JPS6013849A - Stabilizer composition for halogen-containing resin - Google Patents

Abstract

PURPOSE:To provide the titled composition giving a molded article having excellent discoloration resistance, heat resistance and plate-out resistance, and composed of a mixed product obtained by the thermal reaction of a combination of a plural kinds of various specific organotin compounds such as monoalkyltin oxides, and thioglycolic acids, etc. CONSTITUTION:The objective composition is composed of the mixed product [e.g. a mixture of monomethyltin tris(isooctylthioglycolate) and dioctyltin bis (isooctylthioglycolate)] obtained by the thermal reaction of a compound selected from (A) mono- or di(1-12C alkyl)tin oxide and mono- or bis(1-18c alkoxy-2- 3C carboalkyl)-tin oxide with two or more compounds selected from (B) thioglycolic acid, 2-mercaptopropionic acid, maleic anhydride, fatty acid, hydrogen sulfide, mercaptan, and 2-mercaptopropionic acid 4-18C alkyl ester, or the thermal reaction of two or more compounds of the group (A) with one or more compounds of the group (B).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a stabilizer composition for Rodan resin. More specifically, a stabilizer composition for parogen-containing resins, which is based on a combination of organic tin compounds produced by reaction and has excellent coloring resistance, as well as improved heat resistance, roll surface sticking phenomenon (great-out), and transparency. relating to things.

Halogen-containing resins are colored by heating during molding or by photodegradation, mainly from ultraviolet rays, after they are made into processed products.
It is well known that it will no longer be possible to produce an excellent product. In order to improve these drawbacks, various stabilizers have been proposed and put into practical use.

As is well known, the performance required of the stabilizer for chlorine-containing resins is wide-ranging in addition to the above-mentioned heat and light performance. Although the stabilizers used in the past have various characteristics as their effects, no stabilizer has been found to be fully satisfactory.

Even relatively good stabilizers that have been put into practical use have improved effects in order to obtain even better products.

Stabilizers are required.

Organotin compounds are widely used as stabilizers for halogen-containing resins such as polyvinyl chloride (PVO), but since each has different performance, it is difficult to use two or more types together in actual use. is normal.

The present inventor, Tyu, was considering the combination of compounds, mixing method, mode of use, etc. for this combination, and discovered that 2.
Rather than mechanically blending more than one type of organotin-based stable MIJ, a stabilizer composition composed of multiple stabilizers can be synthesized from raw materials or their reaction products can be used. It is a surprising fact that a stabilizer that functions as a stabilizer and is easy to handle in a single package can be obtained more efficiently by producing it during synthesis as an intermediate raw material and blending it into the entire resin. This is the heading that led to the present invention.

[Structure of the invention]

The first aspect of the present invention is to use a compound shown in the following fa), (kiri) as a raw material, and use one kind of the fa) group and two or more kinds of the (kiri group), or <
The second invention includes a mixture product obtained by heat-reacting two or more of Group 83 and one or 12 or more of Group +b), and is used as a stabilizer for a rogen-containing resin. , a mixture obtained by fully heating and mixing two or more reaction products obtained by reacting one type of group (a) and one type of +1) group J, or by allowing two weeks or more to elapse after mixing. The product is used as a stabilizer, and the third invention further includes one kind of reaction product obtained by total reaction of one kind of the taJ group and one kind of the (1)) group, or r1
One or more members of the taJ group and one or more members of the (t)J group are added to a mixture of two or more members, and a mixture product obtained by heating and reacting is used as a stabilizer.

taJ Mono- or dialkyl (CI-12) tin oxide mono-branched hobis [alkoxy (Q+-+s) carboalkyl (C2-11) tin oxide tbl thioglycolic acid 2-mercaptopropionic acid anhydride maleic acid fatty acid sulfide aqueous mercaptan 2-mercapto Alkyl (C4-18) gropionate ester Alkyl (C4-18) thioglycolate ester 1.
4-butadiol thioglycolic acid ester 2-mercaptoethyl fatty tlk ester Malei/acid ester (alcohol: Cl-18) In the present invention, heating during reaction or mixing is performed at 50°C or higher under normal pressure or reduced pressure, preferably at 80°C. It means raising the temperature to ~120°C. or,
It means so-called aging to allow more than two weeks to pass.

[Composition of the composition]

The stabilizer composition of the present invention is considered to be composed of a combination of two or more types of organic tin compounds, depending on the selection of groups (a) and (1).

