JPS5840583B2 - Antique Casareta Gun Halogen Jyushisobutsu - Google Patents

Description

[Detailed description of the invention] The present invention relates to a stabilized halogen-containing resin composition.

More specifically, in the halogen-containing resin, (1) Zn salt, (2
) at least one metal salt selected from Ca, Mg, Ba, Sr and Sn salts, (3) an acetal or ketal compound of a polyhydric alcohol having free OH groups, and (4) an organic phosphite compound. The present invention relates to a stabilized halogen-containing resin composition characterized by comprising:

When halogen-containing resins are subjected to heat molding, they tend to undergo thermal decomposition mainly due to dehydrohalogenation, resulting in deterioration of mechanical properties and color tone of processed products, resulting in significant disadvantages. Maneku.

In order to avoid such disadvantages, it is necessary to add one or more types of heat stabilizers to the resin to suppress deterioration during processing steps.

Many metal soaps have been used for this purpose, and generally satisfactory results have been obtained in terms of thermal stability.

However, the use of these metal soaps, especially cadmium soaps or lead soaps, poses serious toxicity problems. However, its thermal stability is still inferior to that when using cadmium soap or lead soap.

In particular, stabilizers using lead exhibit excellent stability for hard pipes or electric wires, and are therefore prized.

However, toxicity is still a big problem in this case, and to avoid this, some stability has been achieved by reducing the amount added or using a combination of other metals, but it is still not sufficient. Furthermore, improving stability has become a major challenge for the industry.

For this reason, it has been desired to develop a stabilizer that uses metal soaps other than cadmium and lead plates and has further improved thermal stability.

Furthermore, with recent advances in processing technology for halogen-containing resins, there has been a strong demand for excellent non-toxic stabilizers that prevent thermal decomposition during molding at high temperatures, and there is a need for something that can withstand harsh working conditions throughout various molding processes. It is said that

To meet this demand, less toxic dioctyltin compound-based or dimethyltin-based stabilizers have been developed and put into practical use, but problems remain in long-term workability during molding.

In order to solve these problems, the present invention was developed by Nagisa et al. After a long period of intensive research, it has a thermal stability comparable to that of cadmium and lead, and has improved coloring properties and transparency. It has been found that a stabilizer composition having the following properties can be obtained.

That is, the present invention provides a halogen-containing resin containing (1) Zn salt, (2)
At least one metal salt selected from Ca, Mg, Ba, Sr and Sn salts, (3) an acetal or ketal compound of a trivalent or higher polyhydric alcohol having at least one free OH group, and (4) an organic The present invention provides a stabilized halogen-containing resin composition containing a phosphite compound.

The composition of the present invention having the above characteristics will be described in detail below.

Zn salt or Ca + Mg, B used in the present invention
a.

