CA1310786C - Stabilized rigid polyvinyl chloride compositions - Google Patents

Abstract

STABILIZED RIGID POLYVINYL CHLORIDE COMPOSITIONS

Abstract of the Disclosure Polyvinyl chloride compositions are provided which are stabilized against the adverse effects of ultraviolet radiation by the addition thereto of effective amounts of a 2,2,6,6-tetraalkyl-piperidine compound and an organotin carboxylate or alcoholate stabilizer, optionally with reduced amounts of titanium dioxide, organotin mercapto esters and/or organotin mercaptide stabilizers. The compositions do not contain any lead stabilizers. The compositions can be processed to rigid PVC products with excellent resistance to thermal degradation and improved long term stability.

Description

- 1 - 1 3 1 07~6 Rigid polyvinyl chLoride is utilized for a variety of applications including~ for example, siding for houses and window frames. The rigid polyvinyl chloride is generallY
formulated with high levels of titanium dioxide, e.g.
12-15 parts per hundred, in order to provide proper pigmentation and prevent significant color variation upon exposure to UV radiation and with a tin mercaptide compound as a heat and process stabili7er. The combina-tion of the titanium dioxide and the tin mercaptide is included to permit the resin to be ut;tized outdoors, an essent;al characteristic, without undergoing excess;ve photodegradation. This is required by manufacturers who seek assurance that the siding, window frames, and the l;ke, w;ll be functional for substantial periods of time without significant color change, reduced physical properties or resin degradation.

There are, however, certa;n disadventages to these systems. Thus, the tin mercaptides do not provide adequate protection against the UV light-induced degrada-tion commonly encountered during long-term outdoor use.
The use of blends of tin mercaptides and organotin carboxylates has been resorted to in an attempt to resolve this difficulty~ While improvement has been noted with the latter blends~ further protection during such long-term outdoor use is still required.

There are also certain d;sadvantages to the use of the indicated high levels of titanium dioxide. Of pr;mary importance, the high content causes excessive wear and early failure, i.e. scoring and uneven wear of extruder barrels and screws in the polyvinyl chloride processing 1 3 ~ 07~6 equipment, necessitating expens;ve and frequent replacement of parts. A further major shortcom;ng of rigid polyvinyl chlor;de conta;n;ng these h;gh t;tan;um dioxide levels is that s;d;ngs prepared therefrom can only be in ~h;te or pastel colors. Darker shades of s;d;ng are not available because of the h;gh levels. Attempts to lower the titanium dioxide level have resulted in siqnificant reductions ;n light stability of the polyvinyl chlor;de as evidenced by unacceptable color changes, loss o~ impact strength and surface crazing.

It has ~urther been proposed to use piperidine light 3tabili ers together with organotin stabil;zers in order to improve the propert;es of polyvinyl chloride ;n general, 'or example together with lead compounds as further stabilizers~ The use of lead compounds, however, leads to further dra~backs, inter alia because of ecological problem~ caused by lead compounds.

It has now been determined that rigid polyvinyl ~hloride products can be prepared with excellent resis tance to thermal degradation during processing and improved long term resistance to UV degradation and which p~lyvinyl chloride products do not exhibit the drawbacks mention~d hereinbefore, or exhibit said drawbacks to a m~l~h less extent. In addition, levels of titanium dioxide ~an b~ si~nificantly reduced or eliminated totalLy without 3ign;f;cant impact on performance, thereby reducing the wear on and resulting failure of processing equipment Nh;le giving siding and frame manufacturers greater flexibility in the color of the manufactured item, i~e~
availability of darker colors~ All these advantages are I 3 ~ 0786 obtained by the composition of this invention.

The composition of this invention is a rigid polyvinyl chloride composit;on, which comprises ;n addition to said polyvinyl chlor;de, (A) at least one 2,2,6,6-tetra-alkylpiperidine compound which contains at least one group of the formula 5H3 ~R
/---\ ( 1 ) ~r-o ~herein R is hydrogen or methyl;
and (B) at least one organotin compound of the formulae oz1 (Z) 2Sn-OZ
(z)2Sn(OOC-Z3)2 ( IZ)2 ( IZ)2 Z -COO-Sn-O-Sn-OOC-Z
(Z)msn(ooccH=cHcooz )4-m wherein 2 and Z4 independently are C1-C20 alkyl, C3-C20 alkenyl, cycloalkyl, aryl, alkaryl or aralkyl;

z1 is C10-C30 alkyl or phenyl substituted by one or C8 12 alkyl;

1 ~ I U7~6 Z is Z or -Sn(OZ1)(Z)2;

Z is C1-C30 alkyl, C3-C20-alkenyl~ cycloalky~, aryl, alkaryl or aralkyl; and m is an integer from 1 to 3.

The 2~2,6,o-tetraalkyl piperidine compounds to be used according to the invention are generally known and are recognized for their ab;lity to combat light degrada-tion in a variety of substrates including polyvinyl chloride. U~Sa 3,542,729, U.S. 3,547,874, U.S. 3,640,928, U~S. 3,840,494, U~S. 4,021,432, U.S. 4,049,647, U.S. 4,064,102, U.S. 4,086,204 and U~Sa 4,265,805 are typ;cal of the numerous patents that disclose such piper;dine light stabilizers.

The 2,2,6,6-tetraalkylpiperidine compounds containing at least one group of the formula I to be used according to the invention include in particular the following pre~erred classes of compounds:

a) Compounds of the formula II

RCH 2\ CH 3/R
R~ ~ _R2 ( I I ), RCH2~ \CH3 n 1 31 07~6 in which n is a number from 1 to 4, preferably 1 or 2, R is hydrogen or methyl, R1 is hydrogen, oxyl, C1-C18-alkyl, C3-cg-alkenyl~ C3-Cg-alkynyl~ C7-C12-aralkyl, C1-C8-alkanoyl, C3-C5-alkenoyl, glycidyl or a group -CH2CH(OH)-Z, with Z being hydrogen, methyl or phenyl, R preferably being Cl-Cl~-alkyl, allyl, benzyl, acetyl or acryloyl, and R2, if n = l, is hydrogen, C1-C1g-alkyl which may be interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monobasic radical of an aliphatic, cycloaliphatic, arali-phat;cr unsaturated or aromatic carboxylic acid, carbamic a~id or phosphorus-containing acid or a monovalent silyl radic3l, preferably a radical of an aliphatic carboxylic ac;d having 2 to 1~ C atoms, cycloaliphatic carboxylic acid having 7 to 15 C atoms, an ~,~-unsaturated carboxylic acid having 3 to S C atoms or an aromatic carboxylic acid having 7 to 15 C atoms, or, if n = 2, R2 is C1-C12-alkylene, C4-C12-alkenylene, xylylene, a dibasic radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicar-boxylic acid having 2 to 36 C atoms, a cycloaliphatic or aromatic dicarboxylic acid having 8 - 14 C atoms or an ali-phatic, cycloaliphatic or aromatic dicarbamic acid having 8 - 14 C atoms, or, if n = 3, R2 is a tribasic radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or a phosphorus-containing acid or 3 trivalent silyl radical, and, if n = 4~ R2 is a tetra-basic radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.
Any C1-C12-alkyl substituents are, for example, m~thyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

