Stabilizer system for stabilizing pvc

专利摘要:

公开号:AU2003292262A1
申请号:U2003292262
申请日:2003-12-20
公开日:2004-08-13
发明作者:Hans-Helmut Friedrich；Thomas Hopfmann；Karl-Josef Kuhn；Wolfgang Wehner
申请人:Crompton Vinyl Additives GmbH；
IPC主号:C08K3-24

专利说明:
IN THE MATTER OF an Australian Application corresponding to PCT Application PCT/EP2003/014691 RWS Group Ltd, of Europa House, Marsham Way, Gerrards Cross, Buckinghamshire, England, hereby solemnly and sincerely declares that, to the best of its knowledge and belief, the following document, prepared by one of its translators competent in the art and conversant with the English and German languages, is a true and correct translation of the PCT Application filed under No. PCT/EP2003/014691. Date: 20 April 2005 C. E. SITCH Deputy Managing Director - UK Translation Division For and on behalf of RWS Group Ltd WO 2004/065470 PCT/EP2003/014691 Stabilizer system for stabilizing PVC The invention relates to stabilizer mixtures, encompassing at least one alkanolamine, at least one 5 uracil, and, if appropriate, one perchlorate salt, the mixtures being suitable for stabilizing chlorine containing polymers. There are many additives which can stabilize PVC. 10 Compounds of the heavy metals lead, barium and cadmium are particularly well suited to this purpose, but are nowadays subject to criticism on environmental grounds or due to their heavy metal content (cf. "Plastics Additives Handbook", H. Zweifel, Carl Hanser Verlag, 15 5th edn., 2001, pp. 427-483 and "Kunststoff Handbuch PVC" [Plastics Handbook PVC], volume 2/1, W. Becker/D. Braun, Carl Hanser Verlag, 2nd edn., 1985, pages 531 538; and also Kirk-Othmer: "Encyclopedia of Chemical Technology", 4th ed., 1994, Vol. 12, Heat Stabilizers, 20 pp. 1071-1091). Processors and consumers are increasingly refusing to use these stabilizers. Attempts therefore continue to find effective stabilizers and stabilizer mixtures which are free from 25 lead, barium and cadmium. The intention here is also to provide a composition which has stabilizing action with respect to thermal and/or photochemical degradation and which, as a constituent of halogen-containing polymers, gives excellent initial color and also gives color 30 stability. A mixing specification matched to the processing method can be provided here, appropriate for the prevailing requirements, which may be based on health and safety 35 at work, approval restrictions or process reliability. Surprisingly, this invention provides combinations of substances which are physiologically non-hazardous in plastics and which in some cases certainly do not provide satisfactory processing stability when used -2 alone. The applicant's specification WO 02/48249 A2 discloses compounds of the formula (I) in combination with at 5 least one perchlorate salt. The comparative and inventive examples of this specification show that compounds of the general formula (I), used alone, do not contribute to acceptable initial color. 10 It has now been found that mixtures composed of a) at least one alkanolamine or one reaction product of a mono- or polyfunctional epoxide and of ammonia or of a mono- or polyfunctional dialkyl(aryl)- or monoalkyl(aryl)amine of the general formula (I), and of 15 b) at least one uracil of the general formula (II) or, respectively, of their precursors of the general formula (III), and, if appropriate, one perchlorate salt, in particular a perchlorate of an alkali metal or of an alkaline earth metal, are particularly suitable 20 for stabilizing chlorine-containing polymers, in particular PVC. The object set, to provide a stabilizer mixture complying with the requirements placed upon initial color, has been met via this novel combination. Further addition of a perchlorate salt, in particular a 25 perchlorate of an alkali metal or of an alkaline earth metal, can improve the stabilization of chlorine containing polymers, in particular PVC. The use of other classes of amines alone without perchlorate does not give satisfactory processing 30 stability, and in particular the initial color of the desired moldings does not differ substantially from that of an unstabilized specimen, the consequence therefore being that the requirements for good initial color and process reliability desired by processors are 35 not met. The P-hydroxyalkanolamines used in combination with the uracils of structure (II) or with their precursors of structure (III) can assume the function of improving initial color. This permits production of moldings with - 3 service properties complying with expectations over a prolonged period. Surprisingly, synergistic action of the claimed combination, extending beyond the action of comparative 5 mixing specifications comprising the individual components, has also been found in systems with perchlorate. The present invention therefore provides stabilizer 10 mixtures, encompassing at least a) one alkanolamine or/and one reaction product of a mono- or polyfunctional epoxide and of ammonia or of a mono- or polyfunctional 15 dialkyl(aryl)- or monoalkyl(aryl)amine of the formula (I) and b) one uracil of the formula (II) or its precursor of the formula (III), and, if 20 appropriate, c) one perchlorate salt. For the alkanolamine of the formula (I) here 25
