JPH10182907A - Halogen-containing resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition exhibiting an excellent effect, compared with a case when a cadmium, lead-based stabilizer is used and extremely slight in toxicity by combinedly using a specific compound and a polypropylene wax, ester wax, etc. SOLUTION: This stabilized resin composition is obtained by adding (A) 0.1-4.0 pts.wt. at least one kind of an organotin compound represented by the formula [R is a 1-12C alkyl; R' is an alkyl, an alkenyl, an alkylaryl, etc.; (m) is 1 or 2], (B) 0.05-2.0 pts.wt. at least one kind of polypropylene wax, (C) 0.05-3.0 pts.wt. at least one kind of ester wax and petroleum wax and (D) 0.1-3.0 pts.wt. at least one kind of calcium and magnesium salts of aliphatic carboxylic acid to 100 pts.wt. halogen-containing resin. Furthermore, it is preferable to further adding (E) 0.01-4.0 pts.wt. at least one kind of octyltin compound and/or polyethylene wax thereto.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to coloring resistance, heat resistance,
The present invention relates to a halogen-containing resin-stabilized composition having excellent transparency and having improved fixation phenomenon (plate-out phenomenon) during processing.

[0002]

2. Description of the Related Art It is well known that a halogen-containing resin becomes colored and deteriorated due to light deterioration mainly due to ultraviolet rays and cannot be made into an excellent product even after it becomes a high heat during molding or a processed product. In order to eliminate such defects, various stabilizers have been conventionally studied and put to practical use. For example, a stabilizer containing cadmium or lead had excellent properties as a heat stabilizer, an initial coloring inhibitor, and a weather resistance stabilizer. However, in recent years, stabilizers containing cadmium and lead, which have been used very effectively in the past, have become problematic due to the working environment when handling stabilizers and concerns about pollution when treating products containing stabilizers as waste. In response to this, various low-toxicity stabilizers have been studied and proposed. Recently, organotin compounds having low toxicity have been developed and put into practical use. The present inventors have disclosed composition patents for these compounds (JP-A-7-3071). Performance was required.

[0003]

As a result of various studies conducted by the present inventors to solve these problems, the present inventors have found that the use of a cadmium or lead-based stabilizer has an effect superior to that of the case of using a cadmium or lead-based stabilizer, and that it has a very low toxicity. Agent was developed.

[0004]

According to the present invention, (1) at least one organotin compound represented by the general formula [A] is used in an amount of 0.1 to 4.0 parts by weight, based on 100 parts by weight of the halogen-containing resin.

Embedded image (Where R is an alkyl group having 1 to 12 carbon atoms;
Represents an alkyl group, an alkenyl group, an alkylaryl group, an aryl group, and a derivative having a substituent therefor, and m is 1 or 2. ), (2) 0.05 to 2.0 parts by weight of at least one kind of polypropylene wax;
(3) 0.05 to 3.0 parts by weight of at least one of ester wax and petroleum wax, and (4) at least one of calcium and magnesium salts of an aliphatic carboxylic acid.
Seeds. A halogen-containing resin composition which is stabilized by adding 0.1 to 3.0 parts by weight, and further containing (5) at least one of an octyltin compound and / or a polyethylene wax in an amount of 0.01 to 4.0. It is a halogen-containing resin composition which is stabilized by additionally adding parts by weight.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The following are typical examples of the compound represented by the general formula [A] constituting the present invention. Here, X and Y are display in the embodiment, and X corresponds to m = 1 and Y corresponds to m = 2.

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It is known to use the compound represented by the general formula [A] as a stabilizer for a halogen-containing resin.
However, these alone do not always have sufficient effects on heat resistance, initial coloring, and processability, and are used in combination with various additives. As a result of various studies to further improve these properties, the compound was used in combination with a polypropylene wax, an ester wax-based wax, a metal salt of an aliphatic carboxylic acid, and an octyltin compound and / or a polyethylene wax. As specifically shown, the present invention has been achieved after confirming satisfactory effects.

