JP2511030B2 - Stabilization method of chlorine-containing resin - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for stabilizing a chlorine-containing resin by adding an organotin compound and perchloric acid, and widely used in molding of the resin. Can be used.

[Conventional technology]

A 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 JP-B-57-57056 and JP-A-61-113636. Has been done. The perchloric acid compounds used in these are those obtained by impregnating and treating an inorganic compound carrier with a metal salt of perchloric acid or perchloric acid. The third stabilizer was used in combination.

[Problems to be solved by the invention]

Thus, the perchloric acid compound conventionally used as a stabilizer for chlorine-containing resins is a metal salt of perchloric acid, or an inorganic compound carrier such as hydrotalcite, aluminum hydroxide, colloidal alumina, or silicate. Is impregnated and treated with perchloric acid. When a metal salt of perchloric acid or an inorganic compound carrier is added to a chlorine-containing resin,
In order to reduce the transparency of the molded product, and in order not to reduce the transparency, the addition amount of the metal salt of perchloric acid or the inorganic compound carrier must be very small. With the addition, almost no thermal stabilization effect could be expected. In fact, when an organic tin compound is added to a chlorine-containing resin together with an inorganic compound carrier that has been impregnated and treated with a trace amount of a metal salt of perchloric acid or perchloric acid, it is compared to the case where the organotin compound is added alone. Therefore, the heat stabilizing effect was almost unchanged or inferior, and the effect of using both in combination was hardly found.

[Means for solving problems]

In the field where the transparency of the chlorine-containing resin molded product is required from such a viewpoint, the present inventors maintain the transparency originally possessed by the organotin compound as it is, and at the same time, have a color-preventing ability and a heat stabilizing effect. As a result of extensive research on stabilizers that are excellent and have excellent anti-coloring and heat stabilizing effects even in opaque fields using organotin compounds, chlorine-containing resins are used in combination with organotin compounds and trace amounts of perchloric acid. By adding
The present invention has been completed by finding that the coloration-preventing property and heat stability of the resin are remarkably improved and the transparency is not lowered even when the transparency is required.

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-
Polymers such as methacrylic acid ester copolymers, vinyl chloride-acrylonitrile copolymers, internally plasticized polyvinyl chloride, and the like, 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 ester, a butadiene-styrene copolymer, and a melicryl ester-butadiene-styrene copolymer.

Examples of the organotin compound used in the present invention include compounds commonly used, and examples thereof include the general formula (1) and / or the general formula (2). [In the formulas (1) and (2), R and R ¹ are alkyl groups, alkoxycarbonylethyl groups, X and X ¹ are oxygen atoms, sulfur atoms, —S (CH ₂ ) _P COO— and —OCOCH═CHCOO— In the formula, p represents an integer of 1 or 2. Z is -OCOCH = C
_{^{HCOOR 2, -S (CH 2)}} g COOR 3, -OCOR ^4, and -SR be ⁵ groups formulas ^{R 2, R 3, R 4} , R 5 is an alkyl group, a cycloalkyl group,
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, 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. ] Can be mentioned.

The general formulas (1) and (2) will be described in more detail. R and R ¹ are an alkyl group having 1 to 12 carbon atoms and 4 carbon atoms.
Alkoxycarbonylethyl group of ~ 11 can be mentioned, as a specific example, an alkyl group is a group such as methyl, ethyl, propyl, butyl, hexyl, octyl, lauryl,
Examples of the alkoxycarbonylethyl group include groups such as methoxycarbonylethyl, ethoxycarbonylethyl, propoxycarbonylethyl, butoxycarbonylethyl-octoxycarbonylethyl and the like.

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

Specific examples of the organic tin compound represented by the general formula (1) include the following.

