RU2804467C2 - Composition, thermoplastic resin composition using it and the product molded from it - Google Patents

Abstract

FIELD: resins.

SUBSTANCE: group of inventions relates to composition of additives for thermoplastic resin, composition of thermoplastic resin containing it, and moulded product from it. The composition of thermoplastic resin additives comprises: (A) an aluminium salt of a cyclic organophosphorus acid having the following formula (1): where each of R¹-R⁴ represents a tert-butyl group, and R⁵ represents a methylene group; (B) sodium carboxylate; and (C) a fatty acid metal salt having the following formula (2): where R⁶ represents the residue of an aliphatic organic acid containing from 10 to 30 carbon atoms, from which the carboxyl group is excluded, and M¹ represents a lithium or potassium atom, where the thermoplastic resin is a resin based on polypropylene, where (A) an aluminium salt of a cyclic organophosphorus acid, described by formula (1), is hydroxybis[2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate]aluminum, where (B) sodium carboxylate is at least one representative selected from the group consisting of an aromatic sodium carboxylate and a sodium salt of a fatty acid having 10 to 21 carbon atoms, and where the molar ratio between (C) the fatty acid metal salt of formula (2) and (B) the sodium salt of the fatty acid (C)/(B) is in the range of 0.30 to 5.00, and the molar ratio between (A) the aluminium salt of the cyclic organophosphorus acid represented by the formula (1), (B) the sodium salt of the fatty acid, and (C) the salt fatty acid and metal, described by the formula (2), (A)/{(B) + (C)} is in the range from 0.15 to 0.70. A thermoplastic resin composition for the manufacture of moulded articles and a moulded article containing the thermoplastic resin composition are also described.

EFFECT: providing a composition with improved physical properties and improved transparency properties.

6 cl, 7 tbl, 50 ex

Description

Field of technology to which the invention relates

The present invention relates to a composition, a thermoplastic resin composition containing the same, and a molded article thereof. More specifically, the present invention relates to: a composition that can impart excellent clarity and physical properties to a thermoplastic resin; a thermoplastic resin composition containing the same; and a molded product thereof.

State of the art

Thermoplastic resins, depending on their physical properties including formability and low relative density, are widely used in various molded products, such as building materials, automobile materials, household appliance and electronics materials, fiber materials, packaging materials, agricultural materials, household electrical appliance housing materials , various household goods, films, sheets and load-bearing structural elements. In particular, polyolefin-based resins such as polyethylene, polypropylene and polybutene-1 advantageously exhibit excellent moldability, heat resistance, mechanical properties, low relative density and the like; therefore, they are widely used in films, sheets and various molded products (eg load-bearing structural members).

However, polyolefin-based resins have the disadvantages of exhibiting poor molding cycle performance due to their low post-moulding crystallization rates and lacking clarity and strength properties due to the formation of large crystals due to post-thermoforming crystallization. All of these disadvantages are attributed to the crystallinity of the polyolefin resins, and as is known, the problems described above can be resolved by increasing the crystallization temperature of each polyolefin resin and thereby allowing the polyolefin resin to rapidly form fine crystals.

For this purpose, it is known to add a nucleating agent, and examples of known nucleating agents include metal carboxylates such as sodium benzoate, aluminum salt of 4-tert-butylbenzoic acid, sodium adipate and 2-sodium bicyclo[2.2.1]heptane-2,3-dicarboxylate; metal salts and

cyclic organophosphorus acids such as sodium bis(4-tert-butylphenyl)phosphate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate and 2,2'-methylenebis(4,6-di- lithium tert-butylphenyl phosphate; polyhydric alcohol 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-tri(2,2-dimethylpropanamide)benzene.

Among these compounds, metal salts of cyclic organophosphorus acids are known as nucleating agents, which have a high effect on improving the transparency and physical properties of polyolefin resins. For example, Patent Document 1 proposes adding a basic aluminum salt of a cyclic organophosphorus acid and an alkali metal compound such as an alkali metal carboxylate, an alkali metal β-diketonate or an alkali metal β-ketoacetate to a polyolefin or polyethylene terephthalate. In addition, Patent Document 2 proposes a nucleating agent composition containing a polyvalent metal cyclic organophosphorus acid basic salt and an alkali metal salt derivative, and this nucleating agent composition is reported to improve the transparency and toughness of polyolefins.

In addition, Patent Document 3 describes the preference as a nucleating agent for one or a mixture of sodium 2,2'-methylenebis(4,6-di-tert-butylphenoxy)phosphate, sodium di(4-tert-butylphenoxy)phosphate, hydroxybis Aluminum [2,2-methylenebis(4,6-di-tert-butylphenoxy)phosphate], bis(2-alkyl,4-alkylphenoxy)phosphate, sodium bicyclo[2,2,1]heptanedicarboxylate and bicyclo[2,2, 1]calcium heptanedicarboxylate, and the examples section describes resin compositions to which such a nucleating agent and sodium benzoate are added. In addition, Patent Document 4 proposes a nucleating agent composition obtained by mixing aluminum hydroxy-p-tert-butyl benzoate and/or sodium benzoate with aluminum hydroxybis[2,2-methylenebis(4,6-di-tert-butylphenoxy)phosphate . In addition, Patent Document 5 proposes a polypropylene brightener that contains a polyvalent metal salt replacing diarylphosphoric acid and an alkali metal salt of a monobasic fatty acid.

Prior Art Documents

Patent documents

[Patent Document 1] JPH08-120116A

[Patent Document 2] JPH-05-156078A

[Patent Document 3] CN102344609B

[Patent Document 4] CN101845171A

[Patent Document 5] CN101265347B

The essence of the invention

Problems solved by the invention

However, despite the description in Patent Documents 1 and 2 of the combinations of aluminum hydroxybis[2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate and sodium stearate, their nucleation effects are still insufficient, and thus, further improvement is required. In addition, although Patent Document 3 demonstrates an improvement for the creep resistance resin compositions described above, the inclusion of aluminum hydroxybis[2,2-methylenebis(4,6-di-tert-butylphenoxy)phosphate] is not addressed therein, and the transparency and physical properties are not properly assessed. In addition, Patent Document 4 describes compositions obtained by mixing sodium benzoate or a combination of sodium benzoate and aluminum hydroxy-p-tert-hydroxybenzoate with hydroxybis[2,2-methylenebis(4,6-di-tert-butylphenoxy)phosphate ] aluminum; however, there is no further mention of this, and since the incorporation of these compositions into resin is not evaluated, there is still room for research regarding their effects on clarity and physical properties. In addition, Patent Document 5 describes resin compositions that contain aluminum hydroxybis[2,2-methylenebis(4,6-di-tert-butylphenoxy)phosphate], sodium carboxylate such as sodium stearate or sodium resinate, and/or salt an alkali metal and a monobasic fatty acid such as lithium hydroxystearate; however, the effects of these resin compositions are insufficient, and thus further improvement is required.

In view of the above, one object of the present invention is to provide a composition that can impart excellent clarity and physical properties to a thermoplastic resin; a thermoplastic resin composition containing the same; and a molded product thereof.

