JP4530327B2 - Synthetic resin composition containing zinc sulfide with improved weather resistance - Google Patents

Description

  The present invention relates to a resin composition having improved weather resistance, in which zinc sulfide, a hindered amine compound having a specific structure and a benzoate compound are blended with a synthetic resin (hereinafter simply referred to as “resin”), and a resin molded article using the same. . The resin molded product is suitably used as an article used outdoors, particularly for automobile exterior applications.

  Conventionally, titanium oxide is generally used as a white pigment of a resin composition. However, Japanese Patent No. 2813559 discloses that, for long fiber reinforced polyolefin resin and the like, it is preferable to use zinc sulfide because titanium oxide lowers the mechanical strength (see, for example, Patent Document 1).

However, although the decrease in mechanical strength can be suppressed by using zinc sulfide, the weather resistance is greatly decreased. Therefore, JP-A-9-183869 discloses the use of a hindered amine compound and an ultraviolet absorber ( For example, see Patent Document 2).
Japanese Patent Laid-Open No. 2001-192468 proposes improving weather resistance by using a hindered amine compound having a molecular weight of 1000 or more (see, for example, Patent Document 3).

Japanese Patent No. 2813559 (page 2, left column, lines 37 to 42). JP-A-9-183869 (page 7, left column, line 5 to right column, line 4 and Tables 1 and 2). JP 2001-192468 A (Claim 1).

  Even if the hindered amine compound proposed in the prior art is used alone in the resin composition containing zinc sulfide or a resin composition containing it together with an ultraviolet absorber is used, the effect of improving weather resistance is not satisfactory. There wasn't. For this reason, improving the weather resistance of a resin molded product containing zinc sulfide useful as a white pigment has been still a problem to be solved.

  As a result of intensive studies in view of the present situation, the present inventors have formulated a resin composition having excellent weather resistance by blending a hindered amine compound having a specific structure and a benzoate ultraviolet absorber into a resin composition blended with zinc sulfide. The inventors have found that a product can be obtained and have reached the present invention.

（式中、Ｘは−Ｏ−を表し、Ｒはアルキル基を表し、Ａはエステル結合手を有してもよいアリール基を表し、Ｅは水素原子を表し、Ｑ_２はエステル結合手を有してもよいアルキレン基を表し、ｍは２を表し、Ｔは−Ｏ−、−ＮＲ^０−（Ｒ^０は水素原子または炭素原子数１〜８のアルキル基を表す。）、または単結合を表す。）

（式中、Ｒ^１、Ｒ^２は各々独立に炭素原子数１〜１２のアルキル基を、Ｒ^３は炭素原子数１〜３０のアルキル基または炭素原子数４〜６のシクロアルキル基を表す。）
本発明の第２は、ヒンダードアミン化合物（ＩＩ）が、ビス（１−オクトキシ−２，２，６，６−テトラメチル−４−ピペリジル）セバケートである本発明の第１記載の樹脂組成物を提供する。
本発明の第３は、合成樹脂がポリオレフィンである本発明の第１または第２記載の樹脂組成物を提供する。
本発明の第４は、合成樹脂１００重量部にガラス繊維０．１〜２００重量部を配合した本発明の第１〜第３のいずれかに記載の樹脂組成物を提供する。 That is, the first of the present invention has a structure represented by (A) 0.1 to 20 parts by weight of zinc sulfide and (B) general formula (I) or (II) with respect to 100 parts by weight of the synthetic resin. A resin composition comprising 0.01 to 20 parts by weight of a hindered amine compound and 0.01 to 20 parts by weight of a benzoate compound represented by (C) the general formula (III) is provided.

(In the formula, X represents —O—, R represents an alkyl group, A represents an aryl group which may have an ester bond , E represents a hydrogen atom, and Q ₂ has an ester bond. Represents an alkylene group , m represents 2, T represents —O—, —NR ⁰ — (R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), or a single bond; To express.)

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 12 carbon atoms, and R ³ represents an alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 4 to 6 carbon atoms). )
A second aspect of the present invention provides the resin composition according to the first aspect of the present invention, wherein the hindered amine compound (II) is bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate. To do.
A third aspect of the present invention provides the resin composition according to the first or second aspect of the present invention, wherein the synthetic resin is a polyolefin.
4th of this invention provides the resin composition in any one of 1st- 3rd of this invention which mix | blended 0.1-200 weight part of glass fibers with 100 weight part of synthetic resins.

