WO2012117913A1 - Stabilisant pour résine chlorée et composition de résine chlorée le contenant - Google Patents

Stabilisant pour résine chlorée et composition de résine chlorée le contenant Download PDF

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WO2012117913A1
WO2012117913A1 PCT/JP2012/054253 JP2012054253W WO2012117913A1 WO 2012117913 A1 WO2012117913 A1 WO 2012117913A1 JP 2012054253 W JP2012054253 W JP 2012054253W WO 2012117913 A1 WO2012117913 A1 WO 2012117913A1
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salt
chlorine
tetrazole
containing resin
resin composition
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PCT/JP2012/054253
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English (en)
Japanese (ja)
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隆博 和崎
賢作 森本
智史 南野
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日東化成株式会社
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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
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • 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
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • 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
    • C08K5/0091—Complexes with metal-heteroatom-bonds

Definitions

  • the present invention relates to a stabilizer for chlorine-containing resin and a chlorine-containing resin composition containing the stabilizer.
  • a chlorine-containing resin is decomposed by dehydrochlorination by heating at the time of molding processing or by irradiation with ultraviolet rays after the product, thereby inducing the coloring of the molded product and the deterioration of the quality of the product.
  • various stabilizers have been proposed and put into practical use.
  • lead and cadmium stabilizers have been used as relatively excellent stabilizers.
  • replacement of lead and cadmium stabilizers has been It has been focused on.
  • metal soap stabilizers composed of calcium-zinc and barium-zinc complex salts that are less toxic than lead and cadmium stabilizers. It has been.
  • the metal soap-based stabilizer is mainly composed of zinc, the so-called zinc burning phenomenon, that is, the action of promoting the blackening phenomenon of the chlorine-containing resin composition by zinc chloride generated in the composition. There is a problem of triggering.
  • a method for solving the above problems by using a metal soap stabilizer in combination with a stabilizing aid such as a phosphate ester compound, an epoxy compound, a polyol compound or a ⁇ -diketone compound has been proposed.
  • a stabilizing aid such as a phosphate ester compound, an epoxy compound, a polyol compound or a ⁇ -diketone compound.
  • tetrazole has been proposed as another stabilizer for chlorine-containing resins (Patent Documents 8 and 9).
  • tetrazole does not have a sufficient effect as a stabilizer, and also has problems such as thermal decomposition at relatively low temperatures and problems such as difficulty in handling because it is vulnerable to friction and impact. I was not satisfied.
  • an object of the present invention is to provide a stabilizer for a chlorine-containing resin excellent in the effect of improving the stability and a chlorine-containing resin composition containing the stabilizer.
  • a chlorine-containing resin composition containing at least one tetrazole salt selected from the group consisting of a metal salt of tetrazole represented by formula (I), a hydrate of the metal salt, and an ammonium salt, and a chlorine-containing resin is provided.
  • the present inventors examined the use of tetrazoles studied in Patent Documents 8 and 9 as stabilizers for chlorine-containing resins, but as the studies progressed, when the tetrazoles were subjected to friction and impact. It was discovered that the substance is difficult to handle due to the danger of explosion if it decomposes rapidly in an enclosed space. Further, tetrazoles are not sufficiently effective as stabilizers for chlorine-containing resins, and have turned brown in 10 minutes in a heat resistance test using an oven.
  • the tetrazole salt can be used in combination with at least one of a phosphite compound and an aminouracil derivative.
  • the effect of preventing initial coloring is further improved as compared with the case of the tetrazole salt alone.
  • a chlorine-containing resin composition having high heat resistance and heat durability, and excellent thermal stability capable of effectively suppressing coloring when held at a high temperature for a long time is obtained.
  • a stabilizer for chlorine-containing resin excellent in the effect of improving the stability and a chlorine-containing resin composition containing the stabilizer are provided, and a good molded product can be produced.
  • the chlorine-containing resin composition of the present invention contains at least one tetrazole salt selected from the group consisting of a metal salt of tetrazole, a hydrate of the metal salt, and an ammonium salt, and a chlorine-containing resin.
