JP2511101B2 - Stabilization method of chlorine-containing resin - Google Patents

Description

The present invention relates to a method for stabilizing a chlorine-containing resin by adding an organotin compound, a specific thioether compound and a perchloric acid compound together. It can be widely used in molding of the resin.

[Conventional technology]

The chlorine-containing resin is a resin which is liable to be thermally deteriorated mainly by dehydrochlorination during heat molding, and which is very easily colored. Therefore, various stabilizers that suppress deterioration during processing are used. Among them, a method of using an organic tin compound and a perchloric acid compound in combination is disclosed in Japanese Patent Publication No. 57-57056 and Japanese Patent Publication No. 61-113636. Has been done.

[Problems to be solved by the invention]

In the technique of heat-stabilizing the chlorine-containing resin by using the organotin compound and the perchloric acid compound in combination, the heat-stabilizing effect has not yet been satisfactory.

[Means for solving problems]

From the above viewpoints, the present inventors have earnestly conducted research on a stabilizer for further thermally stabilizing a chlorine-containing resin, and as a result, (a) mono- and / or diorganotin compound was added to 100 parts by weight of the chlorine-containing resin. 0.5 to 6
0.001 to 2.0 parts by weight of (b) thioether compound and (c) perchloric acid, metal salt of perchloric acid (metal is Li, Na, K,
Mg, Ca, Sr, Ba and Zn) and at least one kind of perchloric acid-treated inorganic compound in a proportion of 0.0001 to 0.5 part by weight, thereby significantly improving the anti-coloring property and thermal stability of the resin. It was found that the present invention has been completed.

The chlorine-containing resin used in the present invention, for example,
Polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated polyisoprene,
Rubber chloride, 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 Polymer, vinyl chloride-styrene-maleic anhydride terpolymer, vinyl chloride-styrene-acrylonitrile copolymer, vinyl chloride-butadiene copolymer, vinyl chloride-isoprene copolymer, vinyl chloride-chlorinated propylene copolymer Polymer, vinyl chloride-vinylidene chloride-vinyl acetate terpolymer, vinyl chloride-acrylic acid ester copolymer, vinyl chloride-maleic acid ester copolymer, vinyl chloride-
Methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, polymers such as internally plasticized polyvinyl chloride, and chlorine-containing resins thereof and α-olefin polymers such as polyethylene, polypropylene, polybutene and poly-3-methylbutene. Polymer or ethylene-vinyl acetate copolymer, ethylene-propylene copolymer, polystyrene, acrylic resin, copolymer of styrene and other monomer (for example, maleic anhydride, butadiene, acrylonitrile, etc.), acrylonitrile-butadiene Examples thereof include blend polymers such as a styrene copolymer, an acrylic acid ester-butadiene-styrene copolymer, and a methacrylic acid ester-butadiene-styrene copolymer.

Examples of the mono- and / or diorganotin compound used as the component (a) in the present invention include compounds generally used, and examples thereof include the general formula (1) and the general formula (2). [In the formulas (1) and (2), R ¹ and R ² are alkyl groups, alkoxycarbonylethyl groups, X ¹ and X ² are oxygen atoms, sulfur atoms, —S (CH ₂ ) pCOO— and —OCOCH═CHCOO. Represents a group of-in the formula, p represents an integer of 1 or 2. Z is -OCOCH = C
HCOOR ³ , -S (CH ₂ ) qCOOR ⁴ , -OCOR ⁵ and -SR ⁶ are groups of the formula where R ³ , R ⁴ , R ⁵ and R ⁶ are alkyl groups, cycloalkyl groups,
An alkenyl group, an aralkyl group, a phenyl group, an alkoxyalkyl group and a hydroxyalkyl group are shown, and q is an integer of 1 or 2.

Y is R ¹ , Z and a chlorine atom, m is an integer of 0 or 1, and n
Is an integer of 1 to 10, and a is an integer of 1 or 2. ] The compound of these can be mentioned.

To describe the general formulas (1) and (2) in more detail, examples of R ¹ and R ² include an alkyl group having 1 to 12 carbon atoms and an alkoxycarbonylethyl group having 4 to 11 carbon atoms. As an example, an alkyl group is a group such as methyl, ethyl, propyl, butyl, hexyl, octyl, and lauryl, and an alkoxycarbonylethyl group is methoxycarbonylethyl, ethoxycarbonylethyl, propoxycarbonylethyl, butoxycarbonylethyl, octoxycarbonylethyl, etc. A group can be mentioned.

Among the groups represented by Z in the general formula (1), R ³ , R ⁴ , R ⁵ ,
Examples of R ⁶ are alkyl groups having 1 to 18 carbon atoms, cycloalkyl groups, alkenyl groups, aralkyl groups, phenyl groups,
Examples thereof include an alkoxyalkyl group and a hydroxyalkyl group, and specific examples include methyl, ethyl, propyl, isopropyl, butyl, amyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl,
Nonyl, decyl, undecyl, dodecyl, tridecyl,
Examples thereof include groups such as heptadecyl, octadecyl, heneicosyl, allyl, isopropenyl, oleyl, benzyl, methoxybenzyl, isopropylbenzyl, cyclohexyl, methoxyethyl, ethoxyethyl, methoxybutyl, butoxyethyl and hydroxylauryl.

The following are typical examples of the organotin compound represented by the general formula (1).

