JPH01236252A - Stabilization of chlorinated resin - Google Patents

Abstract

PURPOSE:To improve the heat stability of a chlorinated resin and to prevent its discoloration, by adding at least one member selected from among an organotin compound, a specified thioether compound and a perchloric acid (salt) and a perchloric acid-treated inorganic compound to said resin. CONSTITUTION:100pts.wt. chlorinated resin (e.g., PVC resin) is mixed with 0.1-10pts.wt. common mono- and/or di-organotin compounds (e.g., di-n-butyltin maleate), 0.001-2.0pts.wt. thioether compound which is a thioacetal, a thioketal, a thioethercarboxylic acid or a thioether compound (e.g., a compound of the formula), 0.0001-0.5pt.wt. (in terms of perchloric acid) at least one compound selected from perchloric acid (salt) and a perchloric acid-treated inorganic compound, and optionally, additives such as an ultraviolet absorber.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a method of stabilizing a chlorine-containing resin by adding an organotin compound, a specific thioether compound, and a perchloric acid compound in combination. It can be widely used in the molding process of the resin.

[Conventional technology]

Chlorine-containing resins are resins that are susceptible to thermal deterioration, mainly due to dehydrochlorination, and are very susceptible to coloration during hot molding. For this reason, various stabilizers are used to suppress deterioration during processing, and among these, 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 Application Laid-Open No. 61-113636. has been done.

[Problem that the invention seeks to solve]

In the technology of thermally stabilizing chlorine-containing resins by using these organic tin compounds and perchloric acid compounds in combination, the thermal stabilizing effect has not yet been satisfactory.

[Means for solving problems]

From this point of view, the present inventors have conducted intensive research on stabilizers for further thermally stabilizing chlorine-containing resins, and have found that (a) mono and /-! or a diorganic field compound and (bl) a thioether compound and (c) at least one of perchloric acid, perchlorate, and a perchloric acid-treated inorganic compound, thereby improving the coloring prevention properties and thermal stability of the resin. The present invention has been completed based on the discovery that this can significantly improve the

Examples of the chlorine-containing resin used in the present invention include polyvinyl chloride, polyvinylidene chloride, chlorinated polyethylene, chlorinated polypropylene, chlorinated polyisoprene, 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 ternary copolymer Coalescence, chlorination and nyl-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, Polymers such as vinyl chloride-maleic acid ester copolymer, vinyl chloride-methacrylic acid ester copolymer, vinyl chloride-acrylonitrile copolymer, internally plasticized polyvinyl chloride,
In addition, α of these chlorine-containing resins and polyethylene, polypropylene, polybutene, poly-3-methylbutene, etc.
- Olefin polymers or ethylene-vinyl acetate copolymers, ethylene-propylene copolymers, polystyrene, acrylic 811i1, copolymers of styrene and other monomers (e.g. maleic anhydride, butadiene, acrylonitrile, etc.) , acrylonitrile-butadiene-styrene copolymer, acrylic acid ester-butadiene-styrene copolymer, methacrylic acid varnish, 7-rubutadiene-styrene copolymer, and other blend polymers.

The mono- and/or di-organic compounds used as component (a) in the present invention include commonly used compounds, such as -Math. (1) and -Math. (2)
) (R2a 5nX2In f
21 [Formula (11, (in 21, R1 and R2 are alkyl groups, alkoxycarbonylethyl groups, Xl and X2 are oxygen atoms, sulfur atoms, -8(cH2)p Coo- and -0
COCH2C) (coo- group, where p represents an integer of 1 or 2. 2 is 10COCH: CHCOO
R3,5(cH2)qCOOR', -0COR5 and -
8R' group, in which R3, R4, R5, and R6 represent an alkyl group, a cycloalkyl group, an alkenyl group, an aralkyl group, a phenyl group, an alkoxyalkyl group, and a hydroxyalkyl group, and in the formula, q is 1' or 2. indicates an integer.

Y is R1,2 and a chlorine atom, m is an integer of 0 or 1,
n represents an integer of 1 to 10, and a represents an integer of 1 or 2.

) can be mentioned.

To explain the formula il+ and (2) in more detail,
R1 and R2 can include an alkyl group having 1 to 12 carbon atoms, an alkoxycarbonylethyl group having 4 to 11 carbon atoms, and specific examples of the alkyl group include methyl, ethyl,
Groups such as propyl, butyl, hexyl, octyl, lauryl, etc., and alkoxycarbonylethyl groups include groups such as methoxycarbonylethyl, ethoxycarbonylethyl, propoxycarbonylethyl, butoxycarbonylethyl, octoxycarbonylethyl, etc. General formula: Among the groups represented by Z in +11, R3, R4, R
5. Examples of R6 include alkyl groups having 1 to 18 carbon atoms, cycloalkyl groups, alkenyl groups, aralkyl groups,
Phenyl group, alkoxyalkyl group and hydroxyalkyl group can be mentioned, and specific examples include methyl,
ethyl, propyl, isopropyl, butyl, hexyl,
octyl, inoctyl, 2-ethylhexyl, decyl, dodecyl, tridecyl, octadecyl, ole-fle,
benzyl, methoxybenzyl, isopropylbenzyl,
Funds such as cyclohexyl, ethoxyethyl, ethoxyethyl, methoxybutyl, butoxyethyl and hydroxylauryl can be deposited.

Representative examples of the organotin compound represented by general formula (1) include the following.