As a specific example of the polypropylene wax, a polypropylene wax having a softening point in the range of 120 to 170 ° C. is preferable, though it depends on the processing temperature of the halogen-containing resin. If the softening temperature is too high, it will not be uniformly dispersed in the resin during molding, and a stable lubricating effect will not be obtained,
As a result, the physical properties of the molded article are deteriorated, and a product having stable performance and appearance cannot be obtained. On the other hand, if the softening point is too low, the lubricity during processing of the polypropylene wax will be insufficient, and in this case also, appropriate processing characteristics cannot be obtained.

Specific examples of the ester wax include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, ricinoleic acid,
Beheiic acid, erucic acid, coconut fatty acid, pearl fatty acid, tallow fatty acid, acetic acid, methacrylic acid, 2-ethylhexanoic acid, citric acid, phthalic acid, adipic acid, trimellitic acid, carboxylic acid such as pyromellitic acid and methyl alcohol, Ethyl alcohol, isopropyl alcohol, n-
Butyl alcohol, isobutyl alcohol, n-octyl alcohol, 2-ethylhexyl alcohol, n-decyl alcohol, isodecyl alcohol, lauryl alcohol, isotridecyl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, behenyl alcohol, hexyldecyl alcohol An ester compound with a monohydric alcohol such as octyldodecyl alcohol, glycerin fatty acid ester (glycerin monopalmitate, glycerin monostearate, glycerin monooleate, glycerin monoricinoleate, glycerin monobehenate, glycerin mono 12-hydroxystearate, Monoglycerides such as glycerin monocaprylate and glycerin monolaurate, glycerin · Jiparumineto, glycerin mono-distearate, glycerin di-tristearate,
Glycerin monodiolate, glycerin ditriolate, glycerin mono dilinoleate, glycerin mono dibehenate, glycerin mono diricinolate, glycerin mono di-12-hydroxystearate, glycerin mono dioleate stearate, glycerin mono diphosphate Triglycerides such as mono-diglyceride, glycerin tri-2-ethylhexoate, glycerin tricaprylate, glycerin trifatty acid (C _7-11 ) ester, glycerin diacet monolaurate, glycerin diacet monostearate, glycerin diacet monooleate Glycerin diacet monolinoleate, glycerin diacet mono 12-hydroxystearate, glycerin diacet monomyristate, glycerin diacetate Monopalmitate, glycerin diacetomonolaurate, glycerin mono-acetoacetate monostearate, glycerol mono-acetoacetate monomyristate, glycerin mono-acetamide mono palmitate, glycerol mono-acetate Tomonori ricinoleate, glycerol mono-acetamide mono 12-
Hydroxystearate, glycerin monoacetomonobehenate, glycerin monoacetomonooleate, glycerin monoacetomonolaurate, glycerin monoacetodiolate, glycerin monoacetodiricinolate, glycerin monoacetodicaprylate, glycerin monoacetodilaurate, glycerin Organic such as acetylated glyceride such as monoacetodistearate, succinic saturated fatty acid monoglyceride, citric acid saturated fatty acid monoglyceride, citric acid unsaturated fatty acid monoglyceride, diacetyltartaric acid saturated fatty acid monoglyceride, diacetyltartaric acid unsaturated fatty acid monoglyceride, and lactic acid saturated fatty acid monoglyceride. Acid glyceride), pentaerythritol monooleate, pentaerythritol monostearate, pea Taerythritol monomyristate, pentaerythritol monopatmate, pentaerythritol monolaurate, pentaerythritol dioleate, pentaerythritol dilaurate, pentaerythritol dicoco fatty acid ester, pentaerythritol tripal fatty acid ester, dipentaerythritol monooleate, dipenta Erythritol monostearate, dipentaerythritol trilaurate, dipentaerythritol trimiristylate, dipentaerythritol tetrapalmitate, dipentaerythritol tallow fatty acid ester, triethanolpropane monostearate, triethanolpropane monolaurate,