Troubleshooting Tools

The inventors of the present invention have carried out intensive research aimed at solving the problems described above and have therefore discovered the possibility of achieving the above-described object by using sodium carboxylate in combination with a lithium salt of a fatty acid or a potassium salt of a fatty acid at the specified ratio with respect to the aluminum salt of cyclic organophosphorus acid, thus completing the present invention.

That is, the composition of the present invention is a composition containing:

(A) an aluminum salt of cyclic organophosphorus acid, described by the following formula (1):

,

where each of R ¹ -R ⁴ independently represents a hydrogen atom or a linear or branched alkyl group containing from 1 to 9 carbon atoms, and R ⁵ represents an alkylidene group containing from 1 to 4 carbon atoms;

(B) sodium carboxylate; And

(C) a fatty acid metal salt described by the following formula (2):

,

where R ⁶ represents a group that is introduced into an aliphatic organic acid containing from 10 to 30 carbon atoms, and M ¹ represents a lithium or potassium atom,

the composition is characterized by the fact that:

the molar ratio between (C) the fatty acid metal salt represented by formula (2) and (B) the sodium salt of the fatty acid (C)/(B) is in the range of 0.30 to 5.00, and

the molar ratio between (A) the aluminum salt of a cyclic organophosphorus acid described by formula (1), (B) the sodium salt of a fatty acid and (C) the fatty acid metal salt described by formula (2), (A)/{(B) + (C)} ranges from 0.15 to 0.70.

In the composition of the present invention, the sodium carboxylate is preferably an aromatic sodium carboxylate or a sodium salt of a fatty acid.

The thermoplastic resin composition of the present invention is characterized by the content of the composition of the present invention such that (A) the aluminum salt of cyclic organophosphorus acid represented by formula (1) is contained in an amount ranging from 0.001 to 10 parts by mass, relative to 100 parts by mass of the thermoplastic resin.

In the thermoplastic resin composition of the present invention, the thermoplastic resin is preferably a polyolefin-based resin.

The molded article of the present invention is characterized by containing the thermoplastic resin composition of the present invention.

Effects of the invention

In accordance with the present invention, a composition can be provided that can impart to a thermoplastic resin, in particular a polyolefin-based resin, excellent transparency and physical properties; a thermoplastic resin composition containing the same; and a molded product thereof.

Method for carrying out the invention

Now, embodiments of the present invention will be described in detail. The composition of the present invention contains: (A) an aluminum salt of cyclic organophosphorus acid, described by the following formula (1):

;

(B) sodium carboxylate; and (C) a fatty acid metal salt described by the following formula (2):

.

First, the cyclic organophosphorus acid aluminum salt represented by Formula (1) (hereinafter also referred to as “component (A)”) will be described. In formula (1), R ¹ to R ⁴ each independently represents a hydrogen atom or a linear or branched alkyl group containing 1 to 9 carbon atoms, and R ⁵ represents an alkylidene group containing 1 to 4 carbon atoms.

Examples of the linear or branched alkyl group containing 1 to 9 carbon atoms, which is represented by R ¹ to R ⁴ in formula (1), include methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group , tert-butyl group, isobutyl group, amyl group, tert-amyl group, hexyl group, heptyl group, octyl group, isooctyl group, tert-octyl group, 2-ethylhexyl group, nonyl group and isononyl group, including in the composition of the present invention, a tert-butyl group is particularly preferred.

Examples of the alkylidene group containing 1 to 4 carbon atoms, which is represented by R ⁵ in formula (1), include a methylene group, an ethylidene group, a propylidene group and a butylidene group, of which a methylene group is preferred in the composition of the present invention.

Examples of the method for producing the aluminum salt of a cyclic organophosphorus acid represented by formula (1) according to the composition of the present invention include reacting a cyclic organophosphorus acid having a corresponding structure with an aluminum compound such as aluminum hydroxide, aluminum oxide, aluminum halide, aluminum sulfate , aluminum nitrate or aluminum alkoxide compound, using a reagent such as a basic compound, which is used as needed; carrying out a salt exchange reaction between an alkali metal salt of a cyclic phosphoric acid having an appropriate structure and an aluminum compound such as aluminum hydroxide, aluminum oxide, aluminum halide, aluminum sulfate, aluminum nitrate or an aluminum alkoxide compound, using a reagent that is used as required needs; and producing cyclic phosphoric acid by hydrolysis using a cyclic phosphorus-containing oxychloride as a starting material, and subsequently causing the thus obtained cyclic phosphoric acid to react with a metal compound.

Specific examples of the compound represented by formula (1) include the compounds presented below. However, in the composition of the present invention, component (A) is not so limited.

In the composition of the present invention, component (A) is not limited in terms of particle conditions such as particle size and particle size distribution; however, as is known, the dispersibility of the compound (A) in the resin will be improved if its particle size is small, so the volume average particle size is preferably 100 μm or less, more preferably 30 μm or less, even more preferably 20 μm or less. The term “volume average particle size” as used herein refers to the volume weighted average particle size as determined using a laser diffraction scattering particle size analyzer (MICROTRAC MT3000II, manufactured by MicrotracBEL Corp.).

In the composition of the present invention, aluminum hydroxybis[2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate] is preferred because it can impart the most favorable clarity and physical properties to the polyolefin resin.

The composition of the present invention contains component (A) in an amount in the range of preferably 40 to 75% by weight, more preferably 45 to 70% by weight. In the case of a content level of component (A) of less than 40% by mass or more than 75% by mass, the nucleation effect may be unsatisfactory and the heat resistance may be deteriorated.

The amount of component (A) added to the thermoplastic resin is in the range of 0.001 to 10 parts by mass, preferably 0.006 to 5 parts by mass, based on 100 parts by mass of the thermoplastic resin. In the case of an amount of component (A) that is less than 0.001 parts by mass, the nucleation effect may not be obtained, while an amount that is more than 10 parts by mass makes it difficult to disperse component (A) in the thermoplastic resin, and due to the physical properties and appearance of the resulting molded article may thereby be adversely affected.

Next, sodium carboxylate (B) (hereinafter also referred to as “component (B)”) will be described. In the composition of the present invention, the sodium carboxylate (B), for example, is an aromatic sodium carboxylate or a sodium salt of a fatty acid.

Examples of aromatic carboxylic acid include benzoic acid, tert-butylbenzoic acid, methoxybenzoic acid, dimethoxybenzoic acid, trimethoxybenzoic acid, chlorobenzoic acid, dichlorobenzoic acid, trichlorobenzoic acid, acetoxybenzoic acid, biphenylcarboxylic acid, naphthalenecarboxylic acid, anthracenecarboxylic acid y, furancarboxylic acid and thiophenecarboxylic acid. In the composition of the present invention, the aromatic carboxylic acid is preferably benzoic acid or tert-butylbenzoic acid, since it makes the effects of the present invention pronounced.

