JP5193634B2 - Weather resistant resin composition - Google Patents

Description

  The present invention relates to a weather-resistant resin composition that is excellent in weather resistance, impact resistance, and molding processability and that can produce a dark-colored molded product.

Conventionally, a colored composition containing an AES resin has been used as a molding material for forming a molded article that is used outdoors for a long period of time, such as a vehicle outer plate member. For example, Patent Document 1 discloses a graft copolymer obtained by copolymerizing a monomer mixture mainly composed of an aromatic vinyl compound and a vinyl cyanide compound in the presence of an ethylene / α-olefin rubbery polymer. A thermoplastic resin composition containing a polymer resin composition and a copolymer obtained by polymerizing a monomer mixture comprising a methacrylic acid ester compound, an aromatic vinyl compound and a vinyl cyanide compound is disclosed. .
The above molded products are exposed to various climates, so there is little change in color tone and surface gloss over time, appearance is maintained, impact resistance is excellent, and regardless of size, moldability is improved. There is a need for superiority. In addition, the time-dependent changes in color tone and surface gloss, which are evaluation items for weather resistance, are more correlated as the accelerated weather resistance test method using the xenon weather meter than the method using the sunshine weather meter. It is known.

JP 61-34045 A

  An object of the present invention is a weather-resistant resin composition that is excellent in molding processability, suppresses a change in color tone and a decrease in surface gloss when used outdoors for a long period of time, and gives a molded product excellent in impact resistance. Is to provide.

In order to obtain a resin composition with little color change and lowering of surface gloss when the dark colored pigmented molded article is used in an environment exposed to various climates such as outdoors, the inventors Studied. As a result, an AES resin, an acrylonitrile / styrene copolymer having a vinyl cyanide compound unit content in a specific range, a colorant, and an amine compound were blended, and the L value of the molded product was 50 or less. As for the product, a change in color tone and a decrease in surface gloss were suppressed by a method using a xenon weather meter as compared with a conventional molded product obtained using a known AES resin or an AES resin containing a weather resistance improver. As a result, the present invention has been completed.

〔式中、Ｒは、炭素数８〜２２のアルキル基又は炭素数８〜２２のアルケニル基であり、Ｙ及びＺは、同一又は異なって、下記で表される２価の有機基

のいずれかである。ｍ及びｎは１以上の整数であり、ｍ及びｎの和は、２〜５の整数である。〕
２．上記着色剤〔Ｃ〕がカーボンブラックである上記１に記載の耐候性樹脂組成物。
３．上記耐候性樹脂組成物からなる成形品を、キセノンウェザーメーター耐候性試験に供した場合、該試験の前後における色調変化ΔＥが７以下である上記１又は２に記載の耐候性樹脂組成物。
４．上記耐候性樹脂組成物からなる成形品を、キセノンウェザーメーター耐候性試験に供した場合、試験前の光沢度に対する試験後の光沢度が８０％以上である上記１乃至３のいずれかに記載の耐候性樹脂組成物。 The present invention is shown below.
1. [A] Rubber-reinforced vinyl obtained by polymerizing a vinyl monomer (a2) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an ethylene / α-olefin rubber polymer (a1) A rubber-reinforced resin containing a resin and a copolymer [B] an aromatic vinyl compound unit and a vinyl cyanide compound unit, wherein the content ratio of the vinyl cyanide compound unit constitutes the copolymer The total amount of monomer units to be 100% by mass, a copolymer of 33 to 40 % by mass, [C] a colorant, and [D] an amine compound represented by the following general formula (I): The content ratio of the rubber-reinforced resin [A] and the copolymer [B] is 25 to 75 when the total of both is 100% by mass. Mass% and 75-25 mass% The content of the colorant [C] is 0.05 to 5 parts by mass when the total of the rubber-reinforced resin [A] and the copolymer [B] is 100 parts by mass, and the amine The content of the compound [D] is 0.1 to 10 parts by mass when the total of the rubber-reinforced resin [A] and the copolymer [B] is 100 parts by mass, and the weather resistant resin composition The content of the ethylene / α-olefin rubber polymer (a1) contained in the product is 6 to 35% by mass, and the content of the vinyl cyanide compound unit contained in the weather resistant resin composition is 25 to 35. A weather-resistant resin composition having a mass% and an L value of a molded article comprising the weather-resistant resin composition is 50 or less.

[Wherein, R is an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, and Y and Z are the same or different and are divalent organic groups represented by the following:

One of them. m and n are integers of 1 or more, and the sum of m and n is an integer of 2 to 5. ]
2. 2. The weather resistant resin composition according to 1 above, wherein the colorant [C] is carbon black.
3. 3. The weather resistant resin composition according to 1 or 2 above, wherein when the molded article made of the weather resistant resin composition is subjected to a xenon weather meter weather resistance test, the color change ΔE before and after the test is 7 or less.
4). 4. When the molded article comprising the weather resistant resin composition is subjected to a xenon weather meter weather resistance test, the gloss after the test with respect to the gloss before the test is 80% or more. Weather resistant resin composition.

According to the weather-resistant resin composition of the present invention, a molded product excellent in molding processability, suppressed in color tone change and surface gloss reduction when used outdoors for a long time, and excellent in impact resistance. Can be given.
When a molded article formed using the weather resistant resin composition of the present invention is subjected to a xenon weather meter weather resistance test, the color tone change ΔE before and after the test can be set to 7 or less. Moreover, the glossiness after the test with respect to the glossiness before the test can be kept as high as 80% or more.