  According to the present invention, it is possible to provide a resin composition having excellent weather resistance in a synthetic resin blended with zinc sulfide.

The present invention will be described in detail below.
Examples of the resin used in the present invention include polypropylene, high-density polyethylene, low-density polyethylene, linear low-density polyethylene, α-olefin polymers such as polybutene-1, poly-4-methylpentene-1, and ethylene-vinyl acetate. Polymers, polyolefins such as ethylene-propylene copolymers and copolymers thereof; polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, polyvinylidene fluoride, chlorinated rubber, vinyl chloride-vinyl acetate copolymer , Vinyl chloride-ethylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer Combined with vinyl chloride-cyclohexylmaleimide Halogen-containing resins such as coalescence; petroleum resin, coumarone resin, polystyrene, polyvinyl acetate, acrylic resin, styrene and / or α-methylstyrene and other monomers (for example, maleic anhydride, phenylmaleimide, methyl methacrylate, Butadiene, acrylonitrile, etc.) (for example, AS resin, ABS resin, MBS resin, heat-resistant ABS resin, etc.); polymethyl methacrylate, acrylic resin; polyvinyl acetate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral; polyethylene terephthalate And linear polyesters such as polytetramethylene terephthalate: polyamides such as polycaprolactam and polyhexamethylene adipamide; polycarbonates, branched polycarbonates; polyacetals; polyphenylene oxides Polyphenylene sulfide, polyurethane; liquid crystalline polymers; aliphatic polyesters derived from aliphatic dicarboxylic acids, aliphatic diols, aliphatic hydroxycarboxylic acids or cyclic compounds thereof, and aliphatic polyesters whose molecular weight is increased by diisocyanate, etc. Decomposable resins; Thermoplastic resins such as thermoplastic resins such as fiber-based resins and blends thereof, phenol resins, urea resins, melamine resins, epoxy resins, and unsaturated polyester resins. Furthermore, elastomers such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, and styrene-butadiene copolymer rubber may be used. These resins may be recycled resins.

  The above resins are average molecular weight, molecular weight distribution, specific gravity, melt viscosity, ratio of insoluble matter in solvent, presence or type of stereoregularity, type of catalyst used in polymerization, presence or absence of deactivation treatment / removal treatment of catalyst residue It is used regardless of the physical characteristics such as the method, presence / absence / type / concentration of metal components and acid components remaining in the catalyst-derived resin, impact strength and elastic modulus.

  The hindered amine compound used in the present invention has a structure represented by the general formula (I) or (II). In the formula, R represents an alkyl group, E represents a hydrogen atom, and the monovalent organic group represented by A includes an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, a heterocyclic organic group, and a substituent. Halogen atom, hydroxy group, alkoxy group, glycidyl group, glycidyloxy group, alkenyloxy group, alkylcarbonyloxy group, alkenylcarbonyloxy group, alkyl group having isocyanate group, alkenyl group, cycloalkyl group, cycloalkenyl group, aryl group Or the above-described group having an ether bond, an ester bond, a urethane bond, a urea bond, or a carbonate bond as an interrupting bond.

Examples of the ring structure in which A and E are bonded to each other include the following structures.

  The divalent organic group represented by Y and L is not particularly limited, and examples thereof include alkylene groups such as methylene, ethylene, propylene, and tetramethylene; cycloalkylene groups such as 1,4-cyclohexylene; phenylene, An arylene group such as naphthylene; an alkylene group interrupted by an ether bond, an ester bond or an amide bond; an alkylene group substituted with a hydroxy group, a halogen atom or an amino group, a cycloalkylene group, an arylene group or a combination thereof; Can be mentioned.

The organic group represented by Q ₁ is not particularly limited, and may be aliphatic or aromatic, may have a cycloalkyl group or a heterocyclic ring, and has a bond such as an ester bond or an ether bond. It may have a substituent such as hydroxy and halogen. For example, examples of the divalent organic group include alkylene groups such as methylene, ethylene, propylene, tetramethylene, 2,2-dimethylpropylene, octamethylene, decamethylene; 1,3-cyclohexylene, 1,4-cyclohexylene, and the like. A cycloalkylene group; an arylene group such as 1,4-phenylene, 1,5-naphthylene, and 4,4′-biphenylene; an alkylene group such as 1,4-cyclohexanedimethylene and 1,3-phenyldimethylene is a cycloalkyl group; And groups interrupted by an aryl group; groups interrupted by an ether bond such as —CH ₂ CH ₂ —O—CH ₂ CH ₂ — and the like. Examples of the trivalent organic group include 1,2,3-propanetriyl, 2,4,6-tris ((propan-3-yl) amino) -1,3,5-triazine, 1,3,5- And tris (ethylene-2-yl) -1,3,5-triazine-2,4,6-trione.

