicarboxylic acid compound and a dihydroxy compound, ring-opening polycondensation of a polycondensation lactone compound of an oxycarboxylic acid compound, or polycondensation of a mixture of these components. The polyester obtained by these etc. is mentioned, A homopolyester may be sufficient and a copolyester may be sufficient.

  When these are blended and used, the preferable amount is 0.1 parts by mass or more and 10 parts by mass or less when the thermoplastic resin composition is 100 parts by mass.

  Examples of dicarboxylic acid compounds include, but are not limited to, terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, Aromatic dicarboxylic acids such as diphenoxyethanedicarboxylic acid, sodium 3-sulfoisophthalate, aliphatic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, And diphenyl ether dicarboxylic acid, diphenylethane dicarboxylic acid, succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid and other aliphatic dicarboxylic acids, and mixtures of these dicarboxylic acids, including these alkyl, alkoxy, or halogen Replace It is also included. These dicarboxylic acid compounds can also be used in the form of an ester-forming derivative, for example, a lower alcohol ester such as dimethyl ester. In this embodiment, these dicarboxylic acid compounds can be used alone or in combination of two or more. Among these, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedicarboxylic acid are preferable.

  Examples of dihydroxy compounds include, but are not limited to, ethylene glycol, propylene glycol, butanediol, neopentyl glycol, butenediol, hydroquinone, resorcin, dihydroxydiphenyl ether, cyclohexanediol, hydroquinone, resorcin, dihydroxydiphenyl ether, cyclohexanediol, and 2,2-bis (4-hydroxyphenyl) propane and the like, and these polyoxyalkylene glycols and their alkyl, alkoxy or halogen-substituted products may be used. These dihydroxy compounds can be used alone or in combination of two or more.

  Examples of the oxycarboxylic acid compound include, but are not limited to, oxybenzoic acid, oxynaphthoic acid, and diphenyleneoxycarboxylic acid. These alkyl, alkoxy, and halogen-substituted products may be used. These oxycarboxylic acid compounds can be used alone or in combination of two or more. For the production of a polyester elastomer, a lactone compound such as ε-caprolactone may be used.

Examples of the polyamide elastomer include, but are not limited to, for example, an aminocarboxylic acid or lactam having 6 or more carbon atoms, and a nylon mn salt having m + n of 12 or more. The hard segment (X) is not limited to the following. Aminocarboxylic acids such as, for example, ω-aminocaproic acid, ω-aminoenanoic acid, ω-aminocaprylic acid, ω-aminobergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12-aminododecanoic acid; caprolactam laurolactam Lactams such as nylon 6,6, nylon 6,10, nylon 6,12, nylon 11,6, nylon 11,10, nylon 12,6, nylon 11,12, nylon 12,10, nylon 12,12, etc. Nylon salt is mentioned. In addition, the soft segment (Y) such as polyol includes polyethylene glycol, poly (1,2- and 1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene oxide) glycol, and ethylene oxide. Examples thereof include a block or random copolymer of propylene oxide and a block or random copolymer of ethylene oxide and tetrahydrofuran. The number average molecular weight of these soft segments (Y) is preferably 2.0 × 10 ^{2 to} 6.0 × 10 ³ , more preferably 2.5 × 10 ^{2 to} 4.0 × 10 ³ . The number average molecular weight can be measured as a styrene equivalent molecular weight by comparison with standard polystyrene by gel permeation chromatography (GPC). Note that both ends of poly (alkylene oxide) glycol may be aminated or carboxylated.
In the present embodiment, when a lubricant is added to the thermoplastic resin composition, an acid-modified or epoxy-modified modified resin may be further mixed for the purpose of improving the compatibility.

  Further, a part of the thermoplastic resin composition of the present embodiment may be acid-modified or epoxy-modified. For example, the graft copolymer (I) or the styrene copolymer (II) contained in the thermoplastic resin composition is copolymerized with a vinyl monomer containing a carboxyl group or a glycidyl group. Etc. When using these, the preferable quantity is 0.1 to 10 mass parts when the whole thermoplastic resin composition is 100 mass parts.