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 (dimethyltinhexyl 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 melamine)
(Rate) oxide, monomethyltin tris (isooctane)
Tilmercaptoacetate), monomethyltin tris (2
-Ethylhexyl mercaptoacetate), monomethyl
Tin tris (octadecyl mercaptoacetate), mono
Methyl tin tris (oleyl mercaptoacetate),
Nomethyltin tris (methoxybutyl mercaptoacetate
G) Monobutyltin tris (butylmercaptoacetate)
G), monobutyltin tris (octyl mercaptoacetate)
), Monobutyltin tris (isooctyl mercapto)
Acetate), monobutyltin isooctyl mercaptoa
Cetate sulfide, bis [monobutyltin bis (a
Sooctyl mercaptoacetate)) Sulfide, mo
Nobutyltin tris (2-ethylhexyl mercaptoacetate
Tate), monobutyltin tris (octadecyl mercap)
Triacetate), monobutyltin tris (oleyl merca)
Ptoacetate), monobutyltin tris (benzyl mel)
Captoacetate), monobutyltin tris (methoxybu
Tilmercaptoacetate), monooctyltin tris
(Butyl mercaptoacetate), monooctyl tin tri
Su (octyl mercaptoacetate), monooctyl tin
Tris (isooctyl mercaptoacetate), Monoo
Cutyltin tris (2-ethylhexyl mercaptoacetate
), Monooctyl tin tris (methoxybutyl merca)
Putoacetate), 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
Mono) octyl tin tris (butyl 3-mercaptope)
Ropionate), monooctyl tin tris (octyl 3-
Mercaptopropionate), monooctyl tin 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, dis (dibutyltin isooctyl 3-merca
Ptopropionate) sulfide, bis (dimethyltin)
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)
Sulfide, bis (dibutyltin lauryl mercaptai
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 trioct
Ate, monobutyltin trilaurate, monobutyltin
Repalmitate, monobutyltin tristearate, mono
Butyltin tribehenate, Monobutyltin 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), bi
Sus (2-butoxycarbonylethyl) tin bis (lauryl
Mercaptide), monomethyltin tris (monohydroxy)
Silauryl mercaptide), dimethyl tin bis (monohi)
Dorosilauryl mercaptide), monobutyltin tris
(Monohydroxylauryl mercaptide), dibutyl
Tin bis (monohydroxylauryl mercaptide), mo
Nooctyl tin tris (monohydroxylauryl mercap
Tide), dilauryl tin bis (monohydroxylauryl
Mercaptide), 2-butoxycarbonylethyltin tin
Squirrel (monohydroxylauryl mercaptide), bis
(2-Butoxycarbonylethyl) tin bis (monohydro
Xylauryl mercaptide), bis (dibutyltin laur)
Rate) oxide, bis (dibutyltin laurate) polymer
Leate, bis (dibutyltin laurate sulfide,
Monobutyltin tris (butyl maleate), monobutyl
Tin monochlorobis (butyl maleate), monobutyl tin
Monochlorobis (isooctyl mercaptoacetate
G), monobutyltin monochlorobis (isooctyl 3-
Mercaptopropionate), monobutyltin monochloro
Dilaurate, monobutyltin monochlorodilauryl mel
Captide, bis (monobutyltin bis (monobutylmale
Ate) oxide, bis (monobutyltin bis (isoo)
(Cutyl mercaptoacetate)) oxide, bis (molybdenum)
Nobutyltin bis (isooctyl 3-mercaptopropio
Nate) oxide, bis (monobutyltin dilaurate)
G) Oxide, bis (monobutyltin bis (butyl male)
)) Sulfide, bis (monobutyltin bis (ii)
Sooctyl mercaptoacetate)) Sulfide, Bi
Su (monobutyltin bis (isooctyl 3-mercaptope
Ropionate)) Sulfide, bis (monobutyltin di)
Laurate) sulfide, bis (monobutyltin dilaurate)
Rylmercaptide) sulfide, bis (monobutyl)
Tin bis (butyl maleate)) mercaptoacetate,