Examples of Sr or Sn salts include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, neoacid, 2-ethylhexylic acid, pelargonic acid, capric acid, undecanoic acid, lauric acid, Tridecanoic acid, myristic acid, palmitic acid, isostearic acid, stearic acid, 12-hydroxystearic acid, behenic acid, montanic acid, benzoic acid, monochlorobenzoic acid, p
-tert-butylbenzoic acid, dimethylhydroxybenzoic acid, 3,5-di-tert-butyl-4-hydroxybenzoic acid, toluic acid, dimethylbenzoic acid, ethylbenzoic acid, cumic acid, n-propylbenzoic acid, aminobenzoic acid, N,N-dimethylaminobenzoic acid, acetoxybenzoic acid, salicylic acid, p-1eri-octylsalicylic acid, oleic acid, elaidic acid, +77-luic acid, lylunic acid, thioglycolic acid, mercaptopropionic acid, octylmercaptopropionic acid, etc. m pieces of carboxylic acid, oxalic acid, malonic acid, succinic acid, geltanic acid, adipic acid,
pimelic acid, speric acid, azelaic acid, cepatic acid,
Dihydric carboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, oxyphthalic acid, chlorophthalic acid, aminophthalic acid, maleic acid, fumaric acid, citraconic acid, methaconic acid, itaconic acid, aconitic acid, thiodipropionic acid, etc. Carboxylates such as monoesters or monoamide compounds of monovalent carboxylic acids, trivalent or tetravalent carboxylic acids such as hemimellitic acid, trimellitic acid, merophanic acid, pyromellitic acid, mellitic acid, or di- or triester compounds of said carboxylic acids. ), tert-butylphenol, nonylphenol, dinonylphenol,
Cyclohexylphenol, phenylphenol, octylphenol, phenol, cresol, xylenol, n-butylphenol, isopropylphenol, ethylphenol, isopropylphenol, inoctylphenol, 2-ethylhexylphenol, te
rt-nonylphenol, decylphenol, tert
- ferulates such as octylphenol, isohexylphenol, octadecylphenol, diisobutylphenol, methylpropylphenol, cyamylphenol, methylisohexylphenol, methyl-tert-octylphenol, and octylmercaptan, benzylmercaptan, laurylmercaptan, stearylmercaptan, Allyl mercaptan, methyl mercapcoun, ethyl mercaptan, C3-18 mixed alkyl mercaptan, 2-mercaptoethanol, 1-mercapto-2-propatol, ■-chloro-3-mercapto-2-propatur, triethylene glycol dimercaptan, thiophenol , m-thiocresol, dimethylthiophenol, 4-1-butylthiophenol, t-butylthiofresol, chlorothiophenol,
amylthiophenol, mercaptophenol, inoctyl mercaptoacetate, 2-ethylhexyl mercaptoacetate, lauryl mercaptoacetate, inoctyl β-mercaptopropionate, 2-mercaptopropionate
Ethylhexyl, butyl α-mercaptopropionate,
Examples include mercaptides such as mercaptoacetic acid, α-mercaptopropionic acid, β-mercaptopropionic acid, mercaptovaleric acid, furfuryl mercaptan, and 3-(2′-furfurylthio)propionic acid.

Further, as Sn salts, methylstanoitsuccinic acid, butylstanoitsuccinic acid, octylstanoisuccinic acid, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, dimethyltin sulfide, dibutyltin sulfide, dioctyltin sulfide, dicyclohexyl Tin sulfide, monobutyltin oxide sulfide, methylthiostanoic acid, butylthiostanoic acid, octylthiostanoic acid, dibutyltin laurate, dibutyltin stearate, dioctyltin dioleate, dibutyltin basic laurate, dibutyltin Dicrotonate, dibutyltin bis(butoxydiethylene glycol maleate), dibutyltin dimethacrylate, dibutyltin disinnamate, dioctyltin bis(oleyl maleate), dibutyltin bis(stearyl maleate) dibutyltin itaconate, dioctyltin maleate, cyamyltin bis( cyclohexyl maleate), dimethyltin dicrotonate, diethyltin bis(inoctyl citraconate)
, dipropyltin bis(benzyl maleate), diisobutyltin bis(propyl maleate), dicyclohexyltin maleate, dioctyltin bis(butyl maleate), dibutyltin dimethoxide, dibutyltin dilauroxide, dioctyltin ethylene glycoxide, pentaerythritol.
Dibutyltin oxide condensate, dibutyltin bis(lauryl mercaptide), dimethyltin bis(stearyl mercapquid), monobutyltin tris(lauryl mercaptide), dibutyltin-β-mercaptopropionate,
Dioctyltin-β-mercaptopropionate, dibutyltin mercaptoacetate, monobutyltin tris(in-octylmercaptoacetate), monooctyltin tris(2-ethylhexylmercaptoacetate), dibutyltin bis(isooctylmercaptoacetate), dioctyltin Tin bis(in-octyl mercaptoacetate)
, dioctyltin bis(2ethylhexylmercaptoacetate), dimethyltinbis(inoctylmercaptoacetate), dimethyltinbis(isooctylmercaptopropionate), monobutyltintristintris(isooctylmercaptopropionate), bis [Monobutyldi(isooctoxycarbonylmethylenethio)tin] sulfide, bis[dibutylmono(isooctoxycarbonylmethylenethio)tin] sulfide, monobutylmonochlorotinbis(inoctylmercaptopropionate), monobutylmonochlorotinbis(inoctylmercaptopropionate) octyl mercaptoacetate), monobutyl monochlorotin bis(lauryl mercaptide), 2-ethylhexyl epoxy stearate with dioctyl tin oxide insertion, dibutyl monochlorotin stearate, ethylene taconate olicomer with dibutyl tin oxide insertion ( p: 18
, Sn: 6%), butyl acrylate oligomer
・Dioctyltin oxide insert (p: 13, Sn: 5
%), butyl stearate/dibutyltin oxide insert, dimethyltin dilysylte, dibutyltin bis(ethylcellulosobutyl malate) S bis(dioctyltin laurate) malate, bis(dioctyltin butyl maleate) malate, bis(methyltin) diisooctylthioglycolate) disulfide, bis(methyl/dimethyltin7)/diisooctylthioglycolate) disulfide, bis(methyltindiyneoctylthioglycolate) trisulfide, bis(butyltindiisooctylthio) Alkyltin compounds such as glycolate) trisulfide can also be used.