Dimethyltin bis(methyl maleate), dimethyltin bis(ethyl maleate), dimethyltin bis(isopropyl maleate), dimethyltin bis(butyl maleate),
Dimethyltin bis(hexyl maleate), dimethyltin bis(octyl maleate), dimethyltin bis(inoctyl maleate), dimethyltin bis(2-ethylhexyl maleate), dimethyltin bis(decyl maleate)
, dimethyltin bis(dodecyl maleate), dimethyltin bis(tridecyl maleate), dimethyltin bis(octadecyl maleate), dimethyltin bis(oleyl maleate), dimethyltin bis(benzyl maleate), dimethyltin bis(benzyl maleate) (methylbenzyl maleate), dimethyltin bis(cyclohexyl maleate), dimethyltin bis(
methoxybutyl maleate), dibutyltin bis(methyl maleate), dibutyltin bis(ethyl maleate),
Dibutyltin bis(propyl maleate), dibutyltin bis(isopropyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(amyl maleate)
, dibutyltin bis(hexyl maleate), dibutyltin bis(heptyl maleate), dibutyltin bis(octyl maleate), dibutyltin bis(inoctyl maleate), dibutyltin bis(2-ethylhexyl maleate), dibutyl Tin bis (Noni k? L/ate), dibutyl tin bis (decyl maleate), dibutyl tin bis (
dodecyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin bis(octadecyl maleate), dibutyltin bis(allyl maleate), dibutyltin bis(oleyl maleate), dibutyltin bis(benzyl maleate) , dibutyltin bis(cyclohexyl maleate), dibutyltin bis(methoxybutyl maleate), dioctyltin bis(ethyl maleate), dioctyltin bis(propyl maleate), dioctyltin bis(
isoflobil maleate), dioctyltin bis(butyl maleate), dioctyltin bis(hexyl maleate), dioctyltin bis(octyl maleate), dioctyltin bis(isooctyl maleate), dioctyltin bis(2- ethylhexyl maleate), dioctyltin bis(decyl maleate), dioctyltin bis(dodecyl maleate), dioctyltin bis(tridecyl maleate), dioctyltin bis(octadecyl maleate)
, dioctyltin bis(oleyl maleate), dioctyltin bis(benzyl maleate), dioctyltin bis(
cyclohexyl maleate), dioctyltin bis(methoxybutyl maleate), dilauryltin bis(ethyl maleate), dilauryltin bis(isopropyl maleate), dilauryltin bis(butyl maleate), dilauryltin bis(hexyl maleate) , dilauryltin bis(octyl maleate), dilauryltin bis(inoctyl maleate), dilauryltin bis(2-ethylhexyl maleate), dilauryltin bis(decyl maleate), dilauryltin bis(dodecyl maleate), dilauryltin bis(dodecyl maleate) (tridecyl maleate), dilauryltin bis(octadecyl maleate), dilauryltin bis(
oleyl maleate), dilauryltin bis(benzyl maleate), dilauryltin bis(cyclohexyl maleate), dilauryltin bis(methoxybutyl maleate), bis(dimethyltin methyl maleate) maleate,
Bis(dimethyltin ethyl maleate) maleate, Bis(dimethyltin isopropyl maleate) maleate, His(dimethyltin methyl maleate) maleate, His(
dimethyltin hexyl maleate) maleate, bis(dimethyltin octyl maleate) maleate, bis(dimethyltin octyl maleate) maleate, his(dimethyltin 2-ethylhexyl maleate) maleate,
Bis(dimethyltin dodecyl maleate) maleate, bis(dimethyltin dodecyl maleate) maleate, bis(
dimethyltin tridecyl maleate) maleate, bis(
dimethyltin octadecyl maleate) maleate, bis(dimethyltin oleyl maleate) maleate, his(
dimethyltin benzyl maleate) maleate, bis(dimethyltin cyclohexyl maleate) maleate, bis(dimethyltin methoxybutyl maleate) maleate,
Bis(dibutyltin methyl maleate) maleate, Bis(dibutyltin ethyl maleate) maleate, Bis(dibutyltin furobyl maleate) maleate, Bis(dibutyltin inglobyl maleate) maleate, His(dibutyltin butyl maleate) Maleate, Bis(diptyltin amyl maleate) maleate, Bis(dibutyltin hexyl maleate) maleate, Bis(dibutyltin hexyl maleate) maleate, His(diptyltin octyl maleate) maleate, Bis(diptyltin isooctyl maleate) maleate , bis(diptytin2-
Ethylhexyl maleate) maleate, bis(dibutyltin nonyl maleate) maleate, bis(dibutyltin decyl maleate) maleate, bis(cyphthyl 9-dodecyl maleate) maleate, bis(dibutyltin tridecyl maleate) maleate, bis(diptyltin octadecyl maleate) ) maleate, bis(dibutyltin allyl maleate) maleate, bis(dibutyltin oleyl maleate) maleate, bis(dimethyltin benzyl maleate) maleate, bis(dibutyltin cyclohexyl maleate) maleate, bis(diptyltin methoxybutyl maleate) ate) maleate, His(dioctyltin ethyl maleate) maleate, His(dioctyltin flobyl maleate) maleate, Bis(dioctyltin isopropyl maleate) maleate, His(dioctyltin phthyl maleate) maleate, Bis(dioctyltin hexyl maleate) Maleate, Bis(dioctyltin octyl maleate) maleate, Bis(dioctyltin isooctyl maleate) maleate, Bis(dioctyltin 2-ethylhexyl maleate) maleate, Bis(dioctyltin tesyl maleate) maleate, Bis(dioctyltin dodecyl maleate) ) maleate, bis(dioctyltin tridecyl maleate) maleate, bis(dioctyltin octatecyl maleate) maleate, his(dioctyltin oleyl maleate) maleate, bis(dioctyltin benzyl maleate) maleate, bis(dioctyltin cyclo hexyl maleate) maleate, bis(dioctyltin methoxybutyl maleate) maleate, bis(dilauryl ethyl maleate) maleate, bis(dilauryl tin isopropyl maleate) maleate, bis(dilauryl tin butyl maleate) maleate, bis(dilauryl tin ethyl maleate) maleate hexyl maleate) maleate, bis(dilauryltin octyl maleate) male, ate, bis(dilauryltin octyl maleate) maleate, bis(dilauryltin 2-ethylhexyl maleate) maleate, bis(dilauryltin decyl maleate) maleate, bis(dilauryltin dodecyl maleate) maleate, bis(dilauryl 14
) 1 f syl maleate) maleate, bis(dilauryltin octadecyl maleate) maleate, bis(
dilauryltin oleyl maleate) maleate, bis(
dilauryltinbenzyl maleate) maleate, hiss(
dilauryltin cyclohexyl maleate) maleate,
Bis(silacryltin methoxybutyl maleate) maleate, bis(dimethyltin methyl maleate) oxide, bis(dimethyltin butyl maleate) oxide, bis(dimethyltin octyl maleate) oxide,
Bis(dimethyltin benzyl maleate) oxide, bis(dibutyltin methyl maleate) oxide, bis(
Dibutyltin butyl maleate) oxide, bis(diptytin octyl maleate) oxide, bis(dibutyltin penzyl maleate) oxide, bis(dioctyltin butyl maleate) oxide, bis(dioctyltin isooctyl maleate) oxide , bis(dioctyltin benzyl maleate) oxide, bis(dilauryltin butyl maleate) oxide, bis(dilauryltin isooctyl maleate) oxide, bis(dilauryltin benzyl maleate) oxide, monomethyltin tris(in-octyl mercaptoacetate) ), monomethyltin tris (2-ethylhexylmercaptoacetate), monomethyltin tris (octadecylmercaptoacetate), monomethyltin tris (oleyl mercaptoacetate), monomethyltin tris (methoxybutylmercaptoacetate), motuputyltin tris (butylmercaptoacetate) ), motsputyltin tris (octylmercaptoacetate), motsputyltin tris (inoctylmercaptoacetate), motsputyltin isooctylmercaptoacetate sulfide, bis[
Monobutyltin bis(in-octylmercaptoacetate) sulfide, Motuptiltin tris(2-ethylhexylmercaptoacetate), Motuptiltin tris(2-ethylhexylmercaptoacetate)
octadecylmercaptoacetate), motsputyltin tris (oleyl mercaptoacetate), motsputyltin tris (benzyl mercaptoacetate), motsputyltin tris (methoxybutyl mercaptoacetate), monooctyltin tris (butyl mercaptoacetate),
Monooctyltin tris (octylmercaptoacetate), monooctyltin tris (inoctylmercaptoacetate), monooctyltin tris (2-ethylhexylmercaptoacetate), monooctyltin tris (methoxybutylmercaptoacetate), mono(2- methoxycarbonylethyl)tin tris(isooctylmercaptoacetate), mono(2-ethoxycarbonylethyl)tintris(isooctylmercaptoacetate),
Mono(2-butoxycarbonylethyl)tin tris(in-octyl mercaptoacetate), mono(2-octoxycarbonylethyl) tin tris(in-octyl mercaptoacetate), dimethyltin bis(in-octyl mercaptoacetate), dimethyltin bis(in-octyl mercaptoacetate) -ethylhexylmercaptoacetate), dimethyltinbis(octadecylmercaptoacetate), dimethyltinbis(oleylmercaptoacetate), dimethyltinbis(methoxybutylmercaptoacetate), dibutyltinbis(butylmercaptoacetate), dibutyltinbis(octyl mercaptoacetate), dibutyltin bis(inoctyl mercaptoacetate), dibutyltin bis(2-ethylhexylmercaptoacetate), dibutyltin bis(
octadecyl mercaptoacetate), dibutyltin bis(oleyl mercaptoacetate), dibutyltin bis(
benzylmercaptoacetate), dibutyltin bis(cyclohexylmercaptoacetate), dibutyltin bis(methoxybutylmercaptoacetate), dioctyltin bis(butylmercaptoacetate), dioctyltin bis(octylmercaptoacetate), dioctyltin bis(isooctyl) mercaptoacetate), dioctyltin bis(2-ethylhexylmercaptoacetate)
, dioctyltin bis(methoxybutylmercaptoacetate), bis(2-methoxycarbonylethyl)tinbis(inoctylmercaptoacetate), bis(2-ethoxycarbonylethyl)tinbis(inoctylmercaptoacetate), bis(2-butoxy carbonylethyl)tin bis(isooctylmercaptoacetate), bis(2-octoxycarbonylethyl)tinbis(isooctylmercaptoacetate), bis(dimethyltin octylmercaptoacetate) oxide, bis(dimethyltin 2-ethylhexyl) mercaptoacetate) oxide, bis(diptyltin isooctylmercaptoacetate) oxide, bis(dibutyltin 2-ethylhexyl mercaptoacetate) oxide, bis(dioctyltin octylmercaptoacetate) oxide, bis(dioctyltin 2-ethylhexyl) mercaptoacetate) oxide, monobutyltin tris (isooctyl 3-mercaptopropionate), monobutyltin tris (2-ethylhexyl 3-mercaptopropionate), monobutyltin tris (octadecyl 3-mercaptopropionate), monobutyltin tris( oleyl 3-mercaptopropionate), monobutyltin tris (methoxybutyl 3-mercaptopropionate), monobutyltin tris (butyl 3-mercaptopropionate), monobutyltin tris (octyl 3-mercaptopropionate), monobutyl Tin tris (inoctyl 3)
-mercaptopropionate), monobutyltin tris (
2-ethylhexyl 3-mercaptopropionate),
