Resin additive composition, thermoplastic resin composition, and molded article thereof

Abstract

Provided are: a resin additive composition which is capable of imparting excellent physical properties to a thermoplastic resin and which has excellent flowability; a thermoplastic resin composition; and a molded article thereof. A resin additive composition containing (A) a phosphate ester compound represented by general formula (1) in which R1 to R4 each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, R5 represents an alkylene group having 1 to 4 carbon atoms, and (B) a fatty acid sodium salt represented by general formula (2) in which R6 represents a group introduced by an aliphatic organic acid having 7 to 30 carbon atoms, and the mass ratio (B) / (A) is 0.55-2.0. # imgabs0 #

Description

[0001] The present application is a divisional application of an application filed on March 2, 2017, with application number 201780014747.4, and invention name "resin additive composition, thermoplastic resin composition, and molded body thereof". Technical Field

[0002] The present invention relates to a resin additive composition, a thermoplastic resin composition (hereinafter also referred to as "resin composition"), and a molded product thereof, and more specifically, to a resin additive composition, a thermoplastic resin composition, and a molded product thereof that can impart excellent physical properties to a thermoplastic resin and have excellent fluidity. Background Art

[0003] Thermoplastic resins are widely used in various molded bodies such as building materials, automotive materials, household appliances / electronic materials, fiber materials, packaging materials, agricultural materials, housing materials for household appliances, daily necessities, films, sheets, and structural parts due to various physical properties such as molding processability and low specific gravity. In particular, polyolefin resins such as polyethylene, polypropylene, and poly-1-butene have excellent advantages such as molding processability, heat resistance, mechanical properties, and low specific gravity, and are generally used in a wide range of groceries, medical devices, food packaging materials, and automotive materials. However, in order to achieve such a wide range of uses, polyolefin resins need to meet the required physical properties.

[0004] It is known that the crystallization of polyolefin resins during molding can be controlled by adding a composition containing a crystal nucleating agent or a specific compound. Generally, polyolefin resins with promoted crystallization can obtain the following advantages: shortening the molding cycle time, or improving the transparency of the molded product of the polyolefin resin composition, or improving heat resistance and physical properties.

[0005] Known examples of crystal nucleating agents that promote the crystallization of polyolefin resins include carboxylic acid metal salts such as sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate, and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate, phosphate compounds such as sodium bis(4-tert-butylphenyl)phosphate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, and lithium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, dibenzylidene sorbitol, and diisocyanate. Polyol derivatives such as (methylbenzylidene) sorbitol, bis(3,4-dimethylbenzylidene) sorbitol, bis(p-ethylbenzylidene) sorbitol and bis(dimethylbenzylidene) sorbitol, and amide compounds such as N,N',N"-tri[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene dicarboxamide, and 1,3,5-tri(2,2-dimethylpropionamide)benzene.

[0006] Among these compounds, phosphate compounds are known as compounds that have a great effect on improving the transparency and physical properties of polyolefin resins and the crystallization effect. For example, Patent Document 1 proposes adding alkali metal compounds such as cyclic organic phosphate alkaline aluminum salts and alkali metal carboxylates, alkali metal β-diketones or alkali metal salt β-glyoxylates to polyolefins and polyethylene terephthalate. In addition, Patent Document 2 proposes a nucleating agent composition containing an acidic phosphate metal salt and an aliphatic organic acid metal salt, which shows that the transparency and flexural modulus of polyolefins are improved.

[0007] Furthermore, Patent Document 3 proposes a nucleating agent composition containing a lithium salt of a cyclic phosphate, a lithium salt of an aliphatic organic acid, and an aliphatic organic acid salt containing a divalent metal atom, which shows that the transparency of a polyolefin resin is improved. In addition, Patent Documents 4 to 9 propose polyolefin resin compositions in which a cyclic phosphate compound having a hydroxyl group is added during olefin polymerization, and a fatty acid metal salt, an antioxidant, etc. are further added after polymerization and melt-kneaded. In addition, Patent Document 10 proposes a composition containing an aromatic phosphate metal salt and a metal salt of Group I of a higher fatty acid.

[0008] On the other hand, in order to improve the impact resistance of thermoplastic resins, thermoplastic elastomers have been used in combination. However, there is a problem of reduced impact resistance when a nucleating agent is added. In response to such a problem, for example, in Patent Document 11, a composition formed by coordinating ethylene-propylene rubber and ethylene-based polymers in a specific polypropylene is proposed. In addition, in Patent Document 12, a composition formed by combining a specific polypropylene-based resin and a high-density polyethylene treated with ionizing radiation is proposed. Furthermore, in Patent Document 13, a nucleating agent composed of a partial metal salt of rosin acid is proposed in a resin composition comprising a propylene-based polymer and an elastomer. In addition, in Patent Document 14, a partially cross-linked composition of an ethylene-based copolymer comprising an ethylene·α-olefin copolymer and surface vinylsilane-modified inorganic particles is proposed as a modifier.

[0009] In addition, most thermoplastic resins are flammable substances, and flame retardancy is indispensable according to the purpose. As a method of flame retardancy, for example, Patent Document 15 proposes a method of adding inorganic hydroxides such as magnesium hydroxide, basic magnesium carbonate, hydrotalcite, and aluminum hydroxide to ethylene copolymers. In addition, Patent Document 16 proposes a flame retardant polymer composition formed by mixing 80 to 300 parts by weight of an inorganic hydroxide flame retardant with respect to 100 parts by weight of a copolymer of two ethylene-α-olefins. Patent Document 17 proposes a polypropylene molding material formed by mixing 0.1 to 0.5 parts by weight of a nucleating agent, 4 to 6% by weight of a flame retardant and a flame retardant aid with respect to 100 parts by weight of homopolypropylene.

[0010] Furthermore, it is known that when thermoplastic resins are subjected to the effects of heat, oxygen, light, etc., the physical properties of the resins are reduced due to molecular scission and molecular crosslinking, and the appearance deteriorates such as coloration and discoloration, which significantly impairs the product value. In order to solve such problems, various antioxidants / stabilizers such as phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, lactone stabilizers, hydroxylamine antioxidants, vitamin E antioxidants, hindered amine stabilizers, and ultraviolet absorbers are added and melt-kneaded using a processing machine such as an extruder to stabilize the thermoplastic resin composition.

[0011] Among them, hindered amine compounds and ultraviolet absorbers are known to impart a long-term and stable photostabilizing effect to olefin resins. For example, Patent Document 18 proposes a polypropylene composition in which a hindered amine compound and a nucleating agent are blended into polypropylene.

[0012] In addition, phosphorus-based antioxidants having a phosphate structure are known as compounds having a particularly high anti-discoloration effect, and are widely used because they may be combined with other stabilizers to exhibit a further synergistic effect.

[0013] Prior art literature

[0014] Patent Literature

[0015] Patent Document 1: Japanese Patent Application Laid-Open No. 7-48473

[0016] Patent Document 2: Japanese Patent Application Publication No. 2003-313444

[0017] Patent Document 3: Japanese Patent Application Publication No. 2005-54036

[0018] Patent Document 4: Japanese Patent Application Publication No. 2013-256628

[0019] Patent Document 5: Japanese Patent Application Publication No. 2014-95042

[0020] Patent Document 6: Japanese Patent Application Publication No. 2014-95043

[0021] Patent Document 7: Japanese Patent Application Publication No. 2014-95044

[0022] Patent Document 8: Japanese Patent Application Publication No. 2014-95045

[0023] Patent Document 9: Japanese Patent Application Publication No. 2014-95046

[0024] Patent Document 10: Japanese Patent Application Laid-Open No. 63-69853

[0025] Patent Document 11: Japanese Patent Application Laid-Open No. 8-059921

[0026] Patent Document 12: Japanese Patent Application Laid-Open No. 8-269262

[0027] Patent Document 13: Japanese Patent Application Laid-Open No. 9-071695

[0028] Patent Document 14: Japanese Patent Application Laid-Open No. 11-228753

[0029] Patent Document 15: Japanese Patent Application Laid-Open No. 8-316508

[0030] Patent Document 16: Japanese Patent Application Laid-Open No. 9-137010

[0031] Patent Document 17: Japanese Patent Application Publication No. 2003-41073

[0032] Patent Document 18: Japanese Patent Application Laid-Open No. 9-118793 Summary of the invention

[0033] Problem that the invention aims to solve

[0034] However, various nucleating agents have been studied, but there is still a need for a nucleating agent that has higher performance than that required of polyolefin resins and has further improved physical properties. In addition, phosphate compounds have poor fluidity as powders and are easily attached to the wall surface of a mixing tank, and improvement in fluidity is required from the viewpoints of transportability, workability, and metering properties.

[0035] In addition, these patent documents 11 to 14 limit the applicable resins, thereby limiting the scope of use. In addition, the nucleating agent effect is insufficient and unsatisfactory, and the rigidity is insufficient. Therefore, for the existing resin composition, the current situation is that it is difficult to highly satisfy the impact resistance and rigidity, and there is room for further improvement.

[0036] Furthermore, with the expansion of uses, the physical properties required for molded products also increase, and a nucleating agent that can further promote crystallization and impart other characteristics is required. It is known that fatty acid metal salts are used as dispersants for nucleating agents. However, in these documents, there is no suggestion or record that a resin additive composition formed by adjusting a phosphate compound and a fatty acid sodium salt in a specific ratio can impart an excellent nucleating agent effect. In addition, phosphorus-based antioxidants are additives with excellent anti-discoloration effects, but in molding methods with long thermal history such as film molding and bottle molding, the anti-discoloration effect sometimes becomes insufficient. However, when the amount of phosphorus-based antioxidants is increased and other additives are mostly used, there is a problem of damaging the original physical properties of the resin.

[0037] Therefore, an object of the present invention is to provide a resin additive composition having excellent fluidity, a thermoplastic resin composition, and a molded article thereof, which can impart excellent physical properties to a thermoplastic resin.

[0038] Another object of the present invention is to provide a thermoplastic resin composition and a molded article thereof, wherein the thermoplastic resin composition can provide a molded article having both excellent impact resistance and high rigidity.

[0039] Furthermore, another object of the present invention is to provide a thermoplastic resin composition and a molded article thereof, wherein the thermoplastic resin composition can provide a molded article having an excellent crystallization effect and an excellent effect of preventing discoloration due to thermal history.

[0040] Solutions for solving problems

[0041] The present inventors have conducted intensive studies to solve the above problems and, as a result, have found that the above problems can be solved by containing a fatty acid sodium salt at a specific ratio with respect to a specific nucleating agent, thereby completing the present invention.

[0042] That is, the resin additive composition of the present invention is characterized in that (A) the phosphoric acid ester compound represented by the following general formula (1) and (B) the fatty acid sodium salt represented by the following general formula (2) are in a mass ratio of (B) / (A)=0.55 to 2.0,

[0043]

[0044] (In formula (1), R 1 ~R 4 Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, and R 5 represents an alkylene group having 1 to 4 carbon atoms. ),

[0045]

[0046] (In formula (2), R 6 It represents a group introduced from an aliphatic organic acid having 7 to 30 carbon atoms. ).

[0047] The thermoplastic resin composition of the present invention is characterized by containing the resin additive composition of the present invention in an amount of 0.001 to 10 parts by mass of the phosphate ester compound (A) represented by the general formula (1) based on 100 parts by mass of the thermoplastic resin.

[0048] For the resin composition of the present invention, the thermoplastic resin is preferably a polyolefin resin. In addition, for the resin composition of the present invention, it is also preferred to further contain (C) 1 to 80 parts by mass of a thermoplastic elastomer and (D) 1 to 80 parts by mass of a filler. Furthermore, for the resin composition of the present invention, the (C) thermoplastic elastomer is preferably a copolymer of ethylene and α-olefin or a copolymer of ethylene and vinyl ester. Furthermore, for the resin composition of the present invention, it is preferred to further contain (E) 0.01 to 10 parts by mass of a phosphite compound represented by the following general formula (3),

[0049]

[0050] (In formula (3), R 7 , R 8 Each independently represents an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms. )

[0051] The molded article of the present invention is characterized by being produced using the thermoplastic resin composition of the present invention.

[0052] Effects of the Invention

[0053] According to the present invention, it is possible to provide a resin additive composition that can impart excellent physical properties to a thermoplastic resin and has excellent fluidity, a thermoplastic resin composition, and a molded article thereof.

[0054] Furthermore, according to the present invention, there can be provided a thermoplastic resin composition capable of providing a molded article having both excellent impact resistance and rigidity at a high level, and a molded article thereof.

[0055] Furthermore, according to the present invention, a thermoplastic resin composition and a molded article thereof can be provided, wherein the thermoplastic resin composition can provide a molded article having an excellent crystallization effect and an excellent effect of preventing discoloration due to thermal history. DETAILED DESCRIPTION

[0056] The embodiments of the present invention are described in detail below.

[0057] The resin additive composition of the present invention is a resin additive composition comprising (A) a phosphate compound represented by the above general formula (1) and (B) a fatty acid sodium salt represented by the following general formula (2), wherein the mass ratio (B) / (A) is 0.55 to 2.0. By satisfying the above conditions, the resin additive composition can impart excellent physical properties to the thermoplastic resin.

[0058] <(A) Phosphate ester compound represented by general formula (1)>

[0059] The phosphate compound of the resin additive composition of the present invention is represented by the following general formula (1).

[0060]

[0061] As R in the general formula (1) 1 ~R 4 The straight-chain or branched alkyl group having 1 to 9 carbon atoms represented by the above-mentioned group includes methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, isobutyl, pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, tert-octyl, 2-ethylhexyl, nonyl, isononyl, etc., and R 1 ~R 4 Tert-butyl is preferred.

[0062] As R in the general formula (1) 5 Examples of the alkylene group having 1 to 4 carbon atoms include a methylene group, an ethylene group, a propylene group, and a butylene group. In the resin composition of the present invention, a methylene group is preferred.

[0063] Specific examples of the compound represented by the general formula (1) include the following compounds. However, the resin additive composition of the present invention is not limited to these compounds.

[0064]

[0065] In the present invention, sodium [2,2′-methylenebis(4,6-di-tert-butylphenyl)phosphate] is preferred because it can impart excellent physical properties to a polyolefin-based resin.

[0066] <(B) Sodium fatty acid represented by general formula (2)>

[0067] The sodium fatty acid in the resin additive composition of the present invention is represented by the following general formula (2).

[0068]

[0069] R in the general formula (2) 6 The group introduced from an aliphatic organic acid having 7 to 30 carbon atoms includes hydrocarbon groups such as an alkyl group, an alkynyl group, an alkenyl group, and an alkyl group having two or more unsaturated bonds introduced therein having 7 to 30 carbon atoms. These may be substituted with a hydroxyl group and may have a branched chain.

[0070] Specifically, there can be mentioned saturated fatty acids such as decanoic acid, 2-ethylhexanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid, cerotic acid, montanic acid, triacontanoic acid, linear unsaturated fatty acids such as 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, α-linolenic acid, linoleic acid, γ-linolenic acid, octadecatetraenoic acid, octadecenic acid, oleic acid, elaidic acid, vaccenic acid, eicosapentaenoic acid, docosapentaenoic acid, docosahexaenoic acid, and aromatic fatty acids such as trimesic acid. For the resin additive composition of the present invention, aliphatic groups having 10 to 21 carbon atoms are preferred, and saturated fatty acids such as lauric acid, myristic acid, stearic acid, palmitic acid, and 12-hydroxystearic acid are particularly preferred because the effect of the resin additive composition of the present invention becomes significant.

[0071] In the resin additive composition of the present invention, the mass ratio of the phosphate compound represented by the general formula (1) (A) to the sodium salt of the fatty acid represented by the general formula (2) (B) / (A) is in the range of 0.55 to 2.0, more preferably 0.67 to 1.50. When the ratio of (B) to (A) is less than 0.55, the fluidity may be lacking, and when it is greater than 2.00, the nucleating agent effect may be poor.

[0072] The resin additive composition of the present invention is not limited by the particle state such as particle size and particle size distribution, but it is known that if the particle size of the phosphate compound represented by the general formula (1) (A) is fine, the dispersibility in the resin is good, and the volume average particle size is preferably 20 μm or less, and more preferably 10 μm or less.

[0073] Next, the thermoplastic resin composition of the present invention will be described.

[0074] The thermoplastic resin composition according to a preferred embodiment of the present invention contains the resin additive composition of the present invention in an amount of 0.001 to 10 parts by mass of the phosphate ester compound (A) represented by the general formula (1) based on 100 parts by mass of the plastic resin.

[0075] The resin that can be used in the resin composition of the present invention is not limited as long as it is a thermoplastic resin, but from the viewpoint of making the effect of the present invention significant, polyolefin resins, styrene resins, polyester resins, polyether resins, polycarbonate resins, polyamide resins, and halogen-containing resins are preferred, and polyolefin resins are more preferred.