The present invention will be described in detail below.
The weather-resistant resin composition of the present invention includes: [A] a vinyl monomer (a2) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an ethylene / α-olefin rubber polymer (a1). A rubber reinforced resin containing a rubber reinforced vinyl resin obtained by polymerizing (hereinafter also referred to as “component [A]”), and [B] a copolymer containing an aromatic vinyl compound unit and a vinyl cyanide compound unit. A copolymer having a content ratio of the vinyl cyanide compound unit of 33 to 40 % by mass when the total of the monomer units constituting the copolymer is 100% by mass. Hereinafter referred to as “component [B]”), [C] colorant (hereinafter also referred to as “component [C]”), and [D] an amine compound represented by the above general formula (I) (hereinafter referred to as “component [C]”). , Also referred to as “component [D]”) The content ratio of the rubber-reinforced resin [A] and the copolymer [B] is 25 to 75% by mass and 75 to 25% by mass when the total of both is 100% by mass. The content of the colorant [C] is 0.05 to 5 parts by mass when the total of the rubber-reinforced resin [A] and the copolymer [B] is 100 parts by mass. The content of the amine compound [D] is 0.1 to 10 parts by mass when the total of the rubber-reinforced resin [A] and the copolymer [B] is 100 parts by mass. The content of the ethylene / α-olefin rubbery polymer (a1) contained in the curable resin composition is 6 to 35% by mass, and the content of the vinyl cyanide compound unit contained in the weatherable resin composition is 25 to 35% by mass and comprising the above weather resistant resin composition L value of the goods is equal to or is 50 or less.

  The component [A] is obtained by polymerizing a vinyl monomer (a2) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an ethylene / α-olefin rubber polymer (a1). A rubber-reinforced resin containing a rubber-reinforced vinyl resin.

The ethylene / α-olefin rubbery polymer (a1) forming the rubber-reinforced vinyl resin includes an ethylene unit (a11) composed of ethylene and a unit (a12) composed of an α-olefin having 3 or more carbon atoms. If it is a copolymer rubber containing, it will not specifically limit.
The content of the unit (a11) is preferably 5 to 95% by mass when the total amount of the monomer units constituting the ethylene / α-olefin rubbery polymer (a1) is 100% by mass. Preferably it is 50-90 mass%, More preferably, it is 60-88 mass%. When the content of the unit (a11) is within this range, the balance between weather resistance and impact resistance is excellent.

Examples of the α-olefin having 3 or more carbon atoms that form the unit (a12) include propylene, 1-butene, 2-butene, isobutene, 1-pentene, 2-methyl-1-butene, and 2-methyl. Examples include 2-butene, 3-methylbutene, 1-hexene, 4-methyl-1-pentene, 3-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1-undecene and the like. The unit (a12) consisting of these α-olefins may be included singly or in combination of two or more. Of the units (a12), a unit composed of propylene, a unit composed of 1-butene, and the like are preferable.
The content of the unit (a12) is preferably 95 to 5% by mass when the total amount of the monomer units constituting the ethylene / α-olefin rubbery polymer (a1) is 100% by mass. Preferably it is 50-10 mass%, Most preferably, it is 40-12 mass%. When the content of the unit (a12) is within this range, the balance between weather resistance and impact resistance is excellent.

  The ethylene / α-olefin rubbery polymer (a1) may be a binary copolymer composed of the units (a11) and (a12), or these units (a11) and (a12). ) And further units (ternary copolymer, quaternary copolymer, etc.). Examples of other units include units composed of non-conjugated diene compounds.

When the ethylene / α-olefin-based rubbery polymer (a1) is a terpolymer, for example, an ethylene / α-olefin / non-conjugated diene terpolymer can be used.
As the nonconjugated diene compound that forms the nonconjugated diene unit (hereinafter referred to as “unit (a13)”) constituting the ethylene / α-olefin / nonconjugated diene terpolymer, 1,4 -Linear acyclic diene compounds such as hexadiene, 1,5-hexadiene, 1,6-hexadiene, 5-methyl-1,4-hexadiene, 3,7-dimethyl-1,6-octadiene, 5,7- dimethyl-1,6-octadiene, 3,7-dimethyl-1,7-octadiene, 7-methyl-1,6-octadiene, acyclic diene compounds branched chain such as dihydromyrcene, tetrahydroindene, methyl tetrahydrophthalic Indene, dicyclopentadiene, bicyclo [2.2.1] -hepta-2,5-diene, 5-methylene-2-norbornene, 5-ethylidene-2 Norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexylidene-2-norbornene, alicyclic diene compounds such as 5-vinyl-2-norbornene. The unit (a13) consisting of these non-conjugated diene compounds may be included singly or in combination of two or more. Of the units (a13), units composed of 1,4-hexadiene, units composed of dicyclopentadiene, units composed of 5-ethylidene-2-norbornene, and the like are preferable.
The content of the unit (a13) is such that when the total amount of monomer units constituting the ethylene / α-olefin rubbery polymer (a1) is 100% by mass, the use effect of the unit (a13) is as follows. In order to obtain it, Preferably it is 0.1-30 mass%, More preferably, it is 0.3-20 mass%, More preferably, it is 1-10 mass%. When the content of the unit (a13) is in the above range, an effect of improving the graft efficiency can be obtained.

  As the ethylene / α-olefin rubbery polymer (a1), a halogenated copolymer in which a part of hydrogen atoms in the molecule is substituted with a halogen atom such as a chlorine atom or a bromine atom can also be used.

The ethylene / α-olefin rubbery polymer (a1) has a Mooney viscosity (ML _{1 + 4} , measured at 100 ° C.) of preferably 5 to 80, more preferably 10 to 65, still more preferably 15 to 45. is there. When this Mooney viscosity is in the above range, the balance between molding processability and impact resistance is excellent.

  The ethylene / α-olefin rubbery polymer (a1) used for forming the rubber-reinforced vinyl resin can be used singly or in combination of two or more.

  The vinyl monomer (a2) used for forming the rubber-reinforced vinyl resin includes an aromatic vinyl compound and a vinyl cyanide compound. This vinyl monomer (a2) may be composed of an aromatic vinyl compound and a vinyl cyanide compound, an aromatic vinyl compound, a vinyl cyanide compound, and a compound copolymerizable with these compounds. It may consist of. In the present invention, the total amount of the aromatic vinyl compound and the vinyl cyanide compound is preferably 70 to 100% by mass, more preferably 90 to 100% by mass, based on the total amount of the vinyl monomer (a2). is there.

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples include styrene, α-methyl styrene, β-methyl styrene, o-methyl styrene, p-methyl styrene, ethyl styrene, p-tert-butyl styrene, vinyl toluene, vinyl xylene, vinyl naphthalene, monochlorostyrene, dichloromethane. Examples thereof include styrene, monobromostyrene, dibromostyrene, and fluorostyrene. These can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. Of these, acrylonitrile is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types.