  Examples of the vinyl monomer containing a carboxyl group include, but are not limited to, unsaturated compounds containing a free carboxyl group such as acrylic acid, crotonic acid, cinnamic acid, itaconic acid, maleic acid, maleic anhydride, Examples thereof include unsaturated compounds containing an acid anhydride-type carboxyl group such as itaconic anhydride, chloromaleic anhydride, and citraconic anhydride. Among these, acrylic acid, methacrylic acid, and maleic anhydride are preferable. .

  Examples of the vinyl monomer containing the glycidyl group include, but are not limited to, glycidyl methacrylate, glycidyl acrylate, allyl glycidyl ether, methyl glycidyl ether, and methyl glycidyl methacrylate. Among these, glycidyl methacrylate It is preferable that

(Method for producing thermoplastic resin composition)
The thermoplastic resin composition of the present embodiment includes various mixing apparatuses generally used for the production of thermoplastic resin compositions such as single-screw or twin-screw vented extruders, plastmills, kneaders, Banbury mixers, and brabenders. And can be produced by mixing raw materials.

[Molded product (molded product)]
The molded product of the present embodiment is not particularly limited as long as it is a molded product of the thermoplastic resin composition of the present embodiment, and may be manufactured by a known molding method. Known molding methods are not limited to the following, but include, for example, press molding methods, injection molding methods, gas-assisted injection molding methods, welding molding methods, extrusion molding methods, blow molding methods, film molding methods, hollow molding methods, many Examples thereof include a phase molding method and a foam molding method. Among these, the injection molding method and the gas assist injection molding method are preferable from the viewpoint of productivity. When using the injection molding method, the cylinder set temperature is preferably 230 to 300 ° C. In order to ensure sufficient fluidity for injection molding, it is preferably 230 ° C. or higher, more preferably 240 ° C. or higher, and further preferably 250 ° C. or higher. Further, from the viewpoint of preventing thermal deterioration of the resin, it is preferably 300 ° C. or lower, more preferably 290 ° C. or lower, and further preferably 280 ° C. or lower. In the injection molding method, insert molding with metal, outsert molding, gas assist molding, or the like may be used in combination. The die used is not particularly limited, and the gate shape may be any of pin gate, tab gate, film gate, submarine gate, fan gate, ring gate, direct gate, and disc gate. The mold temperature is preferably 40 to 100 ° C, more preferably 60 to 80 ° C. By being 40 degreeC or more, the surface smoothness of a molded article becomes high and the sharpness after coating also becomes high. Since the cooling rate is increased by being 100 ° C. or lower, productivity is improved. Moreover, when using the injection molding method, the injection speed is preferably in the range of 30 to 120 mm / second, and more preferably 50 to 75 mm / second. When the injection speed is 30 mm / second or more, the surface smoothness of the obtained molded product is increased. By being 120 mm / sec or less, it is possible to suppress the occurrence of silver streaks, burns, and the like that can cause poor appearance.

  Since the molded article of this embodiment is formed from the thermoplastic resin composition of this embodiment, it is excellent in impact resistance, tapping strength, and paintability of the thick part. For this reason, it is preferable that it is a molded product with a large thickness, and more specifically, the thickness is preferably 1.0 mm or more, more preferably 1.5 mm or more, and 1.7 mm or more. Further preferred.

[Coated molded products (Coated molded products)]
The molded product of the present embodiment is preferably a coated molded product from the viewpoint of enhancing the design properties and the durability of the molded product. At least one type of coating may be applied, preferably three types of primer coating for improving adhesion to the surface of the molded body, base coating for coloring, and topcoat coating for coating film protection, or the surface of the molded body It is preferable to apply four types: primer coating for improving adhesion, base coating for coloring, metallic coating for brightness, and topcoat coating for protecting the coating. You may change the combination of coating by the designability, color tone, and function which are calculated | required.

  Examples of the coating include one-component coating in which one type of liquid containing only the main agent and no curing agent is applied, and two-component coating in which two types of mixed liquids of the main component and the curing agent are applied. The method for applying these paints is not particularly limited, and examples thereof include air spray coating, airless spray coating, electrostatic coating, electrodeposition coating, powder coating, curtain flow coating, and roll coating. Among these, air spray coating, airless spray coating, and electrostatic coating are preferable. In the case of electrostatic coating, it is preferable to perform electrostatic coating after pretreatment such as application of a conductive primer in advance so that electrostatic coating is possible.