[0076] Examples of the polyolefin resin include polyethylene, low-density polyethylene, linear low-density polyethylene, high-density polyethylene, cross-linked polyethylene, ultra-high molecular weight polyethylene, polypropylene, homopolymer polypropylene, random copolymer polypropylene, block copolymer polypropylene, isotactic polypropylene, syndiotactic polypropylene, hemi-isotactic polypropylene, polybutene, cycloolefin polymers, stereoblock polypropylene, α-olefin polymers such as poly-3-methyl-1-butene, poly-3-methyl-1-pentene, and poly-4-methyl-1-pentene, block or random copolymers of ethylene-propylene, impact copolymer polypropylene, α-olefin copolymers such as ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, and ethylene-vinyl acetate copolymers, polyfluoroolefins, and polyolefin-based thermoplastic elastomers, and copolymers of two or more thereof may be used.

[0077] Examples of styrene-based resins include vinyl-containing aromatic hydrocarbons alone and copolymers of vinyl-containing aromatic hydrocarbons and other monomers (e.g., maleic anhydride, phenylmaleimide, (meth)acrylate, butadiene, (meth)acrylonitrile, etc.), and examples thereof include polystyrene (PS) resins, high impact polystyrene (HIPS), acrylonitrile-styrene (AS) resins, acrylonitrile-butadiene-styrene (ABS) resins, methyl methacrylate-butadiene-styrene (MBS) resins, heat-resistant ABS resins, acrylonitrile-acrylate-styrene (AAS) resins, styrene-maleic anhydride (SMA) resins, methacrylate-styrene Thermoplastic resins such as styrene-isoprene-styrene (SIS) resin, acrylonitrile-ethylene propylene rubber-styrene (AES) resin, styrene-butadiene-butylene-styrene (SBBS) resin, methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin, and hydrogenated styrene-based elastomer resins such as styrene-ethylene-butylene-styrene (SEBS) resin, styrene-ethylene-propylene-styrene (SEPS) resin, styrene-ethylene-propylene (SEP) resin, and styrene-ethylene-ethylene-propylene-styrene (SEEPS) resin obtained by hydrogenating the double bonds of these butadiene or isoprene.

[0078] Examples of the polyester resin include polyalkylene terephthalates such as polyethylene terephthalate, polybutylene terephthalate, and polycyclohexanedimethylene terephthalate; aromatic polyesters such as polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate; linear polyesters such as polytetramethylene terephthalate; and degradable aliphatic polyesters such as polyhydroxybutyrate, polycaprolactone, polybutylene succinate, polyethylene succinate, polylactic acid, polymalic acid, polyglycolic acid, polydioxane, and poly(2-oxetanone).

[0079] Examples of the polyether resin include polyacetal, polyphenylene ether, polyether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone, polyether sulfone, and polyether imide.

[0080] Examples of the polycarbonate-based resin include polycarbonate, polycarbonate / ABS resin, and branched polycarbonate.

[0081] Examples of polyamide resins include polymers such as ε-caprolactam (nylon 6), undecanolactam (nylon 11), dodecanolactam (nylon 12), aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone, and α-piperidone; copolymers obtained by copolymerizing diamines such as hexamethylenediamine, nonanediamine, nonanemethylenediamine, methylpentamethylenediamine, undecanemethylenediamine, dodecanemethylenediamine, and meta-xylylenediamine with carboxylic acid compounds such as adipic acid, sebacic acid, terephthalic acid, isophthalic acid, dodecanedicarboxylic acid, and glutaric acid; and mixtures of polymers or copolymers thereof. In addition, aromatic polyamide resins such as "Kevlar" manufactured by Dupont, "Nomex" manufactured by Dupont, and "Twaron" and "Conex" manufactured by Teijin Limited.

[0082] Examples of the halogen-containing resin include 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-acrylate copolymer, vinyl chloride-maleate copolymer, and vinyl chloride-cyclohexylmaleimide copolymer.

[0083] Further examples of thermoplastic resins include petroleum resins, coumarone resins, polyvinyl acetate, acrylic resins, polymethyl methacrylate, polyvinyl alcohol, polyvinyl formal, polyvinyl butyral, polyphenylene sulfide, polyurethane, cellulose resins, polyimide resins, polysulfones, liquid crystal polymers and other thermoplastic resins and mixtures thereof.

[0084] In addition, the thermoplastic resin can be an elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene copolymer rubber, styrene-butadiene copolymer rubber, fluororubber, silicone rubber, polyester elastomer, nitrile elastomer, nylon elastomer, vinyl chloride elastomer, polyamide elastomer, polyurethane elastomer, and can also be used in combination.

[0085] For the thermoplastic resin composition of the present invention, these thermoplastic resins can be used alone or in combination of two or more. In addition, alloying can also be performed. It should be noted that these thermoplastic resins can be used regardless of molecular weight, degree of polymerization, density, softening point, ratio of insoluble components in solvent, degree of stereoregularity, presence or absence of catalyst residues, monomer types or blending ratios as raw materials, types of polymerization catalysts (e.g., Ziegler catalysts, metallocene catalysts, etc.), etc.

[0086] There is no particular limitation on the method of mixing the components (A) and (B) of the resin additive composition of the present invention into the thermoplastic resin, and the following commonly used methods can be cited: for example, a method of dry-mixing thermoplastic resin powder or pellets with each component; or a method of preparing a masterbatch containing any one of the components at a high concentration and adding it to the thermoplastic resin; or a method of processing the resin additive composition of the present invention into a pellet shape and adding it to the thermoplastic resin. In addition, each component may be added to the olefin resin simultaneously or separately.

[0087] As a method for processing into a pellet shape, for example, the following method can be used to produce: a mixture of the resin additive composition of the present invention, a phenolic antioxidant, and other additives optionally included as needed is heated, and mixed in the presence of a molten phenolic antioxidant. For processing conditions, processing machines, etc., known common processing methods and processing machines can be used without any limitation. As specific production methods, a disk pelletizer method, an extrusion method, etc. can be listed.

[0088] In the resin composition of the present invention, the amount of the resin additive composition to be blended with the thermoplastic resin is 0.001 to 10 parts by mass, more preferably 0.006 to 5 parts by mass, of the phosphate compound represented by the general formula (1) relative to 100 parts by mass of the thermoplastic resin. When the blending amount is less than 0.001 parts by mass, the effect of the nucleating agent may not be obtained, and when it exceeds 10 parts by mass, it may be difficult to disperse in the thermoplastic resin, which may adversely affect the physical properties and appearance of the molded product.

[0089] The resin additive composition or thermoplastic resin composition of the present invention may optionally contain known resin additives (for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet absorbers, hindered amine compounds, nucleating agents different from the phosphate compound represented by general formula (1) (A), flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents, pigments, fluorescent whitening agents, dyes, etc.) within a range that does not significantly impair the effects of the present invention.

[0090] Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 2-tert-butyl-4,6-dimethylphenol, styrenated phenol, 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,2'-thiobis-(6-tert-butyl-4-methylphenol), 2,2'-thiodiethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2-methyl-4,6-bis(octylsulfonylmethyl)phenol, 2,2'-isobutylenebis(4,6-dimethylphenol), isooctyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, N,N'-hexane-1,6-diylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionamide, 2 , 2'-oxalamide-bis[ethyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2-ethylhexyl-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate, 2,2'-ethylenebis(4,6-di-tert-butylphenol), ester of 3,5-di-tert-butyl-4-hydroxy-phenylpropionic acid and C13-15 alkyl, 2,5-di-tert-amylhydroquinone, polymer of hindered phenol (trade name "AO.OH.98" manufactured by ADEKAPALMAROLE Co., Ltd.), 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol], 2-tert-butyl-6-(3-tert-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate, 2-[1-(2-hydroxy -3,5-di-tert-pentylphenyl)ethyl]-4,6-di-tert-pentylphenyl acrylate, 6-[3-(3-tert-butyl-4-hydroxy-5-methyl)propoxy]-2,4,8,10-tetra-tert-butylbenzo[d,f][1,3,2]-dioxaphosphane, hexamethylenebis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, bis[monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate] calcium salt, 5,7-bis(1,1-dimethylethyl)-3-hydroxy-2(3H)-benzofuranone reaction product with o-xylene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazin-2-ylamino)phenol, DL-a-tocopherol (vitamin 2,6-bis(α-methylbenzyl)-4-methylphenol, bis[3,3-bis-(4'-hydroxy-3'-tert-butyl-phenyl)butyric acid]ethylene glycol ester, 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-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-bis(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]ethylene glycol ester, 4,4'-butylenebis(2,6-di-tert-butylphenol), 4,4'-butylenebis(6-tert-butyl-3-methylphenol), 2,2'-ethylenebis(4,6-di-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl 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)propionyl] oxyethyl] isocyanurate, tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]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-methylhydroxycinnamoyloxy)-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, triethylene glycol bis[β-( 3-(3,5-dialkyl-4-hydroxyphenyl) propionic acid derivatives such as 3-tert-butyl-4-hydroxyphenyl) propionic acid ester], stearyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, palmityl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, myristyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid amide, etc. These can be used alone or in combination of two or more. The amount of the phenolic antioxidant when mixed is 0.001 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, relative to 100 parts by mass of the thermoplastic resin. ,

[0091] Examples of the phosphorus antioxidant include triphenyl phosphite, diisooctyl phosphite, heptadecanyl phosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyltridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tri(dipropylene glycol)phosphite, dioleyl hydrogenated phosphite, trilauryl trithiophosphite, bis(tridecyl)phosphite, tri(isodecyl)phosphite, tri(tridecyl)phosphite, diphenyldecyl phosphite, dinonylphenylbis(nonylphenyl)phosphite, poly(dipropylene glycol)phenyl phosphite, tetraphenyldipropylene glycol diphosphite, trisnonylphenyl phosphite, tris(2,4-diisodecyl)phosphite, tert-butylphenyl) phosphite, tris(2,4-di-tert-butyl-5-methylphenyl) phosphite, tris〔2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl〕phosphite, tris(decyl) phosphite, octyl diphenyl phosphite, di(decyl) monophenyl phosphite, mixture of distearyl pentaerythritol and calcium stearate, alkyl (C10) bisphenol A phosphite, tetraphenyl-tetra(tridecyl) pentaerythritol tetraphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra(tridecyl) isopropylidene diphenol diphosphite, tetra(tridecyl)-4,4'-n-butylidene bis(2-tert-butyl-5-methylphenol) diphosphite, hexadecyl (Tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenyl diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propenyl-3-ylidene)tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexa(tridecyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-octadecylphosphite, 2,2'-ethylenebis(4,6-di-tert-butylphenyl)fluorophosphite, 4,4'-butylenebis(3-methyl) -6-tert-butylphenyl ditridecyl) phosphite, tris(2-[(2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphacin-6-yl)oxy]ethyl)amine, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propanediol phosphite, poly-4,4'-isopropylidene biphenol C12-15 alcohol phosphite, bis(diisodecyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, bis(octadecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite, etc. These can be used alone or in combination of two or more. The amount of the phosphorus antioxidant when mixed is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the thermoplastic resin. ,

[0092] Examples of the thioether antioxidant include tetrakis[methylene-3-(laurylthio)propionate]methane, bis(methyl-4-[3-n-alkyl(C12 / C14)thiopropionyloxy]5-tert-butylphenyl)sulfide, ditridecyl-3,3'-thiodipropionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl-3,3'-thiodipropionate, lauryl / stearylthiodipropionate, 4,4'-thiobis(6-tert-butyl-m-cresol), 2,2'-thiobis(6-tert-butyl-p-cresol), and distearyl disulfide. These may be used alone or in combination of two or more. The amount of the thioether antioxidant when added is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the thermoplastic resin.

[0093] Examples of the ultraviolet absorber include 2,4-dihydroxybenzophenone, 2-hydroxybenzophenones such as 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 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'-methylenebis(4-tert-octyl-6-benzotriazolylphenol), polyethylene glycol esters of 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-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-pentyl-5-(2-methacryloyloxyethyl) 2-(2-Hydroxyphenyl)benzotriazoles such as 2-(2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-3-tert-butyl-5-(3-methacryloxypropyl)phenyl)benzotriazole, 2-(2-hydroxy-4-(2-methacryloxymethyl)phenyl)benzotriazole, 2-(2-hydroxy-4-(3-methacryloxy-2-hydroxypropyl)phenyl)benzotriazole, 2-(2-hydroxy-4-(3-methacryloxypropyl)phenyl)benzotriazole, etc.; phenyl salicylate, resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy)benzoate, dodecyl (3,5-di-tert-butyl)benzoate Benzoates such as benzoic acid esters such as 2-ethyl-2'-ethoxy oxalanilide and 2-ethoxy-4'-dodecyl oxalanilide; cyanoacrylates such as ethyl-α-cyano-β,β-diphenylacrylate and methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; various metal salts or metal chelates, in particular, salts or chelates of nickel or chromium. These may be used alone or in combination of two or more.The amount of the ultraviolet absorber when added is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the thermoplastic resin.

[0094] Examples of the hindered amine compound include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate. bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4,4-pentamethyl-4-piperidinyl)-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-piperidinylamino)hexane / 2,4-dichloro -6-morpholinyl-s-triazine polycondensate, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)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-piperidinyl)amino)-s-triazine-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-piperidinyl)amino)-s-triazine-6-yl]-1,5, 8-12-Tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazine-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazine-6-yl]aminoundecane, bis{4-(1-octyloxy-2,2,6,6-tetramethyl)piperidinyl}decane dione ester, bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidinyl)carbonate, etc. These may be used alone or in combination of two or more. The amount of the hindered amine compound added is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the thermoplastic resin.

[0095] Examples of nucleating agents other than the phosphate compound represented by the general formula (1) (A) include carboxylic acid metal salts such as sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate, and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; polyol derivatives such as dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, and bis(dimethylbenzylidene)sorbitol; and amide compounds such as N,N',N"-tris[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene dicarboxamide and 1,3,5-tris(dimethylisopropylamino)benzene. These may be used alone or in combination of two or more. The amount of the nucleating agent when added is in the range of 0.001 to 10 parts by mass, more preferably 0.006 to 5 parts by mass, in total with the phosphate compound represented by the general formula (1) (A), relative to 100 parts by mass of the thermoplastic resin.

[0096] As fillers, for example, talc, mica, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, magnesium hydroxide, magnesium oxide, magnesium sulfate, aluminum hydroxide, barium sulfate, glass powder, glass fiber, clay, dolomite, silica, aluminum oxide, potassium titanate whisker, wollastonite, fibrous basic magnesium sulfate, etc. can be listed, and the particle size (fiber diameter, fiber length and aspect ratio when fibrous) can be appropriately selected for use. These can be used alone or in combination of two or more. In addition, fillers can use surface-treated substances as needed. The amount of the filler when mixed is 1 to 80 parts by mass, more preferably 3 to 50 parts by mass, and further preferably 5 to 40 parts by mass relative to 100 parts by mass of the thermoplastic resin.

[0097] Examples of the flame retardant include triphenyl phosphate, tricresyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dicresyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene)-4,1-phenylenetetraphenyl diphosphate, 1,3-phenylenetetra(2,6-dimethylphenyl) phosphate, and ADK STAB FP-500, ADK STAB FP-600, and ADK STAB FP-700 manufactured by ADEKA Corporation. Aromatic phosphates of "FP-800", phosphonates such as divinyl phenylphosphonate, diallyl phenylphosphonate, (1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, methyl diphenylphosphinate, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives, phosphonates such as bis(2-allylphenoxy)phosphazene, dimethylphenylphosphazene, phosphazene compounds such as melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melem polyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds, phosphorus-based flame retardants such as red phosphorus, magnesium hydroxide, aluminum hydroxide Brominated flame retardants such as metal hydroxides, brominated bisphenol A epoxy resin, brominated phenol novolac epoxy resin, hexabromobenzene, pentabromotoluene, ethylenebis(pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1,2-dibromoethyl)cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis(tribromophenoxy)ethane, brominated polyphenylene ether, brominated polystyrene and 2,4,6-tris(tribromophenoxy)-1,3,5-triazine, tribromophenyl maleimide, tribromophenyl acrylate, tribromophenyl methacrylate, tetrabromobisphenol A dimethacrylate, pentabromobenzyl acrylate and brominated styrene. These can be used alone or in combination of two or more. These flame retardants are preferably used in combination with anti-drip agents such as fluororesins, polyols, flame retardant aids such as hydrotalcite. The amount of the flame retardant when blended is 1 to 100 parts by mass, more preferably 10 to 70 parts by mass, based on 100 parts by mass of the thermoplastic resin.

[0098] As a lubricant, it is added for the purpose of imparting lubricity to the surface of the molded body and improving the anti-scratch effect. Examples of lubricants include: unsaturated fatty acid amides such as oleamide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide, butyl stearate, stearyl alcohol, stearic acid monoglyceride, sorbitan monopalmitate, sorbitan monostearate, mannitol, stearic acid, hardened castor oil, stearic acid amide, oleic acid amide, ethylenebisstearic acid amide, etc. These can be used alone or in combination of two or more. The amount of the lubricant when mixed is 0.01 to 2 parts by mass, more preferably 0.03 to 0.5 parts by mass, relative to 100 parts by mass of the thermoplastic resin.