Dimethyltin bis (methyl maleate), dimethyltin bis
Bis (ethyl maleate), dimethyl tin bis (isopropylamine)
Lumaleate), dimethyltin bis (butyl maleate)
G), dimethyltin bis (hexyl maleate), dimethy
Le tin bis (octyl maleate), dimethyl tin bis (a
Sooctyl maleate), dimethyltin bis (2-ethyl)
Hexyl maleate), dimethyl tin bis (decyl malee)
), Dimethyltin bis (dodecyl maleate), dime
Chill tin bis (tridecyl maleate), dimethyl tin bis
(Octadecyl maleate), dimethyltin bis (oley
Lumaleate), dimethyltin bis (benzyl maleate)
G), dimethyltin bis (methylbenzyl maleate),
Dimethyltin bis (cyclohexyl maleate), Dimethy
Rutin bis (methoxybutyl maleate), dibutyltin vinyl
(Methyl maleate), dibutyl tin bis (ethyl male)
Ate), dibutyltin bis (propyl maleate), di
Butyltin bis (isopropyl maleate), dibutyltin
Bis (butyl maleate), dibutyl tin bis (amylma
), Dibutyltin bis (hexyl maleate),
Dibutyltin bis (heptyl maleate), dibutyltin bis
Su (octyl maleate), dibutyltin bis (isooct
Tilmaleate), dibutyltin bis (2-ethylhexyl)
Lumaleate), dibutyltin bis (nonyl maleate)
G), dibutyltin bis (decyl maleate), dibutyl
Tin bis (dodecyl maleate), dibutyl tin bis (tri
Decyl maleate), dibutyl tin bis (octadecyl maleate)
), Dibutyltin bis (allyl maleate), di
Butyl tin bis (oleyl maleate), dibutyl tin bis
(Benzyl maleate), dibutyltin bis (cyclohexyl
Silmaleate), dibutyltin bis (methoxybutylmerate)
), Dioctyl tin bis (ethyl maleate),
Dioctyl tin bis (propyl maleate), dioctyl
Tin screw (isopropyl maleate), Dioctyl tin screw
(Butyl maleate), Dioctyl tin bis (Hexyluma
), Dioctyl tin bis (octyl male
G), dioctyl tin bis (isooctyl maleate),
Dioctyltin bis (2-ethylhexyl maleate),
Dioctyl tin bis (decyl maleate), dioctyl tin
Bis (dodecyl maleate), dioctyl tin bis (tri
Decyl maleate), dioctyl tin bis (octadecyl)
Maleate), dioctyl tin bis (oleyl malea)
G), dioctyl tin bis (benzyl maleate), geo
Octyl tin bis (cyclohexyl maleate), dioctyl
Rutin bis (methoxybutyl maleate), dilauryl tin
Bis (ethyl maleate), dilauryl tin bis (isoprene
Ropyl maleate), dilauryl tin bis (butyl malee)
), Dilauryl tin bis (hexyl maleate), di
Lauryl tin bis (octyl maleate), dilauryl tin
Bis (isooctyl maleate), dilauryl tin bis
(2-ethylhexyl maleate), dilauryl tin bis
(Decyl maleate), dilauryl tin bis (dodecyl male
), Dilauryl tin bis (tridecyl maleate)
G), dilauryl tin bis (octadecyl maleate),
Dilauryl tin bis (oleyl maleate), dilauryl
Tin bis (benzyl maleate), dilauryl tin bis (shi
Chlohexyl maleate), dilauryl tin bis (meth)
Cibutyl maleate), bis (dimethyltin methyl maleate)
Maleate, bis (dimethyltin ethyl maleate)
G) Maleate, bis (dimethyltin isopropyl male)
Maleate, bis (dimethyltin butyl maleate)
G) Maleate, bis (dimethyltin hexyl maleate
G) Maleate, bis (dimethyltin octyl malea)
G) Maleate, bis (dimethyltin isooctyl malee
Maleate, bis (dimethyltin 2-ethylhexyl)
Lumaleate) maleate, bis (dimethyltin decyluma)
Maleate, bis (dimethyltin dodecyl maleate)
Ate) maleate, bis (dimethyltin tridecyl male)
Ate) maleate, bis (dimethyltin octadecylmerate)
Maleate, bis (dimethyltin oleyl male)
Maleate, bis (dimethyltin benzyl malee)
Maleate, bis (dimethyltin cyclohexylmer)
Maleate, bis (dimethyltin methoxybutyrate)
Lumaleate) maleate, bis (dibutyltin methyl methylate)
Maleate, bis (dibutyltin ethyl malee)
Maleate, bis (dibutyltin propyl maleate)
G) Maleate, bis (dibutyltin isopropyl maleate)
Maleate, bis (dibutyltin butyl maleate)
G) Maleate, bis (dibutyltin amyl maleate)
Maleate, bis (dibutyltin hexyl maleate)
Leate, bis (dibutyltin heptyl maleate) male
ATE, bis (dibutyltin octyl maleate) male
Bis (dibutyltin isooctyl maleate) male
Ate, bis (dibutyltin 2-ethylhexyl maleate
G) Maleate, bis (dibutyltin nonyl maleate)
Maleate, bis (dibutyltin decyl maleate) male
Ate, bis (dibutyltin dodecyl maleate) male
And bis (dibutyltin tridecyl maleate) male
Bis (dibutyltin octadecyl maleate) male
Ate, bis (dibutyltin allyl maleate) maleate
G, bis (dibutyltin oleyl maleate) male
G, bis (dibutyltin benzyl maleate) male
G, bis (dibutyltin cyclohexyl maleate) male
Ate, bis (dibutyltin methoxybutyl maleate)
Maleate, bis (dioctyltin ethyl maleate)
Leate, bis (dioctyl tin propyl maleate)
Leate, bis (dioctyltin isopropyl maleate
G) Maleate, bis (dioctyltin butyl malea)
G) Maleate, bis (dioctyl tin hexyl malea)
G) Maleate, bis (dioctyl tin octyl malea)
G) Maleate, bis (dioctyl tin isooctyl male)
Ate) maleate, bis (dioctyltin 2-ethyl)
Xyl maleate) maleate, bis (dioctyl tinde)
Cyl maleate Maleate, bis (dioctyl tin dode)
Cyl maleate) Maleate, bis (dioctyl tin tri)
Decyl maleate) maleate, bis (dioctyl tin thio)
Kutadecyl Maleate Maleate, Bis (Dioctyl)
Tin oleyl maleate) maleate, bis (dioctyl)
Tin benzyl maleate) maleate, bis (dioctyl)
Tin cyclohexyl maleate) maleate, bis (geo)
Cutyltin methoxybutyl maleate) Maleate, bis
(Dilauryl tin ethyl maleate) Maleate, bis
(Dilauryl tin isopropyl maleate) maleate,
Bis (dilauryl tin butyl maleate) maleate, bi
Su (dilauryl tin hexyl maleate) Maleate, Bi
Su (dilauryl tin octyl maleate) Maleate, Bi
Su (dilauryl tin isooctyl maleate) male
Bis (dilauryl tin 2-ethylhexyl maleate
G) Maleate, bis (dilauryl tin decyl malea)
G) Maleate, bis (dilauryl tin dodecyl malea
G) Maleate, bis (dilauryl tin tridecyl malee
Maleate, bis (dilauryl tin octadecyl sulphate)
Maleate, bis (dilauryl tin oleylma)
Maleate, bis (dilauryltin benzylmareate)
Maleate, bis (dilauryltin cyclohexyl)
Cyl maleate) Maleate, bis (dilauryl tin metho)
Xybutyl maleate) Maleate, bis (dimethyltin)
Methyl maleate) oxide, bis (dimethyltin butyrate)
Lumaleate) oxide, bis (dimethyltin isooctane)
Tilmaleate) oxide, bis (dimethyltin benzide)
Rumaleate) oxide, bis (dibutyltin methylmer)
(Rate) oxide, bis (dibutyltin butyl malee)
Oxide), bis (dibutyltin isooctyl male)
Ato) oxide, bis (dibutyltin benzyl malee)
Oxide), bis (dioctyltin butyl maleate)
G) Oxide, bis (dioctyltin isooctyl male)
Ato) oxide, bis (dioctyltin benzyl male)
Ato) oxide, bis (dilauryltin butyl malee)
Oxide), bis (dilauryltin isooctylmer)
Rate) oxide, bis (dilauryl tin benzyl male)
Oxide), monomethyltin tris (isooctyl)
Rumercaptoacetate), monomethyltin tris (2-
Ethylhexyl mercaptoacetate), Monomethyltin