Examples of the fatty acid in the sodium salt of the fatty acid include fatty acids into which an alkyl or alkenyl group containing 9 to 29 carbon atoms is introduced together with two or more unsaturated bonds, and the hydrogen atom of such fatty acid may be replaced by a hydroxy group, and the fatty acid can also be branched. Specific examples of the fatty acid include saturated fatty acids such as capric acid, 2-ethylhexanoic acid, undecylic acid, lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, 12-hydroxystearic acid, nonadecylic acid , arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid, cerotinic acid, montanic acid and melissic acid; and linear unsaturated fatty acids such as 4-decenoic acid, 4-dodecenoic acid, palmitoleic acid, α-linolenic acid, linoleic acid, γ-linolenic acid, stearidonic acid, petroselic acid, oleic acid, elaidic acid, vaccenic acid, eicosapentaenoic acid acid, docosapentaenoic acid and docosahexaenoic acid. In the composition of the present invention, a fatty acid having 10 to 21 carbon atoms is preferred, and a fatty acid having 12 to 18 carbon atoms is more preferable. Specifically, the fatty acid is particularly preferably lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, oleic acid or linoleic acid, since it makes the effects of the present invention pronounced.

Next, a fatty acid metal salt (C) represented by formula (2) (hereinafter also referred to as “component (C)”) will be described. In formula (2), R ⁶ represents a group containing from 10 to 30 carbon atoms, which is introduced into an aliphatic organic acid, and M ¹ represents a lithium or potassium atom.

In formula (2), examples of the group that is introduced into an aliphatic organic acid containing 10 to 30 carbon atoms and represented by the symbol R ⁶ include hydrocarbon groups into which an alkyl group or an alkenyl group containing 9 to 29 carbon atoms is introduced, together with two or more unsaturated bonds. The alkyl group or alkenyl group may be branched, and the hydrogen atoms of hydrocarbon groups may be replaced by hydroxy groups. Specific examples of the fatty acid metal salt (C) include lithium salts and potassium fatty acid salts, examples of which are presented above for sodium carboxylate.

In the composition of the present invention, the fatty acid of component (C) is preferably a fatty acid containing 10 to 21 carbon atoms, more preferably a fatty acid containing 12 to 18 carbon atoms. Specifically, the fatty acid of component (C) is particularly preferably lauric acid, myristic acid, palmitic acid, stearic acid, 12-hydroxystearic acid, oleic acid or linoleic acid, since it makes the effects of the present invention pronounced.

In the composition of the present invention, the molar ratio between components (B) and (C) (C)/(B) is preferably in the range of 0.30 to 5.00, more preferably 0.35 to 2.50. By controlling the molar ratio within this range, the composition of the present invention is able to improve the physical properties and transparency of a thermoplastic resin, in particular a polyolefin-based resin.

In the composition of the present invention, the total amount of components (B) and (C) in the composition is preferably in the range of 25 to 60% by weight, more preferably from 30 to 55% by weight. In the case of the total amount of components (B) and (C) being less than 25% (w/w) or more than 60% (w/w), the nucleation effect may be unsatisfactory and the composition may be more likely to change color to exposure to heat.

In the composition of the present invention, the molar ratio between components (A), (B) and (C) (A)/{(B) + (C)} is in the range of 0.15 to 0.70, and the molar ratio is particularly preferable is in the range of 0.25 to 0.65, since thereby an excellent crystallization promotion effect is achieved.

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

The resins that can be used in the thermoplastic resin composition of the present invention are not limited as long as they are thermoplastic resins; however, from the viewpoint of making the effects of the present invention more pronounced, it is preferable to use a polyolefin resin, a styrene resin, a polyester resin, a polyester resin, a polycarbonate resin, a polyamide resin or a halogen-containing resin, and more preferably, a polyolefin-based resin is used.

Examples of the polyolefin resin include α-olefin polymers such as polyethylenes, low-density polyethylenes, linear low-density polyethylenes, high-density polyethylenes, cross-linked polyethylenes, ultra-high molecular weight polyethylenes, polypropylenes, homopolypropylenes, random copolymer polypropylenes, block copolymer polypropylenes, isotactic polypropylenes, syndiotactic polypropylenes sawn wood , hemiisotactic polypropylenes, polybutenes, cycloolefin polymers, stereoblock polypropylenes, poly-3-methyl-1-butenes, poly-3-methyl-1-pentenes and poly-4-methyl-1-pentenes; α-olefin copolymers such as ethylene-propylene block or random copolymers, impact polypropylene copolymers, ethylene-methyl methacrylate copolymers, ethylene-methyl acrylate copolymers, ethylene-ethyl acrylate copolymers, ethylene-butyl acrylate copolymers, and ethylene-vinyl acrylate copolymers; polyfluoroolefins; and thermoplastic elastomers based on polyolefin. The polyolefin resin may be a copolymer of two or more of these resins.

Examples of the styrene-based resin include homopolymers of aromatic hydrocarbons containing a vinyl group and copolymers of an aromatic hydrocarbon containing a vinyl group and other monomer(s) (for example, maleic anhydride, phenylmaleimide, (meth)acrylate, butadiene and/or (meth)acrylonitrile ), such as thermoplastic resins such as polystyrene (PS) resins, high impact polystyrenes (HIPS), acrylonitrile-styrene (AS) resins, acrylonitrile-butadiene-styrene (ABS) resins, methyl methacrylate-butadiene-styrene (MBS) resins, heat resistant ABS resin, acrylate-styrene-acrylonitrile (ASA) resin, acrylonitrile-acrylic rubber-styrene (AAS) resin, styrene-maleic anhydride (SMA) resin, methacrylate-styrene (MS) resin, styrene-isoprene-styrene (SIS) resin , acrylonitrile-ethylene-propylene rubber-styrene (AES) resin, styrene-butadiene-butylene-styrene (SBBS) resin and methyl methacrylate-acrylonitrile-butadiene-styrene (MABS) resin; and hydrogenated styrene-based elastomeric resins obtained by hydrogenating the double bond of butadiene or isoprene in the resins described above, such as styrene-ethylene-butylene-styrene (SEBS) resins, styrene-ethylene-propylene-styrene (SEPS) resins, styrene resins -ethylene-propylene (SEP) and styrene-ethylene-ethylene-propylene-styrene (SEEPS) resins.

Examples of the polyester resin include aromatic polyesters such as polyalkylene terephthalates (eg, polyethylene terephthalate, polybutylene terephthalate, and polycyclohexane dimethylene terephthalate) and polyalkylene naphthalates (eg, 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).

Examples of the polyether resin include polyacetal, polyphenylene ether, polyether ether ketone, polyether ether ketone, polyether ketone ketone, polyether ether ketone ketone, polyether sulfone, and polyether ether ketone.

Examples of the polycarbonate-based resin include polycarbonates, polycarbonate/ABS resins, polycarbonate/ASA resins, polycarbonate/AES resins, and branched polycarbonates.