The organic group represented by Q ₂ is not particularly limited, and may be aliphatic or aromatic, may have a cycloalkyl group or a heterocyclic ring, and has a bond such as an ester bond or an ether bond. It may have a substituent such as hydroxy and halogen. For example, examples of the divalent organic group include alkylene groups such as methylene, ethylene, propylene, tetramethylene, 2,2-dimethylpropylene, octamethylene, decamethylene; 1,3-cyclohexylene, 1,4-cyclohexylene, and the like. A cycloalkylene group; an arylene group such as 1,4-phenylene, 1,5-naphthylene, and 4,4′-biphenylene; an alkylene group such as 1,4-cyclohexanedimethylene and 1,3-phenyldimethylene is a cycloalkyl group; And groups interrupted by an aryl group; groups interrupted by an ether bond such as —CH ₂ CH ₂ —O—CH ₂ CH ₂ — and the like. Examples of the trivalent organic group include 1,2,3-propanetriyl, 2,4,6-tris ((propan-3-yl) amino) -1,3,5-triazine, 1,3,5- And tris (ethylene-2-yl) -1,3,5-triazine-2,4,6-trione.

  Examples of the compound represented by the general formula (I) or (II) include the following compound Nos. 1, 3 are mentioned.

  The method for synthesizing the hindered amine compound is not particularly limited, and is synthesized by a known method.

In the benzoate compound represented by the general formula (III), examples of the alkyl group represented by R ¹ and R ² include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, and tert-pentyl. Hexyl, heptyl, octyl and the like.

Similarly, the alkyl group represented by R ³ may be linear alkyl or branched alkyl, methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, pentyl, tert-pentyl, hexyl, heptyl, octyl. Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, behenyl and the like. Examples of the cycloalkyl group having 4 to 6 carbon atoms include cyclohexyl.

  Specific examples of the benzoate compound represented by the general formula (III) include the following compound Nos. 16-20 are mentioned.

  The method for synthesizing the above compound is not particularly limited, and the compound is produced by a known method.

  The synthetic resin composition of the present invention has a zinc sulfide content of 0.1 to 20 parts by weight, preferably 0.5 to 5 parts by weight, particularly preferably 1 to 5 parts by weight, based on 100 parts by weight of the synthetic resin. 0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably 0.1 to 1 part by weight, benzoate compound 0.01 to 20 parts by weight, preferably 0.1 to 5 parts by weight, particularly preferably Is preferably blended in an amount of 0.1 to 1 part by weight. If zinc sulfide is less than 0.1 part by weight, there is no effect as a white pigment, and if it is used more than 20 parts by weight, the mechanical strength of the resin decreases. If the hindered amine compound is less than 0.01 part by weight, there is no sufficient stabilizing effect, and if it is used in an amount of more than 20 parts by weight, the physical properties of the resin are lowered, or the appearance of the resin composition is impaired by bloom. If the benzoate compound is used in an amount of less than 0.01 parts by weight, there is no stabilizing effect.

  The synthetic resin composition of the present invention comprises a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, a hydroxyamine-based antioxidant, other ultraviolet absorbers, other hindered amine compounds, Nucleating agents, flame retardants, flame retardant aids, heavy metal deactivators, processability improvers, other pigments, fillers, plasticizers, metal soaps, hydrotalcites, antistatic agents, lubricants, foaming agents, prevention It is preferable to use a clouding agent, a fogging agent, a pigment and the like in combination.