  The compounds that can be copolymerized with the aromatic vinyl compound and the vinyl cyanide compound include (meth) acrylic acid ester compounds; maleimide compounds; acid anhydrides; hydroxyl groups, amino groups, epoxy groups, amide groups, carboxyl groups. And vinyl compounds having a functional group such as an oxazoline group.

  Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Examples thereof include isobutyl (meth) acrylate and tert-butyl (meth) acrylate. These can be used alone or in combination of two or more.

Examples of the maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like. Can be mentioned. These can be used alone or in combination of two or more. As another method for introducing a unit comprising a maleimide compound, for example, there is a method in which maleic anhydride is copolymerized and then imidized.
Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used alone or in combination of two or more.

  In addition to the above compounds, vinyl compounds having a functional group such as a hydroxyl group, an amino group, an epoxy group, an amide group, a carboxyl group, or an oxazoline group can be used as necessary. For example, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, hydroxystyrene, N, N-dimethylaminomethyl methacrylate, N, N-dimethylaminomethyl acrylate, N, N-diethyl-p-aminomethylstyrene Glycidyl methacrylate, glycidyl acrylate, 3,4-oxycyclohexyl methacrylate, 3,4-oxycyclohexyl acrylate, vinyl glycidyl ether, methallyl glycidyl ether, allyl glycidyl ether, methacrylamide, acrylamide, methacrylic acid, acrylic acid And vinyl oxazoline. These can be used alone or in combination of two or more.

The vinyl monomer (a2) can be used in the following combinations as described above.
(1) Aromatic vinyl compound and vinyl cyanide compound (2) Aromatic vinyl compound, vinyl cyanide compound and other compounds

  In the above aspect (1), the use amount of the aromatic vinyl compound and the vinyl cyanide compound is preferably 55 to 80% by mass and more preferably 45 to 20% by mass, respectively, when the total of these is 100% by mass. Is 55 to 75 mass% and 45 to 25 mass%. By setting it as the above ratio, the balance between molding processability and impact resistance is excellent.

Examples of the method for producing the rubber-reinforced vinyl resin include solution polymerization, emulsion polymerization, bulk polymerization, and bulk-suspension polymerization. In any case, a known method can be applied. Of these polymerization methods, solution polymerization and emulsion polymerization are preferred.
When producing the rubber-reinforced vinyl resin, the polymerization is started by adding the vinyl monomer (a2) in the reaction system in the presence of the total amount of the ethylene / α-olefin rubber polymer (a1). Alternatively, polymerization may be carried out while adding in portions or continuously. In addition, in the presence or absence of a part of the ethylene / α-olefin rubber polymer (a1), the vinyl monomer (a2) may be added all at once to initiate the polymerization, or split. Or may be added continuously. At this time, the remainder of the ethylene / α-olefin-based rubbery polymer (a1) may be added in a batch, divided or continuously during the reaction.

When a rubber-reinforced vinyl resin is produced by solution polymerization, the polymerization initiator is preferably an organic peroxide such as tert-butyl peroxyisopropyl monocarbonate, tert-butyl peroxypivalate, tert-butyl peroxy. Benzoate, tert-butyl peroxyisobutyrate, tert-butyl peroxy octoate, cumyl peroxy octoate, 1,1-bis (tert-butyl peroxy) -3,3,5-trimethylcyclohexane, benzoyl peroxide , Lauroyl peroxide and the like. The usage-amount of the said polymerization initiator is 0.05-2 mass% normally with respect to the said vinylic monomer (a2) whole quantity.
The polymerization initiator can be added to the reaction system all at once or continuously.
As the polymerization solvent, toluene, xylene, ethylbenzene, isopropylbenzene, methyl ethyl ketone, or the like can be used.

  In the case of producing a rubber-reinforced vinyl resin by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.

As the polymerization initiator, a redox in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, or the like and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation are combined. System initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used alone or in combination of two or more. The usage-amount of the said polymerization initiator is 0.1-3 mass% normally with respect to the said vinylic monomer (a2) whole quantity.
The polymerization initiator can be added to the reaction system all at once or continuously.

Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan; Examples include α-methylstyrene dimers. These can be used alone or in combination of two or more. When using the said chain transfer agent, the usage-amount is 0.1-5 mass% normally with respect to the said vinylic monomer (a2) whole quantity.
The chain transfer agent can be added to the reaction system all at once or continuously.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5 mass% normally with respect to the said vinylic monomer (a2) whole quantity.

  The latex obtained by emulsion polymerization of the vinyl monomer (a2) is usually purified by coagulating with a coagulant to form a polymer component in powder form, and then washing and drying. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid.

The graft ratio of the rubber-reinforced vinyl resin obtained as described above is usually 10 to 200% by mass, preferably 20 to 120% by mass, and more preferably 30 to 90% by mass. When the graft ratio is in the above range, the balance of molding processability, impact resistance and molding appearance is excellent.
Here, the graft ratio means x-gram of ethylene / α-olefin-based rubbery polymer (a1) in 1 gram of rubber-reinforced vinyl resin and 1 gram of rubber-reinforced vinyl resin dissolved in acetone. When the insoluble content is y gram, the value is obtained by the following formula.
Graft ratio (mass%) = {(y−x) / x} × 100

  In addition, the intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the rubber-reinforced vinyl resin-soluble component is usually 0.2 to 0.8 dl / g, preferably 0.25 to 0.7 dl / g, more preferably 0.3 to 0.7 dl / g. When the intrinsic viscosity [η] is within the above range, the balance between molding processability and impact resistance is excellent.

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

The component [A] may be a component containing only one type of rubber-reinforced vinyl resin, or may be a component containing two or more types. In the latter case, a combination comprising two or more rubber-reinforced vinyl resins obtained using the vinyl monomer (a2) of the above aspect (1); the vinyl monomer of the above aspect (2) ( a combination comprising two or more rubber-reinforced vinyl resins obtained using a2); one or more rubber-reinforced vinyl resins obtained using the vinyl monomer (a2) of the above aspect (1) And a combination of at least one rubber-reinforced vinyl resin obtained using the vinyl monomer (a2) of the above aspect (2).
Moreover, the said component [A] may be a component which consists only of rubber reinforced vinyl resin, and may be a component containing rubber reinforced vinyl resin and another polymer. Another polymer will not be specifically limited if it is provided with structures other than component [B].