Examples of the polyamide-based resin include polymers of ε-caprolactam (nylon 6), undecan lactam (nylon 11), lauryl lactam (nylon 12), aminocaproic acid, enantholactam, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, α-pyrrolidone , α-piperidone and the like; copolymers obtained by copolymerization of a diamine (for example, hexamethylenediamine, nonanediamine, nonanmethylenediamine, methylpentanediamine, undecanemethylenediamine, dodecanemethylenediamine or m-xylene diamine) and a carboxylic acid compound (for example, a dicarboxylic acid such as adipic acid, sebacic acid, terephthalic acid a, isophthalic acid , dodecanedicarboxylic acid or glutaric acid); and mixtures of these polymers and/or copolymers. Examples of polyamide-based resins also include aramid resins such as the products "KEVLAR®" (trade name) manufactured by DuPont, "NOMEX®" (trade name) manufactured by DuPont, and "TWARON®" (trade name) and " CONEX" (trade name), which are manufactured by TEIJIN Ltd..

Examples of the halogen-containing resin include polyvinyl chloride, polyvinylidene chlorides, chlorinated polyethylenes, chlorinated polypropylenes, polyvinylidene fluorides, chlorinated rubbers, vinyl chloride-vinyl acetate copolymers, vinyl chloride-ethylene copolymers, vinyl chloride-vinylidene chloride copolymers, vinyl chloride-vinylidene chloride-vin terpolymers yl acetate, vinyl chloride-acrylate copolymers, vinyl chloride-acrylate copolymers maleate and vinyl chloride-cyclohexylmaleimide copolymers.

Examples of the thermoplastic resin also include petroleum resins, coumarone resins, polyvinyl acetates, acrylic resins, polymethyl methacrylates, polyvinyl alcohols, polyvinyl formalals, polyvinyl butyrals, polyphenylene sulfides, polyurethanes, cellulose resins, polyimide resins, polysulfones, liquid crystal resins, and mixtures of these thermoplastic resins.

In addition, the thermoplastic resin may be an elastomer such as isoprene rubber, butadiene rubber, acrylonitrile-butadiene rubber, styrene-butadiene rubber, fluorocarbon rubber, silicone rubber, polyester elastomer, nitrile elastomer, elastomer based nylon, vinyl chloride elastomer, polyamide elastomer or polyurethane elastomer, or a combination of these elastomers.

In the resin composition of the present invention, these thermoplastic resins may be used individually, or two or more of them may be used in combination. In addition, these thermoplastic resins can also be fused with each other. Thermoplastic resins can be used regardless of, for example, molecular weight, degree of polymerization, density, softening point, ratio between insoluble component and solvent, degree of stereoregularity, presence or absence of catalyst residues, type and proportion in the mixture of each monomer of the material and type of polymerization catalyst (eg Ziegler catalyst or metallocene catalyst).

The thermoplastic resin composition of the present invention preferably uses a polyolefin-based resin because it makes the effects of the present invention pronounced.

The method of admixing components (A), (B) and (C) of the composition of the present invention to the thermoplastic resin is not particularly limited, and any known technology for admixing the resin additive can be used. For example, any of a method of dry blending a thermoplastic resin in powder or granular form and the components described above, a method of adding components to a polymerization system before polymerization to produce a thermoplastic resin, a method of adding components in the middle of polymerization, and a method of adding components after polymerization may be used. carrying out polymerization. In addition, a method of producing a masterbatch containing any of the components at a high concentration and then adding the masterbatch to a thermoplastic resin, or a method of processing some or all of the components into granular form and then adding the granules to the thermoplastic resin can also be used. Moreover, any of the components can be impregnated into filler and the like or processed into granules and then incorporated into a thermoplastic resin. In addition, the components may be premixed and then added to the thermoplastic resin, or the components may be added to the thermoplastic resin separately.

As for the method of processing the components of the composition of the present invention into granular form, the granules can be produced by heating a mixture of the composition of the present invention, a phenolic antioxidant, a polymer compound, a binder such as petroleum tar, and other additive(s) included as required optionally, but after this mixing the mixture in the presence of a binder in a molten state. There are absolutely no restrictions on the processing conditions, processing equipment and the like, and any well-known and widely used processing method and processing equipment can be used. Specific examples of the production method include a method using a disc granulator and an extrusion method.

In the thermoplastic resin composition of the present invention, optional and known additive(s) (for example, a phenolic antioxidant, a phosphorus-based antioxidant, a thioether-based antioxidant, another antioxidant, an ultraviolet radiation absorber, a hindered amine compound, another nucleating agent other than the component ( A), flame retardant, flame retardant auxiliary, lubricant, filler, hydrotalcite, antistatic agent, fluorescent brightener, pigment and dye) may also be included in an amount within a range that does not impair the effects of the present invention to a significant extent.

Examples of the phenolic antioxidant include 2,6-di-tert-butyl-4-ethylphenol, 4-tert-butyl-4,6-dimethylphenol, styrylated 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(octylsulfanylmethyl)phenol, 2,2'-isobutylidenebis(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'-oxamidebis[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) , esters of 3,5-di-tert-butyl-4-hydroxybenzenepropanoic acid and C13-15 alkyl, 2,5-di-tert-amylhydroquinone, sterically hindered phenolic polymers (for example, a product with the trade name “AO.ON. 98", produced by ADEKA Polymer Additives Europe SAS), 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]dioxaphosphepine, hexamethylenebis[3-(3, 5-di-tert-butyl-4-hydroxyphenyl)propionate], calcium bis[monoethyl(3,5-di-tert-butyl-4-hydroxybenzyl)phosphonate], product of the reaction between 5,7-bis(1,1- dimethylethyl)-3-hydroxy-2(3H)-benzofuranone and o-xylene, 2,6-di-tert-butyl-4-(4,6-bis(octylthio)-1,3,5-triazine-2- ylamino)phenol, DL-α-tocopherol (vitamin E), 2,6-bis(α-methylbenzyl)-4-methylphenol, bis[3,3-bis(4'-hydroxy-3'-tert-butylphenyl)butyric acid]glycolic 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, thiodiethylene bis[(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 4,4'-thiobis(6-tert-butyl-m-cresol), 2-octylthio-4,6-di(3,5-di-tert-butyl-4-hydroxyphenoxy)-s-triazine, 2,2 '-methylenebis(4-methyl-6-tert-butylphenol), bis[3,3-bis(4-hydroxy-3-tert-butylphenyl)butyric acid]glycol ester, 4,4'-butylidenebis(2,6 -di-tert-butylphenol), 4,4'-butylidenebis(6-tert-butyl-3-methylphenol), 2,2'-ethylidenebis(4,6-di-tert-butylphenol), 1,1,3- tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate , 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl)isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate , 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,3,5-tris[(3,5-di-tert-butyl -4-hydroxyphenyl)propionyloxyethyl]isocyanurate, tetrakis[methylene-3-(3',5'-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-methylhydrocinnamoyloxy)-1,1-dimethylethyl]-2,4,8 ,10-tetraoxaspiro[5.5]undecane, triethylene glycolbis[β-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] and 3-(3,5-dialkyl-4-hydroxyphenyl)propionic acid derivatives such as 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 amide -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid and lauryl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid amide. If the phenolic antioxidant is included, the amount thereof will preferably be in the range of 0.001 to 5 parts by mass, more preferably 0.03 to 3 parts by mass, based on 100 parts by mass of the thermoplastic resin.