  The coating thickness of the coating is preferably 1 to 100 μm, more preferably 5 to 80 μm per layer. When the coating thickness is 1 μm or more, the paint concealing property is exhibited, and the design improvement effect by painting tends to be obtained. When the coating film thickness is 100 μm or less, surface defects of the coating film tend not to occur. In the case of metallic coating, the coating thickness is preferably 1 to 50 μm, more preferably 1 to 35 μm. When the coating film thickness is 1 μm or more, a metallic tone is developed and the design improvement effect by painting tends to be obtained. When the coating film thickness is 50 μm or less, the metallic pigment is uniformly dispersed and a good appearance tends to be obtained.

  The paint used for painting is not particularly limited, and paints generally used for resins can be used. The paint is composed of pigments, resins, additives, solvents and the like.

  Although a pigment is not specifically limited, For example, an organic pigment, an inorganic pigment, a metallic pigment etc. are mentioned. Examples of inorganic pigments include, but are not limited to, titanium oxide, carbon black, titanium yellow, iron oxide pigments, ultramarine, cobalt blue, chromium oxide, spinel green, lead chromate pigments, cadmium pigments, and the like. .

  The organic pigment is not particularly limited. Examples thereof include condensed polycyclic pigments such as pigments, perylene pigments, anthraquinone pigments, perinone pigments, and dioxazine violet.

  The metallic pigment is not particularly limited. For example, the metallic pigment of scaly aluminum, the spherical aluminum pigment used for improving the weld appearance, mica powder for pearl-like metallic, and other inorganic materials such as glass. Examples include polyhedral particles coated with metal by plating or sputtering.

  Solvents used in paints are mainly divided into true solvents, cosolvents, and diluents. The true solvent is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents such as mineral spirits; aromatic hydrocarbon solvents such as xylene; ester solvents such as ethyl acetate and n-butyl acetate. Although it does not specifically limit as a cosolvent, For example, alcohol, such as methanol, ethanol, isopropanol, is mentioned. Although it does not specifically limit as a diluent, For example, toluene etc. are mentioned.

  The solvent used in the paint preferably has a boiling point that varies depending on the season and the resin that is the main component of the paint, and is generally a low-boiling solvent having a boiling point of less than 100 ° C or a medium-boiling solvent having a boiling point of 100 to 150 ° C. Is preferably used. The solvent is preferably blended in an amount of 15 to 35 parts by mass in the paint.

  The paint is used in combination with these components and is not particularly limited. For example, lacquer paint, urethane paint, acrylic paint, silicone paint, fluorine paint, alkyd paint, epoxy paint, etc. It is called.

  The drying process of the coating is necessary for releasing the solvent in a short time or curing the paint, and is preferably performed in the range of 70 to 120 ° C. The temperature is 70 ° C. or higher from the viewpoint of solvent release time and 120 ° C. or lower from the viewpoint of avoiding thermal deformation of the molded body.

  The coated molded product of the present embodiment can be suitably used in various applications such as an outer plate, an outside door handle, a roof rail, a door mirror, a fender, a slide rail cover, and an automobile exterior, and particularly preferably used for an automobile exterior. Can do.

  Examples are shown below. Evaluation was performed according to the following method.

[Measurement method of ratio of unsaturated nitrile monomer unit]
(Separation of acetone-soluble matter)
Two dried centrifuge tubes were prepared per sample. First, the centrifuge tube was allowed to cool in a desiccator for 15 minutes or more, and then precisely weighed to 0.1 mg with an electronic balance. Next, about 1 g was cut from the thermoplastic resin composition, weighed into a centrifuge tube, and precisely weighed to 0.1 mg. In addition, about 20 mL of acetone was collected with a graduated cylinder, placed in a centrifuge tube, sealed with a silicon stopper, and shaken for 2 hours with a shaker. After shaking, the sample adhering to the silicon stopper was dropped into a centrifuge tube using a small amount of acetone. Next, set the two centrifuge tubes diagonally to the rotor of a Hitachi high-speed cooling centrifuge manufactured by Hitachi Koki Co., Ltd., operate the Hitachi high-speed cooling centrifuge, and centrifuge for 60 minutes at a rotational speed of 20000 rpm. went. After completion of the centrifugation, the sedimentation tube was removed from the rotor, and the supernatant was decanted. The supernatant was dried at 80 ° C. for 1 hour and then dried under reduced pressure at 100 ° C. for 1 hour to obtain an acetone-soluble component.