The preferred addition amount of these metal salts is 0.01 to 2.0 parts by weight for Zn salts and 0.1 to 5.0 parts by weight for other metal salts, based on 100 parts by weight of the resin. As phyto compounds, diphenyldecyl phosphite,
Triphenyl phosphite, tris-nonylphenyl phosphite, tridecyl phosphite, tris (2-ethylhexyl) phosphite, tributyl phosphite, tris (butoxyethyl) phosphite, dilauryl acid phosphite, dibutyl acid phosphite, tris (Dinonylphenyl) phosphite, trilauryl trithiophosphite, trilauryl phosphite, bis(neopentyl glycol)-1,4-cyclohexane dimethyl phosphite, distearyl pentaerythritol diphosphite, diisodecyl pentaerythritol diphosphite, diphenyl acid phosphite,
Tris(lauryl-2-thioethyl) phosphite, tetratridecyl-1,1,3-tris(-27-methyl-5'-i3butyl-4'-oxyphenyl)butane diphosphite, tetra(C1□~ 1.Mixed alkyl)
4, 4'-isopropylidene diphenyl diphosphite, tris(4-oxy-2,5-di-tert-butylphenyl) phosphite, tris(4-oxy-3,5-di-tert-butylphenyl) phosphite, 2- Ethylhexyl diphenyl phosphite, tris(mono-, di-mixed nonylphenyl) phosphite, hydrogenated-4,47-impropylidene diphenol polyphosphite, diphenyl bis[4,4'-n-butylidene bis(2-st) 3-butyl-5-methylphenol)] thiogetanol diphosphite, bis(octylphenyl) bis[4,4
'-n-butylidenebis(2-tert-butyl-5-methylphenol)) 1,6-hexanediol diphosphite, phenyl-4,4'impropylidenediphenol pentaerythritol diphosphite, phenyl diisodecyl phosphite, Tetratridecyl-4,4'-
Examples include n-butylidenebis(2-tert-butyl-5-methylphenol) diphosphite and tris(1,3-genetearoyloxy isopropyl) phosphite.

The amount of these organic phosphite compounds added is preferably 0.01 to 5 parts by weight, particularly preferably 0.3 to 1.5 parts by weight, based on 10 parts by weight of the resin.

Examples of trihydric or higher polyhydric alcohols include glycerin, 2-methyl-2-methylol-1,3-propanediol, 2,4-dihydroxy-3-methylolpenkune, and 1,2,6-hexane. Tetrol, 1,1.
14-dimethylolpropane, 2,2-dimethylol-3
-Hydroxybutane, 1,1.14-limethylolethane, 2,4-dihydroxy-2,4-dimethyl-3-methylolpenkune, 1,2.3-butanetriol, ■.

2.3-Pentanetriol, 2-methyl-1,2゜3
-propanetriol, erythritol, pentaerythritol, 1,2,3.4-pentanetetrol, 1,
3,4.5-hexanetetrol, dipentaerythritol, xylitol, adonitol, sorbitol, mannitol, heftitol, octitol, glucose, fructose, galactose, saccharose, maltose, lactose, 2.2,6.6-titramethylol Examples include cyclohexanol.