Examples of the phosphorus-based antioxidant include triphenylphosphite, diisooctylphosphite, heptakis(dipropylene glycol)triphosphite, triisodecylphosphite, diphenylisooctylphosphite, diisooctylphenylphosphite, diphenyltridecylphosphite, triisooctylphosphite, trilaurylphosphite, diphenylphosphite, tris(dipropylene glycol) col)phosphite, dioleylhydrophosphite, trilauryl trithiophosphite, bis(tridecyl)phosphite, tris(isodecyl) phosphite, tris(tridecyl)phosphite, diphenyldecylphosphite, dinonylphenylbis(nonylphenyl)phosphite, poly(dipropylene glycol)phenylphosphite, tetraphenyldipropylglycol diphosphite, trisnonylphenylphosphite, 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, tri(decyl)phosphite, octyldiphenylphosphite, di( decyl)monophenylphosphite, mixtures of distearyl pentaerythritol and calcium stearate, alkyl (C10)bisphenol A-phosphite, tetraphenyltetra(tridecyl)pentaerythritol tetraphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite, tetra(tridecyl)isopropylidenediphenol diphosphite it, tetra(tridecyl)-4,4'-n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite, hexa(tridecyl)-1,1,3-tris(2-methyl-4-hydroxy-5-tert -butylphenyl)butanetriphosphite, tetrakis(2,4-di-tert-butylphenyl)biphenylene diphosphonite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, (1-methyl-1-propanyl-3-ylidene) tris(1,1-dimethylethyl)-5-methyl-4,1-phenylene)hexatridecylphosphite, 2,2'-methylenebis(4,6-tert-butylphenyl)-2-ethylhexylphosphite, 2,2'-methylenebis(4, 6-di-tert-butylphenyl)octadecylphosphite, 2,2'-ethylidenebis(4,6-di-tert-butylphenyl)fluorophosphite, 4,4'-butylidenebis(3-methyl-6-tert-butylphenylditridecyl)phosphite, tris( 2-[(2,4,8,10-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-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-propanediolphosphite, phosphite poly-4,4'-isopropylidene diphenol (C12-15 alcohol), 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 and bis(2,4-dicumylphenyl)pentaerythritol diphosphite. If the phosphorus-based antioxidant is included, the amount thereof will preferably be in the range of 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.

Examples of 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/stearyl thiodipropionate, 4,4'-thiobis(6-tert-butyl -m-cresol), 2,2'-thiobis(6-tert-butyl-p-cresol) and distearyl disulfide. If the thioether antioxidant is included, the amount will preferably be in the range of 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.

Examples of the ultraviolet radiation absorber include 2-hydroxybenzophenones such as 2,4-dihydroxybenzophenone and 5,5'-methylenebis(2-hydroxy-4-methoxybenzophenone); 2-(2-hydroxyphenyl)benzotriazoles such as 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-amyl-5-(2-methacryloyloxyethyl)phenyl]benzotriazole, 2-[ 2-hydroxy-3-tert-butyl-5-(3-methacryloyloxypropyl)phenyl]-5-chlorobenzotriazole, 2-[2-hydroxy-4-(2-methacryloyloxymethyl)phenyl]benzotriazole, 2-[2-hydroxy-4 -(3-methacryloyloxy-2-hydroxypropyl)phenyl]benzotriazole and 2-[2-hydroxy-4-(3-methacryloyloxypropyl)phenyl]benzotriazole; benzoates such as 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-4-hydroxy)benzoate, tetradecyl(3,5-di-tert-butyl-4-hydroxy)benzoate, hexadecyl(3,5-di-tert-butyl-4- hydroxy)benzoate, octadecyl(3,5-di-tert-butyl-4-hydroxy)benzoate and behenyl(3,5-di-tert-butyl-4-hydroxy)benzoate; substituted oxanilides such as 2-ethyl-2'-ethoxyoxanilide and 2-ethoxy-4'-dodecyloxanilide; cyanoacrylates such as ethyl α-cyano-β,β-diphenylacrylate and methyl 2-cyano-3-methyl-3-(p-methoxyphenyl)acrylate; triaryltriazines such as 2-(2-hydroxy-4-octoxyphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine, 2-(2-hydroxy-4-methoxyphenyl)-4 ,6-diphenyl-s-triazine and 2-(2-hydroxy-4-propoxy-5-methylphenyl)-4,6-bis(2,4-di-tert-butylphenyl)-s-triazine; and a wide range of metal salts and metal chelates, particularly nickel and chromium salts and chelates. If an ultraviolet radiation absorber is included, the amount thereof will preferably be in the range of 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.

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-butanetetracarboxylate, tetrakis(1, 2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, bis(2,2,6,6-tetramethyl-4-piperidyl)⋅di(tridecyl)-1,2 ,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)⋅di(tridecyl)-1,2,3,4-butanetetracarboxylate, bis(1,2,2,4 ,4-pentamethyl-4-piperidyl)-2-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate, polycondensate 1-(2-hydroxyethyl)-2,2,6,6- tetramethyl-4-piperidinol/diethylsuccinate, polycondensate 1,6-bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-morpholino-s-triazine, polycondensate 1,6- bis(2,2,6,6-tetramethyl-4-piperidylamino)hexane/2,4-dichloro-6-tert-octylamino-s-triazine, 1,5,8,12-tetrakis[2,4-bis( N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8,12-tetraazadodecane, 1,5,8,12 -tetrakis[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl]-1,5,8, 12-tetraazadodecane, 1,6,11-tris[2,4-bis(N-butyl-N-(2,2,6,6-tetramethyl-4-piperidyl)amino)-s-triazin-6-yl] aminoundecane, 1,6,11-tris[2,4-bis(N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino)-s-triazin-6-yl] aminoundecane, bis{4-(1-octyloxy-2,2,6,6-tetramethyl)piperidyl}decanedionate and bis{4-(2,2,6,6-tetramethyl-1-undecyloxy)piperidyl}carbonate. If the hindered amine compound is included, the amount thereof will preferably be in the range of 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.

Examples of other nucleating agent other than component (A) include metal carboxylates such as sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, 2,2'-methylenebis(4,6-di- lithium tert-butylphenyl phosphate, 4-tert-butylbenzoic acid aluminum salt and 2-sodium 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-tri(dimethylisopropylamino)benzene. If another nucleating agent is included, the combined amount of component (A) and the other nucleating agent will preferably be in the range of 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, based on 100 parts by mass of the thermoplastic resin. The composition of the present invention preferably contains neither a polyol derivative nor an amide compound, and more preferably does not contain another nucleating agent.