Bis (monobutyltin bis (isooctyl mercaptoacetate
Tate)) mercaptoacetate, bis (monobutyltin)
Bis (isooctyl 3-mercaptopropionate))
Mercaptoacetate, bis (monobutyltin dilaurate)
G) Mercaptoacetate, bis (monobutyltin dilaurate)
Rilmercaptide) mercaptoacetate, bis
Nobutyltin bis (monobutyl maleate)) 3-merca
Putopropionate, bis (monobutyltin bis (isoo
Butyl mercaptoacetate)) 3-Mercaptopropy
Onate, bis (monobutyltin bis (isooctyl 3-
Mercaptopropionate)) 3-Mercaptopropionate
Nate, bis (monobutyltin dilaurate) 3-merca
Putopropionate, bis (monobutyltin dilauryl ester)
Lucaptide) 3-mercaptopropionate, bis
(Monobutyltin bis (butyl maleate)) Male
Bis (monobutyltin bis (isooctyl mercapto
Acetate)) Maleate, bis (monobutyltin bis)
(Isooctyl 3-mercaptopropionate)) Male
Ate, bis (monobutyltin dilaurate) male
Bis (monobutyltin dilauryl mercaptide)
Leate, bis (monobutyltin monochloromonobutylmer
Rate) oxide or the like, and a preferable example thereof is
Dibutyltin bis (methyl maleate), dibutyltin bis
(Butyl maleate), Dibutyltin bis (isooctyl
Maleate), dibutyltin bis (2-ethylhexylma)
), Dibutyltin bis (tridecyl maleate)
G), dibutyltin bis (octadecyl maleate), di
Butyl tin bis (oleyl maleate), dibutyl tin bis
(Benzyl maleate), dibutyltin bis (cyclohexyl
Syl maleate), dioctyl tin bis (butyl maleate)
G), dioctyl tin bis (isooctyl maleate),
Dioctyltin bis (2-ethylhexyl maleate),
Dioctyl tin bis (tridecyl maleate), Dioctyl
Rutin bis (octadecyl maleate), dioctyl tin bis
Su (oleyl maleate), dioctyl tin bis (benz
Lumaleate), dioctyltin bis (cyclohexylmer)
Maleate), bis (dibutyltin methyl maleate) male
ATE, bis (dibutyltin butyl maleate) male
G, bis (dibutyltin isooctyl maleate) male
Bis (dibutyltin 2-ethylhexyl maleate)
G) Maleate, bis (dibutyltin tridecyl maleate)
G) Maleate, bis (dibutyltin octadecyl malee
Maleate, bis (dibutyltin oleyl maleate)
G) Maleate, bis (dibutyltinbenzylmaleate)
G) Maleate, bis (dibutyltin cyclohexyl male)
Ate) maleate, bis (dioctyltin butyl malee)
Maleate, bis (dioctyltin isooctylmaate)
Maleate, bis (dioctyltin 2-ethyl)
Hexyl maleate Maleate, bis (dioctyl tin)
Tridecyl maleate) maleate, bis (dioctyl)
Tin octadecyl maleate) maleate, bis (dioc
Chill tin oleyl maleate) maleate, bis (dioc
Chill tin benzyl maleate) maleate, bis (dioc
Chill tin cyclohexyl maleate) maleate, bis
(Dibutyltin methyl maleate) oxide, bis (di
Butyltin butyl maleate) oxide, bis (dibutyrate)
Rutin benzyl maleate) oxide, bis (dioctyl)
Rutin butyl maleate) oxide, bis (dioctyl)
Tin benzyl maleate) oxide, dibutyltin bis
(Isooctyl mercaptoacetate), dibutyltin vinyl
Su (2-ethylhexyl mercaptoacetate), geo
Octyl tin bis (isooctyl mercaptoacetate),
Dioctyltin bis (2-ethylhexyl mercaptoacetate
Tate), dibutyltin bis (isooctyl 3-mercap)
Topropionate), dibutyltin bis (2-ethylhexyl)
Sil-3-mercaptopropionate), dibutyltin bis
(Methoxybutyl 3-mercaptopropionate), di
Octyl tin bis (isooctyl 3-mercaptopropio
Nate), dioctyltin bis (2-ethylhexyl 3-
Mercaptopropionate), bis (dibutyltin iseo)
Cutyl 3-mercaptopropionate) Oxide, Bi
Su (dibutyltin 2-ethylhexyl 3-mercaptopro
Pionate) oxide, bis (dioctyltin isooctane)
Tyl 3-mercaptopropionate) oxide, bis
(Dioctyltin 2-ethylhexyl 3-mercaptopro
Pionate) oxide and the like can be mentioned.