[0099] Hydrotalcites are known as natural or synthetic complex salt compounds formed of magnesium, aluminum, hydroxyl, carbonate and any crystal water, and include: substances in which a part of magnesium or aluminum is replaced by other metals such as alkali metals and zinc; substances in which hydroxyl and carbonate are replaced by other anionic groups. Specifically, for example, substances in which the metal of the hydrotalcite represented by the following general formula (4) is replaced by an alkali metal. In addition, as Al-Li hydrotalcites, compounds represented by the following general formula (5) can also be used.

[0100] Mg x1 Zn x2 Al2(OH) 2(x1+x2)+4 (CO3)pH2O (4)

[0101] Here, in the general formula (4), x1 and x2 represent numbers that satisfy the conditions represented by the following formulas: 0≤x2 / x1<10, 2≤x1+x2≤20, respectively, and p represents 0 or a positive number.

[0102] [Li 1 / 3 Al 2 / 3 (OH)2]·[A q- 1 / 3q pH2O] (5)

[0103] Here, in the general formula (5), Aq- represents a q-valent anion, and p represents 0 or a positive number. In addition, a part of the carbonate anions in these hydrotalcites may be replaced by other anions.

[0104] The hydrotalcites may be those obtained by dehydrating the crystal water, or may be those coated with higher fatty acids such as stearic acid, higher fatty acid metal salts such as oleic acid alkali metal salts, organic sulfonic acid metal salts such as dodecylbenzenesulfonic acid alkali metal salts, higher fatty acid amides, higher fatty acid esters, or waxes.

[0105] Hydrotalcites can be natural or synthetic. As a method for synthesizing hydrotalcite compounds, there can be cited the known methods described in Japanese Patent Publication No. 46-2280, Japanese Patent Publication No. 50-30039, Japanese Patent Publication No. 51-29129, Japanese Patent Publication No. 3-36839, Japanese Patent Publication No. 61-174270, Japanese Patent Publication No. 5-179052, etc. In addition, hydrotalcites can be used without being restricted by their crystal structure, crystal particles, etc. These can be used alone or in combination of two or more. The amount of the hydrotalcites when mixed is 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, relative to 100 parts by mass of the thermoplastic resin.

[0106] As antistatic agents, for example, cationic antistatic agents such as fatty acid quaternary ammonium ion salts and polyamine quaternary salts can be listed; anionic antistatic agents such as higher alcohol phosphate ester salts, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic alkyl sulfonates, higher alcohol sulfate ester salts, higher alcohol ethylene oxide adduct sulfate ester salts, and higher alcohol ethylene oxide adduct phosphate ester salts; nonionic antistatic agents such as polyol fatty acid esters, polyethylene glycol phosphate esters, and polyoxyethylene alkyl allyl ethers; amphoteric antistatic agents such as amphoteric alkyl betaines such as alkyl dimethylaminoacetic acid betaine, and imidazoline type amphoteric active agents. These can be used alone or in combination of two or more. The amount of the antistatic agent when mixed is 0.03 to 2 parts by mass, more preferably 0.1 to 0.8 parts by mass, relative to 100 parts by mass of the thermoplastic resin.

[0107] As the pigment, commercially available pigments can be used, for example, Pigment Red 1, 2, 3, 9, 10, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 1 85, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 1 2, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 29, 56, 60, 61, 62, 64; Pigment Violet 1, 15, 19, 23, 27, 29, 30, 32, 37, 40, 50, etc. These may be used alone or in combination of two or more.

[0108] Examples of the dye include azo dyes, anthraquinone dyes, indigo dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, acridine dyes, stilbene dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxazine dyes, phthalocyanine dyes, and cyanine dyes. These may be used alone or in combination of two or more.

[0109] Fluorescent whitening agents are compounds that absorb ultraviolet rays from sunlight and artificial light, convert them into purple to blue visible light, and radiate fluorescence to promote the whiteness and blueness of the molded body. Examples of fluorescent whitening agents include benzoxazole compounds CI Fluorescent Brightner 184; coumarin compounds CI Fluorescent Brightner 52; diaminostilbene disulfonic acid compounds CI Fluorescent Brightner 24, 85, 71, etc. These can be used alone or in combination of two or more. The amount of fluorescent whitening agent used is 0.00001 to 0.1 parts by mass, more preferably 0.00005 to 0.05 parts by mass, relative to 100 parts by mass of the thermoplastic resin.

[0110] When the resin composition of the present invention is molded, known molding methods can be used for molding. For example, a molded product can be obtained by injection molding, extrusion molding, blow molding, vacuum molding, inflation molding, calendaring, slush molding, dipping molding, foaming molding, etc.

[0111] Examples of uses of the resin composition of the present invention include automotive materials such as bumpers, control panels, and instrument panels, housings for refrigerators, washing machines, and vacuum cleaners, household items such as tableware, buckets, and toiletries, sundry goods such as toys, and molded products such as storage and preservation containers such as cans, films, and fibers.

[0112] Next, the resin composition according to other preferred embodiments of the present invention will be described.

[0113] In addition, the resin composition of another preferred embodiment of the present invention is the following resin composition: relative to 100 parts by mass of thermoplastic resin, it contains (A) 0.001 to 10 parts by mass of the phosphate compound represented by the general formula (1), (B) the sodium fatty acid represented by the general formula (2), (C) 1 to 80 parts by mass of the thermoplastic elastomer, and (D) 1 to 80 parts by mass of the filler. For the resin composition of this embodiment, the mass ratio of the component (B) to the component (A) is in the range of (B) / (A)=0.55 to 2.0. By satisfying the above conditions, a resin composition that can obtain a molded body that highly takes into account both impact resistance and rigidity is obtained. For this embodiment, the resin additive composition of the present invention can also be used. In addition, for thermoplastic resins, the above substances can also be used.

[0114] <(C) Thermoplastic elastomer>

[0115] The (C) thermoplastic elastomer of the resin composition according to another preferred embodiment of the present invention is not limited as long as it is a known thermoplastic elastomer, but a copolymer of ethylene and other monomers is preferred because of its excellent compatibility with the polyolefin-based resin.

[0116] Examples of other monomers include linear or branched α-olefins having 3 to 20 carbon atoms, aromatic vinyl compounds having 8 to 20 carbon atoms, other vinyl compounds, conjugated dienes, alkyl methacrylates, alkyl acrylates, etc. These other monomers may be used alone or in combination of two or more.

[0117] Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 3-methyl-1-butene, 3-ethyl-1-butene, 1-pentene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Preferred examples include propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene.

[0118] Examples of the aromatic vinyl compound having 8 to 20 carbon atoms include styrene, o-methylstyrene, p-methylstyrene, m-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, p-tert-butylstyrene, chloromethylstyrene, vinyltoluene, and the like. Preferably, monoalkylstyrene or polyalkylstyrene is used.

[0119] Examples of other vinyl compounds include halogenated olefins, unsaturated amines, unsaturated carboxylic acids, vinyl esters, unsaturated epoxy compounds, and ethylenically unsaturated silane compounds.

[0120] Here, the halogenated olefin is a halogen atom such as chlorine, bromine or iodine added to the above-mentioned α-olefin.

[0121] Examples of the unsaturated amine include allylamine, 5-hexenylamine, and 6-hexenylamine.

[0122] Examples of the unsaturated carboxylic acid include propionic acid, 3-butenoic acid, 4-pentenoic acid, 5-hexenoic acid, 6-hexenoic acid, 7-octenoic acid, 8-nonenoic acid, 9-decenoic acid, and 10-undecenoic acid. The unsaturated carboxylic acid may be substituted with a halogen atom.

[0123] Examples of the vinyl ester include aliphatic vinyl esters such as vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl trimethylacetate, vinyl valerate, vinyl decanoate, vinyl undecanoate, vinyl laurate, vinyl myristate, vinyl pentadecanoate, vinyl palmitate, vinyl stearate, and vinyl versatate (a mixture of carboxylic acids having 9 to 11 carbon atoms), and aromatic vinyl esters such as vinyl benzoate. Preferred vinyl esters include vinyl esters having 3 to 20 carbon atoms, more preferably vinyl esters having 4 to 10 carbon atoms, and still more preferably vinyl acetate.

[0124] Examples of the unsaturated epoxy compound include 4-epoxy-1-butene, 5-epoxy-1-pentene, 6-epoxy-1-hexene, 7-epoxy-1-hexene, 8-epoxy-1-octene, 9-epoxy-1-nonene, 10-epoxy-1-decene, and 11-epoxy-1-undecene.

[0125] Examples of the ethylenically unsaturated silane compound include vinyltriethoxysilane, vinyltrimethoxysilane, 3-acryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-methacryloxypropyltrimethoxysilane.

[0126] Examples of the conjugated diene include 1,3-butadiene, isoprene, 1,3-pentadiene, 2-ethyl-1,3-butadiene, 2,3-dimethylbutadiene, 2-methylpentadiene, 4-methylpentadiene, 2,4-hexadiene, and 1,3-octadiene.

[0127] Examples of the alkyl methacrylate include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isopentyl (meth)acrylate, n-hexyl (meth)acrylate, 2-methylpentyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, and n-octadecyl (meth)acrylate.

[0128] Examples of the alkyl acrylate include 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-(n-propoxy)ethyl acrylate, 2-(n-butoxy)ethyl acrylate, 3-methoxypropyl acrylate, 3-ethoxypropyl acrylate, 2-(n-propoxy)propyl acrylate, and 2-(n-butoxy)propyl acrylate.

[0129] In the resin composition according to another preferred embodiment of the present invention, the (C) thermoplastic elastomer may be obtained by copolymerizing these monomers alone with ethylene, or may be obtained by copolymerizing two or more monomers in combination with ethylene.

[0130] In the resin composition of other preferred embodiments of the present invention, specific examples of the (C) thermoplastic elastomer include block or random copolymers such as ethylene-propylene copolymers, ethylene-butene copolymers, and ethylene-octene copolymers, ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, styrene-ethylene-butene copolymers, styrene-ethylene-butylene-styrene copolymers, and ethylene-vinyl acetate copolymers.

[0131] Examples of thermoplastic elastomers other than combinations of ethylene and other monomers include thermoplastic polyesters and thermoplastic polyurethanes.

[0132] As for the resin composition of another preferred embodiment of the present invention, an ethylene-α-olefin copolymer is preferred because of its excellent compatibility with the olefin resin. In addition, a copolymer of ethylene and a vinyl ester is also preferred.

[0133] For the resin composition of other preferred embodiments of the present invention, these thermoplastic resins and (C) thermoplastic elastomers can be used separately, or two or more can be used in combination. In addition, alloying can also be performed. It should be noted that these thermoplastic resins and (C) thermoplastic elastomers can be used regardless of molecular weight, degree of polymerization, density, softening point, ratio of insoluble components in solvent, degree of stereoregularity, presence or absence of catalyst residues, type of monomers as raw materials, blending ratio, type of polymerization catalyst (e.g., Ziegler catalyst, metallocene catalyst, etc.), etc.

[0134] In the resin composition of another preferred embodiment of the present invention, the compounding amount of the thermoplastic elastomer (C) is 1 to 80 parts by mass, preferably 3 to 50 parts by mass, and more preferably 5 to 40 parts by mass relative to 100 parts by mass of the thermoplastic resin. When it is less than 1 part by mass, the effect of compounding may not be obtained, and when it exceeds 80 parts by mass, the impact strength in a low temperature environment may become insufficient.

[0135] When the resin composition of another preferred embodiment of the present invention is used for automobile interior and exterior materials and housing materials for electrical / electronic components, the (C) thermoplastic elastomer in the resin composition preferably contains 1 to 30% by mass. When it is less than 1% by mass, the effect of adding the thermoplastic elastomer may not be obtained, and when it exceeds 30% by mass, the physical properties of the molded article may be reduced.

[0136] <(D) Filler>

[0137] In the resin composition of other preferred embodiments of the present invention, (D) filler can use known fillers used in thermoplastic resin compositions without limitation. As fillers, for example, talc, calcium carbonate, magnesium sulfate fiber, silicon dioxide, clay, kaolin, aluminum oxide, carbon black, glass fiber, etc. can be listed. From the viewpoint of the mechanical properties of the molded body, talc is particularly preferred. In addition, talc can also be processed by micronization, microgranulation, etc. These can be used alone or in combination of two or more.

[0138] The amount of the filler (D) is 1 to 80 parts by mass, more preferably 3 to 50 parts by mass, and even more preferably 5 to 40 parts by mass relative to 100 parts by mass of the thermoplastic resin. When the amount is less than 1 part by mass, the effect of the addition of the filler (D) may not be obtained, and when the amount exceeds 80 parts by mass, the effect of the present invention may not be obtained.

[0139] When the resin composition of another preferred embodiment of the present invention is used for automobile interior and exterior decoration materials and housing materials for electrical / electronic components, the (D) filler in the resin composition preferably contains 1 to 30% by mass. When it is less than 1% by mass, the effect of adding the (D) filler may not be obtained, and when it exceeds 30% by mass, the physical properties of the molded article may be reduced.

[0140] In the resin composition of other preferred embodiments of the present invention, the method of mixing the component (A), the component (B) and the component (D) with the thermoplastic resin is not particularly limited, and commonly used methods can be cited, such as a method of dry-mixing thermoplastic resin powder or pellets with each component; or a method of preparing a masterbatch containing any one of the components at a high concentration and adding it to the thermoplastic resin; a method of processing the resin additive composition of the present invention into a pellet shape and adding it to the thermoplastic resin. In addition, each component can be added to the olefin resin at the same time or separately.

[0141] As a method for processing into a pellet shape, for example, it can be manufactured as follows: (A) component, (B) component and (D) component, a binder and optional additives as required are mixed, the resulting mixture is heated, and mixed in the presence of a molten binder. As a binder, preferably a compound with a low melting point compared to (A), (B), and (D) components and that can be used as a common resin additive. As a binder, for example, phenolic antioxidants, etc. can be listed. For processing conditions, processing machines, etc., there is no limitation, and known common processing methods, processing machines can be used. As a specific manufacturing method, a disc granulator method, an extrusion method, etc. can be listed.

[0142] The resin composition of other preferred embodiments of the present invention may optionally contain known resin additives (for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet absorbers, hindered amine compounds, nucleating agents different from component (A), flame retardants, flame retardant aids, lubricants, hydrotalcites, fatty acid metal salts, antistatic agents, pigments, fluorescent whitening agents, dyes, etc.) within a range that does not significantly impair the effects of the present invention.

[0143] Examples of nucleating agents other than the phosphate compound represented by the general formula (1) (A) include carboxylic acid metal salts such as sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate, and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; polyol derivatives such as dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, and bis(dimethylbenzylidene)sorbitol; and amide compounds such as N,N',N"-tri[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene dicarboxamide and 1,3,5-tris(dimethylisopropylamino)benzene. These may be used alone or in combination of two or more. When the nucleating agent is added, the total amount of the phosphate compound represented by the general formula (1) (A) is in the range of 0.001 to 10 parts by mass, more preferably 0.006 to 0.5 parts by mass, based on 100 parts by mass of the thermoplastic resin.

[0144] When the resin composition of other preferred embodiments of the present invention is molded, known molding methods can be used for molding. For example, a molded product can be obtained by injection molding, extrusion molding, blow molding, vacuum molding, inflation molding, calendaring, slush molding, dipping molding, foaming molding, etc.

[0145] Examples of uses of the resin composition according to other preferred embodiments of the present invention include automotive materials such as bumpers, control panels, and instrument panels, housing applications for refrigerators, washing machines, and vacuum cleaners, household items such as tableware, buckets, and toiletries, sundry items such as toys, and molded products such as storage and preservation containers such as cans, films, and fibers.

[0146] Next, the resin composition according to still another preferred embodiment of the present invention will be described.

[0147] Furthermore, the resin composition of another preferred embodiment of the present invention contains 0.001 to 10 parts by mass of (A) a phosphate compound represented by the general formula (1), (B) a sodium fatty acid represented by the general formula (2), and (E) 0.01 to 10 parts by mass of a phosphite compound represented by the following general formula (3) relative to 100 parts by mass of a plastic resin, and the mass ratio (B) / (A) is in the range of 0.55 to 2.0. By satisfying the above conditions, a resin composition having excellent crystallization and being able to provide a molded body having excellent anti-discoloration effect caused by thermal history is obtained. In this embodiment, the resin additive composition of the present invention can also be used. In addition, the above substances can also be used for thermoplastic resins.

[0148] <(E) Phosphite compound represented by general formula (3)>

[0149] The phosphite compound of the resin composition of the present invention is represented by the following general formula (3):

[0150]

[0151] In formula (3), R 7 , R 8 Each independently represents an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms.

[0152] In the general formula (3), R 7 and R 8 Examples of the alkyl group having 1 to 40 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a cyclopentyl group, a 4-ethyl-2-methylheptyl group, a hexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 2,4-dimethylhexyl group, a cyclohexyl group, a 1,2,4-trimethylcyclohexyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a tert-heptyl group, a 1-octyl group, an isooctyl group, a tert-octyl group, a nonyl group, an isononyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, an isotridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, an eicosyl group, an adamantyl group, and a norbornyl group.