Examples of these components include the following, but depending on the combination of raw materials and reaction conditions, a partial disproportionation reaction may occur, and the product may not necessarily be the one expected from the combination of raw materials. be.

In addition, raw materials (aJ group mono- or dialkyl tin oxide,
Which basic compound can be easily obtained by reacting mono- or bis[alkoxy (CI-118) carboalkyl (°C2-3)] tin oxide with the corresponding taloride compound and caustic soda? The use of chloride Kongo instead of oxide also falls within the scope of the present invention.

The above-mentioned components include the following.

Monomethyltin tris (inoctylthioglycolate)
, Monobutyltin Tris (Inooctylthioglycolate), Monoofdeltin Tris (Inooctylthioglycolate), Dimethyltin Bis(Inooctylthioglycolate), Dibutyltin Bis(Inooctylthioglycolate), Dioctyltin Bis(Inooctylthioglycolate) thioglycolate) monomethyltin oxide, dimethyltin oxide, monobutyltin oxide, dibutyltin oxide, monooctyltin oxide, dioctyltin oxide, didodecyltin oxide monomethyltin sulfide, dimethyltin sulfide,
Dibutyltin sulfide, dioctyltin sulfide,
Diddenletin sulfide dimethyltin malate, dibutyltin mante, dioctyltin malate, monooctyltin ma- V-) dimethyltin thiodalicolate, dibutyltin thiodalicolate, dioctyltin thioglyconate, monooctyltin thiodalicolate dimethyltin 2-mercaptoglobiont , digtyltin 2-mercaptopropionate, tin 2-mercaptoglobionate, monooctyltin 2
-Mercaptopropionate dimethyltin dilaurate, dibutyltin dilaurate, dioctyltin dilaurate, dioctyltin dilysylute,
Dibutyltin dioleate, monomethyltin trilaurate,
Dibutyltin dilaurate dimethyltin bis (in-octyl maleate), dibutyltin bis (in-octyl maleate), dioctyltin bis (in-octyl maleate), dioctyltin bis (nonyl maleate), monooctyltin tris (in-octyl maleate) Monomethyltin didodecyl mercaptide, dibutyltin didodecyl mercaptide, dioctyltin didodecyl mercaptide, dioctyltin didodecyl mercaptide thiobis [monomethyltin bis(2-mercaptoethyl oleate)]. Thiobis[dimethyltin mono(2-mercaptoethyl oleate)], Thiobis[dibutyltin mono(2-mercaptoethyl oleate)]
-mercaptoethyl oleate)], thiobis[-dioctyltin mono(2-mercaptoethyl oleate)] monomethyltin tris(2-mercaptoethyl oleate)
, dimethyltin bis(2-mercaptoethyl oleate),
Monobutyltin tris (2-mercaptoethyl oleate)
, dibutyltin bis(2-mercaptoethyl oleate),
%'Nooccartin tris(2-mercaptoethyl oleate), dioctyltin bis(2-mercaptoethyl oleate) butoxycarboethyltin tris(inoctylthioglycolate) bis(butoxycarboethyl)tin bis(inoctylthioglycolate) Butoxycarboethyltin tris(2-mercaptoethyl oleate) Bis(butoxycarboethyl)tin bis(2-mercaptoethyl oleate) [Effects of the Invention] The present invention (g. Mixed at room temperature and packaged as a total stabilizer f)K
, T is the combination of raw materials that yields a mixture with the desired composition.
A composition selected from group aJ and group (1)) is produced through reaction by heating or aging over time, and is made into a single packaged stabilizer. Parabolic showed superior stabilizing effects in terms of color resistance, great-out phenomenon, and transparency for I- to rogen-containing resins compared to a composition in which all of the same components were mechanically blended. Furthermore, the stabilizer obtained by such a method may be in the form of a powder, even when the constituent components are in a liquid form alone.
゛Although it shows excellent results in the same way, even when powdered ingredients are used, the product can be liquefied, so the advantages when used by processors are simplification of weighing,
Great for preventing dust diffusion. Normally, when producing powder stabilizers, filtration and drying steps are performed using a certain type of solvent, but since these steps are omitted in the present invention, manufacturing costs are reduced and the contamination of foreign substances can be prevented. Not only is it possible to do this, but it also has the advantage of omitting the liquefaction step, which is difficult when blending single products.

The stabilizer composition of the present invention contains 0.05 to 10 parts by weight, preferably dO, (
It is used in cylinders with 15 to 5 weights.

[Synthesis example]

Next, the first aspect of the present invention. Synthesis examples of compositions corresponding to each of the rounding conditions will be shown to specifically explain the second and third conditions.