  • the metal of the tetrazole salts or hydrates thereof include alkali metals, alkaline earth metals, aluminum, zirconium and the like, and sodium, barium, aluminum and zirconium are particularly preferable.
  • Examples of the metal salt of tetrazole or a hydrate thereof include, for example, a barium salt of 5,5′-bitetrazole, a barium salt hydrate of 5,5′-bitetrazole, and a sodium salt of 5,5′-bitetrazole, Sodium salt hydrate of 5,5′-bitetrazole, aluminum salt of 5,5′-bitetrazole, aluminum salt hydrate of 5,5′-bitetrazole, zirconium salt of 5,5′-bitetrazole, 5, Zirconium salt hydrate of 5′-bitetrazole and the like.
  • an aluminum salt of 5,5′-bitetrazole, 5 Aluminum salt hydrate of 5,5′-bitetrazole, zirconium salt of 5,5′-bitetrazole and zirconium salt hydrate of 5,5′-bitetrazole exhibit particularly excellent effects.
  • the tetrazoles 5,5'-bitetrazole barium salt, 5,5'-bitetrazole barium salt hydrate, 5,5'-bitetrazole sodium salt, 5,5'-bitetrazole sodium Salt hydrate exhibits particularly excellent effects.
  • the tetrazole metal salts or hydrates thereof can be produced by known methods.
  • a manganese salt of 5,5′-bitetrazole in which n in the general formula (1) is 0 can be produced by the production method disclosed in US Pat. No. 2,710,297. Specifically, a mixed aqueous solution of acetic acid, concentrated sulfuric acid and copper sulfate was added dropwise to an aqueous solution of sodium azide, sodium cyanide and manganese dioxide at a low temperature and then reacted at 90 ° C. to react with 5,5′-bi A tetrazole manganese salt can be obtained.
  • the sodium salt of 5,5′-bitetrazole in which n in the general formula (1) is 0 is obtained by reacting the manganese salt of 5,5′-bitetrazole with sodium carbonate in an aqueous solvent. Can be obtained.
  • the metal salt of bis (tetrazol-5-yl) amine in which n in the general formula (1) is 1 or a hydrate thereof can be produced by a known method.
  • it can be produced by the production method disclosed in Non-Patent Literature: Journal of Materials, Chemistry, 2008, 18, p5248-5258 and US Pat. No. 6,214,139B.
  • bis (tetrazol-5-yl) amine is added by dropping hydrochloric acid (2 mol / l) into an aqueous solution of sodium dicyanamide and sodium azide at 60 ° C., followed by reaction under reflux conditions. Can be obtained.
  • metal salts may be obtained in a hydrated state depending on the drying conditions.
  • the hydrate of the metal salt can be dried to an anhydride or a state close to the anhydride using a known drying technique.
  • it absorbs moisture in an environment with a humidity of 10% or more and becomes a hydrated state.
  • these metal salts are hydrates or anhydrides, they do not affect the thermal stabilization effect on the chlorine-containing resin.
  • ammonium salt of 5,5′-bitetrazole in which n in the general formula (1) is 0 can be produced by a known method.
  • it can be produced by the production method disclosed in Japanese Patent Application Laid-Open No. 2008-285360.
  • it can be obtained by reacting 5,5′-bitetrazole sodium salt and ammonium chloride in an aqueous solution.
  • ammonium salt of bis (tetrazol-5-yl) amine in which n in the general formula (1) is 1 can be produced by a known method.
  • it can be produced by the production method disclosed in US Pat. No. 6,214,139B.
  • it can be obtained by reacting bis (tetrazol-5-yl) amine and aqueous ammonium in an aqueous solution.
  • the tetrazole salts can be used in combination of two or more, and the improvement of the initial coloring prevention effect and the long-term thermal stability effect is remarkably recognized as compared with the single use.
  • 5,5′-bitetrazole aluminum salt or hydrate thereof which is excellent in the effect of preventing initial coloration
  • 5,5′-bitetrazole zirconium salt or hydrate, etc. 5'-bitetrazole barium salt or hydrate thereof, and 5,5'-bistetrazole sodium salt or hydrate thereof are used in combination to prevent initial coloring and long-term thermal stability. Both of these can significantly improve the stabilizer.