  Examples of phenolic antioxidants include 2,6-di-tert-butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, stearyl (3,5-di-tert-butyl-4-hydroxyphenyl). ) Propionate, distearyl (3,5-di-tert-butyl-4-hydroxybenzyl) phosphonate, tridecyl 3,5-di-tert-butyl-4-hydroxybenzylthioacetate, thiodiethylenebis [(3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate], 4,4'-thiobis (6-tert-butyl-m-cresol), 2-octylthio-4,6-di (3,5-di-tert -Butyl-4-hydroxyphenoxy) -s-triazine, 2,2'-methylenebis (4-methyl) -6-tert-butylphenol), bis [3,3-bis (4-hydroxy-3-tert-butylphenyl) butyric acid] glycol ester, 4,4'-butylidenebis (2,6-di-tert-butylphenol) ), 4,4′-butylidenebis (6-tert-butyl-3-methylphenol), 2,2′-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2- Methyl-4-hydroxy-5-tert-butylphenyl) butane, bis [2-tert-butyl-4-methyl-6- (2-hydroxy-3-tert-butyl-5-methylbenzyl) phenyl] terephthalate, 1 , 3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) -2, 4,6-trimethylbenzene, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxyethyl] isocyanurate, tetrakis [methylene-3- (3 ′, 5 ′ -Di-tert-butyl-4'-hydroxyphenyl) propionate] methane {also known as tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl] methane}, 2-tert-butyl -4-methyl-6- (2-acryloyloxy-3-tert-butyl-5-methylbenzyl) phenol, 3,9-bis [ 2- (3-tert-butyl-4-hydroxy-5-methylhydrocinnamoyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, triethylene Examples include glycol bis [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate], α-tocopherol, β-tocopherol, γ-tocopherol, and δ-tocopherol. When added, the addition amount is in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the resin. Hereinafter, the same applies to other additives that may not be used.

  Phosphorus antioxidants include triphenyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite, tris (2,5-di-tert-butylphenyl) phosphite, tris (nonylphenyl) Phosphite, Tris (dinonylphenyl) phosphite, Tris (mono, dimixed nonylphenyl) phosphite, Diphenyl acid phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite , Diphenyldecyl phosphite, diphenyloctyl phosphite, di (nonylphenyl) pentaerythritol diphosphite, phenyl diisodecyl phosphite, tributyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, trilaur Ruphosphite, dibutyl acid phosphite, dilauryl acid phosphite, trilauryl trithiophosphite, bis (neopentylglycol) 1,4-cyclohexanedimethyldiphosphite, bis (2,4-di-tert-butylphenyl) penta Erythritol diphosphite, bis (2,5-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2 , 4-Dicumylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, tetra (C12-15 mixed alkyl) -4,4'-isopropylidene diphenyl phosphite, bis [2,2'-methyle Bis (4,6-diamilphenyl)]-isopropylidene diphenyl phosphite, tetratridecyl 4,4'-butylidenebis (2-tert-butyl-5-methylphenol) diphosphite, hexa (tridecyl) 1,1 , 3-tris (2-methyl-5-tert-butyl-4-hydroxyphenyl) butane triphosphite, tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite, 2,4,8,10 -Tetra-tert-butyl-6-fluoro-12-methyl-12H-dibenzo [d, g] [1,3,2] dioxaphosphocin, tris (2-[(2,4,8,10-tetra -Tert-butyldibenzo [d, f] [1,3,2] dioxaphospin-6-yl) oxy] ethyl) amine, 9,10- And dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 2-butyl-2-ethylpropanediol, 2,4,6-tri-tert-butylphenol monophosphite, and the like.

  Examples of sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra (β-dodecyl mercaptopropionate). Examples include β-alkyl mercaptopropionic acid esters.

  Examples of the hydroxylamine-based antioxidant include N, N-dibenzylhydroxylamine, N, N-diethylhydroxylamine, N, N-dioctylhydroxylamine, N, N-dilaurylhydroxylamine, N, N-didi Tetradecylhydroxylamine, N, N-dihexadecylhydroxylamine, N, N-dioctadecylhydroxylamine, N-hexadecyl-N-octadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, dicyclohexylhydroxylamine, hydrogenation And N, N-dialkylhydroxylamine derived from beef tallow amine.