(Measurement of unsaturated nitrile monomer units)
Composition analysis was performed using FT-IR from the acetone-soluble component obtained as described above. Using a calibration curve prepared using the peak value of a copolymer with a known content of unsaturated nitrile monomer units and aromatic vinyl monomer units, unsaturated nitrile monomer units and aromatics The proportion of vinyl monomer units was determined. From these values, the ratio of the unsaturated nitrile monomer unit to the total amount of the unsaturated nitrile monomer unit and the aromatic vinyl monomer unit was determined.

(Production Example 1)
[Production Example of Graft Copolymer (I-1)]
6.2 parts by mass (solid content) of polybutadiene latex having a mass average particle diameter of 160 nm, 44.6 parts by mass (solid content) of polybutadiene latex having a mass average particle diameter of 330 nm, 0.1 parts by mass of t-dodecyl mercaptan, and deionization 125 parts by mass of water was added, the gas phase was replaced with nitrogen, and 0.1603 parts by mass of sodium formaldehyde sulfoxylate, 0.132 parts by mass of ferrous sulfate, and 0.0903 parts by mass of disodium ethylenediaminetetraacetate were added. Thereafter, the temperature was raised to 55 ° C. Subsequently, while the temperature was raised to 70 ° C. over 1.25 hours, a simple substance comprising 20 parts by mass of acrylonitrile, 30 parts by mass of styrene, 0.55 parts by mass of t-dodecyl mercaptan, and 0.12 parts by mass of cumene hydroperoxide. An aqueous solution prepared by dissolving 0.136 parts by mass of sodium formaldehyde sulfoxylate in 15 parts by mass of a monomer mixture and deionized water was added over 5 hours. After the addition was completed, 0.02 part by mass of cumene hydroperoxide was added, and then the polymerization reaction was completed while controlling the reaction vessel at 70 ° C. for 4 hours to obtain ABS latex.

  After adding a silicone resin defoamer and a phenolic antioxidant emulsion to the ABS latex thus obtained, solidify by adding an aqueous aluminum sulfate solution, and after sufficient dehydration and washing with water And dried to obtain a polymer (G-1). Thereafter, the polymer (G-1) was treated with acetone to obtain a graft copolymer (I-1) insoluble in acetone and a styrene copolymer (II-1) soluble in acetone. The ratios of the graft copolymer (I-1) and the styrene copolymer (II-1) in (G-1) were 68% by mass and 32% by mass. As a result of composition analysis using a Fourier transform infrared spectrophotometer (FT-IR), the graft copolymer (I-1) was 10.6 parts by mass of acrylonitrile, 73.5 parts by mass of butadiene, and 15.9 parts by mass of styrene. The graft ratio was 36%, the styrene copolymer (II-1) was 40.1 parts by mass of acrylonitrile and 59.9 parts by mass of styrene, and the reduced viscosity of (II-1) was 0.41 dl / g. It was.

(Production Example 2)
[Production Example of Graft Copolymer (I-2)]
25.5 parts by mass (solid content) of polybutadiene latex having a mass average particle diameter of 160 nm, 26.3 parts by mass (solid content) of polybutadiene latex having a mass average particle diameter of 330 nm, 0.1 part by mass of t-dodecyl mercaptan, and deionization 125 parts by mass of water was added, the gas phase was replaced with nitrogen, 0.0801 parts by mass of sodium formaldehyde sulfoxylate, 0.003 parts by mass of ferrous sulfate, and 0.0207 parts by mass of disodium ethylenediaminetetraacetate were added. Thereafter, the temperature was raised to 55 ° C. Then, while heating up to 70 degreeC over 1.25 hours, the single quantity which consists of 17 mass parts of acrylonitrile, 33 mass parts of styrene, 0.4 mass part of t-dodecyl mercaptan, and 0.1 mass part of cumene hydroperoxide. A body mixture and an aqueous solution prepared by dissolving 0.045 parts by mass of sodium formaldehyde sulfoxylate in 15 parts by mass of deionized water were added over 5 hours. After the addition was completed, 0.02 part by mass of cumene hydroperoxide was added, and then the polymerization reaction was completed while controlling the reaction vessel at 70 ° C. for 4 hours to obtain ABS latex.

