WO2022014338A1 - Composition stabilisante, composition de résine de chlorure de vinyle en contenant et corps moulé à partir de cette dernière - Google Patents

Composition stabilisante, composition de résine de chlorure de vinyle en contenant et corps moulé à partir de cette dernière Download PDF

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Publication number
WO2022014338A1
WO2022014338A1 PCT/JP2021/024850 JP2021024850W WO2022014338A1 WO 2022014338 A1 WO2022014338 A1 WO 2022014338A1 JP 2021024850 W JP2021024850 W JP 2021024850W WO 2022014338 A1 WO2022014338 A1 WO 2022014338A1
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acid
mass
parts
vinyl chloride
group
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PCT/JP2021/024850
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English (en)
Japanese (ja)
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龍典 三田村
靖弘 岸本
一暢 田中
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株式会社Adeka
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K15/00—Anti-oxidant compositions; Compositions inhibiting chemical change
    • C09K15/04—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds
    • C09K15/06—Anti-oxidant compositions; Compositions inhibiting chemical change containing organic compounds containing oxygen

Definitions

  • the present invention relates to a stabilizer composition, a vinyl chloride resin composition containing the stabilizer composition (hereinafter, also simply referred to as “composition” and “resin composition”) and a molded product thereof.
  • the present invention relates to a stabilizer composition capable of imparting excellent thermal stability, color resistance, heat-resistant coloring property and the like, a vinyl chloride resin composition containing the stabilizer composition, and a molded product thereof.
  • Vinyl chloride resin has excellent flame retardancy, chemical resistance, mechanical stability, transparency, adhesiveness, printability, etc., and the hardness can be easily changed from hard to soft by adding a plasticizer. Therefore, it is used for various purposes.
  • a hard vinyl chloride resin composition containing no plasticizer at all or a semi-hard vinyl chloride resin composition containing a small amount of plasticizer is widely used as a building material because of its excellent rigidity. Therefore, they are required to have higher performance in terms of thermal stability, color resistance, heat color resistance, weather resistance, etc., not only during processing exposed to high temperature and high pressure, but also as molded products.
  • vinyl chloride-based resins have the disadvantages that they are not sufficiently stable against light and heat, and that they are prone to decomposition mainly due to dehalogenated hydrogen during heat molding and product use. It is known that there is.
  • Patent Documents 1 and 2 In order to meet the above performance requirements and improve the defects, conventional organic acid metal salts, organotin compounds, organic phosphite compounds, epoxidized vegetable oils, ⁇ -diketone compounds, antioxidants, and UV absorbers have been used. Attempts have been made to improve the stability of vinyl chloride-based resins by blending various stabilizers such as the above (Patent Documents 1 and 2). As such stabilizers, heavy metal stabilizers such as lead and cadmium have been conventionally used from the viewpoint of cost superiority and the like. Further, tin-based stabilizers, which are organic tin compounds, have also been proposed (Patent Documents 3 and 4).
  • tin-based stabilizers are liquid, when they are used, not only the slipperiness of the molten resin during the molding process is lowered, but also the heat distortion temperature (softening point) of the molded product is lowered. There was a problem of doing. As described above, there is a demand for a technique for preventing quality deterioration of a vinyl chloride resin composition due to heating, processing, and use without using lead, cadmium, and tin-based stabilizers.
  • an object of the present invention is a stabilizer composition capable of imparting excellent thermal stability, color resistance, heat-resistant coloring property, etc. to a vinyl chloride resin, a vinyl chloride resin composition containing the stabilizer composition, and a vinyl chloride resin composition thereof.
  • the purpose is to provide a molded body.
  • the stabilizer composition of the present invention contains 5 to 2500 parts by mass of the component (B) and 0.01 to 100 parts by mass of the component (C) with respect to 100 parts by mass of the component (A). It ’s a thing,
  • the component is one or more zinc salts of organic acids
  • (B) One or more epoxy compounds having at least one of a glycidyl ether group and a glycidyl ester group as a component.
  • Ingredient is one or more salts of perchloric acid, It is characterized by being.
  • the oxygen concentration of oxylan oxygen of the epoxy compound of the component (B) is preferably in the range of 3.0 to 15.0% by mass. Further, in the composition of the present invention, it is preferable that the component (C) is a metal perchloric acid salt. Further, the composition of the present invention preferably does not contain a lead-based stabilizer, a cadmium-based stabilizer, and a tin-based stabilizer.
  • the vinyl chloride-based resin composition of the present invention is characterized by containing the vinyl chloride-based resin and the stabilizer composition of the present invention.
  • the stabilizer composition is preferably 0.3 to 15.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
  • the molded product of the present invention is characterized by being obtained from the vinyl chloride resin composition of the present invention.
  • a stabilizer composition capable of imparting excellent thermal stability, color resistance, heat-resistant coloring property, etc. to a vinyl chloride resin, a vinyl chloride resin composition containing the stabilizer composition, and a molded product thereof. Can be provided.
  • the composition of the present invention is a composition containing 5 to 2500 parts by mass of the component (B) and 0.01 to 100 parts by mass of the component (C) with respect to 100 parts by mass of the component (A).
  • the component (A) is one or more of zinc salts of organic acids
  • the component (B) is one or more of epoxy compounds having at least one of a glycidyl ether group or a glycidyl ester group
  • the component (C) is a excess.
  • One or more of the salts of chloric acid is one or more of zinc salts of organic acids
  • the component (B) is one or more of epoxy compounds having at least one of a glycidyl ether group or a glycidyl ester group
  • the component (C) is a excess.
  • One or more of the salts of chloric acid is one or more of the salts of chloric acid.
  • the component (A) of the composition of the present invention is one or more zinc salts of organic acids.
  • the zinc salt of such an organic acid include zinc salts of organic carboxylic acids, phenols, organic phosphoric acids and the like.
  • organic carboxylic acid examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, 2-ethylhexic acid (octyl acid), neodecanoic acid, capric acid, undecanoic acid and isoundecylic acid.
  • Esther or monoamide compounds examples thereof include di or triester compounds of trivalent or tetravalent carboxylic acids such as butane tricarboxylic acid, butane tetracarboxylic acid, hemmellitic acid, trimellitic acid, merophan acid, pyromellitic acid and the like.
  • phenols include tertiary butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, and 2-ethylhexylphenol.
  • Tertiary nonylphenol decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamilphenol, methylisohexylphenol, methyltertiary octylphenol and the like.
  • organic phosphoric acid examples include mono or dioctyl phosphoric acid, mono or didodecyl phosphoric acid, mono or dioctadecyl phosphoric acid, mono or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester and the like. Be done.
  • the zinc salt of the organic acid which is the component (A) of the composition of the present invention is a hyperbasic complex obtained by neutralizing a part or all of the bases of an acidic salt, a neutral salt, a basic salt or a basic salt with carbonic acid. May be.
  • the zinc salt of the organic acid which is the component (A) of the composition of the present invention may be composed of two or more kinds of organic acids.
  • a zinc salt made of a monovalent organic acid the same organic acid may form an anion moiety and form a salt with a divalent zinc forming a cation moiety, and different monovalent organic acids 2 may be formed.
  • the seed may form a salt with a divalent zinc that forms an anionic moiety and forms a cation moiety.
  • the zinc salt of the organic acid of the component (A) is preferably a zinc salt of an organic carboxylic acid from the viewpoint of thermal stability, color resistance, and heat-resistant coloring, and zinc benzoate, zinc tolurate, and 4-tert-butyl benzoate.