Tris (octadecyl mercaptoacetate), monomer
Chill tin tris (oleyl mercaptoacetate), mono
Methyl tin tris (methoxybutyl mercaptoacetate)
), Monobutyltin tris (butyl mercaptoacetate)
G), monobutyltin tris (octyl mercaptoacetate)
), Monobutyltin tris (isooctyl mercapto)
Acetate), monobutyltin isooctyl mercaptoa
Cetate sulphide, bis [monobutyltin bisiso
Octyl mercaptoacetate)) Sulfide, Mono
Butyltin tris (2-ethylhexyl mercaptoacetate
), Monobutyltin tris (octadecyl mercapto)
Acetate), monobutyltin tris (oleyl mercap)
Triacetate), monobutyltin tris (benzyl merca)
Buttoacetate), monobutyltin tris (methoxybutyrate)
Rumercaptoacetate), monooctyl tin tris
Tilmercaptoacetate), monooctyltin tris
(Octyl mercapto acetate), Monooctyl tint
Squirrel (isooctyl mercaptoacetate), monooctane
Chill tin tris (2-ethylhexyl mercaptoacetate
G), monooctyltin tris (methoxybutyl mercap)
Acetate, mono (2-methoxycarbonylethyl)
Le) tin tris (isooctyl mercaptoacetate),
Mono (2-ethoxycarbonylethyl) tin tris (iso
Octyl mercaptoacetate), mono (2-butoxy)
Carbonylethyl) tin tris (isooctyl mercapto)
Acetate), mono (2-octoxycarbonylethyl)
Le) tin tris (isooctyl mercaptoacetate),
Dimethyltin bis (isooctyl mercaptoacetate
), Dimethyltin bis (2-ethylhexyl mercapto)
Acetate), dimethyltin bis (octadecyl mercap)
Acetate, dimethyltin bis (oleyl mercapto)
Acetate), dimethyltin bis (methoxybutyl merca)
Acetate, dibutyltin bis (butylmercapto)
Acetate), dibutyltin bis (octyl mercaptoa)
Cetate), dibutyltin bis (isooctyl mercapto)
Acetate), dibutyltin bis (2-ethylhexylme)
Lucaptoacetate), dibutyltin bis (octadecyl)
Mercaptoacetate), dibutyltin bis (oleylme
Lucaptoacetate), dibutyltin bis (benzyl mel
Captoacetate), dibutyltin bis (cyclohexyl)
Mercaptoacetate), dibutyltin bis (methoxybuthate
Tilmercaptoacetate), dioctyltin bis (butyrate)
Rumercaptoacetate), Dioctyltin bis (octy
Rumercaptoacetate), dioctyltin bis (iso
Octyl mercapto acetate), dioctyl tin bis (2
-Ethylhexyl mercaptoacetate), dioctyl
Tin bis (methoxybutyl mercaptoacetate), bis
(2-Methoxycarbonylethyl) tin bis (isooctyl
Rumercaptoacetate), bis (2-ethoxycarbo)
Nylethyl) tin bis (isooctylmercaptoacetate)
G), bis (2-butoxycarbonylethyl) tin bis
(Isooctyl mercaptoacetate), bis (2-o
Ctoxycarbonylethyl) tin bis (isooctyl mel)
Captoacetate), bis (dimethyltinisooctylmeth)
Rucaptoacetate) oxide, bis (dimethyltin 2)
-Ethylhexyl mercaptoacetate) oxide,
Bis (dibutyltin isooctyl mercaptoacetate)
Oxide, bis (dibutyltin 2-ethylhexyl mel)
Captoacetate) oxide, bis (dioctyltin)
Sooctyl mercaptoacetate) oxide, bis
(Dioctyltin 2-ethylhexyl mercaptoacetate
G) Oxide, monomethyltin tris (isooctyl 3
-Mercaptopropionate), monomethyltin tris
(2-ethylhexyl 3-mercaptopropione
G), monomethyltin tris (octadecyl 3-mercap)
Topropionate), monomethyltin tris (oleyl 3
-Mercaptopropionate), monomethyltin tris
(Methoxybutyl 3-mercaptopropionate), mo
Nobutyltin tris (butyl 3-mercaptopropione
G), monobutyltin tris (octyl 3-mercaptope)
Ropionate), monobutyltin tris (isooctyl 3
-Mercaptopropionate), monobutyltin tris
(2-ethylhexyl 3-mercaptopropione
G), monobutyltin tris (octadecyl 3-mercap)
Topropionate), monobutyltin tris (oleyl 3
-Mercaptopropionate), monobutyltin tris
(Benzyl 3-mercaptopropionate), monobutyrate
Rutin tris (methoxybutyl 3-mercaptopropione
), Monooctyltin tris (butyl 3-mercapto)
Propionate), monooctyl tin tris (octyl 3)
-Mercaptopropionate), monooctyltin tris
(Isooctyl 3-mercaptopropionate), mono
Octyl tin tris (2-ethylhexyl 3-mercapto
Propionate), monooctyltin tris (methoxybutyrate)
Chill 3-mercaptopropionate), monolauryl tin
Tris (2-ethylhexyl 3-mercaptopropione
), Mono (2-methoxycarbonylethyl) tin tri
Su (isooctyl 3-mercaptopropionate), moth
No (2-ethoxycarbonylethyl) tin tris (iso)
Cutyl 3-mercaptopropionate), Mono (2-bu
Toxycarbonylethyl) tin tris (isooctyl 3-
Mercaptopropionate), Mono (2-octoxyca)
Lubonylethyl) tin tris (isooctyl 3-mercap)
Topropionate), dimethyltin bis (isooctyl 3
-Mercaptopropionate), dimethyltin bis (2-
Ethylhexyl 3-mercaptopropionate), dime
Chill tin bis (octadecyl 3-mercaptopropione
), Dimethyltin bis (oleyl 3-mercaptopropy
Onate), dimethyltin bis (methoxybutyl 3-mel)
Captopropionate), dibutyltin bis (butyl 3-
Mercaptopropionate), dibutyltin bis (octy
3-mercaptopropionate), dibutyltin bis
(Isooctyl 3-mercaptopropionate), dib
Cyltin bis (2-ethylhexyl 3-mercaptopropyi
Onate), dibutyltin bis (octadecyl 3-merca
(Ptopropionate), dibutyltin bis (oleyl 3-
Mercaptopropionate), dibutyltin bis (benzi)
3-mercaptopropionate), dibutyltin bis
(Cyclohexyl 3-mercaptopropionate), di
Butyltin bis (methoxybutyl 3-mercaptopropio
Nate), dioctyltin bis (butyl 3-mercaptope)
Ropionate), dioctyl tin bis (octyl 3-mel
Captopropionate), dioctyltin bis (isooctane)
Chill 3-mercaptopropionate), dioctyltin vinyl chloride
Sus (2-ethylhexyl 3-mercaptopropione
G), dioctyltin bis (methoxybutyl 3-mercap)
Topropionate), dilauryl tin bis (2-ethyl
Xyl 3-mercaptopropionate), bis (2-me
Toxycarbonylethyl) tin bis (isooctyl 3-me
Lucaptopropionate), bis (2-ethoxycarbo)
Nylethyl) tin bis (isooctyl 3-mercaptopro
Pionate), bis (2-butoxycarbonylethyl)
Tin bis (isooctyl 3-mercaptopropione
G), bis (2-octoxycarbonylethyl) tin bis
(Isooctyl 3-mercaptopropionate), bis
(Dimethyltin isooctyl 3-mercaptopropione
G) Oxide, bis (dimethyltin 2-ethylhexyl)
3-mercaptopropionate) oxide, bis (di)
Butyltin isooctyl 3-mercaptopropionate)
Oxide, bis (dibutyltin isooctyl 3-merca
Ptopropionate) Sulfaide, Bis (dibutyltin)
2-ethylhexyl 3-mercaptopropionate)
Side, bis (dioctyl tin isooctyl 3-merca
Bis (dioctyltin) oxide, bis (dioctyltin) oxide
2-ethylhexyl 3-mercaptopropionate)
Cide, bis (dibutyltin lauryl mercaptide)
Sulfaid, bis (dibutyltin lauryl mercap tie
De) Mercaptoacetate, bis (dibutyltin lauryl)
Mercaptide) 3-mercaptopropionate, mono
Methyltin triacetate, monomethyltin tripropione
, Monomethyltin trioctoate, monomethyltin
Lilaurate, monomethyltin tripalmitate, monomer
Chill tin tristearate, monomethyl tin tribehenene
Monomethyltin tribenzoate, monomethyltin tribenzoate
Methacrylate, monobutyltin triacetate, monobu
Chill tin tripropionate, monobutyl tin trioctoe
Monobutyltin trilaurate, monobutyltin trilaurate