  After adding a silicone resin defoamer and a phenolic antioxidant emulsion to the ABS latex thus obtained, solidify by adding an aqueous aluminum sulfate solution, and after sufficient dehydration and washing with water And dried to obtain a polymer (G-2). Thereafter, (G-2) was treated with acetone to obtain a graft copolymer (I-2) insoluble in acetone and a styrene copolymer (II-2) soluble in acetone. The ratio of the graft copolymer (I-2) and the styrene copolymer (II-2) in (G-2) was 77.5% by mass and 22.5% by mass. As a result of composition analysis using a Fourier transform infrared spectrophotometer (FT-IR), the graft copolymer (I-2) was 10.9 parts by mass of acrylonitrile, 69.0 parts by mass of butadiene, and 20.2 parts by mass of styrene. The graft ratio was 45%, the styrene copolymer (II-2) was 34.8 parts by mass of acrylonitrile and 65.2 parts by mass of styrene, and the reduced viscosity of (II-2) was 0.40 dl / g. It was.

(Production Example 3)
[Production Example of Graft Copolymer (I-3)]
To 45.9 parts by mass (solid content) of polybutadiene latex having a mass average particle size of 330 nm, 0.1 part by mass of t-dodecyl mercaptan and 138 parts by mass of deionized water are added, and the gas phase part is substituted with nitrogen, and sodium formaldehyde sulfone is added. After adding 0.0819 parts by mass of xylate, 0.0044 parts by mass of ferrous sulfate and 0.0499 parts by mass of disodium ethylenediaminetetraacetic acid, the temperature was raised to 55 ° C. Subsequently, while raising the temperature to 70 ° C. over 1.25 hours, 16.5 parts by mass of acrylonitrile, 38.5 parts by mass of styrene, 0.35 parts by mass of t-dodecyl mercaptan, 0.115 parts by mass of cumene hydroperoxide A monomer mixture consisting of 5 parts and an aqueous solution prepared by dissolving 0.08 parts by weight of sodium formaldehyde sulfoxylate in 15 parts by weight of deionized water were added over 5 hours. After the addition was completed, 0.02 part by mass of cumene hydroperoxide was added, and then the polymerization reaction was completed while controlling the reaction vessel at 70 ° C. for 4 hours to obtain ABS latex.

  After adding a silicone resin defoamer and a phenolic antioxidant emulsion to the ABS latex thus obtained, solidify by adding an aqueous aluminum sulfate solution, and after sufficient dehydration and washing with water And dried to obtain a polymer (G-3). Thereafter, (G-3) was treated with acetone to obtain a graft copolymer (I-3) insoluble in acetone and a styrene copolymer (II-3) soluble in acetone. The ratios of the graft copolymer (I-3) and the styrene copolymer (II-3) in (G-3) were 64% by mass and 36% by mass. As a result of composition analysis using a Fourier transform infrared spectrophotometer (FT-IR), the graft copolymer (I-3) was 8.9 parts by mass of acrylonitrile, 70.4 parts by mass of butadiene, and 20.7 parts by mass of styrene. The graft ratio was 42%, the styrene copolymer (II-3) was 30.0 parts by mass of acrylonitrile and 70.0 parts by mass of styrene, and the reduced viscosity of (II-3) was 0.36 dl / g. It was.