  Content of the said component [A] contained in the weather resistant resin composition of this invention is 25-75 mass% when the sum total of a component [A] and [B] is 100 mass%, Preferably Is 27 to 73 mass%, more preferably 30 to 73 mass%. When the content of the component [A] is within the above range, the balance between weather resistance and impact resistance is excellent. In addition, when there is too much content of the said component [A], it will be inferior to a weather resistance. On the other hand, when there is too little content of the said component [A], it will be inferior to a weather resistance and impact resistance.

The component [B] includes an aromatic vinyl compound unit and a vinyl cyanide compound unit, and the content ratio of the vinyl cyanide compound unit is 100% by mass of the monomer units constituting the component [B]. In this case, the copolymer is 33 to 40 % by mass. This component [B] may contain a structural unit (monomer unit) derived from another compound.
The said component [B] can be used individually by 1 type or in combination of 2 or more types.

The aromatic vinyl compound that forms the aromatic vinyl compound unit and the vinyl cyanide compound that forms the vinyl cyanide compound unit are both rubber-reinforced components contained in the component [A]. Aromatic vinyl compounds and vinyl cyanide compounds used for the formation of vinyl resins can be used.
The content of the aromatic vinyl compound unit constituting the component [B] is usually 50 to 67% by mass, preferably 100% by mass when the total of the monomer units constituting the component [B] is 100% by mass. Is 52 to 66 mass%, more preferably 55 to 65 mass%. Further, the content of the vinyl cyanide compound unit is the sum of the monomer units constituting the component (B) is 100 mass%, a 33 to 40 wt%, preferably 34-40 wt %, More preferably 35 to 40 % by mass. When the content ratio of the vinyl cyanide compound unit is in the above range, the molding processability, weather resistance and impact resistance are excellent. In addition, when there is too little content rate of the said vinyl cyanide compound unit, a weather resistance will be inferior, and when too large, moldability and impact resistance will be inferior.

When the component [B] contains other structural units, it is a compound that can be copolymerized with the above aromatic vinyl compound and vinyl cyanide compound, (meth) acrylic acid ester compound; maleimide compound; acid anhydride A structural unit derived from a vinyl compound having a functional group such as hydroxyl group, amino group, epoxy group, amide group, carboxyl group or oxazoline group.
When the said component [B] contains another structural unit, the content rate is normally 10 mass% or less when the sum total of the monomer unit which comprises this component [B] is 100 mass% , Preferably 5% by mass or less.

  The component [B] can be produced by polymerizing a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence or absence of a polymerization initiator. As the polymerization method, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like are suitable, and these polymerization methods may be used in combination. The method for producing the component [B] may be a method using a polymerization initiator, or may be a thermal polymerization method without using a polymerization initiator. When using a polymerization initiator, the polymerization initiator etc. which are applied to manufacture of the rubber reinforced vinyl resin contained in the said component [A] can be used. In addition, a chain transfer agent etc. can be used as needed.

  In the production of the component [B], the polymerization may be started in a state where the total amount of the vinyl monomer is accommodated in the reaction system, and the arbitrarily selected monomer component is added in portions or continuously. The polymerization may be carried out. Further, when a polymerization initiator is used, it can be added to the reaction system all at once or continuously.

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the component [B] is preferably 0.42 to 0.80 dl / g, more preferably 0.45 to 0.80 dl / g. When this intrinsic viscosity [η] is within the above range, the balance of molding processability, weather resistance and impact resistance is excellent. The intrinsic viscosity [η] of the component [B] can be controlled by the production conditions.

  Content of the said component [B] contained in the weather resistant resin composition of this invention is 25-75 mass% when the sum total of a component [A] and [B] is 100 mass%, Preferably Is 27-73 mass%, More preferably, it is 27-70 mass%. When the content of the component [B] is within the above range, the balance between weather resistance and impact resistance is excellent. In addition, when there is too little content of the said component [B], it will be inferior to a weather resistance. On the other hand, when there is too much content of the said component [B], it will be inferior to a weather resistance and impact resistance.

  Next, the said component [C] is a coloring agent used in order to make L value of the molded article which consists of a weather resistant resin composition of this invention into 50 or less, and shall consist of 1 type, or 2 or more types. be able to. This component [C] may be either a pigment or a dye, or a combination thereof.

As the pigment, either an organic pigment or an inorganic pigment may be used.
Examples of the organic pigment include perinone pigments; phthalocyanine pigments; quinacridone pigments; azo pigments such as permanent red, lake red, and first yellow; nitroso pigments; nitro pigments, and the like. Of these, phthalocyanine pigments and azo pigments are preferred.
Examples of inorganic pigments include carbon black; calcined pigments; ultramarine pigments; cobalt pigments such as cobalt blue (cobalt aluminate); iron oxide pigments such as bengara; sulfide pigments such as iron sulfide and cadmium sulfide; chromium Examples thereof include chromate pigments such as lead oxide and zinc chromate; carbonate pigments; metal powder pigments; zinc oxide pigments such as zinc white; titanium oxide pigments such as titanium white and titanium yellow. Of these, carbon black, ultramarine pigments and iron oxide pigments are preferred.
Examples of the dye include heterocyclic dyes; anthraquinone dyes; azo dyes; perinone dyes; chlorinated dye lakes such as rhodamine lakes.

  Content of the said component [C] contained in the weather resistant resin composition of this invention is 0.05-5 mass parts when the sum total of said component [A] and [B] is 100 mass parts. Preferably, it is 0.1-4 mass parts, More preferably, it is 0.1-3 mass parts. When there is too little content of this component [C], a weather resistance will be inferior. On the other hand, if the content is too large, the moldability and impact resistance are poor. When the component [C] is composed of a plurality of components, for example, even when a black colorant and a white colorant are used in combination, the L value of the obtained molded product is 50 or less. The content of the component [C] is adjusted within the above range.