Synthesis Example 1 (First Invention) Toluene 150? Inoctylthioglycolate ((b3 group') 68,
49- and while stirring monomethyltin oxide (
faJ group) 10.6.9- and dioctyltin oxide (
(Group 83) 24. Of was added at the same time. Dehydration reaction was carried out at 120°C by gradually heating. Subsequently, toluene was distilled off to produce monomethyltin tris (inoctylthioglyconaute) and dimethyltin bis(inoctylthioglycolate).
A mixture 99.55' was obtained, corresponding to the same weight ratio of . Yield: 99.5 cm.

Synthesis Example 2 (First Invention) Into a system purged with nitrogen gas, 57.2 ft of inoctylthioglycolate (cut group) was charged, and while stirring, monomethyltin oxide (faJ group) 53? Dimethyltin oxide (group (a)) 7.41, monooctyltin oxide (group ia) 7.6y-, and dioctyltin oxide (group (a)) zsPe were added at the same time.

Gradual heating and dehydration reaction under reduced pressure at a maximum of 10 s 'C yields monomethyltin tris (in-octyl thioglycolate), dimethyltin bis (in-octyl thioglycolate), and mono-octyl tin tris (in-octyl thioglycolate). ), 99.0 Pi of a mixture corresponding to the same weight ratio of dioctyltin oxide was obtained. Yield '99.0.

Synthesis Example 3 (First Invention) In a system purged with nitrogen gas, ino-octi-1-thioglycole-) ((k13 group) is, sy- and 2-mercaptoethyl oleate ((b) group) 40.25' all monomethyltin oxide ((aJ IP )
14.9? , dimethyltin oxide (group (a)) 24.
After gradually adding 4 tons and heating to 80℃, sulfurization occurred.

Continue the reaction for 15 minutes while gradually blowing in hydrogen gas (regular group). -Continue heating at 105℃ for the entire dehydration reaction, monomethyltin tris(inoctylthioglycolate),
Dimethyltin bis(inoctylthioglycolate), monomethyltin tris(2-mercaptoethyl oleate),
Dimethyltin bis(2-mercaptoethyl oleate), Thiobis[monomethyltin bis(2-mercaptoethyl oleate))), Thiobis[dimethyltin mono(2-mercaptoedelole))), Monomethyltin sulfide, Dimethyltin Mixture corresponding to the quaternary electric ratio of sulfide 99
1? (J! Tomo. Yield 99, 1.

Synthesis Example 4 (First Invention) In a reaction vessel, inoctylthioglycolate (it) J
group) 32.0p, lauric acid (lbl#) 13.5
y-, thioglycolic acid (group (b)) 531 was added and while stirring, monooctyltin oxide (laJ group) 7.
4y-, dioctyltin oxide (group (a)) 4t8?
' and then add at the same time. Gradually heat up to 105% under reduced pressure
The dehydration reaction was carried out at ℃, and the ratio was equivalent to that of monooctyltin tris(in-octylthioglycolate), dioctyltin bis(in-octylthioglycolate), dioctyltin dilaurate, and dioctyltin deoglycolate. A mixture of 99.89- was obtained.

Yield 99.8%.

Synthesis Example 5 (First Invention) Maleic anhydride (ft.
lJ group) li, 4g- and Inoctatool 8.1? was added, heated to 90°C with stirring, and then cooled to 40°C. followed by inoctylthioglycolate (+'b
Group J) 31.8y-i was added and stirred. Monooctyltin ogicide (laJ group) 3B, 6f2. After simultaneously adding dioctyltin oxide (laJ group) 12.0.9-, dehydration reaction was carried out under reduced pressure at maximum ios°C.

Monooctyltin tris (inoctylthioglyco V-)
), dioctyltin bis(isooctylthioglycov
h), dioctyltin malate, dioctyltin bis(
98.97 f of a mixture corresponding to the same weight ratio of octyl malate) was obtained. Yield 98.9 inches.

Synthesis Example 6 (First Invention) In a system purged with nitrogen gas, inoctylthioglycolate ((bJ group) 39.0P, 2-mercaptoethyl oleate ((b) group) 16.9!t12~ Add mercaptopropionate (fbJ group) to, s9-, and add monomethyltin oxide (laJ group) 5.3 with stirring.
5', dimethyltin oxide (LA) #) 31.8
After completely adding P and heating to ao'c, hydrogen sulfide gas (group (b)) was gradually blown into the reactor to continue the reaction for 30 minutes. Continue heating to finish the dehydration reaction at 105℃,
Monomethyltintrij-(in-octylthioglycolate), dimethyltinbis(in-octylthioglycolate)
, thiobis[dimethyltin mono(2-mercaptoethyl oleate)], dimethyltin 2-mercaptopropioid -
The mixture, which corresponds to the same -ti ratio of 99.2 y-, was superior. Yield 99.2%.