[0153] Examples of the aryl group having 6 to 40 carbon atoms include phenyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, indenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 4-vinylphenyl, 3-isopropylphenyl, 4-isopropylphenyl, 4-butylphenyl, 4-isobutylphenyl, 4-tert-butylphenyl, 4-hexylphenyl, 4-cyclohexylphenyl, 4-octylphenyl, 4-(2-ethylhexyl)phenyl, 4-stearylphenyl, 2,3-dimethylphenyl, 2,4 -dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,4-di-tert-butylphenyl, 2,5-di-tert-butylphenyl, 2,6-di-tert-butylphenyl, 2,4-di-tert-amylphenyl, 2,5-di-tert-amylphenyl, 2,5-di-tert-octylphenyl, 2,4-dicumylphenyl, 4-cyclohexylphenyl, (1,1'-biphenyl)-4-yl, 2,4,5-trimethylphenyl, ferrocenyl, etc.

[0154] Specific examples of the phosphate compound represented by the general formula (3) include, for example, bis(diisodecyl)pentaerythritol diphosphite, bis(tridecyl)pentaerythritol diphosphite, bis(octadecyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4,6-tri-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, bis(2,4-dicumylphenyl)pentaerythritol diphosphite, and the like.

[0155] For the resin composition according to still another preferred embodiment of the present invention, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, and bis(2,4-dicumylphenyl)pentaerythritol diphosphite are particularly excellent in heat stabilization effect and are therefore preferred.

[0156] In the resin composition of another preferred embodiment of the present invention, the phosphite compound preferably has a molecular weight of 300 to 1000, more preferably 400 to 700. When the molecular weight is less than 300, it is easy to volatilize from the resin, sometimes impairing the appearance of the molded article, and when the molecular weight exceeds 1000, the heat stabilization effect is sometimes lacking.

[0157] In the resin composition of another preferred embodiment of the present invention, the amount of the phosphite compound represented by the general formula (3) (E) relative to the thermoplastic resin is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass relative to 100 parts by mass of the thermoplastic resin. When the amount is less than 0.01 parts by mass, the effect of the present invention may not be obtained, and when it exceeds 10 parts by mass, it may be difficult to disperse in the thermoplastic resin, which may adversely affect the physical properties and appearance of the molded product.

[0158] In the resin composition of another preferred embodiment of the present invention, the method of mixing the component (A), the component (B) and the component (E) into the thermoplastic resin is not particularly limited, and commonly used methods can be cited, such as a method of dry-mixing thermoplastic resin powder or pellets with each component; or a method of preparing a masterbatch containing any one of the components at a high concentration and adding it to the thermoplastic resin; a method of processing the resin additive composition of the present invention into a pellet shape and adding it to the thermoplastic resin. In addition, each component can be added to the olefin resin at the same time or separately.

[0159] As a method for processing into a pellet shape, for example, it can be manufactured as follows: (A) component, (B) component and (D) component, a binder and optional additives as required are mixed, the resulting mixture is heated, and mixed in the presence of a molten binder. As a binder, it is preferred that the compound with a low melting point compared to (A), (B), and (D) components and that can be used as a common resin additive. As a binder, for example, phenolic antioxidants etc. can be listed. There is no limitation on processing conditions, processing machines, etc., and known common processing methods and processing machines can be used. As a specific manufacturing method, a disc granulator method, an extrusion method etc. can be listed.

[0160] The resin composition of another preferred embodiment of the present invention may optionally contain known resin additives (for example, phenolic antioxidants, phosphite compounds different from the phosphite compound represented by the general formula (3) (E), thioether antioxidants, ultraviolet absorbers, hindered amine compounds, nucleating agents different from the phosphate compound represented by the general formula (1) (A), flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents, pigments, dyes, etc.) within a range that does not significantly impair the effects of the present invention.

[0161] Examples of the phosphate compound different from the component (E) include triphenyl phosphite, diisooctyl phosphite, heptadecanyl phosphite, triisodecyl phosphite, diphenylisooctyl phosphite, diisooctylphenyl phosphite, diphenyltridecyl phosphite, triisooctyl phosphite, trilauryl phosphite, diphenyl phosphite, tri(dipropylene glycol) phosphite, dioleyl hydrogenated phosphite, trilauryl trithiophosphite, bis(tridecyl) phosphite, tri(isodecyl) phosphite, tri(tridecyl) phosphite, diphenyldecyl phosphite, dinonylphenylbis(nonylphenyl)phosphite, poly(dipropylene glycol)phenyl phosphite, tetraphenyldipropylene phosphite, and the like. Diol diphosphite, trisnonylphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butyl-5-methylphenyl) phosphite, tris[2-tert-butyl-4-(3-tert-butyl-4-hydroxy-5-methylphenylthio)-5-methylphenyl] phosphite, tris(decyl) phosphite, octyl diphenyl phosphite, di(decyl) monophenyl phosphite, mixture of distearyl pentaerythritol and calcium stearate, alkyl(C10) bisphenol A phosphite, tetraphenyl-tetra(tridecyl) pentaerythritol tetraphosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, tetra(tridecyl) isopropylidene diphenol diphosphite Ester, tetra(tridecyl)-4,4'-n-butylenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tri(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, tetra(2,4-di-tert-butylphenyl)biphenyl diphosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propenyl-3-ylidene)tri(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexa(tridecyl)phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexylphosphite tert-butylphenyl)-octadecyl phosphite, 2,2'-ethylenebis(4,6-di-tert-butylphenyl)fluorophosphite, 4,4'-butylenebis(3-methyl-6-tert-butylphenylditridecyl)phosphite, tris(2-〔(2,4,8,10-tetra-tert-butyldibenzo〔d,f〕〔1,3,2〕dioxaphosphacin-6-yl)oxy〕ethyl)amine, 3,9-bis(4-nonylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane, 2,4,6-tri-tert-butylphenyl-2-butyl-2-ethyl-1,3-propylene glycol phosphite, poly 4,4'-isopropylidene diphenol C12-15 alcohol phosphate, etc.The amount of the phosphate compound different from the component (E) when added is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the thermoplastic resin and the total amount of the phosphite compound represented by the general formula (3) (E).

[0162] When the resin composition of further other preferred embodiments of the present invention is molded, known molding methods can be used for molding. For example, a molded product can be obtained by injection molding, extrusion molding, blow molding, vacuum molding, inflation molding, calendaring, slush molding, dipping molding, foaming molding, etc.

[0163] As applications of the resin composition according to still other preferred embodiments of the present invention, there can be listed automotive materials such as bumpers, control panels, and instrument panels, housing applications for refrigerators, washing machines, and vacuum cleaners, household items such as tableware, buckets, and toiletries, sundry goods such as toys, and molded products such as storage and preservation containers such as cans, films, and fibers.

[0164] Next, the resin composition according to still another preferred embodiment of the present invention will be described.

[0165] The resin composition of another preferred embodiment of the present invention contains 0.001 to 10 parts by mass of a phosphate compound represented by (A) general formula (1), (B) a sodium fatty acid represented by general formula (2), and (F) 1 to 100 parts by mass of a flame retardant relative to 100 parts by mass of a plastic resin, and the mass ratio of the component (B) to the component (A) is in the range of (B) / (A)=0.55 to 2.0. By satisfying the above conditions, a thermoplastic resin composition capable of providing a molded product having a high degree of flame retardancy and excellent physical properties is obtained. In this embodiment, the resin additive composition of the present invention can also be used. In addition, the above substances can also be used for thermoplastic resins.

[0166] <(F) Flame retardant>

[0167] In the resin composition of the further preferred embodiment of the present invention, there is no particular limitation on the flame retardant (F), and known flame retardants can be used. For example, as the flame retardant (F), phosphate compounds can be listed, and for the resin composition of the present invention, a phosphate flame retardant represented by the general formula (6) is preferably used.

[0168]

[0169] (In formula (6), R 9 , R 10 , R 11 and R 12Each independently represents an alkyl group having 1 to 10 carbon atoms, or an aromatic group represented by the following general formula (7), R 13 represents a divalent aromatic group represented by the following general formula (8), (9) or (10), and r represents a number from 0 to 30.

[0170]

[0171] (H in formula (7) 1 and H 2 Each independently represents a hydrogen atom, a hydroxyl group or an alkyl group having 1 to 10 carbon atoms. )

[0172]

[0173] (In formulas (8), (9) and (10), H 3 , H 4 , H 5 , H 6 , H 7 , H 8 , H 9 , H 10 , H 11 and H 12 Each independently represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, an aryl group, an alkoxy group, a nitro group, a halogen atom, or a cyano group. L represents a direct bond, a divalent sulfur atom, a sulfonyl group, or an alkylidene group or an alkylene group having 1 to 5 carbon atoms.

[0174] In formula (6), as R 9 , R 10 , R 11 and R 12 The alkyl group having 1 to 10 carbon atoms shown herein includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonyl, decyl and the like.

[0175] In the general formula (6), R 9 , R 10 , R 11 and R 12 In the formula (7), examples of the aromatic group include a phenyl group, a 2,6-dimethylphenyl group, a tolyl group, a xylyl group, an isopropylphenyl group, and a tert-butylphenyl group.

[0176] In the general formula (7), H 1 and H 2Examples of the alkyl group having 1 to 10 carbon atoms include the same groups as described above.

[0177] R in the general formula (6) 13 It represents a divalent aromatic group selected from the group consisting of the above-mentioned general formulae (8), (9) and (10).

[0178] In the general formulas (8), (9) and (10), H 3 , H 4 , H 5 , H 6 , H 7 , H 8 , H 9 , H 10 , H 11 and H 12 The alkyl group having 1 to 10 carbon atoms shown in the above formula (I) includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonyl, decyl and the like, preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably a methyl group and a tert-butyl group.

[0179] In the general formulas (8), (9) and (10), H 3 , H 4 , H 5 , H 6 , H 7 , H 8 , H 9 , H 10 , H 11 and H 12 Examples of the cycloalkyl group include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. A cycloalkyl group having 3 to 7 carbon atoms is preferred, and a cyclohexyl group is particularly preferred.

[0180] In the general formulas (8), (9) and (10), H 3 , H 4 , H 5 , H 6 , H 7 , H 8 , H 9 , H 10 , H 11 and H 12 Examples of the aryl group include a phenyl group, a tolyl group, a xylyl group, a 2,6-xylyl group, a 2,4,6-trimethylphenyl group, a butylphenyl group, and a nonylphenyl group.

[0181] In the general formulas (8), (9) and (10), H 3 , H 4 , H 5 , H 6 , H 7 , H 8 , H 9 , H 10 , H 11 and H 12 Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group.

[0182] In the general formulas (8), (9) and (10), H 3 , H 4 , H 5 , H 6 , H 7 , H 8 , H 9 , H 10 , H 11 and H 12 Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0183] L in the general formula (9) represents a direct bond, a divalent sulfur atom, a sulfonyl group, or an alkylidene group or an alkylene group having 1 to 5 carbon atoms.

[0184] Examples of the alkylidene group having 1 to 5 carbon atoms represented by L in the general formula (9) include ethylidene, isopropylidene, butylidene, isobutylidene, and the like. Examples of the alkylene group having 1 to 5 carbon atoms include methylene, ethylene, propylene, butylene, isobutylene, and heptylene, and the like.

[0185] Specific examples of the divalent aromatic group represented by the general formula (8) include 1,4-phenylene and 1,3-phenylene.

[0186] Specific examples of the divalent aromatic group represented by the general formula (9) include 1,4′-biphenylyl, (1-methylethylidene)-di-4,1-phenylene, 4,4′-thiodiphenylene, and 4,4′-sulfonyldiphenylene.

[0187] Specific examples of the divalent aromatic group represented by the general formula (10) include 1,5-naphthylene and 2,6-naphthylene.

[0188] In general formula (6), r represents a number of 0 to 30, and the phosphate ester compound as a condensate has higher flame retardancy. In the resin composition of still another preferred embodiment of the present invention, r is more preferably 1 to 10, and more preferably 1 to 5.

[0189] In the resin composition of another preferred embodiment of the present invention, specific examples of the phosphate-based flame retardant represented by the general formula (6) include trimethyl phosphate, triethyl phosphate, tributyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate, tricresyl phosphate, octyl diphenyl phosphate, xylyl diphenyl phosphate, tri(isopropylphenyl) phosphate, 2-ethylhexyl diphenyl phosphate, tert-butylphenyl diphenyl phosphate, bis(tert-butylphenyl)phenyl phosphate, tri(tert-butylphenyl) phosphate, isopropylphenyl diphenyl phosphate and the compounds shown below.

[0190] However, the resin composition of the present invention is not limited to these exemplified compounds.

[0191]

[0192] Examples of products of phosphate-based flame retardants include “ADK STAB PFR”, “ADK STAB FP-500”, “ADK STAB FP-600”, “ADK STAB FP-700”, “ADK STAB FP-800”, and “ADK STAB FP-900” manufactured by ADEKA Corporation, “CR-504L” and “CR-570” manufactured by Daihachi Chemical Industry Co., Ltd., and “Kronitex TXP”, “Durad TXP”, “Reofos 35”, “Reofos 50”, “Reofos 65”, “Reofos 95”, and “Reofos 110” manufactured by Ajinomoto Fine-Techno Co., Inc.

[0193] Next, a brominated flame retardant may also be used in the resin composition of further other preferred embodiments of the present invention. For the resin composition of the present invention, the brominated flame retardant may use a known substance without particular limitation. From the viewpoint of flame retardancy and ease of acquisition, it is preferred to contain at least one selected from the group consisting of brominated diphenyl compounds, brominated bisphenol compounds, brominated bisphenol-bis (alkyl ether) compounds, brominated phthalimide compounds, brominated triazine compounds, and brominated thermoplastic resins.

[0194] Examples of the brominated diphenyl compound include brominated diphenyl ether compounds, brominated diphenyl alkane compounds, brominated diphenyl ketone compounds, etc. Among them, brominated diphenyl ether compounds such as decabromodiphenyl ether and octabromodiphenyl ether, and halogenated diphenyl alkane compounds such as decabromodiphenyl ethane are preferred.

[0195] Examples of brominated bisphenol compounds include brominated bisphenylalkanes, brominated bisphenyl ethers, brominated bisphenyl sulfides, brominated bisphenyl sulfones, brominated bisphenol A epoxy resins, modified products obtained by capping part or all of the glycidyl groups at the molecular chain terminals of brominated bisphenol A epoxy resins, and polycarbonate oligomers synthesized from brominated bisphenol A. Among them, brominated bisphenylalkanes such as tetrabromobisphenol A and halogenated bisphenyl sulfides such as bis(3,5-dibromo-4-hydroxyphenyl)sulfone are preferred.

[0196] Examples of the brominated bisphenol-bis(alkyl ether) compounds include brominated bisphenol A-bis(alkyl ether), brominated bisphenol S-bis(alkyl ether), brominated bisphenol F-bis(alkyl ether), etc. Among them, brominated bisphenol A (brominated aliphatic ether) such as 2,2-bis(3,5-dibromo-4-2,3-dibromopropoxyphenyl)propane, brominated bisphenol S (brominated aliphatic ether) such as (3,5-dibromo-4-2,3-dibromopropoxyphenyl)-(3-bromo-4-(2,3-dibromopropoxyphenyl)) sulfone, and bis(3,5-dibromo-4-2,3-dibromopropoxyphenyl) sulfone are preferred.

[0197] Examples of the brominated phthalimide-based compound include ethylenebis(tetrabromophthalimide) and the like.

[0198] Examples of the brominated triazine-based compound include tris(brominated phenoxy)-1,3,5-triazine such as 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine.

[0199] Examples of the brominated thermoplastic resin include brominated polystyrene, brominated polyacrylate, brominated polyphenylene ether, etc. Among them, brominated polystyrene such as poly(tribromostyrene) and brominated polyphenylene ether such as poly(dibromophenylene ether) are preferred.

[0200] In the resin composition of another preferred embodiment of the present invention, the content of the flame retardant (F) is 1 to 100 parts by mass, more preferably 10 to 70 parts by mass, relative to 100 parts by mass of the thermoplastic resin. If it is less than 1 part by mass, a sufficient flame retardant effect cannot be obtained, and if it exceeds 100 parts by mass, the physical properties of the resin may be reduced.

[0201] <(G) Flame retardant additives>

[0202] In the resin composition of the further preferred embodiment of the present invention, a flame retardant additive (G) may be used. For the resin composition of the further preferred embodiment of the present invention, there is no particular limitation as the flame retardant additive (G), and known substances may be used. Among them, from the viewpoint of performance and availability as the flame retardant additive (G), antimony compounds, boron compounds, metal oxides and anti-drip agents are preferred.

[0203] Examples of antimony compounds include antimony oxide, alkali metal salts of antimonic acid, alkaline earth metal salts of antimonic acid, metallic antimony, antimony chloride, antimony sulfide, etc. Among them, antimony oxides such as antimony trioxide and antimony pentoxide, and alkali metal salts of antimonic acid such as sodium antimonate are preferred.

