JP2019019236A - Thermoplastic resin composition and its molded body, and vehicle exterior component - Google Patents

Abstract

To provide a thermoplastic resin composition having good weather resistance, impact resistance and surface appearance, and a molded body formed by molding the thermoplastic resin composition.SOLUTION: A thermoplastic resin composition contains a thermoplastic resin (G), a photostabilizer (D), an ultraviolet absorber (E) and an antioxidant (F). The thermoplastic resin composition is composed of the thermoplastic resin (G), a graft copolymer (A), a graft copolymer (B) and a vinyl copolymer (C). The graft copolymer (A) is a graft copolymer obtained by grafting a rubbery polymer (a) that contains an acrylic ester monomer unit and a polyfunctional monomer unit, contains no conjugated diene monomer in its main chain and has a volume average particle size of 0.3-0.6 μm, with a vinyl monomer, and the graft copolymer (B) is a graft copolymer obtained by grafting a rubbery polymer (b) that contains an acrylic ester monomer unit and a polyfunctional monomer unit, contains no conjugated diene monomer in its main chain and has a volume average particle size of 0.07-0.2 μm, with a vinyl monomer unit.SELECTED DRAWING: None

Description

  The present invention relates to a thermoplastic resin composition capable of obtaining a molded article having excellent weather resistance, impact resistance, and surface appearance, a molded article obtained from the thermoplastic resin composition, and a vehicle including the molded article. Related to exterior parts.

  Many of the vehicle exterior parts use a molded body made of a thermoplastic resin from the viewpoint of light weight and freedom of design. Usually, these exterior parts are often subjected to a coating treatment for the purpose of imparting weather resistance and decorative properties.

  However, the paint used in the painting process contains a volatile organic compound (VOC) that may affect the human body and the environment. In recent years, there has been an increasing demand for non-painting of vehicle exterior parts for the purpose of reducing the load on the human body and the environment. By making the exterior parts unpainted, VOCs generated during painting can be reduced, cost savings due to omission of the painting process, reduction of the defective rate caused by painting, and reduction of lead time can be expected. is there.

  Since the vehicle exterior parts are exposed to the outdoors, the weather resistance is required for the molded body when it is unpainted. The required level of weather resistance is classified into four stages according to the mounting position of the parts. The lowest required level of weather resistance is the part that is not directly irradiated with sunlight (for example, a lamp housing), and the next is below the belt line. Parts to be installed (for example, side molding, mud guard, assist step, bumper, etc.), and parts to be mounted on the inclined surface above the belt line (for example, cowl vent, pillar, radiator grill, door mirror housing, etc.) The parts requiring the highest level of weather resistance are components (for example, spoilers) mounted on the horizontal surface above the belt line. Generally, a higher level of weather resistance is required as the mounting position of components in a vehicle becomes higher. This is because the amount of radiation exposure received from sunlight differs depending on the mounting position.

For example, in the xenon weather meter, when performing the accelerated weather resistance test assuming each of the above-described exterior parts, when the illumination intensity of light having a wavelength of 340 nm is set to 0.55 W / m ² , the radiation exposure amount of each exterior part is parts direct sunlight is not irradiated 1250kJ / ^{m 2,} parts 2500 kJ / ^{m 2} to the belt line is attached to the lower parts to be mounted on the inclined surface of the upper than belt line 3500kJ / ^{m 2,} the belt line The part mounted on the upper horizontal plane is 4500 kJ / m ² .

  In addition to the weather resistance as described above, a molded body that is applied uncoated to a vehicle exterior part is required to exhibit an excellent surface appearance without coating. In addition, since impact resistance is also required to reduce the thickness and weight of vehicle exterior parts, there is an increasing need for resin materials that can provide molded products that combine these multiple characteristics at a high level when no paint is applied. ing.

  An acrylonitrile-butadiene-styrene copolymer (ABS resin) is known as a typical thermoplastic resin from which a molded article excellent in impact resistance and surface appearance can be obtained. However, the ABS resin uses polybutadiene, which is a conjugated diene rubber, as a rubber component, and since this is easily decomposed by ultraviolet rays, there is a drawback that a molded product obtained from the ABS resin is inferior in weather resistance.

  As a resin having improved weather resistance of ABS resin, an acrylate-styrene-acrylonitrile copolymer (ASA resin) containing an acrylate rubber as a rubber component is known. However, molded articles obtained from ASA resins generally tend to be inferior in impact resistance as compared to molded articles obtained from ABS resins.

  As a thermoplastic resin composition excellent in weather resistance, impact resistance, and surface appearance, for example, Patent Document 1 discloses an acrylic rubber-based graft copolymer, a diene-based graft copolymer, and an aromatic vinyl copolymer. A thermoplastic resin composition containing a light stabilizer and an ultraviolet absorber is disclosed. Moreover, as a thermoplastic resin composition excellent in impact resistance, rigidity, and surface appearance, Patent Document 2 discloses a thermoplastic resin composition containing an acrylic rubber-based graft copolymer.

Special table 2015-537090 gazette JP 2012-214734 A

  However, the thermoplastic resin composition described in Patent Document 1 uses a diene graft copolymer that is inferior in weather resistance. In view of the results of the weather resistance test in Patent Document 1, the molded product is used as a vehicle. When applied to exterior parts, the level of weather resistance is limited to parts that are not directly exposed to sunlight, such as lamp housings.

  In addition, Patent Document 2 does not include a description that specifically verifies the effect on weather resistance. Considering the configuration of the embodiment, if the component is mounted below the belt line, the required level of weather resistance is required. However, for parts that require a higher level of weather resistance, such as parts that are mounted on an inclined surface or a horizontal surface above the belt line, the required level may not be satisfied. Absent.

  The present invention provides a thermoplastic resin composition having both weather resistance and surface appearance required for non-painting of various vehicle exterior parts and impact resistance necessary for thinning, and molding the thermoplastic resin composition. An object of the present invention is to provide a molded body and a vehicle exterior part using the molded body.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention controlled the particle diameter and graft ratio of two types of graft copolymers as thermoplastic resins, and the photostable light having a specific structure in this thermoplastic resin. It has been found that the above-mentioned problems can be solved by blending an agent, an ultraviolet absorber, and an antioxidant in a predetermined ratio, and the present invention has been completed.

  That is, this invention includes the following aspects.

[1] The following thermoplastic resin (G), light stabilizer (D), ultraviolet absorber (E), and antioxidant (F) are included, and 100 parts by weight of the thermoplastic resin (G) is light. Thermoplastic containing 0.1 to 1.5 parts by mass of stabilizer (D), 0.1 to 1.5 parts by mass of ultraviolet absorber (E), and 0.1 to 3 parts by mass of antioxidant (F) Resin composition.
Thermoplastic resin (G): composed of graft copolymer (A), graft copolymer (B), and vinyl copolymer (C). Graft copolymer (A) is an acrylic ester-based monomer A rubber-based polymer (a) having a volume average particle size of 0.3 to 0.6 μm, comprising a body unit and a polyfunctional monomer unit and not containing a conjugated diene monomer unit in the main chain; The graft copolymer is a graft copolymer having a graft ratio of 40 to 80%, and the graft copolymer (B) contains an acrylate monomer unit and a polyfunctional monomer unit. Graft ratio in which vinyl monomer is grafted to rubbery polymer (b) having a volume average particle size of 0.07 to 0.2 μm and containing no conjugated diene monomer unit in the chain is 40 to 80% A graft copolymer of the vinyl copolymer (C) is an aromatic vinyl monomer Of a rubber polymer contained in the thermoplastic resin (G), or a copolymer formed by copolymerizing at least a vinyl cyanide monomer and an aromatic vinyl monomer. Thermoplastic resin light stabilizer (D) containing 20 to 70% by mass of rubbery polymer (a) and 30 to 80% by mass of rubbery polymer (b) in a total amount of 100% by mass: molecular weight 400 to 2, 000 hindered amine light stabilizer UV absorber (E): benzophenol UV absorber having a molecular weight of 300 to 800 and / or triazine UV absorber antioxidant (F): hindered phenol oxidation having a molecular weight of 500 to 800 Inhibitor

[2] Rubber polymer (a) The content of acrylate monomer units in 100% by mass is 75% by mass or more, and the content of polyfunctional monomer units is acrylate ester units. 0.3 to 3 parts by mass with respect to 100 parts by mass of the monomer unit, and the graft copolymer (A) is added to the rubbery polymer (a) with a vinyl cyanide monomer and an aromatic vinyl monomer. A graft copolymer (A) 100 is obtained by graft polymerization of a vinyl monomer mixture containing a monomer and other monomers copolymerizable with these vinyl monomers used as necessary. The content of the rubber polymer (a) in the mass part is 10 to 90 parts by mass, and the content of the acrylate monomer unit in 100% by mass of the rubber polymer (b) is 75 mass. %, The content of polyfunctional monomer units is acrylic acid ester monomer units It is 0.05-3 parts by mass with respect to 00 parts by mass, and the graft copolymer (B) is added to the rubbery polymer (b), a vinyl cyanide monomer and an aromatic vinyl monomer, And a vinyl monomer mixture containing other monomers copolymerizable with these vinyl monomers used as needed, in 100 parts by mass of the graft copolymer (B). The thermoplastic resin composition according to [1], wherein the content of the rubber polymer (b) is 10 to 90 parts by mass.

[3] The graft copolymer (A) contained in 100 parts by mass of the thermoplastic resin (G), which is the total amount of the graft copolymer (A), the graft copolymer (B), and the vinyl copolymer (C). ) And the graft copolymer (B) is 20 to 60 parts by mass, and the vinyl copolymer (C) is 40 to 80 parts by mass, according to [1] or [2] Thermoplastic resin composition.

[4] The vinyl copolymer (C) is a homopolymer of an aromatic vinyl monomer, or a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer (C-1 And / or a copolymer (C-2) of an N-substituted maleimide monomer, an aromatic vinyl monomer and a vinyl cyanide monomer [1] to [3] The thermoplastic resin composition according to any one of the above.

[5] The content ratio of the copolymer (C-1) and the copolymer (C-2) in 100 parts by mass of the vinyl copolymer (C) is (C-1) :( C-2) = 10. -100 mass parts: The thermoplastic resin composition as described in [4] which is the range of 0-90 mass parts.

[6] The thermoplastic resin according to any one of [1] to [5], further including one or more of a phosphorus-based antioxidant, carbon black, and an oxide of a Group 2 element of the periodic table. Composition.

[7] A molded article obtained by molding the thermoplastic resin composition according to any one of [1] to [6].

[8] A vehicle exterior part including the molded article according to [7].

  By using the thermoplastic resin composition of the present invention, it is possible to obtain a molded product satisfying all of the weather resistance, surface appearance, and impact resistance required for unpainting and thinning of vehicle exterior parts. it can.

  Hereinafter, embodiments of the present invention will be described in detail.

In the following description, the “molded body” is obtained by molding the thermoplastic resin composition of the present invention.
In addition, “unit” refers to a structural portion derived from a monomer compound (monomer) before polymerization. For example, “acrylate monomer unit” refers to “acrylate monomer”. “Derived structural part”. The content ratio of each monomer unit in the polymer corresponds to the content ratio of the monomer in the monomer mixture used for producing the polymer.
“(Meth) acryl” means one or both of “acryl” and “methacryl”.