Synthesis example 7. (Third invention) - Monobutyltin oxide (+aJ group) and inoctylthioglycole 1-
Monobutyltin tris(in-octylthioglycolate) 25f obtained from (+bJ group), dibutyltin oxide (FaJ group) and inoctarchioglycolate (+)cov-)
Dibutyltin bis(inoctylthioglycolate) obtained from (group (fb)) 25 f, dodecyl mercaptan ((bJ group) 15.97, 2-mercaptopropionic acid (group (b)) 7.9y-t - While adding and stirring,
Dibutyltin oxide (laJ group) 18.3f/-gold was added and gradually heated under reduced pressure to complete the dehydration reaction at a maximum temperature of 110°C. thioglycolate), dibutyltin bis(dodecyl mercaptan)
, a mixture of 99.8% corresponding to the same weight ratio of dibutyltin 2-mercaptoethyl oleate was obtained. Yield 99.8
%.

Synthesis Example 8 (First Invention) Toluene 1001 and inoctylthioglycole) (fbJ group) 40.7 in a system purged with nitrogen gas
? Add everything and add dioctyltin and oxide while stirring.
(aJ group) 55.7 P was gradually added and a dehydration reaction was performed at 120°C. Subsequently, when the temperature was cooled to 80°C, 5.3 Pi of maleic anhydride (group (b)) was added, and the reaction was heated to 120°C again. Toluene was distilled off to form dioctyltin bis(in-octylthioglycolate) and dioctyl. A mixture of 99.5% tin malate corresponding to a ratio of 3:1 was obtained. Yield: 99.5 cm.

Synthesis sequence 9 (second invention) Mono(butoxycarboethyl)tin tris(inoctylthioglycolate) soP obtained from butoxycarboethyltin oxide (lad group) and inoctylthioglycolate ((b1 group) Dibutyltin oxide (t
aJ group) and inoctylthioglycolate' ((1)
Dibutyltin bis(inoctylthioglycolate) 505' obtained from J group) was stirred at room temperature and left at room temperature for two weeks to form mono(butyccarboethyl)tin and dibutyltin bis(inoctylthioglycolate). 10 oz of the mixture was obtained corresponding to the same weight ratio of Yield 100%.

Synthesis Example 10 (Second Invention) Dibutyltin oxide (1ILJ group) and inoctylmale (tb) group) or c-2-predominant dibutyltin bis(
Dibutyltin trilaurate (50ff) obtained from monooctyltin oxide ((a) group) and lauric acid ((bt group)) was stirred at room temperature and left at room temperature for 3 weeks to form dibutyltin bis A mixture 1005' corresponding to the same weight ratio of monooctylmalate and monooctyltin trilaurate was obtained. Yield: 100
%.

[Resin to be stabilized]

The chlorine-containing resins to be stabilized in the present invention include polyvinyl chloride, polyvinyl chloride monodene, chlorinated polyethylene, chlorinated polypropylene, polyvinyl bromide, polyvinylidene bromide, brominated Homocarbon 13-t-1 or vinyl chloride such as polyethylene, brominated polypropylene, polyvinyl fluoride, polyvinylidene fluoride, chlorinated rubber, post-chlorinated vinyl, etc. can be copolymerized.
A halogenated monomer, vinyl acetate, ethylene, chlorine, styrene, inbutylene, inglene, butadiene, methylstyrene, maleic acid, maleic ester, acrylic ester, methacrylic ester, acrylic nitrile, Two types arbitrarily selected from vinyl laurate, vinyl ether, vinylidene chloride, chlorinated ethylene, propylene chloride, vinyl bromide, vinyl chloride, vinyl fluoride, vinyl fluoride, etc. These include multi-component copolymers with the above, and monomeric polymers of these with each other or with other polymers.