[0204] Preferred examples of the boron compound include boric acid including orthoboric acid, metaboric acid, perboric acid, boric acid, boron, diboric acid, and tetraboric acid.

[0205] Examples of the metal oxide include zinc oxide, titanium oxide, magnesium oxide, and silicon oxide. Among them, zinc oxide is preferred. The metal oxide may also be surface treated.

[0206] Examples of the anti-drip agent include fluorine-based anti-drip agents, silicone rubbers, and layered silicates.

[0207] Examples of layered silicates include montmorillonite, saponite, hectorite, beidellite, stevensite, nontronite and other montmorillonite clay minerals, vermiculite, halloysite, swelling mica, talc and the like, and may also be materials in which organic cations, quaternary ammonium cations and phosphonium cations are embedded between the layers.

[0208] Among the anti-drip agents, fluorine-based anti-drip agents are particularly preferred. As specific examples of fluorine-based anti-drip agents, for example, fluorine-based resins such as polytetrafluoroethylene, polyvinylidene fluoride, and polyhexafluoropropylene, perfluoromethanesulfonic acid sodium salt, perfluoro-n-butanesulfonic acid potassium salt, perfluoro-tert-butanesulfonic acid potassium salt, perfluorooctanesulfonic acid sodium salt, perfluoro-2-ethylhexanesulfonic acid calcium salt and other perfluoroalkanesulfonic acid alkali metal salt compounds or perfluoroalkanesulfonic acid alkaline earth metal salts can be listed. Among the above-mentioned fluorine-based anti-drip agents, polytetrafluoroethylene is particularly preferred from the viewpoint of anti-drip properties.

[0209] In the resin composition of another preferred embodiment of the present invention, the content of the flame retardant auxiliary (G) is 1 to 30 parts by mass, more preferably 3 to 30 parts by mass, relative to 100 parts by mass of the thermoplastic resin. When it is less than 1 part by mass, the flame retardant auxiliary effect cannot be obtained sufficiently, and when it exceeds 30 parts by mass, the properties of the resin may be reduced.

[0210] In the resin composition of another preferred embodiment of the present invention, the method of mixing the component (A), the component (B) and the component (F) into the thermoplastic resin is not particularly limited, and commonly used methods can be cited, such as a method of dry-mixing a powder or pellet of a thermoplastic resin with each component; or a method of preparing a masterbatch containing any one of the components at a high concentration and adding it to the thermoplastic resin; a method of processing the resin additive composition of the present invention into a pellet shape and adding it to the thermoplastic resin. In addition, each component may be added to the olefin resin simultaneously or separately.

[0211] As a method for processing into a pellet shape, for example, it can be manufactured as follows: (A) component, (B) component and (F) component, a binder and optional additives as required are mixed, the resulting mixture is heated, and mixed in the presence of a molten binder. As a binder, it is preferred that the compound with a low melting point compared to (A), (B), and (F) components and that can be used as a common resin additive. As a binder, for example, phenolic antioxidants, etc. can be listed. There is no limitation on processing conditions, processing machines, etc., and known common processing methods and processing machines can be used. As a specific manufacturing method, a disc granulator method, an extrusion method, etc. can be listed.

[0212] The resin composition of further preferred embodiments of the present invention may optionally contain known resin additives (for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, ultraviolet absorbers, hindered amine compounds, nucleating agents different from the phosphate compound represented by general formula (1) (A), lubricants, fillers, hydrotalcites, antistatic agents, pigments, fluorescent whitening agents, dyes, etc.) within a range that does not significantly impair the effects of the present invention.

[0213] When the resin composition of further other preferred embodiments of the present invention is molded, known molding methods can be used for molding. For example, a molded product can be obtained by injection molding, extrusion molding, blow molding, vacuum molding, inflation molding, calendaring, slush molding, dipping molding, foaming molding, etc.

[0214] As applications of the resin composition according to still other preferred embodiments of the present invention, there can be listed automotive materials such as bumpers, control panels, and instrument panels, housing applications for refrigerators, washing machines, and vacuum cleaners, household items such as tableware, buckets, and toiletries, sundry goods such as toys, and molded products such as storage and preservation containers such as cans, films, and fibers.

[0215] Next, the resin composition according to still another preferred embodiment of the present invention will be described.

[0216] The resin composition of another preferred embodiment of the present invention contains 0.001 to 10 parts by mass of (A) a phosphate compound represented by the general formula (1), (B) a sodium fatty acid represented by the general formula (2), and (H) a light stabilizer, relative to 100 parts by mass of a plastic resin, and the mass ratio of (B) component to (A) component (B) / (A) is 0.55 to 2.0. The resin composition satisfying the above conditions becomes a resin composition capable of providing a thermoplastic resin composition containing a light stabilizer and showing an excellent nucleating agent effect and a molded product thereof. For this embodiment, the resin additive composition of the present invention can also be used. In addition, the above substances can also be used for thermoplastic resins.

[0217] <(H) Light Stabilizer>

[0218] Next, the (H) light stabilizer used in the resin composition according to another embodiment of the present invention will be described. In the resin composition according to another embodiment of the present invention, the (H) light stabilizer preferably contains (I) a hindered amine compound and / or (J) an ultraviolet absorber.

[0219] The (I) hindered amine compound that can be used in the resin composition of another preferred embodiment of the present invention includes compounds having a 2,2,6,6-tetramethylpiperidyl structure, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6,6-tetramethyl-4-piperidyl benzoate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, 6,6-tetramethyl-1-(octyloxy)piperidinyl-4-yl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, butane-1,2,3,4-tetracarboxylic acid tetrakis (2,2,6,6-tetramethyl-4-piperidinyl), butane-1,2,3,4-tetracarboxylic acid tetrakis (1,2,2,6,6-pentamethyl-4-piperidinyl), bis (2,2,6,6-tetramethyl-4-piperidinyl) di (tridecyl)-1,2,3,4-butane tetracarboxylate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) di (decyl) trialkyl)-1,2,3,4-butane tetracarboxylic acid ester, bis(1,2,2,4,4-pentamethyl-4-piperidinyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-piperidinol / succinic acid diethanol condensation product, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane / 2,4-dichloro-6-morpholino-s-triazine condensation product, 1,6-bis(2,2,6,6-tetramethyl-4-piperidinylamino)hexane / 2,4-dichloro-6-tert-butyl-4-hydroxybenzyl Octylamino-s-triazine polycondensate, polycondensate of 1-methyl-10-(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, butanetetracarboxylic acid tetramethyl ester, ester with spirodiol and N-methylpiperidinol, polycondensate of butanetetracarboxylic acid, ester with 3-hydroxy-2,2-dimethylvaleraldehyde and N-methylpiperidinol, 1,2,3,4-butanetetracarboxylic acid tetramethyl ester, 2,2,6,6-tetramethyl-4-piperidinol and β,β,β',β'-tetramethyl-2,4,8,10-tetraoxaspiro[5.5] Undecane-3,9-diethanol condensation product, 2,4-dichloro-6-(1,1,3,3-tetramethylbutylamino)-1,3,5-triazine-N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexanediamine condensation product, 2,4-dichloro-6-(1,1,3,3-tetramethylbutylamino)-1,3,5-triazine, 1,5,8,12-tetrakis[2,4-bis(2,2,6,6-tetramethyl-4-piperidinyl)hexanediamine condensation product (N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12-tetraazadodecane, 2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazine-6-yl]-1,5,8,12-tetraazadodecane, 1,6,11-tri 2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)amino)-s-triazin-6-yl]aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino)-s-triazin-6-yl]aminoundecane, bis{4-(1-octyloxy-2,2,6,6-tetramethyl)piperidinyl}decanedione ester, bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidinyl)carbonate, BASF trade name “CHIMASSORB 119”, BASF trade name “CHIMASSORB 944”, BASF trade name “CHIMASSORB 2020”, BASF trade name “TINUVIN XT850}, TINUVIN NOR 371 manufactured by BASF, ADK STAB LA-77, ADK STAB LA-94, ADK STAB LA-402XP, ADK STAB LA-402AF, ADK STAB LA-40MP, ADK STAB LA-502XP, etc. manufactured by ADEKA Corporation.

[0220] In addition, for the resin composition of another preferred embodiment of the present invention, the hindered amine compound (I) may be a mixture of two or more, or a masterbatch containing them. In addition, when the hindered amine compound (I) has liquid properties at room temperature and becomes fluid without heating or by heating, it can be impregnated in the carrier described below.

[0221] In the resin composition according to still another preferred embodiment of the present invention, as the (I) hindered amine compound that can be preferably used, the compound represented by the following general formula (11) will be described.

[0222]

[0223] In formula (11), R 14 represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 30 carbon atoms, a hydroxyalkyl group, an alkoxy group, a hydroxyalkoxy group or an oxy radical, and R 15 represents a linear or branched aliphatic hydrocarbon group having 1 to 31 carbon atoms, or a substituent represented by the following general formula (12), j represents an integer of 1 to 4, R 15 When it is a substituent represented by the general formula (12), j is 1.

[0224]

[0225] In formula (12), R 14 Same as formula (11).

[0226] In the general formula (11), R 14 The straight-chain or branched alkyl group having 1 to 30 carbon atoms shown herein includes, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, triacontyl and the like.

[0227] In the general formula (11), R 14 Examples of the hydroxyalkyl group having 1 to 30 carbon atoms include hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and the like, and hydroxyl-substituted products of the above alkyl groups.

[0228] In the general formula (11), R 14 Examples of the alkoxy group having 1 to 30 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, octyloxy, 2-ethylhexyloxy, undecyloxy, triacontyloxy and the like corresponding to the above-mentioned alkyl groups.

[0229] In the general formula (11), R 14 Examples of the hydroxyalkoxy group having 1 to 30 carbon atoms include hydroxyethyloxy, 2-hydroxypropyloxy, 3-hydroxypropyloxy, 4-hydroxybutyloxy, 2-hydroxy-2-methylpropyloxy, 6-hydroxyhexyloxy, and hydroxy-substituted products of the above alkoxy groups.

[0230] In the general formula (11), R 15The linear or branched aliphatic hydrocarbon group having 1 to 31 carbon atoms shown in the figure includes a monovalent, divalent, trivalent or tetravalent aliphatic hydrocarbon group. Examples of the linear or branched monovalent aliphatic hydrocarbon group having 1 to 31 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, a cyclopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, an isopentyl group, a tert-pentyl group, a cyclopentyl group, a hexyl group, a 2-hexyl group, a 3-hexyl group, a cyclohexyl group, a bicyclohexyl group, a 1-methylcyclohexyl group, a heptyl group, a 2-heptyl group, a 3-heptyl group, an isoheptyl group, a tert-heptyl group, a n-octyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, a Alkyl groups such as monoalkyl, dodecyl, and triacontyl; alkenyl groups such as vinyl, 1-methylvinyl, 2-methylvinyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, heptadecenyl, eicosenyl, and triacontyl (the position of the double bond may be α-position, internal, or ω-position), etc.

[0231] Examples of the linear or branched divalent aliphatic hydrocarbon group having 1 to 31 carbon atoms include alkylene groups such as methylene, ethylene, propylene, butylene, and butanediol; substances in which the methylene chains of the alkylene groups are replaced by -O-, -S-, -CO-O-, or -O-CO-; residues of diols such as ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol; residues of dithiols such as ethanedithiol, propylenethiol, butanediol, pentanediol, and hexanediol; and the like.

[0232] Examples of the linear or branched trivalent aliphatic hydrocarbon group having 1 to 31 carbon atoms include alkane triyl groups such as propane triyl, butane triyl, and heptane triyl groups; alkane triyl groups such as butene triyl and hexene triyl groups; and alkylene groups such as propylidene and 1,1,3-butylidene groups.

[0233] Examples of the linear or branched tetravalent aliphatic hydrocarbon group having 1 to 31 carbon atoms include alkanetetrayl groups such as butanetetrayl, pentanetetrayl and octanetetrayl, and alkenetetrayl groups such as pentenetetrayl, hexenetetrayl and octenenetetrayl.

[0234] As specific structures of the hindered amine compound represented by the general formula (11), for example, the following compounds can be cited. However, the resin composition of further preferred embodiments of the present invention is not limited to the following compounds. It should be noted that R in the general formula (11) 15 For R A The compound represents R 15 A mixture of hindered amine compounds having an alkyl group with 15 to 17 carbon atoms, wherein R in the above general formula (11) 15 For R B The compound represents R15 A mixture of hindered amine compounds having an alkyl group having 13 to 19 carbon atoms.

[0235]

[0236] Commercial products using the compound represented by the general formula (11) include "Cyasorb UV-3808PP5" and "Cyasorb Cynergy V-703" manufactured by Cytec, and "ADK STAB LA-77", "ADK STAB LA-81", "ADK STAB LA-402AF" (masterbatch) and "ADK STAB LA-402XP" (masterbatch) manufactured by ADEKA Corporation.

[0237] In the resin composition according to still another preferred embodiment of the present invention, examples of the (I) hindered amine compound that can be preferably used include compounds represented by the following general formulas (13) to (16).

[0238]

[0239] In formula (13), R 14 Same as formula (11).

[0240]

[0241] In formula (14), multiple R 14 represents the same group as in formula (11), Y represents a direct bond or a methylene group, and k represents an integer of 1 to 20.

[0242]

[0243] In formula (15), R 14 represents the same group as in formula (11), R 16 represents a linear or branched alkyl group having 1 to 31 carbon atoms, a linear or branched alkenyl group having 2 to 31 carbon atoms, a 2,2,6,6-tetramethylpiperidinyl group, or a 1,2,2,6,6-pentamethylpiperidinyl group; and l represents an integer of 2 to 20.

[0244]

[0245] In formula (16), m represents a number from 2 to 20.

[0246] Commercial products using the compound represented by the general formula (13) include "ADK STAB LA-52", "ADK STAB LA-57", and "ADK STAB LA-502XP" (masterbatch) manufactured by ADEKA Corporation.

[0247] Commercial products using the compound represented by the general formula (14) include "ADK STAB LA-63P" and "ADK STAB LA-68" manufactured by ADEKA Corporation.

[0248] Commercial products using the compound represented by the general formula (15) include "ADKSTAB LA-94" manufactured by ADEKA Corporation, "Chimassorb 944", "Tinuvin 783", "Tinuvin 791", "Irgastab FS-210", and "Irgastab FS-410" manufactured by BASF.

[0249] Commercial products using the compound represented by the general formula (16) include "Tinuvin 622", "Tinuvin 111", and "Tinuvin 783" manufactured by BASF.

[0250] In the resin composition according to still another preferred embodiment of the present invention, the amount of the hindered amine compound (I) added is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the thermoplastic resin.

[0251] Next, the (J) ultraviolet absorber used in the resin composition of another preferred embodiment of the present invention is described. In the present invention, the (J) ultraviolet absorber can be used without particular limitation as long as it is a known compound. Specific compounds include, for example, 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'-methylenebis(4-tert-octyl-6-benzotriazolylphenol), 2,2'-methylenebis(4-ethylhydroxy-6-benzotriazolylphenol), 2,2'-methylenebis(4-methyl-6-benzotriazolylphenol), polyethylene glycol ester of 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-chlorobenzotriazole, 2-[2-hydroxy-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[2-hydroxy-3-tert-pentyl-5-(2-methacryloyloxyethyl) 2-(2-Hydroxyphenyl)benzotriazoles such as 2-[2-hydroxy-3-tert-butyl-5-(3-methacryloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methacryloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4-(3-methacryloxy-2-hydroxypropyl)phenyl]benzotriazole and 2-[2-hydroxy-4-(3-methacryloxypropyl)phenyl]benzotriazole;2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(octyloxy)phenol, 2-(4,6-bis(4-butoxy-2-methylphenyl)-1,3,5-triazine-2-yl)-3,5-dibutoxyphenol, 2-(4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl)-5- Phenol-containing triazines such as (3-(2-ethylhexyloxy)-2-hydroxypropoxy)phenol, 2-(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl)-5-hexyloxyphenol, and 2-methylhexyl-2-(4,(4,6-di([1,1'-biphenyl]-4-yl)-1,3,5-triazine-2-yl)-3-hydroxyphenoxy)propionate; 2,2'-dihydroxy-4,4'-dimethyl 2-Hydroxybenzophenones such as oxybenzophenone, 2,4-dihydroxybenzophenone, 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone), 1,4-bis(4-benzoyl-3-hydroxyphenoxy)-butane; resorcinol monobenzoate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, octyl (3,5-di-tert-butyl-4-hydroxy) benzoate, dodecyl (3,5-di-tert-butyl-4 Benzoates such as 2-ethyl-2'-ethoxy oxalyl dianilide and 2-ethoxy-4'-dodecyl oxalyl dianilide;Ethyl-2-cyano-3,3-diphenylacrylate, 2'-ethylhexyl-2-cyano-3,3-diphenylacrylate, ethyl-α-cyano-β,β-diphenylacrylate, methyl-2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate, 4-(2-cyano-3-(4-ethylphenoxy)-3-oxopropenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-ethylphenoxy)-3-oxopropenyl)phenyl-4-propylbenzene 4-(2-cyano-3-oxo-3-(4-propylphenoxy)propenyl)benzoate, 4-(2-cyano-3-(4-cyanophenoxy)-3-oxopropenyl)phenyl-4-pentylbenzoate, 4-(2-cyano-3-(4-fluorophenoxy)-3-oxopropenyl)phenyl-4-methylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-methoxyphenoxy)-3-oxopropenyl)phenyl-4-hexylcyclohexane-1-carboxylate, 4-(2-cyano-3-(4-ethoxyphenoxy)-3-oxopropenyl)phenyl-4-octylcyclohexane-1-carboxylate, 4-(2-cyano-3-oxo-3-(4-propoxyphenoxy)propenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2-cyano-3-oxo-3-(4-pentylphenoxy)propenyl)phenyl-4-propylcyclohexane-1-carboxylate, 4-(2-cyano-3-oxo-3-(4-octylphenoxy)-3-oxopropenyl)-4-propylcyclohexane- Cyanoacrylates such as 1-carboxylate, 1,3-bis-[(2'-cyano-3',3'-diphenylacryl)oxy]-2,2-bis-[[(2'-cyano-3',3'-diphenylacryl)oxy]methyl]propane; salicylic acids such as 4-tert-butylphenyl salicylate, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropylphenyl salicylate, etc.; various metal salts or metal chelates, especially salts or chelates of nickel and chromium. ;

[0252] In addition, for the resin composition of further other preferred embodiments of the present invention, the (J) ultraviolet absorber may be a mixture of two or more, or a masterbatch containing them. In addition, the ultraviolet absorber may be impregnated in the carrier described later when it has liquid properties at room temperature or becomes fluid without heating or by heating.