  • Zinc acid acid, zinc stearate, zinc laurate, zinc versatic acid, zinc octylate, zinc oleate, zinc palmitin, and zinc myristin are preferred.
  • zinc salts of aromatic carboxylic acids are more preferable from the viewpoint of thermal stability, coloring resistance, and heat-resistant coloring resistance, and specifically, zinc benzoate, zinc toluic acid, and 4-tert-butylbenzoic acid. Zinc is more preferred.
  • the zinc salt of the organic acid of the component (A) may be used alone or in combination of two or more.
  • the component (B) of the composition of the present invention is one or more of epoxy compounds having at least one of a glycidyl ether group and a glycidyl ester group.
  • Examples of the epoxy compound having at least one of a glycidyl ether group or a glycidyl ester group include a polyglycidyl ether compound or a diglycidyl ether compound of a mononuclear polyhydric phenol compound such as hydroquinone, resorcin, pyrocatechol, and fluoroglucolinol; dihydroxy.
  • Polyglycyl ether compounds of polynuclear polyvalent phenol compounds such as ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolak, ethylphenol novolak, butylphenol novolak, octylphenol novolak, resorcinnovolac, terpenphenol.
  • diglycidyl ether compounds ethylene glycol, propylene glycol, butylene glycol, hexanediol, diethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polyglycol, thiodiglycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A.
  • -Polyglycidyl ethers or diglycidyl ethers of polyhydric alcohols such as ethylene oxide adducts, dicyclopentadiene dimethanol; maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sevacin Fats, aromatics or aliphatics such as acids, dimer acids, trimeric acids, phthalates, isophthalates, terephthalic acids, trimellitic acids, trimesic acids, pyromellitic acids, tetrahydrophthalic acids, hexahydrophthalic acids, endomethylenetetrahydrophthalic acids and the like.
  • Examples thereof include homopolymers or copolymers of glycidyl esters of alicyclic polybasic acids and glycidyl methacrylates such as polyglycidyl methacrylate.
  • an epoxy compound having at least one of a glycidyl ether group or a glycidyl ester group, n-butyl glycidyl ether, C12 to C14 alkyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cres.
  • Examples thereof include jylglycidyl ether, 2-phenylphenol glycidyl ether, p-sec-butylphenylglycidyl ether, t-butylphenylglycidyl ether, glycidyl methacrylate, tertiary carboxylic acid glycidyl ester, and further, for example, ethylene glycol di.
  • Examples thereof include glycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like.
  • glycidyl ether propylene glycol diglycidyl ether, butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and the like.
  • trimethylolpropane triglycidyl ether, glycerin triglycidyl ether and the like can be mentioned.
  • the epoxy compound having at least one of the glycidyl ether group and the glycidyl ester group of the component (B) is preferably an epoxy compound having a glycidyl ether group from the viewpoint of thermal stability, coloring resistance and heat-resistant coloring resistance, and the glycidyl ether group is preferable.
  • the epoxy compound contained include bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and alkyl glycidyl ether having 12 to 13 carbon atoms.
  • Cresyl glycidyl ether, 2-phenylphenol glycidyl ether is preferable, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 2 -Phenylphenol glycidyl ether is more preferable, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, 2-phenylphenol glycidyl ether are even more preferable, and bisphenol A.
  • the epoxy compound of the component (B) may have one or two or more glycidyl ether groups or glycidyl ester groups in its structure. Further, as the epoxy compound of the component (B), only one kind may be used, or two or more kinds may be used in combination.
  • the epoxy compound having a glycidyl ether group as the component (B) can be obtained, for example, by reacting a compound having a phenolic hydroxyl group or an alcoholic hydroxyl group with epichlorohydrin.
  • a commercially available product may be used.
  • the compound having a glycidyl ester group as the component (B) can be obtained, for example, by reacting a compound having a carboxyl group with epichlorohydrin.
  • a commercially available product may be used.
  • epoxidized vegetable oils such as epoxidized soybean oil and epoxidized flaxseed oil, which have been conventionally used as stabilizers and plasticizers for vinyl chloride resins, have either a glycidyl ether group or a glycidyl ester group in their structure. Also, it is not included in the epoxy compound having at least one of the glycidyl ether group and the glycidyl ester group of the component (B) of the present invention.
  • the epoxidized vegetable oil Since the epoxidized vegetable oil is obtained by oxidizing the double bond of the vegetable oil to form an oxylan ring, the epoxidized vegetable oil does not contain either a glycidyl ether group or a glycidyl ester group in its structure.
  • the epoxy compound having at least one of the glycidyl ether group and the glycidyl ester group of the component (B) has an oxylan oxygen concentration of 3.0 to 15.0 mass from the viewpoint of thermal stability, color resistance and heat color resistance. It is preferably in the range of%, more preferably in the range of 4.0 to 14.0% by mass, further preferably in the range of 5.0 to 13.0% by mass, and 6. It is particularly preferably in the range of 0 to 12.0% by mass, and most preferably in the range of 7.0 to 11.0% by mass.
  • the oxylan oxygen concentration was measured according to ASTMD1652-11e1.
  • the content of the component (B) in the composition of the present invention is 5 to 2500 parts by mass with respect to 100 parts by mass of the zinc salt of the organic acid of the component (A), and has thermal stability and color resistance. From the viewpoint of heat-resistant coloring, 10 parts by mass or more is preferable, 50 parts by mass or more is more preferable, 100 parts by mass or more is further preferable, 150 parts by mass or more is further preferable, 200 parts by mass or more is further preferable, and 250 parts by mass is more preferable. More than 300 parts by mass is particularly preferable, and 300 parts by mass or more is most preferable.
  • the upper limit exceeds 2500 parts by mass, it is not preferable from the viewpoint of effect and cost, preferably 2000 parts by mass or less, more preferably 1400 parts by mass or less, still more preferably 1200 parts by mass or less, and particularly preferably. Is 1000 parts by mass or less, most preferably 900 parts by mass or less.
  • the component (C) of the composition of the present invention is one or more salts of perchloric acid.
  • perchloric acid salts include perchloric acid metal salts, ammonium perchlorate, perchloric acid-treated hydrotalcites, perchloric acid-treated silicates and the like.
  • perchloric acid metal salt is preferable from the viewpoint of thermal stability, color resistance, and heat color resistance.
  • the metal constituting the perchlorate metal salt examples include lithium, sodium, potassium, calcium, magnesium, strontium, barium, zinc, cadmium, lead, aluminum and the like.
  • the perchloric acid metal salt may be an anhydride or a hydrous salt, or may be dissolved in an alcohol-based or ester-based solvent such as butyl diglycol or butyl diglycol adipate, or a dehydrated product thereof.
  • care must be taken when dissolved in a solvent because the Vicut softening point of the molded product may decrease.
  • Perchloric acid treatment hydrotalcite some or all carbonate anions of the hydrotalcite compound (CO 3 2-) is perchlorate anion - are those substituted with (ClO 4). 2 mol of perchlorate anion replaces 1 mol of carbonate anion.
  • Perchloric acid-treated hydrotalcite can be easily produced, for example, by adding a hydrotalcite compound to a dilute aqueous solution of perchloric acid, stirring the mixture, and then filtering, dehydrating or drying as required. ..