  Examples of other ultraviolet absorbers include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 5,5′-methylenebis (2-hydroxy-4-methoxy). 2-hydroxybenzophenones such as benzophenone); 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-tert-octylphenyl) benzotriazole, 2- (2-hydroxy-3) , 5-Di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3) , 5-Dicumylphenyl) benzotriazole, 2,2'- Polyethylene glycol ester of tylene bis (4-tert-octyl-6-benzotriazolylphenol), 2- (2-hydroxy-3-tert-butyl-5-carboxyphenyl) benzotriazole, 2- [2-hydroxy-3 -(2-acryloyloxyethyl) -5-methylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] benzotriazole, 2- [2-hydroxy -3- (2-Methacryloyloxyethyl) -5-tert-octylphenyl] benzotriazole, 2- [2-hydroxy-3- (2-methacryloyloxyethyl) -5-tert-butylphenyl] -5-chlorobenzo Triazole, 2- [2-hydroxy- -(2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert -Amyl-5- (2-methacryloyloxyethyl) phenyl] benzotriazole, 2- [2-hydroxy-3-tert-butyl-5- (3-methacryloyloxypropyl) phenyl] -5-chlorobenzotriazole, 2- [2-hydroxy-4- (2-methacryloyloxymethyl) phenyl] benzotriazole, 2- [2-hydroxy-4- (3-methacryloyloxy-2-hydroxypropyl) phenyl] benzotriazole, 2- [2-hydroxy -4- (3-methacryloyloxy 2- (2-hydroxyphenyl) benzotriazoles such as propyl) phenyl] benzotriazole; 2- (2-hydroxy-4-methoxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- ( 2-hydroxy-4-hexyloxyphenyl) -4,6-diphenyl-1,3,5-triazine, 2- (2-hydroxy-4-octoxyphenyl) -4,6-bis (2,4-dimethyl) Phenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (3-C12-13 mixed alkoxy-2-hydroxypropoxy) phenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2- [2-hydroxy-4- (2-acryloyloxyethoxy) phenyl] -4,6-bis (4-methylphenyl) -1 3,5-triazine, 2- (2,4-dihydroxy-3-allylphenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4,6-tris 2- (2-hydroxyphenyl) -4,6-diaryl-1,3,5-triazines such as (2-hydroxy-3-methyl-4-hexyloxyphenyl) -1,3,5-triazine; phenyl Benzoates such as salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; 2-ethyl-2′-ethoxyoxanilide, 2- Substituted oxanilides such as ethoxy-4′-dodecyloxanilide; ethyl-α-cyano-β, β-diphenylacrylate, methyl-2-cyano-3-me -3-cyanoacrylates such as (p- methoxyphenyl) acrylate; various metal salts or metal chelates, especially mentioned salts or chelates of nickel or chromium and the like.

  Examples of other hindered amine compounds include 2,2,6,6-tetramethyl-4-piperidinol-1-oxy, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2 , 6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,2,2,6,6-pentamethyl-4-piperidylmethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl Methyl methacrylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis (2,2,6,6-tetramethyl-4-piperidyl) bis (Tridecyl) -1,2,3,4-butanetetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) .bis (tridecyl) -1,2,3,4-butane Tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-tert-butyl-4-hydroxybenzyl) malonate, 1- ( 2-hydroxyethyl) -2,2,6,6-tetramethyl-4-piperidinol / diethyl succinate polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) Hexa / Dibromoethane polycondensate, 1,6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-morpholino-s-triazine polycondensate, 1, 6-bis (2,2,6,6-tetramethyl-4-piperidylamino) hexane / 2,4-dichloro-6-tert-octylamino-s-triazine polycondensate, 1,5,8,12- Tetrakis [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-yl] -1,5,8,12- Tetraazadodecane, 1,5,8,12-tetrakis [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazine- 6-yl] -1,5,8,12-tetraaza Decane, 1,6,11-tris [2,4-bis (N-butyl-N- (2,2,6,6-tetramethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane 1,6,11-tris [2,4-bis (N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) amino) -s-triazin-6-ylamino] undecane 3,9-bis [1,1-dimethyl-2- [tris (2,2,6,6-tetramethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy] ethyl] -2,4,8,10 -Tetraoxaspiro [5.5] undecane, 3,9-bis [1,1-dimethyl-2- [tris (1,2,2,6,6-pentamethyl-4-piperidyloxycarbonyloxy) butylcarbonyloxy ]ethyl〕 2,4,8,10-tetra oxa spiro [5.5] undecane.

  Examples of the nucleating agent include aromatic carboxylic acid metal salts such as aluminum pt-butylbenzoate and sodium benzoate; sodium bis (2,4-di-tert-butylphenyl) phosphate, bis (2,4- Acid phosphate metal salts such as lithium di-tert-butylphenyl) phosphate, sodium-2,2′-methylenebis (4,6-di-tert-butylphenyl) phosphate; dibenzylidene sorbitol, bis (methylbenzylidene) Examples include polyhydric alcohol derivatives such as sorbitol.