Monobutyltin tris (octadecyl 3-mercaptopropionate), monobutyltin tris (oleyl 3-mercaptopropionate), monobutyltin tris (benzyl 3-mercaptopropionate), monobutyltin tris (methoxybutyl λ-mercaptopropionate) Nate),
Monooctyltin tris (butyl 3-mercaptopropionate), monooctyltin tris (octyl 3-mercaptopropionate), monooctyltin tris (inoctyl 3-mercaptopropionate), monooctyltin tris (2- ethylhexyl 3-mercaptopropionate), monooctyltin tris(methoxybutyl 3-mercaptopropionate),
mercaptopropionate), monolauryltin tris(
2-ethylhexyl 3-mercaptopropionate),
Mono(2-methoxycarbonylethyl)tin tris(inoctyl 3-mercaptopropionate), mono(2-
ethoxycarbonylethyl)tintris(inoctyl3)
-mercaptopropionate), mono(2-butoxycarbonylethyl)tin tris(isooctyl 3-mercaptopropionate), mono(2-octoxycarbonylethyl)tin tris(inoctyl 3-mercaptopropionate), dimethyl Tin bis(isooctyl 3-mercaptopropionate), dimethyltin bis(2-ethylhexyl 3-mercaptopropionate), dimethyltin bis(octadecyl 3-mercaptopropionate), dimethyltin bis(oleyl 3-mercaptopropionate) dimethyltin bis(methoxybutyl 3-mercaptopropionate), diptyltin bis(butyl 3-mercaptopropionate), diptyltin bis(octyl 3-mercaptopropionate), diptyltin bis(isooctyl 3-mercaptopropionate) mercaptopropionate), diptyltin bis(2-ethylhexyl 3-mercaptopropionate)
, diptyltin bis(octadecyl 3-mercaptopropionate), diptyltin bis(oleyl 3-mercaptopropionate), diptyltin bis(benzyl 3-mercaptopropionate), diptyltin bis(cyclohexyl 3-mercaptopropionate) dibutyltin bis(methoxybutyl 3-mercaptopropionate), dioctyltin bis(butyl 3-mercaptopropionate), dioctyltin bis(octyl 3-mercaptopropionate), dioctyltin bis(inoctyl 3-mercaptopropionate), dioctyltin bis(2-ethylhexyl 3-mercaptopropionate), dioctyltin bis(methoxybutyl 3-mercaptopropionate), dilauryltin bis(2-ethylhexyl 3-mercaptopropionate) ), bis(2-methoxycarbonylethyl)tin bis(ynoctyl 3-mercaptopropionate), bis(2-ethoxycarbonylethyl)tin bis(ynoctyl 3-mercaptopropionate),
Bis(2-butoxycarbonylethyl)tin bis(inoctyl 3-mercaptopropionate), bis(2-octoxycarbonylethyl)tin bis(inoctyl 3-mercaptopropionate)
mercaptopropionate), bis(dimethyltinisooctyl 3-mercaptopropionate) oxide, bis(dimethyltin 2-ethylhexyl 3-mercaptopropionate) oxide, bis(dibutyltinisooctyl 3-mercaptopropionate) Kiside, screw (
diptyltin isooctyl 3-mercaptopropionate) sulfide, bis(diptyltin 2-ethylhexyl 3-mercaptopropionate) oxide, bis(dioctyltin isooctyl 3-mercaptopropionate) oxide, bis(dioctyltin 2-ethylhexyl 3) -mercaptoacetate) oxide, bis(dibutyltin lauryl mercaptide) sulfide, bis(dibutyltin lauryl mercaptide) mercaptoacetate, bis(dibutyltin lauryl mercaptide) 3-mercaptobrobionate, monomethyltin Triacetate, monomethyltin tripropionate, monomethyltin trioctoate, monomethyltin trilaurate, monomethyltin tripalmitate, monomethyltin tristearate, monomethyltin tribehenate, monomethyltin tribenzoate, monomethyltin trimethacrylate, motuputyltin triacetate, motuputiltin Tripropionate, Motsputyltin Trioctoate, Motsputyltin Trilaurate, Motsputyltin Tripalmitate, Motsputyl Tin Tristearate, Motsputyltin Tribehenate, Motsputyltin Tribenzoate, Motsputyltin Trimethacrylate, Monooctyltin Triacetate, Monooctyltin Tripropio monooctyltin triactoate, monooctyltin trilaurate, monooctyltin tripalmitate, monooctyltin tristearate,
Monooctyltin Tribehenate, Monooctyltin Tribenzoate, Monooctyltin Trimethacrylate, Monolauryl Pot Triacetate, Monolauryltin Tripropionate, Monolauryltin Trioctoate, Monolauryltin Trilaurate, Monolauryltin Tripalmitate, Monolauryl Tin tristearate, monolauryltin tribehenate, monolauryltin tribe/shade, monolauryltin trimethacrylate, 2-butoxycarbonylethyltin trilaurate, dimethyltin dilaurate, diptyltin dilaurate, dioctyltin dilaurate, dilauryltin dilaurate, bis(2) -butoxycarbonylethyl)tin dilaurate, monomethyltin tris(
lauryl mercaptide), monomethyltin tris (stearyl mercaptide), monobutyltin tris (lauryl mercaptide), monobutyltin tris (stearyl mercapmade), monooctyltin tris (lauryl mercaptide), monooctyltin Tris (stearyl mercaptide), monolauryl tin tris (lauryl mercaptide), monolauryl tin tris (stearyl mercapmade), 2-butoxycarbonylethyltin tris (lauryl mercaptide), 2-butoxycarbonylethyl tin Tris (stearyl mercapmade), dimethyltin bis (lauryl mercaptide), diptyltin bis (lauryl mercaptide), diptyltin bis (benzyl mercaptide), dioctyltin bis (lauryl mercaptide), dilauryl tin Bis(lauryl mercaptide), bis(2-butoxycarbonylethyl)tin bis(lauryl mercaptide), monomethyltin tris(monohydroxylauryl mercaptide), dimethyltin bis(monohydroxylauryl mercaptide), monobutyl Tin tris (monohydroxy lauryl mercaptide), diptyl tin bis (mono hydroxy lauryl mercaptide), monooctyl tin tris (mono hydroxy lauryl mercaptide), dilauryl tin bis (mono hydroxy lauryl mercaptide)', 2 -Butoxycarbonylethyltintris(monohydroxylaurylmercaptide), bis(2-butoxycarbonylethyl)tinbis(monohydroxylaurylmercaptide), bis(
Diptyltin laurate) oxide, bis(diptyltin laurate) maleate, bis(diptyltin laurate sulfide, motuptyltin tris(butyl maleate), monobutyltin monochlorobis(butyl maleate))
, monobutyltin monochlorobis (inoctyl mercaptoacetate)), monobutyltin monochlorobis (inoctyl 3-mercaptopropionate), motsputyltin monochlorodilaurate, motsputyltin monochlorodilauryl mercaptide, butyl maleate) oxide, bis(monobutyltin bis(isooctyl mercaptoacetate)) oxide, bis(monobutyltin bis(isooctyl 3-mercaptopropionate)) oxide, bis(monobutyltin dilaurate) oxide, bis(monobutyltin bis(isooctyl mercaptopropionate)) oxide (
butyl maleate)) sulfide, bis(monobutyltin bis(isooctyl mercaptoacetate)) sulfide, bis(monobutyltin bis(isooctyl 3-mercaptopropionate)) sulfide, bis(monobutyltin dilaurate) sulfide, bis(monobutyltin dilaurate) sulfide, bis(monobutyltin bis(isooctyl mercaptopropionate)) dilauryl mercaptide) sulfide, bis(
Monobutyltin bis(in-octyl mercaptoacetate)) mercaptoacetate, bis(monobutyltin bis(in-octyl mercaptoacetate)) mercaptoacetate, bis(monobutyltin bis(in-octyl 3-mercaptopropionate)) mercaptoacetate, bis(monobutyltin dilaurate) mercaptoacetate, bis(monobutyltin dilauryl mercaptide) mercaptoacetate, bis(monobutyltin bis(monobutyl maleate))
3-mercaptopropionate, bis(monobutyltin bis(in-octyl mercaptoacetate)) 3-mercaptopropionate, bis(monobutyltin bis(in-octyl 3-mercaptopropione-￥)) 3-mercaptopropionate, Bis(monobutyltin dilaurate)
3-mercaptopropionate, bis(monobutyltin dilauryl mercaptide) 3-mercaptopropionate, bis(monobutyltin bis(butyl maleate)) maleate, bis(monobutyltin bis(inoctyl mercaptoacetate)) maleate , bis(monobutyltin bis(isooctyl 3-mercaptopropionate))
Maleate, bis(monobutyltin dilaurate) maleate, bis(monobutyltin dilauryl mercaptide)
maleate, bis(monobutyltin monochloromotsbutyl maleate) oxide, etc., and preferred examples include dibutyltin bis(methyl maleate), dibutyltin bis(butyl maleate), dibutyltin bis(inoctyl maleate), Dibutyltin bis(2-ethylhexyl maleate), dibutyltin bis(tridecyl maleate), dibutyltin bis(octadecyl maleate), dibutyltin bis(oleyl maleate), dibutyltin bis(
benzyl maleate), dibutyltin bis(cyclohexyl maleate), dioctyltin hiss(butyl maleate), dioctyltin bis(inoctyl maleate), dioctyltin bis(2-ethylhexyl maleate), dioctyltin bis(tridecyl) dioctyltin bis(octadecyl maleate), dioctyltin bis(oleyl maleate), dioctyltin bis(benzyl maleate), dioctyltin bis(cyclohexyl maleate), bis(cyphthyl 8-methyl maleate) maleate, Bis(cyphtyltin phthyl maleate) maleate, bis(diptyltin isooctyl maleate) maleate, bis(diptyltin 2-ethylhexyl maleate)
maleate, bis(cyphthyl u) I) f-syl maleate) maleate, his(cyphtyltin octadecy maleate) maleate, bis(diptyltin oleyl maleate) maleate, vinyl(dibutyltin benzyl maleate) maleate, bis(diptyltin cyclohexyl maleate) ate) maleate, bis(dioctyltin butyl maleate) maleate, bis(dioctyltin octyl maleate), maleate, bis(dioctyltin 2-ethylhexyl maleate) maleate, bis(dioctyltin tridecyl maleate) maleate, bis (dioctyltin octadecyl maleate) maleate, bis(dioctyltin oleyl maleate) maleate, bis(dioctyltin benzyl maleate) maleate, bis(dioctyltin cyclohexyl maleate) maleate, bis(diptyltin methyl maleate) oxide, bis (
diptyl 2-butyl maleate) oxide, bis(diptyltin benzyl maleate) oxide, bis(dioctyltin butyl maleate) oxide, bis(dioctyltin benzyl maleate) oxide, diptyltin bis(isooctylmercaptoacetate), diptyltin bis (2-ethylhexylmercaptoacetate), dioctyltin bis(inoctylmercaptoacetate),
Dioctyltin bis(2-ethylhexyl mercaptoacetate), diptyltin bis(inoctyl 3-mercaptopropionate), diptyltin bis(2-ethylhexyl 3-mercaptopropionate), diptyltin bis(methoxybutyl 3-mercaptopropionate) mercaptopropionate), dioctyltin bis(inoctyl 3-mercaptopropionate), dioctyltin bis(2-ethylhexyl 3-
mercaptopropionate), bis(diptyltininoctyl 3-mercaptopropionate) oxide, bis(diptyltin 2-ethylhexyl 3-mercaptopropionate) oxide, bis(dioctyltininoctyl 3-mercaptopropionate) oxide , bis(dioctyltin 2-ethylhexyl 3-mercaptopropionate) oxide, and the like.