Further, as compounds that generate acetals or ketals, there are aldehydes or ketones represented by the following general formula.

R. Indicates a furfuryl group and substituted groups thereof.

When the same symbols are in the same molecule, they may be the same or different.

) Specific examples of the compound represented by the above general formula include the following.

That is, examples of aldehydes include formaldehyde, acetaldehyde, and propionaldehyde.

-butyraldehyde, isobutyraldehyde.

- valeraldehyde, isovaleraldehyde, methylethylaldehyde, trimethylaldehyde, n-hexaldehyde, methyl-n-propylaldehyde, isohexaldehyde, enanthol, octaldehyde, nonaldehyde, decaldehyde, undecaldehyde, tridecaldehyde, myristaldehyde, pentadecaldehyde, palmitaldehyde, stearaldehyde,
Acrolein, crotonaldehyde, vinyl acetaldehyde, α-methylcrotonaldehyde, furfural, nicotinaldehyde, metaldehyde, glycolaldehyde, glyoxal, adipinealdehyde, 2
-Methylglitaraldehyde, α-methylacrolein, 3-methyl-2-buten-1-al, 2-ethylcrotonaldehyde, 2-vinylcrotonaldehyde, hexenal, 2-ethyl-2-hexenal, citronellal, citral, decenal , undecenal, chloroacetaldehyde, dichloroacetaldehyde, trichloroacetaldehyde, chloropropionaldehyde, tribromoacetaldehyde, 3-hydroxy-2,2-dimethylpropanal, 3-hydroxybutyraldehyde, 2,2.4-)! J Methyl-3-hydroxybutyraldehyde, hydroxycitronellal, glyceraldehyde, trimethylolacetaldehyde, citronellyloxyacetaldehyde, 3,7-dimethyl-2゜6-octanonin-1-yl oxyacetaldehyde, methoxycitronellal, 2-mercapto Methylpropionaldehyde, β-methylthiopropionaldehyde, benzaldehyde, m-tolualdehyde, p-tolualdehyde, chlorobenzaldehyde, nitrobenzaldehyde, aminobenzaldehyde, oxybenzaldehyde, methoxybenzaldehyde, p-dimethylaminobenzaldehyde, acetylaldehyde , pyruvaldehyde, ■, 1-dimethoxy 3,5
- Hebucdione, phthalaldehyde, tolylaldehyde, humic aldehyde, tolylacetaldehyde, 3-phenylpropenal, 2-7-chicinnamaldehyde, phenylethylaldehyde, p-butylphenylpropylaldehyde, 2-methyl-3 -(p-isopropylphenyl)propionaldehyde, α-bromocinnamaldehyde, 4-(N,N-dimethylamino)-2-methylbenzaldehyde, 4'-N,N-dimethylaminocinnamaldehyde, 4- Diethylaminobenzaldehyde, 4-(N,N'-diethylamino)
-2-methylbenzaldehyde, 2-methyl-4-(N
-Methyl-N-benzylamino)benzaldehyde, 4
-(N-methyl-N-β-chloroethylamino)benzaldehyde, 4-(N-ethyl-N-β-chloroethylamino))-2-methylbenzaldehyde, 4-(N-methyl-N-β-hydroxyethylamine ) Benzaldehyde, 4-(N-ethyl-N-β-ethyl doxyethyl a))-2-methylbenzaldehyde% 4-(N-
Ethyl N-β-acetoxyethyl)azidobenzaldehyde, 4-acedo□dobenzaldehyde, 4-(N-
methyl-N-cyanoethylamine)benzaldehyde,
4-(N-cyanoethyl-N-benzyl)aminobenzaldehyde, 4-(N,N-dicyanoethylamino)benzaldehyde, 2-methyl-4-(N,N-dicyanoethylamino)benzaldehyde, 4-azidobenzaldehyde, 2 -nitro-5-chlorobenzaldehyde,
Methoxycinnamaldehyde, ethoxybenzaldehyde, butoxybenzaldehyde, acetoxybenzaldehyde, p-Cs56a alkyloxybenzaldehyde, dihydroxybenzaldehyde, 3,4-dimethoxybenzaldehyde, 2-(3゜4-dimethoxyphenyl)acetaldehyde, hydroxymethoxybenz Aldehyde, hydroxybenzaldehyde, 3-benzyloxy-4-methoxybenzaldehyde, 2-methyl-4,5-dimethoxybenzaldehyde, 3-methoxy-4-acetoxybenzaldehyde, 4-hydroxy-