(Production Example 4)
[Production Example of Graft Copolymer (I-4)]
13.1 parts by mass (solid content) of polybutadiene latex having a mass average particle diameter of 160 nm, 38.3 parts by mass (solid content) of polybutadiene latex having a mass average particle diameter of 330 nm, 0.2 parts by mass of t-dodecyl mercaptan, and deionization 125 parts by mass of water was added, the gas phase was replaced with nitrogen, 0.0801 parts by mass of sodium formaldehyde sulfoxylate, 0.0015 parts by mass of ferrous sulfate, and 0.0207 parts by mass of disodium ethylenediaminetetraacetate were added. Thereafter, the temperature was raised to 55 ° C. Subsequently, while raising the temperature to 70 ° C. over 1.25 hours, 13.5 parts by mass of acrylonitrile, 36.5 parts by mass of styrene, 0.125 parts by mass of t-dodecyl mercaptan, 0.1 parts by mass of cumene hydroperoxide An aqueous solution prepared by dissolving 0.045 parts by mass of sodium formaldehyde sulfoxylate in 15 parts by mass of deionized water and a monomer mixture consisting of the above was added over 5 hours. After the addition was completed, 0.02 part by mass of cumene hydroperoxide was added, and then the polymerization reaction was completed while controlling the reaction vessel at 70 ° C. for 4 hours to obtain ABS latex.

  After adding a silicone resin defoamer and a phenolic antioxidant emulsion to the ABS latex thus obtained, solidify by adding an aqueous aluminum sulfate solution, and after sufficient dehydration and washing with water And dried to obtain a polymer (G-4). Thereafter, (G-4) was treated with acetone to obtain a graft copolymer (I-4) insoluble in acetone and a styrene copolymer (II-4) soluble in acetone. The ratios of the graft copolymer (I-4) and the styrene copolymer (II-4) in (G-4) were 73.5% by mass and 26.5% by mass. As a result of composition analysis using a Fourier transform infrared spectrophotometer (FT-IR), the graft copolymer (I-4) was 8.0 parts by weight of acrylonitrile, 68.0 parts by weight of butadiene, and 24.0 parts by weight of styrene. The graft ratio was 47%, the styrene copolymer (II-4) was 25.1 parts by mass of acrylonitrile and 74.9 parts by mass of styrene, and the reduced viscosity of (II-4) was 0.38 dl / g. It was.

Styrene copolymer (II)
(Production Example 5)
[Production Example of Styrene Copolymer (II-5)]
A mixture of 35 parts by weight of acrylonitrile, 35 parts by weight of styrene, 30 parts by weight of toluene as a solvent, and 0.05 parts by weight of t-butylperoxy-2-ethylhexanoate as a polymerization initiator was bubbled using nitrogen gas. After that, continuously using a spray nozzle in a reaction vessel having an internal volume of 150 l provided with a two-stage inclined paddle type (inclination angle of 45 degrees) stirring blade similar to that described in Example 2 of Japanese Patent No. 3664576 At a rate of 37.5 kg / hr.

  The polymerization temperature was 130 ° C., and the same amount of the reaction liquid as that of the supply liquid was continuously withdrawn so that the filling rate of the reaction liquid in the reaction tank could be maintained at 70% by volume. A jacket for temperature control was provided in a portion corresponding to the liquid phase portion of the reaction tank, and the jacket temperature was 128 ° C. The power required for stirring was 4 kW / m, and the polymerization conversion rate was 39.8 wt% / hr.

  The extracted reaction solution was introduced into a volatile component removing apparatus maintained at 250 ° C. and 10 mmHg in a high vacuum, and the unreacted monomer and organic solvent were degassed and recovered, and the produced copolymer (B-9) was recovered. Collected as pellets.

  The composition of (II-5) was 40.6% by mass of acrylonitrile and 59.4% by mass of styrene as a result of composition analysis using a Fourier transform infrared spectrophotometer (FT-IR). The reduced viscosity was 0.58 dl / g.

(Production Example 6)
[Production Example of Styrene Copolymer (II-6)]
Styrene was produced in the same manner as in Production Example 5 for styrene-based copolymer (II), except that 28 parts by mass of acrylonitrile and 42 parts by mass of styrene were used as the feed liquid to the reaction vessel, and 30 parts by mass of toluene was used as the solvent. A copolymer (II-6) was produced. The composition of (II-6) was 34.8% by mass of acrylonitrile and 65.2% by mass of styrene as a result of composition analysis using a Fourier transform infrared spectrophotometer (FR-IR). The reduced viscosity was 0.67 dl / g.