  • the former / the latter is preferably in the range of 1/99 to 99/1, more preferably in the range of 5/95 to 95/5, and particularly preferably in the range of 10/90 to 90/10.
  • the content of the tetrazole salt is not particularly limited, but is usually 0.01 parts by mass or more, preferably 0.2 parts by mass or more with respect to 100 parts by mass of the chlorine-containing resin. When it is in the above range, the reduction of initial coloring and the improvement of heat resistance are more effectively exhibited.
  • the above-mentioned tetrazole salt can be used in combination with at least one of a phosphite compound and an aminouracil derivative.
  • the initial coloring prevention effect and the long-term thermal stability effect are improved more than the single use of the tetrazole salt.
  • 5,5′-bitetrazole barium salt or hydrate thereof which has an excellent long-term thermal stability effect
  • sodium salt of 5,5′-bistetrazole or hydrate thereof, and a phosphite compound or amino acid By using the uracil derivative in combination, it is possible to obtain a stabilizer that is remarkably excellent in both the initial coloring prevention effect and the long-term thermal stability effect.
  • both the phosphite compound and the aminouracil derivative can be used in combination with a tetrazole salt, and the initial coloring prevention effect and the long-term thermal stability effect are significantly improved compared to the use of either one. Is recognized. In particular, the effect of preventing the initial coloring is noticeable.
  • the combined use ratio is preferably in the range of 1 to 100 parts by mass in total of the phosphite compound and aminouracil derivative per 100 parts by mass of the tetrazole salt, more preferably in the range of 5 to 65 parts by mass.
  • a range is particularly preferred.
  • the total of the phosphite compound and the aminouracil derivative is, for example, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55 per 100 parts by mass of the tetrazole salt. , 60, 65, 70, 75, 80, 85, 90, 95, 100 parts by mass, and may be within a range between any two of the numerical values exemplified here.
  • Examples of the phosphite compound used in the present invention include triphenyl phosphite, trisnonylphenyl phosphite, tricresyl phosphite, triethyl phosphite, tris (2-ethylhexyl) phosphite, tridecyl phosphite, Trilauryl phosphite, tris (tridecyl) phosphite, trioleyl phosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, trilauryl trithiophosphite, diethyl hydrogen phosphite Phyto, bis (2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphit
  • phosphite triesters are preferable, especially trisnonylphenyl phosphite, diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, tetra (C12-C15 alkyl) -4,4′-isopropylidene diphenyl diphosphite
  • Distearyl pentaerythritol diphosphite and hydrogenated bisphenol A / pentaerythritol phosphite polymer are desirable.
  • the aminouracil derivative used in the present invention has the following general formula (2): (In the formula, R 1 and R 2 represent an alkyl group having 1 to 8 carbon atoms, an aralkyl group, an alkenyl group, an unsubstituted or alkyl group, and a phenyl group substituted with a halogen, and R 1 and R 2 are: Y may be the same or different, and Y is a compound represented by S or O).
  • chlorine-containing resin examples include polyvinyl chloride, chlorinated polyvinyl chloride, polyvinyl chloride, chlorinated polyethylene, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene copolymer, and chloride.
  • Synthetic resins containing no other chlorine such as acrylonitrile-styrene copolymer, ethylene-vinyl acetate copolymer, ethylene-ethyl (meth) acrylate copolymer, blends with polyester, block copolymers, etc. Or a graft copolymer etc. can be mentioned.
  • a commercial item can be used as said chlorine containing resin. Examples of commercially available products include TH-800 (manufactured by Taiyo PVC Co., Ltd.).
  • the chlorine-containing resin composition of the present invention can further contain other additive components in any blending ratio as long as the object of the present invention is not impaired.
  • antioxidant stabilizers examples include organic acid salts, organic phosphates, and organic tin stabilizers of Group 1, 2 or 12 metals.