  • the molar ratio of the hydrotalcite compound to the perchloric acid can be arbitrarily set, but in general, the ratio is 0.1 to 2 mol of the perchloric acid with respect to 1 mol of the hydrotalcite compound. It is preferably used, more preferably 0.2 to 2 mol.
  • the hydrotalcite compound is a carbonated double salt compound of magnesium and / or zinc and aluminum, and is preferably a compound represented by the following general formula (I).
  • x1 and x2 each indicate a number satisfying the conditions represented by the following equation, and m indicates a real number. 0 ⁇ x2 / x1 ⁇ 10,2 ⁇ x1 + x2 ⁇ 20)
  • the hydrotalcite compound may be a natural product or a synthetic product.
  • a method for synthesizing the synthetic product 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 Application Laid-Open No. 61-174270 and the like are exemplified. be able to.
  • the composition of the present invention it can be used without being limited by the crystal structure of the hydrotalcite compound, the presence or absence of crystal particle system or water of crystallization, and the amount thereof.
  • the surface thereof is a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as oleic acid alkali metal salt, and an organic sulfonic acid such as dodecylbenzene sulfonic acid alkali metal salt.
  • a metal salt, a higher fatty acid amide, a higher fatty acid ester, a wax or the like can also be used.
  • perchloric acid-treated silicate examples include silicate metal salts such as calcium silicate, magnesium silicate, barium silicate, and zinc silicate, various silicate clay minerals, or processed products thereof, for example, kaolin, bentonite, mica powder, talc, diatomaceous earth, and acid.
  • silicate metal salts such as calcium silicate, magnesium silicate, barium silicate, and zinc silicate
  • various silicate clay minerals or processed products thereof, for example, kaolin, bentonite, mica powder, talc, diatomaceous earth, and acid.
  • examples thereof include those obtained by treating natural or synthetic silicates such as white clay, active white clay and zeolite with an aqueous solution of perchloric acid.
  • these perchloric acid-treated silicates calcium silicate, magnesium silicate, barium silicate, kaolin, etc. Bentnite, talc, acidic white clay, active white clay and treated products of zeolite are preferable.
  • the perchloric acid-treated silicate can be easily produced, for example, by adding the silicate to a dilute aqueous solution of perchloric acid, stirring the mixture, and then filtering, dehydrating or drying as necessary.
  • the molar ratio of the above silicate to perchloric acid can be set arbitrarily, but in general, it is used at a ratio of 0.1 to 2 mol of perchloric acid with respect to 1 mol of silicate. Is preferable.
  • composition of the present invention only one kind of these salts of perchloric acid may be used, or two or more kinds thereof may be used in combination.
  • perchloric acid-treated hydrotalcite As the salt of perchloric acid, perchloric acid-treated hydrotalcite, calcium perchlorate, sodium perchlorate, barium perchlorate are preferable, and perchloric acid is preferable from the viewpoint of thermal stability, coloring resistance, and heat-resistant coloring. Calcium, sodium perchlorate and barium perchlorate are more preferred, and sodium perchlorate and barium perchlorate are even more preferred.
  • the content of the component (C) in the composition of the present invention is 0.01 to 100 parts by mass with respect to 100 parts by mass of the zinc salt of the organic acid of the component (A), and has thermal stability and color resistance. From the viewpoint of property and heat-resistant coloring, 1.0 to 90 parts by mass is preferable, 5.0 to 80 parts by mass is more preferable, 5.0 to 70 parts by mass is further preferable, and 5.0 to 60 parts by mass is particularly preferable. Preferably, 10.0 to 50 parts by mass is most preferable.
  • the composition of the present invention further comprises one or more ⁇ -diketone compounds in an amount of 5 to 300 parts by mass with respect to 100 parts by mass of the component (A). It is preferably contained, more preferably 10 to 250 parts by mass, and even more preferably 20 to 200 parts by mass.
  • ⁇ -diketone compound examples include acetylacetone, triacetylmethane, 2,4,6-heptatrione, butanoylacetylmethane, lauroylacetylmethane, palmitoylacetylmethane, stearoylbenzoylmethane, palmitoylbenzoylmethane, distearoylmethane and stearoyl.
  • the ⁇ -diketone compound may be used alone or in combination of two or more.
  • dibenzoylmethane, stearoylbenzoylmethane, and acetylacetone zinc salt are preferable from the viewpoint of thermal stability, color resistance, and heat resistance.
  • one or more phosphite ester compounds may be added to 5 to 100 parts by mass of the component (A). It is preferably contained in an amount of 700 parts by mass, more preferably 50 to 600 parts by mass, and even more preferably 100 to 500 parts by mass.
  • phosphite ester compound examples include phosphite trialkyl ester, phosphite dialkyl ester, phosphite dialkyl monoallyl ester, phosphite alkyl allyl ester, phosphite monoalkyl diallyl ester, phosphite diallyl ester, and the like. Examples thereof include phosphite triallyl ester.
  • either a triester or a diester can be used, but it is preferable to use a triester from the viewpoint of thermal stability, color resistance and heat color resistance. Thioester can also be used.
  • phosphite ester compound examples include triphenyl phosphite, tricresyl phosphite, tris (2,4-ditriary butylphenyl) phosphite, tris (nonylphenyl) phosphite, and tris (dinonylphenyl).
  • Phosphite Tris (mono- and di-mixed nonylphenyl) phosphite, Tris (2,4-di-tertiary butylphenyl) phosphite, diphenylphosphite, 2,2'-methylenebis (4,6-dith) Tributylphenyl) octylphosphite, 2,2'-methylenebis (4,6-third butylphenyl) -2-ethylhexylphosphite, 2,2'-methylenebis (4,6-third butylphenyl) -octadecylphos Fight, 2,2'-Etilidenebis (4,6-dithiary butylphenyl) fluorophosphite, octyldiphenylphosphite, diphenyldecylphosphite, diphenyl (2-ethylhexyl)
  • phosphite ester compound only one type of phosphite ester compound may be used, or two or more types may be used in combination.
  • these subphosphate ester compounds it is preferable to use a subphosphate ester compound having 12 to 80 carbon atoms, and 12 to 46 carbon atoms, from the viewpoint of thermal stability, coloring resistance, and heat-resistant coloring. It is more preferable to use the subphosphate ester compound of, further preferably to use the subphosphate ester compound having 12 to 36 carbon atoms, and to use the subphosphate ester compound having 18 to 30 carbon atoms. Is particularly preferable.
  • one or more phenolic antioxidants are further added to 100 parts by mass of the component (A) from 5 to It is preferably contained in an amount of 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 15 to 100 parts by mass.
  • phenolic antioxidant examples include 2,6-ditertiary butyl-p-cresol, 2,6-diphenyl-4-octadecyloxyphenol, and stearyl (3,5-ditritiary butyl-4-hydroxy).
  • phenolic antioxidant only one type of phenolic antioxidant may be used, or two or more types may be used in combination.
  • pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] is selected from the viewpoint of thermal stability, color resistance, and heat-resistant color resistance. preferable.
  • one or more sugar alcohols are further added in an amount of 1 to 1000 parts by mass with respect to 100 parts by mass of the component (A). It is preferably contained, more preferably 2 to 200 parts by mass, further preferably 6 to 100 parts by mass, and particularly preferably 10 to 60 parts by mass.