;1 3 1 ~7~6 C1-C1g-alkyl radicals R1 or R2 can be, for example, the groups listed above and in addition also, for example, n-tridecyl, n-tetradecyl, n-hexadecyl, or n-octa-decyl.
A C3-C8-alkenyl radical R1 can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert.-butyl-2-butenyl.
A C3-Cg-alkynyl radical R1 is preferably propargyl.
A C7-C12-aralkyl radical R1 is in particular phenethyl or especially benzyl.
A C1-C8-alkanoyl radical R1 is~ for example, formyl, propionyl, butyryl, octanoyl or preferably acetyl, and C3-C5-alkenoyl is especially acryloyl.
If R2 is a monobasic radical of a carboxylic acid, this is, for example, an acetic acid, caproic acid, stearic acid, acryl;c acid, methacrylic acid, benzoic acid or ~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionic acid radical.
If R2 is a dibasic radical of a dicarboxylic acid, it is, for example, a malonic acid, adipic acid, suberic ac;d, sebacic acid, maleic acid, phthalic acid, dibutylmal-onic acid, dibenzylmalonic acid, butyl-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonic acid or bicycloheptenedicarboxylic acid radical If R is a tribasic radical of a tr;carboxyl;c acid, it is, for example a trimellitic acid or nitrilotri-acetic acid radical.
If R2 is a tetrabasic radical of a tetracarboxylic acid, it is, for example, the tetrabasic radical of butane-1,2,3,4-tetracarboxylic acid or of pyromellitic ac;d.
If R2 is a dibasic radical of a dicarbamic acid, it is, for example, a hexamethylene-dicarbamic acid or 2,4-toluylene-dicarbamic acid radical.
Those compounds of the formula II should be 13 1 U7.,6 especially mentioned in which n is 1 or 2, R is hydrogen, R1 is hydrogen~ o~y~, C1-C6-alky~, C3-Cg-alkenyl~ ~or example llyl, benzyl~ C2-C6-alkanoy~ C3-C5-alkenoyl, for example acryloyl or methacryloyl, g~ycidyl or -C~2CH(OH)-Zl with Z1 being hydrogen or methy~, and R2, if n = 1, is hydrogen, C1-C12-alkyl, benzyl or the radical of an aliphatic carboxylic acid having ~-18 C atoms, an ~ unsaturated carboxylic acid having 3-5 C atoms or an aromatic carboxylic acid having 7-l~ C atoms, and, if n = 2, R2 is C1-C6-alkylene, C4-C8-alkenylene or the radical of an aliphatic saturated or un-satur3ted d;carboxylic acid having 2-18 C atoms.
Examples of tetraalkylpiperidine compounds from this ~13~ ~re the follow;ng compounds: 1) 4-hydroxy-2,2,6,6-tetram2thylpiperidine, 2) 1 allyl-4-hydroxy-2,2,6,6-tetra-methylpiperidine, 3) 1-benzyl-4-hydroxy-2,2,6,6-tetramethyl-piperidine, 4) 1-t4-tert~-butyl-2-butenyl)-4-hydroxy-2,2, 6,~-tetramethylpiperidine, S) 4-stearoyloxy-2,2,6,6-tetra-methylpiperidine, 6) 1-ethyl-4-salicyloyloxy-2,2,6,6-tetra-methylpiperidine, 7) 4-methacryloyloxy-1,2,2,6,6-penta-methylpiperidine, 8) 1,2,2,6,6-pentamethylpiperid-4-yl ~-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate, 9) di-(l-benzyl-2,2,6,6-tetramethylpiperid-4-yl) maleate, 10) di~
~2,2,6,6-tetramethylp;perid-4-yl) adipate, 11~ di-(2,2,6,6-tetramethylpiperid-4-yl) sebacate, 12) di-(1,2,3,6-tetra-methyl-2~6-diethyl-Piperid-4-yl) sebacate, 13) di-(1-allyl-~,~,6,6-tetramethylpiperid-4-yl) phthalate, 14) 1-propargyl-4-~-cyanoethoxy-2,2,6,6-tetramethylpiperidine, 15) 1-acetyl-,6-tetramethylpiPerid-4-yl acetate, 16) tri-(2,2,6,6-tetramethylp;perid-4-Yl) trimellitate, 17) 1-acryloyl-4-ben2yloxy-2,2,6,6-tetramethYlpiperidine~ 18) c1i-(1,2,2,6,6-pent3methylpiperid-4-Yl) dibutylmalonate, 19) di-(1,2,2,6,6-pentamethylpiPerid-4-yl) butyL-(3,5-di tert.-butyl-4-hydroxy-benzyl)-malonate, 20) di-(1,Z,2,6,6-pentamethylpiperjd-4-yl) dibenzylmalonate, 21) d~ 2~3~6-tetramethyl-2~6-diethyl piperid-4-yl) dibenzylmalonate, 22) hexane-1',6'-bis-(4-carbamoyloxy-1-n-butYl-2~2~6~6-tetramethylpiperidine)~
23) toluene-2',4'-biS-(4-carbamoyloxy-1-n-propyl-2~2~6~6 131U7~6 tetramethylpiperidine), 24) dimethyl-bis-(2,2,6,6-tetra-methylpiperid-4-yloxy)-silane, 25) phenyl~tris-(2,2,6,6-tetramethylpjperid-4-yloxy)-silane~ 26) tris-(1-propyl-2,2,~,6-tetramethylpiperid-4-yl) phosphite, 27) tris-(1-pr~pyl-2,2,6,6-tetramethylpiperid-4-yl) phosphate, 28) bis-(1,2,2,b,6-pentamethylpiperid-4-yl) phenylphosphonate, 29~ di-(1,2,2,6,6-pentamethylpiperid-4-Yl) sebacate, ~9a) 4-hydroxy-1,2,2,6,6-PentamethYlPiperidine~ 29b) 4-hyd-roxy-N-hydroxyethyl-2~2~6~6-tetramethylpiperidine~ 29c) 4-hydroxy-,~-(2-hydroxypropyl)-2,2,6,6-tetramethylpiperidine ~nd 29d) 1-glycidyl-4-hydroxy-2,2,6,6-tetramethylpiperid;ne, and part;cularly the compounds bis~,2,~,c,-tetramethyl-4-piperidinyl)sebacate, bis~l-3cetyl-2~2~6~6-tetramethyl-4-piperidinyl) sebacate~
bis~-ben2yl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate or N-butyl-(3,5-di-tert.butyl-4-hydroxybenzyl)-bis-~ ,6,6-pentamethyl-4-piperidinyl)malonate.
b) Compounds of the formula (III) RCH
R~ -R~ (III~
RCH2 CH3 n in which n is the number 1 or 2, R and R1 are as defined under a~ ;nclud;ng the preferred definitions, R3 is hydro-9~R, Cl-C12-alkyl, C2-C5-hydroxyalkyl, C5-C7-cycloalkyl"
C7-C~-aralkyl, c2-C1g-alkanoyl, C3-Cs-alkenoyl or benzoyl and R4, if n = 1, is hydrogen, Cl-Clg-alkyl~ C3-C8-alkenyl, Cs-C7-cycloalkyl~ C1-C4-alkyl substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group, gly-cidyl or a group of the formula -CHz-CH(OH)-Z or of the formula -CONH-Z, ~ith Z being hydrogen, methyl or phenyl, 1 3 1 07~6 or, if n = 2, R is C2-C12-alkylene, CS-C12-arylene, xylylene, a -CH2-cHtOH)-cH2- group or a -CH2-CH(OH)-CH2-0-D-o-cH2-rH(oH)-cH2- sroup~ with D being C2-C10-alkylene, C6-C15-arylene or C6-C12-cycloalkylene, or R4, provided that R3 is not alkanoyl, alkenoyl or benzoylr can also be a dibasic radical of an aliphatic, cycloaliphatic or aro-matic dicarboxYliC acid or dicarbamic acid or the group -CO-, or R and R together, if n = 1, can be the dibasic radical of an aliphatic, cycloaliphatic or aromatic 1,2-or 1,3-dicarboxylic acid.
Any C1-C12- or C1-C18-alkyl substituents are as already defined under a).
Any Cs-C7-cycloalkyl substituents are especially cyclohexyl.
A C7-Cg-aralkyl radical R3 is in particular phenylethyl or especially benzyl. A C~-Cs-hydroxyalkyl radical R3 is especially 2-hydroxyethyl or 2-hydroxypropyl.
A C2-C1g-alkanoyl radical R3 is, for example pro-pionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl or octadecanoyl, and preferably acetyl, and C3-Cs-alkenoyl is especially acryloyl.
A C2-Cg-alkenyl radical R4 is, for example, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl or 2-octenyl.
A C1-C4-alkyl radical R4 which is substituted by a hydroxyl, cyano, alkoxycarbonyl or carbamide group can be, for example, 2-hydroxyethyL, 2-hydroxypropyl, 2-cyano-ethyl, methoxycarbonylmethyl, 2-ethoxycarbonylethyl, 2-amino carbonylpropyl or 2-(dimethylaminocarbonyl)-ethyl.
Any C2-C12-alkylene substituents are, for example, ethylene, propylene, 2,2-dimethylpropylene~ tetramethylene, hexamethylene, octamethylene, decamethylene or dodeca-methylene.