〔式中、Ｒは、炭素数８〜２２のアルキル基又は炭素数８〜２２のアルケニル基であり、Ｙ及びＺは、同一又は異なって、下記で表される２価の有機基

のいずれかである。ｍ及びｎは１以上の整数であり、ｍ及びｎの和は、２〜５の整数である。〕 The component [D] is a compound represented by the following general formula (I).

[Wherein, R is an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, and Y and Z are the same or different and are divalent organic groups represented by the following:

One of them. m and n are integers of 1 or more, and the sum of m and n is an integer of 2 to 5. ]

Examples of the compound represented by the general formula (I) include lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyl diethanolamine, lauryl diisopronolamine, myristyl diisopropanolamine, palmityl diisopropanolamine, stearyl diisopropanolamine. Oleyl diisopropanolamine, N, N-bishydroxyethylalkylamine (alkyl group having 12 to 22 carbon atoms), and the like.
The said component [D] can be used individually by 1 type or in combination of 2 or more types.

  Content of the said component [D] contained in the weather resistant resin composition of this invention is 0.1-10 mass parts when the sum total of said component [A] and [B] is 100 mass parts. Preferably, it is 0.2-8 mass parts, More preferably, it is 0.2-5 mass parts. When the content of this component [D] is in the above range, the effect of improving weather resistance is excellent.

The weather resistant resin composition of the present invention may contain additives, other polymers having a configuration other than the component [B], etc., depending on the purpose and application.
Examples of the additives include antioxidants, ultraviolet absorbers, anti-aging agents, plasticizers, weathering agents, weathering improvers, flame retardants, antistatic agents, compatibilizers, processing aids, lubricants, mold release agents, Filler, light scattering agent, heat stabilizer, antibacterial agent, antifungal agent, antifouling agent, coupling agent, silicone oil, mineral oil, foaming agent (chemical foaming agent, physical foaming agent), foaming aid, fluorescent enhancement Examples include whitening agents.

Examples of the antioxidant include hindered phenols; phosphorus compounds; hindered amines; hydroquinones; sulfur-containing compounds. These can be used alone or in combination of two or more.
Examples of hindered phenols include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, tert-butylhydroxyanisole, 3 -(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) -N-octadecylpropionate, 2,2'-methylenebis- (4-methyl-6-tert-butylphenol), 4,4 '-Butylidenebis- (3-methyl-6-tert-butylphenol), 4,4'-thiobis- (3-methyl-6-tert-butylphenol), tetrakis- [methylene-3- (3', 5'-di- -Tert-butyl-4'-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy) -5-tert-butylphenyl) butane, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5) -Methylbenzyl) -4-methylphenyl acrylate and the like.
Examples of the phosphorus compound include pentaerythritol diphosphite and alkyldiaryl phosphite.
Content of the said antioxidant is 0.1-5 mass parts normally, when the sum total of said component [A] and [B] is 100 mass parts.

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more.
Content of the said ultraviolet absorber is 0.1-3 mass parts normally, when the sum total of said component [A] and [B] is 100 mass parts.

Antiaging agents include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiobisphenols. Compounds, hindered phenol compounds, phosphite compounds, imidazole compounds, nickel dithiocarbamate salts, phosphate compounds and the like. These can be used alone or in combination of two or more.
The content of the anti-aging agent is usually 0.1 to 3 parts by mass when the total of the components [A] and [B] is 100 parts by mass.

Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, diisodecyl phthalate, and the like; dimethyl adipate, Diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di- ( 2-ethylhexyl) fatty acid esters such as sebacate and diisooctyl sebacate; trimellitic acid isodecyl ester, trimellitic acid octyl ester Trimellitic acid esters such as tellurium, trimellitic acid n-octyl ester, trimellitic acid isononyl ester; di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinoleate, trilauryl phosphate, tristearyl phosphate , Tri- (2-ethylhexyl) phosphate and the like. These can be used alone or in combination of two or more.
Content of the said plasticizer is 0.1-5 mass parts normally, when the sum total of said component [A] and [B] is 100 mass parts.

Examples of the weathering agent include organic phosphorus compounds, organic sulfur compounds, and organic compounds containing a hydroxyl group. These can be used alone or in combination of two or more.
Content of the said weathering agent is 0.1-3 mass parts normally, when the sum total of said component [A] and [B] is 100 mass parts.

Examples of the weather resistance improver include benzotriazole compounds and hindered amine compounds, but it is preferable to use a mixture thereof.
The benzotriazole-based compound is not particularly limited as long as it has a benzotriazole skeleton in the molecule. For example, 2- (2′-hydroxy-5′-methylphenyl) -benzotriazole, 2- (2′- Hydroxy-3 ′, 5′-di-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-benzotriazol-2′-yl) -4,6-bis (1-methyl-1-phenylethyl) -Phenol, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2H-benzotriazol-2-yl) -p-cresol, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- [5-chloro (2H) -benzotri Azol-2-yl] -4-methyl-6- (tert-butyl) phenol, 2,4-di-tert-butyl-6- (5-chlorobenzotriazol-2-yl) phenol, 2- (2H- Benzotriazol-2-yl) -4-6-di-tert-pentylphenol, 2- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol, 2 , 2-methylenebis [6- (2H-benzotriazol-2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol and the like. These can be used alone or in combination of two or more.
The hindered amine compound is not particularly limited as long as it is a compound having a hindered amine skeleton in the molecule. For example, bis (2,2,6,6-tetramethyl-4-piperidyl) -sebacate, bis (1 , 2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl 1,2,2,6,6-pentamethyl-4-piperidyl sebacate, bis (2,2,6,6-tetradecanedioic acid) And methyl-1- (octyloxy) -4-piperidinyl) ester. These can be used alone or in combination of two or more.
The mixing ratio of the benzotriazole-based compound and the hindered amine-based compound is preferably 0 to 80% by mass and 100 to 20% by mass, more preferably 10 to 70% by mass, when the total of both is 100% by mass. And 90 to 30% by mass.
The content of the weather resistance improver is usually 0.1 to 3 parts by mass when the total of the components [A] and [B] is 100 parts by mass.