  • Examples of the organic acid of the organic acid salt include octylic acid (isooctylic acid, 2-ethylhexylic acid), lauric acid, stearic acid, hydroxystearic acid, ricinoleic acid, oleic acid, caproic acid, palmitic acid, 12-hydroxystearic acid, Examples include myristic acid or dibasic acids such as maleic acid, malonic acid, sebacic acid, azelaic acid, adipic acid, phthalic acid, and cyclohexanedicarboxylic acid.
  • octylic acid isooctylic acid, 2-ethylhexylic acid
  • lauric acid stearic acid
  • hydroxystearic acid hydroxystearic acid
  • ricinoleic acid oleic acid
  • caproic acid palmitic acid
  • palmitic acid 12-hydroxystearic acid
  • Examples include myristic acid or dibasic acids such as maleic acid
  • organic phosphates of the organic phosphate include mono- or dioctyl phosphate, mono- or dododecyl phosphate, mono- or dioctadecyl phosphate, mono- or di- (nonylphenyl) phosphate, phosphonate nonylphenyl ester, stearyl phosphonate Examples include esters.
  • organic tin stabilizer examples include dibutyltin bis (butyl malate), dibutyltin bis (2-ethylhexylmalate), dibutyltin bis (benzylmalate), dioctyltin bis (ethylmalate), dioctyltin bis (2- Dialkyltin bis (maleic acid ester salt) such as ethylhexylmalate), dialkyltin malate of dibutyltin malate and dioctyltin malate, and dialkyltin malate polymer of dibutyltin malate polymer and dioctyltin malate polymer, methyltin tris (2-ethylhexyl thioacetate), butyltin tris (2-ethylhexyl thioacetate), octyltin tris (isooctyl thioacetate), octyltin
  • antioxidants As stabilizers, antioxidants, ⁇ -diketone compounds, polyol compounds, epoxy compounds, zeolite compounds, hydrotalcite compounds, perchlorates, ultraviolet absorbers, hindered amine light stabilizers and the like can be contained.
  • antioxidants examples include phenolic antioxidants and sulfur-based antioxidants.
  • phenolic antioxidants include alkylated phenols, alkylated phenol esters, alkylene or alkylidene bisphenols, polyalkylated phenol esters, and the like, such as butylated hydroxytoluene, 4-hydroxymethyl-2,6- Di-t-butylphenol, 2,6-diphenyl-4-octadecyloxyphenol, 4,4'-dihydroxy-2,2'-diphenylpropane, 2,2'-methylenebis (4-methyl-t-butylphenol), 4,4'-thiobis (6-t-butyl-3-methylphenol) and the like.
  • alkylated phenols alkylated phenol esters, alkylene or alkylidene bisphenols, polyalkylated phenol esters, and the like, such as butylated hydroxytoluene, 4-hydroxymethyl-2,6- Di-t-butylphenol, 2,6-diphenyl-4-octadecyloxy
  • sulfur-based antioxidants include dialkylthiodipropionates such as dilauryl, dimyristyl, myristylstearyl, and distearyl esters of thiodipropionic acid, and polyols such as pentaerythritol tetra ( ⁇ -dodecyl mercaptopropionate). and ⁇ -alkyl mercaptopropionic acid esters.
  • ⁇ -diketone compound examples include dibenzoylmethane, benzoylacetone, stearoylbenzoylmethane, caproylbenzoylmethane, dehydroacetic acid, tribenzoylmethane, 1,3-bis (benzoylacetyl) benzene, and the like.
  • polyol compound examples include trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, polypentaerythritol, mannitol, sorbitol, pentaerythritol or dipentaerythritol stearic acid half ester, bis (dipentaerythritol) adipate.
  • Examples of the epoxy compound include epoxidized soybean oil, epoxidized linseed oil, epoxidized tung oil, epoxidized fish oil, epoxidized beef tallow oil, epoxidized castor oil, and epoxidized safflower oil, and epoxidized stearin oil.
  • Acid ester epoxidized polybutadiene, tris (epoxypropyl) isocyanurate, vinylcyclohexene diepoxide, dicyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bisphenol type or novolac type epoxy resin, 3- (2-Xenoxy) -1,2 epoxy propane, epoxy polybutadiene, bisphenol-A-diglycidyl ether, epoxy group-containing acrylic resin, epoxidized polymer compound, etc. It is below. It is.