[Other additives]

The stabilizer of the present invention may contain one or more other commonly used stabilizers or additives. These include, for example, plasticizers, functional phosphate esters,
Organic phosphate ester, organic or inorganic antimony compound,
Organic or inorganic titanium compounds, metallic soaps, epoxy compounds, ultraviolet absorbers, antioxidants, viscosity modifiers, pigments, dyes, processing aids, impact reinforcement agents, mold release agents, surface treatment agents, anti-fungal agents , fluorescent brighteners, antifogging agents, non-drip agents, droplets, anti-banding agents, polyhydric or higher alcohols, straight chain or saturated and unsaturated fatty acids (having their own side chains) and other organic solvents, Lubricants, fillers, flame retardants, fragrances, organic compounds or their salts,
These include crosslinking agents and plate-out prevention agents.

Specific examples of the organic saliva/acid esters mentioned above include triphenyl phosphite, trisnonyl 7-enyl phosphite, tricresyl phosphite, triisooctyl phosphite, tridecyl phosphite, tri-2-ethylhexyl phosphite. (T, tridecyl phosphite,
Tri(octylphenyl)phosphite, tricyclohexylphenylphosphite, triscyclohexylphosphite, tridecylthiophosphite, triisooctylphosphite, phenyldi-2-ethylhexylphosphite, phenyldiindecylphosphite, phenyl synchro xyl phosphite, phenyl diindecyl phosphite, phenyl di(tridecyl) phosphite, 7-enyl dicyclohexyl phosphite, diphenyl octyl phosphite, diphenyl 2-ethylhexyl phosphite, diphenyl indecyl phosphite, diphenyl phosphite , diphenylcyclohexylphenyl phosphite, diphenyl)' IJ
f V-ruthiophosphite, nonylphenyl di(tridecyl) phosphite, phenyl p-tert-butyldodecyl phosphite, diinglobyl phosphite, monoinglobyl phosphite, diphenyl phosphite, diinooctyl phosphite, monoinooctyl E, sulfite, didodecyl phosphite, monododecyl phosphite, dicyclohexyl phosphite, monocyclohexyl phosphite, dicyclohexyl phenyl phosphite, monodicyclohexol phenyl phosphite, cy(p-tertiary) butylphenyl) phosphite, tetra(tridecyl)-4,4'-butylidenebis(2-1-chary-phthyl-5-methylphenyl) diphosphite, tetra(tridecyl)-4,4'-
Thiobis(2-tert-7-methyl-5-methylphenol) diphosphite, tetranonylphenyl polypropylene glycol-thiphosphite 1-11,1.3
-1-11suC(2'-methyl-4-citrizofluphosphite-5-tert-butyl)phenyl]butane, 4,4'-inopropylide/diphenolalkyl(
C12-C1,) phosphite, tetra(tridecyl)
Diglobylene glycol diphosphite, tetratridecyl-4,4'-impropylidenecyclohexyl diphosphite, pentakis (nonylphenyl) bispolyglobylene glycol triphosphite, heptakis (nonylphenyl) tetrakis polypropylene/glycol pentaphos Phyto, heptakis (nonylphenyl) tetrakis (hisphenol A) pentaphosphite, decakis (nonylphenyl) hebutakis (diglobylene glycol) octaphosphite l-, 7"caffeinyl hebutadiglopine glycol octaphosphite, Tetrakis(inoctoxylpomethylenedeo) 1,2-oxycarponylmethylene/deo, ethylene diphosphite,
Dibutoxycarboethylenethio (pentaerythritol tetrathioglycol) diphosphite, diine octoki 7 carpomethylenethio (pentaerythritol tetrathioglycol) diphosphite, tetrakis (mercaptrauryl) 1,2-dimercapto-ethylene diphosphite, tetrakis (mercaptrauryl) 1 .6-
dimercapto-hexylene diphosphite, tetrakis (mercaptrolauryurine β, β'-dimercagto ethyl ether diphosphite, pentakis (dodecyl-mercapto) bis(1,6-hexyl diphosphite/dimercapto)
Triphosphite, tris(2,4-ditertiary-butylphenyl)bosphite, 4,4'-butylidene-
bis(3-methyl-6-tajaributylphenyl-
phosphite, hydrogenated 4,4'-inglobilite/diphenol phosphite, 2-tertiary
Butyl-α(3-tert-butyl-4-hydroxyphenyl)p-cumenylbis(p-nonylphenyl)phosphite, 4,4'-bitylidenebis(3-methyl-〇-tert-butylphenylditridecylphosphite, distearyl) Pentaerythritol diphosphite, tricyclohexylphenyl phosphite, tridodecyl mercaptopo27ite, tecaffeinylhegtadipcopylene glycol octaphosphite, dibutylbentae IJ x ritol diphosphite, didecyl pentaerythritol diphosphite, Dioctylpentaerythritol diphosphite and the like.