Examples of the flame retardant include aromatic phosphates such as triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, cresyl diphenyl phosphate, cresyl 2,6-dixylenyl phosphate, resorcinol bis(diphenyl phosphate), (1-methylethylidene)-4,1-phenylenetetraphenyl diphosphate and 1,3-phenylene tetrakis(2,6 -dimethylphenyl)phosphate, as well as the products “ADK STAB FP-500”, “ADK STAB FP-600” and “ADK STAB FP-800” (trade names manufactured by ADEKA Corporation); phosphonates such as divinylphenylphosphonate, diallylphenylphosphonate and (1-butenyl)phenylphosphonate; phosphinates such as phenyldiphenylphosphinate, methyldiphenylphosphinate and 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide derivatives; phosphazene compounds such as bis(2-allylphenoxy)phosphazene and dicresylphosphazene; phosphorus-based flame retardants such as melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melampolyphosphate, ammonium polyphosphate, piperazine phosphate, piperazine pyrophosphate, piperazine polyphosphate, phosphorus-containing vinylbenzyl compounds and red phosphorus; metal hydroxides such as magnesium hydroxide and aluminum hydroxide; and bromine-based flame retardants such as brominated bisphenol A type epoxy resins, brominated phenolic novolac type epoxy resins, hexabromobenzene, pentabromotoluene, ethylenebis(pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4-(1, 2-dybrometil) cycloglogsan, tetrabromecycliccicucitan, hexabromcyclododecan, bis (tribromfenox) ethane, broken polyphenylene simple ether, brominated polystyrene, 2.4.6-lane (tribromfenox) -1.3.5-triazine, tribromfenialact, tribromfrifrylate, tribromfenilate Enilmakrilat, Dimakrilate , belonging to the tetrabromobisphenol A type, pentabromobenzyl acrylate and brominated styrene. These flame retardants are preferably used in combination with a caking inhibitor such as a fluorocarbon resin and/or a flame retardant auxiliary such as a polyhydric alcohol or hydrotalcite. If a fire retardant is included, the amount thereof will preferably be in the range of 1 to 100 parts by mass, more preferably 10 to 70 parts by mass, based on 100 parts by mass of the thermoplastic resin.

The hydrotalcite described above is a complex salt derivative which is known as a natural or synthetic product and is formed from magnesium, aluminum, hydroxy groups, a carbonate group and an arbitrary amount of water of crystallization, and examples thereof include hydrotalcites in which a certain amount of magnesium or aluminum atoms substituted by another metal such as an alkali metal or zinc; and hydrotalcites in which the hydroxy group(s) and/or the carbonate group are replaced by another anionic group(s), specifically, hydrotalcites represented by Formula (3) below, in which the metal is replaced by an alkali metal. In addition, the compound represented by Formula (4) below can also be used as the Al-Li hydrotalcite.

where each of x1 and x2 represents a number that satisfies the conditions described by the following equations; and p represents 0 or a positive number: 0 ≤ x2/x1 < 10, 2 ≤ (x1 + x2) ≤ 20).

where A ^q is an anion characterized by valence q; and p represents 0 or a positive number.

In addition, the carbonate anion in these hydrotalcites can be partially replaced by other anions.

These hydrotalcites may be dehydrated to remove water of crystallization, and the hydrotalcites may be coated with, for example, a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as an alkali metal oleate, an organic metal sulfonate such as an alkali metal dodecylbenzenesulfonate, a higher fatty acid amide, a higher fatty acid ester or a wax.

Hydrotalcite can be naturally occurring or synthetic hydrotalcite. Examples of the method for its synthesis include known methods, which are described in publications JPS46-2280B, JPS50-30039B1, JPS51-29129B1, JPH03-36839B2, JPS61-174270A, JPH05-179052A and the like. Moreover, the hydrotalcites exemplified above can be used without any limitation being imposed on the crystal structure, crystal particles and the like. If hydrotalcite is included, the amount thereof will preferably be in the range of 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, based on 100 parts by mass of thermoplastic resin.

The lubricant is added for the purpose of imparting anti-friction properties to the surface of the resulting molded article and improving the damage prevention effect. Examples of the lubricant include unsaturated fatty acid amides such as oleic acid amide and erucic acid amide; saturated fatty acid amides such as behenic acid amide and stearic acid amide; butyl stearate; stearyl alcohols; stearic acid monoglyceride; sorbitan monopalmitate; sorbitan monostearate; mannitol; stearic acid; hardened castor oil; stearic acid amide; oleic acid amide; and ethylene bisstearic acid amide. These lubricants may be used individually, or two or more of them may be used in combination. If a lubricant is included, the amount thereof will preferably be in the range of 0.01 to 2 parts by mass, more preferably 0.03 to 0.5 parts by mass, based on 100 parts by mass of thermoplastic resin.

Examples of the antistatic agent include cationic antistatic agents such as fatty acid quaternary ammonium salts and polyamine quaternary salts; anionic antistatic agents such as higher alcohol phosphates, higher alcohol EO adducts, polyethylene glycol fatty acid esters, anionic alkyl sulfonates, higher alcohol sulfates, higher alcohol ethylene oxide adduct sulfates and higher alcohol ethylene oxide adduct phosphates; nonionic antistatic agents such as polyol fatty acid esters, polyglycol phosphates and polyoxyethylene alkyl allyl ethers; amphoteric antistatic agents, such as amphoteric alkyl betaines (eg, alkyldimethylaminoacetic acid betaines) and amphoteric activators of the imidazoline type; and polymer-type antistatic agents such as polyetheretheramides and polyesteretheramides. These antistatic agents can be used individually, or two or more of them can be used in combination. If an antistatic agent is included, the amount thereof will preferably be in the range of 0.03 to 2 parts by mass, more preferably 0.1 to 0.8 parts by mass, based on 100 parts by mass of thermoplastic resin.

A fluorescent brightener is a compound that improves the whiteness or bluishness of a molded article through a fluorescent effect caused by the absorption of ultraviolet radiation from sunlight and artificial light, the conversion of the absorbed ultraviolet radiation into visible light with a hue ranging from purple to blue, and the emission of visible light. Examples of fluorescent brightener include C.I. Fluorescent Brightener 184, which is a benzoxazole-based compound; C.I. Fluorescent Brightener 52, which is a coumarin-based compound; and C.I. Fluorescent Brighteners 24, 85 and 71, which are diaminostyryl benzyl sulfone compounds. If fluorescent brightener is included, the amount thereof will preferably be in the range of 0.00001 to 0.1 parts by mass, more preferably 0.00005 to 0.05 parts by mass, based on 100 parts by mass of thermoplastic resin.

A commercially available pigment may also be used as the pigment described above, and examples thereof include 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, 185, 192, 200, 202, 209, 215, 216, 216. 217, 220, 223, 224, 226, 227, 228, 240 and 254; PIGMENT ORANGE 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65 and 71; PIGMENT YELLOW 1, 3, 12, 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 and 185; PIGMENT GREEN 7, 10 and 36; PIGMENT BLUE 15, 15:1, 15:2, 15:3, 15:4, 15:5, 15:6, 22, 24, 29, 56, 60, 61, 62 and 64; and PIGMENT VIOLET 1, 15, 19, 23, 27, 29, 30, 32, 37, 40 and 50.

Examples of the dye include azo dyes, anthraquinone dyes, indigoid 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, and a variety of these dyes can be mixed and used in combination.

The molded article of the present invention is obtained by molding the thermoplastic resin composition of the present invention. The thermoplastic resin composition of the present invention can be molded using any known molding method. The molded article may be produced, for example, by injection molding, extrusion molding, blow molding, vacuum molding, blow molding, calender molding, slip molding, dip molding, or foam molding.