Palmitate, monobutyltin tristearate, monobu
Chill tin tribehenate, monobutyl tin tribenzoate
Monobutyltin trimethacrylate, monooctyltin
Triacetate, monooctyltin tripropionate,
Monooctyl tin trioctoate, Monooctyl tin tri
Laurate, monooctyl tin tripalmitate, monoo
Octyl tin tristearate, monooctyl tin tribehene
, Monooctyl tin tribenzoate, monooctyl
Tin trimethacrylate, monolauryl tin triacetate
G, monolauryl tin tripropionate, monolauryl
Tin trioctoate, monolauryl tin trilaurate,
Monolauryl tin tripalmitate, monolauryl tin tri
Stearate, monolauryl tin tribehenate, monora
Uryl tin tribenzoate, monolauryl tin trimetac
Relate, 2-butoxycarbonylethyl tin trilaurate
, Dimethyltin dilaurate, dibutyltin dilaurate
Dioctyl tin dilaurate, dilauryl tin dilaurate
Bis (2-butoxycarbonylethyl) tin dilaurate
Rate, monomethyltin tris (lauryl mercaptai
De), monomethyltin tris (stearyl mercaptai)
De), monobutyltin tris (lauryl mercaptie)
De), monobutyltin tris (stearyl mercaptie)
De), monooctyl tin tris (lauryl mercap tie)
De), monooctyl tin tris (stearyl mercaptai)
De), monolauryl tin tris (lauryl mercap tie
De), monolauryl tin tris (stearyl mercaptie)
De), 2-butoxycarbonylethyl tin tris (lauri
Rumercaptide), 2-butoxycarbonylethyltin
Tris (stearyl mercaptide), dimethyltin bis
(Lauryl mercaptide), dibutyltin bis (lauryl
Rumercaptide), dibutyltin bis (benzylmerca)
Ptide, dioctyl tin bis (lauryl mercap tie)
De), dilauryl tin bis (lauryl mercaptide),
Bis (2-butoxycarbonylethyl) tin bis (lauri
Rumercaptide), monomethyltin tris (monohydro)
Xylauryl mercaptide), dimethyltin bis (mono)
Hydroxylauryl mercaptide), monobutyltin
Squirrel (monohydroxylauryl mercaptide), jib
Chill tin bis (monohydroxy lauryl mercap tie
De), monooctyl tin tris (monohydroxylauryl)
Mercaptide), dilauryl tin bis (monohydroxy)
Lauryl mercaptide), 2-butoxycarbonyl ether
Chill tin tris (monohydroxy lauryl mercap tie
), Bis (2-butoxycarbonylethyl) tin bis
(Monohydroxylauryl mercaptide), bis (di
Butyl tin laurate) oxide, bis (dibutyl tin la)
Urate) maleate, bis (dibutyltin laurate)
Sulfaid, Monobutyltin Tris (Butyl Malea)
G), monobutyltin monochlorobis (butyl malee)
G), monobutyltin monochlorobis (isooctyl mel)
Captoacetate), monobutyltin monochlorobis (a)
Sooctyl 3-mercaptopropionate), monobutyrate
Le tin monochloro dilaurate, monobutyl tin monochloro
Dilauryl mercaptide, bis (monobutyltin bis
(Monobutyl maleate) oxide, bis (monobutyrate)
Rutin bis (isooctyl mercaptoacetate))
Side, bis (monobutyltin bis (isooctyl 3-me
(Lucaptopropionate)) oxide, bis (monobu)
Chill tin dilaurate) oxide, bis (monobutyl tin)
Bis (butyl maleate) sulphide, bis (mono)
Butyltin bis (isooctyl mercaptoacetate))
Sulfaid, bis (monobutyltin bis (isooctyl
3-Mercaptopropionate)) Sulfaide, bis
(Monobutyltin dilaurate) Sulfaide, Bis
Nobutyltin dilauryl mercaptide) sulphide,
Bis (monobutyltin bis (butyl maleate)) Merca
Putoacetate, bis (monobutyltin bis (isooctyl
Rumercaptoacetate)) Mercaptoacetate, Bi
Su (monobutyltin bis (isooctyl 3-mercaptope
Ropionate)) mercaptoacetate, bis (monobu)
Chill tin dilaurate) mercaptoacetate, bis (molybdenum)
Nobutyltin dilauryl mercaptide) mercaptoacetate
Tate, bis (monobutyltin bis (monobutyl maleate
)) 3-Mercaptopropionate, bis (monobutyrate)
Rutin bis (isooctyl mercaptoacetate)) 3-
Mercaptopropionate, bis (monobutyltin bis
(Isooctyl 3-mercaptopropionate)) 3-
Mercaptopropionate, bis (monobutyltin dilau
Rate) 3-mercaptopropionate, bis (monobu
Chill tin dilauryl mercaptide) 3-mercaptopro
Pionate, bis (monobutyltin bis (butyl malea
G)) Maleate, bis (monobutyltin bis (isooctane)
Tilmercaptoacetate)) maleate, bis (mono)
Butyltin bis (isooctyl 3-mercaptopropione
)) Maleate, bis (monobutyltin dilaurate)
G) Maleate, bis (monobutyltin dilauryl merca)
Ptide, maleate, bis (monobutyltin monochloro)
Monobutyl maleate) oxide and the like, which are preferable.
Examples include dibutyltin bis (methyl maleate), dibutyltin bis (methyl maleate),
Butyl tin bis (butyl maleate), dibutyl tin bis
(Isooctyl maleate), dibutyltin bis (2-d)
Tylhexyl maleate), dibutyltin bis (tridecyl)
Lumaleate), dibutyltin bis (octadecyl malee
), Dibutyltin bis (oleyl maleate), jib
Chill tin bis (benzyl maleate), dibutyl tin bis
(Cyclohexyl maleate), dioctyl tin bis (butene)
Til maleate), dioctyl tin bis (isooctylma
), Dioctyltin bis (2-ethylhexylma)
Dioctyl tin bis (tridecyl maleate)
G), dioctyl tin bis (octadecyl maleate),
Dioctyl tin bis (oleyl maleate), dioctyl
Tin bis (benzyl maleate), Dioctyl tin bis (Si
Chlohexyl maleate), bis (dibutyltin methyl methacrylate)
Maleate, bis (dibutyltin butyl malee)
Maleate, bis (dibutyltin isooctyl male)
Ate) maleate, bis (dibutyltin 2-ethylhexe)
Cyl maleate) Maleate, bis (dibutyltin tride)
Syl maleate) Maleate, bis (dibutyltin octa)
Decyl maleate) maleate, bis (dibutyl tin ole)
Il maleate) Maleate, bis (dibutyltin benzide)
Lumaleate) maleate, bis (dibutyltin cyclohexyl)
Xylmaleate) maleate, bis (dioctyltin sulphate)
Chill maleate) maleate, bis (dioctyl tin iso)
Octyl maleate Maleate, bis (dioctyl tin)
2-ethylhexyl maleate) maleate, bis (diethyl)
Octyl tin tridecyl maleate) maleate, bis
(Dioctyl tin octadecyl maleate) Maleate,
Bis (dioctyl tin oleyl maleate) maleate,
Bis (dioctyltin benzyl maleate) maleate,
Bis (dioctyltin cyclohexyl maleate) male
Bis (dibutyltin methyl maleate) oxai
Bis (dibutyltin butyl maleate) oxide,
Bis (dibutyltin benzyl maleate) oxide, Bi
Su (dioctyltin butyl maleate) oxide, bis
(Dioctyltin benzyl maleate) Oxide, dib
Chill tin bis (isooctyl mercaptoacetate), di
Butyltin bis (2-ethylhexyl mercaptoacetate
), Dioctyl tin bis (isooctyl mercaptoacetate
Tate), dioctyltin bis (2-ethylhexyl mel)
Captoacetate), dibutyltin bis (isooctyl 3
-Mercaptopropionate), dibutyltin bis (2-
Ethylhexyl 3-mercaptopropionate), dib
Chilltin bis (methoxybutyl 3-mercaptopropione
Dioctyltin bis (isooctyl 3-mercap)
Topropionate), dioctyltin bis (2-ethyl
Xyl 3-mercaptopropionate), bis (dibutyrate)
Rutin isooctyl 3-mercaptopropionate) Oki
Side, bis (dibutyltin 2-ethylhexyl 3-mel
Captopropionate) oxide, bis (dioctyl)
Tin isooctyl 3-mercaptopropionate) oxa
Id, bis (dioctyltin 2-ethylhexyl 3-mel
Captopropionate) oxide, etc.
Wear.