[Thermoplastic resin composition]
The thermoplastic resin composition of the present invention comprises a thermoplastic resin (G) comprising a graft copolymer (A), a graft copolymer (B), and a vinyl copolymer (C), which will be described in detail below. It contains a light stabilizer (D), an ultraviolet absorber (E), and an antioxidant (F).

[Graft Copolymer (A)]
The graft copolymer (A) includes an acrylate monomer unit and a polyfunctional monomer unit, and does not include a conjugated diene monomer unit in the main chain, and has a volume average particle size of 0.3 to 0. A graft copolymer having a graft ratio of 40 to 80%, in which a vinyl monomer is grafted to a rubber polymer (a) of .6 μm. The graft copolymer (A) is a vinyl monomer, preferably an aromatic vinyl monomer in the presence of a specific rubbery polymer (a) having a volume average particle size of 0.3 to 0.6 m. It is obtained by graft polymerization of a monomer mixture containing a monomer, a vinyl cyanide-based monomer, and other monomers copolymerizable with these used as necessary.

  The rubbery polymer (a) contains an acrylate monomer unit and a polyfunctional monomer unit.

  Examples of the acrylate ester monomer constituting the acrylate ester monomer unit of the rubber polymer (a) include, for example, an ester moiety of methyl, ethyl, n-propyl, n-butyl, isobutyl, t-butyl. Alkyl acrylates having 1 to 12 carbon atoms such as 2-ethylhexyl and n-lauryl; haloesters such as chloroacrylate; acrylate arylesters such as benzyl acrylate or phenethyl acrylate; arylalkyl acrylates Etc., and preferably an alkyl acrylate ester having an alkyl group having 1 to 12 carbon atoms. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the polyfunctional monomer constituting the polyfunctional monomer unit include allyl methacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, 1,6-hexanediol diacrylic acid. Di (meth) acrylic esters of diols such as esters, 2-propenyl acrylate, divinylbenzene, triallyl isocyanurate, triallyl cyanurate, triallyl trimetate, etc. are used, preferably allyl methacrylate, triallyl isocyanurate, 1 , 3-butanediol dimethacrylate. These can be used individually by 1 type or in combination of 2 or more types.

Moreover, the rubber-like polymer (a) can use other monomers copolymerizable with an acrylic ester monomer or a polyfunctional monomer as necessary.
Examples of other monomers copolymerizable with acrylic acid ester monomers and polyfunctional monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene, acrylonitrile, And vinyl cyanide monomers such as methacrylonitrile, and methacrylic acid ester monomers such as methyl methacrylate and butyl methacrylate. These can be used individually by 1 type or in combination of 2 or more types.

  The content of the acrylate monomer units in 100% by mass of the rubber polymer (a) is preferably 75% by mass or more, and particularly preferably 85% by mass or more. When the content of the acrylate ester monomer unit is less than the above lower limit, any of weather resistance, impact resistance, rigidity, and surface appearance of the obtained graft copolymer (A) and the thermoplastic resin composition may be May decrease.

  The content of the polyfunctional monomer unit in the rubber polymer (a) is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the acrylate ester monomer unit. 0.5 parts by mass or less is particularly preferable, while 0.3 parts by mass or more is preferable, 0.4 parts by mass or more is more preferable, and 0.5 parts by mass or more is particularly preferable. When the polyfunctional monomer unit content exceeds the above upper limit, the impact resistance of the resulting graft copolymer (A) and the thermoplastic resin composition may be lowered. May decrease.

  In addition, when the rubbery polymer (a) contains other monomer units copolymerizable with an acrylate monomer or a polyfunctional monomer, the content thereof is the rubbery polymer (a). It is preferably 25% by mass or less, particularly preferably 15% by mass or less. When the content ratio of other monomer units exceeds the above upper limit, any of the weather resistance, impact resistance, rigidity, and surface appearance of the resulting thermoplastic resin composition may be lowered.

  Furthermore, as the rubber polymer (a), a rubber polymer containing an acrylate monomer unit and a polyfunctional monomer unit, and a monomer unit other than the acrylate monomer unit It is also possible to use a composite rubber with a rubbery polymer comprising In this case, as the rubbery polymer comprising monomer units other than the acrylate ester monomer unit, a rubbery polymer excellent in weather resistance not containing a conjugated diene monomer unit in the main chain should be used. Examples thereof include ethylene-propylene rubber (EPR), ethylene-propylene-diene rubber (EPDM), and polyorganosiloxane. There is no restriction | limiting in particular as a method of obtaining a composite rubber, A well-known method can be used.

  The rubbery polymer (a) used in the present invention is a rubbery polymer that does not contain a conjugated diene monomer unit in the main chain. That is, the rubbery polymer (a) according to the present invention has a conjugated diene monomer such as butadiene, isoprene, dimethylbutadiene, chloroprene and cyclopentadiene so as not to contain a conjugated diene monomer unit in the main chain. Manufactured as a rubbery polymer that does not contain body units. Since the rubber polymer (a) is a rubber polymer that does not contain a conjugated diene monomer unit in the main chain, the weather resistance of the thermoplastic resin composition of the present invention is good.

  The rubbery polymer (a) according to the present invention is preferably produced by emulsion polymerization of a mixture of monomers constituting the rubbery polymer (a) as described above. There is no restriction | limiting in particular as an emulsifier and a catalyst used by emulsion polymerization, Any conventionally well-known thing can be used conveniently.

The rubbery polymer (a) according to the present invention has a volume average particle size of 0.3 to 0.6 μm, preferably 0.35 to 0.55 μm. When the volume average particle diameter of the rubber polymer (a) is less than the above lower limit, the impact resistance of the obtained graft copolymer (A) and the thermoplastic resin composition may be deteriorated. Appearance may deteriorate.
The volume average particle diameter of the rubber polymer (a) and the rubber polymer (b) to be described later and the method for measuring the following particle diameter are as shown in the Examples section below.

  Further, in the rubber polymer (a), the content of the rubber polymer having a particle diameter of 0.2 μm or less is preferably 10% by mass or less with respect to 100% by mass of the rubber polymer (a). When the content of the rubbery polymer having a particle size of 0.2 μm or less is not more than the above upper limit, the impact resistance of the resulting graft copolymer (A) and the thermoplastic resin composition is improved.

  For adjusting the particle size of the rubbery polymer (a), a known method can be applied. For example, enlargement due to agglomeration during the polymerization of the rubbery polymer, A method of producing and enlarging a copolymer latex containing an acid group, an acid, a salt, or the like, and a method of enlarging by shearing stress by stirring can be used.

  The graft copolymer (A) of the present invention is obtained by graft polymerization of a vinyl monomer in the presence of such a rubbery polymer (a). The vinyl monomers used in this graft polymerization are vinyl cyanide monomers and aromatic vinyl monomers, and other monomers copolymerizable with these vinyl monomers used as necessary. A vinyl monomer mixture containing a monomer is preferable.

  Examples of the vinyl cyanide monomer include acrylonitrile and methacrylonitrile. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, vinyltoluene and the like. These can be used alone or in combination of two or more.

  Other monomers are monomers that are copolymerizable with vinyl cyanide monomers and aromatic vinyl monomers, excluding vinyl cyanide monomers and aromatic vinyl monomers. It is a monomer. Other monomers include methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, 2-ethylhexyl acrylate, methyl acrylate, ethyl acrylate, n-butyl acrylate, 2-hydroxyethyl methacrylate, methacryl Examples thereof include glycidyl acid, N, N-dimethylaminoethyl methacrylate, acrylamide, methacrylamide, maleic anhydride, and N-substituted maleimide. Also about another monomer, 1 type may be used independently and 2 or more types may be used together.

  As the vinyl monomer to be graft-polymerized to the rubber polymer (a), an aromatic vinyl monomer such as styrene and a vinyl cyanide monomer such as acrylonitrile are used because the molded article obtained has excellent impact resistance. A monomer mixture containing a monomer as an essential component is preferable, and a mixture of styrene and acrylonitrile is particularly preferable.

  The proportion of the vinyl cyanide monomer in the monomer mixture to be graft polymerized with the rubber polymer (a) is preferably 3 to 50% by mass, and 10 to 40% by mass in 100% by mass of the monomer mixture. Is more preferable. When the proportion of the vinyl cyanide monomer is not less than the above lower limit, the resulting molded article has good impact resistance. If the ratio of the vinyl cyanide monomer is not more than the above upper limit, discoloration due to heat of the obtained molded product can be suppressed. Further, the proportion of the aromatic vinyl monomer is preferably 20 to 97% by mass, more preferably 30 to 80% by mass in 100% by mass of the monomer mixture. When the ratio of the aromatic vinyl monomer is equal to or more than the above lower limit, the fluidity during molding is good. When the ratio of the aromatic vinyl monomer is equal to or lower than the above upper limit, the impact resistance of the obtained molded article is good.

  The proportion of the other monomer is preferably 50% by mass or less, more preferably 40% by mass or less, in 100% by mass of the monomer mixture. When the ratio of the other monomer is not more than the above upper limit, the balance between impact resistance and surface appearance is good.

  The graft copolymer (A) of the present invention is produced by emulsion polymerization of the above monomer mixture in the presence of the rubbery polymer (a) latex. There is no restriction | limiting in particular as an emulsifier and a catalyst used by emulsion polymerization, Any conventionally well-known thing can be used conveniently.

There is no particular limitation on the method of adding the monomer mixture in the emulsion polymerization, and methods such as batch addition, divided addition, sequential addition, etc. can be used, such as adding a part in a batch and adding the remainder in a sequential manner. In addition, these methods can be used in combination. Further, it is possible to use a method in which a monomer mixture is added and held for a while and then a polymerization initiator is added to start polymerization.
If necessary, an emulsifier may be added for the purpose of stabilizing the polymerization system, and a chain transfer agent for controlling the graft ratio and the molecular weight of the graft component may be used.

  After the polymerization, the grafted copolymer (A) can be obtained from the latex by coagulation by a known method, followed by washing, dehydration, and drying steps.

  The graft copolymer (A) has a rubbery polymer (a) content of 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, particularly 100 parts by weight of the graft copolymer (A). Preferably it is 30-70 mass parts. If the content of the rubbery polymer (a) is not less than the above lower limit, the resulting graft copolymer (A) and the thermoplastic resin composition have higher impact resistance, and the rubbery polymer (a) If content is below the said upper limit, the obtained graft copolymer (A) and a thermoplastic resin composition can maintain a favorable surface external appearance.

  The graft ratio of the graft copolymer (A) is 40 to 80%, preferably 50 to 75%. When the graft ratio of the graft copolymer (A) is within the above range, a good surface appearance can be maintained. Furthermore, the reduced viscosity of the acetone soluble part of the graft copolymer (A) is preferably 0.40 to 1.00 g / dL, particularly preferably 0.50 to 0.80 g / dL. The impact strength of the thermoplastic resin composition obtained when the reduced viscosity of the acetone-soluble part of the graft copolymer (A) is not less than the above lower limit is higher, and if it is not more than the above upper limit, good surface appearance and moldability are obtained. Can keep.