Examples of the flame retardant include organic flame retardants, inorganic flame retardants, and reactive flame retardants. These can be used alone or in combination of two or more.
Organic flame retardants include brominated epoxy compounds, brominated alkyltriazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene resins Halogenated flame retardants such as brominated bisphenol cyanurate resin, brominated polyphenylene ether, decabromodiphenyl oxide, tetrabromobisphenol A and oligomers thereof; trimethyl phosphate, triethyl phosphate, tripropyl phosphate, tributyl phosphate, tripentyl phosphate, tripentyl phosphate Hexyl phosphate, tricyclohexyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate Phosphate esters such as phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, dimethyl ethyl phosphate, methyl dibutyl phosphate, ethyl dipropyl phosphate, hydroxyphenyl diphenyl phosphate, compounds modified with these substituents, various condensed types Phosphorus ester compounds, phosphorus flame retardants such as phosphazene derivatives containing phosphorus element and nitrogen element; polytetrafluoroethylene, guanidine salts, silicone compounds, phosphazene compounds, and the like. These can be used alone or in combination of two or more.

Examples of the inorganic flame retardant include aluminum hydroxide, antimony oxide, magnesium hydroxide, zinc borate, zirconium compound, molybdenum compound, and zinc stannate. These can be used alone or in combination of two or more.
Reactive flame retardants include tetrabromobisphenol A, dibromophenol glycidyl ether, brominated aromatic triazine, tribromophenol, tetrabromophthalate, tetrachlorophthalic anhydride, dibromoneopentyl glycol, poly (pentabromobenzyl polyacrylate) , Chlorendic acid (hett acid), chlorendic anhydride (hett acid anhydride), brominated phenol glycidyl ether, dibromocresyl glycidyl ether and the like. These can be used alone or in combination of two or more.

Content of the said flame retardant is 3-35 mass parts normally, when the sum total of said component [A] and [B] is 100 mass parts.
In addition, when making a weather resistant resin composition of this invention contain a flame retardant, it is preferable to use a flame retardant adjuvant. As this flame retardant aid, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, antimony tartrate and other antimony compounds, zinc borate, barium metaborate, hydrated alumina, zirconium oxide, Examples thereof include ammonium polyphosphate, tin oxide, and iron oxide. These can be used alone or in combination of two or more.

Examples of the antistatic agent include a low molecular weight antistatic agent and a high molecular weight antistatic agent. Moreover, these may be an ion conduction type or an electron conduction type.
The low molecular weight antistatic agent includes an anionic antistatic agent; a cationic antistatic agent; a nonionic antistatic agent; an amphoteric antistatic agent; a complex compound; a metal alkoxide such as alkoxysilane, alkoxytitanium, alkoxyzirconium, and the like. Derivatives thereof: coated silica, phosphate, phosphate ester and the like. These can be used alone or in combination of two or more.
Examples of the polymer antistatic agent include vinyl copolymers having a sulfonic acid metal salt in the molecule, alkyl sulfonic acid metal salts, alkyl benzene sulfonic acid metal salts, and betaines. Furthermore, a polyamide elastomer, a polyester elastomer, etc. can also be used. These can be used alone or in combination of two or more.
The content of the antistatic agent is usually 1 to 20 parts by mass when the total of the components [A] and [B] is 100 parts by mass.

Examples of the filler include talc, mica, clay, calcium carbonate, silica, alumina, glass beads, glass balloons, milled fibers, and glass flakes. These can be used alone or in combination of two or more.
Content of the said filler is 1-35 mass parts normally, when the sum total of said component [A] and [B] is 100 mass parts.

As antibacterial agents, zeolite-based antibacterial agents such as silver-based zeolite and silver-zinc-based zeolite, silica gel-based antibacterial agents such as complexed silver-silica gel, glass-based antibacterial agents, calcium phosphate-based antibacterial agents, zirconium phosphate-based antibacterial agents, Inorganic antibacterial agents such as silicate antibacterial agents such as silver-magnesium aluminate, titanium oxide antibacterial agents, ceramic antibacterial agents, whisker antibacterial agents; formaldehyde releasing agents, halogenated aromatic compounds, road propargyl Derivatives, thiocyanato compounds, isothiazolinone derivatives, trihalomethylthio compounds, quaternary ammonium salts, biguanide compounds, aldehydes, phenols, pyridine oxide, carbanilide, diphenyl ether, carboxylic acids, organometallic compounds, etc .; inorganic / organic hybrids Antibacterial agent; natural antibacterial agent And the like. These can be used alone or in combination of two or more.
Content of the said antibacterial agent is 0.01-3 mass parts normally, when the sum total of said component [A] and [B] is 100 mass parts.

  In the weather resistant resin composition of the present invention, the content of the ethylene / α-olefin rubber polymer (a1) derived from the component [A] is 6 to 35% by mass, preferably 7 to 34% by mass. %, More preferably 7 to 30% by mass. When the content of the ethylene / α-olefin rubber polymer (a1) is in the above range, the balance of molding processability, weather resistance and impact resistance is excellent. If the content of the ethylene / α-olefin rubber polymer (a1) is too small, the weather resistance and impact resistance are inferior. If it is too much, the moldability is inferior.

  In the weather resistant resin composition of the present invention, the content of the vinyl cyanide compound unit derived from the polymer component contained is 25 to 35% by mass, preferably 26 to 35% by mass, more preferably 27 to 27%. 34% by mass. When the content of the vinyl cyanide compound unit is in the above range, the balance between weather resistance and impact resistance is excellent. In addition, when there is too little content of this vinyl cyanide compound unit, a weather resistance will be inferior, and when too much, a weather resistance and impact resistance will be inferior.

  The weather resistant resin composition of the present invention can be prepared by kneading raw material components using an extruder, a Banbury mixer, a kneader, a roll, a feeder ruder, etc., and can be formed into pellets of a predetermined shape. . The kneading temperature is usually 180 ° C to 300 ° C, preferably 190 ° C to 280 ° C. The method of using the raw material components is not particularly limited, and the respective components may be mixed and kneaded in a lump, or may be mixed and mixed in multiple stages.