[0253] In the present invention, (J) the ultraviolet absorber can preferably be a compound represented by the following general formulas (17) to (21).

[0254]

[0255] Here, R 17 and R 18Each independently represents a hydrogen atom, a chlorine atom, or a linear or branched alkyl group having 1 to 4 carbon atoms, and R 19 and R 20 Each independently represents a hydrogen atom, or a linear or branched alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a hydroxyalkoxy group having 1 to 18 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, and R 21 , R 22 Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 4 carbon atoms.

[0256]

[0257] Here, R 26 represents a hydrogen atom, a chlorine atom, or a linear or branched alkyl group having 1 to 4 carbon atoms, R 24 , R 25 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a hydroxyalkoxy group having 1 to 18 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms, and n represents 1 or 2,

[0258] When n is 1, R 23 represents a hydrogen atom, a linear or branched alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a hydroxyalkoxy group having 1 to 18 carbon atoms, or an alkylaryl group having 7 to 30 carbon atoms,

[0259] When n is 2, R 23 represents an alkanediyl group having 1 to 20 carbon atoms, R 24 , R 25 and R 26 The methylene groups in the alkyl, hydroxyalkyl, alkoxy, hydroxyalkoxy, alkylaryl and alkanediyl groups shown may be replaced by ethylene glycol, propylene glycol, -O-, -CO-, -OCO- or -COO-.

[0260]

[0261] Here, R 27 represents a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an alkenyl group having 3 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms,

[0262] R 28 represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, or an alkenyl group having 3 to 8 carbon atoms,

[0263] R 29 and R 30 represents a hydrogen atom, a hydroxyl group, or a linear or branched alkyl group having 1 to 8 carbon atoms,

[0264] R 31 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 20 carbon atoms, or -OR 27 ,

[0265] R 27 ~R 31 The carbon atoms forming the ring structure of the methylene group and the cycloalkyl group in the alkyl, alkenyl, alkylaryl, and arylalkyl groups may be replaced by -O-, -S-, -CO-, -O-CO-, -CO-O-, or -NR'-, and the hydrogen atoms of the alkyl, cycloalkyl, alkenyl, aryl, alkylaryl, and arylalkyl groups may be replaced by hydroxyl groups, halogen atoms, alkyl groups having 1 to 12 carbon atoms, or alkoxy groups having 1 to 12 carbon atoms. R' represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms. Multiple R 27 , R 28 , R 29 , R 30 and R 31 They can be the same or different.

[0266]

[0267] Here, R 32 represents a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 8 carbon atoms, and multiple R 32 They may be the same or different, and t represents a number from 2 to 14.

[0268]

[0269] Here, R 33 , R 34 and R 37 each independently represents a hydrogen atom, a hydroxyl group, a carboxyl group, a linear or branched alkyl group having 1 to 18 carbon atoms, a hydroxyalkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms, a hydroxyalkoxy group having 1 to 18 carbon atoms, an alkylaryl group having 7 to 30 carbon atoms, an alkoxyaryl group having 7 to 30 carbon atoms, an acetophenone group, an acryloyloxyalkoxy group having 4 to 15 carbon atoms, or a methacryloyloxyalkoxy group having 5 to 15 carbon atoms, and R 35 , R 36 Each independently represents a hydrogen atom, a hydroxyl group, a sulfonyl group, a sodium sulfonyl group, or a hydroxysulfonyl group.

[0270] In the general formula (17), R 17 ,R18 ,R 21 and R 22 Examples of the linear or branched alkyl group having 1 to 4 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl.

[0271] In the general formula (17), R 19 and R 20 The straight-chain or branched alkyl group having 1 to 18 carbon atoms shown in the figure includes, in addition to the above-mentioned alkyl groups, pentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, tert-octyl, nonyl, isononyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl and the like.

[0272] In the general formula (17), R 19 and R 20 Examples of the hydroxyalkyl group having 1 to 18 carbon atoms include hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl and the like, and hydroxyl-substituted products of the above alkyl groups.

[0273] In the general formula (11), R 19 and R 20 Examples of the alkoxy group having 1 to 18 carbon atoms include methoxy, ethoxy, propoxy, isopropoxy, butoxy, octyloxy, 2-ethylhexyloxy, undecyloxy, octadecyloxy and the like corresponding to the above-mentioned alkyl groups.

[0274] In the general formula (17), R 19 and R 20 Examples of the hydroxyalkoxy group having 1 to 18 carbon atoms include hydroxyethyloxy, 2-hydroxypropyloxy, 3-hydroxypropyloxy, 4-hydroxybutyloxy, 2-hydroxy-2-methylpropyloxy, 6-hydroxyhexyloxy, and hydroxy-substituted products of the above alkoxy groups.

[0275] In the general formula (17), R 19 and R 20 The alkylaryl group having 7 to 30 carbon atoms shown in the figure may be a group in which one hydrogen atom of the above alkyl group is substituted by an aryl group, and examples of the aryl group include phenyl, tolyl, xylyl, 2,6-xylyl, 2,4,6-trimethylphenyl, butylphenyl, nonylphenyl, biphenylyl, naphthyl, anthracenyl and the like.

[0276] The following compounds are exemplified as specific structures of the compound represented by the general formula (17), but the present invention is not limited to these compounds.

[0277]

[0278] Examples of commercially available products containing the compound represented by the general formula (17) include "ADK STAB LA-31", "ADK STAB LA-31G", and "ADK STAB LA-31RG" manufactured by ADEKA Corporation, "RUVA-100" manufactured by Otsuka Chemical Co., Ltd., and "Mixxim BB / 150" and "Mixxim BB / 200" manufactured by Fairmout.

[0279] In the general formula (18), R 23 , R 24 and R 25 The alkyl groups having 1 to 18 carbon atoms, the hydroxyalkyl groups having 1 to 18 carbon atoms, the alkoxy groups having 1 to 18 carbon atoms, the hydroxyalkoxy groups having 1 to 18 carbon atoms, and the alkylaryl groups having 7 to 30 carbon atoms shown represent the same groups as described above, but may also be groups in which the methylene groups of the alkyl groups, hydroxyalkyl groups, alkoxy groups, hydroxyalkoxy groups, and alkylaryl groups are replaced by ethylene glycol, propylene glycol, -O-, -CO-, -OCO-, or -COO-.

[0280] In the general formula (18), R 23 , R 24 and R 25 The arylalkyl group having 7 to 30 carbon atoms shown herein includes a group in which one hydrogen atom of the above aryl group is substituted with the above alkyl group.

[0281] In the general formula (18), R 23 , R 24 and R 25 Examples of the alkenyl group having 3 to 20 carbon atoms include vinyl, 1-methylvinyl, 2-methylvinyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, and eicosenyl.

[0282] In the general formula (18), R 23 Examples of the alkanediyl group having 1 to 20 carbon atoms include methanediyl, ethanediyl, hexanediyl, octanediyl, and the like, and examples include groups in which the methylene group of the alkanediyl group is replaced by ethylene glycol, propylene glycol, -O-, -CO-, -OCO-, or -COO-. Specifically, examples thereof include 1,6-hexanediyl-dibutyrate, and the like.

[0283] In the general formula (18), R 23Examples of the alkanediyl group having 1 to 20 carbon atoms include methanediyl, ethanediyl, hexanediyl, and octanediyl, and examples include alkanediyl groups in which the methylene group is replaced by ethylene glycol, propylene glycol, -O-, -CO-, -OCO-, or -COO-. Specifically, examples include 1,6-hexanediyl-dibutyrate.

[0284] The following compounds are exemplified as specific structures of the compound represented by the general formula (18), but the present invention is not limited to these compounds.

[0285]

[0286] Examples of products containing the compound represented by the general formula (18) include “ADK STAB LA-29”, “ADK STAB LA-32”, “ADK STAB LA-36”, and “ADK STAB LA-36RG” manufactured by ADEKA Corporation, “Seesorb 704”, “Seesorb 705”, “Seesorb 706”, “Seesorb 707”, “Seesorb 708”, and “Seesorb 709” manufactured by SHIPROKASEI KAISHA, LTD., “RUVA 93” manufactured by Otsuka Chemical Co., Ltd., “Sumisorb 250” manufactured by Sumitomo Chemical Co., Ltd., and “Tinuvin PS”, “Tinuvin 109”, “Tinuvin 213”, “Tinuvin 234”, “Tinuvin 327”, “Tinuvin 328”, “Tinuvin 350”, “Tinuvin 384”, “Tinuvin 571”, and “Tinuvin 1130” manufactured by BASF.

[0287] In the general formula (19), R 27 Examples of the linear or branched alkyl group having 1 to 20 carbon atoms include nonadecyl group, eicosyl group, and the like in addition to the above-mentioned alkyl groups.

[0288] In the general formula (19), R 27 Examples of the cycloalkyl group having 3 to 8 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl.

[0289] In the general formula (19), R 27Examples of the alkenyl group having 3 to 20 carbon atoms include vinyl, 1-methylvinyl, 2-methylvinyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, bicyclohexenyl, heptenyl, octenyl, decenyl, pentadecenyl, and eicosenyl.

[0290] In the general formula (19), R 27 and R 31 Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2,4,6-trimethylphenyl, butylphenyl, nonylphenyl, biphenylyl, indenyl, naphthyl, dimethylnaphthyl, anthracenyl, and phenanthryl.

[0291] In the general formula (19), R 27 The alkylaryl group having 7 to 30 carbon atoms shown herein includes a group in which one hydrogen atom of the above-mentioned alkyl group is substituted with the above-mentioned aryl group.

[0292] In the general formula (19), R 27 The arylalkyl group having 7 to 30 carbon atoms shown herein includes a group in which one hydrogen atom of the above aryl group is substituted with the above alkyl group.

[0293] In the general formula (19), R 28 , R 29 , R 30 and R 31 Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, and tert-octyl.

[0294] In the general formula (19), R 28 Examples of the alkenyl group having 3 to 8 carbon atoms include 1-methylvinyl, 2-methylvinyl, 2-propenyl, 1-methyl-3-propenyl, 3-butenyl, 1-methyl-3-butenyl, isobutenyl, 3-pentenyl, 4-hexenyl, cyclohexenyl, heptenyl, and octenyl.

[0295] The compound represented by general formula (19) may also have a structure in which the carbon atoms forming the ring structure of the methylene group and cycloalkyl group in the above-mentioned alkyl, alkenyl, alkylaryl and arylalkyl groups are replaced by -O-, -S-, -CO-, -O-CO-, -CO-O-, or -NR'-.

[0296] The hydrogen atoms of the above-mentioned alkyl, cycloalkyl, alkenyl, alkylaryl and arylalkyl groups of the compound represented by general formula (19) may be substituted by hydroxyl groups, halogen atoms, linear or branched alkyl groups having 1 to 12 carbon atoms, or alkoxy groups having 1 to 12 carbon atoms.

[0297] The following compounds are exemplified as specific structures of the compound represented by the general formula (19), but the present invention is not limited to these compounds.

[0298]

[0299] Examples of products containing the compound represented by the general formula (19) include "ADKSTAB LA-46" and "ADK STAB LA-F70" manufactured by ADEKA Corporation, "Cyasorb 1164" manufactured by Cytec, and "Tinuvin 400", "Tinuvin 405", "Tinuvin 460", "Tinuvin 477", "Tinuvin 479", "Tinuvin 1577", and "Tinuvin 1600" manufactured by BASF.

[0300] In the general formula (20), R 32 Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, sec-pentyl, tert-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, and tert-octyl.

[0301] The following compounds are exemplified as specific structures of the compound represented by the general formula (20), but the present invention is not limited to these compounds.

[0302]

[0303] In the general formula (21), R 33 , R 34 and R 37 Examples of the alkyl group having 1 to 18 carbon atoms, the hydroxyalkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms, the hydroxyalkoxy group having 1 to 18 carbon atoms, and the alkylaryl group having 7 to 30 carbon atoms include the same groups as described above.

[0304] In the general formula (21), R 33 , R 34 and R 37 Examples of the alkoxyaryl group having 7 to 30 carbon atoms include groups in which one hydrogen atom of the above-mentioned alkoxy group having 1 to 18 carbon atoms is substituted with an aryl group, and examples thereof include benzyloxy and the like.

[0305] In the general formula (21), R 33 , R 34 and R 37 Examples of the acryloyloxyalkoxy group having 4 to 15 carbon atoms or the methacryloyloxyalkoxy group having 5 to 15 carbon atoms include a (meth)acryloyloxymethoxy group, a (meth)acryloyloxyethoxy group, and a (meth)acryloyl(2-hydroxy)propoxy group.

[0306] The following compounds are exemplified as specific structures of the compound represented by the general formula (21), but the present invention is not limited to these compounds.

[0307]

[0308] Examples of commercially available products containing the compound represented by the general formula (21) include “ADK STAB 1413” and “ADK STAB LA-51” manufactured by ADEKA Corporation, “Seesorb 100”, “Seesorb 101”, “Seesorb 104”, “Seesorb 106”, “Seesorb 107” and “Seesorb 151” manufactured by SHIPRO KASEI KAISHA, LTD., “Cyasorb UV-21”, “Cyasorb UV-24”, “Cyasorb UV-207”, “Cyasorb UV-284” and “Cyasorb UV-2126” manufactured by Cytec, and “Uvinul 3030” and “Uvinul 3048” manufactured by BASF.

[0309] In the resin composition according to still another preferred embodiment of the present invention, the amount of the (J) ultraviolet absorber added is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, based on 100 parts by mass of the thermoplastic resin.

[0310] In the resin composition of another preferred embodiment of the present invention, the preferred compounding amount of the (H) light stabilizer is 0.001 to 10 parts by mass, more preferably 0.01 to 0.5 parts by mass, relative to 100 parts by mass of the thermoplastic resin. When the amount of the light stabilizer is less than 0.001 parts by mass, weather resistance may not be imparted, and when it exceeds 10 parts by mass, the effect of the addition amount may not be obtained, and the light stabilizer may ooze out on the surface of the molded body and impair the appearance. The (H) light stabilizer may be compounded with the (I) hindered amine compound or the (J) ultraviolet absorber alone, or two or more of these compounds may be compounded.

[0311] In the resin composition of further other preferred embodiments of the present invention, the (H) light stabilizer can be added to the thermoplastic resin after being impregnated in the carrier as needed. In order to be impregnated in the carrier, it can be directly heated and mixed, or it can be a method of diluting with an organic solvent as needed and then impregnating in the carrier, and then removing the solvent. As such a carrier, a substance known as a filler or filler for a synthetic resin, or a flame retardant or light stabilizer that is solid at room temperature, such as calcium silicate powder, silicon dioxide powder, talcum powder, aluminum oxide powder, titanium oxide powder, or a substance chemically modified on the surface of these carriers, a solid substance in the flame retardant or antioxidant listed below, etc. Among these carriers, a substance that is chemically modified on the surface of the carrier is preferred, and a substance that is chemically modified on the surface of the silicon dioxide powder is more preferred. The average particle size of these carriers is preferably 0.1 to 100 μm, and more preferably 0.5 to 50 μm.