  • sugar alcohols examples include mannitol, maltitol, lactitol, sorbitol, erythritol, xylitol, and inositol. Only one type of sugar alcohol may be used, or two or more types may be used in combination. Among these sugar alcohols, mannitol, maltitol, lactitol, and sorbitol are preferable, and sorbitol is particularly preferable, from the viewpoint of thermal stability, coloring resistance, and heat-resistant coloring resistance.
  • one or more hindered amine-based photostabilizers may be added to 100 parts by mass of the component (A) from 5 to 5 to 100 parts by mass. It is preferably contained in an amount of 200 parts by mass, more preferably 10 to 150 parts by mass, further preferably 20 to 100 parts by mass, and particularly preferably 30 to 80 parts by mass.
  • the hindered amine-based light stabilizer is not particularly limited as long as it is a conventionally known hindered amine-based light stabilizer, and is, for example, 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2.
  • examples of the hindered amine-based light stabilizer include compounds having a group represented by the following general formula (1), preferably from the viewpoint of thermal stability, color resistance, and heat-resistant color resistance.
  • R 1 is a hydrogen atom, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and a hydroxyalkyl group having 1 to 30 carbon atoms.
  • a hydroxyalkoxy group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, or an oxyradic is represented, and these alkyl groups, alkoxy groups, hydroxyalkyl groups, hydroxyalkoxy groups, and alkenyl groups are oxygen atoms. It may be interrupted by one or more carbonyl groups.
  • the group represented by the general formula (1) is bonded at the position of * in the general formula (1).
  • the group represented by the general formula (1) may have one or two or more groups in the compound.
  • Examples of the alkyl group having 1 to 30 carbon atoms that R 1 of the general formula (1) can take include a linear alkyl group and a branched alkyl group.
  • Examples of the linear alkyl group include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group and a tetradecyl group.
  • Examples of the branched alkyl group include a group in which one or two or more of the above linear alkyl groups are substituted with an alkyl group having 1 to 9 carbon atoms.
  • Examples of the alkoxy group having 1 to 30 carbon atoms that can be taken by R 1 of the general formula (1) include an alkoxy group corresponding to the above-mentioned alkyl group.
  • Examples of the hydroxyalkyl group having 1 to 30 carbon atoms that R 1 of the general formula (1) can take include a hydroxyalkyl group corresponding to the above-mentioned alkyl group.
  • Examples of the hydroxyalkoxy group having 1 to 30 carbon atoms that can be taken by R 1 of the general formula (1) include a hydroxyalkoxy group corresponding to the above-mentioned alkoxy group.
  • Examples of the alkenyl group having 2 to 30 carbon atoms that R 1 of the general formula (1) can take include an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group and a nonenyl group.
  • R 1 is preferably a hydrogen atom or an alkyl group having 1 to 30 carbon atoms, and the number of carbon atoms is preferable, from the viewpoint of thermal stability, coloring resistance, and heat-resistant coloring resistance.
  • Alkyl groups of 1 to 30 are more preferable, alkyl groups having 1 to 4 carbon atoms are more preferable, and those having a methyl group are most preferable.
  • R 1 of the general formula (1) is a hydrogen atom
  • R 1 of the general formula (1) is a hydrogen atom
  • the group R 1 represented by the general formula (1) is preferably a hydrogen atom or a methyl group, and a methyl group is preferable. More preferred.
  • composition of the present invention may further contain a barium salt of an organic acid in consideration of thermal stability, color resistance and heat color resistance.
  • a barium salt of an organic acid is contained, it is preferably contained in an amount of 5 to 700 parts by mass, more preferably 25 to 600 parts by mass, and 50 to 500 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable to include it.
  • barium salt of an organic acid examples include barium salts such as organic carboxylic acids, phenols and organic phosphoric acids.
  • organic carboxylic acid examples include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, pelargonic acid, 2-ethylhexic acid, neodecanoic acid, capric acid, undecanoic acid, isoundecylic acid and lauric acid.
  • Telephthalic acid hydroxyphthalic acid, chlorphthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, metaconic acid, itaconic acid, aconitic acid, thiodipropionic acid and other divalent carboxylic acids or monoesters or monoamide compounds thereof.
  • di or triester compounds of trivalent or tetravalent carboxylic acids such as butane tricarboxylic acid, butane tetracarboxylic acid, hemmellitic acid, trimellitic acid, melophane acid and pyromellitic acid.
  • phenols include tertiary butylphenol, nonylphenol, dinonylphenol, cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isoamylphenol, ethylphenol, isopropylphenol, isooctylphenol, and 2-ethylhexylphenol.
  • Tertiary nonylphenol decylphenol, tertiary octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, diamilphenol, methylisohexylphenol, methyltertiary octylphenol and the like.
  • organic phosphoric acid examples include mono or dioctyl phosphoric acid, mono or didodecyl phosphoric acid, mono or dioctadecyl phosphoric acid, mono or di- (nonylphenyl) phosphoric acid, phosphonic acid nonylphenyl ester, phosphonic acid stearyl ester and the like. Be done.
  • the barium salt of an organic acid may be composed of two or more kinds of organic acids.
  • the same organic acid may form an anion moiety and form a salt with a divalent barium forming a cation moiety, and different monovalent organic acids 2 may be formed.
  • the seed may form a salt with a divalent barium that forms an anionic moiety and forms a cation moiety.
  • the barium salt of an organic acid may be an acid salt, a neutral salt or a basic salt.
  • composition of the present invention may further contain a calcium salt of an organic acid in consideration of thermal stability, color resistance and heat color resistance.
  • a calcium salt of an organic acid is contained, it is preferably contained in an amount of 5 to 700 parts by mass, more preferably 25 to 600 parts by mass, and 50 to 500 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable to include it.
  • Examples of the calcium salt of the organic acid include calcium salts of organic carboxylic acids, phenols, organic phosphoric acids and the like.
  • Examples of the organic carboxylic acid include those exemplified by the above-mentioned barium salt.
  • examples of the phenols include those exemplified by the above-mentioned barium salt.
  • examples of the organic phosphoric acids include those exemplified by the above-mentioned barium salt.
  • the calcium salt of an organic acid may be composed of two or more kinds of organic acids.
  • a calcium salt made of a monovalent organic acid the same organic acid may form an anion moiety and form a salt with a divalent calcium forming a cation moiety, and different monovalent organic acids 2 may be formed.
  • the seed may form a salt with a divalent calcium that forms an anionic moiety and forms a cation moiety.
  • the calcium salt of the organic acid may be used alone or in combination of two or more. Further, the calcium salt of the organic acid may be an acid salt, a neutral salt or a basic salt.
  • composition of the present invention may further contain a perbasic barium carbonate salt in consideration of thermal stability, coloring resistance, and heat-resistant coloring resistance.
  • the superbasic barium carbonate When the superbasic barium carbonate is contained, it is preferably contained in an amount of 5 to 700 parts by mass, more preferably 25 to 600 parts by mass, and 50 to 500 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable to add a portion. However, when a perbasic barium carbonate salt is blended in the composition, care must be taken because the molded product may foam during the molding process.
  • the superbasic barium carbonate salt is a liquid superbasic carboxylate / carbonate complex of barium.
  • This complex unlike a simple mixture of barium carboxylic acid positive salt and barium carbonate, is a complex formed by some interaction and has a high metal content in an organic solvent. It has the characteristic of showing a uniform liquid.