Here, the “graft ratio” is the ratio of the monomer component that is directly grafted to the rubber with respect to the rubber polymer.
The method for measuring the graft ratio of the graft copolymer (A) and the graft copolymer (B) described later is as described in the Examples section below.
Moreover, the reduced viscosity of the acetone soluble part of a graft copolymer (A) and the below-mentioned graft copolymer (B) is measured by the following method.
<Reduced viscosity of acetone-soluble matter of graft copolymer>
About the N, N-dimethylformamide solution prepared so that the concentration of the acetone soluble part of the graft copolymer is 0.2 dL / g, the reduced viscosity at 25 ° C. using an Ubbelohde viscometer: ηsp / C (unit : DL / g).

  In the present invention, only one type of graft copolymer (A) may be used. The monomer composition and physical properties of the rubbery polymer (a), vinyl graft-polymerized to the rubbery polymer (a) You may mix and use 2 or more types of things from which the kind and composition of a system monomer, the physical property of a graft copolymer (A), etc. differ.

[Graft Copolymer (B)]
The graft copolymer (B) contains an acrylate monomer unit and a polyfunctional monomer unit, and does not contain a conjugated diene monomer unit in the main chain, and has a volume average particle size of 0.07 to 0. A graft copolymer having a graft ratio of 40 to 80%, in which a vinyl monomer is grafted to a rubber polymer (b) of 2 μm. The graft copolymer (B) is a vinyl monomer, preferably an aromatic vinyl monomer in the presence of a specific rubbery polymer (b) having a volume average particle size of 0.07 to 0.2 μm. It is obtained by graft polymerization of a monomer mixture containing a monomer, a vinyl cyanide-based monomer, and other monomers copolymerizable with these used as necessary.

  The rubbery polymer (b) includes an acrylate monomer unit and a polyfunctional monomer unit.

  Examples of the acrylate monomer and polyfunctional monomer used in the rubber polymer (b) include the same monomers as those mentioned for the rubber polymer (a).

  The content of the acrylate monomer units in 100% by mass of the rubbery polymer (b) is preferably 75% by mass or more, more preferably 85% by mass or more, and particularly preferably 95% by mass or more. If the content of the acrylic ester monomer unit is less than the above lower limit, any of weather resistance, impact resistance, rigidity, and surface appearance of the obtained graft copolymer (B) and the thermoplastic resin composition may be May decrease.

  The content of the polyfunctional monomer unit in the rubber polymer (b) is preferably 3 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the acrylate monomer unit. Particulate mass or less is particularly preferred, while 0.05 mass part or more is preferred and 0.1 mass part or more is particularly preferred. When the polyfunctional monomer unit content exceeds the above upper limit, the impact resistance of the obtained graft copolymer (B) and the thermoplastic resin composition may be lowered. May decrease.

  Moreover, the rubber-like polymer (b) can use other monomers which can be copolymerized with an acrylate ester monomer or a polyfunctional monomer, if necessary. As other monomers, the same monomers as those mentioned for the rubber polymer (a) can be used.

  When the rubber polymer (b) contains other monomer units copolymerizable with an acrylate monomer unit or a polyfunctional monomer, the content thereof is in the rubber polymer (b). The ratio is preferably 25% by mass or less, particularly preferably 15% by mass or less. When the content ratio of other monomer units exceeds the above upper limit, any of the weather resistance, impact resistance, rigidity, and surface appearance of the resulting thermoplastic resin composition may be lowered.

  Furthermore, the rubbery polymer (b) includes a rubbery polymer containing an acrylate monomer unit and a multifunctional monomer unit, and a monomer unit other than the acrylate monomer unit. It is also possible to use a composite rubber with a rubbery polymer comprising As the rubber polymer composed of monomer units other than the acrylate monomer units, the same polymers as those mentioned for the rubber polymer (a) can be used. There is no restriction | limiting in particular as a method of obtaining composite rubber, A well-known method can be used.

  The rubbery polymer (b) used in the present invention is a rubbery polymer that does not contain a conjugated diene monomer unit in the main chain. That is, the rubbery polymer (b) according to the present invention contains a conjugated diene monomer such as butadiene, isoprene, dimethylbutadiene, chloroprene, or cyclopentadiene so that the main chain does not contain a conjugated diene monomer unit. It is produced as a rubbery polymer that does not contain any body. Since the rubber polymer (b) is a rubber polymer that does not contain a conjugated diene monomer unit in the main chain, the weather resistance of the thermoplastic resin composition of the present invention is good.

  The rubbery polymer (b) according to the present invention is preferably produced by emulsion polymerization of a mixture of monomers constituting the rubbery polymer (b) as described above. There is no restriction | limiting in particular as an emulsifier and a catalyst used by emulsion polymerization, Any conventionally well-known thing can be used conveniently.

  The rubbery polymer (b) according to the present invention has a volume average particle size of 0.07 to 0.2 μm, preferably 0.08 to 0.15 μm. If the volume average particle diameter of the rubber polymer (b) is less than the lower limit, the mechanical strength of the resulting thermoplastic resin composition may be lowered. On the other hand, when the volume average particle diameter exceeds the above upper limit, the surface appearance may deteriorate.

  For adjusting the particle size of the rubbery polymer (b), a known method can be applied. For example, enlargement due to agglomeration during the polymerization of the rubbery polymer, a small rubbery polymer is produced in advance. Further, a method of adding an acid group-containing copolymer latex, an acid, a salt, or the like to enlarge it, or a method of enlarging it by a shearing stress by stirring can be used.

  The graft copolymer (B) of the present invention is obtained by graft polymerization of a vinyl monomer in the presence of such a rubbery polymer (b). As this vinyl monomer, the same vinyl monomer that can be used for the graft copolymer (A) can be used. Is the same.

  The graft copolymer (B) of the present invention is produced by emulsion polymerization of the monomer mixture as described above in the presence of the rubbery polymer (b) latex. There is no restriction | limiting in particular as an emulsifier and a catalyst used by emulsion polymerization, Any conventionally well-known thing can be used conveniently.

There is no particular limitation on the method of adding the monomer mixture in the emulsion polymerization, and methods such as batch addition, divided addition, sequential addition, etc. can be used, such as adding a part in a batch and adding the remainder in a sequential manner. In addition, these methods can be used in combination. Further, it is possible to use a method in which a monomer mixture is added and held for a while and then a polymerization initiator is added to start polymerization.
If necessary, an emulsifier may be added for the purpose of stabilizing the polymerization system, and a chain transfer agent for controlling the graft ratio and the molecular weight of the graft component may be used.

  After polymerization, it is solidified by a known method, and a powder graft copolymer (B) can be obtained from the latex through washing, dehydration and drying steps.

  In the graft copolymer (B), the content of the rubber-like polymer (b) is 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, particularly 100 parts by weight of the graft copolymer (B). Preferably it is 30-70 mass parts. When the content of the rubbery polymer (b) is not less than the above lower limit, the resulting graft copolymer (B) and the thermoplastic resin composition have higher impact resistance, and the rubbery polymer (b) If content is below the said upper limit, the obtained graft copolymer (B) and thermoplastic resin composition can maintain a favorable surface external appearance.

  The graft ratio of the graft copolymer (B) is 40 to 80%, preferably 50 to 75%. When the graft ratio of the graft copolymer (B) is within the above range, a good surface appearance can be maintained. Furthermore, the reduced viscosity of the acetone-soluble component of the graft copolymer (B) is preferably 0.40 to 1.00 g / dL, particularly preferably 0.50 to 0.80 g / dL. The impact strength of the thermoplastic resin composition obtained when the reduced viscosity of the acetone-soluble part of the graft copolymer (B) is not less than the above lower limit becomes higher, and if it is not more than the above upper limit, good surface appearance and moldability. Can keep.

  In the present invention, only one type of graft copolymer (B) may be used, and the monomer composition and physical properties of the rubbery polymer (b), and the vinyl graft-polymerized to the rubbery polymer (b). Two or more different types and compositions of the monomer and the physical properties of the graft copolymer (B) may be mixed and used.

[Vinyl copolymer (C)]
The vinyl copolymer (C) is a homopolymer of an aromatic vinyl monomer, or at least a vinyl cyanide monomer and an aromatic vinyl monomer, and other used as necessary. It is a copolymer obtained by copolymerizing the above monomers.

Specific examples of vinyl cyanide monomers, aromatic vinyl monomers and other monomers include vinyl cyanide monomers and aromatic vinyl monomers used in the production of graft polymer (A). Monomers and those listed as other monomers are applicable. The vinyl copolymer (C) may contain an N-substituted maleimide monomer unit for the purpose of improving heat resistance. Specific examples of the N-substituted maleimide monomer include N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like.
As the vinyl copolymer (C), a homopolymer of an aromatic vinyl monomer, or a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer (C-1), Or a copolymer (C-2) of an N-substituted maleimide monomer, an aromatic vinyl monomer and a vinyl cyanide monomer, or a copolymer of these copolymers (C-1) The combination (C-2) is preferred.

An aromatic vinyl monomer unit contained in a homopolymer of an aromatic vinyl monomer or a copolymer (C-1) of a vinyl cyanide monomer and an aromatic vinyl monomer The ratio is preferably 20 to 100% by mass, more preferably 30 to 90% by mass, and more preferably 50 to 80% as the content in 100% by mass of the monomer mixture used when producing the copolymer (C-1). Mass% is particularly preferred. When the ratio of the aromatic vinyl monomer is within the above range, the moldability of the resulting thermoplastic resin composition will be good.
Moreover, the ratio of the vinyl cyanide-type monomer unit contained in a copolymer (C-1) is 100 mass% of monomer mixtures used when manufacturing a vinyl-type copolymer (C-1). As content, 0-80 mass% is preferable, 10-70 mass% is further more preferable, 20-50 mass% is especially preferable. When the ratio of the vinyl cyanide monomer is within the above range, the resulting molded article has good chemical resistance.

  The weight average molecular weight of the copolymer (C-1) is not particularly limited, but the weight average molecular weight of the copolymer (C) is in the range of 40,000 to 200,000, particularly from the balance of moldability / impact resistance. It is preferably in the range of 50,000 to 180,000.

  Here, the mass average molecular weights of the copolymer (C-1) and the copolymer (C-2) described later were measured using GPC (gel permeation chromatography) and calculated by a standard polystyrene conversion method. And

The proportion of the N-substituted maleimide monomer unit contained in the copolymer (C-2) of the N-substituted maleimide monomer, aromatic vinyl monomer and vinyl cyanide monomer is as follows: The content in 100% by mass of the monomer mixture used when producing the copolymer (C-2) is preferably 5 to 65% by mass, and more preferably 10 to 60% by mass. When the content of the N-substituted maleimide monomer unit is within the above range, a thermoplastic resin composition having a good balance between impact resistance and molding processability and excellent heat resistance can be obtained.
Moreover, the ratio of the aromatic vinyl-type monomer unit contained in a copolymer (C-2) is content in 100 mass% of monomer mixtures used when manufacturing a copolymer (C-2). Is preferably from 5 to 90 mass%, more preferably from 10 to 80 mass%, particularly preferably from 15 to 65 mass%. When the ratio of the aromatic vinyl monomer is within the above range, the moldability of the resulting thermoplastic resin composition will be good.
The proportion of the vinyl cyanide monomer units contained in the copolymer (C-2) is the content in 100% by mass of the monomer mixture used when the copolymer (C-2) is produced. Is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and particularly preferably 10 to 50% by mass. When the ratio of the unsaturated nitrile monomer is within the above range, the resulting molded article has good chemical resistance.