The following are typical examples of the organotin compound represented by the general formula (2).

Methylstannoic acid, butylstannoic acid, octylstannoic acid, laurylstannoic acid, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dimethyltin sulphide, dibutyltin sulphide, dioctyltin Sulfaide, monobutyltin oxide / sulfaide, methyl thiostannoic acid, butyl thiostannoic acid,
Octyl thiostanoic acid, lauryl thiostanoic acid, monomethyltin mercaptoacetate, dimethyltin mercaptoacetate, monobutyltin mercaptoacetate, dibutyltin mercaptoacetate, monooctyltin mercaptoacetate, dioctyltin mercaptoacetate, monolauryltin mercaptoacetate , Dilauryltin mercaptoacetate, 2-butoxycarbonylethyltin mercaptoacetate, bis (2-butoxycarbonylethyl) tin mercaptoacetate, monomethyltin 3-mercaptopropionate, dimethyltin 3-mercaptopropionate, monobutyltin 3-mercapto Propionate, dibutyltin 3-mercaptopropionate, monooctyltin 3-mercaptopropionate, dioctyltin 3-me Mercaptopropionate, monolauryl tin 3-mercaptopropionate, dilauryl tin 3-
Mercaptopropionate, 2-butoxycarbonylethyltin 3-mercaptopropionate, bis (2-butoxycarbonylethyl) tin 3-mercaptopropionate, monomethyltin maleate, dimethyltin maleate,
Monobutyl tin maleate, dibutyl tin maleate, monooctyl tin maleate, dioctyl tin maleate, monolauryl tin maleate, dilauryl tin maleate and polymers thereof, and the like, with preferred examples being dibutyl tin mercapto acetate and dibutyl tin 3-mercaptopropio. And dioctyltin mercaptoacetate, dioctyltin 3-mercaptopropionate, dibutyltin maleate, dioctyltin maleate and polymers thereof.