  • This complex is composed of a carboxylic acid positive salt of barium, barium carbonate, and a composite salt of barium carboxylic acid and carbonic acid as constituents, and is composed mainly of barium carbonate, barium carboxylic acid positive salt and barium carboxylic acid.
  • a complex salt of carbonic acid and carbonic acid exists in the vicinity thereof, and a so-called micelle-like substance is formed to show a uniform liquid state in an organic solvent.
  • These liquid hyperbasic carboxylate / carbonate complexes of barium can be produced, for example, by the production method shown in JP-A-2004-238364.
  • liquid perbasic carboxylate / carbonate complex of barium various commercially available complexes can be used as they are.
  • these hyperbasic barium carbonate salts may be used alone or in combination of two or more.
  • composition of the present invention may further contain a hyperbasic calcium carbonate salt in consideration of thermal stability, color resistance and heat color resistance.
  • a hyperbasic calcium carbonate salt in consideration of thermal stability, color resistance and heat color resistance.
  • the superbasic calcium carbonate salt is contained, it is preferably contained in an amount of 5 to 700 parts by mass, more preferably 25 to 600 parts by mass, and 50 to 500 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable to add a portion.
  • the hyperbasic calcium carbonate salt is blended in the stabilizer composition, the molded product may foam during the molding process.
  • the hyperbasic calcium carbonate salt is a liquid perbasic carboxylate / carbonate complex of calcium.
  • This complex is different from a simple mixture of a positive carboxylic acid salt of calcium and calcium carbonate, which is a complex by some interaction, and has a high metal content in an organic solvent. It has the characteristic of showing a uniform liquid.
  • This complex is composed of a positive carboxylic acid salt of calcium, calcium carbonate, and a complex salt of carboxylic acid of calcium and carbonic acid as constituents.
  • a complex salt of calcium and calcium exists in the vicinity thereof, and a so-called micelle-like substance is formed to show a uniform liquid state in an organic solvent.
  • these hyperbasic calcium carbonate salts may be used alone or in combination of two or more.
  • the composition of the present invention may further contain a hydrotalcite compound in consideration of thermal stability, color resistance, and heat color resistance.
  • a hydrotalcite compound in consideration of thermal stability, color resistance, and heat color resistance.
  • the hydrotalcite compound is contained, it is preferably contained in an amount of 10 to 500 parts by mass, more preferably 30 to 400 parts by mass, and 50 to 300 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable to let it.
  • care must be taken because the molded product may foam during the molding process and the molded product may cause stress whitening.
  • the hydrotalcite compound is a carbonated double salt compound of magnesium and / or zinc and aluminum, and is preferably a compound represented by the following general formula (II).
  • x1 and x2 each indicate a number satisfying the conditions represented by the following equation, and m indicates a real number. 0 ⁇ x2 / x1 ⁇ 10,2 ⁇ x1 + x2 ⁇ 20)
  • the hydrotalcite compound may be a natural product or a synthetic product.
  • a method for synthesizing the synthetic product 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 Application Laid-Open No. 61-174270 and the like are exemplified. be able to.
  • the composition of the present invention it can be used without being limited by the crystal structure of the hydrotalcite compound, the presence or absence of crystal particle system or water of crystallization, and the amount thereof.
  • the surface thereof is a higher fatty acid such as stearic acid, a higher fatty acid metal salt such as oleic acid alkali metal salt, an organic sulfonic acid metal salt such as dodecylbenzene sulfonic acid alkali metal salt, a higher fatty acid amide, and a higher grade.
  • a higher fatty acid such as stearic acid
  • a higher fatty acid metal salt such as oleic acid alkali metal salt
  • an organic sulfonic acid metal salt such as dodecylbenzene sulfonic acid alkali metal salt
  • a higher fatty acid amide such as a higher fatty acid amide
  • a higher grade such as stearic acid
  • a higher fatty acid metal salt such as oleic acid alkali metal salt
  • an organic sulfonic acid metal salt such as dodecylbenzene sulfonic acid alkali metal salt
  • a higher fatty acid amide
  • composition of the present invention only one type of hydrotalcite compound may be used, or two or more types may be used in combination.
  • composition of the present invention may further contain a polyhydric alcohol compound other than the sugar alcohol in consideration of thermal stability, color resistance and heat color resistance.
  • a polyhydric alcohol compound other than the sugar alcohol in consideration of thermal stability, color resistance and heat color resistance.
  • the polyhydric alcohol compound is contained, it is preferably contained in an amount of 0.01 to 100 parts by mass, more preferably 0.1 to 75 parts by mass, and 1 to 1 to 75 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable to contain 50 parts by mass.
  • polyhydric alcohol compound examples include pentaerythritol, dipentaerythritol, tripentaerythritol, polypentaerythritol, neopentyl glycol, trimethylolpropane, ditrimethylolpropane, and 1,3,5-tris (2-hydroxyethyl) isocia.
  • examples thereof include nurate, polyethylene glycol, glycerin, diglycerin, xylose, sucrose (sucrose), trehalose, inositol, fructose, maltose, lactose and the like. Only one kind of polyhydric alcohol compound may be used, or two or more kinds may be used in combination.
  • the composition of the present invention may contain a solvent as long as the effect of the present invention is not impaired.
  • the solvent is preferably an organic solvent, more preferably an organic solvent having a boiling point of 100 ° C. or higher, further preferably an organic solvent having a boiling point of 120 ° C. or higher, and particularly preferably an organic solvent having a boiling point of 150 ° C. or higher, from the viewpoint of solubility of the stabilizer component. preferable.
  • preferable organic solvents include alcohol-based organic solvents such as 3-methoxy-n-butanol, 2-ethylhexanol, undecanol, and tridecanol, and glycol-based organic solvents such as methyldiglycol, butyldiglycol, and methylpropylene glycol.
  • alcohol-based organic solvents such as 3-methoxy-n-butanol, 2-ethylhexanol, undecanol, and tridecanol
  • glycol-based organic solvents such as methyldiglycol, butyldiglycol, and methylpropylene glycol.
  • examples thereof include liquid paraffin, naphthenic solvent, normal paraffin solvent, isoparaffin solvent, aliphatic hydrocarbon solvent, aromatic hydrocarbon solvent, and hydrocarbon solvent such as mineral oil. Only one type of solvent may be used, or two or more types may be used in combination.
  • the blending amount is preferably 5 to 700 parts by mass, more preferably 10 to 600 parts by mass, and 15 to 500 parts by mass with respect to 100 parts by mass of the component (A). It is more preferable to do so.
  • the stabilizer composition of the present invention can be preferably blended with a vinyl chloride resin and used as a vinyl chloride resin composition.
  • the solvent may be mixed according to the above, and various mixers can be used for mixing. It may be heated at the time of mixing. Examples of mixers that can be used include tumbler mixers, henschel mixers, ribbon blenders, V-type mixers, W-type mixers, super mixers, nower mixers and the like. Further, the above-mentioned components may be directly blended with the vinyl chloride-based resin individually or at the same time in two or more kinds to prepare a vinyl chloride-based resin composition.
  • the vinyl chloride-based resin composition of the present invention contains a vinyl chloride-based resin and a stabilizer composition of the present invention.
  • the vinyl chloride-based resin is not particularly limited in its polymerization method such as bulk polymerization, solution polymerization, suspension polymerization, and emulsion polymerization, and is, for example, polyvinyl chloride, chlorinated polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, and the like.