Triethanolpropane dipearl fatty acid ester, triethanolpropanediolate, sorbitan fatty acid ester (sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan tristearate, sorbitan oleate, sorbitan triolate,
Sorbitan behenate, sorbitan tribehenate, sorbitan dilaurate, sorbitan distearate, sorbitan dipalminate, sorbitan monoelsinate, sorbitan monolisinolate, sorbitan coconut fatty acid ester, sorbitan palm fatty acid ester, sorbitan bovine fatty acid ester, etc.) , Polyglycerin fatty acid esters (diglycerin laurate, diglycerin stearate, diglycerin oleate, diglycerin caprylate, diglycerin behenate, diglycerin myristate, diglycerin palm fatty acid ester, diglycerin palm fatty acid ester, diglycerin Diglycerin fatty acid esters such as bovine fatty acid ester, tetraglycerin stearate, tetraglycerin oleate, hexaglycerin laurate, deca Polyglycerin fatty acid esters such as lysine laurate, decaglycerin oleate, polyglycerin polyricinoleate, etc., propylene glycol fatty acid esters (propylene glycol monolaurate, propylene glycol monopalmate, propylene glycol monomyristate, propylene glycol monostearate) Propylene glycol monobehenate, propylene glycol monooleate, propylene glycol monococoate fatty acid ester, propylene glycol palm fatty acid ester, etc.) and polyethylene glycol fatty acid ester (polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol monooleate, Polyethylene glycol monopalm fatty acid ester, Ethylene glycol mono coconut fatty acid ester, polyethylene glycol distearate, polyethylene glycol dioleate,
Polyethylene glycol dipalm fatty acid ester),
Ethylene oxide adduct (polyoxyethylene (6)
Sorbitan monolaurate, polyoxyethylene (2
0) Sorbitan monolaurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene 20) sorbitan tristearate, polyoxyethylene (20) sorbitan triolate, poly Oxyethylene (30) sorbitan monomyristate, polyoxyethylene (20) sorbitan tetraoleate, polyoxyethylene (40) sorbitan dipearl fatty acid ester, polyoxyethylene (60) sorbitan tetraoleate, polyoxyethylene (60) sorbitan trilate Coconut fatty acid ester, polyoxyethylene bisphenol A laurate ester, polyoxyethylene lauryl ether stearate, polyoxyethylene lauryl ether myristate Polyoxyethylene lauryl ether laurate, polyoxyethylene cetyl ether caprylate, polyoxyethylene cetyl ether coconut fatty acid ester, polyoxyethylene stearyl ether laurate, polyoxyethylene stearyl ether palmitate, polyoxyethylene stearyl Ether tallow fatty acid ester, polyoxyethylene oleyl ether stearate, polyoxyethylene oleyl ether acetate, polyoxyethylene oleyl ether 2-ethylhexoate, polyoxyethylene oleyl ether pearl fatty acid ester, polyoxyethylene octyl phenol ether stearate, poly Oxyethylene octyl phenol ether laurate, polyoxyethylene octyl pheno Fatty acid ester, polyoxyethylene nonylphenol ether laurate, polyoxyethylene nonylphenol ether oleate, polyoxyethylene nonylphenol ether stearate, polyoxyethylene nonylphenol ether palmitate, polyoxyethylene polyoxypropylene block polymer and aliphatic carboxylic acid Ester compounds).