R
2 RN - (CHR )T-CHR - H n I x = 1, 2 or 3; y = 1, 2, 3, 4, 5 or 6; 30 n = from 1 to 10; Ri and R2 = independently of one another H, Ci-C 22 -alkyl, - [ (CHR a) y-CHR bO-] I-H, - [ (CHR 3 a) y-CHR 3 b-O- n-CO-R,
C
2
-C
20 -alkenyl, C 2 -Ci-acyl, C 4 -C-cycloalkyl, where this may have OH substitution in the P-position, C 6 -Cio-aryl, 35 C 7 -Cio-alkaryl or C 7 -Co-aralkyl, or, if x = 1, R1 and R2 may also, together with the N, form a closed ring having from 4 to 10 members, composed of carbon atoms and, where appropriate, of up to 2 heteroatoms, or if x = 2, R' may also be C 2 -Ci 8 -alkylene which, at both 5 -carbon atoms, may have OH substitution and/or have interruption by one or more 0 atoms and/or by one or more NR groups, or be dihydroxy-substituted tetrahydrodicyclopentadienylene, dihydroxy-substituted ethylcyclohexanylene, dihydroxy-substituted 10 4,4'-(bisphenol A dipropyl ether)ylene, isophoronylene, dimethylcyclohexanylene, dicyclohexylmethanylene or 3,3'-dimethyldicyclohexylmethanylene, and if x = 3, R' may also be trihydroxy-substituted (tri-N-propyl isocyanurate)triyl; 15 R 3 a and R 3 b = independently of one another Ci-C 2 2 -alkyl,
C
2 -C-alkenyl, C 6 -Cio-aryl, H or CH 2 -X-R , where X = 0, S, -0-CO- or -CO-O-;
R
4 = C 1 -Ci-alkyl/alkenyl or phenyl; and R = H, Ci-C 22 -alkyl, C 2
-C
22 -alkenyl or C 6 -Cio-aryl. 20 The invention also provides stabilizer mixtures where the alkanolamine is a reaction product of a mono- or polyfunctional epoxide and of ammonia or of a mono- or polyfunctional dialkyl(aryl)- or monoalkyl(aryl)amine. 25 Examples of the alkanolamines of the general formula (I) are compounds where R1 and R2 = methyl, ethyl, propyl, butyl, cyclohexyl, octyl, lauryl, tetradecyl, hexadecyl, stearyl, oleyl, allyl, phenyl or benzyl or 30 hydroxyalkyl and R 3 = H, methyl, ethyl, propyl or butyl. Preference is given to alkanolamines where R' = lauryl, tetradecyl, hexadecyl, stearyl, or oleyl, where R2 hydroxyalkyl. It is also possible to use ethoxylates and propoxylates of triethanol- and tri 35 isopropanolamine, and also of fatty amines of vegetable or animal origin. Preference is given to trialkanolamines and monoalkyl/alkenyldialkanolamines where R 3 = H or methyl and y = 1, in particular fatty amines which have been reacted twice with ethylene - 5 oxide or with propylene oxide. Other compounds with very good suitability can be found in the following list. 5 Methyl- or dimethylamine reacted once or twice with ethylene oxide or with propylene oxide. Propyl- or dipropylamine reacted once or twice with ethylene oxide or with propylene oxide. 10 Isopropyl- or diisopropylamine reacted once or twice with ethylene oxide or with propylene oxide. Butyl- or dibutylamine reacted once or twice with 15 ethylene oxide or with propylene oxide. Isobutyl- or diisobutylamine reacted once or twice with ethylene oxide or with propylene oxide. 20 Pentyl- or dipentylamine reacted once or twice with ethylene oxide or with propylene oxide. Isopentyl- or diisopentylamine reacted once or twice with ethylene oxide or with propylene oxide. 25 Hexyl- or dihexylamine reacted once or twice with ethylene oxide or with propylene oxide. Isohexyl- or diisohexylamine reacted once or twice with 30 ethylene oxide or with propylene oxide. Heptyl- or diheptylamine reacted once or twice with ethylene oxide or with propylene oxide. 35 Isoheptyl- or diisoheptylamine reacted once or twice with ethylene oxide or with propylene oxide. Octyl- or dioctylamine reacted once or twice with ethylene oxide or with propylene oxide.
- 6 Isooctyl- or diisooctylamine reacted once or twice with ethylene oxide or with propylene oxide. 5 Nonyl- or dinonylamine reacted once or twice with ethylene oxide or with propylene oxide. Isononyl- or diisononylamine reacted once or twice with ethylene oxide or with propylene oxide. 10 Decyl- or didecylamine reacted once or twice with ethylene oxide or with propylene oxide. Isodecyl- or diisodecylamine reacted once or twice with 15 ethylene oxide or with propylene oxide. Undecyl- or diundecylamine reacted once or twice with ethylene oxide or with propylene oxide. 20 Isoundecyl- or diisoundecylamine reacted once or twice with ethylene oxide or with propylene oxide. Dodecyl- or didodecylamine reacted once or twice with ethylene oxide or with propylene oxide. 25 Isododecyl- or diisododecylamine reacted once or twice with ethylene oxide or with propylene oxide. Tridecyl- or ditridecylamine reacted once or twice with 30 ethylene oxide or with propylene oxide. Isotridecyl- or diisotridecylamine reacted once or twice with ethylene oxide or with propylene oxide. 35 Tetradecyl- or ditetradecylamine reacted once or twice with ethylene oxide or with propylene oxide. Hexadecyl- or dihexadecylamine reacted once or twice with ethylene oxide or with propylene oxide.