3,5-Dimethoxybenzaldehyde, 3,4゜5-trimethoxybenzaldehyde, 5-chlorosalicylaldehyde, 4-N,N-diethylamino-2-oxybenzaldehyde, 5-nitrosalicylaldehyde, 2-hydroxy-3-methoxy- Examples of ketones include acetone, methyl ethyl ketone, n- Propyl methyl ketone, diethyl ketone, hexanone-2, hexanone-3, methyl t-butyl ketone, diisobutyl ketone, diimpropyl ketone, diisobutyl ketone, dioctyl ketone, stearone, chloroacetone, cyclohexylpropanone, furfurylacetone, acetylacetone, mesityl Oxide, cyclohexanone, benzophenone, acetophenone, propiophenone-di-2-furyl ketone, deoxybenzoin, ■-indenone, pyridone, piperidone, C1-16
Mixed alkyl methyl ketone, n-butyl ethyl ketone,
Ethyl amyl ketone, dioctyl ketone, diethyl ketone, propionylacetone, butyl methyl diketone, C
1~, mixed alkylmethyl diketone, farnesylacetone, 2゜6-dimethyl-2,5-pentadiene-4-
on, methyl vinyl ketone, methyl impropenyl ketone, allyl acetone, 4-methyl-3-pentene-2-
one, 3-decen-2-one, 6-methyl-5-hebuten-2-one, 3,6.10-)dimethylol-3,
9-undedien-2-one, diallylacetone, geranylacetone, protomethylionone, 1,3-dimethacroyl-1-methylpropane, hexachloroacetone, chlorobutanone-2,3,5-dichloro-2-pentanone, 3 -chloroacetylacetone, hexafluoroacetone, 6-anohexan-2-one, acetylmethyl rubisol, 2-methylbutan-2-ol-3
-one, 4-hydroxy-4-methyl-2-pentanone, 5-octano-4-one, 3-hydroxymethyl-2-nonanone, 1-hydroxy-3-decanone, 6,
10-dimethyl-9-undecen-4-ol-2-one, 1,3-dihydroxyacetone, 1.1,3.3-
Tetramethylolacetone, 4-methyl-4-methoxypentaone-2, acetyl aldehyde, virpine aldehyde, 1-dimethoxy-3,5-hebutanedione, methylacetophenone, p-isobutylacetophenone, 4-1-butyl -2,6-dimethylacetophenone, phenylacetone, 6〒phnynyl-5-ethylhexan-4-one, benzylacetone, styryl ethyl ketone, 4-methyl-1-phenyl-1-hexene-3
-one, 5-phenyl-4-hexen-2-one, 5-
Phenylhexen-3-one, 4-phenyl-4-methylpentan-2-one, chloroacetophenone, bromoacetophenone, α-4-dibromoacetophenone, bromoacetyl-4-chlorobenzene, α,α-dibromo-4-chloroacetophenone, ω, ω-dibromo3.
4-dichloroacetophenone, aminoacetophenone,
2-(2'-phenylethylcarbonyl)aniline, p
-dimethylaminoacetophenone, 2-(dimethyla□
))-1-Methyethyl phenyl ketone, 4-acetaminochloroacetophenone, nitroacetophenone, 3
．． 5-dinitro-4-t-butyl-2,6-dimethylacetophenone, 3-nitro-α-bromoacetophenone, ω-(ethylbenzylamino)-m-nitroacetophenone, hydroxyacetophenone, 2-hydroxypropio Phenone, p-hydroxypropiophenone, 4
-(p-hydroxyphenyl)-2-butanone, 2-hydroxy-5-methylacetophenone, methoxyacetophenone, 4-methoxyacetophenone, 0-aminoacetone, 4-(4-methoxyphenyl)-2-butanone, α-phenyl Thioacetophenone, dihydroxyacetophenone, 2-hydroxy-4-methoxyacetophenone, 2,4-dimethoxyacetophenone, 3,4-dimethoxyphenylacetone, 2,4.6-trihydroxypropiophenone, 2,3,4-)dimethoxy Acetophenone, p-chloroacetylphenol, 4-chloroaceto-1,2-diacetoxybenzene, 3,4-dihydroxy-ω-chloroacetophenone, 2-bromo-
4-hydroxyacetophenone, 4-aminoaceto-1
, 2-dihydroxybenzene, 3゜4-dihydroxy-
ω-Methylaminophenone, cyclohexyl phenyl ketone, 4-methylbenzophenone, 2-benzylidenecyclohexanone, chlorobenzophenone, bromobenzophenone, 4,4′-cyanobenzophenone, 4,4
'-Bis(dimethylamino)benzophenone, 4.4'
-bis(diethylamino)benzophenone, 2-amino-5-chlorobenzophenone, 2-ano5゜2'-
Dichlorobenzophenone, 2-(bromoacetylamino)-5-chlorobenzophenone, 2-(bromoacetylamino)-5-chloro-27-chlorobenzophenone,
4.4'-dihydroxybenzophenone, p-methoxybenzophenone, 4-methyl-4'-methoxybenzophenone, 3,4-dimethoxy-4'-methylbenzophenone, 4-octoxybenzophenone, bis(benzoyl-methoxyphenyl)methane, Examples include 4-acryloylhydroxybenzophenone and 4-methacryloylbenzophenone.