Specific examples of organic phosphate esters include nonylphenoxypolyethoxyphosphoric acid, tridecylhydroxypolyethoxyphosphoric acid, octyloxypolyethoxyphosphoric acid, lauryloxypolyethoxyphosphoric acid, stearyloxyboriethoxy7phosphate, and tert-butylphenoxypolyethoxyphosphoric acid,
These include octylphenoxypolyethoxyphosphoric acid, dinonylphenoxypolyethoxyphosphoric acid, dodecylphenoxypolyethoxyphosphoric acid, and the like.

Specific examples of organic or inorganic antimony compounds include tris(in-octylthioglycolate) antimony, monobutylantimony bis(in-octylthioglycolate), cyphitylantimony mono(in-octylthioglycolate), tris(2- antimony (mercaptoethyl oleate), antimony trioxide, etc.

Examples of organic titanium/compounds include tetrastearyl titanate, tetrakis (2-ethylhexyl titanate)
, Improvir instearyl titanate, Diimpropoxy bis(acetylacetone) titanate, Tributoxy monostearyl titanate, Dihydroquicumbis(raftiquacid) titanate, Improvir tridecylpenze y x A, Honi nf tie=-), (Cyclo Pyrtris (dioctyl pyrophosphate) titanate, Tetrain propulbis (dioctyl phosphite)
Titanate, Tetraoctylbis(citrizofluphosphite) titanate, Tetra(2,2-diallyloxymethyl-1-butyl)bis(citrizoflu)phosphite titanate, Bis(dioctylpyrophosphate)
Oxyacetate titanate, tris(dioctylpyrox 7ate) ethylene titanate, (mono or a)
Di) butyl butane (tri or di) laurate, (mono or di) buty, ruti, -J1! These include (tris or bis) inoctyl thioglycolate, tetrakis (in octyl thioglycolate) titanium, tetrakis (dodecyl mercagutoate) titanium, titanium didide, and the like.

Specific examples of metal soaps include botanicals, lithium, sodium,
Potassium, calcium, strontium, barium, zinc, cadmium, aluminum, tin,
Saturated and unsaturated fatty acid salts with straight or side chains of lead, aromatic carboxylates, polyvalent carboxylates, and organic acid salts of these acids with substituent groups, such as acidic salts, neutral salts,
It means one or more metal salts selected from basic salts, and examples of the organic acids include 5 to 30 unsubstituted, substituted, saturated,
Unsaturated aliphatic or aromatic carboxylic acids such as cabroic acid, heptanoic acid, 2-ethylheginic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid,
Pentadecanoic acid, valmitic acid, hegel decanoic acid, stearic acid, hydroxystearic acid, dihydroquine stearic acid, nonadeca/acid, aralginic acid, henicosanoic acid, behenic acid, tricosanoic acid, lidanoceric acid, hentacosanoic acid, montanic acid, nonacosa /acid, melisic acid,
hentriacontanoic acid, mixed odd-numbered acids with 21 to 31 carbon atoms derived from α-olefins, oleic acid, ricinoleic acid, acrylic acid, linolic acid, linoleic acid, crotonic acid, acetoacetic acid, instearin acids, aliphatic carboxylic acids such as inoctylic acid, neoacid, octylic acid, dibasic acids such as malonic acid, acihinic acid, azelaic acid, sepacic acid, phthalic acid, thioshifurohionic acid, dithioprobio 79, and these dibasic acids. Acid and a linear or side chain substituted or unsubstituted alkyl alkyl having 1 to 8 carbon atoms: l Ki'/
7 L: L, cycloalkyl having 1 to 8 carbon atoms,
Semi-esters of arylalkyl, aryl, and alkylaryl alcohols, benzoic acid, methylbenzoic acid, butylbenzoic acid, benzoylbenzoic acid, phenylacetic acid, salicylic acid, fumaric acid, naphthoic acid, sodium chloride acid,
Abietic acid, dihydroabinib 7flk, phenylstearic acid, bialido 7carboxylic acid, cinnamic acid, p-tertiary-butylbenzoic acid, rosin acid, naphthi/acid, epoxy compound with epoxy group, as specific examples. , epoxidized soybean oil, epoxidized beef tallow oil, epoxidized lard oil, epoxidized beef tallow oil, epoxidized beef tallow oil, epoxidized brass oil, epoxidized whale oil, epoxidized tall oil, epoxidized sunflower oil, epoxidized fish oil, epoxy diacetomonoglyceride of oxidized soybean oil, epoxidized diacetomonoolein, benzyl epoxystearate, butyl epoxystearate, cyclohexyl epoxystearate, dihydrononyl epoxy7sudearate, 2-ethylbutyl epoxystearate, epoxystearate (ll methoxyethyl, epoxy stearate/indecyl acid, epoxy stearate indecyl, epoxy stearate tetrahydrofuryl, epoxy stearate phenyl, epoxy stearate acetoxyethyl, epoxy oleate butyl, n-octyl, inoctyl and Ethylhexyl ester, epoxy diacetomonolycylinic acid glyceride, epoxystearate-tert-7-arybutylphenyl, 3.4-epoxycyclohexylmethanol (1) 9.10-epoxystearate, epoxystearyl benzoate,
9.10 of 3,4-epoxycyclohexylmethanol
．． 12.13- Dieboxystearate, 3
, 2-ethyl-1,3-hexa-diol ester of 4-epoxycyclohexylcarbo/acid, di-n-butyl, di-n-hexyl of epoxyhexahydrofuric acid,
Di-2-ethylhexypur, diyneoctyl, di-11-
Esters such as decyl, diindecyl and n-butyldel, 3,4-epoxycyprohekiflumethyl-3,4-
Evoxin clohexane carboxylate, 3',4-
These include epoxy-6-methylcuchlorohexanecarboxylate, bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate, and a condensate of epichlorohydrin and bisphenol A.