  Heavy metal deactivators include N, N′-diphenyloxamide, N-salicyl-N′-salicyloylhydrazine, N, N′-bis (salicyloyl) hydrazine, 3-salicyloylamino-1,2 , 4-triazole, bis (benzylidene) oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenyl hydrazide, N, N′-diacetyladipoyl dihydrazide, N, N′-bis (salicyloyl) oxalyl dihydrazide, N, N′-bis (salicyloyl) thiopropionyl dihydrazide, disalicyloyl hydrazide decamethylene dicarboxylate, N, N′-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine Etc.

  Flame retardants include halogen flame retardants such as decabromobiphenyl ether and tetrabromobisphenol A; triphenyl phosphate, resorcinol / phenol / phosphate condensate, resorcinol / 2,6-xylenol / phosphate condensate, bisphenol A / Phosphoric acid ester compounds such as phenol-phosphoric acid condensates and phosphoric acid ester compounds of polyphenols and organic phosphorus flame retardants such as 9,10-dihydro-9-phospha-10-oxyphenanthrene-9-one; phosphoric acid Melamine, melamine cyanurate, nitrogen-based flame retardants; metal hydroxides such as magnesium hydroxide and aluminum hydroxide, and inorganic flame retardants such as red phosphorus and ammonium phosphate, flame retardants include antimony oxide, Metal oxides such as zirconium oxide and polytetrafluoroethylene Such as anti-drip agents such as silicone polymers.

  Other pigments may be organic or inorganic, black pigments such as carbon black; green pigments such as chromium oxide, chrome green, zinc green, copper chloride phthalocyanine green, phthalocyanine green, naphthol green, malachite green lake; ultramarine blue, Blue pigments such as bitumen, copper phthalocyanine blue, cobalt blue, phthalocyanine blue, phossky sky blue, indanthrene blue; red lead, bengara, basic zinc chromate, chrome vermilion vermilion, cadmium red, rose red, brilliant carmine , Brilliant scarlet, quinacridone red, risor red, vermilion, thioindigo red, mingamiya red, etc .; yellow lead, zinc yellow, yellow iron oxide, titanium yellow, first yellow, hansaiero , Aura Min rake, benzidine yellow, and yellow pigments such as indanthrene yellow.

  As the filler, glass fiber, carbon fiber, Kevlar fiber, talc, silica, calcium carbonate and the like are used. In particular, when a long fiber glass fiber is used, the composition of the present invention is preferable because it does not break the glass fiber. The filler is preferably surface-treated to improve the affinity with the resin. The filler is used in an amount of 5 to 200 parts by weight, preferably 10 to 100 parts by weight, based on 100 parts by weight of the resin.

  As the metal soap, metals such as magnesium, calcium, aluminum and zinc and salts of saturated or unsaturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and oleic acid are used. Moisture content, melting point, particle size, fatty acid composition, production method is a metathesis method by reaction of fatty acid salt of alkali metal and metal (hydroxide) or in the presence or absence of solvent of fatty acid and metal (water) oxide Regardless of whether it is a direct method in which the neutralization reaction is carried out below, it is used even if either fatty acid or metal is in excess.

  Hydrotalcites may be natural products or synthetic products, and may be those modified with an alkali metal such as lithium. In particular, the composition represented by the following general formula (IX) is preferable, and it can be used regardless of the presence or absence of crystal water or the presence or absence of surface treatment. Further, the particle size is not particularly limited, but it is desirable that the particle size is small as long as the characteristics as hydrotalcite are not lost. When the particle size is large, the dispersibility is lowered and the stabilization effect is reduced, and further, the physical properties such as mechanical strength and transparency of the obtained resin composition are lowered.

  The above-mentioned various blends are appropriately selected in terms of blending amount, quality, etc. according to the type of resin, processing conditions, and usage. In addition, as a method of adding to the resin, each compound is separately added to the resin, mixed with a Henschel mixer and then supplied to the processing machine, and any combination of compounds other than the resin as a mixture in advance A method of adding powder or granules into a resin, a method of adding a master pellet by blending at a high concentration in the resin, a method of adding to a resin, and an extruder having a plurality of supply ports. A known addition method such as a method of adding to the resin from the supply port is used.