(Production Example 7)
[Production Example of Styrene Copolymer (II-7)]
Styrene was produced in the same manner as in Production Example 5 of styrene-based copolymer (II), except that 21 parts by mass of acrylonitrile and 47 parts by mass of styrene were used as the feed liquid to the reaction vessel, and 32 parts by mass of toluene was used as the solvent. A copolymer (II-6) was produced. The composition of (II-7) was 29.8% by mass of acrylonitrile and 70.2% by mass of styrene as a result of composition analysis using a Fourier transform infrared spectrophotometer (FR-IR). The reduced viscosity was 0.65 dl / g.

(Production Example 8)
[Production Example of Styrene Copolymer (II-8)]
Styrene was produced in the same manner as in Production Example 5 for styrene-based copolymer (II), except that 19 parts by mass of acrylonitrile and 51 parts by mass of styrene were used as the feed liquid to the reaction vessel, and 30 parts by mass of toluene was used as the solvent. A copolymer (II-8) was produced. The composition of (II-8) was 24.8% by mass of acrylonitrile and 75.2% by mass of styrene as a result of composition analysis using a Fourier transform infrared spectrophotometer (FR-IR). The reduced viscosity was 0.75 dl / g.

  As polyamide (III), (III-1) UBE nylon 1015B (polyamide 6) manufactured by Ube Industries, Ltd. was used.

(IV-1) MS-L2A (N-phenylmaleimide / styrene / maleic anhydride copolymer) manufactured by Denka Co., Ltd. was used as the modified styrene copolymer (IV).

Example 1
Using a twin screw extruder (TEM58SS, manufactured by Toshiba Machine Co., Ltd.) with the composition shown in Table 1, materials were supplied from the top feeder and side feeder of the extruder and melt-kneaded to obtain resin composition pellets. It was. The melt-kneading conditions at that time were performed at a temperature of 250 to 300 ° C., a rotation speed of 300 to 400 rpm, and a discharge amount of 500 kg / h. The following evaluation was performed on the pellets thus obtained.

(1) MVR (melt volume flow rate)
Measurement was performed by a method based on ISO 1133 using pellets of the thermoplastic resin composition. The measurement conditions were a temperature of 240 ° C. and a load of 5 kg.

(2) IZOD impact value (thickness 6.4mm)
Using an injection molding machine (Toshiba Machine Co., Ltd., EC75S), a strip test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 6.4 mm in accordance with ASTM D638 was measured at a cylinder temperature of 260 ° C. and a mold temperature. Molding was performed at 50 ° C. After cutting the strip test piece at a position of 63.5 mm in length from the side opposite to the gate, notching was performed to obtain a test piece based on ASTM D256. The IZOD impact value (6.4 mm) was measured by the method based on ASTM D256 using the test piece thus obtained. In addition, the test value used the average value of five test pieces.

(3) Charpy impact value (thickness 4.0 mm)
Using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., EC75S), a multi-dumbbell test piece (TYPE B) having a thickness of 4.0 mm conforming to ISO294-1 is used. Molded under conditions. A test piece having a length of 80 mm and a width of 10 mm was cut out from the dumbbell test piece, then notched, and then subjected to a test to obtain a test piece based on ISO179. A Charpy impact test based on ISO179 was performed using this test piece. In addition, the test value used the average value of five test pieces.

(4) Using a gasoline resistant injection molding machine (Toshiba Machine Co., Ltd., EC75S), a strip test piece having a length of 127 mm, a width of 12.7 mm, and a thickness of 6.4 mm, a cylinder temperature of 260 ° C. and a mold Molding was performed at a temperature of 50 ° C. After annealing at 90 ° C. for 3 hours, it was left in a desiccator at 23 ° C. for 24 hours so as not to absorb moisture. This test piece was fixed to a bending foam jig, and commercially available regular gasoline was applied to the surface. The minimum strain value at which cracks occurred after standing for 24 hours was determined as the critical strain.