Specific examples of processing aids and impact Z8 reinforcing agents include silane, chlorinated polyethylene, ethylene propylene copolymer, ethylene vinyl acetate copolymer, styrene butadiene copolymer, acrylonitrile styrene copolymer, acrylonitrile butane ensutin. These include methacrylic acid ester butadiene/styrene copolymer, methacrylic acid ester butadiene/styrene copolymer, polystyrene, acrylic resin, and the like.

Specific examples of lubricants include polyethylene wax, paraffin wax derived from petroleum or coal, higher fatty acids, higher alcohols, natural or synthetic polymer ester waxes, ethylene bisstearamide, and lubricants other than the metal soaps mentioned above. It is a metal salt etc. having

Examples of fillers include oxides, hydroxides, chlorides, sulfides, carbonates, sulfates of metals of Group 1-Y or I of the periodic table;
Sulfites, IJ phosphates, silicate, nitrates, nitrites, and phosphates may also be used in combination. Specific examples include seaweed, calcium carbonate, calcium oxide, calcium hydroxide, zinc oxide, zinc chloride, zinc hydroxide, zinc carbonate,
Zinc sulfide, zinc phosphite, zinc halinate, magnesium oxide, magnesium hydroxide, magnesium carbonate, aluminum oxide, aluminum hydroxide, alumina, sodium silicate, aluminum silicate, magnesium silicate, calcium silicate, zeolite, etc. Silicate metal salts, activated clay, talc, clay, benzene/gala, bentonite, kaolin, diatomaceous earth, /) hydrotalcite, asbestos,
Antimony trioxide, barium hydroxide, barium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, barium sulfate, etc.

Specific examples of organic compounds or salts thereof include 2-phenylindole, diphenylthiourea, ethylenethiourea, be/diylthiourea Lo-tolylthiourea, cetyl and stearyl β-aminocrot/acid esters, 1,3 and 1,4 Nitrogen-containing compounds such as butanediol bis β-aminocrotonic acid ester, thiodiethylene glycol bis β-aminocrotonic acid ester, incyanuric acid and its derivatives such as tris(2-hydroxyethyl) cyanurate, pentaerythritol, ma/nitol,
Polyhydric alcohols such as nrubitol, benzoic acid, methylbenzoic acid, linoleic acid, maleic acid, cinnamic acid, p-tert-butylbenzoic acid, carboxylic acids such as crotonic acid, halogen acid esters, thiodiglycolic acid esters, acetylacetone , diyne/(lumethane, benzoylacetone, etc.) β-diketones and their metal salts, acetoacetate,
Diketo acid esters, metal salts of diketo acid esters, dehydroacetic acid esters, their esters, and their salts.
Thritol Tetrakis (Mercaptopropionate),
Pentaerys IJ Toll Tetrakis (Mercaptoacetate), Diandiamide, Ri/Nine, Kuyuba Ester, MacC'7CIL Ester, 2-(a/-Diphenyl in Methoxy-47-Hydro)indole, Dilaurylthiodibu-Bio , diprobione tnt nysdel, sodium dialkyl sulfosuccinate, 〇-benzoic acid sulfimito, distearyl thiodipropyl ester, distearyl thiodipropyl ester, fluorine ethanolamine, 6-anili/-1,3゜5 -triazine-2,4-dithiol,
6-butylamino1.3.5-triazine-2,4
-dithiolmelamine, 2-amino-6-methylbenzothiazole, piperazine adipate, thioumilno(cyto°, 6-methyl-2-thiouramyl, 2-mercaptoethyl oleate, octylthiodalicolate, 2-mercaptoethanol, β-mercaptoethanol) These include gutpropionic acid, thioglycolic acid, and hexamethylenetetramine.