Octadecyl- or dioctadecylamine reacted once or twice with ethylene oxide or with propylene oxide. 5 Eicosyl- or dieicosylamine reacted once or twice with ethylene oxide or with propylene oxide. Docosyl- or didocosylamine reacted once or twice with ethylene oxide or with propylene oxide. 10 N-Methylbutylamine reacted with ethylene oxide or with propylene oxide. N-Ethylbutylamine reacted with ethylene oxide or with 15 propylene oxide. Allyl- or diallylamine reacted once or twice with ethylene oxide or with propylene oxide. 20 Crotyl- or dicrotylamine reacted once or twice with ethylene oxide or with propylene oxide. Octadecenyl- or dioctadecenylamine reacted once or twice with ethylene oxide or with propylene oxide. 25 Benzyl- or dibenzylamine reacted once or twice with ethylene oxide or with propylene oxide. Cyclohexyl- or dicyclohexylamine reacted once or twice 30 with ethylene oxide or with propylene oxide. N-Methylcyclohexylamine reacted with ethylene oxide or with propylene oxide. 35 N-Ethylcyclohexylamine reacted with ethylene oxide or with propylene oxide. 4-Vinyl-1-cyclohexene diepoxide reacted twice with diethanol- or diisopropanolamine.
- 8 Dicyclopentadiene diepoxide reacted twice with diethanol- or diisopropanolamine. Bisphenol A diglycidyl ether reacted twice with 5 diethanol- or diisopropanolamine. Trisglycidyl isocyanurate reacted three times with diethanol- or diisopropanolamine. 10 Preference is given to trialkanolamines and monoalkyl/ alkenyldialkanolamines where R 3 a and R 3 b = independently of one another H or methyl and y = 1. The compounds of the general formula (I) where y = from 15 1 to 6, i.e. having up to 6 methylene groups between the amino group and the hydroxy-substituted carbon atom, have been found to be suitable for use as a PVC stabilizer in combination with a perchlorate salt. 20 According to the invention it is also possible to use compounds of the general formula (I) where x = 2, i.e. compounds which have two hydroxyalkylamino groups per molecule. Examples of these are N,N,N',N' tetrakis(2-hydroxyethyl)ethylenediamine, N,N,N',N' 25 tetrakis(2-hydroxy-l-propyl)ethylenediamine, N,N,N',N' tetrakis(2-hydroxyethyl)propylenediamine and N,N,N',N' tetrakis(2-hydroxy-l-propyl)propylenediamine and N,N,N' , N'-tetrakis (2-hydroxyethyl) hexamethylenediamine, preference being given to four-fold reactions of 30 1,6-hexamethylene- or 1,8-octamethylenediamine or neopentanediamine with ethylene oxide or with propylene oxide, or analogous reactions of bisaminomethylcyclo hexane or isophoronediamine or 4,4'-diaminodicyclo hexylmethane or 3,3'-dimethyl-4,4'-diaminodicyclo 35 hexylmethane. According to the invention, it is also possible to use compounds of the general formula (I) where x = 3, i.e. those which have three hydroxyalkylamino groups per - 9 molecule. An example of these is a reaction product of trisglycidyl isocyanurate with mono- or diethanolamine or mono- or dipropanolamine. 5 The alkanolamines of the general formula (I) are chemicals which can be purchased or can be prepared by known methods via N-alkylation of an appropriate amine or ammonia (cf. Kirk-Othmer, Vol. 2, Alkanolamines). 10 Examples of the preferred alkanolamines of the general formula (I) are tris(2-hydroxyethyl)amine, tris(2-hydroxy-l-propyl)amine, bis(2-hydroxyethyl) 2-hydroxy-l-propylamine, N-n-butyl-N,N-bis(2-hydroxy ethyl)amine, N,N-bis(n-butyl)-N-(2-hydroxyethyl)amine, 15 N-(3-n-butyloxy-2-hydroxy-1-propyl)-N,N-bis(2 hydroxyethyl)amine, N-(1,3-dihydroxy-2-hydroxymethyl 2-propyl)-N,N-bis(2-hydroxyethyl)amine, N,N-bis (2-hydroxyethyl)-N-palmitylamine, N,N-bis(2-hydroxy ethyl)-N-oleylamine, N,N-bis(2-hydroxyethyl)-N 20 stearylamine, N,N-bis(2-hydroxyethyl)-N-stearylamine, N-(2-hydroxyethyl)morpholine and N-(2,3-dihydroxy-l propyl)morpholine, bishydroxyethylpiperazine and bishydroxyisopropylpiperazine and reaction products of glycidyl ethers with mono- or dialkylamine or ammonia, 25 and also the alkanolamines derived therefrom, for example ethanolamine, diethanolamine, n-propanolamine, isopropanolamine, n-dipropanolamine, or isodipropanolamine. 30 Very particular preference is given to adducts of olefin oxides, such as octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, eicosene oxide and docosene oxide, and also epoxystearyl alcohol with diethanol- or 35 diisopropanolamine. These compounds with an OH function in the P-position at both ends of a relatively long alkyl chain, for example N-(2-hydroxyhexadecyl)di ethanolamine, N-(2-hydroxy-3-octyloxypropyl)diethanol amine, N-(2-hydroxy-3-decyloxypropyl)diethanolamine, - 42 to this end the inventive stabilizer mixture and, if appropriate, other additives are mixed with the PVC, using apparatus known per se, such as the above mentioned processing apparatus. The stabilizers here 5 can be added individually or in a mixture, or else in the form of what are known as masterbatches. The PVC stabilized by the present invention may be converted to the desired form by known methods. 10 Examples of these processes are milling, calendering, extrusion, injection molding, or spinning, or else extrusion blow molding. The stabilized PVC can also be processed to give foams. 