(5) Using a paint sharpness injection molding machine (Toshiba Machine Co., Ltd., EC75S), a 100 mm x 100 mm, 2.5 mm thick flat plate was molded under conditions of a cylinder temperature of 260 ° C and a mold temperature of 50 ° C. did. This flat plate was left in a desiccator at 23 ° C. for 24 hours. An acrylic paint (manufactured by Campehapio Co., Ltd., Camperacquer Spray A red) was used for this test piece, and spray coating was performed on the sample to obtain a coated molded body. After drying, the fluorescent lamp was reflected on the surface of the coated molded body, and the visual clarity was evaluated visually according to the following criteria.
S: Fluorescent lamp appears almost straight A: Fluorescent lamp appears slightly distorted B: Fluorescent lamp appears quite distorted C: Fluorescent lamp is blurred and almost invisible

(6) Paint adhesion Using the test pieces used in the paint sharpness evaluation, the coating film adhesion was evaluated by a multi-cross cutter on the gate side and the non-gate side with a grid cross cut (100 squares of 1 × 1 mm) ), And then a cellophane tape peeling test was conducted. The evaluation was made as follows by calculating the average of (number of cells not peeled) / (total number of cells) on the gate side and anti-gate side of the three test pieces.
A: No peeling B: 1 to 5 peelings C: 6 or more peelings

(7) Tapping strength A bossed flat plate was molded under conditions of a cylinder temperature of 260 ° C. and a mold temperature of 50 ° C. using an injection molding machine (manufactured by Toshiba Machine Co., Ltd., EC75S). As the flat plate with boss, one having a boss having an outer diameter of 8.0 mm, an inner diameter of 4.0 mm, and a height of 25 mm at the center of a 100 mm × 100 mm × 3.0 mmt flat plate was used. This bossed flat plate was left in a desiccator at 23 ° C. for 24 hours. After this M5 × 12 mm tapping screw was inserted into this boss with a torque of 1.5 Nm, the presence or absence of cracks was visually determined. Twenty bossed flat plates were tested and evaluated according to the following criteria.
S: No crack generation A: 1 to 2 cracks generated B: 3 to 4 cracks generated C: 5 or more cracks generated

(Examples 2 to 13, Comparative Examples 1 to 3)
Pellets were obtained in the same manner as in Example 1 with the composition shown in Table 1, and evaluated.

  The thermoplastic resin composition of this embodiment is excellent in impact resistance, chemical resistance, paintability, tapping strength, and moldability at the time of thick wall, so it has an outer plate, outside door handle, roof rail, door mirror, fender, slide rail cover Etc., and can be suitably used in various applications such as automobile exteriors.

Claims (9)

5-30 parts by mass of a graft copolymer (I) obtained by graft copolymerizing at least an unsaturated nitrile monomer and an aromatic vinyl monomer to a rubber polymer,
5 to 85 parts by mass of a styrene copolymer (II) containing at least an unsaturated nitrile monomer unit and an aromatic vinyl monomer unit,
0.1 to 40 parts by mass of a modified styrene copolymer (IV) containing 5 to 40 parts by mass of polyamide (III) and at least a maleic anhydride monomer unit and an aromatic vinyl monomer unit, The total amount of I), (II), (III), and (IV) is 100 parts by mass,
IZOD impact strength in a 1/4 inch-thick molded product in accordance with ASTM D256 is 90 J / m or more,
Thermoplastic resin composition.   2. The thermoplastic resin composition according to claim 1, wherein the mass ratio of the modified styrene copolymer (IV) to the polyamide (III) is (IV) / (III) = 0.16 to 1.00.   The ratio of the unsaturated nitrile monomer unit to the total amount of the unsaturated nitrile monomer unit and the aromatic vinyl monomer unit in the styrene copolymer (II) is 25 to 50% by mass. The thermoplastic resin composition according to 1 or 2.   The thermoplastic resin composition according to any one of claims 1 to 3, wherein the modified styrene copolymer (IV) does not contain an unsaturated nitrile monomer unit.   The thermoplastic resin composition according to any one of claims 1 to 4, wherein the modified styrenic copolymer (IV) comprises a maleimide monomer unit.   The molded article of the thermoplastic resin composition as described in any one of Claims 1-5.   The molded article according to claim 6, wherein the thickness is 1.0 mm or more.   The molded product according to claim 6 or 7, which is a painted molded product.   The paint molded article according to claim 8, wherein the paint molded article is for automobile exterior use.