- Representative examples of the organotin compound represented by formula (2) include the following.

Methyl stanoitsuccinic acid, butyl stanoic acid, octylstannoitsucic acid, lauryl stanoitsuccinic acid, dimethyltin oxide, diptylstannoic acid, dioctyltin oxide, di, lauryltin oxide, dimethyltin sulfide, diptylstanoscinic acid, Dioctyltin sulfide, motuputil pot oxide sulfide, methylthiostanoitsucic acid, butylthiostanoitsucic acid,
Octylthiostanoitsuccinic acid, laurylthiostanoitsuccinic acid, monomethyltin mercaptoacetate, dimethyltin mercaptoacetate, motuputyltin mercaptoacetate, dibutyltin mercaptoacetate, monooctyltin mercaptoacetate, dioctyltin mercaptoacetate, monolauryltin mercaptoacetate , dilauryltin mercaptoacetate, 2-butoxycarbonylethyl mercaptoacetate, bis(2-butoxycarbonylethyl)tin mercaptoacetate, monomethyltin 3-mercaptopropionate, dimethyltin 3-mercaptopropionate, motuputyltin 3-mercapto Propionate, diptyltin 3-mercaptopropionate, monooctyltin 3-mercaptopropionate, dioctyltin 3-mercaptopropionate, monolauryltin 3-mercaptopropionate, dilauryltin 3-mercaptopropionate
Mercaptopropionate, 2-butoxycarbonylethyltin 3-mercaptopropionate, bis(2-butoxycarbonylethyl)tin 3-mercaptopropionate, monomethyltin maleate, dimethyltin maleate,
Monobutyltin maleate, dibutyltin maleate, monooctyltin maleate, dioctyltin maleate, monolauryltin maleate, dilauryltin maleate, and polymers thereof, and preferred examples include dibutyltin mercaptoacetate, dibutyltin 3-mercaptopropio Mention may be made of dioctyltin ester, dioctyltin mercaptoacetate, dioctyltin 3-mercaptopropionate, dibutyltin maleate, dioctyltin maleate and polymers thereof.