Examples of the thioether compounds used as the component (b) in the present invention include thioacetals, thioketals, thioethercarboxylic acids and thioether compounds. To describe in more detail, the thioacetal compounds are represented by the general formulas (3) and (4) (In the formula, R ⁷ is hydrogen, a C ₁ -C ₁₈ alkyl group, a C ₆ -C ₁₄ aryl group and a hydroxyaryl group, and R ⁸ is a C ₁ -C ₁₈ alkyl group, C ₆ -C ₁₄ Aryl group and hydroxyaryl group, C _{7 to} C ₁₅ aralkyl group, R ⁹ is C _{1 to} C ₁₈ alkylene group, C _{6 to} C ₁₄ cycloalkylene group, arylene group and hydroxyarylene group and direct bond) The thioketal compound, which is a compound represented by the general formula (5), (6), (7) and (8) (In the formula, R ¹⁰ is hydrogen, a C _{1 to} C ₁₈ alkyl group, a cyclohexyl group, a C _{6 to} C ₁₄ aryl group and a hydroxyaryl group, a C _{2 to} C ₂₇ hydroxycarbonylalkyl group,
Alkyloxycarbonyl group, an aralkyloxycarbonyl group and cyclohexyl oxycarbonyl alkyl group, a C ₃ -C _10, hydroxyalkyl alkylthioalkyl group alkyloxycarbonyl group, an aralkyloxycarbonyl group and cyclohexyl oxycarbonyl group, R ¹¹ is , A C ₁ -C ₅ alkylene group, R ¹² is a C ₁ -C ₁₅ alkanetriyl group, M
¹ is hydrogen, a C ₁ -C ₁₈ alkyl group, a hydroxyalkyl group, an aryl group and a metal, a cyclohexyl group, a hydroxycyclohexyl group), and the thioethercarboxylic acid compound is, for example, a compound represented by the general formula (9 ), (10), (11), (1
2), (13) and (14) R ¹³ -S-R ¹⁴ COOM ² (9) S (-R ¹⁴ COOM ² ) ₂ (10) S (-R ¹⁶ -S-R ¹³ ) ₂ (13) (In the formula, R ¹³ is hydrogen, a C _{1 to} C ₁₈ alkyl group and a hydroxyalkyl group, a C _{6 to} C ₁₈ aryl group, a hydroxyaryl group, an aralkyl group and a hydroxyaralkyl group, a cyclohexyl group, a hydroxycyclohexyl group. Group, R ¹⁴ is a C _{1 to} C ₅ alkylene group, R ¹⁵ is a C _{1 to} C ₅ alkanetriyl group, R ¹⁶ and R ¹⁷ are of the formula —R ¹⁴ —COOR ¹⁴ —
Group, M ² is a compound represented by M ¹ synonymous), thioether compounds, for example, the general formula ^{(15) R 18 -S-R} 19 (15) ( wherein, R ¹⁸ and R ^19, R ¹³ and synonyms, except for the case where both are hydrogen).