15 By way of example, a PVC stabilized according to the invention is particularly suitable for hollow articles (bottles), packaging foils (thermoforming foils), blown foils, pipes, foams, heavy profiles (window frames), thin-wall profiles, construction profiles, external 20 cladding, fittings, office foils, and apparatus casings (computers, household devices). The inventive PVC is particularly suitable for semi rigid and plasticized formulations, in particular in 25 the form of plasticized formulations for wire sheathing, or cable insulation, which is particularly preferred. In the form of semirigid formulations, the inventive PVC is particularly suitable for decorative foils, foams, agricultural sheeting, hoses, sealing 30 profiles, and office foils. Examples of use of the inventive PVC in the form of plastisol are synthetic leather, flooring, textile coatings, wall, coverings, metal coatings coil coatings 35 and underbody protection for motor vehicles. Examples of sintered-PVC uses of the PVC stabilized according to the invention are slush coatings and coil coatings for plastisol formulations, for semirigid - 10 N-(2-hydroxy-3-octyloxypropyl)diethanolamine and bis-N (2-hydroxy-3-phenyloxypropyl)ethanolamine are a particularly suitable component in the stabilizer systems of the invention. 5 This list is given only by way of example and does not claim to be comprehensive. The amounts to be used of the compounds of the formula 10 (I) to achieve stabilization in chlorine-containing polymer are advantageously from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, in particular from 0.1 to 3% by weight. 15 The inventive composition comprises, alongside at least one representative of the alkanolamines of the structure (I), at least one representative of the uracils of the general structure (II). According to the invention, the group of the uracils is defined as that 20 of the derivatives of structure (II) and also that of the cyanoacetylureas of the structure (III), which are precursors of the uracils. Compounds of the formula (II) have previously been 25 described in DE-A-1 694 873, EP-A-0 065 934, EP-A-0 041 479, and EP-A-0 768 336, and can be prepared by known methods in a process involving one or more steps. 0 R Y N
NH
2 30 where R1 and R2, independently of one another, are Cl-C24 alkyl, which may have interruption by -C0 2 - and/or by 1 or more oxygen atoms, and/or may have substitution by one or more OH groups, examples here being 35 -CH 2 -0-CH 2
-CH
2 -0-CH 3 , -CH 2
-O-CH
2
-CH
2
-CH
2 -0-CH 3
,
- 11 -CH 2 -0-CH 2
-CH
2
-CH
2
-CH
2 -0-CH 3 , -CH 2
-CH
2
-O-CH
2
-CH
2 -0-CH 2
-CH
3 ,
-CH
2
-CH
2 -0-CH 2
-CH
2 -0-CH 2
-CH
2 -0-CH 2
-CH
3 , etc. or are C3-C24-alkenyl, branched or unbranched, or are C5-C8 cycloalkyl, unsubstituted or substituted with from 1 to 5 3 Cl-C4-alkyl, Cl-C4-alkoxy, or C5-C8-cycloalkyl groups, or with hydroxy groups, or with Cl atoms, or are C7-C9-phenylalkyl, unsubstituted or substituted on the phenyl ring with from 1 to 3 C1-C4-alkyl, C1-C4 alkoxy, or C5-C8-cycloalkyl groups, or with hydroxy 10 groups, or with Cl atoms, and R1 or R2 may also be hydrogen, and Y is S or 0. For compounds of the formula (II) here: examples of Cl-C4-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. 15 Preference is given to Cl-C4-alkyl, if appropriate with interruption by -C0 2 -. Examples of Cl-C24-alkyl other than the radicals just mentioned are pentyl, hexyl, heptyl, octyl, 2 ethylhexyl, isooctyl, decyl, nonyl, undecyl, dodecyl, 20 tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl or tetracosyl. Examples of the alkenyl radicals are vinyl, allyl, methallyl, 1-butenyl or 1-hexenyl, 1-octenyl, 25 2-octenyl, decenyl, undecenyl, tetradecenyl, hexa decenyl, octadecenyl and eicosenyl, preferably allyl. The alkyl or alkenyl radicals may be branched or unbranched radicals. 30 Examples of Cl-C4-alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy or isobutoxy. Examples of C5-C8-cycloalkyl are cyclopentyl, cyclo hexyl, cycloheptyl or cyclooctyl. Examples of C7-C9-phenylalkyl are benzyl, 1- or 35 2-phenylethyl, 3-phenylpropyl, a,a-dimethylbenzyl or 2-phenylisopropyl, preferably benzyl. If the cycloalkyl groups or the phenyl group of the phenylalkyl radicals have substitution, preference is - 12 then given to two or one substituent(s), particular preference among the substituents being given to chlorine, hydroxy, methyl or methoxy. Examples of C3-C6-alkenyl are vinyl, allyl, methallyl, 5 1-butenyl or 1-hexenyl, preferably allyl. If the alkyl radicals have interruption, they necessarily include at least 2 carbon atoms. -C02- here 0 means a O group. 10 Examples of C1-C22-alkyl radicals with interruption by -C02- are branched or straight-chain radicals, e.g. methoxycarbonylmethyl, methoxycarbonylethyl, methoxy carbonylpropyl, methoxycarbonylbutyl, methoxycarbonyl 15 hexyl, methoxycarbonyloctyl, ethoxycarbonylmethyl, ethoxycarbonylethyl, ethoxycarbonylpropyl, ethoxy carbonylbutyl, ethoxycarbonylhexyl, ethoxycarbonyl octyl, n-propoxycarbonylmethyl, n-propoxycarbonylethyl, n-propoxycarbonylbutyl, n-propoxycarbonylhexyl, 20 n-propoxycarbonyloctyl, isopropoxycarbonylmethyl, iso propoxycarbonylethyl, isopropoxycarbonylbutyl, iso propoxycarbonylhexyl, isopropoxycarbonyloctyl, n-butoxycarbonylmethyl, n-butoxycarbonylethyl, n-butoxycarbonylbutyl, n-butoxycarbonylhexyl or tert 25 butoxycarbonylmethyl. This list makes no claim to be comprehensive, but gives the structural principle, which is readily comprehensible to