The thioether compounds used as component (b) in the present invention include, for example, thioacetals, thioketals,
Mention may be made of thioether carboxylic acids and thioether compounds. To explain in more detail, thioacetal compounds have, for example, formulas (3) and (4).
) (wherein, R7 is hydrogen, C1 to C18 alkyl group, C
6-C14 aryl group and hydroxyaryl group, R
8 is a C1-cis alkyl group, a 06-C14 aryl group and a hydroxyaryl group, a C7-C15 aralkyl group, R9 is a 01-C18 alkylene group, C1-
A cycloalkylene group, an arylene group, a hydroxyarylene group, and a direct bond) of C18, and the thioketal compounds are, for example, - Formulas 15), (6), (7), and (8) RlQ
/” \SR8 RllCOOM1 (wherein, R10 is hydrogen, an alkyl group of 01 to C18,
Cyclohexyl group, C6-C14 aryl group and hydroxyaryl group, 02-C27 hydroxycarbonylalkyl group, alkyloxycarbonylalkyl group, aralkyloxycarbonylalkyl group, and cyclohexyloxycarbonyl group, C3
~C10, hydroxyalkylthioalkyl group, alkyloxycarbonylalkyl group, aralkyloxycarbonylnarkyl group, and hiscyclohexyloxycarbonylalkyl group, R11 is C1-C5 alkylene group, R
12 is a C1-C5 alkane) IJyl group Ml is hydrogen, a C1-C18 alkyl group, hydroxyalkyl group, aryl group and metal, cyclohexyl group, hydroxycyclohexyl group), and thioether carbon The acidic compound is, for example, - Formula (9), liG, αυ, C3,
C3 and l R13-S -R14COOM2 f9
1S (-R14COOM2)2 α
03(-R16-8-R')2 C3(
In the formula, R13 is hydrogen, C1 to C18 alkyl groups and hydroxyalkyl groups, 06 to C1B aryl groups, hydroxyaryl groups, aralkyl groups and hydroxyaralkyl groups, cyclohexyl groups, hydroxycyclohexyl groups, R14 is C1 ~C5 alkylene group, R
15 is a self-C5 alkantriyl group, R16 and R
17 is a compound represented by the formula -R14-COOR14- group, M2 is synonymous with Ml), and the thioether compound is, for example, -R185-Rl9 αR (in the formula, R
(18 and R14 have the same meaning as R13, except when both are hydrogen).