  In addition, when the copolymers (C-1) and (C-2) contain other monomer units copolymerizable with the aromatic vinyl monomer and the vinyl cyanide monomer, the content thereof The amount is a content in 100% by mass of the monomer mixture used for producing the copolymers (C-1) and (C-2), and is preferably 40% by mass or less, particularly preferably 0 to 30% by mass.

  The mass average molecular weight of the copolymer (C-2) is not particularly limited, but the weight average molecular weight of the copolymer (C-2) is in the range of 40,000 to 200,000 from the balance of moldability / impact resistance. In particular, the range of 50,000 to 180,000 is preferable.

Copolymer (C-1) and copolymer (C-2) are not particularly limited in their production methods, and known emulsion polymerization methods, suspension polymerization methods, bulk polymerization methods, and solution polymerization methods. Etc. can be obtained.
As the vinyl copolymer (C), the copolymers (C-1) and (C-2), only one kind may be used, and two or more kinds having different vinyl monomer compositions and physical properties may be used. You may mix and use.

[Thermoplastic resin (G)]
The thermoplastic resin (G) according to the present invention is composed of the above-described graft copolymer (A), graft copolymer (B), and vinyl copolymer (C).

  The thermoplastic resin (G) according to the present invention is a rubbery polymer derived from the graft copolymer (A) when the total amount of the rubbery polymer contained in the thermoplastic resin (G) is 100% by mass, that is, The rubbery polymer (a) is contained in an amount of 20 to 70% by mass, and the rubbery polymer derived from the graft copolymer (B), that is, the rubbery polymer (b) is contained in an amount of 30 to 80% by weight. Preferably, the content ratio is 30 to 60% by mass of the rubbery polymer (a) derived from the graft copolymer (A), and 40 to 40% of the rubbery polymer (b) derived from the graft copolymer (B). 70% by weight. When the content of the rubbery polymer (a) is more than the above range and the content of the rubbery polymer (b) is less than the above range, the resulting molded article has impact resistance, surface appearance, and weather resistance. On the contrary, when the content of the rubbery polymer (a) is less than the above range and the content of the rubbery polymer (b) is more than the above range, the resistance of the resulting molded product is similarly reduced. Impact resistance, surface appearance, and weather resistance are reduced.

  Moreover, when the thermoplastic resin (G) is 100% by mass, the ratio of the rubbery polymer contained in the thermoplastic resin (G) is 10 to 40% by mass, particularly 10 to 30% by mass. Is preferable from the viewpoint of weather resistance, impact resistance, and heat resistance of the resulting thermoplastic resin composition.

  When the thermoplastic resin (G), which is the total amount of the graft copolymer (A), the graft copolymer (B), and the vinyl copolymer (C), is 100 parts by mass, the graft copolymer (A ) And the graft copolymer (B) in a content of 20 to 60 parts by mass, and the vinyl copolymer (C) in a content of 40 to 80 parts by mass. From the viewpoint of impact resistance, rigidity, heat resistance, surface appearance and weather resistance, among the vinyl-based vinyl copolymers (C), the copolymer (C-1) and the copolymer (C-2) The ratio of copolymer (C-1): copolymer (C-2) = 10 to 100 parts by mass: 0 to 90 parts by mass is the moldability, and the heat resistant viewpoint of the resulting molded article To preferred.

  Therefore, in the present invention, the content of each component of the graft copolymer (A), the graft copolymer (B), and the vinyl copolymer (C) and the content of the rubbery polymer are within the above preferred ranges. It mixes so that it may become and uses as a thermoplastic resin (G).

[Light stabilizer (D)]
In the thermoplastic resin composition of the present invention, as a light stabilizer (D), a hindered amine light stabilizer having a molecular weight of 400 to 2,000 is added in an amount of 0.1 to 100 parts by mass of the thermoplastic resin (G). -1.5 mass parts included. If the content of the light stabilizer (D) is not less than the above lower limit, the weather resistance of the resulting thermoplastic resin composition will be good, and if it is not more than the above upper limit, bleed out when used outdoors for a long time. Appearance defects can be suppressed. The preferable content of the light stabilizer (D) is 0.3 to 1.0 part by mass.
In addition, if it is a hindered amine light stabilizer of the molecular weight range of molecular weight 400-2,000 used as a light stabilizer (D) in this invention, the weather resistance of the molded object obtained will become favorable.

  Examples of the light stabilizer (D) include bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (molecular weight 481), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) ) -1,2,3,4-butanetetracarboxylate (molecular weight 791), tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate (Molecular weight 847), 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl) ( Molecular weight 685), bis (1,2,2,6,6-pentamethyl-4-piperidyl) = decanedioate (molecular weight 509), N, N′-bisformyl-N, N′-bis- (2,2, 6, 6 Tetramethyl-4-piperidinyl) -hexamethylenediamine (molecular weight 450), 1,2,3,4-butanetetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β Condensate with ', β'-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] undecane) diethanol (molecular weight 1900), 1,2,3,4-butane Tetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl-3,9- (2,4,8,10-tetraoxaspiro [5.5] Undecane) Condensates with diethanol (molecular weight: 2,000), and the like, but are not limited thereto. A light stabilizer (D) can be used individually by 1 type or in mixture of 2 or more types.

[Ultraviolet absorber (E)]
In the thermoplastic resin composition of the present invention, as the ultraviolet absorber (E), a benzophenol ultraviolet absorber and / or a triazine ultraviolet absorber having a molecular weight of 300 to 800 is added to 100 parts by mass of the thermoplastic resin (G). On the other hand, 0.1 to 1.5 parts by mass are included. If the content of the ultraviolet absorber (E) is not less than the above lower limit, the weather resistance of the resulting thermoplastic resin composition will be good, and if it is not more than the above upper limit, bleed out when used outdoors for a long period of time. Appearance defects can be suppressed. The preferable content of the ultraviolet absorber (E) is 0.3 to 1.0 part by mass.
In the present invention, if the ultraviolet absorber (E) having a molecular weight of 300 to 800 used as the ultraviolet absorber (E) is used, the resulting molded article has good weather resistance, and the benzophenol-based ultraviolet absorber. In the case of a triazine ultraviolet absorber, since it has high stability against heat and light, discoloration during processing can be suppressed.

  Examples of the benzophenol ultraviolet absorber (E) include 2 (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole (molecular weight 315), 2- (2H-benzotriazole- 2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (molecular weight 323), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1) -Phenylethyl) phenol (molecular weight 447), 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] (molecular weight 659) Examples of the triazine-based ultraviolet absorber (E) include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2-ethylhexene). Sanoyloxy) ethoxy] phenol (molecular weight 512), 2,4,6-tris (2-hydroxy-4hexyloxy-3-methylphenyl) -1,3,5-triazine (molecular weight 700), 2- (4,6- Examples include, but are not limited to, diphenyl-1,3,5-triazin-2-yl) -5-((hexyl) oxy) -phenol (molecular weight 426). An ultraviolet absorber (E) can be used individually by 1 type or in mixture of 2 or more types.

[Antioxidant (F)]
In the thermoplastic resin composition of the present invention, as the antioxidant (F), a hindered phenol antioxidant having a molecular weight of 500 to 800 is added in an amount of 0.1 to 100 parts by mass of the thermoplastic resin (G). Contains 3 parts by mass. If the content of the antioxidant (F) is not less than the above lower limit, the weather resistance of the resulting thermoplastic resin composition will be good, and if it is not more than the above upper limit, bleeding out when used outdoors for a long period of time. Appearance defects due to occurrence can be suppressed. The preferable content of the ultraviolet absorber (E) is 0.2 to 3 parts by mass.
In the present invention, if the antioxidant (F) has a molecular weight range of 500 to 800 and is used as the antioxidant (F), discoloration due to weathering deterioration of the resulting molded article is reduced, and a hindered phenol type is used. If it is antioxidant, discoloration of a molded object by generation | occurrence | production of pinking can be suppressed.

  Examples of the antioxidant (F) include tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (molecular weight 784), n-octadecyl-β- (3,5-di -Tert-butyl-4-hydroxyphenyl) propionate (molecular weight 531), 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] (molecular weight 639), 3 , 6-dioxaoctane-1,8-diyl = bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate] (molecular weight 587), but not limited thereto. Antioxidant (F) can be used individually by 1 type or in mixture of 2 or more types.

<Other ingredients>
In addition to the thermoplastic resin (G), the light stabilizer (D), the ultraviolet absorber (E), and the antioxidant (F), the thermoplastic resin composition of the present invention includes a phosphorus-based antioxidant, carbon black, and Any one or more oxides of Group 2 element of the periodic table may be included. The weather resistance is further improved by adding a phosphorus-based antioxidant or carbon black. In addition, by adding Group 2 group element oxides, the gas generated during molding is reduced, reducing molding defects such as the occurrence of silver streaks and gas adhesion to the molded product, and the maintenance frequency of the mold. The effect of improving productivity by reduction can be expected.

  As an example of phosphorus antioxidant, the thing of the range of molecular weight 500-1500 is preferable, for example, 3,9-bis (octadecyloxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [ 5.5] Undecane (molecular weight 733), 3,9-bis (2,6-di-tert-butyl-4-methylphenoxy) -2,4,8,10-tetraoxa-3,9-diphosphaspiro [5. 5] undecane (molecular weight 633), 2,2′-methylenebis (4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite (molecular weight 583), tris (2,4-di-tert-butylphenyl) phos Fight (molecular weight 647) and the like are exemplified, but not limited thereto. A phosphorus antioxidant can be used individually by 1 type or in mixture of 2 or more types.

  Although there is no restriction | limiting in particular as a kind of carbon black, It is preferable to use carbon black whose average primary particle diameter is less than 100 nm. When the average primary particle diameter of carbon black exceeds 100 nm, the appearance and weather resistance of the resulting molded product tend to be reduced.

  When adding phosphorus antioxidant and carbon black, these addition amounts are preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin (G). When the addition amount is less than the above lower limit, the effect of addition cannot be sufficiently obtained, and when it is more than the above upper limit, impact resistance, heat resistance, tensile elongation characteristics and the like are lowered.

  Examples of oxides of Group 2 elements of the periodic table include beryllium oxide, magnesium oxide, calcium oxide, strontium oxide, and barium oxide. These may be used alone or in a mixture of two or more. Of these, magnesium oxide and calcium oxide are preferable from the viewpoint of safety and economy, and these can also be obtained from magnesium hydroxide, calcium hydroxide, magnesium carbonate, and the like. When adding an oxide of a Group 2 element of the periodic table, the amount added is 0.3 parts by mass or less, particularly 0.01 to 0.2 parts by mass with respect to 100 parts by mass of the thermoplastic resin (G). It is preferable. When the addition amount of the oxide of the Group 2 element of the periodic table exceeds 0.3 parts by mass, flow marks, silver streaks, defects and the like are generated in the obtained molded body, and the surface appearance of the molded body is impaired.