Next, a specific example of acetal or kekool is shown.
Formaldehyde mono-1,1,1-trimethylolethane acecool, acetaldehyde human monoerythritol acetal, acetaldehyde monomannitol acecool, formaldehyde monosorbitol acetal, fropionaldehyde monolbitol acetal, myristaldehyde 7-no-1 .2.6-hexanetriol acetal, crotonaldehyde-1,2,3-
7-tantriol acetal, vinyl acetaldehyde-2,2-dimethylol-3-hydroxybutane acecool, furfural monogalactose acetal, tribromoacetaldehydoxylitol acetal, 3
-Hydroxybutyraldehyde monomannitol acetal, isobutyraldehyde mono-2,2,6,6-titramethylolcyclohexanol acecool, cyclopropanaldehyde monopentaerythritol acetal, acetylaldehyde monoglucose acetal, methoxycitronellal monoglucose acecool, benzaldehyde Monopentaerythritol acetal, p
- Dimethylaminobenzaldehyde monosorbitol acecool, methoxycinnamaldehyde monomannitol acetal, dihydroxybenzaldehyde mononrubitol acecool, benzaldehyde monosorbitol acecool, benzaldehyde heptugalactose acecool, penzaldehyde monomannitol acecool, ethoxy Benzaldehyde seven-no-1.1.1-trimethylolethane acecool, benzaldehyde monodipentaerythritol, 2-hydroxy-3-methoxy-
5-nitrobenzaldehyde monoglycerin acetal, benzaldehyde mono-2,4-dihydroxy-2,
4-dimethyl-3-methylolpentane acetal, benzaldehyde 7-no-1.1.1-trimethylolpropane acetal, acetone monoglycerin ketal, diethyl ketone diglycerin ketal, diisopropyl ketone monopentaerythritol ketal furfuryl acetone monon rubitol ketal, Dicyclohexylketone mono-1,2,3-butanetriol ketal, methyl ethyl ketone mono-1,3,4,5-hexanetetrol ketal, stearone monomannitol ketal,
Pyridone monok IJ serine ketal, bromophenone monoheptitol ketal, methyl vinyl ketone monomannitol ketal, 3-hydroxymethyl-2-nonanone monopentaerythritol ketal, acetone monosorbitol ketal, acetone monosaccharo-sketal, n -butyl ethyl ketone monolacto-skekur,
Aminoacetophenone mono-1,2,3-pentanetriol ketal, 2-hydroxypropiophenone monosorbitol ketal, methoxyacetone mono-1,1
, 1-) Limethylolethane ketal, propionyl monoheptitol ketal, bromoacetophenone mono-
2-Methyl-1,2,3-propanetriol ketal, furfurylacetone monoerythritol ketal, 4
-(N-ethyl-N-β-ethoxyethylamino)benzaldehyde monoglycerin acecool, 4-(N,N
-dimethylamino)-2-methylbenzaldehyde monopentaerythritol acecool, 4-diethylaminobenzalde'human monosorbitol acecool, 2-
(3,4-Dimethoxyphenyl)acetaldehydemonone lbitol acecur, acetophenone monosorbitol quecur, acetophenone monopentaerythritol quecur, acetophenone 7-no 1.1.1-)rimethylolpropane ketal, acetophenone Nonmonomannitol ketal, fropiophenone monodipentaerythritol ketal, p-inbutylacetophenone mono-2-methyl-1,2,3-propanetriol ketal, chloroacetophenone mono-1,2,3,4- Pentanetetrol ketal, methoxyacetophenone monogalacto-skecur, cyclohexyl phenyl ketone monomalt-skecur, benzophenone monoglycerin ketal, benzophenone monosorbitol ketal, penzophenone monodipentaerythritol ketal, chlorobenzophenone mono-2-methyl-2- Methylol-1゜3-propanediol ketal, 4,4'-
Bis(dimethylamino)benzophenone monomannitol ketal, 2,2'-dihydroxy-4,4'-jethoxybenzophenone mono-2,4-dihydroxy-3
Examples include -methylolpentankecool, 4,4'-dihydroxybenzophenone monoadonitol ketal, benzophenone monomannitol ketal, cyclohexane monoglycerin ketal, and cyclopropanaldehyde monooctitol acetal.