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

H”' ”SC2H4COOK A 32 Cl8H37SCH 2COOH0O
H 1533 Cl2H25SC2HaCOOHA
34 C4H900CC10H20SCHCOO
HCH2C00H A 37 Cl2) (258CHCOOHCH2
C0OH 7 paper 38 C8H1700CCH2SCHCOO
HCH2C00H HOOCC)T2 CH2C0OH, % 40 (4H17SC2H4COONa/
ぢ41 C6H17SC2H4COOLiA 4
2 C3H17SC2H4COOKyi643
((4H+7SC2H4COO')2Ca464
4 (c6H17SC2H4COO)2Bay%
45 (c, BH17SC2HaCOO) 2
Sr/1646 (c6H17SC2H4CO
O) 3Ceyt647 (c6H17SC2H4
COO)2Zn/1650 HOOCC10H2
0SCHCOOC18H37CH2COOC18)13
7 A651 Cl2H2500CC2HaSC2H
4COOC12H2sA52 HOOCC2Ha
SC2HaCOOHHOH H20H Tomo3 A 56 HOC2HaSCH2CHCOOHA
660 H8C2H4C00Hy1661
H8C2H4C00C8H17A662 H3
C2H4COOCH2Q(2H8C2H4C00CH2
CH2 CH2CH2COOCH2CH2 7564 HOC2H4SC2H40H Next, the perchloric acid compound used as component (c) in the present invention will be specifically explained. Perchlorates include metal salts and ammonium salts of perchloric acid. As for the metal,
Li, NasK, Mg, Ca, Sr, Ba
, Zn, Sn, etc.