the person skilled in the art. 30 By way of example, methoxycarbonylethyl is preferred. Preference is given here to compounds of the formula (II), where R1 and R2, independently of one another, are Cl-C18 35 alkyl and hydrogen. It is particularly preferable either that R1 and R2 are identical and are methyl, ethyl, propyl, - 13 butyl, allyl or octyl, or that they are different and are ethyl and allyl. If only one of the two substituents R1 or R2 is 5 hydrogen, the carbon chain of the remaining radical is larger than C2, and the above then applies correspondingly to the possible further substitution pattern. R1 or R2 can therefore be C3-C24-alkyl, which may have interruption by -C0 2 - and/or by 1 or more 10 oxygen atoms, and/or may have substitution by one or more OH groups, or can be C3-C24-alkenyl, branched or unbranched, or can be CS-C8-cycloalkyl, unsubstituted or substituted with from 1 to 3 C1-C4-alkyl, C1-C4 alkoxy, or C5-C8-cycloalkyl groups, or with hydroxy 15 groups, or with Cl atoms, or can be C7-C9-phenylalkyl, unsubstituted or substituted on the phenyl ring with from 1 to 3 C1-C4-alkyl, Cl-C4-alkoxy, or C5-C8 cycloalkyl groups, or with hydroxy groups, or with Cl atoms. Preference is given to the monosubstituted, in 20 the 1- or 3-position of the formula (II), alkyl, alkenyl or alkoxyalkyl derivatives where R1 or R2 is propyl or butyl or cyclohexyl or is C3-C6-alkyl interrupted by an oxygen atom. Examples of particularly preferred compounds are: 1-propyl-2-aminouracil, 25 1-propyl-4-aminouracil, 1-allyl-2-aminouracil, 1-allyl 4-aminouracil, 1-methoxyethyl-2-aminouracil, 1-methoxy ethyl-4-aminouracil. According to the invention, it is also possible to use 30 the cyanoacetylureas (III), which are the synthetic precursors of the uracils, in combination with the structures of the formula (I) . These are known to the person skilled in the art and are described in US Patent 2,598,936, and in the applicant's specification 35 US 6211270, and in J. Org. Chem. 16, 1897-1890 (1951), and can be prepared by known methods. The starting ureas are commercially available or can be prepared by known processes.
- 14 Cyanoacetylureas of the formula (III) Y 11 ,CO-CH 2 -CN
R
2 NH-C-N
R
1 where 5 Y is oxygen or sulfur, and R1 is C1-C24-alkyl, which may have interruption by
-CO
2 - and/or by oxygen atoms, and/or may have substitution by from 1 to 3 OH groups, or is C3-C24 alkenyl, C7-C1O-phenylalkyl, C5-C8-cycloalkyl, C7-C1O 10 alkylphenyl, phenyl or naphthyl, where in each case the aromatic radical may have substitution by -OH, C1-C12 alkyl and/or OCl-C4-alkyl, and R2 is as defined for R1, or, if R1 is hydrogen then R2 can also be C3-C24-alkyl, which may have interruption by -CO 2 - and/or by oxygen 15 atoms and/or may have substitution by from 1 to 3 OH groups, or can be C3-C24-alkenyl, C7-C1O-phenylalkyl, C5-C8-cycloalkyl, C7-ClO-alkylphenyl, phenyl or naphthyl, where in each case the aromatic radical may have substitution by -OH, by Cl-C12-alkyl and/or by 20 OCl-C4-alkyl, have particularly good suitability in the combination described according to the invention for stabilizing chlorine-containing polymers, e.g. PVC. For compounds of the formula (III): 25 Examples of Cl-C4-alkyl are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl. Examples of C1-C24-alkyl, other than the radicals just mentioned, are pentyl, hexyl, heptyl, octyl, 2-ethyl hexyl, isooctyl, decyl, nonyl, undecyl or dodecyl, and 30 also tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl or tetracosyl. Preference is given to Cl-C8-alkyl, if appropriate having interruption by -CO 2 -. Examples of C5-C8-cycloalkyl are cyclopentyl, cyclohexyl, cyclo heptyl or cyclooctyl, preferably cyclohexyl. 35 Examples of C7-ClO-alkylphenyl are tolyl or mesityl, in - 15 particular tolyl. Examples of C7-C1O-phenylalkyl are benzyl, 1- or 2-phenylethyl, 3-phenylpropyl, x,c-di methylbenzyl or 2-phenylisopropyl, preferably benzyl and 2-phenethyl, in particular benzyl. 5 If the aromatic radical has substitution, it preferably has three, two or in particular one substituent, and the substituents are in particular hydroxy, methyl, ethyl, methoxy or ethoxy. 10 Examples of C3-C8-alkenyl are allyl, methallyl, 1-butenyl, 1-hexenyl, 1-octenyl or 2-octenyl, preferably allyl. If the alkyl radicals have interruption, they 15 necessarily include at least 2 carbon atoms. 0
-CO
2 - here is a A group. Examples of alkyl radicals with interruption by -C02 can be found in the text associated with formula (II). 20 Preference is given here to compounds of the formula (III) where Y is oxygen, and also to those where the radicals R1 and R2 are identical. Other advantageous compounds are those where Y is sulfur. 25 Further preference is given to compounds of the formula (III) where R1 and R2 are C1-C8-alkyl, C3-C5-alkenyl, benzyl or 2-phenethyl. Particular preference is given to compounds of the formula (III) where R1 and R2 are Cl-C4-alkyl, allyl or 30 benzyl. Examples which may be mentioned are N,N'-dimethyl-N cyanoacetylurea, N,N'-diethyl-N-cyanoacetylurea, N,N'-dioctyl-N-cyanoacetylurea, etc. This list is given 35 only by way of example and does not make any claim to be comprehensive.