  The thermoplastic resin composition of the present invention may contain other thermoplastic resins other than the thermoplastic resin (G) and additives other than those described above, as long as the effects of the present invention are not impaired.

  Examples of other thermoplastic resins include rubber-reinforced styrene resins such as ASA resin, AES resin, and SAS resin, as well as polystyrene resin, styrene-maleic anhydride copolymer, styrene-maleic anhydride-N-phenyl. Examples include maleimide copolymers, polycarbonate resins, polyamide resins, methacrylic resins, polyvinyl chloride resins, polybutylene terephthalate resins, polyethylene terephthalate resins, and polyphenylene ether resins. These other thermoplastic resins may be used alone or in a blend of two or more. Moreover, you may mix | blend the said resin modified | denatured with the compatibilizing agent, the functional group, etc. The content of other thermoplastic resins in the thermoplastic resin composition of the present invention is the total of the thermoplastic resin (G), light stabilizer (D), ultraviolet absorber (E), and antioxidant (F). When it is 100 mass parts, 0-50 mass parts is preferable.

  Additives include other additives commonly used during resin composition production (mixing) and molding, such as lubricants, stabilizers, pigments, dyes, fillers, heat-resistant agents, mold release agents, plasticizers, antistatic agents An agent, a flame retardant, etc. can be mix | blended. These additives may be used alone or in combination of two or more.

[Method for producing thermoplastic resin composition]
The thermoplastic resin composition of the present invention comprises a graft copolymer (A), a graft copolymer (B), a vinyl copolymer (C), a light stabilizer (D), an ultraviolet absorber (E), and It can be manufactured by mixing the antioxidant (F) and other additives blended as necessary by a known method using a known device. For example, there is a melt mixing method as a general method, and examples of an apparatus used in this method include an extruder, a Banbury mixer, a roller, and a kneader. Either a batch type or a continuous type may be employed for mixing. Moreover, there is no restriction | limiting in particular in the mixing order of each component, etc., All the components should just be mixed uniformly.

[Molded body]
The molded body of the present invention is formed by molding the above-described thermoplastic resin composition of the present invention. Examples of the molding method include an injection molding method, an injection compression molding method, an extrusion molding method, a blow molding method, a vacuum molding method, a pressure forming method, a press molding method, a calendar molding method, and an inflation molding method.

  The molded article of the present invention formed by molding the thermoplastic resin composition of the present invention is excellent in weather resistance, impact resistance, and surface appearance, and is useful for various applications. In particular, a vehicle exterior that requires weather resistance is required. It is suitable as a component, particularly as a vehicle exterior component used without painting, and its excellent impact resistance makes it possible to reduce the thickness and weight of the vehicle exterior component.

As vehicle exterior parts to which the vehicle exterior parts of the present invention are applied, the weather resistance requirement levels of the side molding, mud guard, assist step, bumper, etc. are slightly higher than the lowest weather resistance requirement levels such as lamp housings. Parts installed below the belt line, such as cowl vents, pillars, radiator grills, door mirror housings, and other parts that require higher weather resistance and are mounted on inclined surfaces above the belt line, and spoilers The parts mounted on the horizontal surface above the belt line having the highest required level of weather resistance are listed.
However, it goes without saying that the molded body of the present invention can be applied not only to vehicle exterior parts but also to vehicle interior parts.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to synthesis examples, examples, and comparative examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the following examples, “parts” and “%” are based on mass unless otherwise specified.

[Measurement and evaluation]
In the following, the physical properties of rubbery polymers, graft copolymers and copolymers were measured and evaluated by the following methods.

<Particle size and volume average particle size of rubbery polymer>
It calculated | required from the dynamic light-scattering method using Nikkiso Co., Ltd. Nanotrac UPA-EX150.

<Graft ratio>
The graft ratio of the graft copolymer was calculated by the following method.
1 g of the graft copolymer is added to 80 mL of acetone, heated to reflux at 65 to 70 ° C. for 3 hours, and the resulting suspension acetone solution is centrifuged at 14,000 rpm for 30 minutes in a centrifuge to precipitate. A component (acetone insoluble component) and an acetone solution (acetone soluble component) were collected. The precipitation component (acetone insoluble component) was dried and its mass (Y (g)) was measured, and the graft ratio was calculated by the following formula (1). In formula (1), Y is the mass (g) of the acetone-insoluble component of the graft copolymer, X is the total mass (g) of the graft copolymer used to determine Y, and the rubber fraction is the graft copolymer. It is the content ratio in terms of solid content of the rubber-like polymer of the polymer.
Graft rate (mass%) = {(Y-X × rubber fraction) / X × rubber fraction} × 100
... (1)

<Mass average molecular weight of vinyl copolymer (Mw)>
A solution obtained by dissolving a vinyl-based vinyl copolymer in tetrahydrofuran was measured using GPC (gel permeation chromatography) (manufactured by Tosoh Corp.) and calculated by a standard polystyrene conversion method. .

[Synthesis Example 1: Production of acid group-containing copolymer latex (K)]
200 parts of deionized water (hereinafter simply referred to as water), 2 parts of potassium oleate, 4 parts of sodium dioctylsulfosuccinate, 0.003 part of ferrous sulfate heptahydrate, disodium ethylenediaminetetraacetate 009 parts and 0.3 part of sodium formaldehyde sulfoxylate were charged under a nitrogen flow, and the temperature was raised to 60 ° C. When the temperature reached 60 ° C., a mixture comprising 82 parts of n-butyl acrylate, 18 parts of methacrylic acid and 0.5 part of cumene hydroperoxide was continuously added dropwise over 120 minutes. After completion of the dropwise addition, the mixture was aged for 2 hours at 60 ° C., and an acid group-containing copolymer latex (K) having a solid content of 33% and an acid group-containing copolymer having a volume average particle diameter of 0.150 μm was obtained. Obtained.

[Synthesis Example 2: Production of Graft Copolymer (A-1)]
In a reactor, 310 parts of water, dipotassium alkenyl succinate (manufactured by Kao Corporation, Latemul ASK), 80 parts of n-butyl acrylate, 0.48 parts of allyl methacrylate, 0.42 parts of triallyl isocyanurate, t-butylhydro After 0.2 parts of peroxide was charged with stirring and the inside of the reactor was purged with nitrogen, the contents were heated. At an internal temperature of 55 ° C., an aqueous solution consisting of 0.3 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate heptahydrate, 0.0003 part of disodium ethylenediaminetetraacetate and 10 parts of water was added to polymerize. Was started. After the polymerization exotherm was confirmed, the jacket temperature was set to 75 ° C., and the polymerization was continued until the polymerization exotherm was not confirmed, and was further maintained for 1 hour. The resulting rubbery polymer had a volume average particle size of 0.100 μm. 1 part of 5% sodium pyrophosphate aqueous solution was added thereto as a solid content (the pH of the mixed solution was 9.1), and the jacket temperature was controlled so that the internal temperature became 70 ° C.
To this, 3 parts of acid group-containing copolymer latex (K) was added as a solid content at an internal temperature of 70 ° C., and the mixture was stirred for 30 minutes while maintaining the internal temperature of 70 ° C. to enlarge. The volume average particle size after enlargement was 0.420 μm.
Further, an aqueous solution comprising 0.03 part of sodium formaldehyde sulfoxylate, 0.002 part of ferrous sulfate heptahydrate, 0.006 part of disodium ethylenediaminetetraacetate and 80 parts of water was added at an internal temperature of 70 ° C. Then, a mixed solution consisting of 20 parts of n-butyl acrylate, 0.12 part of allyl methacrylate, 0.1 part of triallyl isocyanurate, and 0.02 part of t-butyl hydroperoxide was added dropwise over 1 hour. After completion of the dropwise addition, the state at a temperature of 70 ° C. was maintained for 1 hour and then cooled, and a latex of the rubbery polymer (a-1) having a solid content of 18% and a volume average particle diameter of the rubbery polymer of 0.450 μm was obtained. Obtained.

230 parts of water (including water in rubbery polymer latex), 50 parts of latex of rubbery polymer (a-1) (as solids), dipotassium alkenyl succinate (La Kamul ASK, manufactured by Kao Corporation) 0.5 parts and 0.3 parts of sodium formaldehyde sulfoxylate were charged and the inside of the reactor was sufficiently purged with nitrogen, and then the internal temperature was raised to 70 ° C. with stirring. Subsequently, it heated up to 80 degreeC, adding the liquid mixture which consists of 15 parts of acrylonitrile, 35 parts of styrene, and 0.5 part of t-butyl hydroperoxide over 100 minutes. After completion of the dropping, the state at a temperature of 80 ° C. was maintained for 30 minutes and then cooled to obtain a graft copolymer (A-1) latex. Next, 100 parts of a 1.5% sulfuric acid aqueous solution is heated to 80 ° C., and while stirring the aqueous solution, 100 parts of the graft copolymer (A-1) latex is gradually added dropwise to the aqueous solution. A-1) was solidified, further heated to 95 ° C. and held for 10 minutes. Next, the solidified product was dehydrated, washed and dried to obtain a powdered graft copolymer (A-1).
The content of the acrylate monomer unit in 100% by mass of the rubber polymer (a-1) is 98.7% by mass, and the polyfunctional monomer unit with respect to 100 parts by mass of the acrylate ester monomer unit. The content of the rubber polymer (a-1) in 100 parts by weight of the graft copolymer (A-1) is 48.5 parts by weight, the rubbery polymer (a- The composition of the aromatic vinyl monomer grafted to 1) and the vinyl cyanide monomer are 70% by mass for the aromatic vinyl monomer and 30% by mass for the vinyl cyanide monomer, respectively. there were. The graft ratio of the graft copolymer (A-1) was 58%.

[Synthesis Example 3: Production of Graft Copolymer (A-2)]
In the same manner as in Synthesis Example 2, except that the 5% sodium pyrophosphate aqueous solution added at the time of enlargement was changed to 1 part as a solid content and the acid group-containing copolymer latex (K) as 10 parts as a solid content, A polymer (A-2) was obtained. The volume average particle diameter of the rubber polymer (a-2) in the graft copolymer (A-2) is 0.250 μm, and the acrylate monomer in 100% by mass of the rubber polymer (a-2) The content of the unit is 98.7% by mass, the content of the polyfunctional monomer unit with respect to 100 parts by mass of the acrylate monomer unit is 1.12 parts by mass, and the graft copolymer (A-2) 100. The content of the rubber polymer (a-2) in parts by mass is 45.3 parts by mass, and the aromatic vinyl monomer grafted on the rubber polymer (a-2) and the vinyl cyanide monomer The composition of the monomer was 70% by mass for the aromatic vinyl monomer and 30% by mass for the vinyl cyanide monomer. The graft ratio of the graft copolymer (A-2) was 60%.