Examples of uses of the thermoplastic resin composition of the present invention include automotive materials such as bumpers, dashboards and dashboards; areas of application of housings, such as in the case of refrigerators, washing machines and vacuum cleaners; household items such as tableware, buckets and bath products; a variety of goods such as toys; molded products, including storage/protection containers such as tanks; films; and fibers.

EXAMPLES

The present invention will now be described more specifically using examples thereof; however, the present invention is not to be limited in any way by the examples presented below and the like.

[Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-16]

To homopolypropylene as a thermoplastic resin (melt flow rate: 8 g/10 min; 2.16 kg × 230°C in accordance with ISO Standard 1133) 0.05 parts by weight of a phenolic antioxidant (tetrakis[methylene) was added in an amount of 100 parts by weight -3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.1 mass part of phosphorus-based antioxidant (tris(2,4-di-tert-butylphenyl)phosphite) , 0.05 parts by mass of hydrotalcite (trade name "DHT-4A", manufactured by Kyowa Chemical Industry Co., Ltd.) and each composition shown in Tables 1 to 3, and these materials were mixed at 1000 rpm for for 1 minute using a Henschel mixer, and subsequently granulated at an extrusion temperature of 230°C using a biaxial extruder. Each of the granules obtained by granulation in this manner was dried at 60° C. for 8 hours, after which the turbidity was measured under the conditions described below. The results of this are demonstrated in Tables 1 to 3. As should be noted herein, in Tables 1 to 3 the unit of measure for the amount of each component is parts by mass.

[Example 2-1 and Comparative Examples 2-1 and 2-2]

To homopolypropylene as a thermoplastic resin (melt flow rate: 8 g/10 min; 2.16 kg × 230°C in accordance with ISO Standard 1133) 0.05 parts by weight of a phenolic antioxidant (tetrakis[methylene) was added in an amount of 100 parts by weight -3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.1 mass part of phosphorus-based antioxidant (tris(2,4-di-tert-butylphenyl)phosphite) , 0.05 parts by weight of calcium stearate and each composition shown in Table 4, and these materials were mixed at 1000 rpm for 1 minute using a Henschel mixer, and subsequently granulated at an extrusion temperature of 230°C using a biaxial extruder. Each of the granules obtained by granulation in this manner was dried at 60° C. for 8 hours, after which the turbidity was measured under the conditions described below. The results of this are shown in Table 4. As it should be noted in this case, in Table 4 the unit of measure for the amount of each component is parts by mass.

[Examples 3-1 to 3-9 and Comparative Examples 3-1 to 3-7]

To homopolypropylene as a thermoplastic resin (melt flow rate: 8 g/10 min; 2.16 kg × 230°C in accordance with ISO Standard 1133) 0.05 parts by weight of a phenolic antioxidant (tetrakis[methylene) was added in an amount of 100 parts by weight -3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.1 mass part of phosphorus-based antioxidant (tris(2,4-di-tert-butylphenyl)phosphite) , 0.05 part by weight hydrotalcite (trade name "DHT-4A", manufactured by Kyowa Chemical Industry Co., Ltd.) and each composition shown in Tables 5 and 6, and these materials were mixed at 1000 rpm for 1 minute using a Henschel mixer and subsequently granulated at an extrusion temperature of 230°C using a biaxial extruder. Each of the granules obtained by granulation in this manner was dried at 60° C. for 8 hours, after which the crystallization temperature, half-time of crystallization, and flexural modulus were measured under the conditions described below. The results of this are demonstrated in Tables 5 and 6. As it should be noted in this case, in Tables 5 and 6 the unit of measure for the amount of each component is parts by mass.

[Examples 4-1 to 4-3 and Comparative Examples 4-1 to 4-5]

To homopolypropylene as a thermoplastic resin (melt flow rate: 8 g/10 min; 2.16 kg × 230°C in accordance with ISO Standard 1133), 0.05 parts by mass of a phenolic antioxidant (tetrakis[methylene) -3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane), 0.1 mass part of phosphorus-based antioxidant (tris(2,4-di-tert-butylphenyl)phosphite) , 0.05 parts by weight of calcium stearate and each composition shown in Table 7, and these materials were mixed at 1000 rpm for 1 minute using a Henschel mixer, and subsequently granulated at an extrusion temperature of 230°C using a biaxial extruder. Each of the granules obtained by granulation in this manner was dried at 60° C. for 8 hours, after which the turbidity, heat deformation resistance under load (HDT), crystallization temperature, half-crystallization time and flexural modulus were measured under the conditions described below . The results of this are shown in Table 7. As it should be noted in this case, in Table 7 the unit of measure for the amount of each component is parts by mass.

<Turbidity>

Using an injection molding machine (EC100-2A manufactured by Toshiba Machine Co., Ltd.), each of the pellets obtained above was injection molded at a mold temperature of 50°C and a resin temperature of 200°C to obtain test samples. In Examples 1-1 to 1-11, Comparative Examples 1-1 to 1-16, Example 2-1 and Comparative Examples 2-1 and 2-2, test specimens having dimensions of 60 mm × 60 mm × 1 were prepared. mm, and in Example 2-1, Comparative Examples 2-1 and 2-2, Examples 4-1 to 4-3 and Comparative Examples 4-1 to 4-5, test specimens having dimensions of 60 mm × 60 were obtained mm × 2 mm. Immediately after molding, the test specimens were left to incubate at 23°C for at least 48 hours followed by turbidity (%) measurements using a Haze Guard II device (manufactured by BYK Additives & Instruments, Ltd.) in accordance with document ISO14782.

<Crystallization temperature>

A small piece was cut from each of the granules obtained above, and their crystallization temperature was measured using a differential scanning calorimeter (DIAMOND, manufactured by PerkinElmer Co., Ltd.). As for the measurement, the diagram obtained as a result of heating a piece from room temperature to 230°C at a rate of 50°C/min, holding the piece for 10 minutes, and after that cooling the piece to 50°C at a rate of - 10° C/min, the temperature at which the endothermic reaction formed the top of the peak was determined as the crystallization temperature.

<Half crystallization time>

A small piece was cut from each granule obtained above, and using a differential scanning calorimeter (DIAMOND, manufactured by PerkinElmer Co., Ltd.), the resulting piece was heated to 230°C at a rate of 50°C/min, held for 10 minutes , and then cooled to 135°C at a rate of 200°C/min. After reducing the temperature to 135°C, this temperature was maintained for 15 minutes and the time required to reduce the endothermic enthalpy required for crystallization to half, which was defined as half the crystallization time.

<Flexural modulus (MPa)>

Using an injection molding machine (EC100-2A manufactured by Toshiba Machine Co., Ltd.), each of the pellets obtained above was injection molded at a mold temperature of 50°C and a resin temperature of 200°C to obtain test specimens having dimensions 80 mm × 10 mm × 4 mm, and after leaving the test pieces thus obtained to stand for at least 48 hours in a thermostat at 23°C, the flexural modulus of elasticity (MPa) was measured in accordance with ISO178 when using bend test devices "AG-IS", manufactured by Shimadzu Corporation.