Specific examples of the organotin compound represented by the general formula (2) include the following.

Methyl stanoic acid, butyl stanoic acid, octyl stanoic acid, lauryl stanoic acid, dimethyltin oxide, dibutyltin oxide, dioctyltin oxide, dilauryltin oxide, dimethyltin sulfide, dibutyltin sulfide, dioctyltin oxide Sulfide, monobutyltin oxide sulfide, 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, and preferable examples include dimethyl tin mercaptoacetate and dibutyl tin 3-mercaptopropio. And dioctyltin mercaptoacetate, dioctyltin 3-mercaptopropionate, dibutyltin maleate, dioctyltin maleate and polymers thereof.

The perchloric acid used in the present invention is preferably used in the state of an aqueous solution. When the organic tin compound and the aqueous solution of perchloric acid are used in one pack, it is preferable to dehydrate them in advance.

In the present invention, the amount of the organotin compound added to the chlorine-containing resin can be used without particular limitation, but the effective range is 0.1 to 10 parts by weight, preferably 1 to 6 parts by weight with respect to 100 parts by weight of the resin. Parts by weight.

Also, the amount of perchloric acid used in combination may be very small, and the purity is 10
0.005 to 0.5 wt% of the organic tin compound is preferable in terms of 0%, and 0.01 to 0.3 wt% is particularly preferable.

The method of adding the stabilizer used in the present invention to the chlorine-containing resin may be carried out by a conventionally known technique, for example,
The resin and the stabilizer may be mixed with a Henschel mixer, a ribbon blender, a Banbury mixer, or the like, or an organotin compound and perchloric acid that have been prepacked in one pack are mixed with the resin with the above-described mixer. Good.

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

〔Example〕

Hereinafter, the present invention will be described in detail 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 stabilizers and their abbreviations used in this example are shown below.