Specific examples of the aliphatic carboxylic acid constituting the calcium and magnesium salts of the aliphatic carboxylic acid include 2-ethylhexanoic acid, caprylic acid, capric acid,
Lauric acid, palmic acid, myric acid, stearic acid,
Behenic acid, oleic acid, ricinoleic acid, erucic acid, benzoic acid, tert-butyl benzoic acid, maleic acid, fumaric acid, phthalic acid, acrylic acid, acrylic acid polymer, methacrylic acid, methacrylic acid polymer, adipic acid, trimellit Acid, monoethylmalate, monomethylmalate, monopropylmalate, monobutylmalate, monoamylmalate, monohexylmalate, mono-2-ethylhexylmalate, monooctylmalate,
Monononyl malate, monostearyl malate, monooleyl malate, monolauryl malate, monocetyl malate, coconut fatty acid, pearl fatty acid, tallow fatty acid, and the like.

Specific examples of octyltin compounds include mono (or di) octyltin tris (or di) (methyl mercaptoacetate), mono (or di) octyltin tris (or di) (ethyl mercaptoacetate), Or di) octyltin tris (or di) (isopropylmercaptoacetate), mono (or di) octyltin tris (or di) (butylmercaptoacetate), mono (or di) octyltin tris (or di) (hexylmercaptoacetate) ), Mono (or di) octyltin tris (or di) (heptylmercaptoacetate), mono (or di) octyltin tris (or di) (2-ethylhexylmercaptoacetate), mono (or di) octyltin tris (or Di) (isooctyl mercaptoacetate), mono (or di) Chill tin tris (or di) (nonyl mercaptoacetate), mono (or di) octyl tin tris (or di) (decyl mercaptoacetate),
Mono (or di) octyltin tris (or di) (laurylmercaptoacetate), mono (or di) octyltin tris (or di) (tridecylmercaptoacetate),
Mono (or di) octyltin tris (or di) (cetylmercaptoacetate), mono (or di) octyltin tris (or di) (stearylmercaptoacetate), mono (or di) octyltin tris (or di) (benzyl) Mercaptoacetate), mono (or di) octyltin tris (or di) (cyclohexylmercaptoacetate), mono (or di) octyltin tris (or di) (isopropylmercaptopropionate), mono (or di) octyltin tris (Or di) (stearylmercaptopropionate), mono (or di) octyltin tris (or di) (isooctylmercaptopropionate), mono (or di) octyltin tris (or di) (methoxybutylmercaptopro Pionate), mono (or di) octyltin tris (or ) (2-ethylhexyl mercaptopropionate), mono (or di) octyl tin tris (or di) (methyl maleate), mono (or di) octyl tin tris (or di) (Echirumareto)
Mono (or di) octyltin tris (or di) (isopropylmalate), mono (or di) octyltin tris (or di) (butylmalate), mono (or di) octyltin tris (or di) (amylmalate), Things (or di)
Octyltin tris (or di) (hexylmalate), mono (or di) octyltin tris (or di) (heptylmalate), mono (or di) octyltin tris (or di)
(Isooctylmalate), mono (or di) octyltin tris (or di) (2-ethylhexylmalate), mono (or di) octyltin tris (or di) (nonylmalate), mono (or di) octyltin Tris (or di)
(Decyl maleate), mono (or di) octyl tin tris (or di) (isodecyl malate), mono (or di) octyl tin tris (or di) (lauryl malate), mono (or di) octyl tin tris ( Or di) (tridecyl malate), mono (or di) octyltin tris (or di)
(Cetyl malate), mono (or di) octyl tin tris (or di) (stearyl malate), mono (or di) octyl tin tris (or di) (benzyl malate), mono (or di) octyl tin tris (or Di) (cyclohexyl maleate), mono (or di) octyl tin tris (or di) (oleyl maleate), mono (or di) octyl tin maleate polymer, mono (or di) octyl tin tri (or di) ( Acetate), mono (or di) octyltin tri (or di) (propionate), mono (or di) octyltin tri (or di) (hexanoate), mono (or di) octyltin tri (or di) (2- Ethyl hexanoate), mono (or di) octyltin tri (or di) (caprinate), mono (or di) octyltin tri (or di) (laurate) Mono (or di) octyltin tri (or di) (palmitate), mono (or di) octyltin tri (or di) (myristate) mono (or di) octyltin tri (or di) (stearate), mono (Or di) octyltin tri (or di) (oleate) mono (or di) octyltin tri (or di) (ricinoleate), mono (or di) octyltin tri (or di) (behenate) mono (or di) Octyltin tri (or di) (acrylate), mono (or di) octyltin maleate polymer, mono (or di) octyltin acrylate polymer, mono (or di) octyltin mercaptopropionate, mono (or di) ) Octyltin mercaptoacetate,
Mono (or di) octyltin oxide, mono (or di)
Octyltin sulfide, mono (or di) octyltin tri (or di) (mercaptoethanol), mono (or di) octyltin tris (or di) (2-mercaptoethyl oleate), mono (or di) octyltin tris ( Or di) (2-mercaptoethyl stearate), mono (or di) octyltin tris (or di) (2-mercaptoethyloctanoate) and the like.