  The weather resistant resin composition of the present invention is suitable for molding methods such as injection molding, extrusion molding (film extrusion molding, sheet extrusion molding, profile extrusion molding), vacuum molding, press molding, blow molding, injection press and the like. The obtained molded article exhibits a dark color, and the L value measured by a multi-light source spectrometer or the like is 50 or less, preferably 48 or less, more preferably 45 or less. When this L value is too large, the weather resistance is poor.

  The weather resistant resin composition of the present invention gives a molded article excellent in weather resistance and impact resistance, and when this molded article is subjected to a xenon weather meter weather resistance test, the color change ΔE before and after the test is preferably It can be 7 or less, more preferably 6 or less, and still more preferably 5 or less. When the molded product is subjected to the above test, the gloss after the test with respect to the gloss before the test is preferably 80% or more, more preferably 83% or more, and still more preferably 85% or more. it can.

  The weather-resistant resin composition of the present invention is suitable as a molding material for molded products used in the fields of vehicles / ships, furniture / building materials, sports equipment, OA / home appliances, toys and the like. In particular, because it gives molded products with excellent weather resistance and impact resistance, vehicles such as radiator grills, pillars, door mirror parts, license garnishes, moldings, fenders, bumpers, front grills, cowls, wiper arms, roof rails, air spoilers, etc. It is suitable as a molding material for a molded product that is used outdoors for a long period of time, typified by an outer plate member.

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

1. Raw material components The components used in the production of the composition are shown below.
1-1. Ingredient [A]
(1) A-1
Styrene and acrylonitrile in the presence of an ethylene / α-olefin rubber having a Mooney viscosity of 33, consisting of 63% ethylene units, 32% propylene units and 5% dicyclopentadiene units in a toluene solvent and having a Mooney viscosity (ML _{1 + 4} , 100 ° C.) of 33 It is a rubber-reinforced vinyl resin obtained by solution polymerization of a vinyl monomer comprising: tert-butyl peroxyisopropyl monocarbonate at 100 ° C. using a polymerization initiator. This rubber-reinforced vinyl resin has a graft ratio of 61%, an ethylene / α-olefin rubber content of 30%, a styrene unit amount of 45.5%, and an acrylonitrile unit amount of 24.5%. The acrylonitrile unit amount of the acetone-soluble component is 35%.
(2) A-2
It is a rubber reinforced vinyl resin obtained in the same manner as A-1. This rubber-reinforced vinyl resin has a graft ratio of 72%, an ethylene / α-olefin rubber content of 20%, a styrene unit amount of 56.0%, and an acrylonitrile unit amount of 24.0%. The acrylonitrile unit amount of the acetone-soluble component is 30%.
(3) A-3
It is a rubber reinforced vinyl resin obtained in the same manner as A-1. This rubber-reinforced vinyl resin has a graft ratio of 54%, an ethylene / α-olefin rubber content of 40%, a styrene unit amount of 37%, and an acrylonitrile unit amount of 23%. Moreover, the acrylonitrile unit amount of an acetone soluble component is 38.3%.
(4) A-4
It is a rubber reinforced vinyl resin obtained in the same manner as A-1. This rubber-reinforced vinyl resin has a graft ratio of 59%, an ethylene / α-olefin rubber content of 30%, a styrene unit amount of 55%, and an acrylonitrile unit amount of 15%. The acrylonitrile unit amount of the acetone-soluble component is 21.4%.
(5) A′-1
This resin is a rubber-reinforced vinyl resin used in the comparative example.
A rubber-reinforced vinyl resin obtained by emulsion polymerization of a vinyl monomer composed of styrene and acrylonitrile at a temperature of 70 ° C. using cumene hydroperoxide as a polymerization initiator in the presence of polybutadiene rubber. This rubber-reinforced vinyl resin has a graft ratio of 62%, a polybutadiene rubber content of 30%, a styrene unit amount of 45.6%, and an acrylonitrile unit amount of 24.4%. The acrylonitrile unit amount of the acetone-soluble component is 34.9%.

1-2. Ingredient [B]
(1) B-1
A styrene / acrylonitrile copolymer comprising 66% styrene units and 34% acrylonitrile units. The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) is 0.52 dl / g.
(2) B-2
It is a styrene / acrylonitrile copolymer composed of 62% styrene units and 38% acrylonitrile units. The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) is 0.52 dl / g.
(3) B-3
It is a styrene / acrylonitrile copolymer composed of 60% styrene units and 40% acrylonitrile units. The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) is 0.52 dl / g.
(4) B-4
It is a styrene / acrylonitrile copolymer composed of 60% styrene units and 40% acrylonitrile units. The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) is 0.40 dl / g.
(5) B-5
It is a styrene / acrylonitrile copolymer composed of 58% styrene units and 42% acrylonitrile units. The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) is 0.51 dl / g.
(6) B-6
This copolymer is the styrene / acrylonitrile copolymer used in the comparative example.
A styrene / acrylonitrile copolymer comprising 68% styrene units and 32% acrylonitrile units. The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) is 0.52 dl / g.

1-3. Ingredient [C]
Carbon black was used.
1-4. Ingredient [D]
Lauryl diethanolamine (trade name “TB-128K”, manufactured by Matsumoto Yushi Seiyaku Co., Ltd.) was used.
1-5. Ingredient [E]
2- (2′-hydroxy-5′-methylphenyl) benzotriazole (trade name “Tomisoap 100”, manufactured by Yoshitomi Fine Chemical Co., Ltd.) and bis (2,2,6,6-tetramethyl-4-piperidyl sepacate (product) A 1: 1 mixture of the name “Adekastab LA-77”) was used, which is known as a weathering improver.

2. Production of weather resistant resin composition and evaluation thereof Examples 1 to 9 and Comparative Examples 1 to 21
After supplying said component [A]-[E] to the Henschel mixer in the ratio of Table 1-Table 3, and mixing for 3 minutes at room temperature, a twin-screw extruder (model name "TEX44", Nippon Steel) Melt-kneading (barrel temperature: 220 ° C.) using the Tokushu company. Then, this was made into a pellet (weather resistant resin composition).