[Synthesis Example 4: Production of Graft Copolymer (A-3)]
A graft copolymer (A-3) was obtained in the same manner as in Synthesis Example 2 except that the 5% sodium pyrophosphate aqueous solution added during enlargement was changed to 3 parts as a solid content. The volume average particle diameter of the rubber polymer (a-3) in the graft copolymer (A-3) is 0.650 μm, and the acrylate monomer in 100% by mass of the rubber polymer (a-3) The content of the unit is 98.7% by mass, the content of the polyfunctional monomer unit with respect to 100 parts by mass of the acrylate monomer unit is 1.12 parts by mass, and the graft copolymer (A-3) 100. The content of the rubber polymer (a-3) in parts by mass is 48.5 parts by mass, the aromatic vinyl monomer and vinyl cyanide monomer grafted on the rubber polymer (a-3) The composition of the monomer was 70% by mass for the aromatic vinyl monomer and 30% by mass for the vinyl cyanide monomer. The graft ratio of the graft copolymer (A-3) was 43%.

[Synthesis Example 5: Production of Graft Copolymer (A-4)]
In a reactor, 310 parts of water, dipotassium alkenyl succinate (manufactured by Kao Corporation, Latemul ASK), 80 parts of n-butyl acrylate, 0.12 part of allyl methacrylate, 0.1 part of triallyl isocyanurate, t-butylhydro After 0.2 parts of peroxide was charged with stirring and the inside of the reactor was purged with nitrogen, the contents were heated. At an internal temperature of 55 ° C., an aqueous solution consisting of 0.3 part of sodium formaldehyde sulfoxylate, 0.0001 part of ferrous sulfate heptahydrate, 0.0003 part of disodium ethylenediaminetetraacetate and 10 parts of water was added to polymerize. Was started. After the polymerization exotherm was confirmed, the jacket temperature was set to 75 ° C., and the polymerization was continued until the polymerization exotherm was not confirmed, and was further maintained for 1 hour. The resulting rubbery polymer had a volume average particle size of 0.100 μm. 1 part of 5% sodium pyrophosphate aqueous solution was added thereto as a solid content (the pH of the mixed solution was 9.1), and the jacket temperature was controlled so that the internal temperature became 70 ° C.
To this, 3 parts of acid group-containing copolymer latex (K) was added as a solid content at an internal temperature of 70 ° C., and the mixture was stirred for 30 minutes while maintaining the internal temperature of 70 ° C. to enlarge. The volume average particle size after enlargement was 0.420 μm.
Further, an aqueous solution comprising 0.03 part of sodium formaldehyde sulfoxylate, 0.002 part of ferrous sulfate heptahydrate, 0.006 part of disodium ethylenediaminetetraacetate and 80 parts of water was added at an internal temperature of 70 ° C. Then, a mixed solution composed of 20 parts of n-butyl acrylate, 0.03 part of allyl methacrylate, 0.025 part of triallyl isocyanurate, and 0.02 part of t-butyl hydroperoxide was added dropwise over 1 hour. After completion of the dropping, the temperature is maintained at 70 ° C. for 1 hour, followed by cooling to obtain a rubbery polymer latex (a-4) having a solid content of 18% and a rubbery polymer volume average particle size of 0.450 μm. It was. Thereafter, a graft copolymer (A-4) was obtained in the same manner as in Synthesis Example 2. The content of the acrylate monomer unit in 100% by mass of the rubber polymer (a-4) is 99.5% by mass, and the polyfunctional monomer unit with respect to 100 parts by mass of the acrylate monomer unit. The content of the rubber polymer (a-4) in 100 parts by mass of the graft copolymer (A-4) is 0.275 parts by mass, and the content of the rubbery polymer (a-4) is 48.3 parts by mass. The composition of the aromatic vinyl monomer grafted to 4) and the vinyl cyanide monomer are 70% by mass for the aromatic vinyl monomer and 30% by mass for the vinyl cyanide monomer, respectively. there were. The graft ratio of the graft copolymer (A-4) was 30%.

[Synthesis Example 6: Production of Graft Copolymer (A-5)]
In a stainless steel autoclave reactor, 145 parts of water, 1.0 part of potassium rosinate, 1.0 part of potassium oleate, 0.06 part of sodium hydroxide, 0.4 part of sodium sulfate, t-dodecyl mercaptan. After charging 3 parts and purging with nitrogen, 125 parts of 1,3-butadiene was charged and the temperature was raised to 60 ° C. Subsequently, polymerization was started by press-fitting an aqueous solution in which 0.3 part of potassium persulfate was dissolved in 5 parts of water. During the polymerization, the polymerization temperature was adjusted to 65 ° C., and unreacted 1,3-butadiene was recovered when the internal pressure reached 4.5 kg / cm ² (gauge pressure) after 12 hours. Thereafter, the internal temperature was kept at 80 ° C. for 1 hour to obtain a small particle diene rubber (a-5-1) latex having a volume average particle size of 0.080 μm and a solid content of 41%.

The acid group-containing copolymer latex (K) is added to 100 parts in terms of solid content of the small particle diene rubber (a-5-1) latex while stirring and 1.2 parts by mass in terms of solid content, and further 30 The mixture was stirred for a minute to obtain an enlarged diene rubber (a-5-2) latex having a volume average particle size of 0.350 μm.
50 parts in terms of solid content of the enlarged diene rubber (a-5-2) latex were charged into the reactor, 140 parts of water was added, and the temperature was raised to 70 ° C. Subsequently, it heated up to 80 degreeC, adding the liquid mixture which consists of 15 parts of acrylonitrile, 35 parts of styrene, and 0.5 part of t-butyl hydroperoxide over 100 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 30 minutes and then cooled to obtain a graft copolymer (A-5) latex. Thereafter, the same operation as in Synthesis Example 2 was performed to obtain a graft copolymer (A-5). The content of the acrylate monomer unit in 100% by mass of the rubber polymer (a-5) is 0% by mass, and the content of the polyfunctional monomer unit with respect to 100 parts by mass of the acrylate monomer unit. The amount is 0 part by mass, the content of the rubber polymer (a-5) in 100 parts by mass of the graft copolymer (A-5) is 49.4 parts by mass, and the graft to the rubber polymer (a-5) The composition of the aromatic vinyl monomer and the vinyl cyanide monomer was 70% by mass for the aromatic vinyl monomer and 30% by mass for the vinyl cyanide monomer, respectively. The graft ratio of the graft copolymer (A-5) was 58%.

[Synthesis Example 7: Production of Graft Copolymer (A-6)]
In a stainless steel autoclave reactor, 145 parts of water, 1.0 part of potassium rosinate, 1.0 part of potassium oleate, 0.06 part of sodium hydroxide, 0.4 part of sodium sulfate, t-dodecyl mercaptan. After charging 3 parts and purging with nitrogen, 125 parts of 1,3-butadiene was charged and the temperature was raised to 60 ° C. Subsequently, polymerization was started by press-fitting an aqueous solution in which 0.3 part of potassium persulfate was dissolved in 5 parts of water. During the polymerization, the polymerization temperature was adjusted to 65 ° C., and unreacted 1,3-butadiene was recovered when the internal pressure reached 4.5 kg / cm ² (gauge pressure) after 12 hours. Thereafter, the internal temperature was maintained at 80 ° C. for 1 hour to obtain a small particle diene rubber (a-6-1) latex having a mass average particle diameter of 0.080 μm and a solid content of 41%.

The acid group-containing copolymer latex (K) is added to 100 parts in terms of solid content of the small particle diene rubber (a-6-1) latex while stirring with 1.5 parts in terms of solid content, and further for 30 minutes. By stirring, an enlarged diene rubber (a-6-2) latex having a volume average particle size of 0.300 μm was obtained.
20 parts by mass in terms of solid content of the enlarged diene rubber (a-6-2) was charged into the reactor, and then 1.0 part of potassium rosinate and 150 parts of water were added to perform nitrogen substitution. The temperature was raised to 70 ° C. To this was added an aqueous solution in which 0.12 part of potassium persulfate was dissolved in 10 parts of water. Subsequently, 80 parts of n-butyl acrylate, 0.33 parts of allyl methacrylate, ethylene glycol dimethacrylate, which had been previously substituted with nitrogen, were added. A monomer mixture consisting of .17 parts was continuously added dropwise over 2 hours. After completion of the dropping, the internal temperature is raised to 80 ° C. and maintained for 1 hour, and the composite rubber weight having a volume average particle diameter of 0.320 μm consisting of an enlarged diene rubber and a cross-linked acrylic ester copolymer Combined (a-6-3) latex was obtained.

  50 parts in terms of solid content of the composite rubber polymer (a-6-3) latex was charged into a reactor, and 140 parts of water was added and the temperature was raised to 70 ° C. Subsequently, it heated up to 80 degreeC, adding the liquid mixture which consists of 15 parts of acrylonitrile, 35 parts of styrene, and 0.5 part of t-butyl hydroperoxide over 100 minutes. After completion of dropping, the temperature was maintained at 80 ° C. for 30 minutes and then cooled to obtain a graft copolymer (A-6) latex. Thereafter, the same operation as in Synthesis Example 2 was performed to obtain a graft copolymer (A-6). The content of the acrylate monomer unit in 100% by mass of the rubbery polymer (a-6) is 79.8% by mass, and the polyfunctional monomer unit with respect to 100 parts by mass of the acrylate ester monomer unit. The content of rubber polymer (a-6) in 100 parts by mass of graft copolymer (A-6) is 49.8 parts by mass, and the content of rubber polymer (a-) is 0.625 parts by mass. The composition of the aromatic vinyl monomer and the vinyl cyanide monomer grafted on 6) is 70% by mass for the aromatic vinyl monomer and 30% by mass for the vinyl cyanide monomer, respectively. there were. The graft ratio of the graft copolymer (A-6) was 55%.

[Synthesis Example 8: Production of Graft Copolymer (B-1)]
In a reactor, 240 parts of water, 0.7 parts of dipotassium alkenyl succinate (manufactured by Kao Corporation, Latemul ASK), 50 parts of n-butyl acrylate, 0.15 part of allyl methacrylate, 1,3-butanediol dimethacrylate 0.05 part and 0.1 part of t-butyl hydroperoxide were charged with stirring, and after the reactor was purged with nitrogen, the contents were heated. At an internal temperature of 55 ° C, an aqueous solution consisting of 0.2 parts of sodium formaldehyde sulfoxylate, 0.00015 parts of ferrous sulfate heptahydrate, 0.00045 parts of ethylenediaminetetraacetate, and 10 parts of water was added to polymerize. Was started. After the polymerization exotherm was confirmed, the jacket temperature was set to 75 ° C., and the polymerization was continued until the polymerization exotherm was not confirmed, and was further maintained for 1 hour. The resulting rubbery polymer (b-1) had a volume average particle size of 0.105 μm.
The internal temperature is controlled at 70 ° C., 0.2 parts of dipotassium alkenyl succinate (Laomul ASK, manufactured by Kao Corporation), 0.3 parts of sodium formaldehyde sulfoxylate, 0.001 part of ferrous sulfate heptahydrate, ethylenediamine tetra An aqueous solution consisting of 0.003 parts disodium acetate and 10 parts water was added. Subsequently, it heated up to 80 degreeC, adding the liquid mixture which consists of 12 parts of acrylonitrile, 28 parts of styrene, and 0.2 part of t-butyl hydroperoxide over 80 minutes. After completion of dropping, the temperature is maintained at 80 ° C. for 30 minutes, and then cooled to 75 ° C., and consists of 3 parts of acrylonitrile, 7 parts of styrene, 0.02 part of normal octyl mercaptan, and 0.05 part of t-butyl hydroperoxide. The mixture was added dropwise over 20 minutes. After completion of dropping, the mixture was kept at 75 ° C. for 60 minutes and then cooled to obtain a graft copolymer (B-1) latex. Next, 100 parts of a 2.0% sulfuric acid aqueous solution is heated to 40 ° C., and 100 parts of the graft copolymer (B-1) latex is gradually added dropwise to the aqueous solution while stirring the aqueous solution. B-1) was solidified, further heated to 95 ° C. and held for 10 minutes. Next, the solidified product was dehydrated, washed and dried to obtain a powdered graft copolymer (B-1). The content of the acrylate monomer unit in 100% by mass of the rubbery polymer (b-1) is 99.4% by mass, and the polyfunctional monomer unit with respect to 100 parts by mass of the acrylate monomer unit. The content of the rubber polymer (b-1) in 100 parts by mass of the graft copolymer (B-1) is 49.9 parts by mass, the rubbery polymer (b- The composition of the aromatic vinyl monomer grafted to 1) and the vinyl cyanide monomer are 70% by mass for the aromatic vinyl monomer and 30% by mass for the vinyl cyanide monomer, respectively. there were. The graft ratio of the graft copolymer (B-1) was 53%.