Any C6-C15-arylene substituents are~ for example, ~r m- or p-phenylene, 1,4-naphthylene, 4,4'-diphenylene or . _ . . _ .
~ C(DI)(D2)--\ ~-- in ~hich D1 and D2 independently .--. ~=.
o~ one another are hydrogen or methyl.
A C6-C12-cycloalkylene radical D is especially cyclohexylene.
Those compounds of the formula III should especially be mentioned in ~hich R and R1 have the preferred meanings defined under a), R3 is hydrogen or C1-C6-alkyl and R4, if n - l, ;s hydrogen, C1-C12-alkyl, C3-Cg-alkenyl, C1-C4-31kyl sub~tituted by hydroxyl, cyano or carbamido, ~N7~(0~ Z or CONH-Z and~ if n = 2, R4 iS as defined under the formula III, with the exception of R3+R4 combined.
Examples of tetraalkylpiperidine compounds from this Cl3ss are the following compounds: 30) N,N'-bis-~2,2,6,6-tetramethylpiperid-4-yl)-hexamethylene-1,6-diamine, 31) N,N'-bis-(2,2,6,6-tetramethylpiperid-4-yl)-hexamethylene-1,6-diacetamide, 32) 1-acetyl-4-(N-cyclohexylacetamido)-2,2,6,6-tetramethylpiperidine, 33) 4-benzoylamino-2,2,6,6-tetra-methylpiperidine, 34) N,N'-bis-(2,2,6,6-tetramethylpiPerid-4-yl~-N,N'-dibutyl-adipamide, 35) N~N'-bis-(2,2,6,6-tetra-methylpiperid-4-yl)-N,N'-dicyclohexyl-2-hydroxypropylene-1~3-diamine, 36) N,N'-bis-(2,2,6,6-tetramethylpiperid-4-yl)-p-xylylenediamine, 37) the compound of the formula \~/ o ~4Hg GH3~cH2-cH(OH)-cH2- 1 i!, ~!
CH3-¢-CH3 ~i ~t CH3~ ~CH3 \
CH3- ~-CH2-CH(OH)-CH2-CH3 \CH3 4Hg 38~ 4-(bis-2-hydroxyethylamino)-1,2,2,6,6-pentamethylpiper-;dine, 39) 4-(3-methyl-4-hydroxy-5-tert.-butyl-benzamido)-2,2,6,6-tetramethylpiperidine and 40) 4-methacrylamido-1,2,2,6,6-pentamethylpiperidine.
c) Compounds of the formuLa (IV) ~ RCH2~ ~CH3~ ol ¦ RCH 5 \CH3 ~ (IV) ;n wh;ch n is the number 1 or 2, R and R1 are as defined under a) including the preferred defin;tions and R5, if n = 1, is C2-Cg-alkylene or -hydroxyalkylene or C4-C22-acyloxyalkylene and, if n = 2, is the group (-CH2)2C(CH2-)2 A C2-Cg-alkylene or -hydroxyalkylene radical R5 is, for example, ethylene, 1-methylethylene, propylene, 2-ethyl-propylene or 2-ethyl-2-hydroxymethylpropylene.
A C4-C22-acyloxyalkylene radical RS is, for example, 2-ethy~-2-acetoxymethylpropylen2 Thus, in the case of n = 2, R5 is the complement to form a spiro-6-ring and, in the case of n = 1, preferably is the complement to form a spiro-5- or -6-ring.
Examples of tetraalkylpiperidine compounds ~rom this class are the following compounds: 41) 9-aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecaner 42) 9-aza-8,8,10r10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]undecane, 43) 8-aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane, 44) 9-aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro t5.5]undecane, 45) 9-aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10~10-tetramethyl-1,5-dioxaspiro[5~5]undecane and 46) 2,2,6,6-tetramethylpiperidine-4-spiro-2'-(1',3'-dioxane)-5'-spiro-5"-(1",3"-dioxane)-2"-spiro-4"'-(2"',2"',6"',6"'-tetra-methylpiperidine).
d) Compounds of the formulae VA, VB and VC

RCff2\ ~CH3/R 1~
= (VA) RCH2 \CH3 ~ n- R7 RCHz~ /CH3~ l --'--T 2 ~ ~ (VB) ~7 '=0 RCH2/ \CH3 RCH2\ ~CH

RCHa/ C113 B --R7 - 13 - I 3 1 07~6 in wh;ch n is the number 1 or 2, R and R1 are as defined under a) including the preferred definitions, R6 is hydro-gen, C1-C12-alkyl, allyl, benzyl, glycidyl or Cz-C6-alkoxy-alkyl and R7, if n = 1, is hydrogen, C1-C12-alkyl, C3-Cs-~lkenyl, C7-Cg-aralkyl~ Cs-C7-cycloalkyl, C2-C4-hydroxy-alkyl, C2-C6-alkoxyalkyl, C6-C10-aryl, glycidyl or a group of the formula -tCH2)p-COO-Q or of the formula -~C~2)p-0-CO-~, wherein p is 1 or 2 and Q is C1-C4-alkyl or phenyl, or, if n = 2, R7 is Cz-C12-alkylene, C4-C12-alkenylene, C6-C12-arylene, a group -CH2-CH(OH)-CH2-0-D-O-CH2-CH(OH)-CH2-, wherein D is C2-C10-alkylene, C6-C1S-arylene or C6-C12-cycloalkylene or a group -~H~C~O~')CH2-(OCH2-CH(OZ')CH2)2- ~herein Z' is hydrogen, ~1-Clg-alkyl, allyl, benzyl, C2-C12-alkanoy or benzoyl, and Tl and T2 independently of one another are hydrogen, C1-C18-3lkyl or are C6-C1o-aryl or C7-Cg-aralkyl which are unsubsti-tuted or substituted by halogen or C1-C4-alkyl, or T1 and ~2 together with the C atom linking them, form a Cs-C12-cyclo-alkane ring.
Any C1-C12-alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
Any C1-C1g-alkyl substituents can be, for example, the groups l;sted above and additionally also, for example~
n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.
Any C2-C6-alkoxyalkyl substituents are, for example, m~thoxymethyl, ethoxymethyl, propoxymethyl, tert.-butoxymethyl, eeho~yethyl, ethoxypropyl, n-butoxyethyl, tert~-butoxyethyl, i~opropoxyethyl`or propoxypropyl.
A C3-Cs-alkenyl radical R7 is, for example, 1 3 1 07~6 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.
C7-Cq-aralkyl radicals R7, T1 and T2 are in par-ticular phenethyl or especially benzyl. T1 and T2 forming a cycloalkane ring together with the C atom can be, for example, a cyclopentane, cyclohexane, cyclooctane or cyclododecane ring.
A C2-C4-hydroxyalkyl radical R7 is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxy-butyl.
C6-C10-aryl radicals R7, T1 and T2 are in particu-lar phenyl or ~- or ~-naphthyl which are unsubstituted or substituted by halogen or C1-C4-alkyl.
A C2-C12-alkylene radical R7 is, for example, eth-ylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexa-methylene, octamethylene, decamethylene or dodecamethylene.
A C4-C12-a~kenylene radical R7 is in particular Z-butenylene, 2-pentenylene or 3-hexenylene.
A C6-C12-arylene radical R7 is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.
A C2-Cl2-alkanoyl radical Z' is, for example, propio-nyl, butyryl, octanoyl or dodecanoyl, and preferably acetyl.
A C2-C10-alkylene, C6-C1s-arylene or C6-C12-cyclo-alkylene radical D is as preferably defined under b).
Examples of tetraalkylpiperidine compounds from this class are the following compounds: 47) 3-benzyl-1~3,8-tr;aza-7,7,9,9-tetramethylsp;roC4.5]decane-2,4-d;one, 48) 3-n-octyl-1~3,8-triaza-7,7,g,9-tetramethylsp;roC4.5]decane-2,4-d;one, 49) 3-allyl-1,3,8-tr;aza-1,7,7,9,9,-pentamethylspiro[4~5]-decane-2,4-d;one, 50) 3-glycidyl-1,3,8-tr;aza-7,7,8,9,9-penta-methylsp;roC4.5]decane-2,4-d;one, 51) 2-;sopropyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiroC4.5]decane, 52) 2,2-dibutyl-7,7,9,9-tetramethyl-1-oxa-3,8-d;aza-4-oxo-spiro[4.5]-decane, 53) 2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-d;spiroC5.1.11.2]heneicosane, 54) 2-butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxo-sp;ro[4.5]decane and 54a) 8-acetyl-3-dodecyl-1,3,8-tr;aza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione or the compounds of the following formulae:

. ~ , t 7i 1 078~

U~

~.

5:

~'i i'~

Z
"\ A /'' N C,~ O I_ ~ C;><
T~
3 T~ ;~, U.

O

o ~, , , ^
` X

I ) I 0786 e) Compounds of the formula VI
~8 R9 W -Rl (VI), in which n is the number 1 or 2 and R8 is a group of the formula ~CH3~ ~CH2R

--E-~A) ~ _ in wh;ch R and R1 are as defined under a) including the preferred definitions, E is -O- or -NR11-, A is C2-C6-alkylene or -(CH2)3-0- and x is one of the numbers O or 1, R9 is identical to R8 or one of the groups -NR11R12, -oR13, -NHCH2oR13 or -N(CH2oR13)2, R10 is, if n = 1, identical to R8 or R9 and, if n = 2, a group -E-B-E-~wherein B is C2-C6-alkylene which may be interrupted by -N(R11)-, R11 is C1-C12-alkyl, cyclohexyl, benzyl or C1-C4-hydroxyalkyl or a group of the formula ~CH3~ ~CH2R

~ Rl R1~ is C1-C12-alkyl, cyclohexyl, benzyl or C1-C4-hydroxy-alkyl and Rl3 is hydrogen, C1-C12-alkyl or phenyl, or R11 and R12 together are C4-Cs-alkylene or -oxaalkylene, ~ar e~ample -CH2CH2~ -CH2CH2 ~. , or a group of the formula ~N--R
-CH2CH2 ff H2CH2 1 3 t 07~S

or R11 and R12 can also each be a group of the formula N~ N~-A-C4Hs~~
Ca3\i \~~CH3 CH 3 b' CH 3 Any C1-C12-alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.
Any C1-C4-hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybu~yl or 4-hydroxybutyl.
A C2-C6-alkylene radical A is, -for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexa-methylene.
If R11 and R12 together are C4-C5-alkylene or oxaalkylene, they are, for example, tetramethylene, penta-methylene or 3-oxapentamethylene.
Examples of tetraalkylpiperidine compounds from this class are the compounds of the following formulae:

I ~ 1 07~6 ÇH3 H3C\ /~\ /CH3 H3C'~ \CH3 59) ~-C4Hg (CH3CH2)2N~ ~ CH2CH3)2 ~(CIHs) 2 CH3\ /CH3 ~ CH3\ /CH3 ~0) C2Hg~ -C2Hs CH3' \CH3 2~s 2Hs CH3' \CH3 ~ H3C\ /CH3 61) ~ ~ with R = -NH-CH2CH2CH2-0~ CH3 R ~ R H3C/ CH3 131~)786 c~`

.\.
~s~
x ~

r~
ro \,A ~
~ ~ ~ ! ! ~ ~ ,~ ;3~ o o T ~

S~ 7; :1:1 ~"~ ,o N

_ ~ ~\~
T
~1 1,' ~ I i t5, :Z ~ o~ Z ", ,~

.

.

- 20 - ~3107~

CH3~ ~CH3 C8HI7~ H
~ ~ CH3 CH3 64) C.3HI7 ~ H(CHz)3- - _ CH3~ CH3 CH3 H~ CH3 2 ÇH2cH2oH
CH3~ ~CH3 CH3~ \CH3 65) ~-C4Hg CH3~ ~CH3 ~ ~ CH3~ ~CH3 H0-CH2CH2~ -CH2CH2-OH

ÇH2-CH=CH2 H3C~ CH3 H3C/I\ ~I\CH3 ~-C4H~
(66~ H3C~ ~CH3 ~ ~ . f, 3 H2CaHC-H2C~ N~ -CH2-C~kCH2 ,~. 4Hg 4Hg ._.
H3C CH3 CH3~ \CH3 13107~6 f) Compounds of the formula VII

\ 3 \ / 2 O
/ ~N 1~ (VII) CH/ \CH R n ;n which n is the number 1 or 2; R is as def;ned under the formula (I)~ and R14 when n i s '1~ iS C-4~C18 alkyL, .
C -C 2 aralkyl, the group -CO-R15, or C1-C4 alkyl which is substituted by -CN, -COOR16, -OH, -OCOR17 or CH -CH(OH)-~ wherein R15 is C1 C12 Y ~ 2 4 ~k~nyl or phenyl~ R16 is C1-C18 alkyl, R17 1 18 alkyl, C2-C10 alkenyl, cyclohexyl, ben~yl or C6-C10 aryl;
ar R14 when n is 2 is C4-C12 alkylene, 2-butenylene-1,4, xylylene, the group H2 2 18 2 2 group -CH2-OOC-R19-COO-CH2- wherein R18is C2-C10 alkylene~
phenylene or cyclohexylene, and R19 is C2-C10 alkylene, xylylene or cyclohexylene.

If any substituents are C1~C12 alkyl, they are for example methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl~ n-nonyl, n-~ecyl, n-undecyl or n-dodecyl.

Any subst;tuents which are C1-C18 alkyl can be for example the groups ment;oned above~ and in addition for example n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

- 22 - ~ 6 If any groups are C2-C~O alkylene, these are in particular ethylene, propylene, 2,2-dimethylpropyLene, tetramethylene, hexamethylene, octamethylene or deca-methylene.

As C4-C18 alkyl, R14 is for example n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, 1~1-dimethyl-2-tert-butylethyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl~
n-tetradecyl, n-hexadecyl or n-octadecyl.

If R14 is a C1-C4 alkyl group substituted by -CN, ;t is for example cyanomethyl, cyanoethyl, 3-cyano-n-propyl or 4-cyano-n-butyl.

If R14 is C4-C12 alkylene, it is for example 2 2-dimethylpropylene, tetramethylene, hexamethylene, octa-methylene, decamethylene or dodecamethylene.

If R14 is C7-C12 aralkyl, ;t ;s in particular phenethyl, p-methyl-benzyl or especially benzyl.

As C2-C4 alkenyl, R15 is for example vinyl, ~-propenyl, allyl, methallyl or 2-butenyl.

As C2-C10 alkenyl, R17 ;s for example the groups mentioned for R15 as alkenyl, and in addition for example crotyl, 2-hexenyl, 2-octenyl or 2-decenyl.

If Rj7 is C6-C10 aryl, it is for example phenyl which is unsubstituted or substituted in the o- or p-position by methyl, ethyl, isopropyl, n-butyl or tert-butyl.