Typical examples of the thioether compounds as the component (b) include the following.

No.33 C ₁₂ H ₂₅ SC ₂ H ₄ COOH No. 40 C ₈ H ₁₇ SC ₂ H ₄ COONa No. 41 C ₈ H ₁₇ SC ₂ H ₄ COOLi No. 42 C ₈ H ₁₇ SC ₂ H ₄ COOK No. 43 (C ₈ H ₁₇ SC ₂ H ₄ COO) ₂ Ca No.44 (C ₈ H ₁₇ SC ₂ H ₄ COO) ₂ Ba No. 45 (C ₈ H ₁₇ SC ₂ H ₄ COO) ₂ Sr No. 46 (C ₈ H ₁₇ SC ₂ H ₄ COO) ₃ Ce No.47 (C ₈ H ₁₇ SC ₂ H ₄ COO) ₂ Zn No. 51 C ₁₂ H ₂₅ OOCC ₂ H ₄ SC ₂ H ₄ COOC ₁₂ H ₂₅ No. 52 HOOCC ₂ H ₄ SC ₂ H ₄ COOH No.60 HSC ₂ H ₄ COOH No.61 HSC ₂ H ₄ COOC ₈ H ₁₇ No.64 HOC ₂ H ₄ SC ₂ H ₄ OH Next, the perchloric acid compound used as the component (c) in the present invention will be specifically described. The perchlorate is a metal salt of perchloric acid or Examples thereof include ammonium salts, and examples of the metal include LI, Na, K, Mg, Ca, Sr, Ba and Zn. Further, the perchloric acid-treated inorganic compound is a compound which is generally commercially available, for example, an inorganic compound such as hydrotalcite, alumina, aluminum hydroxide, silicic acid and silicate treated with perchloric acid or the aqueous solution thereof. However, the ratio of the inorganic compound and perchloric acid at the time of treatment may be arbitrary, and the form after treatment is preferably powder.

Typical examples of the perchloric acid compound as the component (c) include the following.

Perchloric acid Barium perchlorate Calcium perchlorate Zinc perchlorate Magnesium perchlorate Sodium perchlorate Lithium perchlorate Potassium perchlorate Strontium perchlorate Ammonium perchlorate Perchloric acid treatment Hydrotalcite perchloric acid treatment Alumina Perchloric acid-treated aluminum hydroxide Perchloric acid-treated silicate Perchloric acid-treated silicic acid In the present invention, the addition amount of the mono- and / or diorganotin compound of the component (a) to the chlorine-containing resin is particularly limited. However, it is usually based on 100 parts by weight of the resin.
The amount is 0.1 to 10 parts by weight, and the amount less than 0.1 parts by weight has almost no heat stabilizing effect, and the amount exceeding 10 parts by weight does not show the expected heat stabilizing effect, preferably about 0.5 to 6.0 parts by weight. The addition amount of the thioether compound represented by the general formulas (3) to (15) of the component (b) is usually 0.001 to 2.0 parts by weight. If it is less than 0.001 parts by weight, there is almost no heat stabilizing effect and 2.0 parts by weight is added. If it exceeds, the heat stabilization effect is inferior or the coloration of the resin becomes strong, preferably 0.01 to 1.0.
Parts by weight. Further, the addition amount of perchloric acid, perchlorate, and perchloric acid-treated inorganic compound as the component (c) is usually 0.0001 to 0.5 parts by weight in terms of perchloric acid, and if less than 0.0001 parts by weight, there is almost no heat stabilizing effect. If the amount exceeds 0.5 parts by weight, there is no heat stabilizing effect and the deterioration of the resin occurs rapidly.
The preferable addition amount is about 0.0005 to 0.1 part by weight.

The method of adding the stabilizers of the components (a), (b) and (c) used in the present invention to the chlorine-containing resin may be a conventionally known method. For example, the resin and the stabilizer may be Henschel. Mixing may be carried out with a mixer, ribbon blender, Banbury mixer or the like, or one-pack of the stabilizer used in the present invention may be mixed with the resin by the above-mentioned mixer.

Further other additives to the stabilizer used in the present invention, for example, ultraviolet absorbers, epoxy compounds, organophosphorus compounds,
Processing aids, lubricants, plasticizers, fillers, pigments and the like can be used in combination.

〔Example〕

Hereinafter, the present invention will be described specifically with reference to Examples.
The present invention is not limited by these. The number of parts added in the examples means parts by weight. The mono- and / or di-organotin compounds of the component (a) used in this example are represented by the following a to i, and the thioether compounds represented by the general formulas (3) to (15) of the component (b) are described in detail. N in the book
o.1 to No. 64, and the component (c), perchloric acid, perchlorate and perchloric acid-treated inorganic compound, is in the specification.

[Organotin compound]

I. Di-n-butyltin maleate b. Di-n-butyltin bis (butyl maleate) c. Di-n-butyltin bis (cyclohexyl maleate) d. Di-n-butyltin bis (2-ethylhexyl maleate) e. Di-n-butyltin bis (benzyl maleate) f. Di-n-butyltin bis (methoxybutyl maleate). Di-n-butyltin bis (oleyl maleate) C. Bis (di-n-butyltin methyl maleate) maleate Di-n-octyltin bis (2-ethylhexyl maleate) Nu. Dimethyltin bis (isooctyl mercaptoacetate) ru. Di-n-butyltin bis (isooctyl mercaptoacetate) e. Di-n-butyltin bis (isooctyl 3-mercaptopropionate) Wa. Di-n-butyltin bis (methoxybutyl 3-mercaptopropionate) moss. Bis (di-n-butyltin isooctyl 3-mercaptopropionate) oxide yo. Di-n-octyltin bis (isooctyl mercaptoacetate) ta. Di-n-lauryl tin bis (isooctyl mercaptoacetate) Re. Bis (2-butoxycarbonylethyl) tin bis (isooctyl mercaptoacetate) So. Di-n-butyltin sulfoxide. Di-n-butyltin dilauryl mercaptide Ne. Di-n-butyltin dilaurate Na. Di-n-butyltin mercaptoacetate La. Di-n-butyltin 3-mercaptopropionate. Mono-n-butyl thiostannoic acid c. Mono-n-butyltin tris (isooctyl mercaptoacetate) 〰. Mono-n-butyltin monochlorobis (isooctyl mercaptoacetate) The perchloric acid used in this example is actually a 1% aqueous solution, but the number of parts described in the examples is 100% perchloric acid conversion value. The addition amount of the perchlorate and the perchloric acid-treated inorganic compound is the amount of the compound itself.

The evaluation of the coloring property by the press test in the examples is abbreviated as follows.