[Synthesis Example 9: Production of Graft Copolymer (B-2)]
The graft copolymer (B-2) was prepared in the same manner as in Synthesis Example 8 except that the amount of dipotassium alkenyl succinate (manufactured by Kao Corporation, Latemul ASK) used in producing the rubber polymer was changed to 8 parts. Got. The volume average particle diameter of the rubber polymer (b-2) is 0.050 μm, and the content of the acrylate monomer unit in 100% by mass of the rubber polymer (b-2) is 99.4% by mass, The content of the polyfunctional monomer unit with respect to 100 parts by mass of the acrylate monomer unit is 0.2 parts by mass, and the rubbery polymer (b-) in 100 parts by mass of the graft copolymer (B-2) The content of 2) is 49.9 parts by mass, and the compositions of the aromatic vinyl monomer and the vinyl cyanide monomer grafted on the rubber polymer (b-2) are aromatic vinyl monomers. The monomer was 70% by mass and the vinyl cyanide monomer was 30% by mass. The graft ratio of the graft copolymer (B-2) was 60%.

[Synthesis Example 10: Production of Graft Copolymer (B-3)]
240 parts of water in a reactor, 0.1 part of bovine fatty acid potassium (manufactured by Kao Corporation, KS soap), 50 parts of n-butyl acrylate, 0.15 part of allyl methacrylate, 1,3-butanediol dimethacrylate 0 .05 parts and 0.1 part of t-butyl hydroperoxide were charged with stirring, and the inside of the reactor was purged with nitrogen, and then the contents were heated. At an internal temperature of 55 ° C, an aqueous solution consisting of 0.2 parts of sodium formaldehyde sulfoxylate, 0.00015 parts of ferrous sulfate heptahydrate, 0.00045 parts of ethylenediaminetetraacetate, and 10 parts of water was added to polymerize. Was started. After the polymerization exotherm was confirmed, 0.3 parts of dipotassium alkenyl succinate (manufactured by Kao Corporation, Latemul ASK) was dropped at a dropping rate of 0.015 parts / minute, the jacket temperature was set to 75 ° C., and no polymerization exotherm was confirmed. Then, 0.3 parts of dipotassium alkenyl succinate (manufactured by Kao Corporation, Latemul ASK) was further added and held for another hour. The rubbery polymer (b-3) obtained had a volume average particle size of 0.230 μm. Thereafter, a graft copolymer (B-3) was obtained in the same manner as in Synthesis Example 8. The content of the acrylic acid ester monomer unit in 100% by mass of the rubber polymer (b-3) is 99.4% by mass, and the polyfunctional monomer unit with respect to 100 parts by mass of the acrylic acid ester monomer unit. The content of the rubber polymer (b-3) in 100 parts by mass of the graft copolymer (B-3) is 49.9 parts by mass, the rubbery polymer (b- The composition of the aromatic vinyl monomer and the vinyl cyanide monomer grafted on 3) is 70% by mass for the aromatic vinyl monomer and 30% by mass for the vinyl cyanide monomer, respectively. there were. The graft ratio of the graft copolymer (B-3) was 55%.

[Synthesis Example 11: Production of Graft Copolymer (B-4)]
The graft copolymer was prepared in the same manner as in Synthesis Example 8 except that allyl methacrylate used in the production of the rubber polymer was changed to 0.075 parts and 1,3-butanediol dimethacrylate was changed to 0.025 parts. A polymer (B-4) was obtained. The volume average particle diameter of the rubbery polymer (b-4) in the graft copolymer (B-4) is 0.105 μm, and the acrylate monomer in 100% by mass of the rubbery polymer (b-4) The content of the unit is 99.6% by mass, the content of the polyfunctional monomer unit with respect to 100 parts by mass of the acrylate monomer unit is 0.1 parts by mass, and the graft copolymer (B-4) 100. The content of the rubber polymer (b-4) in part by mass is 49.9 parts by mass, the aromatic vinyl monomer grafted on the rubber polymer (b-4) and the vinyl cyanide monomer The composition of the monomer was 70% by mass for the aromatic vinyl monomer and 30% by mass for the vinyl cyanide monomer. The graft ratio of the graft copolymer (B-4) was 35%.

  Table 1 shows the volume average particle diameters of the rubber copolymers of the graft copolymers (A-1) to (A-6) and (B-1) to (B-4), the content of the diene component and the graft ratio. Show.

[Synthesis Example 12: Production of Vinyl Copolymer (C-1)]
In a reactor, 125 parts of water, 0.4 parts of calcium phosphate, 0.0025 parts of potassium alkenyl succinate, 0.04 parts of 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1, From 0.06 part of 1-di (t-hexylperoxy) cyclohexane, 0.03 part of t-butylperoxy-2-ethylhexyl carbonate, 0.4 part of t-dodecyl mercaptan, 72 parts of styrene, and 28 parts of acrylonitrile A monomer mixture was prepared and reacted. The reaction was carried out by heating from an initial temperature of 65 ° C. for 6.5 hours to 125 ° C. while sequentially adding water, acrylonitrile and a portion of styrene. Furthermore, after reacting at 125 ° C. for 1 hour, the polymer was taken out to obtain a vinyl copolymer (C-1). The obtained vinyl copolymer (C-1) had a mass average molecular weight of 104,000.

[Synthesis Example 13: Production of vinyl copolymer (C-2)]
Using a monomer mixture consisting of 28 parts of acrylonitrile, 24 parts of styrene, 37 parts of α-methylstyrene and 11 parts of N-phenylmaleimide, styrene, α-methylstyrene and a part of N-phenylmaleimide were sequentially added. Except for this, polymerization was carried out in the same manner as in Synthesis Example 12 to obtain a vinyl copolymer (C-2). The weight average molecular weight of the obtained vinyl copolymer (C-2) was 129,000.

[Light Stabilizer (D-1)]
As the hindered amine light stabilizer (D-1), “ADEKA STAB LA-77Y” (bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate (molecular weight 481)) manufactured by ADEKA was used.

[Light stabilizer (D-2)]
As the hindered amine light stabilizer (D-2), “ADEKA STAB LA-57” (tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetra manufactured by ADEKA) Carboxylate (molecular weight 791)) was used.

[Light stabilizer (D-3)]
As the hindered amine light stabilizer (D-3), “ADEKA STAB LA-63P” (1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ′, β′-tetramethyl manufactured by ADEKA Co., Ltd. -3,9- (2,4,8,10-tetraoxaspiro [5.5] undecane) condensate with diethanol (molecular weight 2,000) was used.

[Light stabilizer (D-4)]
As the hindered amine light stabilizer (D-4), “Uvinul 5050H” (N- (2,2,6,6, -tetramethyl-4-piperidine) maleimide and α-olefin (C20-24) manufactured by BASF Corporation. ) Copolymer (molecular weight 3000-4000)).

[Light stabilizer (D-5)]
As the hindered amine light stabilizer (D-5), “ADEKA STAB LA-82” (1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (molecular weight 225)) manufactured by ADEKA was used.

[Ultraviolet absorber (E-1)]
As an benzotriazole-based ultraviolet absorber (E-1), “ADEKA STAB LA-31” (2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H— Benzotriazol-2-yl) phenol] (molecular weight 659)) was used.

[Ultraviolet absorber (E-2)]
As the benzotriazole ultraviolet absorber (E-2), “ADEKA STAB LA-32” (2- (2′-hydroxy-5′-methylphenyl) benzotriazole (molecular weight 225)) manufactured by ADEKA was used.

[Ultraviolet absorber (E-3)]
As the triazine-based ultraviolet absorber (E-3), “ADEKA STAB LA-46” (2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- ( 2-ethylhexanoyloxy) ethoxy] phenol (molecular weight 512)) was used.

[Ultraviolet absorber (E-4)]
As the triazine ultraviolet absorber (E-4), “ADEKA STAB LA-F70” (2,4,6-tris (2-hydroxy-4hexyloxy-3-methylphenyl) -1,3,5-triazine manufactured by ADEKA Corporation (Molecular weight 700)) was used.

[Ultraviolet absorber (E-5)]
As a cyanoacrylate ultraviolet absorber (E-5), “Uvinul 3030FF” (2,2-bis {[(2-cyano-3,3-diphenylacryloyl) oxy] methyl} propane-1,3-, manufactured by BASF Diyl bis (2-cyano-3,3-diphenyl acrylate) (molecular weight 1060)) was used.

[Antioxidant (F-1)]
As the hindered phenolic antioxidant (F-1), “ADEKA STAB AO-50” (n-octadecyl-β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (molecular weight 531) manufactured by ADEKA ))It was used.

[Antioxidant (F-2)]
As the phenolic antioxidant (F-2), “ADEKA STAB AO-40” (6,6′-di-tert-butyl-4,4′-butylidenedi-m-cresol (molecular weight 383)) manufactured by ADEKA is used. did

[Antioxidant (F-3)]
As the hindered phenol-based antioxidant (F-3), “ADEKA STAB AO-60” (pentaerythritol = tetrakis [3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl)) manufactured by ADEKA Propionate] (molecular weight 1178)).

[Examples 1 to 10 and Comparative Examples 1 to 22: Production of thermoplastic resin composition]
Graft copolymer (A), graft copolymer (B), vinyl copolymer (C), light stabilizer (D), ultraviolet absorber (E), antioxidant (F), and carbon black part (Mitsubishi Chemical Corporation “# 966B”, average primary particle size 17 nm) 1 part was mixed in the ratio shown in Tables 2 to 4, and ethylene bisstearylamide (“Alfro H50S” manufactured by NOF Corporation) as a lubricant was added. .5 parts and 0.1 part of magnesium oxide (“Kyowa Mug 150” manufactured by Kyowa Chemical Industry Co., Ltd.) were added and blended with a Henschel mixer. This mixture was melt-kneaded at a cylinder temperature of 240 ° C. and pelletized using a 28 mmφ twin screw extruder (“TEX28V” manufactured by Nippon Steel Works).