:

1 3 1 07~

The following compounds are examples of polyalkyl-piperidine light stabilizers of this class:

67) bis-[~-(2,2,6,6-tetramethylpiperidino)-ethyl]~
sebacate, 68) a-(2,2,6,6-tetrame~hylpiperidino)-acetic acid-n-octyl ester, and ~9) 1,4-bis-(2,2,6,6-~teiramethylpiperidino)-2-butene.

9) Compounds of the formula VIII

E CO-NH-CH2-OR20 (VIII ) RCH / \CH

tR21) or -0-; E is C1-C3 alkylene, the yroup -CH2~CH(Z4)-0- wherein Z4 is hydrogen, methyl or phenyl, the group -(CH2)3-NH- or a s;ngle bond; R is hydrogen or methyl; R1 is hydrogen, C1-C18 alkyl~, C3-C8 3 l kenyl, C3-C8 alkynyl, C7-C12 aralkyl, C1-C8 alkanoyl, C3-C5 alkenoyl or glycidyl; R20-is hydrogen or C1-C18 3lkyl; R.21 is hydrogen, C1-C18 alkyl, C5-C7 cycloalkyl~
C7-C12 aralkyl, cyanoethyl, C6-C10 aryl, the group -CH2-CHt~4)-QH, a group of the formula 2\ ~CH3 /R

`~
~ ~ ~ 0 ~ 3 ~

or a group of the formula --G~E--C~O-NH-CH2-OR20 / \ /
CH3~¦ I 3 RCH2 \~/ CH2R

wherein G can be C2-C6 alkylene or C6-C12 arylene; or R21 is a group ~E-CO-NH-CH2-OR20.

If any substituents are C1-C18 alkyl, they are for ~xample methyl, ethyl, n-propyl, n-butyl, sec-butyl, tert-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

If any substituents are C7-C12 aralkyl, they are for example phenethyl or in particular benzyl.

If R1 is C3-C8 alkenyl, it can be for example 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2~octenyl or 4~tert-butyl-2-butenyl.

As C3-C8 alkynyl, R1 is preferably propargyl. As C1-C~ alkanoyl, R1 ;s for example formyl, propionyl, butyryl, octanoyl but preferably acetyl; and as C3-C5 alkenoyl, R1 is espec;ally acryloyl.

As C5-C7 cycloalkyl, R21 ;s in part;cular cyclohexyl~

As C6-C10 aryl, R21 is particularly phenyl, or a- or 13~07~6 ~-naphthyL which is unsubstituted or substituted with halogen or C1-C4 alkyl~ As ~1-C3 alkylene, E is for example methylene, ethylene or propylene.

As C2-C6 alkylene, G is for example ethylene, propylene, 2,2-dimethylpropylene~ tetramethylene or hexamethylene;
and as C6-C12 arylene, G is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

Thè'follQwing compounds are examples o~ polyalkyl-piperidine light stabilizers of this class:

70) N-hydroxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-urea, 71) N-methoxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-urea, 72) N-methoxymethyl-N'-n-dodecyl-N'-2,2,6,6-tetramethyl-piperidin-4-yl-urea, and 73) 0-(2,2,6,6-tetramethylpiperidin-4-yl)-N-methoxy-methyl-urethane.

h) Oligomeric or polymeric compounds, the recurrent structural unit of which contains a 2,2,6,6-tetraalkylpiper-idine radical of the formula (I), in particular polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly~meth)acrylates, poly(meth)acryl-amides and copolymers thereof, which contain such radicals~
Examples of 2,2,6,6-tetraalkylpiperidine light stab-ilizers from this class are the compounds of the following ~ormulae, m being a number from 2 to 200.

~ 3 1 07~6 ~ 26 ~6) CH3\ ~CH3 ~C--CH2--CH2~ CH2--CH2--N~ ~-~;;
CH3~ \CH3 77)CH3\ /CH3 CH3~ ~CH3 CH2-CH2~ -O-C-(CH2~4-C-0-~\ ~ -CH2-CH2-0-C-(CHz)4-C

7B)CH3~ /C2Hs CH3~ /C2Hs - ~CH 2)3 - ~ ~. - NH-~ t -C-NH--\ ~ -(CH 2 )3-NH~
CH3 C2Hs ~ CH; C2Hs ~-79) H3 H3 ~H ~ - CH2- --CH3 .~ CH3 H3 (CH2) ~I t~ CH3\~ i/cH3 80) CH3 ~ CH3 CH3 ~ CH3 [ ~ --CH2--CH(OII)--CH2~
CH t' 't CH
CH3 ~ CH3 81) CH3\ ~CH3 CH3\ /CH3 CH2--CH=CH--CH2--h~~- ~ C--~--C

_ ~ (CH 2 ~ 6 - ~ ]~
~ 3~1 t/ 3 CH ~ & H

CH3\t/ \t~CH3 CH3/ ~ ~CH3 CH3 ~ \CH3 1 3 t 07~, 83) CH3\ ~CH3 CH3\ /CH3 _ -0-~ CH2~ -CH2- ~o-8-(CHz)~- ~ _ ._, .=, ,_.
CH3 CH3 CH3 CH3 m ~4) CH3\ /CH3 -o--CH2-CH2- ~ /-~S) H3 CH2 ~

O= , \./
~,/ ~ - CH3 CH3f \CH3 86) H3 E ---CH2 ~
CH3\ /CH3 O=
C~Hl3- 1-~/ ~ - CH3 CH3/ \CH3 ,/o\~
\~

,~ , ~ ~ (CH~) CH 1~ \i CH CH / \ CH
CH3/ ~ \CH3 CH3/ y \CH3 88) (CH2)6 ~ - CHz-CH2 CH t' ' CH
CH3f ~ \CH3 CH3 ~ CH3 1 3 1 07~6 89) [ ~ -~cH2)6 ~ 8_ CH2- 8 CH I~ `- CH CH3~, i/CH3 CH3 ~ CH3 CH3 ~ CH3 with compounds 76 and 79 be;n~ preferred.

;) Compounds of the formula IX
2\ / 3~R

L RC~ CH3 nR23 (IX) wherein n is an integer of 1 to 4, preferably 2, R22 is H, OH or C1-C8 alkoxy, and ;f n is 1, R23 is C1-C20 alkyl, C5 C12 y C7-C14 aralkyl, and ;f n ;s 2~ R23 is C2-C12 alky~ene, C6 C12 Y
C8-C16 c~cloalkylene-dialkylene~ C8-E14 aralkylene, C4-C9 mono- or dioxaalkylene, and 23 3 12 lkane triyl and ' 23 4 12 ane tetrayl, and R and R1 are as defined before.

1 3 t 07~6 Preferred piperidine compounds carry polar substituents in the 4-position of the piperidine ring or carry a spiro ring in this position. Particularly preferred piperidine compounds are those of the above mentioned classes a~ to e~ and h).

The organotin carboxylates and alcoholates to be used according to the invention (component (B)) are generally known and are recognized for their ability to combat thermal degradation in polyvinyl chloride.