(I) Organotin compound (1) Monomethyltin tris (isooctylmercaptoacetate) MM (TGIO) ₃ (2) Dimethyltin bis (isooctylmercaptoacetate) DM (TGIO) ₂ (3) Dimethyltin bis (isooctyl 3- Mercaptopropionate) DM (MPIO) ₂ (4) Mono-n-butyltin thiostanoic acid MBS (5) Mono-n-butyltin tris (isooctylmercaptoacetate) MB (TGIO) ₃ (6) Mono-n- Butyltin monochlorobis (isooctylmercaptoacetate) MBC (TGIO) ₂ (7) Di-n-butyltin dilaurate DBL (8) Di-n-butyltin maleate DBM (9) Di-n-butyltin bis (methylmale) ) DB (M
eM) ₂ (10) Di-n-butyltin bis (butyl maleate) DB (B
uM) ₂ (11) Di-n-butyltin bis (cyclohexyl maleate) DB (CyHM) ₂ (12) Di-n-butyltin bis (2-ethylhexyl maleate) DB (2EHM) ₂ (13) Di- n-Butyltin bis (benzyl maleate) DB
(BeM) ₂ (14) Di-n-butyltin bis (methoxybutyl maleate) DB (MeOBuM) ₂ (15) Di-n-butyltin bis (oleyl maleate) DB
(OlM) ₂ (16) Di-n-butyltin sulfide DBS (17) Di-n-butyltin bis (lauryl mercaptide) DB (SL) ₂ (18) Di-n-butyltin mercaptoacetate DBTG (19 ) Di-n-butyltin bis (isooctyl mercaptoacetate) DB (TGIO) ₂ (20) Di-n-butyltin bis (2-ethylhexylmercaptoacetate) DB (TG2EH) ₂ (21) Di-n-butyltin Bis (methoxybutyl mercaptoacetate) DB (TGMeOBu) ₂ (22) di-n-butyltin 3-mercaptopropionate
DBMP (23) Di-n-butyltin bis (2-ethylhexyl 3-
Mercaptopropionate) DB (MP2EH) ₂ (24) Di-n-butyltin bis (isooctyl 3-mercaptopropionate) DB (MPIO) ₂ (25) Di-n-butyltin bis (methoxybutyl 3-mercapto Propionate) DB (MPMeOBu) ₂ (26) Bis (di-n-butyltin isooctyl 3-mercaptopropionate) oxide (DB (MPIO)) ₂ O (27) Di-n-octyltin bis (2- Ethylhexyl maleate) DO (2EHM) ₂ (28) Di-n-octyltin bis (isooctyl mercaptoacetate) DO (TGIO) ₂ (29) Di-n-octyltin bis (isooctyl 3-mercaptopropionate) DO (MPIO) ₂ (30) Di-n-lauryltin bis (isooctyl mercaptoacetate) DL (TGIO) ₂ (31) Di-n-lauryltin bis (isooctyl 3-mercaptopropionate) DL (MPIO) ₂ ( 32) Screw (2 Butoxycarbonyl-ethyl) tin bis (isooctyl _{mercaptoacetate) (BCE) 2 (TGIO)} 2 (33) bis (di -n- butyl tin maleate) maleate (DBMeM) ₂ M (II) perchlorate compound (1 ) Perchloric acid ^* PCA (2) Magnesium perchlorate PCMg (3) Calcium perchlorate PCCa (4) Zinc perchlorate PCZn (5) Barium perchlorate PCBa (6) Perchloric acid treated hydrotalcite PCTHT ( 7) Perchloric acid treated alumina PCTAl (8) Perchloric acid treated aluminum silicate PCTSiAl (9) Perchloric acid treated aluminum hydroxide PCTAlH (10) Perchloric acid impregnated silicate PCSSiS (11) Perchloric acid impregnated silicic acid PCSSi (*) The actually used perchloric acid (PCA) is a 1% aqueous solution, but the number of parts described in the following examples is the PCA 100% conversion value. (6) to (9) are the corresponding inorganic compounds Per 100 g of perchloric acid It was treated at a rate of 10 g in 100% conversion, and the compounds (10) and (11) contained 1% of perchloric acid in 100% conversion per 100 g of the corresponding inorganic compound.
It was impregnated at a rate of 0 g. ) Further, the evaluation of the coloring property and the transparency by the press test in the examples is abbreviated as follows. Coloring Colorless-A Yellow-brown-E Light yellow-B Brown-F Yellow-C Black-brown-G Dark yellow-D Black-H Transparency is very good-A Poor-D Good-B Very poor-E Somewhat inferior -C None -F Example 1 Polyvinyl chloride [Nippon Zeon Co., Ltd., Geon 103EP-
8] A mixture having 100 parts of the stabilizers shown in [Table-1] to [Table-4] 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 piled up, put in a press mold, and a plate is molded by a heating press machine at 195 ° C. for 40 minutes at 100 kg / cm ² ,
The colorability and transparency of the plate were visually evaluated.

As is apparent from the effects of [Table-1] and [Table-2], comparing Sample Nos. 1 and 1'shows that the combined use of the organic tin compound and perchloric acid shows the thermal stability by the gear type aging tester. It can be seen that the transparency and the colorability by the press test are excellent, and the transparency is not deteriorated. Also, comparing sample No. 1 and 2'to 15 ', a combination of an organotin compound and a metal salt of perchloric acid or a combination of an inorganic compound carrier impregnated with perchloric acid and treated It can be seen from the results that the combination of the organic tin compound and the trace amount of perchloric acid is remarkably excellent in thermal stability, colorability and transparency.

As is clear from the effects of [Table-3] and [Table-4], sample Nos. 1 and 1 ', 2 and 2', 3 and 3 ', 4 and 4', 5 and 5 ', 6 and 6 'Compared respectively, the combined effect of the organic tin compound and perchloric acid is excellent in thermal stability and colorability,
It can be seen that the decrease in transparency is not seen.
Also, it can be seen that perchloric acid alone has almost no thermal stability.

Example 2 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, colorability and transparency. The results are shown in [Table-5] and [Table-6].