  • Vinyl chloride-vinyl acetate copolymer vinyl chloride-ethylene copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, Vinyl chloride-styrene-maleic anhydride ternary copolymer, vinyl chloride-styrene-acrylonilittle copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer Combined, vinyl chloride-vinylidene chloride-vinyl acetate ternary copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, vinyl chloride-various vinyl ethers Vinyl chloride-based resins such
  • vinyl chloride resins may be a mixture of two or more kinds, or may be a mixture with other synthetic resins.
  • the vinyl chloride-based resin used is preferably polyvinyl chloride from the viewpoint of thermal stability, color resistance, and heat-resistant color resistance.
  • a lubricant When adding the composition of the present invention to a vinyl chloride resin, it is preferable to further add a lubricant in consideration of processability.
  • the lubricant may be added to the composition before being added to the vinyl chloride resin.
  • examples of lubricants are hydrocarbon-based lubricants such as low-molecular-weight waxes, paraffin waxes, polyethylene waxes, chlorinated hydrocarbons, and fluorocarbons; natural wax-based lubricants such as carnauba wax and candelilla wax; lauric acid, stearic acid, and behenin.
  • Higher fatty acids such as acids, or fatty acid-based lubricants such as oxy fatty acids such as hydroxystearic acid; aliphatic amide compounds such as stearylamide, laurylamide, oleylamide or alkylenebis such as methylenebisstearylamide, ethylenebisstearylamide.
  • Fatty acid amide-based lubricants such as aliphatic amides; fatty acid monovalent alcohol ester compounds such as stearyl stearate, butyl stearate, and distearyl phthalate, or glycerin tristearate, sorbitan tristearate, pentaerythritol tetrastearate, dipenta.
  • Fatty acid polyvalent alcohol ester compounds such as erythritol hexastearate, polyglycerin polylysinolate, and hardened castor oil, or monovalent fatty acids such as dipentaerythritol adipic acid / stearic acid ester and polybasic organic acids and polyvalents.
  • Fatty acid alcohol ester-based lubricants such as composite ester compounds of alcohol; Stearic acid-based lubricants such as steearic acid, lauryl alcohol, and palmityl alcohol; Metal soaps; ; Silicone oil and the like can be mentioned. Only one kind of these lubricants may be used, or two or more kinds thereof may be used in combination.
  • the amount added is preferably 0.01 to 5.0 parts by mass, and 0.05 to 4.0 parts by mass from the viewpoint of processability with respect to 100 parts by mass of the vinyl chloride resin. Is more preferable, and 0.1 to 3.0 parts by mass is further preferable.
  • the processing aid may be added to the composition of the present invention before being added to the vinyl chloride resin.
  • the processing aid can be appropriately selected from known processing aids. Examples of processing aids are homopolymers or copolymers of alkyl methacrylates such as methyl methacrylate, ethyl methacrylate and butyl methacrylate; co-polymers of the above alkyl methacrylate and alkyl acrylates such as methyl acrylate, ethyl acrylate and butyl acrylate.
  • Polymer Polymer of the above alkyl methacrylate with an aromatic vinyl compound such as styrene, ⁇ -methylstyrene, vinyltoluene; copolymer of the above alkyl methacrylate with a vinyl cyan compound such as acrylonitrile or methacrylnitrile And so on. Only one kind of these processing aids may be used, or two or more kinds thereof may be used in combination.
  • the amount added is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the vinyl chloride resin.
  • the vinyl chloride-based resin includes other additives usually used for vinyl chloride-based resins, such as sulfur-based antioxidants, epoxy compounds other than the component (B), and plasticizers.
  • additives usually used for vinyl chloride-based resins such as sulfur-based antioxidants, epoxy compounds other than the component (B), and plasticizers.
  • additives may be added to the composition before being added to the vinyl chloride resin.
  • sulfur-based antioxidants examples include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate). ⁇ -Alkyl mercaptopropionic acid esters and the like. Only one of these sulfur-based antioxidants may be used, or two or more of them may be used in combination.
  • epoxy compounds other than the component (B) include epoxidized vegetable oils such as epoxidized soybean oil, epoxidized flaxseed oil, epoxidized tung oil, epoxidized ash oil, and epoxidized safflower oil. Only one kind of these epoxidized vegetable oils may be used, or two or more kinds thereof may be used in combination.
  • plasticizers include dibutylphthalate, butylhexylphthalate, diheptylphthalate, dioctylphthalate, diisononylphthalate, diisodecylphthalate, dilaurylphthalate, dicyclohexylphthalate, dioctylterephthalate and other phthalate plasticizers; dioctyl adipate, diisononyl adipate, etc.
  • Adipate-based plasticizers such as diisodecyl adipate and di (butyl diglycol) adipate; triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tri (isopropylphenyl) phosphate, triethyl phosphate, tributyl phosphate, trioctyl phosphate, tri ( Butoxyethyl) phosphate, octyldiphenyl phosphate and other phosphate plasticizers; ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butanediol, 1,4-butane Polyhydric alcohols such as diols, 1,5-hexanediols, 1,6-hexanediols and neopentylglycols, and oxalic acid, malonic acid, succin
  • UV absorbers examples include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 5,5'-methylenebis (2-hydroxy-4-methoxybenzophenone).
  • 2-Hydroxybenzophenones such as 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2-hydroxy-5-third octylphenyl) benzotriazole, 2- (2-hydroxy-3, 5-Ditertiary Butylphenyl) -5-Chlorobenzotriazole, 2- (2-Hydroxy-3-3rd Butyl-5-Methylphenyl) -5-Chlorobenzotriazole, 2- (2-Hydroxy-3,5) -Dicumylphenyl) benzotriazole, 2,2'-methylenebis (4-thioctyl-6-benzotriazolyl) phenol, 2- (2-hydroxy-3-third butyl-5-carbox
  • impact improvers examples include polybutadiene, polyisoprene, polychloroprene, fluororubber, styrene-butadiene copolymer rubber, methyl methacrylate-butadiene-styrene copolymer, methyl methacrylate-butadiene-styrene graft.
  • Copolymer acrylonitrile-styrene-butadiene copolymer rubber, acrylonitrile-styrene-butadiene graft copolymer, styrene-butadiene-styrene block copolymer rubber, styrene-isoprene-styrene copolymer rubber, styrene-ethylene -Butylene-styrene copolymer rubber, ethylene-propylene copolymer rubber, ethylene-propylene-diene copolymer rubber (EPDM), silicone-containing acrylic rubber, silicone / acrylic composite rubber graft copolymer, silicone rubber And so on.
  • EPDM ethylene-propylene copolymer rubber
  • EPDM diene examples include 1,4-hexanediene, dicyclopentadiene, methylenenorbornene, ethylidenenorbornene, propenylnorbornene and the like. Only one kind of these impact improvers may be used, or two or more kinds thereof may be used in combination.
  • fibrous, plate-like, granular, or powder-like materials that are usually used for reinforcing synthetic resin can be used.
  • Inorganic fibrous reinforcing materials such as elestadite, gypsum fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, silicon nitride fiber and boron fiber, polyester fiber, nylon fiber, acrylic fiber, recycled cellulose fiber, acetate fiber,
  • Organic fibrous reinforcements such as Kenaf, ramie, cotton, jute, hemp, sisal, flax, linen, silk, Manila hemp, sugar cane, wood pulp, paper scraps, waste paper and wool, glass flakes, non-swelling mica, graphit
  • reinforcing materials may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin, and may be coated with a coupling agent such as aminosilane or epoxysilane. It may have been processed. Only one kind of these reinforcing materials may be used, or two or more kinds thereof may be used in combination.