- 16 Other preferred compounds here are those of the formula (III) where Y is oxygen, and also those where the radicals Rl and 5 R2 differ from one another. In particular for Rl = H. R2 is then C3-C12-alkyl which may have interruption by -C0 2 - and/or by oxygen atoms, and/or may have substitution by from 1 to 3 OH groups, or is then C3-C12-alkenyl, C7-C10-phenylalkyl, C5-C8-cycloalkyl, 10 C7-Cl0-alkylphenyl, phenyl or naphthyl, where in each case the aromatic radical may have substitution by -OH, by Cl-C12-alkyl and/or by OC1-C4-alkyl. Other advantageous compounds are those where Y is sulfur. Particular preference is given to compounds of the 15 formula (III) where R1 = H and R2 = C3-C8-alkyl, methoxyethyl, allyl or benzyl. It should expressly be mentioned here that the reaction of the cyanoacetylureas of the general formula (III) to 20 give the corresponding uracils of the general formula (II) can take place even before preparation of the stabilizer has ended. This is known to the person skilled in the art from the literature and derives from the synthetic principle of preparation of uracils from 25 cyanoacetylureas. By way of example, N,N'-dibutyl-N cyanoacetylurea (formula (III): R1 = R2 = butyl) will react to give the analogous 1,3-dibutyl-4-aminouracil. Particularly if the matrix here comprises basic compounds. This precondition is moreover met merely by 30 the other possible components of the matrix, e.g. commercially available calcium stearate or zeolite. In this context, the matrix in the selected inventive examples comprises the alkanolamine alone, or one or more compounds from the group of the plastics additives 35 and plastics stabilizers and of the halogen-containing organic plastics. If the matrix comprises liquid constituents, this reaction is accelerated in accordance with the kinetics of chemical reactions.
- 17 Representatives of the general formula (I) which are liquid at room temperature or at processing temperature are particularly suitable for this purpose. 5 This reaction of the cyanoacetylurea to give the uracil is in particular also promoted by temperature increases brought about via mixing or processing, or brought about via the preparation of the stabilizer, and these may be spray processes or melting processes. It is not 10 necessary for the reaction here to proceed to completion. The two species may be present alongside one another in various ratios. However, certain conditions can give practically quantitative conversion. There are no restrictions per se on the 15 selection of the basic compounds for the reaction of the cyanoacetylurea intermediate to give the uracil. Suitable compounds are any of those whose aqueous or alcoholic extract reacts as a base, or which in any other way induce the reaction, examples being: 20 alkali metal hydroxides, alkaline earth metal hydroxides, zeolites, Alcamizer products or amines. The reaction may take place before the end of the process to prepare the stabilizer, or during the process of 25 mixing the stabilizer components alone, or in the presence of the entire formulation, either in the mixer or in the subsequent course of processing. The amount of the compounds of the formula (III) to be 30 used to achieve stabilization in the chlorine containing polymer is advantageously from 0.01 to 10% by weight, preferably from 0.05 to 5% by weight, in particular from 0.1 to 3% by weight. 35 The invention also provides combinations of the stabilizer mixtures encompassing at least alkanolamine or a reaction product of a mono- or polyfunctional epoxide and of ammonia or of a mono- or polyfunctional dialkyl(aryl)- or monoalkyl(aryl)amine of the formula - 18 (I) and uracils of the formula (II) or their precursors of the formula (III) encompassing at least one halogen containing oxyacid, e.g. a perchlorate salt. 5 The perchlorate salts are known to the person skilled in the art, examples are those of the formula M(Cl0 4 )n, where M is Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, La, Ce, or a hydrotalcite layer-lattice cation, or an organic onium salt cation. The index n is 1, 2 or 3, as 10 appropriate for the valency of M, or if a hydrotalcite layer-lattice cation is present 0 < n 1. These perchlorate salts may be used in various familiar supply forms; e.g. in the form of a salt or solution in 15 water or in an organic solvent, as they stand, or absorbed onto a carrier material such as PVC, Ca silicate, zeolites or hydrotalcites. Examples are perchlorate salts dissolved or complexed using alcohols (polyols, cyclodextrins) or using ether alcohols or 20 ester alcohols or crown ethers or plasticizers. Partial esters of the polyols are to be regarded as ester alcohols here. In the case of polyhydric alcohols or polyols it is also possible to use their dimers, trimers, oligomers and polymers, examples being di-, 25 tri-, tetra- and polyglycols, and also di-, tri- and tetrapentaerythritol or polyvinyl alcohol in various degrees of polymerization. Other solvents which may be used are phosphate esters, and also cyclic and acyclic carbonic esters. Other embodiments are described in EP 30 0 394 547, EP 0 457 471 and WO 94/24200. Depending on the carrier material used or process for application to the carrier, the structure of the perchlorate salts may be either amorphous or else semicrystalline or crystalline. The person skilled in the art is also 35 aware of mixtures of the various states of aggregation. It is preferable to use sodium/potassium perchlorate salts.