<Deformation heat resistance under load (°C)>

Using an injection molding machine (EC100-2A manufactured by Toshiba Machine Co., Ltd.), each of the pellets obtained above was injection molded at a mold temperature of 50°C and a resin temperature of 200°C to obtain test specimens having dimensions 80 mm × 10 mm × 4 mm, and after leaving the thus obtained test specimens to stand for at least 48 hours in a thermostat at 23°C, the deformation heat resistance under load (°C) was measured for each test specimen at in accordance with document ISO75 (load: 1.8 MPa).

Table 4 Example 2-1 Comparative Example 2-1 Comparative Example 2-2 (A)-1 0.067 0.067 0.067 (B)-1 0.017 0.033 - (C)-1 0.017 - 0.033 (C)/(B) (molar ratio) 1.31 - - (A)/{(B) + (C)} (molar ratio) 0.52 0.61 0.47 Turbidity (%)/1mm 19.0 19.2 21.9 Turbidity (%)/2mm 49 53 50

According to Comparative Examples 1-1 to 1-6, in which a composition formed from a combination of components (A) and (C) was used, and Comparative Examples 1-7 to 1-13, in which a composition formed from of components (A) and (B), the molded articles did not exhibit satisfactory transparency. In addition, according to Comparative Examples 1-14 to 1-16, in which a composition whose ratio (C)/(B) was outside the range of 0.30 to 5.00 was used, none of molded products did not demonstrate satisfactory transparency.

In comparison with the molded articles of Comparative Examples 1-3, 1-9, 1-15 and 1-16, which were obtained by using a composition containing component (B) and/or component (C) in a total amount of 0.033 parts by weight relative to 0.067 parts by weight of component (A), it was confirmed that those molded articles from Examples 1-3 and 1-7 to 1-11, which were obtained using the composition of the present invention, which contained the same amount of component (A ) and the combined amount of components (B) and (C) in 0.033 parts by weight, excellent clarity was imparted.

According to the results of Comparative Examples 3-1 to 3-7 shown in Table 6, molded articles obtained using a composition other than the composition of the present invention did not show a satisfactory improvement effect in terms of physical properties. On the other hand, according to the results of Examples 3-1 to 3-9 shown in Table 5, molded articles obtained using the composition of the present invention achieved an excellent physical property improvement effect. Particularly, according to Examples 3-1 to 3-7, the half crystallization time was shortened to a large extent, and a pronounced crystallization promotion effect was achieved in those molded articles obtained by using the composition having the ratio (A)/{( B) + (C)} ranged from 0.25 to 0.65. It was confirmed that the molded articles exhibited excellent physical properties also in cases in which a composition containing a lithium salt derivative or a potassium salt derivative in combination was used as component (C).

Based on the results of Comparative Example 4-2 shown in Table 7, it was confirmed that the composition other than the composition of the present invention showed an unsatisfactory effect of improving physical properties even though the composition contained components (A), (B) and ( WITH). Based on Comparative Examples 4-3 to 4-5, it was confirmed that using a composition devoid of any one of components (A), (B) and (C) showed an unsatisfactory effect of improving transparency. In contrast, according to the results of Examples 4-1 and 4-2 shown in Table 7, it was confirmed that when using the composition of the present invention, the resulting molded articles exhibited excellent crystallization promotion effect, and were not only bright pronounced effect of improving transparency and physical properties, but also excellent promotion of crystallization.

In accordance with the above, the composition of the present invention provides a composition that can greatly improve the physical properties and transparency of a thermoplastic resin.

Claims (32)

1. Composition of additives to thermoplastic resin containing: (A) an aluminum salt of cyclic organophosphorus acid, described by the following formula (1): , wherein each of R ¹ -R ⁴ represents a tert-butyl group and R ⁵ represents a methylene group; (B) sodium carboxylate; And (C) a fatty acid metal salt described by the following formula (2): , where R ⁶ represents the remainder of an aliphatic organic acid containing from 10 to 30 carbon atoms, from which the carboxyl group is excluded, and M ¹ represents a lithium or potassium atom, wherein the thermoplastic resin is a polypropylene-based resin, where (A) the aluminum salt of a cyclic organophosphorus acid described by formula (1) is aluminum hydroxybis[2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, wherein (B) sodium carboxylate is at least one member selected from the group consisting of an aromatic sodium carboxylate and a sodium salt of a fatty acid containing from 10 to 21 carbon atoms, and where the molar ratio between (C) the fatty acid metal salt represented by formula (2) and (B) the sodium salt of the fatty acid (C)/(B) is in the range from 0.30 to 5.00, and the molar ratio between (A) the aluminum salt of a cyclic organophosphorus acid described by formula (1), (B) the sodium salt of a fatty acid and (C) the fatty acid metal salt described by formula (2), (A)/{(B) + (C)} ranges from 0.15 to 0.70. 2. The composition according to claim 1, wherein (B) sodium carboxylate is at least one member selected from the group consisting of aromatic sodium carboxylate, sodium laurate, sodium myristate, sodium palmitate, sodium stearate, sodium 12-hydroxystearate, sodium oleate and sodium linoleate. 3. A thermoplastic resin composition for making molded articles, containing the composition according to claim 1 or 2 so that (A) the aluminum salt of cyclic organophosphorus acid represented by formula (1) is contained in an amount ranging from 0.001 to 10 parts by mass relative to 100 parts by weight of polypropylene-based resin. 4. A molded article containing the thermoplastic resin composition according to claim 3. 5. A thermoplastic resin composition for making molded articles, containing a thermoplastic resin and a composition, wherein the thermoplastic resin is a polypropylene-based resin, and the composition contains: (A) an aluminum salt of cyclic organophosphorus acid, described by the following formula (1): , wherein each of R ¹ -R ⁴ represents a tert-butyl group and R ⁵ represents a methylene group; (B) sodium carboxylate; And (C) a fatty acid metal salt described by the following formula (2): , where R ⁶ represents the remainder of an aliphatic organic acid containing from 10 to 30 carbon atoms, from which the carboxyl group is excluded, and M ¹ represents a lithium or potassium atom, where (A) the aluminum salt of a cyclic organophosphorus acid described by formula (1) is aluminum hydroxybis[2,2'-methylenebis(4,6-di-tert-butylphenyl)phosphate, wherein (B) sodium carboxylate is at least one member selected from the group consisting of an aromatic sodium carboxylate and a sodium salt of a fatty acid, where the molar ratio between (C) the fatty acid metal salt described by formula (2) and (B) sodium carboxylate (C)/(B) is in the range from 0.30 to 5.00, and the molar ratio between (A) the aluminum salt of a cyclic organophosphorus acid, described by formula (1), (B) sodium carboxylate and (C) the fatty acid metal salt, described by formula (2), (A)/{(B) + (C )} ranges from 0.15 to 0.70, and wherein the thermoplastic resin composition contains the composition so that (A) the aluminum salt of a cyclic organophosphorus acid represented by formula (1) is contained in an amount ranging from 0.001 to 10 parts by mass relative to 100 parts by mass of the polypropylene-based resin. 6. A molded article containing the thermoplastic resin composition according to claim 5.