  The processing method of the synthetic resin composition of the present invention is not particularly limited, and a known processing method is appropriately used depending on the resin used, the presence or absence of a filler, and the like. Examples of the processing method include injection molding, extrusion molding, coextrusion molding, blow molding, press molding, cast molding, roll molding, and the like.

  The use of the synthetic resin composition of the present invention is not particularly limited, but it is particularly preferably used for automotive exterior materials such as bumpers, building materials such as window frames, and other applications exposed to outdoor light.

〔Example〕
Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited by the examples.

[Example 1]
100 parts by weight of polypropylene resin (H-700: manufactured by Idemitsu Petrochemical Co., Ltd.), 2.0 parts by weight of zinc sulfide, tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxymethyl ] 0.05 part by weight of methane, 0.05 part by weight of tris (2,4-di-tert-butylphenyl) phosphite, 0.05 part by weight of calcium stearate and the hindered amine compound and benzoate compound listed in Table 1 at 250 ° C. Were extruded into pellets and injection molded at 260 ° C. to obtain a test piece having a thickness of 2 mm. The obtained test piece was evaluated as a bloom by visual evaluation for the presence or absence of surface blowout after 240 hours in a 120 ° C. oven. Moreover, the time until a crack occurred on the surface of the test piece was evaluated as weather resistance with a sunshine weatherometer (temperature 63 ° C., with water spray). The results are shown in Table 1. In addition, about bloom, the thing in which a blown-out thing is not recognized is set to (circle), the thing recognized to a part of surface is set to (triangle | delta), and the thing recognized on the whole surface is set to x.

[Example 2]
100 parts by weight of glass fiber reinforced polypropylene resin (Mostron L: manufactured by Idemitsu Petrochemical Co., Ltd., containing 30% by weight of glass fiber), 2.0 parts by weight of zinc sulfide, tetrakis [3- (3,5-di-tert-butyl -4-hydroxyphenylpropionyl) oxymethyl] methane 0.05 parts by weight, tris (2,4-di-tert-butylphenyl) phosphite 0.05 parts by weight, calcium stearate 0.05 parts by weight and Table 1 The hindered amine compound and the benzoate compound were extruded at 280 ° C. to give pellets, and injection molded at 280 ° C. to obtain a test piece having a thickness of 2 mm. The obtained test piece was evaluated as a bloom by visual evaluation for the presence or absence of surface blowout after 240 hours in a 120 ° C. oven. In addition, the time until cracks occurred on the surface of the test piece was evaluated as weather resistance with a sunshine weatherometer (temperature 63 ° C., with water spray). The results are shown in Table 2. In addition, about bloom, the thing in which a blown-out thing is not recognized as (circle), the thing recognized as a part of surface is set as (triangle | delta), and the thing recognized over the whole surface is set as x.

  Comparative compound 1 is not practical because it has a small stabilizing effect when used alone or in combination with benzoate and has a strong bloom. In Comparative Compound 2, although the bloom is small, the stabilization effect by itself is small, and the weather resistance improvement effect is small even in combination with the benzoate compound. The specific hindered amine compound of the present invention also has a small stabilizing effect with the comparative compound 3 which is a benzoate compound alone. However, when the specific hindered amine compound of the present invention and an alkylbenzoate compound are used in combination, the weather resistance is remarkably improved.

Claims (4)

(A) 0.1 to 20 parts by weight of zinc sulfide, (B) 0.01 to 20 parts by weight of a hindered amine compound having a structure represented by the general formula (I) or (II) with respect to 100 parts by weight of the synthetic resin (C) The resin composition which mix | blended 0.01-20 weight part of benzoate compounds represented by general formula (III).

(In the formula, X represents —O—, R represents an alkyl group, A represents an aryl group which may have an ester bond , E represents a hydrogen atom, and Q ₂ has an ester bond. Represents an alkylene group , m represents 2, T represents —O—, —NR ⁰ — (R ⁰ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms), or a single bond; To express.)

(Wherein R ¹ and R ² each independently represents an alkyl group having 1 to 12 carbon atoms, and R ³ represents an alkyl group having 1 to 30 carbon atoms or a cycloalkyl group having 4 to 6 carbon atoms). )   The resin composition according to claim 1, wherein the hindered amine compound (II) is bis (1-octoxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate. The resin composition according to claim 1 or 2 , wherein the synthetic resin is a polyolefin. The resin composition according to any one of claims 1 to 3 blended with glass fibers 0.1 to 200 parts by weight of a synthetic resin 100 parts by weight.