When the ~ substituents in the organotin compounds of component (B) of the composition according to this inv~ntion are alkyl, they may typically contain from 1 to ~0 or 10 to 30, respectively, carbon atoms in a linear or branched chain including~ for example, methyl, ethyl, n-propyl, isopropyl, n-butyl~ isobutyl, sec-butyl, tert-butyl, n-amyl, neopentyl, isoamyl, n-hexyl, isohexyl heptyl, octyl, decyl, dodecyl, tetradecyl, octadecyl and eicosyl. When they are cycloalkyl, they may typically be C5-C8 cycloalkyl, for example cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl. When they are aralkyl, they may typically be C7-C15-aralkyl, preferably phenyl-C1-C4-alkyl~ Examples are benzyl, ~-phenylethyl~ y-phenylpropyl or ~-phenylpropyl. When they are aryl, they may typ;cally b~ C6-Cl4-aryl, for example naphthyl or preferably phenyl.
~hen they are alkaryl, they may typically be naphthyl or ~r~-ferably phenyl substituted by 1 to 3, preferably 1 or 2, most preferably 1, C1-C18(preferably C1-C12) alkyl group(s).
E~amples are tolyl, xylyl, p-ethylphenyl or p-nonylphenyl.
This may also be substituted in that they may bear substituents such as alkyl, aryl, cycloalkyl, aralkyl, 1 3 1 07~6 alkaryl, alkoxy, etc. Typical substituted aryl radicals include anisyl and biphenyl. Substi-tuted aralkyl includes chlorobenzyl, p-phenylbenzyl and p-methylbenzyl.
Substituted alkaryl includes 2,6-di-tert-butyl-4-methyl-phenyl.

Illustrative of these organotin carboxylates and alcoholates are the following:

dibutyl-t;n d;tetradecyl ox;de, dibutyl-tin di-isotridecyl oxide, dibutyl-tin-bis-(p-oc~ylphenyl ox;de), d;octyl-t;n-b;s-(p-nonylphehyl ox;de), dioctyl-tin (ditetradecyl oxide), bis(dibutyl-p-nonylphenyloxy-tin) oxide, bis(dioctyl-p-octylphenyloxy-tin) oxide, bis(dibutyl-isotridecyloxy-t;n) ox;de, bis(d;butyl-tetradecyloxy-tin) oxide, d;butylt;n d;laurate, b;s(dibutyl-;sodecanoylt;n)oxide, dibutyltin d;-isooctadecyiate butylt;n tr;octanoate, d;phenylt;n d;laurate, 1 3 1 07~6 dibutyltin bis(isooctylmaleate), dibutyltin dipelargonate, d;butyltin distearate, dihexyltin dioleate, dioctyltin ditallate, dioctyltin diundecylenate, dibutyltin b;s~(neodecanoate), dioctyltin bis-~neotridecanoate), dibutyltin bis-(monomethyl maleate3, dihexyltin bis-(monohexyl maleate), dihexyltin bis-~monoisooctyl maleate), dibutyltin bis~(monocetyl maleate3, dibutyltin bis-(monooctadecyl maleate), dibutyltin bis-(mono-2-ethoxyethyl maleate), dioctyltin bis-(monocyclohexyl maleate), dihexyltin bis-(monobenzyl maleate) and butylhexyltin bis(mono-tert.butylbenzyl maleate).

Preferred organotin components are mi~tures of at least one compound of the formula (Z)zSn~ 2 and at least one 0~
compound of the formula (Z)2Sn(OOC-Z )2 Further preferred organotin compounds are dibutyltin d;-;sotr;decylox;de, d;butyltin d;-isostearate, dibutyltin d;-2-ethylhexanoate, d;butyltin dilaurate, dibutyltin d;tetradecanoate or mixtures thereof.

Add;t;onal stab;lizers, especially tin stabilizers, m~y be opt;onally blended w;th the above noted carboxylates orland alcoholates to form the heat stabilizer component of the compos;t;ons of this invention, such blends being pre-~erred for use ;n the instant invention. Such additional tin stab;l;~ers include, for example, organotin mercaptoesters and/or organotin mercaptides. Preferred organotin mercaptoesters correspond to the formula (Z)msn(s-cpH2pcooz )4~m 21~89-711-~ 3 ~ 07~6 wherein ~, Z4 and m are as previously defined, and p is an integer from 1 to 5, preferably 1 or 2, in particular 2 The aforementioned preferred members for these various substituents likewise apply in this instance.

Examples of such compounds are octyltin tris-~dodecyl-~-mercaptopropionate), dibutyltin bis~;sotridecyl-~-mercaptopropionate), dibutyltin bis~-ethylhexyl-~-mercaptopropionate), dibutyltin bis~tetradecyl-~-mercaptopropionate~, octyltin tris~alfyl-thioglycolate3, tributyltin isooctyl thi~ col~te, butyltin tris(cyclohexyl thioglycolate), ~ty~tin tris(isooctyl mercaptoacetate) and the like, with diblJ~yltin bis~isotridecyl-~-mercaptopropionate3, dibutyltin bis~tetradecyl-~-mercaptopropionate~, octyltin ~r;stdodecyl-~-mercaptopropionate) or dibutyltin bist~-ethylhexyl-~-mercaptopropionate) or mixtures thereof being preferred.

As previously noted, the organotin carboxylates and alc~h~lates as well as the organotin mercaptoesters and m~th~ds f~r their preparat;on are generally known.
U.3~ 2,8~û,182~ U.S. 3,398,114, U.S. 3,562,305, U~S. 3,o40,950, U.S. 3,640,947, U.S. 3,657,2Y4, U.3~ 3~33,741, U.SO 4~193,913, U~S~ 4,358,555, ~nad;an 1,152~735 and Canadian 1,170,031 are typical of ~h~ numerous patents that disclose such organotin materials.
Mix~lres of carboxylates and mercaptoesters are particularly d;sclosed, for example, in U,S. 3,562,305, U.S. 3,933,741, ~anadian 1,152,735 and Canadian 1,170,031.

As a further optional but preferred system~ the organo-tin carboxylate or alcoholate by itself or inc~mbintaion with the 13 1 07~G

~ 7117 mercaptoester can be combined with an organotin mercaptide. The organotin mercaptides are also com-mercially available and well known to those skilled in the art. Such mercaptides correspond, for example, to the general formula (Z ~) Sn(Z )4 y wherein Z and Z are individually selected from alkyl, cycloalkyl, aryl, alkaryl or aralkyl radicals among others (specific substituents listed hereinabove) and y is 1-3. A w;de variety of tin mercaptides and methods for preparation thereof are disclosed in U.S. 2,641,588~ U.S. 2,726,227, U.S. 3,933,741 and U.S. 3,953,285. Likewise, mixtures of carboxylates and mercaptides are disclosed, for example, in U.S. 3,562,305 and U.S. 3,933,741.

Representive mercaptides include dibutyltin bis(lauryl mercaptide), butyltin tris(lauryl mercaptide), dibutyltin bis(octyl mercaptide), dibut~ltin bis(benzyl mercaptide), dioctyltin bis(cyclohexyl mercaptide), dioctyltin bis(octyl mercaptide), dimethyltin bis~lauryl mercaptide) and dicyclohexyltin bis(lauryl mercaptide)n With respect to concentrations of the components, the 2,2,6,6-tetraalkylpiperidine is preferably present in amounts ranging from 0.1 to 3.0 /O~ by weight of resin, and preferably 0.25 to 1.5 %, and the organot;n carboxylate or alcoholate ;s preferably present ;n amounts ranging from 1.0 to 5.0 %, by we;ght of resin, and preferably 1.5 to 4.0 %. When the organotin mercaptoester and/or the tin mercaptide are present, they can replace, for example, 1 ~ 1 07~6 either individually or together a maximum of about 70 ~., by weight, of the carboxylate and preferably up to about 40 %, by weight.

The titanium dioxides that are conventionally utilized in rigid polyvinyl chloride formulations are known and comnlercially available~ The preferred titanium dioxides are rutile grades. For purposes of th;s invention, for e~ample 0 to 1G.0 ~ of titanium dioxide, per weight of resin ;s applicable, with 1 to 10 ~, especially 2 to ~ %, for example 4.0 to 6.0 % being preferred when said titanium dioxide is present. These concentrations can provide 3dditional photodegradative inhibition when comb;ned with the stabilization systems while substant;ally eliminating the aforementioned disadvantages of high titanium d;oxide levels.

The compos;t;on of th;s ;nvent;on preferably does not contain any lead compounds (lead stab;l;zers) which are frequently present in polyvinyl chloride compositions.