The amount of these acetal or ketal compounds added is preferably 0.01 to 5.0 parts by weight, particularly preferably 0.1 to 2.0 parts by weight, based on 10 parts by weight of the resin.

The resin composition of the present invention is made by adding the above-mentioned four specific components, and in addition, a phthalate plasticizer or other ester plasticizer, a polyester plasticizer, or a phosphate ester. Needless to say, plasticizers such as plasticizers, epoxy plasticizers, chlorine plasticizers, and other plasticizers can be added as appropriate depending on the application.

Furthermore, it goes without saying that other additives may be added to the composition of the present invention to further improve its performance. Examples of these other additives include antioxidants, light stabilizers, etc. agent, nucleating agent, filler, epoxy stabilizer, organic chelator-1 pigment, antistatic agent, antifogging agent, plate-out inhibitor, surface treatment agent, lubricant, flame retardant, fluorescent agent, antifungal agent, sterilizer agents, photodegradants, non-metallic stabilizers, borate esters, processing aids, mold release agents, and the like.

As these other additives, conventionally well-known compounds can be used. For example, as antioxidants, phenol-based, amine-based, phosphite-based, and sulfur-based antioxidants are used. The one disclosed in Japanese Patent No. 4-9-78692 is used.

As the light stabilizer, benzophenone-based, benzotriazole-based, salicylate-based, substituted acrylonitrile-based, various metal salts or metal chelates, triazine-based, and piperidine-based light stabilizers can be used.
The material disclosed in Japanese Patent No. 9-78692 can be used.

Examples of the halogen-containing resin used in the present invention include the following.

For example, polyvinyl chloride, polyvinyl bromide, polyvinyl fluoride, polyvinylidene chloride, epichlorohydrin rubber, chlorinated polyethylene, chlorinated polypropylene, brominated polyethylene, chlorinated rubber, vinyl chloride-vinyl acetate copolymer, vinyl chloride-ethylene Copolymer, vinyl chloride-propylene copolymer, vinyl chloride-styrene copolymer, vinyl chloride-isobutylene copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl chloride-styrene-maleic anhydride terpolymer , vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer , vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer,
Polymer-containing synthetic resins such as vinyl chloride/acrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, and internally plasticized polyvinyl chloride, or these resin-containing resins and polyethylene, polypropylene, polybutene, polyester, etc. - Polyolefins such as α-olefin polymers such as 3-methylbutene or ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, and copolymers thereof, polymethylene, acrylic resins, styrene and other monomers ( (for example, maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene-styrene copolymers, acrylic ester-butadiene-styrene copolymers, and blends with methacrylic ester-butadiene-styrene copolymers. , block copolymers, graft copolymers, and the like.