Specific examples of polyethylene wax include:
General polymerization type high density type (molecular weight of 8000 to 90
0), low density type (molecular weight 7200-1000),
Modified types include copolymers with other monomers such as acrylic acid, vinyl acetate, styrene, and maleic acid, and partially oxidized decomposition types.

The halogen-containing resins usable in the present invention include polyvinyl salts, copolymers of vinyl chloride and monomers copolymerizable therewith, graft polymers, block polymers, (examples of comonomer are ethylene, Olefins such as propylene, vinyl acetate vinyl laurate, acrylic acid esters, saturated acid vinyl esters such as methacrylic acid methyl ester, unsaturated acid alkyl esters, alkyl vinyl ethers such as lauryl vinyl ether, maleic acid, acrylonitrile, styrene, methyl styrene chloride Terpolymers of polyvinyl chloride and, for example, acrylonitrile-butadiene-sterene, methyl methacrylate-butadiene-sterene, chlorinated polyethylene, ethylene-vinyl acetate copolymer Polymer blends, also the post-processing was due to alcohol polyvinyl chloride with a halogen-containing resins such as post-chlorinated.

The stabilizer composition of the present invention may contain one or more other commonly used stabilizers or additives. For example, a plasticizer, an organic phosphite, an esteryl organic phosphate, an organic tin compound, an organic or inorganic antimony compound, an organic or inorganic titanium compound,
Metal soaps, epoxy compounds, ultraviolet absorbers, antioxidants other than those exemplified above, pigments other than the present invention, dyes, processing aids, impact resistance enhancers, mold release agents, antistatic agents, polyhydric or higher alcohols, Examples include saturated or unsaturated fatty acids having linear or side chains, other organic solvents, lubricants, fillers, flame retardants, fragrances, organic compounds or salts thereof, cross-linking agents and plate-out inhibitors.

Specific examples of the organic phosphite include triphenyl phosphite, tricresyl phosphite,
Triisooctyl phosphite, tridecyl phosphite, tri-2-ethylhexyl phosphite, trisnonylphenyl phosphite, tri (octylphenyl)
Phosphite, tricyclohexylphenyl phosphite, tricyclohexyl phosphite, tridecylthiophosphite, triisodecylthiophosphite, phenyl di-2-ethylhexyl phosphite, phenyl diisodecyl phosphite, phenyl dicyclohexyl phosphite, phenyl Diisooctyl phosphite, phenyl di (tridecyl) phosphite, phenyl di-cyclohexyl phosphite, diphenyl
Isooctyl phosphite, diphenyl 2-ethylhexyl phosphite, diphenyl isodecyl phosphite, diphenyl cyclohexyl phenyl phosphite, diphenyl tridecyl thiophosphite, nonylphenyl di (tridecyl) phosphite, phenyl
p-tert-butyl dodecyl phosphite, diisopropyl phosphite, monoisopropyl phosphite, diisodecyl phosphite, diisooctyl phosphite, monoisooctyl phosphite, didodecyl phosphite, monododecyl phosphite, dicyclohexyl phosphite, mono Cyclohexyl phosphite,
Dicyclohexylphenyl phosphite, monodicyclohexylphenyl phosphite, di (p-tert-butylphenyl) phosphite, tetra (tridecyl)
-4,4'-isopropylidenediphenol-diphosphite, tetra (tridecyl) -4,4'-butylidenebis (2-tert-butyl-5-methylphenyl)
Diphosphite, tetraisooctyl [4,4'-thiobis (2-tert-butyl-5-methylphenol)] diphosphite, tetranonylphenyl polypropylene glycol-diphosphite, tetra (tridecyl) dipropylene glycol diphosphite, tetratridecyl- 4,4'-isopropylidenecyclohexyl diphosphite, pentakis (nonylphenyl) bispolypropylene glycol triphosphite, heptakis (nonylphenyl) tetrakispolypropylene glycol pentaphosphite, heptakis (nonylphenyl) tetrakis (bisphenol A) pentaphosphite, decaquis (Nonylphenyl) heptakis (dipropylene glycol) octaphosphite, decaphenylheptadipropyleneglycol Octaphosphite, tetrakis (isooctoxycarbomethylenethio) 1,2-
Oxycarbonylmethylenethioethylene diphosphite, dibutoxycarboethylenethio (pentaerythritol tetrathioglycol) diphosphite, diisooctoxycarbomethylenethio (pentaerythritol tetrathioglycol) diphosphite, tetrakis (mercaptolauryl) 1,2-dimercapto- Ethylene diphosphite, tetrakis (mercaptolauryl) 1,
6-dimercapto-hexylene phosphite, tetrakis (mercaptolauryl) β, β′-dimercapto-
Ethyl ether diphosphite, pentakis (dodecyl-mercapto) bis (1,6-hexylene dimercapto) triphosphite, diphenyl phosphite, hydrogenated 4,4'-isopropylidene diphenol phosphite, 4,4'-isopropyl Li diphenol alkyl _(C 12 _{-C 15)} phosphite, 2-tert-butyl-.alpha. (3-tert-butyl-4-hydroxyphenyl) p-Kumenirubisu (p- nonylphenyl) phosphite, 4,4'- Butylidenebis (3-methyl-5-t
tert-butylphenylditridecyl phosphite, distearylpentaerythritol diphosphite, tricyclohexylphenyl phosphite, 1,1,3-tris [(2'-methyl-4'-ditridecyl phosphite 5'-tert-butyl )] Phenyl] butane, tridodecylmercaptophosphite, decaphenylheptadipropylene glycol octaphosphite, dibutylpentaerythritol diphosphite, didecylpentaerythritol diphosphite, dioctylpentaerythritol diphosphite, and the like.