The instant ;nvention realtes to a composition of r;3;d polyvinyl chloride, i.e. unplasticized polyvinyl chlor;de resin, as well as materials containing at least 85 ~ of polyvinyl chloride resin. Such resins generally conta;n further conventional additives including processing 3;ds, impact modifiers, lubricants, pigments, fillers, and th~ l;ke~ It is also possible to combine the systems with canvent;onal U~ absorbers and antioxidants such as ben~oates, ben20triazoles, benzophenones, hindered phenols ~r mixtures thereof. Techniques for processing rigid polyv;nyl chloride are also known to those skilled ;n the art and such techniques are applicable herein.

1 3 1 07~6 Compounding follwed by extrusion is the conven~10nal technique for siding manufacture.

As previously noted, the stabilized rigid polyvinyl chlorides of this invention exhibit a broad range of desirable properties. Of particular value they exhibit excellent thermal and UV stabilization over prolonged periods of time. They permit the reduction of titanium dioxide levels without sacrificing the light stability and impact strength provided by the high levels. In addition, the lowerins or elimination of the titanium dioxide content allows for significantly reduced wear on the processing machinery and for an expansion of the number of pigmented systems that can be readily utilized therein.
Thus~ wh;le the high titanium dioxide levels restrict the ava;lable colors to white and pastels, the instant systems are available in a broad range of light, pastel and dark colors.

Ihe following example ;llustrates some preferred embodiments of the invention. In this example, all parts given are by weight unless otherwise specified.

Example The following rig;d polyvinyl chloride base ~ormulat;ons are util;zed ;n the following tests.

I ~ 1 07~6 parts II III IV VVI VII
polyvinyl chloride resin1 100 1on ~ -- 100 polyv;nyl chloride res;n --- --- 100100 100 100 -~-methacryl;c acid~ester processing aid 1~0 1.0 2.02.0105 1.5 2.5 acrylic impact modifier4 7.0 7.07.07.0 7.0 7.0 ---Calcium stearate --- --- 0.8 --- 0~8 ~~~ ~~~
paraffin wax 0.6 ---1.0 1.0 1.0 1-0 ~~~
polyethylene wax 0.3 0~20.2 0.2 2.0 0.2 ---titanium dioxide (rutile, non-chalking) variable light stab;l;zer variable heat stab;l;zer variable 1 - ~Diamond Shamrock 500 2 - ~ EON 103EP-76 3 - ~ACRYLOID K120N
!4 - ~ACRYLOID K323B

The ingred;ents are blended including the ;nd;cated amounts of TiO2 and stab;lizer. The samples are milled on a two roll mill (front roll ~ 171C - back roll @ 165C) for a period of three minutes after band formation. The resulting material is then compression molded (temperature 182C, 2 minutes contact pressure, 1 minute pump;ng pressure, 2 m;nutes full pressure, cool to 38C) and cut ;nto test plaques (5~1 cm. x 5~1 cm.) The follow;ng stab;l;zers are ut;l;zed in these tests.
~2,6,6-t~tramethylpiperidine compounds 1 3 ~ Q7~6 - 37 ~

A - 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-tri-azaspiro(4,5)decane-2,4-dione B - bis~2,2,6,6-tetramethyl-4-piperidinyl)sebacate C - bis(1-acetyl-2,2,6~6-tetramethyl-4-piperidinYl)-sebacate D - b;s(l-benzyl-2~2,6,6-tetramethyl-4-piperidinyl)-sebecate E - poly[6-(1,1~3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl-~2,2,6,6-tetramethyl-4-piperidinyl)imino-hexamethylene-(2,2,6,6-tetramethyl-4-p;per;d;nyl)-;mino] (= compound 79 above) F - N-butyl-(3,5-d;-tert.butyl-4-hydroxybenzyl)-bis-(1,2,2,6,6-pentamethyi-4-piperidinyl)malonate - polysuccinate of 4~hydroxy-1-hydroxyethyl-2,2,6,6-tetramethylpiperidine (= compound 76 above) Tin Stabilizers -H - A blend of approximately 9:1, by weight, of m;xed ` d;butylt;n b;s(;sooctyl th;oglycolate)/butyltin tris (;sooctyl th;oglycolate) and mixed butvlth;ostanno;c acid/d;butyLtin sulfide I - A blend o~ approx;mately 3:1, by we;ght, of dimethyl-t;n bis(2-ethylhexylthioglycolate) and methylt;n tris(2-ethylhexylthioglycolate) J - A blend of apporximately 2:1, by weight, of mixed dibutylt;n di-;sotridecyl oxide/dibutyltin d;-;sostearate and dibutyltin bis(isotridecyl-~-mercaptoprop;onate) 1 3 1 07~6 21~9-7117 K - A blend of approximately 2:1, by weight, of dibutyltin bistmixed 2-ethylhexanoate and laurate) and dibutyltin bis(tetradecyl-~-mercaptoporpionate) L - A blend of 3 2, by weight, of dibutyltin bistmixed 2-ethylhexanoate and tetradecanoate) and dibutyltin bis (isotridecyl-~-mercaptopropionate) M - A blend of 2:1, by weight, of dibutyltin bis(mixed 2-ethylhexanoate and laurate) and dibutyltin bis (isotridecyl-~-mercaptopropionate) N - A blend of 2:1, by weight, of mixed dibutyltin di-tetradecanoateldibutyltin di-isotridecyl oxide and dibutyltin bis(isotridecyl-~ mercaptopropionate) O - dibutyltin bis(methylmaleate~

Other Additives P - 2-(2-hydroxy-3,5-diamylphenyl)benzotriazole Q - 1,6-hexanediol-bis-(3,5-di-tert.butyl-4-hydroxy-benzoate) The formulated samples are submitted to the following test procedures:

Test I - Dry Xenon Weatherometer Exposure .. . . . _ G~
Exposed in Xenon Weatherometer at black panel temperature of oO-66C and relative humidity of 25-35 %.
Samples are withdrawn at periodic intervals and yellowness index measured according to ASTM D-1925-63T. Higher values are indicative of lower stability. "Failure"
reflects a yellowness index greater than 40 .

1~107~6 Test II - Spray Xenon Weatherometer Exposure Exposed as in Test I with identical bLack panel temperature, relative humidity of 65-75 %, 102 m;nutes of dry cycle and 18 minutes of water spray cycle. Me~sured by yellowness index~

Test III - Arizona Exposure Exposed outdoor in Arizona at an angle of 45 from the horizontal facing south. Yellowness index measured in;t;ally~ after n;ne months exposure at 140,000 langleys and after twelve months exposure at 181,000 langleys~

The results obtained in these tests are noted in the following tables:

Table I
Test Procedure I

Base Formulation II YeLLowness Index Stab;lizers Conc. Conc.0 2045 4322 Stabilizers TiO2 hrs. hrs. hrs.
(parts) (parts~

1 3 1 07$6 Table II
. . .
Test Procedure III

Base Formulation IV Yellowness Index St~bilizers Conc. Conc~ 0 9 12 Stabilizers Tio2 months months months (parts) (parts) Table III
Test Procedure II
Base Formulation V Yellowness Index Stabilizers Conc~ Conc 0 2500 3500 Stabilizers TiO2hrs. hrs.hrs.
(parts) (parts) -E/H 0.3/2 5 6 7 12 B~se For~ulation VI
~ .