- 19 Examples of the amount of the perchlorates that can be used are from 0.001 to 5 parts by weight, advantageously from 0.01 to 3 parts by weight, particularly preferably from 0.01 to 2 parts by weight, 5 based on 100 parts by weight of PVC. The use of ethanolammonium perchlorate salts for inhibiting discoloration of chlorine-containing resin is disclosed in JP-A 61-9451. These are perchlorate 10 salts with ammonium-salt structure, which can be obtained via addition of primary, secondary or tertiary ethanolamines to a perchloric acid solution. Ammonium perchlorate salts are generally compounds sensitive to heat and shock and therefore create a certain risk of 15 explosion, making them unsuitable for industrial applications. The invention also provides combinations of the stabilizer mixtures composed of at least one alkanol 20 amine or of a reaction product of a mono- or polyfunctional epoxide and of ammonia or of a mono- or polyfunctional dialkyl(aryl)- or monoalkyl(aryl)amine of the formula (I) and of uracils of the formula (II) or of their precursors of the formula (III) with at 25 least one other conventional additive or conventional stabilizer. The invention also provides combinations of the stabilizer mixtures composed of at least one alkanol 30 amine or one reaction product of a mono- or polyfunctional epoxide and of ammonia or of a mono- or polyfunctional dialkyl(aryl)- or monoalkyl(aryl)amine of the formula (I) and of uracils of the formula (II) or of their precursors of the formula (III) with at 35 least one perchlorate salt and with at least one other conventional additive or conventional stabilizer. The inventive compositions may therefore also have been treated with other conventional additives, such as - 20 polyols and disaccharide alcohols, hydroxycarboxylic acids or their salts, glycidyl compounds, hydrotalcites, zeolites (aluminosilicates of alkali metals or alkaline earth metals) , compounds from the 5 group of the calcium aluminum hydroxides or their hydrates, compounds from the group of the calcium aluminum hydroxohydrogenphosphites or their hydrates, compounds from the group of the aluminum hydroxides or their hydrates, compounds from the group of the calcium 10 aluminum hydroxo(hydrogen)carbonates or their hydrates, compounds from the group of the lithium layer-lattice compounds or their hydrates, fillers, metal soaps, alkali metal compounds and alkaline earth metal compounds, fillers/pigments, lubricants, plasticizers, 15 phosphites, pigments, epoxidized fatty acid esters and other epoxy compounds, flame retardants, antioxidants, UV absorbers, gelling agents, compatibilizers, antistatic agents, antifogging agents, light stabilizers, optical brighteners and blowing agents. 20 Particular preference is given to epoxidized soy oils, alkaline earth metal soaps or aluminum soaps and phosphites. Examples of these additional components are listed and 25 explained at a later stage below (cf. "Handbook of PVC Formulating" by E.J. Wickson, John Wiley & Sons, New York 1993). Stabilization of chlorine-containing polymers, in 30 particular PVC, by means of hydrocalumites, catoites and calcium aluminum hydroxohydrogenphosphites is disclosed in WO 92/13914, WO 93/25613, DE 3 941 902 and DE 4 106 411. The compounds from the group of the calcium aluminum hydroxides or their hydrates are 35 generally described in "Ullmann's Encyclopedia of Industrial Chemistry" (5th edition, 1986): Vol. AS Cement and Concrete (pp. 505 et seq.); Kirk-Othmer "Encyclopedia of Chemical Technology" (4th edition, 1993): Vol. 5 - Cement (pp. 572 et seq.); P. Barnes - 21 "Structure and Performance of Cements" (Appl. Sci. Publ. N. Y., 1983); F.M. Lea "The Chemistry of Cement and Concrete" (E. Arnold Publ. London, 1971); H.F.W. Taylor "Cement Chemistry" (Acad. Press, London, 5 1992) - chapter 6: Hydrated aluminate phases (pp. 167 et seq.). The stabilizing action of lithium layer-lattice compounds on the PVC is described by way of example in 10 EP-A-0 761 756 and in DE-A-4 425 275. All of these compounds may have been surface-modified, if desired. Polyols and disaccharide alcohols 15 Examples of compounds of this type which may be used are: pentaerythritol, dipentaerythritol, tripenta erythritol, trimethylolethane, bistrimethylolpropane, inositol (cyclitols), polyvinyl alcohol, bistrimethyl olethane, trimethylolpropane, sorbitol (hexitols), 20 maltitol, isomaltitol, cellobiitol, lactitol, Lycasin, mannitol, lactose, leucrose, tris(hydroxyethyl) iso cyanurate, tris(hydroxypropyl) isocyanurate, Palatinitol, tetramethylolcyclohexanol, tetramethylol cyclopentanol, tetramethylolcyclopyranol, xylitol, 25 arabinitol (pentitols), tetritols, glycerol, diglycerol, polyglycerol, thiodiglycerol or 1-0-a-D glycopyranosyl-D-mannitol dihydrate. Among these, preference is given to the disaccharide alcohols. It is also possible to use polyol syrups, such as sorbitol 30 syrup, mannitol syrup and maltitol syrup. Examples of the amount which may be used of the polyols are from 0.01 to 20 parts by weight, advantageously from 0.1 to 20 parts by weight and in particular from 35 0.1 to 10 parts by weight, based on 100 parts by weight of PVC.