  • fillers include calcium carbonate, calcium oxide, calcium hydroxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, sodium alumina silicate, Hydrocarbamite, aluminum silicate, magnesium silicate, calcium silicate, silicate metal salts such as zeolite, active clay, talc, clay, red iron oxide, asbestos, antimony trioxide, silica, glass beads, mica, sericite, glass Examples thereof include flakes, asbestos, wollastonite, potassium titanate, PMF, gypsum fiber, zonolite, MOS, phosphate fiber, glass fiber, carbon fiber and aramid fiber. Only one kind of these fillers may be used, or two or more kinds thereof may be used in combination.
  • Zeolites are alkali or alkaline earth metal aluminosilicates with a unique three-dimensional zeolite crystal structure, typically A-type, X-type, Y-type and P-type zeolites, monodenites, and analsites. , Sodalite aluminosilicate, clinobtyrolite, erionite, chavasite, etc., and water-containing substances having crystalline water (so-called zeolite water) of these zeolite compounds or anhydrous products from which crystalline water has been removed.
  • zeolite water water-containing substances having crystalline water
  • any of these may be used, and those having a particle size of 0.1 to 50 ⁇ m can be used, and those having a particle size of 0.5 to 10 ⁇ m are particularly preferable. Only one kind of these zeolite compounds may be used, or two or more kinds thereof may be used in combination.
  • magnesium salt of an organic acid examples include magnesium salts of organic carboxylic acids, phenols, organic phosphoric acids and the like.
  • Examples of the organic carboxylic acid include those exemplified by the barium salt of the above-mentioned organic acid.
  • Examples of the phenols include those exemplified by the above-mentioned barium salt of an organic acid.
  • Examples of the organic phosphoric acids include those exemplified by the barium salt of the above-mentioned organic acid.
  • the magnesium salt of an organic acid may be composed of two or more kinds of organic acids. For example, in the case of a magnesium salt made of a monovalent organic acid, the same organic acid may form an anion moiety and form a salt with a divalent magnesium forming a cation moiety, and different monovalent organic acids 2 may be formed.
  • the seed may form a salt with a divalent magnesium that forms an anionic moiety and forms a cation moiety.
  • the magnesium salt of the organic acid may be used alone or in combination of two or more. Further, the magnesium salt of the organic acid may be an acid salt, a neutral salt or a basic salt.
  • the hyperbasic magnesium carbonate salt is a liquid perbasic carboxylate / carbonate complex of magnesium.
  • This complex unlike a simple mixture of magnesium, a positive carboxylic acid salt, and magnesium carbonate, is a complex formed by some interaction, and has a high metal content in an organic solvent. It has the characteristic of showing a uniform liquid.
  • This complex is composed of magnesium carboxylic acid positive salt, magnesium carbonate, and a composite salt of magnesium carboxylic acid and carbonic acid as constituents, and is composed mainly of magnesium carbonate, magnesium carboxylic acid positive salt, and magnesium carboxylic acid.
  • a complex salt of magnesium and carbonic acid exists in the vicinity thereof, and a so-called micelle-like substance is formed to show a uniform liquid state in an organic solvent.
  • the liquid perbasic carboxylate / carbonate complex of magnesium can be produced by the same method as the above-mentioned liquid superbasic liquid carboxylate / carbonate complex of barium. Further, a commercially available complex can be used as it is. These hyperbasic magnesium carbonate salts may be used alone or in combination of two or more.
  • foaming agents examples include azodicarbonamide, azobisisobutyronitrile, p, p'-oxybisbenzenesulfonyl hydrazide, n, n'-dinitrosopentamethylenetetramine, p-toluenesulfonyl semicarbazide, trihydrazo.
  • foaming agents include a decomposition-type organic foaming agent such as triazine and a decomposition-type inorganic foaming agent such as sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, ammonium nitrite, azido compound, and sodium borohydride. Only one kind of these foaming agents may be used, or two or more kinds thereof may be used in combination.
  • flame retardants and flame retardants include triazine ring-containing compounds, metal hydroxides, other inorganic phosphorus, halogen-based flame retardants, silicon-based flame retardants, phosphoric acid ester-based flame retardants, condensed phosphoric acid ester-based flame retardants. , Intomescent flame retardant, antimony oxide such as antimony trioxide, other inorganic flame retardant, organic flame retardant and the like.
  • triazine ring-containing compound examples include melamine, ammeline, benzguanamine, acetoguanamine, phthalodiguanamine, melamine cyanurate, melamine pyrophosphate, butyreneguanamine, norbornenediguanamine, methylenediguanamine, ethylenedimelamine, and trimethylenedi.
  • examples thereof include melamine, tetramethylene dimelamine, hexamethylene dimelamine, 1,3-hexylene dimeramine and the like.
  • metal hydroxide examples include magnesium hydroxide, aluminum hydroxide, calcium hydroxide, barium hydroxide, zinc hydroxide, Kismer 5A (magnesium hydroxide: manufactured by Kyowa Chemical Industry Co., Ltd.) and the like.
  • chlorine-based flame retardants such as tris (chloropropyl) phosphate, tris (tribromoneopentyl) phosphate, brominated bisphenol A type epoxy resin, brominated phenol novolac type epoxy resin, hexabromobenzene, etc.
  • Pentabromotoluene ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromo) Phenoxy) ethane, brominated polyphenylene ether, brominated (poly) styrene, 2,4,6-tris (tribromophenoxy) -1,3,5-triazine, tribromophenylmaleimide, tribromophenyl acrylate, tribromophenyl Methacrylate, tetrabromobisphenol A-type dimethacrylate, pentabromobenzyl acrylate, commercially available products manufactured by Daihachi Chemical Industry Co., Ltd .; bromine-based flame retardants such as CR-504
  • Examples of phosphoric acid ester flame retardants include, for example, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tributoxyethyl phosphate, trischloroethyl phosphate, trisdichloropropyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate.
  • Trixylenyl phosphate Trixylenyl phosphate, Octyldiphenyl phosphate, Xylenyldiphenyl phosphate, Trisisopropylphenyl phosphate, 2-Ethylhexyldiphenyl phosphate, t-butylphenyldiphenyl phosphate, Bis- (t-butylphenyl) phenyl phosphate, Tris- (t-) Examples thereof include butylphenyl) phosphate, isopropylphenyldiphenyl phosphate, bis- (isopropylphenyl) diphenyl phosphate, tris- (isopropylphenyl) phosphate and the like.
  • condensed phosphoric acid ester flame retardant examples include 1,3-phenylene bis (diphenyl phosphate), 1,3-phenylene bis (dixylenyl phosphate), bisphenol A bis (diphenyl phosphate) and the like.
  • Examples of the intomescent flame retardant include ammonium salts and amine salts of (poly) phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, and piperazine pyrophosphate.
  • ammonium salts and amine salts of (poly) phosphoric acid such as ammonium polyphosphate, melamine polyphosphate, piperazine polyphosphate, ammonium pyrophosphate, melamine pyrophosphate, and piperazine pyrophosphate.
  • inorganic flame retardant aids include inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc, and surface-treated products thereof.
  • inorganic compounds such as titanium oxide, aluminum oxide, magnesium oxide, and talc, and surface-treated products thereof.