The following Examples show the effects of the halogen-containing resin composition of the present invention, but the present invention is not limited by these Examples.

Example 1 In order to examine the effects of the halogen-containing resin composition according to the present invention on thermal stability, etc., a sheet with a thickness of 1 mm was prepared by cross-roll processing using the following formulation, and subjected to a thermal deterioration test at 190°C, initial coloring, A transparency test was conducted.

The results are shown in Table 1 below.

Blend> Polyvinyl chloride resin 100 parts by weight Butyl stearate 1.0 Zinc octoate
1.0 Calcium Stearate
2.0 Trisnonylphenyl phosphite 0.5 Acetal/ketal compounds (Table 1) 0
．． 5 Example 2 In order to examine the effects of the halogen-containing resin composition according to the present invention on thermal stability, etc., a sheet with a thickness of 1 mm was prepared by cross-roll processing with the following formulation, and its thermal stability was measured using a heat aging tester. , Initial colorability and transparency by hot pressing were measured.

The results are shown in Table 2 below.

※※Kusei
Polyvinyl chloride resin Calcium stearate Zinc stearate Tetra C mixed alkyl bisphenol A/diphosphite Citrate stearyl ester acetal/ketal compound (Table 2) Example 3 Thermal stability of halogen-containing resin composition according to the present invention In order to see the effects, a sheet with a thickness of 1 mm was prepared by kneading roll processing with the following formulation, and the same performance test as in Example 1 was conducted.The results are shown in Table 3 below.

Mixture> Vinyl chloride/vinyl acetate (5%) 100 parts by weight Copolymer resin Zinc octoate Magnesium stearate Calcium stearate P-wax Hydrogenated-4,4'-isopropylidene diphenol polyphosphite acetal/ketal Compounds (Table 3) 1.0 Example 4 In order to examine the effects of the halogen-containing resin composition according to the present invention on thermal stability, etc., the following formulation was used to form a halogen-containing resin composition with a thickness of 1.
A sheet was prepared, and its thermal stability using a heat aging tester and initial coloring properties were measured using a heat press process.

The results are shown in Table 4. Blend> Polyvinyl chloride resin 80 parts by weight ABS resin Zinc stearate Calcium stearate Dibutyl tin stearate Distearyl stearate Pentaerythritol diphosphite acetal/ketal compound (Table 4) Example 5 Halogen-containing compound according to the present invention In order to examine the effects of the resin composition on thermal stability, etc., a sheet having a thickness of 1 mm was prepared by kneading roll processing using the following formulation, and the same performance test as in Example 1 was conducted.

The results are shown in Table 5 below.

Blend> Polyvinyl chloride resin 100 parts by weight * * Dioctyl phthalate Epoxidized soybean oil Zinc octoate Barium nonyl phenate Tris (4-oxy-3,5-di-t-butylphenyl) phosphite acetal/ketal compound (No. Table 5) 0.5 Example 6 In order to examine the effects of the combined use of other additives in the halogen-containing resin composition of the present invention, a performance test similar to that of Example 1 was conducted using the following formulation.

However, the thermal deterioration test was conducted at 200°C and the results are shown in Table 6 below.

Polyvinyl chloride resin 100 parts by weight Zinc stearate Calcium benzoate Magnesium stearate 2-ethylhexyl diphenyl phosphite Benzaldehyde Monoterbitol Acecool 0.5 Other additives (Table 6) 0.2

Claims (1)

[Claims] 1. In the halogen-containing resin, (1) Zn salt, (2) Ca,
Mg. At least one metal salt selected from Ba, Sr and Sn salts, (3) an acetal or ketal compound of a trivalent or higher polyhydric alcohol having at least one free OH group, and (4) an organic phosphite compound. A stabilized halogen-containing resin composition.