[Evaluation method of effectiveness]

Next, the stabilizing effect of the chlorine-containing resin according to the present invention will be shown in Examples.

In the Examples below, the following criteria were followed for evaluation of plate-out.

0 nibrate out at all 1: Very few great outs 2: Slight plate out 3: Obvious plate out 4: Slightly significant plate out 5: Xt new plate out Transparency rating 11IIIi-1, in accordance with the following criteria.

(Evaluation of the sheet obtained by pressing with a heating compression machine) 0:
No turbidity at all 1: Very slight turbidity 2: Slight turbidity 3: Obvious turbidity 4: Slightly significant turbidity 5: Significant turbidity Evaluation of heat resistance indicates the time taken to reach a point in a gear oven.

The evaluation of initial coloration is based on the following criteria. The initial coloration here indicates the degree of coloration after 5 minutes of the gear oven test.

0: Colorless, very slightly yellow 2: Slight yellow 3: Yellow 4: Slight yellowish brown 5: Yellowish brown Example 1 Tri-blend the product of the synthesis example to the basic formulation and mix on a mixer roll at 175°C for 5 minutes. 0.4 after crosstalk
Intestine sheet 1 - created.

Basic composition (parts by weight) PVC (P=1050) l 00 MB5 1 0 ABS a Ri IJ serine monostearate 0.8 Calcium stearate o, i Zinc stearate 0.1 Subsequently, several of these roll sheets were stacked, A press sheet with a thickness of 2.0 words was produced using a heating compression molding machine under the conditions of 175° C., 100 kp, and 2 to 10 minutes per minute. Transparency at this time,
Table 1 shows the results of initial colorability, heat resistance, and plasticity.
Shown below.

(Margin below) Table 1

Claims (1)

[Claims] +11 The following (obtained by total heating reaction of one species of the ri group, two or more species of the ibJ group, or two or more species of the taJ group, and (b) #01 species or two or more species) Stabilizer composition for halogen-containing resins comprising a mixed product. taJ mono- or dialkyl (CI-1t) tin oxide mono-bis[alkoxy (Cl-18) carboalkyl C02-8)] tin oxide (e) thioglycol Acid 2-Mercagutoglobio/Acid Maleic Anhydride Fatty Acid Hydrogen Sulfide Mercaptan 2-Mercagutobrobionic Acid Alkyl (04-□) Ester Thiocricholic Acid Argyl (C4-111) Ester 1
．． 47” tandiol thioglycolic acid ester 2-mercaptoethyl fatty acid IX f & ruic acid ester (
Alcohol: Cl-1,) (2) Below (ILJ-1)
A mixture of two or more reaction products obtained by reacting a seed with one of the four groups, or by mixing them for two weeks or more. Stabilizer composition for resins. (C3 mono- or dialkyl (Ol-□) tin oxide mono- or bis [alkoxy (CI-111) carboalkyl (Cffi-)) tin oxide, ibJ thioglycolic acid 2-mercargtoprobion Acid maleic anhydride fatty acid hydrogen sulfide mercaptan 2-mercagtogropionate alkyl (C4□・8) ester thiocricolate alkyl (C4-18) ester 1.
4 plucoolthioglycolic acid ester 2-mercaptoethyl fatty acid ester maleic acid ester (alcohol = Cl-18) (3)
141i or more of the taJ group and ( 1) A stabilizer composition for Rodan resin containing a mixed product obtained by adding one or more of the three groups and reacting with heat. taJ mono- or dialkyl (CI-12) tin oxide mono- or bis[alkoxy (CI-111) carboalkyl (C2-J) tin oxide tbJ thioglycolic acid 2-mercaptopropionic acid anhydride maleic acid fatty acid hydrogen sulfide mercaptan 2-mercagut Alkyl (C4-18) probionic acid ester Alkyl (C4-18) thiotalicolate ester 1.
4. Butanediol thioglycolic acid ester 2-mercaptoethyl fatty acid ester maleic acid ester (alcohol: C+=+s)