In addition, examples of inorganic compounds treated with perchloric acid include generally commercially available compounds, such as inorganic compounds such as hydrotalcite, alumina, aluminum hydroxide, silicic acid, and silicates, treated with perchloric acid or the water bath solution. The ratio of the inorganic compound and perchloric acid during treatment may be arbitrary, and the form after treatment is preferably a powder.

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

■ Perchloric acid■ Barium perchlorate■ Calcium perchlorate■ Zinc perchlorate■ Magnesium perchlorate■ Sodium perchlorate■ Tin perchlorate■ Lithium perchlorate■ Potassium perchlorate■ Strontium perchlorate■ Ammonium perchlorate ■ Hydrotalcite treated with chloric acid O Perchloric acid treated alumina ■ Aluminum hydroxide treated with perchloric acid @ Silicate treated with perchloric acid ■ Silicate treated with perchloric acid In the present invention, fa) component for chlorine-containing resin The amount of the mono- and/or di-organotin compound added is not particularly limited, but is usually 0.1 to 10 parts by weight per 100 parts of the resin, and less than 0.1 parts by weight. There is almost no heat stabilizing effect, and when the amount exceeds 10 parts by weight, the expected heat stabilizing effect is not observed, and preferably about 0.5 to 6 parts by weight.
．． It is 0 parts by weight. In addition, general formulas (3) to α of component (b)
The amount of the thioether compound as component (c) shown by is usually 0.001 to 2.0 parts by weight, and
If it is less than 1 part, there will be almost no heat stabilizing effect, and if it exceeds 20 parts by weight, the heat stabilizing effect will be poorer or the resin will become more colored, and preferably it is about 0.01 to 1.0 parts by weight. Furthermore, the amount of perchloric acid, perchlorate, and perchloric acid-treated inorganic compound of component (c) is usually 0.0001 to Q, 5 parts by weight in terms of perchloric acid, and less than 0.0001 part by weight. There is almost no thermal stabilizing effect, and if it exceeds 0.5 parts by weight, there is no thermal stabilizing effect and the resin deteriorates rapidly. The preferred amount added is approximately 10,005 to 0.1 parts by weight.

The stabilizers (a), fb), and (c) used in the present invention may be added to the chlorine-containing resin by any conventionally known method. For example, the resin and the stabilizer may be mixed in a Henschel mixer, The resin may be mixed using a ribbon blender, a Banbury mixer, etc., or a prepacked stabilizer used in the present invention may be mixed with the resin using the above-mentioned mixer.

Furthermore, the stabilizer used in the present invention may contain other additives, such as
Ultraviolet absorbers, epoxy compounds, organic phosphorus compounds, processing aids, lubricants, plasticizers, fillers, pigments, etc. can be used in combination.

〔Example〕

The present invention will be specifically explained below with reference to Examples, but the present invention is not limited thereto. The number of parts added in the examples refers to parts by weight. The mono- and/or di-organotin compounds used in this example (al component) are shown in the following A to I, and the general formula (3) to S of the component (b)
The thioether compounds represented by 1 to A in the specification are
64, and the perchloric acid, perchlorate, and perchloric acid-treated inorganic compound of component (c) are ① to ② in Mei M.

[Organic tin compound]

A. Di-n-butyltin malenitro, di-n-butyltin bis(butyl maleate) C. Di-17thyltin bis(cyclohexyl maleate) 2. Di-n-butyltin bis(2-ethylhexyl maleate) H , sea n-7” chill tin bis(benzyl maleite)
) to, di-n-butyltin bis(methoxybutyl maleate)), di-n-7'thyltin bis(oleyl maleate)
), bis(di-n-butyltin methyl maleate) maleate +), di-n-octyltin bis(2-ethylhexyl maleate), dimethyltin bis(isooctylmercaptoacetate), di-n-butyltin Bis(in-octyl mercapto acetate), di-n-butyltin bis(in-octyl 3-mercaptopropionate), di-n-butyl anchor bis(methoxybutyl 3-mercaptopropionate), bis(di- n-butyltin isooctyl 3-mercaptopropionate) oxide 3, di-n-octyltin bis(isooctylmercaptoacetate), di-n-lauryltin bis(isooctylmercaptoacetate), bis(2-butoxycarbonylethyl) ) tin bis(in-octyl mercaptoacetate), di-n-butyltin sulfide, di-n-butyltin dilauryl mercapmadene, di-n-butyltin dilaurate, di-n-butyltin mercaptoacetate , G-n
-Butyltin 3-mercaptopropionate, 7-n-butyltinthiostanoic acid, mono-
n-Butyltin tris(isooctylmercaptoacetate) Mono-n-butyltin monochlorobis(isooctylmercaptoacetate) The perchloric acid used in this example was actually a 1% aqueous solution, but it was described in the example. The number of parts is the value converted to 100% perchloric acid. The amount of perchlorate and perchlorate-treated inorganic compound added is the amount of the compound itself.

In addition, evaluation of colorability by press test in Examples is abbreviated as follows.