[0312] There is no particular limitation on the method of mixing the component (A), component (B), and component (H) (component (I) and / or component (J)) of the resin composition of another preferred embodiment of the present invention with a thermoplastic resin, and commonly used methods may be cited, such as a method of dry-blending thermoplastic resin powder or pellets with each component; or a method of preparing a masterbatch containing any one of the components at a high concentration and adding it to a thermoplastic resin; or a method of processing the component (A), component (B), and component (H) (component (I) and / or component (J)) into a pellet shape and adding it to a thermoplastic resin. In addition, each component may be added to the olefin resin simultaneously or separately.

[0313] As a method for processing into a pellet shape, for example, the following method can be used to produce: any one of the components (A), (B), and (H) (components (I) and / or (J)) and a phenolic antioxidant and other additives optionally included as required are mixed, the resulting mixture is heated, and mixed in the presence of a molten phenolic antioxidant. There is no limitation on processing conditions, processing machines, etc., and known conventional processing methods and processing machines can be used. As specific production methods, a disk pelletizer method, an extrusion method, etc. can be cited.

[0314] The resin composition of further preferred embodiments of the present invention may optionally contain known resin additives (for example, phenolic antioxidants, phosphorus antioxidants, thioether antioxidants, nucleating agents different from the phosphate compound represented by general formula (1) (A), flame retardants, flame retardant aids, lubricants, fillers, hydrotalcites, antistatic agents, pigments, fluorescent whitening agents, dyes, etc.) within a range that does not significantly impair the effects of the present invention.

[0315] Examples of the nucleating agent other than the phosphate compound represented by the formula (1) above include carboxylic acid metal salts such as sodium benzoate, 4-tert-butylbenzoic acid aluminum salt, sodium adipate, and disodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; polyol derivatives such as dibenzylidene sorbitol, bis(methylbenzylidene)sorbitol, bis(3,4-dimethylbenzylidene)sorbitol, bis(p-ethylbenzylidene)sorbitol, and bis(dimethylbenzylidene)sorbitol; and amide compounds such as N,N',N"-tri[2-methylcyclohexyl]-1,2,3-propanetricarboxamide, N,N',N"-tricyclohexyl-1,3,5-benzenetricarboxamide, N,N'-dicyclohexylnaphthalene dicarboxamide and 1,3,5-tris(dimethylisopropylamino)benzene. These may be used alone or in combination of two or more. When the nucleating agent is added, the total amount of the phosphate compound (A) represented by the formula (1) is 0.001 to 10 parts by mass, more preferably 0.006 to 0.5 parts by mass, based on 100 parts by mass of the thermoplastic resin (A).

[0316] When the resin composition of further other preferred embodiments of the present invention is molded, known molding methods can be used for molding. For example, a molded product can be obtained by injection molding, extrusion molding, blow molding, vacuum molding, inflation molding, calendaring, slush molding, dipping molding, foaming molding, etc.

[0317] As applications of the resin composition according to still other preferred embodiments of the present invention, there can be listed automotive materials such as bumpers, control panels, and instrument panels, housing applications for refrigerators, washing machines, and vacuum cleaners, household items such as tableware, buckets, and toiletries, sundry goods such as toys, and molded products such as storage and preservation containers such as cans, films, and fibers.

[0318] Example

[0319] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples and the like.

[0320] (Preparation of resin additive composition)

[0321] [Examples 1-1 to 1-6 and Comparative Examples 1-1 to 1-3]

[0322] Resin additive compositions of (A) a phosphate compound represented by the general formula (1) and (B) a sodium fatty acid represented by the general formula (2) were prepared in the ratios shown in Table 1. The units of the blending amounts in the table are parts by mass. For each of the obtained compositions, the angle of repose and the adhesion were measured and evaluated according to the following procedures.

[0323] (1) Angle of repose

[0324] The resin additive composition described in Table 1 was put into a cylindrical container (500 mL) to make half the capacity of the cylindrical container and cover it with a lid. The repose angle measuring device (Revolving Cylinder Test) manufactured by Tsutsui Rikagaku Instrument Co., Ltd. was used to rotate it at a constant speed at a speed of 2.0 rpm to evaluate the fluidity of the sample. When the cylindrical container rotates, the sample rises along the rotating container, and the sample collapses from a high position. When the inclined surface formed by the collapsed sample reaches a certain state, the angle formed by the inclined surface of the sample and the horizontal plane is measured as the repose angle. The results obtained are shown in Table 1. It should be noted that, since the collapse of the sample in Comparative Example 1-1 is intermittent and the inclined surface is not planar, the repose angle is not measured.

[0325] (2) Adhesion

[0326] Using a Henschel mixer, 2.5 kg of the resin additive composition described in Table 1 was mixed at 1000 rpm × 1 minute, and then the state of the resin additive composition adhering to the inner wall of the stirring tank of the Henschel mixer was evaluated. The case where the resin additive composition adhered to more than 50% of the inner wall of the stirring tank of the Henschel mixer was evaluated as "×", the case where the resin additive composition adhered to less than 50% of the wall surface was evaluated as "△", and the case where the resin additive composition adhered to the inner wall was a small amount was evaluated as "○". The obtained results are shown in Table 1.

[0327] [Table 1]

[0328]

[0329] (A)-1: Sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate

[0330] (B)-1: Sodium stearate

[0331] According to Comparative Example 1-1 in Table 1, the resin additive composition composed only of the phosphate compound represented by the general formula (1) (A) has poor fluidity. In addition, from Comparative Examples 1-2 and 1-3, it was confirmed that the resin additive composition having a mass ratio of (B) / (A) of less than 0.55 has poor fluidity and a large amount of the resin additive composition adheres to the wall surface of the Henschel mixer. In contrast, it was confirmed that the resin additive compositions of the present invention of Examples 1-1 to 1-6 have a small angle of repose and excellent fluidity.

[0332] [Examples 2-1 to 2-4, Comparative Examples 2-1 to 2-5]

[0333] (Evaluation of resin composition)

[0334] Relative to 100 parts by mass of homopolypropylene (Prime Polymer Co., Ltd. product name "H700", melt flow rate = 8.0 g / 10 minutes (according to ISO standard 1133 2.16 kg × 230 ° C)), 0.05 parts by mass of phenolic antioxidant (tetrakis [methylene-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane), 0.1 parts by mass of phosphorus antioxidant (tris (2,4-di-tert-butylphenyl) phosphite), 0.05 parts by mass of calcium stearate and the resin additive composition shown in Tables 2 and 3 were mixed with a Henschel mixer at 1000 rpm × 1 minute, and then kneaded using a twin-screw extruder under the conditions of extrusion temperature = 230 ° C, screw speed = 150 rpm, and feed rate = 7.2 kg / hour to produce pellets. The unit of the compounding amount in the table is mass part. The obtained resin composition was evaluated by the following method. The obtained results are shown in Tables 2 and 3.

[0335] (3) Crystallization temperature

[0336] A small amount of the obtained pellets was cut and the crystallization temperature was measured using a differential scanning calorimeter (manufactured by Diamond Parkinson Elmer). The measurement method was to raise the temperature from room temperature to 230°C at a rate of 50°C / min, hold for 10 minutes, and then cool to 50°C at a rate of 10°C / min. The temperature at which the endothermic reaction reached the peak was taken as the crystallization temperature.

[0337] (4) Flexural modulus

[0338] The obtained pellets were injection molded using an injection molding machine (EC100-2A; manufactured by Toshiba Machine Co., Ltd.) at an injection temperature of 200°C and a mold temperature of 50°C to produce test pieces with a size of 80 mm×10 mm×4 mm. After molding, the test pieces were immediately placed in a constant temperature machine at 23°C and allowed to stand for 48 hours. The test pieces were then taken out and the flexural modulus (MPa) of the test pieces was measured in accordance with ISO-178.

[0339] (5)HAZE

[0340] The obtained pellets were injection molded using an injection molding machine (EC100-2A; manufactured by Toshiba Machine Co., Ltd.) at an injection temperature of 200°C and a mold temperature of 50°C to produce test pieces with a size of 60 mm×60 mm×1 mm. After molding, the test pieces were immediately placed in a constant temperature machine at 23°C and allowed to stand for 48 hours. The test pieces were then taken out and the HAZE of the test pieces was measured in accordance with ISO-14782.

[0341] [Table 2]

[0342]

[0343] [Table 3]

[0344]

[0345] (A)-1: Sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate

[0346] (B)-1: Sodium stearate

[0347] (B)-2: Sodium laurate

[0348] (B)-3: Sodium myristate

[0349] (B)-4: Sodium palmitate

[0350] (B)'-1: Lithium stearate

[0351] (B)'-2: Magnesium stearate

[0352] (B)'-3: Zinc stearate

[0353] (B)'-4: Aluminum stearate

[0354] According to the comparison of Comparative Examples 2-1 to 2-4 and Comparative Example 2-5 in Tables 2 and 3, it can be seen that the physical properties of the resin composition of the present invention are superior to those of the resin composition of Comparative Example 2-5 when a fatty acid metal salt different from the fatty acid sodium salt is mixed and added compared to the case where the resin additive composition consisting of only the phosphate compound represented by the general formula (A) (1) is added. In contrast, according to Examples 2-1 to 2-4, it was confirmed that the resin composition of the present invention has excellent physical properties compared to the resin composition of Comparative Example 2-5.

[0355] [Examples 3-1 to 3-8, Comparative Examples 3-1 to 3-7]

[0356] In the impact copolymer of polypropylene (Prime Polymer Co., Ltd. product name "J705P", melt flow rate = 11.5g / 10min (according to ISO standard 1133 A peroxide (2,5-dimethyl-2,5-di(tert-butylperoxy)hexane) was added to 100 parts by mass of a polyolefin resin prepared so as to have a melt flow rate of 40 g / 10 minutes, 0.05 parts by mass of a phenolic antioxidant (tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.1 parts by mass of a phosphorus antioxidant (tris(2,4-di-tert-butylphenyl)phosphite), 0.05 parts by mass of calcium stearate and the resin additive composition shown in Tables 4 and 5 were added, and the mixture was mixed at 1000 rpm for 1 minute using a Henschel mixer, and then kneaded using a twin-screw extruder under the conditions of an extrusion temperature of 230° C., a screw speed of 150 rpm and a feed rate of 7.2 kg / hour to produce pellets. In Comparative Example 3-1, the resin additive composition was not blended and kneaded to obtain pellets.

[0357] [Table 4]

[0358]

[0359] [Table 5]

[0360]

[0361] (A)-1: Sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate

[0362] Comparative nucleating agent 1: Milliken, trade name "HPN-20E" (calcium dicyclohexane-1,2-dicarboxylate compound)

[0363] (B)-1: Sodium stearate

[0364] From the comparison between Comparative Examples 3-1 and 3-4 in Table 5, it can be seen that the nucleating agent effect of sodium stearate is small. In addition, from the comparison between Comparative Examples 3-6 and 3-7, it is confirmed that when a nucleating agent different from the phosphate compound represented by (A) general formula (1) is used, the effect of the present invention cannot be obtained. In contrast, from Examples 3-1 to 3-8, it is confirmed that the resin additive composition of the present invention can impart excellent physical properties to a thermoplastic resin by mixing (A) the phosphate compound represented by general formula (1) and (B) the sodium fatty acid represented by general formula (2) at a specific ratio.

[0365] [Examples 4-1 to 4-4, Comparative Examples 4-1 to 4-4]

[0366] 0.05 parts by mass of a phenolic antioxidant (tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.1 parts by mass of a phosphorus antioxidant (tris(2,4-di-tert-butylphenyl)phosphite), 0.05 parts by mass of calcium stearate, and the resin additive composition described in Tables 6 and 7 were blended with 100 parts by mass of homopolypropylene (melt flow rate = 8.0 g / 10 minutes (according to ISO standard 11332.16 kg × 230°C)), mixed with a Henschel mixer at 1000 rpm × 1 minute, and then kneaded with a twin-screw extruder under the conditions of extrusion temperature = 230°C, screw speed = 150 rpm, and feed rate = 7.2 kg / hour to produce pellets. In addition, YI (yellowness) was evaluated according to the following procedure.

[0367] (6)YI

[0368] The obtained pellets were molded into test pieces with a size of 60 mm × 60 mm × 2 mm using an injection molding machine (EC100-2A; manufactured by Toshiba Machine Co., Ltd.) at an injection temperature of 200° C. and a mold temperature of 50° C. Immediately after molding, the test pieces were left at a standard temperature of 23° C. for 48 hours, and then the YI of the test pieces was measured using a spectrocolorimeter (SC-T; manufactured by Suga Test Instruments Co., Ltd.).

[0369] [Table 6]

[0370]

[0371] [Table 7]

[0372]

[0373] (A)-1: Sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate

[0374] Comparative nucleating agent 2: Milliken product name "Hyperform(R) HPN-20E"

[0375] Comparative Nucleating Agent 3: Sodium Benzoate

[0376] (B)-1: Sodium stearate

[0377] Blue Outremer 32: Made by Holliday Pigments SAS (ColorIndex: pigment blue 29)

[0378] Violet Outremer 11: Holliday Pigments SAS (ColorIndex: pigmentviolet15)

[0379] Fluorescent brightener: 2.5-thiophenediylbis(5-tert-butyl-1,3-benzoxazole)

[0380] By comparing Comparative Example 4-1 with Comparative Example 4-2, it was confirmed that when the mass ratio of (B) / (A) exceeds the range of 0.55 to 2.0, the effect of the present invention cannot be obtained. In addition, according to Comparative Examples 4-3 and 4-4, it was confirmed that when a nucleating agent different from the phosphate compound is used, there is a lack of physical property improvement effect. In contrast, by comparing Example 4-1 with Comparative Example 4-2, it was confirmed that the resin composition mixed with the resin additive composition of the present invention has an improved nucleating agent effect compared to the resin composition mixed with the phosphate compound alone.

[0381] [Examples 5-1 to 5-6, Comparative Examples 5-1 to 5-6]

[0382] Impact copolymer with respect to polypropylene {Prime Polymer Co., Ltd. product name "J708P", melt flow rate = 45g / 10min (according to ISO standard 1133 The mixture was mixed with 100 parts by mass of tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane as a phenolic antioxidant, 0.167 parts by mass of tris(2,4-di-tert-butylphenyl)phosphite as a phosphorus antioxidant, 0.083 parts by mass of calcium stearate and the components (A) and (B) shown in Tables 8 and 9, and mixed at 1000 rpm for 1 minute using a Henschel mixer (FM200; manufactured by Mitsui Mining and Mining Co., Ltd.), and then the components (C) and (D) were mixed, mixed for 30 minutes using a rock mixer (manufactured by Aichi Electric Co., Ltd.), and granulated at an extrusion temperature of 230° C. under vacuum pressure to produce pellets. After the pellets were dried at 60° C. for 8 hours, the following evaluations (7) to (9) were performed. In addition, the unit of the compounding amount in Tables 8 and 9 is part by mass.

[0383] (7) Crystallization temperature and half crystallization time

[0384] The obtained pellets were crushed finely, weighed 5 mg and filled into an aluminum pan, and the crystallization temperature and half crystallization time were measured using a differential scanning calorimeter (device: diamond made by PerkinElmer). For the measurement, the temperature was raised to 230°C at a rate of 50°C / min, maintained for 5 minutes, and then cooled to 50°C at 10°C / min. The temperature of the exothermic peak measured was obtained as the crystallization temperature. In addition, for the half crystallization time, the temperature was raised to 230°C at a rate of 50°C / min, maintained for 5 minutes, and then cooled to 135°C at 100°C / min and maintained. The half crystallization time was obtained by the 50% time point of the total area of ​​the exothermic peak measured.

[0385] (8) Izod impact strength

[0386] The obtained pellets were injection molded using an injection molding machine (device: EC100-2A manufactured by Toshiba Machine Co., Ltd.) at an injection temperature of 200° C. and a mold temperature of 40° C. to form a test piece with a notch of 80 mm×10 mm×4 mm. The notched test piece was immediately left to stand in a thermostat at 23° C. for 48 hours after molding, and then the test piece was taken out and the Izod impact strength (J / m) was measured in accordance with ISO-180.

[0387] (9) YI (yellowness)

[0388] The obtained pellets were molded into test pieces of 60 mm × 60 mm × 2 mm using an injection molding machine (EC100-2A; manufactured by Toshiba Machine Co., Ltd.) at an injection temperature of 200° C. and a mold temperature of 50° C. Immediately after molding, the test pieces were left at room temperature of 23° C. for 48 hours under standard conditions, and then the YI of the test pieces was measured using a spectrocolorimeter (SC-T; manufactured by Suga Test Instruments Co., Ltd.).

[0389] [Table 8]

[0390]

[0391] (A)-1: Sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate

[0392] (B)-1: Sodium stearate

[0393] (C)-1: Dow's product name: polyolefin elastomer "Engage 8200"

[0394] (D)-1: Matsumura Industrial Co., Ltd. Product name "CROWN TALC PP"

[0395] Comparative nucleating agent 1: "Hyperform HPN20E" manufactured by Milliken

[0396] Comparative Nucleating Agent 2: Sodium Benzoate

[0397] [Table 9]

[0398]

[0399] According to the comparison results of Comparative Example 5-4 and Comparative Example 5-5, even if sodium fatty acid is mixed with a nucleating agent that is not a phosphate compound, almost no effect on the nucleating agent effect is observed. In contrast, according to the comparison results of Examples 5-1 to 5-6 and Comparative Example 5-3, it is confirmed that the resin composition containing a phosphate compound and sodium fatty acid at a specific ratio has a significantly improved nucleating agent effect compared to the case where the phosphate compound is added alone. In addition, it is confirmed that the molded body using the resin composition of the present invention has excellent impact resistance and can suppress yellowing compared to the case where the phosphate compound is added alone.