<Compounding> Geon103EP-8 100 parts MBS (BTA-3S) ^* 5 parts Stabilizers Shown in [Table-5] and [Table-6].

(* Methacrylic acid ester-butadiene-styrene copolymer manufactured by Kureha Co., Ltd.) <Kneading conditions> Roll temperature 160 ° C Kneading time 5 minutes <Test conditions> Gear type aging test 195 ° C Press test 190 ° C, 50 minutes, 100kg / cm ² As is clear from the effects of [Table-5] and [Table-6], sample Nos. 1 and 1'and 1 ", 2 and 2 ', 3 and 3', 4 and 4 ', 5
And 5 ', 6 and 6', respectively, show that the effect of the combined use of the organotin compound and perchloric acid is that the organotin compound alone or the organotin and the perchloric acid-treated inorganic compound carrier. It can be seen that it is far superior to the case of using it together.

Example 3 The press colorability was evaluated with the same formulation as in Example 2. The results are shown in [Table-7] to [Table-11].

The colorability of the press test shows the colorability after 190 minutes at 190 ° C.

Sample No.1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,1
7, 18 and 19 are examples, respectively, and sample Nos. 1 ', 2', 3 ', 4',
5 ', 6', 7 ', 8', 9 ', 10', 11 ', 12', 12 ", 13 ', 14',
15 ', 16', 17 ', 18' and 19 'are comparative examples.

As is clear from the effects of [Table-7] to [Table-11], sample Nos. 1 and 1 ', 2 and 2', 3 and 3'4 and 4 ', 5 and 5', 6 and 6 ', 7 and 7', 8 and 8'9 and 9 ', 10 and 10', 11
11 ', 12 and 12' and 12 ", 13 and 13 ', 14 and 14', 15 and 15 ', 16
And 16 ', 17 and 17', 18 and 18 ', 19 and 19', respectively, comparing the organotin compound with perchloric acid, the organotin compound alone or the organotin compound and the compound It can be seen that the coloring property is far superior to the case where the metal salt of chloric acid is used in combination.

Example 4 Acrylonitrile-butadiene-styrene copolymer [manufactured by Mitsubishi Monsanto Kasei Co., Ltd., Tflex TFX-41
0] 50 parts, polyvinyl chloride [Neon Zeon Co., Geon
103EP-8] A mixture having 50 parts of the stabilizers shown in [Table-12] and [Table-13] was kneaded for 5 minutes with an 8-inch test roll adjusted to 160 ° C, and then a sheet having a thickness of 0.5 mm. Was produced.

This sheet was cut, and the sheet was put in a gear type aging tester set at 220 ° C. and the time (minutes) until deterioration was measured to evaluate thermal stability.

Also, stack the 8 cut sheets and put them in the press mold.
A plate was molded with a heating press machine at 210 ° C. for 60 minutes at 50 kg / cm ² , and the colorability of the plate was visually evaluated.

As is clear from the effects of [Table-12] and [Table-13], sample Nos. 1 and 1 ', 1 ", 1, 2 and 2', 3 and 3 ', 4 and 4', 5 and 5 ′ Is compared, the case where the organotin compound and the perchloric acid are used together, the organotin alone or the metal salt of perchloric acid or the inorganic compound carrier impregnated with perchloric acid is used in combination. It is clear that the effect is far superior to the case.

〔The invention's effect〕

The present invention, when stabilizing the chlorine-containing resin, by adding an organic tin compound and a trace amount of perchloric acid together, it is possible to significantly improve the coloration-preventing property and the thermal stability, and the transparency is improved. The required molded product can be stabilized without lowering the transparency.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hirokazu Ono, 788, Kuchi, Takatsu-ku, Kawasaki City, Sansan Machinery Co., Ltd. (56) Reference JP-A-62-252445 (JP, A)

Claims (1)

(57) [Claims] 1. An organic tin compound is added to 100 parts by weight of a chlorine-containing resin.
0.1-10 parts by weight and perchloric acid 0.005-0.5 of the organotin compound
A method for stabilizing the resin, characterized in that the resin is added together with wt%.