A, colorless or white D, tan B, pale yellow or pale yellow-white E, brown C0 yellow or yellow-white
F, Black Example 1 Polyvinyl chloride [Nippon Zeon Co., Ltd. ff, GeonIQ
3EP-8) 100 copies [Table-1] and [Table-2]
After kneading Formulation 1 containing the stabilizer shown in Table 1 for 5 minutes with an 8-inch test roll adjusted to 160 °C, the mixture was mixed to a thickness of O.5.
A sample of Iljl exploded.

This sheet was cut, and the sheet was placed in a gear type aging tester set at 195° C., and the time (minutes) until deterioration (browning or blackening) was measured at 7 to evaluate thermal stability.

Also, stack 8 cut sheets, put them in a press mold, and press them with a heating press at 200'C for 40 minutes at 100kg/C1.
A prototype of the plate was prepared in A, and the colorability and transparency of the plate were evaluated with the naked eye.

[Table 1] [Table 2] Sample numbers 1 to 12 are examples of the present invention, and samples 13 to 19 are comparative examples.

As is clear from the effects in [Table 1] and [Table 2], the thermal stability of polyvinyl chloride is improved by the combined use of an organotin compound, a thioether compound, and perchloric acid, as shown in samples 1 to 412. It can be seen that the properties are greatly improved and the press colorability is also excellent. Furthermore, the combination of organotin compound, thioether compound, and perchloric acid was higher than the combination of organotin compound of sample shoulder 13, the combination of organotin compound and thioether compound of sample 414, and the combination of organotin compound and perchloric acid of sample A615. It can be seen that the effect of the combined use of the king is excellent. Furthermore, in the case of sample 416, which is a thioether compound alone, and sample No. 17, which is a single chlorine acid compound, when the amount of thioether compound added is too large as in sample A618, the amount of perchloric acid added is too large as in sample A619. It can be seen that when the amount is too large, the thermal stabilization effect is significantly inferior.

Example λ Tests were conducted in the same manner as in Example 1 under the following formulation, crosstalk conditions, and test conditions to evaluate thermal stability and colorability. The results are shown in [Table-3] to [Table-5].

Formulations> Ge0n103Ep-8 100 parts Kane Ace FM" 20 parts Stabilizer Shown in [Table 4] to [Table 6].

(*Acrylic reinforcement manufactured by Kanekabuchi Chemical Co., Ltd.) Mixing conditions> Roll temperature 160°C Kneading time 5 minutes Test conditions> Gear aging test 190°C Press test 190°C, 50 minutes, 80 kg
/d [Table-3] [:A-4'] (:!!-S) Sample numbers 1 to 29 are examples of the present invention, and sample numbers 30 to 3
6 is a comparative example.

Among perchloric acid, perchlorate, and perchloric acid-treated inorganic compounds, ■, e, ■, ■, and ■ are respectively the following compounds 1
It was treated with perchloric acid in an amount of L5 mol per mol.

■Hydrotalcite HT from Kyowa Chemical Industry Co., Ltd.
-4A O is fine powder alumina ■ is aluminum hydroxide ■ is calcium silicate ■ is to Shionogi & Co., Ltd. Carplex 4#8゜ It is clear from the effects of [Table 3] to [Table 5] Nayoi Sample Demon 1
~/1629, it can be seen that the combination of various organic tin mercaptides as f31 component, the thioether compound as component (b) of the present invention, and the perchloric acid compound as cl component has an excellent thermal stabilizing effect. .

In addition, as shown in Sample 30, /VA31.436, if any one component is missing, the heat stabilizing effect is inferior, and as in Sample 32, /1633, thioether compounds alone or chloric acid It can be seen that the compound alone has almost no thermal stabilizing effect.

Furthermore, as shown in Sample Scrap 34 and Δ635, it can be seen that if the amount of thioether compound or perchloric acid compound added is too large, the thermal stabilization effect will be greatly reduced even if the combination of the two is used.

Example 1 Tests were conducted in the same manner as in Example 1 under the following formulation, crosstalk conditions, and test conditions to evaluate thermal stability and colorability. The results are shown in [Table-6] and [Table-r].

Formulations> Kanevinyl S-1007*50 parts Tuflex TFX-410'' 50 parts di-n-butyltin maleate 3 parts Other stabilizers (Iwa-61 and [shown in Table-71).

C*Polyvinyl chloride manufactured by Jongbuchi Chemical Co., Ltd. (**Acrylonitrile-butadiene-styrene copolymer manufactured by Mitsubishi Nonsanto Kasei Co., Ltd.) Mixing conditions> Roll temperature 155°C Kneading time 5 minutes Test conditions 〉 Gear type aging test 220℃ Press test 210℃, 60 minutes, 20 listens/i-・
'5,・(・ [%-6] [Table-7] Sample numbers 1 to 20 are examples of the present invention, Sample numbers 21 to
26 is a comparative example.

■ used in the examples was used in Example 2.

As is clear from the effects in [Table 6] and [Table 7], even with this formulation, as in samples /161 to 420, (a)
It can be seen that the combined use of the organic tin compound as the component, the thioether compound as the fbl component, and the perchloric acid compound as the cl component has an excellent thermal stabilizing effect.

〔Effect of the invention〕

The present invention dramatically improves the thermal stability of a chlorine-containing resin by simultaneously adding an organotin compound, a specific thioether compound, and the king of perchloric acid compounds to the chlorine-containing resin. In addition, coloring of the resin can be prevented.

Patent applicant: Sankyoki Gosei Co., Ltd.

Claims (1)

[Claims] 1. When stabilizing a chlorine-containing resin, (a) a mono- and/or diorganotin compound, (b) a thioether compound, and (c) perchloric acid, perchlorine, etc. are added to the chlorine-containing resin. A method for stabilizing a chlorine-containing resin, which comprises adding at least one of an acid salt and a perchloric acid-treated inorganic compound.