[0400] From the above, it was confirmed that the resin composition of the present invention can be suitably used in applications requiring particularly impact resistance, such as automotive materials.

[0401] [Examples 6-1 to 6-5, Comparative Examples 6-1 to 6-13]

[0402] 100 parts by mass of an impact copolymer {Prime Polymer Co., Ltd. product name "J708P", melt flow rate = 45 g / 10 minutes (according to ISO standard 1133 2.16 kg × 230°C)}, 0.05 parts by mass of a phenolic antioxidant (tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.05 parts by mass of calcium stearate and the resin additive composition described in Tables 10 to 12 were blended, mixed with a Henschel mixer at 1000 rpm × 1 minute, and then pelletized with a twin-screw extruder at an extrusion temperature of 230°C. The pelletized pellets were dried at 80°C for 2 hours, and then pelletized repeatedly with the same twin-screw extruder at an extrusion temperature of 230°C, and the influence of the thermal history on the following (10) to (12) was evaluated. In addition, the unit of the compounding amount in Tables 10 to 12 is part by mass.

[0403] (10) YI (yellowness)

[0404] Each pellet with different thermal history was molded into a test piece with a size of 60 mm × 60 mm × 2 mm using an injection molding machine (EC100-2A; manufactured by Toshiba Machine Co., Ltd.) at an injection temperature of 200° C. and a mold temperature of 50° C. Immediately after molding, the test piece was left at room temperature of 23° C. for 48 hours under standard conditions, and then the YI of the test piece was measured using a spectrocolorimeter (SC-T; manufactured by Suga Test Instruments Co., Ltd.).

[0405] (11) Crystallization temperature

[0406] A small amount of the obtained pellets was cut and the crystallization temperature was measured using a differential scanning calorimeter (manufactured by Diamond Parkinson Elmer). The measurement method was to raise the temperature from room temperature to 230°C at a rate of 50°C / min, hold for 10 minutes, and then cool to 50°C at a rate of -10°C / min. The temperature at which the endothermic reaction reached the peak was taken as the crystallization temperature.

[0407] (12) Izod impact strength

[0408] Each pellet with different thermal history was injection molded by an injection molding machine (EC100-2A; manufactured by Toshiba Machine Co., Ltd.) at an injection temperature of 200°C and a mold temperature of 50°C to form a notched test piece of 10 mm×4 mm×100 mm in size. Immediately after molding, the pellet was placed in a constant temperature machine at 23°C and left to stand for 48 hours, then the test piece was taken out and the Izod impact strength rate (J / m) of the notched test piece was measured in accordance with ISO-180.

[0409] [Table 10]

[0410]

[0411] (A)-1: Sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate

[0412] (B)-1: Sodium stearate

[0413] (E)-1: PEP-24 (3,9-bis(2,4-di-tert-butylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane)

[0414] Comparative Nucleating Agents: Sodium Benzoate

[0415] Comparison of phosphites: tris(2,4-di-tert-butylphenyl) phosphate

[0416] [Table 11]

[0417]

[0418] [Table 12]

[0419]

[0420] According to 6-4, when the nucleating agent is different from the (A) component used in the resin composition of the present invention, the discoloration caused by the thermal history is large and the crystallization temperature cannot be met. In addition, according to 6-2 and Comparative Example 6-3, it is confirmed that when the (B) / (A) mass ratio exceeds the range of 0.55 to 2.0, the yellowing degree caused by the thermal history becomes higher. In addition, according to Comparative Examples 6-5 to 6-8, it is confirmed that when the phosphate compound is different from the (B) component used in the resin composition of the present invention, the yellowing degree caused by the thermal history is high and the crystallization temperature is slightly reduced. It is confirmed that when the thermal history of the usual granulation process is repeated, the Izod impact strength of the molded product decreases, but the impact strength of the molded product using the resin composition of the present invention is not reduced by the thermal history, but is improved.

[0421] [Examples 7-1 to 7-7, Comparative Examples 7-1 to 7-2]

[0422] Relative to 100 parts by mass of the impact copolymer {Prime Polymer Co., Ltd. product name "J708P", melt flow rate = 45g / 10 minutes (according to ISO standard 1133 2.16kg×230°C)}, 0.05 parts by mass of a phenolic antioxidant (tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane), 0.05 parts by mass of calcium stearate and the resin additive composition described in Tables 13 and 14 were mixed, and mixed using a Henschel mixer at 1000rpm×1 minute, and then granulated using a twin-screw extruder at an extrusion temperature of 230°C. After drying the granulated pellets at 80°C for 2 hours, the same twin-screw extruder was used to repeat granulation at an extrusion temperature of 230°C, and the effect on the melt flow rate (MFR) caused by the thermal history was evaluated. It should be noted that the unit of the compounding amount in the table is mass part.

[0423] (13) MFR (g / 10min)

[0424] According to ISO1133, the obtained pellets were melted at 230°C, a load of 2.16 kg was applied and the weight of the extruded molten resin was measured, and the discharge amount of the resin converted in 10 minutes was taken as the melt flow rate (MFR: g / 10 minutes).

[0425] [Table 13]

[0426]

[0427] (A)-1: Sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate

[0428] Comparative Nucleating Agents: Sodium Benzoate

[0429] (B)-1: Sodium stearate

[0430] (E)-2: PEP-36 (3,9-bis(2,6-di-tert-butyl-4-methylphenoxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane

[0431] [Table 14]

[0432]

[0433] According to the comparison results of Comparative Example 7-1 and Comparative Example 7-2, it was confirmed that when the nucleating agent is different from the (A) component of the resin composition of the present invention, the MFR increases compared with the resin composition without a nucleating agent when the thermal history is repeated. In contrast, according to Examples 7-1 to 7-7, it was confirmed that when the olefin resin composition of the present invention is used, the increase in the MFR value caused by the thermal history can be suppressed.

[0434] From the above results, it was confirmed that the resin composition of the present invention provides an olefin resin composition having an excellent effect of preventing discoloration due to thermal history and excellent physical properties.

[0435] [Examples 8-1 to 8-13, Comparative Examples 8-1 to 8-11]

[0436] 0.05 parts by mass of a phenolic antioxidant (tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.1 parts by mass of a phosphorus antioxidant (tris(2,4-di-tert-butylphenyl)phosphite) and 0.05 parts by mass of calcium stearate were mixed with the resin compositions described in the following Tables 15 to 18, mixed at 1000 rpm × 1 minute using a Henschel mixer, and then kneaded using a twin-screw extruder at an extrusion temperature of 230°C, a screw speed of 150 rpm, and a feed rate of 7.2 kg / hour to produce pellets. The pellets were used to perform the following evaluations (14) to (16). It should be noted that the units of the compounding amounts in Tables 15 to 18 are parts by mass.

[0437] (14) Crystallization temperature

[0438] A small amount of the obtained pellets were cut and the crystallization temperature was measured using a differential scanning calorimeter (manufactured by Diamond PerkinElmer). The measurement method was to raise the temperature from room temperature to 230°C at a rate of 50°C / min, hold for 10 minutes, and then cool to 50°C at a rate of 10°C / min. The temperature at which the endothermic reaction reached the peak was taken as the crystallization temperature.

[0439] (15) Flexural modulus

[0440] The obtained pellets were injection molded using an injection molding machine (EC100-2A; manufactured by Toshiba Machine Co., Ltd.) at an injection temperature of 200°C and a mold temperature of 50°C to produce test pieces with a size of 80 mm×10 mm×4 mm. After molding, the test pieces were immediately placed in a constant temperature machine at 23°C and allowed to stand for 48 hours. The test pieces were then taken out and the flexural modulus (MPa) of the test pieces was measured in accordance with ISO-178.

[0441] (16) Flame retardancy UL-94V test

[0442] The obtained flame retardant UL-94V test test piece (127mm×12.7mm×1.6mm) was kept vertical, and the lower end was contacted with the flame of the burner for 10 seconds to ignite it, and then the flame was removed, and the time for the flame of the test piece to go out was measured. Then, if the flame is extinguished, it is ignited for a second time for 10 seconds at the same time, and the time for the ignition flame to go out is measured in the same way as the first time. In addition, it is also evaluated whether the cotton under the test piece is ignited by the falling fire. Based on the burning time of the first and second times and the presence or absence of cotton ignition, the combustion level is set according to the UL-94V standard. Combustion level V-0 is the most excellent flame retardancy, and the flame retardancy decreases as it becomes V-1 and V-2. Anything that does not belong to the V-0 to V-2 levels is NR.

[0443] [Table 15]

[0444]

[0445] Thermoplastic resin: impact copolymer (Prime Polymer Co., Ltd. product name "J705P", melt flow rate = 11.5 g / 10 min (according to ISO standard 1133 2.16 kg × 230 ° C))

[0446] (A)-1: Sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate

[0447] Comparative nucleating agent 1: dicyclohexane-1,2-dicarboxylic acid calcium compound

[0448] Comparative Nucleating Agent 2: Sodium Benzoate

[0449] (B)-1: Sodium stearate

[0450] (F)-1: Intumescent flame retardant; trade name of ADEKA Corporation (ADK STAB FP-2500S)

[0451] (F)-2: Intumescent flame retardant; trade name of ADEKA Corporation (ADK STAB FP-2100JC)

[0452] (F)-3: Ammonium polyphosphate

[0453] (F)-4: Decabromodiphenylethane

[0454] (G)-1: THEIC (tris(2-hydroxyethyl)isocyanurate)

[0455] (G)-2: Antimony trioxide (G)-3: Polytetrafluoroethylene [Table 16]

[0456]

[0457] [Table 17]

[0458]

[0459] [Table 18]

[0460]

[0461] According to the comparison between Comparative Example 8-3 and Examples 8-7 and 8-8, it was confirmed that the resin additive composition of the present invention, which is a mixture of (A) a phosphate compound represented by the general formula (1) and (B) a sodium salt of a fatty acid represented by the general formula (2), can impart excellent physical properties compared to the resin composition in which the phosphate compound represented by the general formula (1) is solely mixed.

[0462] From the above results, it was confirmed that the resin composition of the present invention can obtain excellent physical property improvement effects when a flame retardant is blended.

[0463] [Examples 9-1 to 9-20, Comparative Examples 9-1 to 9-5]

[0464] With respect to 100 parts by mass of the impact copolymer {Prime Polymer Co., Ltd. product name "J705P", melt flow rate = 11.5 g / 10 minutes (according to ISO standard 1133 2.16 kg × 230 ° C)}, 0.05 parts by mass of a phenolic antioxidant (tetrakis [methylene-3- (3', 5'-di-tert-butyl-4'-hydroxyphenyl) propionate] methane) 0.05 parts by mass, 0.05 parts by mass of calcium stearate and the resin additive composition of Tables 19 to 23 were mixed, and mixed with a Henschel mixer at 1000 rpm × 1 minute, and then granulated at an extrusion temperature of 230 ° C using a twin-screw extruder to obtain pellets. It should be noted that the unit of the compounding amount in Tables 19 to 23 is mass parts.

[0465] (17) Crystallization temperature [℃]

[0466] The obtained pellets were crushed finely, weighed 5 mg and filled into an aluminum pan, and the crystallization temperature was measured using a differential scanning calorimeter (device: diamond manufactured by PerkinElmer). For the measurement, the temperature was raised to 230°C at a rate of 50°C / min, maintained for 5 minutes, and then cooled to 50°C at a rate of 10°C / min, and the temperature of the exothermic peak measured was determined as the crystallization temperature.

[0467] (18) Flexural modulus [MPa]

[0468] The obtained pellets were injection molded using an injection molding machine (EC100-2A; manufactured by Toshiba Machine Co., Ltd.) at an injection temperature of 200°C and a mold temperature of 50°C to produce test pieces with a size of 80 mm×10 mm×4 mm. After molding, the test pieces were immediately placed in a constant temperature machine at 23°C and allowed to stand for 48 hours. The test pieces were then taken out and the flexural modulus (MPa) of the test pieces was measured in accordance with ISO-178.

[0469] [Table 19]

[0470]

[0471] [Table 20]

[0472]

[0473] [Table 21]

[0474]

[0475] [Table 22]

[0476]

[0477] [Table 23]

[0478]

[0479] Thermoplastic resin: impact copolymer {Prime Polymer Co., Ltd. product name "J705P", melt flow rate = 11.5 g / 10 minutes (according to ISO standard 1133 2.16 kg × 230 ° C)

[0480] (A)-1: Sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate

[0481] Comparative nucleating agent 1: Milliken product name "Hyperform(R) HPN-20E"

[0482] Comparative Nucleating Agent 2: Sodium Benzoate

[0483] (B)-1: Sodium stearate

[0484] (I)-1: Trade name "ADK STAB LA-77Y" manufactured by ADEKA Co., Ltd.

[0485] (I)-2: Trade name "ADK STAB LA-72" manufactured by ADEKA Co., Ltd.

[0486] (I)-3: Trade name "ADK STAB LA-52" manufactured by ADEKA Co., Ltd.

[0487] (I)-4: Trade name "ADK STAB LA-502" manufactured by ADEKA Co., Ltd.

[0488] (I)-5: Trade name "ADK STAB LA-63P" manufactured by ADEKA Co., Ltd.

[0489] (I)-6: Trade name "ADK STAB T-1640L" manufactured by ADEKA Co., Ltd.

[0490] (I)-7: Trade name "ADK STAB LA-81" manufactured by ADEKA Co., Ltd.

[0491] (I)-8: Trade name "ADK STAB LA-704" manufactured by ADEKA Co., Ltd.

[0492] (I)-9: Trade name "ADK STAB LA-40" manufactured by ADEKA Co., Ltd.

[0493] (I)-10: Trade name "ADK STAB LA-402" manufactured by ADEKA Co., Ltd.

[0494] (I)-11: BASF product name "Chimassorb 944"

[0495] (I)-12: BASF product name "Chimassorb 2020"

[0496] (I)-13: Cytec, trade name "Cyasorb UV-3808PP5"

[0497] (I)-14: BASF, trade name "Tinuvin XT-855FF"

[0498] (J)-1: Trade name "ADK STAB LA-36" manufactured by ADEKA Co., Ltd.

[0499] (J)-2: Trade name "ADK STAB LA-29" manufactured by ADEKA Co., Ltd.

[0500] (J)-3: Cytec, trade name "Cyasorb UV-1164"

[0501] According to the comparison between Comparative Example 9-1 and Examples 9-1 to 9-5, when the mass ratio (B) / (A) exceeds the range of 0.55 to 2.0, the nucleating agent effect is lacking. In addition, as can be seen from Comparative Examples 9-3 and 9-4, the case where a nucleating agent different from the phosphate compound represented by the general formula (1) is mixed, and as can be seen from Comparative Example 9-2, the case where the nucleating agent is the phosphate compound represented by the general formula (1) but no fatty acid sodium is mixed, both lack the nucleating agent effect.

[0502] On the other hand, it was confirmed that the thermoplastic resin composition of the present invention exhibits an excellent nucleating agent effect.

Claims

1. A resin additive composition, characterized in that: (A) the phosphoric acid ester compound represented by the following general formula (1) and (B) the fatty acid sodium salt represented by the following general formula (2) are in a range of (B) / (A)=0.55 to 2.0 in terms of mass ratio, In formula (1), R 1 ~R 4 Each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 9 carbon atoms, and R 5 represents an alkylene group having 1 to 4 carbon atoms, In formula (2), R 6 It represents a group introduced from an aliphatic organic acid having 7 to 30 carbon atoms.

2. A thermoplastic resin composition, characterized in that The resin additive composition according to claim 1 is contained in an amount of 0.001 to 10 parts by mass of the phosphate ester compound (A) represented by the general formula (1) based on 100 parts by mass of the thermoplastic resin.

3. The thermoplastic resin composition according to claim 2, wherein The thermoplastic resin is a polyolefin resin.

4. The thermoplastic resin composition according to claim 2, wherein The composition further contains 1 to 80 parts by mass of (C) a thermoplastic elastomer and 1 to 80 parts by mass of (D) a filler.

5. The thermoplastic resin composition according to claim 4, wherein The (C) thermoplastic elastomer is a copolymer of ethylene and α-olefin or a copolymer of ethylene and vinyl ester.

6. The thermoplastic resin composition according to claim 2, wherein (E) 0.01 to 10 parts by mass of a phosphite compound represented by the following general formula (3), In formula (3), R 7 , R 8 Each independently represents an alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 40 carbon atoms.

7. A molded body, characterized in that The thermoplastic resin composition according to claim 2 is used.

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