  • the zeolite compound examples include an aluminosilicate of an alkali or alkaline earth metal. Typical examples include A-type, X-type, Y-type and P-type zeolites, monodenite, analsite, sodalite aluminosilicate, clinobutyrolite, erionite and chabazite. These zeolite compounds may be either a hydrate containing crystal water (so-called zeolite water) or an anhydride from which crystal water has been removed.
  • zeolite water a hydrate containing crystal water
  • hydrotalcite compound examples include a carbonate double salt compound of magnesium and aluminum. Typical examples include magnesium and aluminum, or a carbonate double salt compound composed of zinc, magnesium and aluminum. These hydrotalcite compounds may be natural products or synthetic products. Further, any of a crystal structure, a crystal particle system, a hydrate containing crystal water, or an anhydride from which crystal water has been removed may be used.
  • perchlorates include lithium perchlorate, sodium perchlorate, potassium perchlorate, strontium perchlorate, magnesium perchlorate, calcium perchlorate, barium perchlorate, zinc perchlorate, perchlorate.
  • perchlorates include cadmium chlorate, lead perchlorate, aluminum perchlorate, and ammonium perchlorate.
  • These perchlorates may be anhydrous or hydrated salts, and may be those dissolved in alcoholic and esteric solvents such as butyl diglycol and butyl diglycol adipate and their dehydrates.
  • ultraviolet absorber examples include benzophenone, benzotriazole, salicylate, cyanoacrylate, metal chelate, particularly nickel and chromium salts.
  • hindered amine light stabilizer examples include 2,2,6,6-tetramethyl-4-piperidyl stearate, 1,2,2,6,6-pentamethyl-4-piperidyl stearate, 2,2,6. , 6-tetramethyl-4-piperidylbenzoate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butanetetracarboxylate, tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) butanetetracarboxylate, bis (1,2 , 2,6,6-Pentamethyl-4-piperidyl) -2-butyl-2- (3,5-di-t-butyl-4-hydroxybenzyl) malone Such as theft and the like.
  • plasticizers for example, plasticizers, fluorescent agents, antibacterial fungicides, plate-out prevention agents, antifogging agents, crosslinking agents, lubricants, surfactants, reinforcing agents, processing aids, mold release agents And a viscosity reducing agent can be contained.
  • the chlorine-containing resin composition of the present invention can be prepared by kneading the metal salt of bistetrazole, a hydrate and ammonium salt of the metal salt, a chlorine-containing resin, and, if necessary, each of the above-described additive components. What is necessary is just to adjust suitably about the addition amount of each component at the time of kneading
  • the order of kneading the components is not particularly limited.
  • the chlorine-containing resin composition of the present invention can be used regardless of the processing method of the chlorine-containing resin.
  • calendering, roll processing, extrusion molding, melt rolling, pressure molding, powder It can be suitably used for body molding and the like.
  • Production Example 1 (5,5′-bitetrazole sodium salt: BTNa) A 3 liter four-necked flask equipped with a stirrer was charged with 500 ml of water, 65 g (1.0 mol) of sodium azide and 50 g (1.0 mol) of sodium cyanide, cooled to 10 ° C., and 45 g (0.52 mol) of manganese dioxide. 200 g of acetic acid was added dropwise at 30 ° C. or lower over 20 minutes, and reacted at 25 to 35 ° C. for 3 hours. Thereafter, the reaction solution was heated to 90 ° C. and reacted for 5 hours.
  • a 2 liter four-necked flask equipped with a stirrer was charged with 1 liter of water, 83 g of manganese salt hydrate of 5,5′-bitetrazole (Mn content 23.9%, 0.36 mol), and 38.2 g (0.36 mol) of sodium carbonate. Stir for 4 hours under reflux conditions. The reaction solution was cooled to room temperature and then filtered, and the filtrate was concentrated under reduced pressure. The precipitated crystals were dried under reduced pressure at 80 ° C. and 30 torr and recrystallized with water to obtain 43.4 g of sodium salt of 5,5′-bitetrazole.