  • TIPAQUE R-680 titanium oxide: Ishihara Sangyo (Titanium oxide: Ishihara Sangyo)
  • Kyowamag 150 magnesium oxide: manufactured by Kyowa Kagaku Kogyo Co., Ltd.
  • Only one kind of these flame retardants and flame retardant aids may be used, or two or more kinds thereof may be used in combination.
  • organic flame-retardant aid examples include pentaerythritol and dipentaerythritol.
  • a stabilizing aid usually used for a vinyl chloride resin can be added within a range that does not impair the effect of the composition of the present invention.
  • a stabilizing aid for example, diphenylthiourea, anilinodithiotriazine, melamine, benzoic acid, silicate, p-tertiary butyl benzoic acid and the like are used.
  • additives usually used for vinyl chloride resins such as cross-linking agents, antistatic agents, antifogging agents, plate-out inhibitors, surface treatment agents, fluorescent agents, antifungal agents, and bactericidal agents.
  • Metal deactivators, mold release agents, white pigments such as titanium dioxide, pigments such as blue pigments such as ultramarine blue and phthalocyanine blue, etc. can be blended within a range that does not impair the effects of the present invention. Only one of these optional components may be used, or two or more thereof may be used in combination. These stabilizing aids and optional components may be added to the composition of the present invention before being added to the vinyl chloride resin.
  • metal stabilizers used in vinyl chloride resins the addition of lead stabilizers, (organic) tin stabilizers, and cadmium stabilizers is not preferable from the viewpoint of environmental impact and toxicity. ..
  • the resin composition of the present invention contains a vinyl chloride resin and the composition of the present invention.
  • the content of the composition of the present invention in the vinyl chloride resin composition is preferably 0.3 to 15.0 parts by mass, preferably 0.3 to 10.0 parts by mass with respect to 100 parts by mass of the vinyl chloride resin. Parts are more preferable, 0.5 to 8.0 parts by mass are even more preferable, and 0.8 to 6.0 parts by mass are even more preferable.
  • the vinyl chloride-based resin composition of the present invention contains the above-mentioned lubricants, processing aids, and other additives usually used for vinyl chloride-based resins without impairing the effects of the present invention. It can be contained in a range.
  • the resin composition of the present invention can be molded by a known molding method such as roll processing, extrusion molding processing, melt casting method, pressure molding processing, injection molding processing, calendar molding and the like.
  • the molded product of the present invention is obtained from the vinyl chloride resin composition of the present invention.
  • the molded product obtained from the resin composition of the present invention is a piping material such as a pipe, a joint, and a piping component; a building material / structural material such as a wall material, a floor material, a window frame, a corrugated sheet, and a rain gutter; an interior / exterior material for an automobile. ; Coating material for electric wires; Agricultural materials; Food packaging materials; Packing, gaskets, hoses, sheets, trays, bottles, toys and other miscellaneous goods, daily necessities, stationery, decorative boards, industrial boards, IC cases, etc. Can be done.
  • the resin composition of the present invention is particularly suitable for molded articles for hard or semi-hard applications.
  • Epoxy compound 1 Hydrogenated bisphenol A diglycidyl ether (oxygen oxygen concentration 7.4% by mass)
  • Epoxy compound 2 Bisphenol A diglycidyl ether (oxygen oxygen concentration 8.4% by mass)
  • Comparative epoxy compound epoxidized soybean oil (oxygen oxygen concentration 6.7% by mass)
  • Stabilizer compositions 1 to 8 were blended in 100 parts by mass of the vinyl chloride resin in the blending amounts shown in the table. Furthermore, 0.3 parts by mass of stearoylbenzoylmethane as a ⁇ -diketone compound, 1.0 part by mass of decyldiphenylphosphite as a phosphite ester compound, and pentaerythritol tetrakis as an antioxidant and a phenolic antioxidant [3].
  • Adecastab AO-60 0.1 part by mass
  • sugar alcohol is 0.2 parts by mass of sorbitol.
  • Adecastab LA-63P a hindered amine-based light stabilizer
  • a composite ester-based internal lubricant Roxyol G72 manufactured by Emeryoleo Chemicals Japan Co., Ltd.
  • An acrylic processing aid Kaneace PA-20 manufactured by Kaneka Co., Ltd. was blended in an amount of 1.5 parts by mass as an auxiliary agent, and these were mixed with a Henshell mixer to produce a vinyl chloride resin composition.
  • the obtained vinyl chloride resin composition was calendar-molded to prepare a sheet.
  • the roll kneading conditions were 170 ° C. ⁇ 30 rpm ⁇ 0.6 mm.
  • the thermal stability, coloring resistance, and heat-resistant coloring resistance were evaluated by the following test method. The evaluation results are also shown in Tables 3 and 4.
  • the comparative vinyl chloride resin composition was prepared using the comparative stabilizer compositions 1 to 3 in the same manner as in Examples, and a sheet was prepared and evaluated in the same manner as in Examples. The evaluation results are also shown in Tables 3 and 4.
  • the obtained sheet was placed in a gear oven at 190 ° C. and 200 ° C., and the blackening time (minutes) was measured.
  • the results are also shown in Tables 3 and 4. It can be said that the longer the blackening time, the better the thermal stability.
  • composition of the present invention can impart excellent thermal stability, color resistance and heat color resistance to the vinyl chloride resin.
  • the resin composition of the present invention can provide a molded product having excellent thermal stability, coloring resistance and heat-resistant coloring resistance.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne : une composition stabilisante pouvant conférer à une résine de chlorure de vinyle une excellente stabilité thermique, une excellente résistance à la décoloration, une excellente résistance à la décoloration thermique et équivalent ; une composition de résine de chlorure de vinyle qui contient cette composition stabilisante ; et un article moulé à partir de ladite composition de résine de chlorure de vinyle.　L'invention concerne également une composition stabilisante qui contient, pour 100 parties en masse d'un composant (A), de 5 à 2 500 parties en masse d'un composant (B) et de 0,01 à 100 parties en masse d'un composant (C), le composant (A) étant composé d'un ou de plusieurs sels de zinc d'un acide organique ; le composant (B) étant composé d'un ou de plusieurs composés époxy qui comportent un groupe éther glycidylique et/ou un groupe ester glycidylique ; et le composant (C) étant composé d'un ou de plusieurs sels d'un acide perchlorique.
PCT/JP2021/024850 2020-07-17 2021-06-30 Composition stabilisante, composition de résine de chlorure de vinyle en contenant et corps moulé à partir de cette dernière WO2022014338A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07292197A (ja) * 1994-04-15 1995-11-07 Ciba Geigy Ag 安定化された軟質ｐｖｃ
JPH07292196A (ja) * 1994-04-15 1995-11-07 Ciba Geigy Ag 安定化されたポリ塩化ビニル
WO2005033197A1 (fr) * 2003-09-30 2005-04-14 Asahi Denka Co., Ltd. Composition de resine a base de chlorure de vinyle destinee a un vehicule

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07292197A (ja) * 1994-04-15 1995-11-07 Ciba Geigy Ag 安定化された軟質ｐｖｃ
JPH07292196A (ja) * 1994-04-15 1995-11-07 Ciba Geigy Ag 安定化されたポリ塩化ビニル
WO2005033197A1 (fr) * 2003-09-30 2005-04-14 Asahi Denka Co., Ltd. Composition de resine a base de chlorure de vinyle destinee a un vehicule

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