[Evaluation of thermoplastic resin composition]
The following tests were performed using the obtained resin composition pellets, and the results are shown in Tables 2 to 4. The weather resistance was evaluated using a molded body of 30 × 70 × 2 mmt.

<Impact resistance: Charpy impact strength>
The Charpy impact strength of the molded body was measured on a test piece with a V notch that was allowed to stand for 12 hours or more in an atmosphere at 23 ° C. by a method according to ISO 179.

<Rigidity: Flexural modulus>
The bending elastic modulus of the molded body was measured at a measurement temperature of 23 ° C. and a test piece thickness of 4 mm by a method based on ISO test method 178.

<Heat resistance: deflection temperature under load>
The deflection temperature under load of the compact was measured according to the ISO test method 75, 1.8 MPa, 4 mm, and the flatwise method.

<Surface appearance; glossiness>
The glossiness of the molded product was measured at a reflection angle of 60 ° using a digital variable gloss meter UGV-5D (manufactured by Suga Test Instruments Co., Ltd.).

<Weather resistance; degree of discoloration (ΔE)>
Using a xenon weather meter Ci4000 (manufactured by Atlas), accelerated weathering test of 2500 kJ / m ² and 4500 kJ / m ² irradiation according to SAE J2527 was performed. The degree of color change (ΔE) before and after the test was evaluated using a colorimeter CM-508d (manufactured by Konica Minolta).

<Weather resistance; gloss retention>
Using a xenon weather meter Ci4000 (manufactured by Atlas Co., Ltd.), an accelerated weathering test of 2500 kJ / m ² and 4500 kJ / m ² irradiation in accordance with SAE J2527 was performed. The glossiness before and after the test at an incident reflection angle of 60 ° was measured using a digital variable glossmeter UGV-5D (manufactured by Suga Test Instruments Co., Ltd.), and the gloss retention was determined by the following formula.
Gloss retention (%) = Glossiness before test / Glossiness after test × 100

<Weather resistance; occurrence of bleed-out>
Using a xenon weather meter Ci4000 (manufactured by Atlas Co., Ltd.), an accelerated weathering test of 4500 kJ / m ² irradiation based on SAE J2527 was performed, and the occurrence of bleed-out by visual observation was determined for the molded product after the test.
○: No bleed out occurs on the specimen surface ×: Bleed out occurs on the specimen surface

  In the following Tables 2 to 4, “Rubber amount of (A): Rubber amount of (B)” means the graft copolymer (A) in 100% by mass of the rubbery polymer contained in the thermoplastic resin (G). The ratio (mass%) of the rubber polymer (a) of the rubber polymer (b) and the ratio (mass%) of the rubber polymer (b) of the graft copolymer (B).

As apparent from Tables 2 to 4, molded articles having excellent weather resistance, impact resistance, and surface appearance were obtained from the thermoplastic resin composition obtained in each Example.
On the other hand, in the case of each comparative example, the result was inferior to any one or more of weather resistance, impact resistance, and surface appearance.

  According to the present invention, a thermoplastic resin composition capable of obtaining a molded article having a high level of weather resistance, impact resistance, and surface appearance, a molded article formed by molding this thermoplastic resin composition, and this A vehicle exterior part including a molded body can be provided, and the industrial utility value is extremely high.

[1] The following thermoplastic resin (G), light stabilizer (D), ultraviolet absorber (E), and antioxidant (F) are included, and 100 parts by weight of the thermoplastic resin (G) is light. Thermoplastic containing 0.1 to 1.5 parts by mass of stabilizer (D), 0.1 to 1.5 parts by mass of ultraviolet absorber (E), and 0.1 to 3 parts by mass of antioxidant (F) Resin composition.
Thermoplastic resin (G): composed of graft copolymer (A), graft copolymer (B), and vinyl copolymer (C). Graft copolymer (A) is an acrylic ester-based monomer A rubber-based polymer (a) having a volume average particle size of 0.3 to 0.6 μm, comprising a body unit and a polyfunctional monomer unit and not containing a conjugated diene monomer unit in the main chain; The graft copolymer is a graft copolymer having a graft ratio of 40 to 80%, and the graft copolymer (B) contains an acrylate monomer unit and a polyfunctional monomer unit. Graft ratio in which vinyl monomer is grafted to rubbery polymer (b) having a volume average particle size of 0.07 to 0.2 μm and containing no conjugated diene monomer unit in the chain is 40 to 80% A graft copolymer of the vinyl copolymer (C) is an aromatic vinyl monomer Of a rubber polymer contained in the thermoplastic resin (G), or a copolymer formed by copolymerizing at least a vinyl cyanide monomer and an aromatic vinyl monomer. Thermoplastic resin light stabilizer (D) containing 20 to 70% by mass of rubbery polymer (a) and 30 to 80% by mass of rubbery polymer (b) in a total amount of 100% by mass: molecular weight 400 to 2, 000 hindered amine light stabilizer UV absorber (E): benzotriazole UV absorber with molecular weight 300-800 and / or triazine UV absorber antioxidant (F): hindered phenol oxidation with molecular weight 500-800 Inhibitor

[Ultraviolet absorber (E)]
In the thermoplastic resin composition of the present invention, as the ultraviolet absorber (E), a benzotriazole ultraviolet absorber and / or a triazine ultraviolet absorber having a molecular weight of 300 to 800 is added to 100 parts by mass of the thermoplastic resin (G). On the other hand, 0.1 to 1.5 parts by mass are included. If the content of the ultraviolet absorber (E) is not less than the above lower limit, the weather resistance of the resulting thermoplastic resin composition will be good, and if it is not more than the above upper limit, bleed out when used outdoors for a long period of time. Appearance defects can be suppressed. The preferable content of the ultraviolet absorber (E) is 0.3 to 1.0 part by mass.
In the present invention, if the ultraviolet absorber (E) having a molecular weight of 300 to 800 used as the ultraviolet absorber (E) is used, the resulting molded article has good weather resistance, and the benzotriazole- based ultraviolet absorber. In the case of a triazine ultraviolet absorber, since it has high stability against heat and light, discoloration during processing can be suppressed.

Examples of the benzotriazole ultraviolet absorber (E) include 2 (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole (molecular weight 315), 2- (2H-benzotriazole- 2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol (molecular weight 323), 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1) -Phenylethyl) phenol (molecular weight 447), 2,2-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] (molecular weight 659) Examples of the triazine-based ultraviolet absorber (E) include 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5- [2- (2-ethyl) Xanoyloxy) ethoxy] phenol (molecular weight 512), 2,4,6-tris (2-hydroxy-4hexyloxy-3-methylphenyl) -1,3,5-triazine (molecular weight 700), 2- (4,6- Examples include, but are not limited to, diphenyl-1,3,5-triazin-2-yl) -5-((hexyl) oxy) -phenol (molecular weight 426). An ultraviolet absorber (E) can be used individually by 1 type or in mixture of 2 or more types.

Claims (8)

The following thermoplastic resin (G), light stabilizer (D), ultraviolet absorber (E), and antioxidant (F) are included. A thermoplastic resin composition containing 0.1 to 1.5 parts by weight of D), 0.1 to 1.5 parts by weight of the ultraviolet absorber (E), and 0.1 to 3 parts by weight of the antioxidant (F). .
Thermoplastic resin (G): consisting of graft copolymer (A), graft copolymer (B), and vinyl copolymer (C),
The graft copolymer (A) includes an acrylate monomer unit and a polyfunctional monomer unit, and does not include a conjugated diene monomer unit in the main chain, and has a volume average particle size of 0.3 to 0. A graft copolymer having a graft ratio of 40 to 80% obtained by grafting a vinyl monomer to a rubber polymer (a) of .6 μm,
The graft copolymer (B) contains an acrylate monomer unit and a polyfunctional monomer unit, and does not contain a conjugated diene monomer unit in the main chain, and has a volume average particle size of 0.07 to 0. A graft copolymer having a graft ratio of 40 to 80% in which a vinyl monomer is grafted to a rubber polymer (b) of 2 μm,
The vinyl copolymer (C) is a homopolymer of an aromatic vinyl monomer or a copolymer obtained by copolymerizing at least a vinyl cyanide monomer and an aromatic vinyl monomer. Yes,
Heat containing 20 to 70% by mass of the rubbery polymer (a) and 30 to 80% by mass of the rubbery polymer (b) in 100% by mass of the total amount of the rubbery polymer contained in the thermoplastic resin (G). Plastic resin light stabilizer (D): hindered amine light stabilizer having a molecular weight of 400 to 2,000 UV absorber (E): benzophenol UV absorber and / or triazine UV absorber antioxidant having a molecular weight of 300 to 800 (F): Hindered phenol antioxidant having a molecular weight of 500 to 800 The content of the acrylate monomer unit in the rubber polymer (a) 100% by mass is 75% by mass or more, and the content of the polyfunctional monomer unit is the acrylate monomer unit. 0.3 to 3 parts by mass with respect to 100 parts by mass, the graft copolymer (A) is a rubbery polymer (a), a vinyl cyanide monomer and an aromatic vinyl monomer, And a vinyl monomer mixture containing other monomers copolymerizable with these vinyl monomers used as needed, in 100 parts by mass of the graft copolymer (A). The content of the rubber polymer (a) is 10 to 90 parts by mass,
The content of the acrylate monomer unit in the rubber polymer (b) 100% by mass is 75% by mass or more, and the content of the polyfunctional monomer unit is the acrylate monomer unit. It is 0.05-3 mass parts with respect to 100 mass parts, and the graft copolymer (B) is a rubbery polymer (b), a vinyl cyanide monomer and an aromatic vinyl monomer, And a vinyl monomer mixture containing other monomers copolymerizable with these vinyl monomers used as needed, in 100 parts by mass of the graft copolymer (B). The thermoplastic resin composition according to claim 1, wherein the content of the rubber polymer (b) is 10 to 90 parts by mass.   Graft copolymer (A) and graft contained in 100 parts by mass of thermoplastic resin (G), which is the total amount of graft copolymer (A), graft copolymer (B), and vinyl copolymer (C) The thermoplastic resin composition according to claim 1 or 2, wherein the content of the copolymer (B) is 20 to 60 parts by mass and the content of the vinyl copolymer (C) is 40 to 80 parts by mass. .   The vinyl copolymer (C) is a homopolymer of an aromatic vinyl monomer, or a copolymer of a vinyl cyanide monomer and an aromatic vinyl monomer (C-1), and 4. The copolymer (C-2) of an N-substituted maleimide monomer, an aromatic vinyl monomer, and a vinyl cyanide monomer is included. The thermoplastic resin composition described in 1.   The content ratio of the copolymer (C-1) and the copolymer (C-2) in 100 parts by mass of the vinyl copolymer (C) is (C-1) :( C-2) = 10 to 100 mass. Part: The thermoplastic resin composition of Claim 4 which is the range of 0-90 mass parts.   Furthermore, the thermoplastic resin composition of any one of Claim 1 thru | or 5 containing the 1 type (s) or 2 or more types of a phosphorus antioxidant, carbon black, and the oxide of a periodic table group 2 element.   The molded object formed by shape | molding the thermoplastic resin composition of any one of Claim 1 thru | or 6.   A vehicle exterior part comprising the molded body according to claim 7.