  The following evaluation was performed about the obtained weather resistant resin composition. The results are shown in Tables 1 to 3. In addition, the test piece used for evaluation of weather resistance and impact resistance both uses an injection molding machine (model name “J-100E”, manufactured by Nippon Steel Works), barrel temperature 220 ° C. and mold temperature 50 It was produced under the condition of ° C.

(1) Weather resistance Using a super xenon weather meter (model name “SX75”, manufactured by Suga Test Instruments Co., Ltd.), a test piece having a length of 80 mm, a width of 55 mm, and a thickness of 2.5 mm was subjected to a rain cycle of 18 minutes / 120 minutes. The sample was exposed for 370 hours at a black panel temperature of 63 ° C. and an irradiation energy of 180 W / m ² , and color change ΔE and gloss retention before and after the exposure were determined.
The color change ΔE is measured using the multi-light source spectrometer (manufactured by Suga Test Instruments Co., Ltd.) by colorimetry by the SCE method, and the color change Lab (L: lightness, a: redness, b: yellowness) is measured. It was calculated by the following formula.
ΔE = √ [(L ₁ −L ₂ ) ² + (a ₁ −a ₂ ) ² + (b ₁ −b ₂ ) ² ]
(In the formula, L ₁ , a ₁ and b ₁ represent values before exposure, and L ₂ , a ₂ and b ₂ represent values after exposure.)
The smaller the value of ΔE, the smaller the degree of color change and the better the color tone. Note that L ₁ means “L value of molded product” in the detailed description.
Further, the gloss retention rate is determined by measuring the glossiness of the surface of the test piece before and after exposure according to JIS K7105 using a digital gloss meter (model name “GM-26D”, manufactured by Murakami Color Research Laboratory Co., Ltd.) at an angle of measurement of 60 degrees. After the measurement, the glossiness after exposure / the glossiness before exposure was determined.
(2) Charpy impact strength Measured according to ISO 179.
(3) Melt mass flow rate (MFR)
According to ISO 1133, measurement was performed under conditions of a temperature of 220 ° C. and a load of 10 kgF.

From Tables 1 to 3, the following is clear.
Comparative Example 1 4, the content of the component [C] is a small example outside the scope of the present invention, L value of the molded article is more than 50, poor weather resistance. Comparative Example 15 is an example in which the component [B] having a vinyl cyanide compound unit content of less than 33% by mass is used, and the weather resistance is poor. Comparative Example 16 is an example in which the content of the ethylene / α-olefin rubber in the composition is less than 6% by mass, and the weather resistance and impact resistance are inferior. Comparative Example 17 is an example in which the content of the vinyl cyanide compound unit in the composition is less than 25% by mass, and the weather resistance is inferior. Comparative Example 18 is an example in which the content of the component [A] is small outside the scope of the present invention, and the content of the component [B] is large outside the scope of the present invention, and weather resistance and impact resistance Is inferior. Comparative Example 19 is an example in which the content of the component [A] is large outside the scope of the present invention, and the content of the component [B] is small outside the scope of the present invention, and the weather resistance is poor. The comparative example 20 is an example using an ABS resin in place of the component [A] according to the present invention, and is inferior in weather resistance. Moreover, although the comparative example 21 is an example which mix | blended component [E] (weathering improver) with respect to the composition of the comparative example 15 , the weather resistance made into the objective of this invention was not acquired.
On the other hand, Examples 1-3 and Examples 5-9 are examples containing an amine compound [D], and are more weatherproof than the compositions of the corresponding Comparative Examples 1-3, 6, 8, 10 and 12. Had improved.

  The weather-resistant resin composition of the present invention is suitable as a molding material for molded products used in the fields of vehicles / ships, OA / home appliances, furniture / building materials, sports goods, toys and the like. In particular, because it gives molded products with excellent weather resistance and impact resistance, vehicles such as radiator grills, pillars, door mirror parts, license garnishes, moldings, fenders, bumpers, front grills, cowls, wiper arms, roof rails, air spoilers, etc. It is suitable as a molding material for a molded product that is used outdoors for a long period of time, typified by an outer plate member.

Claims (4)

[A] Rubber-reinforced vinyl obtained by polymerizing a vinyl monomer (a2) containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of an ethylene / α-olefin rubber polymer (a1) Rubber-reinforced resin containing a resin,
[B] A copolymer containing an aromatic vinyl compound unit and a vinyl cyanide compound unit, wherein the content ratio of the vinyl cyanide compound unit is 100 masses of the total of monomer units constituting the copolymer. %, When the copolymer is 33 to 40 % by mass,
[C] a colorant;
[D] an amine compound represented by the following general formula (I) :
A weather resistant resin composition comprising:
The content ratio of the rubber-reinforced resin [A] and the copolymer [B] is 25 to 75% by mass and 75 to 25% by mass, respectively, when the total of both is 100% by mass,
The content of the colorant [C] is 0.05 to 5 parts by mass when the total of the rubber-reinforced resin [A] and the copolymer [B] is 100 parts by mass,
The content of the amine compound [D] is 0.1 to 10 parts by mass when the total of the rubber-reinforced resin [A] and the copolymer [B] is 100 parts by mass,
The content of the ethylene / α-olefin rubbery polymer (a1) contained in the weather resistant resin composition is 6 to 35% by mass,
The content of the vinyl cyanide compound unit contained in the weather resistant resin composition is 25 to 35% by mass, and
A weather resistant resin composition, wherein an L value of a molded article comprising the weather resistant resin composition is 50 or less.

[Wherein, R is an alkyl group having 8 to 22 carbon atoms or an alkenyl group having 8 to 22 carbon atoms, and Y and Z are the same or different and are divalent organic groups represented by the following:

One of them. m and n are integers of 1 or more, and the sum of m and n is an integer of 2 to 5. ] The weather resistant resin composition according to claim 1, wherein the colorant [C] is carbon black.   3. The weather resistant resin composition according to claim 1, wherein when the molded product comprising the weather resistant resin composition is subjected to a xenon weather meter weather resistance test, the color change ΔE before and after the test is 7 or less.   The glossiness after the test with respect to the glossiness before the test is 80% or more when the molded product comprising the weatherable resin composition is subjected to a xenon weather meter weatherability test. Weather resistant resin composition.