  • Production Example 3 (Synthesis of 5,5′-bitetrazole aluminum salt (BTAl)) 2,5-g-tetrazole sodium salt (21.8 g, 0.12 mol) obtained in the same manner as in Production Example 1 was charged into a 500 ml four-necked flask equipped with a stirrer, 100 ml of water was added, and the temperature was raised to 50 ° C. An aqueous solution in which 26.7 g (0.04 mol) of aluminum sulfate 18 hydrate was dissolved in 200 ml of water was added, and the mixture was stirred at 50 ° C. for 1 hour. Then, it cooled to room temperature and stirred for 4 hours.
  • BTAl 5,5′-bitetrazole aluminum salt
  • Production Example 10 Synthesis of 6-amino-1,3-di (normal octyl) uracil The same method as in Production Example 9 except that 20 g (129 mmol) of normal octylamine and 16.7 g (129 mmol) of normal octyl isocyanate were used as raw materials. 1,3-di (normal octyl) urea was synthesized. Next, 6-amino-1,3-di (normal octyl) uracil was synthesized in the same manner as in Production Example 9 using 25 g (88 mmol) of 1,3-di (normal octyl) urea. For purification, column chromatography on silica gel was used.
  • Examples 1 to 59 and Comparative Examples 1 to 3 A chlorine-containing resin composition was obtained by mixing the blending components described in Tables 1 to 6 in proportions (parts by mass) described in Tables 1 to 6. Of the tetrazole metal salts in Tables 1 to 3 and 5 to 6, barium and zirconium salts were dehydrated at 150 ° C. and 20 Torr for each metal salt hydrate prepared in the above production example. The anhydrous product was used. In Table 4, dehydration treatment was not performed on barium and zirconium salts, and they were used as hydrates.
  • Product name “TH-800” Chlorine-containing resin (manufactured by Taiyo PVC Co., Ltd.), polyvinyl chloride resin (PVC), polymerization degree 800
  • Product name “5,5′-bitetrazole diammonium salt” ammonium salt of 5,5′-bitetrazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
  • Product name “AC316A” polyethylene wax, lubricant (made by Allied Signal, USA)
  • Product name “Alkamizer II” Hydrotalcite (manufactured by Kyowa Chemical Industry Co., Ltd.) Calcium stearate: manufactured by Kishida Chemical Co., Ltd. zinc stearate: manufactured by Kishida Chemical Co., Ltd.
  • 1,3-diphenyl-1,3-propanedione manufactured by Tokyo Chemical Industry Co., Ltd. dipentaerythritol: manufactured by Alfa Aesar 2,6-di-t-butyl-p-cresol: trisnonylphenyl phosphite manufactured by Kishida Chemical Co., Ltd .: trade name “JP-351” (manufactured by Johoku Chemical Industry Co., Ltd.) Diphenyl monodecyl phosphite: Trade name “JPM-311” (manufactured by Johoku Chemical Industry Co., Ltd.) Tetra (C12-C15 alkyl) -4,4′-isopropylidene diphenyl diphosphite: Trade name “JA-805” (manufactured by Johoku Chemical Industry Co., Ltd.) Distearyl pentaerythritol diphosphite: Trade name “JPP-2000PT” (manufactured by Jo
  • Test example 1 (roll test) The blend was kneaded with a hot roll (180 ° C / 5 minutes with two rolls) to prepare a sheet. The degree of coloring of the obtained sheet was confirmed. Evaluation was performed by the following method. The results are shown in Tables 1 to 6. S: colorless A: light yellow B: yellow C: brown D: dark brown E: black
  • Test Example 2 (Colorability test) The obtained sheet was cut into 2 ⁇ 3 cm square test pieces, placed in a gear oven at 195 ° C., and the colorability was visually observed every 5 minutes. Evaluation was performed by the following method. Tables 1 to 6 show the results of colorability and blackening time at each time. S: colorless A: light yellow B: yellow C: brown D: dark brown E: black
  • Example 2 Al salt
  • Example 3 Zr salt
  • Example 7 Na salt
  • Example 12 Ba salt
  • the Al salt and the Zr salt effectively improve initial coloring. It is excellent in the point which suppresses, and it turns out that Na salt and Ba salt are excellent in the point which suppresses blackening over a long time.