Specific examples of the organic phosphoric acid ester include nonylphenoxypolyethoxyphosphoric acid, tridecylhydroxypolyethoxyphosphoric acid, octyloxypolyethoxyphosphoric acid, lauryloxypolyethoxyphosphoric acid, stearyloxypolyethoxyphosphoric acid, oleyl Oxypolyethoxyphosphoric acid, tert-butylphenoxypolyethoxyphosphate octylphenoxypolyethoxyphosphate, dinonylphenoxypolyethoxyphosphate dodecylphenoxypolyethoxyphosphate, and the like.

Specific examples of the organotin compound include mono (or di) methyltin tris (or bis) (isooctylthioglycolate) and mono (or di) butyltin tris (or bis) (isooctylthioglycolate). ), Mono (or di) methyltin tri (or di) laurate, mono (or di) butyltin tri (or di) laurate, mono (or di) methyltin tris (or bis) (isooctylmalate), mono (Or di) butyltin tris (or bis) (isooctylmalate), mono (or di) butyltin tris (or bis) (2-mercaptoethyl oleate), mono (or di) butyltin or mono) (2 -(Merptoethyl oleate) sulfide, mono (or di) butyltin bis (or mono) (2-mercaptoethyl stearate) sulfide, mono (or ) Butyltin tri (or di) oleate, mono (or di) butyltin sulfide, mono (or bis) (butyl acrylate) tin tris (or bis) (isooctylthioglycolate), mono (or bis) (acrylic) Acid) methyl tris (or bis) (isooctyl thioglycolate), mono (or di) butyl tin oxide, mono (or di) methyl tin malate polymer, mono (or di) methyl tin tris (or di) ( 2-ethylhexylthioglycolate), mono (or di) butyltin malate polymer, mono (or di) butyltin-β-
Mercaptopropionate, mono (or di) butyltin thioglycolate, mono (or di) butyltin tri (or di) mercaptoethanol, mono (or di) butyltin tri (or di) ricinoleate, mono (or di) Butyltin tri (or di) oleate, poly (thiobis-n-butyltin sulfide) and the like.