B~K/P 1/2/1 5 3 3 6 E/K 0.3/2 5 5 3 5 F/K/P 0.3/2/1 5 4 5 7 E/J 0.3/2 5 3 4 8 B/N~Q 1/2/1 5 4 3 5 13107~6 Table IV
Test Procedure I

Base Formulation VII YelLowness Index Stabilizers Conc. Conc, 0 400 700 1300 1900 StabiLizers TiO2 - hrs.h'rs.hrs.hrs.hrS.
_ _ (parts)(parts) F/I 0.5/2.5 0 8 20 40 Fail Fail G/I 0.5/2.5 0 8 16 41 Fail Fail F/0 0~5/2.5 0 16 12 11 12 9 G/0 0~5/2~5 0 16 4 4 7 7

Claims (16)

1. A rigid polyvinyl chloride composition comprising in addition to said polyvinyl chloride, (A) at least one 2,2,6,6-tetraalkylpiperidine compound which contains at least one group of the formula wherein R is hydrogen or methyl;
and (B) at least one organotin compound of the formulae (Z) 2Sn-OZ2 (Z)2Sn(OOC-Z3)2 (Z)mSn(OOCCH=CHCOOZ4)4-m wherein Z and Z4 independently are C1-C20 alkyl, C3-C20 alkenyl, cycloalkyl, aryl, alkaryl or aralkyl;

Z1 is C10-C30 alkyl or phenyl substituted by one or two C8-C12 alkyl;

Z2 is 11 or -Sn(OZ1)(Z)2;

Z3 is C1-C30 alkyl, C3-C20-alkenyl, cycloalkyl, aryl, alkaryl or aralkyl; and m is an integer from 1 to 3, with the proviso that the composition does not contain any lead stabilizer.

2. The composition of claim 1, wherein said 2,2,6,6-tetraalkylpiperidine compound corresponds to the formula (II), in which n is a number from 1 to 4, R is hydrogen or methyl, R1 is hydrogen, oxyl, C1-C18-alkyl, C3-C8-alkenyl, C3-C8-alkynyl, C7-C12-aralkyl, C1-C8-alkanoyl, C3-C5-alkenoyl, glycidyl or a group -CH2CH(OH)-Z, with Z being hydrogen, methyl or phenyl, and R2, if n = 1, is hydrogen, C1-C18-alkyl which may be interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monobasic radical of an aliphatic, cycloaliphatic, araliphatic, unsaturated or aromatic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, or, if n = 2, R2 is C1-C12-alkylene, C4-C12-alkenylene, xylylene, a dibasic radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, or, if n = 3, R2 is a tribasic radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, an aromatic tricarbamic acid or a phosphorus-containing acid or a trivalent silyl radical, and, if n = 4, R2 is a tetra-basic radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid

3. The composition of claim 2, wherein said 2,2,6,6-tetraalkylpiperidine compound is bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1-acteyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate or N-butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)-bis-(1,2,2,6,6-pentameth-1-4-piperidinyl)malonate.

4. The composition of claim 1, wherein said 2,2,6,6-tetraalkylpiperidine compound corresponds to the formulae (VA) (VB) (VC) in which n is the number 1 or 2, R and R1 are as defined in claim 1, R6 is hydrogen, C1-C12-alkyl, allyl, benzyl, glycidyl or C2-C6-alkoxyalkyl and R7, if n = 1, is hydrogen, C1-C12-alkyl, C3-C5-alkenyl, C7-C9-aralkyl, C5-C7-cyclo-alkyl, C2-C4-hydroxyalkyl, C2-C6-alkoxyalkyl, C6-C10-aryl, glycidyl or a group of the formula -(CH2)p-COO-Q or of the formula -(CH2)p-O-CO-Q, wherein p is 1 or 2 and Q is C1-C4-alkyl or phenyl, or, if n = 2, R7 is C2-C12-alkylene, C4-C12-alkenylene, C6-C12-arylene, a group -CH2-CH(OH)-CH2-O-D-O-CH2-CH(OH)-CH2-, wherein D is C2-C10-alkylene, C6-C15-arylene or C6-C12-cycloalkylene or a group -CH2CH(OZ')CH2-(OCH2-CH(OZ')CH2)2- wherein Z' is hydrogen, C1-C18-alkyl, allyl, benzyl, C2-C12-alkanoy or benzoyl, and T1 and T2 independently of one another are hydrogen, C1-C18-alkyl or are C6-C10-aryl or C7-C9-aralkyl which are unsubsti-tuted or substituted by halogen or C1-C4-alkyl, or T1 and T2, together with the C atom linking them, form a C5-C12-cyclo-alkane ring.

5. The composition of claim 4, wherein said 2,2,6,6-tetraalkylpiperidine compound is 8-acetyl-3-dode-cyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro (4,5)decane-2,4-dione.

6. The composition of claim 1, wherein said 2,2,6,6-tetraalkylpiperidine compound is a polymeric compound of which the recurring structural unit contains the 2,2,6,6-tetraalkylpiperidine group of claim 1.

7. The composition of claim 6, wherein said polymeric compound is poly[6-(1,1,3,3-tetramethylbutyl)-amino-1,3,5-triazine-2,4-diyl-(2,2,6,6-tetramethyl-4-piperidinyl)imino-hexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)imino] or polysuccinate of 4-hydroxy-1-hydroxyethyl-2,2,6,6-tetramethylpiperidine.

8. The composition of claim 1, wherein said piperidine compound is present in a concentration of from 0.1 to 3.0 % and said carboxylate is present in a concentration of from 1.0 to 5.0 %, each by weight of polyvinyl chloride resin.

9. The composition of claim 8, wherein said concentrations are 0.25 to 1.5 % and 1.5 to 4.0 %
respectively, by weight of polyvinyl chloride resin.

10. The composition of claim 1, wherein said organotin component is a blend of at least one compound of the formula and at least one compound of the formula (Z)2Sn(OOC-Z3)2.

11. The composition of claim 1, wherein said organotin component is dibutyltin di-isotridecyloxide, dibutyltin di-isostearate, dibutyltin di-2-ethylhexanoate, dibutyltin dilaurate, dibutyltin ditetradecanoate or mixtures thereof.

12. The composition of claim 1, which contains at least one additional organotin compound of the formulae (Z)mSn(S-CpH2pCOOZ4)4-m or/and (Z5S)ySn(Z6)4-y wherein Z, Z4, Z5 and Z6 independently are C1-C20 alkyl, cycloalkyl, aryl, alkaryl or aralkyl, and Z and Z4 additionally C3-C20-alkenyl m and y are integers from 1-3, and p is an integer from 1-5.

13. The composition of claim 12, wherein said additional organotin compound is dibutyltin bis(isotridecyl-.beta.-mercaptopropionate), dibutyltin bis(tetradecyl-.beta.-mercaptopropionate), octyltin tris(dodecyl-.beta.-mercaptopropionate) or dibutyltin bis(2-ethylhexyl-.beta.-mercaptopropionate) or mixtures thereof.

14. The composition of claim 12, wherein said piperidine compound is bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, bis(1-benzyl-2,2,6,6-tetramethyl-4-piperidinyl)sebacate, N-butyl-(3,5-di-tert.butyl-4-hydroxybenzyl)-bis-(1,2,2,6,6-pentamethyl-4-piperidin-yl)malonate, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro (4,5)decane-2,4-dione, poly[6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-triazine-2,4-diyl-(2,2,6,6-tetramethyl-4-piperidinyl)imino-hexamethylene-(2,2,6,6-tetramethyl-4-piperidinyl)imino] or polysuccinate of 4-hydroxy-1-hydroxyethyl-2,2,6,6-tetramethylpiperidine;
said tin carboxylate or alcoholate is dibutyltin di-isotridecyl-oxide, dibutyltin di-isostearate, dibutyltin di-2-ethylhexanoate, dibutyltin dilaurate, dibutyltin ditetradecanoate or mixtures thereof; and said additional organotin compound is dibutyltin bis(isotridecyl-.beta.-mercaptopropionate), dibutyltin bis(tetradecyl-.beta.-mercaptopropionate), octyltin tris(dodecyl-.beta.-mercaptopropionate) or dibutyltin bis(2-ethylhexyl-.beta.-mercaptopropionate).

15. The composition of claim 1 which also contains a maximum of 10% titanium dioxide, by weight of polyvinyl chloride resin.

16. The composition of claim 1 which also contains benzotaes, benzotriazoles, benzophanones, hindered phenols or mixtures thereof.