  • Examples 15 to 34 one kind of Na salt and Ba salt and one kind of Al salt and Zr salt are used. In these Examples, initial coloring is suppressed and blackening is achieved. It can be seen that a very favorable result was obtained that was suppressed for a long time.
  • barium and zirconium salts are used as hydrates, but it can be seen that the same results as in the case of anhydrides were obtained.
  • Example 39 to 59 when at least one of a phosphite compound and an aminouracil derivative was used in combination with a tetrazole salt, better results were obtained than when the tetrazole salt was used alone.
  • Example 7 Na salt only
  • Example 19 Na salt + Al salt
  • Example 40 Na salt + phosphite compound
  • Example 44 Na salt + aminouracil derivative
  • Example 47 When comparing (Na salt + phosphite compound + aminouracil derivative), the combined use of at least one of the phosphite compound and aminouracil derivative further improves the effect of preventing initial coloration and maintains the temperature at a high temperature for a long time.
  • Example 12 (Ba salt only), Example 26 (Ba salt + Al salt), Example 57 (Ba salt + phosphite compound), Example 59 (Ba salt + aminouracil derivative), Example The same can be said by comparing 58 (Ba salt + phosphite compound + aminouracil derivative).
  • Test Example 3 (Stabilizer Degradability Test) About each stabilizer used in said Test Example 1 and 2, the decomposition temperature of each stabilizer was measured using melting
  • the test conditions are as follows. Equipment used: BUCHI melting point measuring equipment B-545 Measurement conditions: temperature 200 ° C. ⁇ 250 ° C., temperature increase rate 1 ° C./min Measurement method: A sample finely ground in a mortar into a capillary for melting point measurement was filled to a height of about 5 mm, and the decomposition temperature was measured under the above conditions.
  • Decomposition temperature The melting point measurement method based on the amount of light transmission defined in JISK0064 (Measuring method of melting point and melting range of chemical products) was used. Specifically, the sample filled in the capillary is decomposed to create a space, and the amount of transmitted light changes. The decomposition temperature was measured by detecting the change in the amount of transmitted light with a measuring device.
  • BTH 5,5′-bitetrazole decomposed at around 220 ° C.
  • BTH has an effect of preventing initial coloring but has a short blackening time.
  • One of the causes of the short blackening time is considered to be that the thermal stability of BTH itself is low and decomposed early, and therefore the decomposition of the chlorine-containing resin was not sufficiently suppressed.
  • the metal salt and ammonium salt of 5,5′-bitetrazole had a decomposition temperature sufficiently higher than the PVC processing temperature.

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Abstract

Cette invention a pour objet de pourvoir à un stabilisant pour résine chlorée ayant un remarquable effet d'augmentation de sa stabilité, et à une composition de résine chlorée le contenant. Pour ce faire, cette invention utilise une composition de résine chlorée comprenant une résine chlorée et au moins un type de sel de tétrazole choisi dans le groupe constitué par les sels métalliques, les hydrates de sels métalliques, et les sels d'ammonium du tétrazole représenté par la formule générale (I) [où n = 0 ou 1].
PCT/JP2012/054253 2011-03-01 2012-02-22 Stabilisant pour résine chlorée et composition de résine chlorée le contenant WO2012117913A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014080755A1 (fr) * 2012-11-21 2014-05-30 日東化成株式会社 Agent stabilisant pour résines chlorées, et composition de résine chlorée le contenant

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5496553A (en) * 1977-12-29 1979-07-31 Ciba Geigy Ag Molding material consisting of chlorineecontaining thermoplastic resin containing tetrasol heat stabilizer

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5496553A (en) * 1977-12-29 1979-07-31 Ciba Geigy Ag Molding material consisting of chlorineecontaining thermoplastic resin containing tetrasol heat stabilizer

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014080755A1 (fr) * 2012-11-21 2014-05-30 日東化成株式会社 Agent stabilisant pour résines chlorées, et composition de résine chlorée le contenant

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