Specific examples of the organic or inorganic antimony compound include tris (isooctylthioglycolate) antimony, monobutylantimonybis (isooctylthioglycolate) dibutylantimony mono (isooctylthioglycolate), tris (2- Mercaptoethyl oleate) antimony, antimony trioxide and the like. Examples of the organic titanium compound include tetrastearyl titanate, tetrakis (2-ethylhexyl titanate), isopropylisostearyl titanate, diisopropoxybis (acetylacetone) titanate, tributoxymonostearyl titanate, dihydroxybis (lactide acid) titanate, Decylbenzenesulfonyl titanate, isopropyltris (dioctylpyrophosphate) titanate, tetraisopropylbis (dioctylphosphite) titanate, tetraoctylbis (ditridecylphosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (Ditridecyl) phosphite titanate,
Bis (dioctyl pyrophosphate) oxyacetate titanate, tris (dioctyl pyrophosphate) ethylene titanate, (mono or di) butyl titanium (tri or di) laurate, (mono or di) butyl titanium (tris or bis) isooctyl thioglycolate ,
Tetrakis (isooctylthioglycolate) titanium,
Tetrakis (dodecyl mercaptoate) titanium, titanium dioxide and the like.

Specific examples of the metallic soap include lithium,
Sodium, potassium, strontium, barium, zinc, cadmium, aluminum, saturated and unsaturated fatty acid salts having linear or side chains of lead, aromatic carboxylate, polyvalent carboxylate, and a substituent for these acids. And the like.

Specific examples of epoxy compounds include epoxidized soybean oil, epoxidized linseed oil, epoxidized lard oil,
Epoxidized tallow oil, epoxidized cottonseed oil, epoxidized safflower oil, epoxidized whale oil, epoxidized tall oil, epoxidized sunflower oil, epoxidized fish oil, diacet monoglyceride of epoxidized soybean oil, epoxidized diacet monoolein, epoxy stearin Benzoyl acid, butyl epoxy stearate, cyclohexyl epoxy stearate, dihydrononyl epoxy stearate, 2-ethylbutyl epoxy stearate, methoxyethyl epoxy stearate, isodecyl epoxy stearate, isooctyl epoxy stearate, tetrahydrofuryl epoxy stearate, epoxy stearin Phenyl acid,
Acetoxyethyl epoxystearate, butyl, n-octyl, isooctyl and 2
Ethylhexyl ester, epoxytriacetomonoricinoleic acid glyceride, epoxystearate-tert-butylphenyl, 9,10-epoxystearic acid ester of 3,4-epoxycyclohexylmethanol, epoxystearyl benzoate, 3,4-epoxycyclohexylmethanol 9,10,12,13-diepoxystearic ester, 2-ethyl-1,3-hexadiol ester of 3,4-epoxycyclohexylcarboxylic acid, di-epoxyhexahydrophthalic acid
esters such as n-butyl, di-n-hexyl, di-2-ethylhexyl, diisooctyl, di-n-decyl, diisodecyl and n-butyldecyl, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexanecarboxylate, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, condensates of shrimp chlorohydrin and bisphenol A, and the like.

Specific examples of the processing aid and impact modifier include chlorinated polyethylene, ethylene propylene copolymer, ethylene vinyl acetate copolymer, styrene butadiene copolymer, acrylonitrile styrene copolymer, acrylonitrile butadistyrene styrene. Polymer, acrylate butadiene styrene copolymer, methacrylate butadiene styrene copolymer (MBS), polystyrene,
Acrylic resin and the like. Specific examples of the lubricant include higher fatty acids, higher alcohols, and ethylenebisstearamide.

Specific examples of the filler include calcium carbonate,
Calcium oxide, calcium hydroxide, zinc oxide, zinc hydroxide, zinc carbonate, zinc sulfide, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide,
Aluminum hydroxide, alumina sodium silicate, hydrotalcite, hydrocalumite, aluminum silicate, magnesium silicate, calcium silicate, zeolite and other metal silicates, activated clay, talc, clay, red iron oxide, asbestos, trioxide Antimony and the like.