A. Colorless or white D. Yellow brown B. Light yellow or light yellow white E. Brown C. Yellow or yellow white F. Black Example 1 Polyvinyl chloride [Neon Zeon Co., Ltd., Geon 103EP-
8] A mixture having 100 parts of the stabilizers shown in [Table-1] and [Table-2] was kneaded with an 8-inch test roll adjusted to 160 ° C for 5 minutes, and then a sample having a thickness of 0.5 mm was prepared. did.

This sheet was cut, and the sheet was put into a gear type aging tester set at 195 ° C. and the time (minutes) until deterioration (brown or blackening) was measured to evaluate thermal stability.

In addition, eight cut sheets are stacked, put in a press die, and a plate is molded with a heating press at 200 ° C for 40 minutes at 100 kg / cm ² ,
The colorability and transparency of the plate were visually evaluated.

Sample Nos. 1 to 12 are examples of the present invention, and Nos. 13 to 19 are comparative examples.

As is clear from the effects of [Table-1] and [Table-2], as shown in Samples No. 1 to No. 12, the combination of the organic tin compound, the thioether compound, and perchloric acid It can be seen that the thermal stability is greatly improved and the press coloring property is also excellent. Organotin compounds and thioethers were used more than sample No. 13 organotin compounds alone, sample No. 14 organotin compounds with thioether compounds, and sample No. 15 organotin compounds with perchloric acid. It can be seen that the combined effect of the compound and perchloric acid is excellent. Furthermore, in the case of thioether compounds alone in sample No.16 and perchloric acid in sample No.17 alone, when the addition amount of thioether compounds was too large as in sample No.18, the excess amount as in sample no.19 was observed. It can be seen that when the amount of chloric acid added is too large, the heat stabilizing effect is significantly inferior.

Example 2. Similar to Example 1, a test was conducted under the following formulation, kneading conditions and test conditions to evaluate thermal stability and colorability.
The results are shown in [Table-3] to [Table-5].

<Compounding> Geon103Ep-8 100 parts Kane Ace FM ^* 20 parts Stabilizers Shown in [Table-3] to [Table-5].

(* Kanebuchi Chemical Industry Co., Ltd. acrylic toughener) <Kneading conditions> Roll temperature 160 ℃ Kneading time 5 minutes <Test conditions> Gear type aging test 190 ℃ Press test 190 ℃, 50 minutes, 80kg / cm ² Sample Nos. 1 to 28 are Examples of the present invention, and Nos. 29 to 35 are Comparative Examples.

Among the inorganic compounds treated with perchloric acid, perchlorate and perchloric acid ,,, and are treated with 0.5 mol of perchloric acid per 1 mol of the following compound, respectively.

Hydrotalcite DHA-4A manufactured by Kyowa Chemical Industry Co., Ltd. is a fine powder alumina, aluminum hydroxide, calcium silicate, Carprex # 80 manufactured by Shionogi Pharmaceutical Co., Ltd. [Table-3] to [Table- As is apparent from the effect of [5], various organotin mercaptides of the component (a), the thioether compounds of the component (b) of the present invention, and the perchloric acid of the component (c), as in Samples No. 1 to No. 28. It can be seen that the combined use with the compound has an excellent heat stabilizing effect.

Also, as can be seen from Samples No. 29, No. 30, and No. 35, it can be seen that the thermal stabilization effect is inferior even if any one component is missing. It can be seen that the compound alone or the perchloric acid compound alone has almost no heat stabilizing effect.

Furthermore, if the amount of thioether compounds and the amount of perchloric acid compounds added are too large, as in Samples No. 33 and No. 34, the heat stabilization effect will be significantly reduced even with the combination of the three. I understand.

Example 3. Tests were carried out under the following formulation, kneading conditions and test conditions in the same manner as in Example 1 to evaluate thermal stability and colorability.
The results are shown in [Table-6] and [Table-7].

<Compounding> Kanevinyl S-1007 ^* 50 parts Tufflex TFX-410 ^** 50 parts Di-n-butyltin maleate 3 parts Other stabilizers [Table-6] and [Table-7].

(* Polyvinyl chloride manufactured by Kanegafuchi Chemical Co., Ltd.) (* Acrylonitrile manufactured by Mitsubishi Monsanto Kasei Co., Ltd.)
Butadiene-styrene copolymer) <Kneading conditions> Roll temperature 155 ℃ Kneading time 5 minutes <Test conditions> Gear type aging test 220 ℃ Press test 210 ℃, 60 minutes, 20kg / cm ² Sample numbers 1 to 20 are examples of the present invention, and sample numbers 21 to 26 are comparative examples.

Used in the examples are those used in Example 2.

As is apparent from the effects of [Table-6] and [Table-7], the organotin compound of the component (a) and the thioether compound of the component (b) are also present in this formulation as in Samples No. 1 to No. 20. It can be seen that the combination of (3) with the perchloric acid compound as the component (c) has an excellent heat stabilizing effect.

〔The invention's effect〕

The present invention significantly improves the thermal stability of a chlorine-containing resin by adding together an organotin compound, a specific thioether compound and a perchloric acid compound to the chlorine-containing resin when stabilizing the resin. It is also possible to prevent the resin from being colored.

Front page continuation (72) Inventor Masaharu Akitsu 788, Hisachi, Takatsu-ku, Kawasaki-shi, Kanagawa Sansha Machinery Co., Ltd. (56) Reference JP 62-252445 (JP, A) JP 61-231041 ( JP, A) JP 53-59744 (JP, A) JP 63-268756 (JP, A)

Claims (1)

(57) [Claims] 1. When stabilizing a chlorine-containing resin, 0.5 to 6 parts by weight of (a) mono- and / or diorganotin compound and 0.001 to 2.0 parts of (b) thioether compound are added to 100 parts by weight of chlorine-containing resin. Parts by weight and (c) perchloric acid, metal salts of perchloric acid (metals are Li, Na, K, M
g, Ca, Sr, Ba and Zn) and at least one of perchloric acid-treated inorganic compounds in a proportion of 0.0001 to 0.5 parts by weight, which is a method for stabilizing a chlorine-containing resin.