Specific examples of the organic compounds or salts thereof include 2-phenylindole, diphenylthiourea, cetyl and stearyl β-aminocrotonate,
Nitrogen-containing compounds such as 3 and 1,4-butanediol bis β-aminocrotonate, thiodiethylene glycol bis β-aminocrotonate, isocyanuric acid and derivatives thereof such as tris (2-hydroxyethyl) cyanurate, pentaerythritol, Polyhydric alcohols such as mannitol and sorbitol, benzoic acid, methylbenzoic acid, richolic acid, maleic acid, cinnamic acid, carboxylic acids such as p-tert-butylbenzoic acid and crotonic acid, borate esters, thiodiglycolate esters, and acetylacetone Β-diketones such as dibenzoylmethane, benzoylacetone and the like and metal salts thereof, acetoacetate ester, dehydroacetic acid or its ester or metal salt, pentaerythritol tetrakis (mercaptopropionate), pentaerythr Tall tetrakis (mercaptoacetate), dicyandiamide, tannic, oxalic acid esters, malonic acid esters, 2- (3'-methoxy -
4'-hydroxyphenyl) indole, thiodipropionate such as dilaurylthiodipropionate, distearylthiodipropionate, 6-anilino-
1,3,5-triazine-2,4-dithiol, 6-butylamino-1,3,5-triazine-2,4-dithiolmelamine, 2-mercaptoethyl oleate, octylthioglycolate, 2-mercaptoethanol, β-
Mercaptopropionic acid, thioglycolic acid, hexamethylenetetramine and the like.

[0023]

Next, the stabilizing effect of the halogen-containing resin according to the present invention will be described with reference to examples. In the following examples, the evaluation values of plate-out and initial coloring property are based on the following criteria, and the thermal stability is the time until the sheet piece turns black. Plateout: 0) no plateout, 1) negligible plateout, 2) slight plateout, 3) obvious plateout, 4) significant plateout. Initial coloring: 0) no coloring, 1) negligible coloring, 2) slight coloring, 3) obvious coloring, 4) significant coloring.

Example 1 Each additive sample shown in Table 1 was blended with 100 parts by weight of a polyvinyl chloride resin, dry-blended and kneaded with a mixing roll at 180 ° C. for 5 minutes to prepare a 0.4 mm sheet. did. Each of the sheet pieces was subjected to a gear oven test under the condition of 195 ° C., and the initial coloring and the thermal stability were examined. Plate-out properties were observed by roll kneading. Each additive sample and the results of each test are shown in Table 1 below.

Example 2 Various additive samples shown in Table 2 were blended in the following basic formulation, dry-blended, kneaded with a mixing roll at 180 ° C. for 5 minutes, and a 0.4 mm sheet was prepared. Each sheet piece was subjected to a gear oven test under the condition of 200 ° C. to examine the initial coloring and thermal stability. Further, the adhesion time to a roll was measured by a roll kneading test. The initial coloring was compared with the degree of yellowing using a formula difference meter manufactured by Nippon Denshoku Industries Co., Ltd. Table 2 shows various additive samples and test results. Basic blend PVC (P = 1050) 100 parts by weight MBS resin 10 ABS resin 5 TiO ₂ 2 Various additive samples and test results are shown in Table 2.

[0026]

As is evident from the above results, the halogen-containing resin composition of the present invention provides a composition having excellent coloring properties and thermal stability, and having less sticking phenomenon (plate-out) during processing. Is possible.

[0027]

[Table 1]

[0028]

[Table 2]

Claims (2)

[Claims] Claims: 1. A 100 parts by weight of a halogen-containing resin,
(1) 0.1 to 4.0 parts by weight of at least one of the organotin compounds represented by the general formula [A] (Where R is an alkyl group having 1 to 12 carbon atoms;
Represents an alkyl group, an alkenyl group, an alkylaryl group, an aryl group, and a derivative having a substituent therefor, and m is 1 or 2. ), (2) 0.05 to 2.0 parts by weight of at least one kind of polypropylene wax;
(3) 0.05 to 3.0 parts by weight of at least one of ester wax and petroleum wax, and (4) at least one of calcium and magnesium salts of an aliphatic carboxylic acid.
A halogen-containing resin composition stabilized by adding 0.1 to 3.0 parts by weight of a seed. 2. The halogen-containing resin composition according to claim 1, which is stabilized by adding 0.01 to 4.0 parts by weight of at least one kind of an octyltin compound and / or a polyethylene wax.