- 22 Hydroxycarboxylic acids Use may be made of salts or mixtures of salts of hydroxycarboxylic acids having fewer than 4 hydroxy 5 groups and fewer than 10 carbon atoms. Among these are compounds listed in detail in the patent application WO 02/06389. Compounds having one or two hydroxy groups have proven particularly effective. Other substitution patterns may be present, examples being aldehyde, keto, 10 acyl, amino, aminoalkyl, aminoaryl and/or halide substituents. If the compound bears two or more acid functions, at least one of these is in salt form. The salts are preferably those selected from the group Li, K, Na, Ca, Mg, Ba, Sr, Al, Fe, La, Ce, Mn or zinc. 15 Preference, depending on the application, is particularly given to the salts of lactic acid, e.g. sodium lactate, or salts of citric acid. Glycidyl compounds 20 0 They contain the glycidyl group -CH--(CH 2 )n R, R2 R3 bonded directly to carbon, to oxygen atoms, to nitrogen atoms or to sulfur atoms, where either R 1 and R 3 are both hydrogen, R 2 is hydrogen or methyl and n = 0 or R 1 25 and R 3 together are -CH 2
-CH
2 - or -CH 2
-CH
2
-CH
2 -, R 2 is then hydrogen and n = 0 or 1. It is preferable to use glycidyl compounds having two functional groups. However, it is also possible in 30 principle to use glycidyl compounds having one, three or more functional groups. Diglycidyl compounds having aromatic groups are mainly used. The amount preferably used of the terminal epoxy compounds is at least 0.1 part, for example from 0.1 to 35 50 parts by weight, advantageously from 1 to 30 parts by weight and in particular from 1 to 25 parts by weight, based on 100 parts by weight of PVC.
- 23 Hydrotalcites The chemical composition of these compounds is known to the person skilled in the art, e.g. from the patents 5 DE 3 843 581, US 4,000,100, EP 0 062 813 and WO 93/20135. Compounds from the hydrotalcite series may be described by the following general formula 10 M 2+ 1 -M 3+x (OH)2(Ab-) x/b o d H 2 0, where M2+ = one or more of the metals selected from the group consisting of Mg, Ca, Sr, Zn and Sn M 3 = Al or B, 15 An is an anion of valency n, b is a number from 1 to 2, 0 < x 0.5, m is a number from 0 to 20. Preference is given to compounds with n 2 20 A. OH, ClO4, HC0 3 , CH 3 COO, C 6
H
5 COO, C03 (CHOHCOO) 22-, (CH 2 COO)2 2-, CH 3 CHOHCOO, HPO 3 or HO2 H P0 4 > Examples of hydrotalcites are A1 2 0 3 . 6MgO. C0 2 . 12H 2 0 (i) , Mg 4
.
5 A12 (OH) 13 .CO3. 3. 5H 2 0 (ii) , 25 4MgO.Al 2 0 3
.CO
2 .9H20 (iii), 4MgO.Al 2 0 3
.CO
2 .6H 2 0, ZnO.3MgO.Al2O 3
.CO
2 .8-9H 2 0 and ZnO.3MgO.Al 2 0 3
.CO
2 .5-6H 2 0. Types i, ii and iii are very particularly preferred. Zeolites (aluminosilicates of alkali metals and/or of 30 alkaline earth metals) These may be described by the following general formula Mx/.[(AlO 2 )x(SiO 2 )y].wH 2 0, where n is the charge on the cation M; 35 M is an element of the first or second main group, such as Li, Na, K, Mg, Ca, Sr or Ba; y : x is a number from 0.8 to 15, preferably from 0.8 to 1.2; and w is a number from 0 to 300, preferably from 0.5 to 30.
- 24 Examples of zeolites are sodium aluminosilicates of the formulae Na 1 2 Al1 2 Si 1 2
O
48 . 27 H 2 0 [zeolite A], Na 6 Al 6 Si 6
O
2 4 . 2 NaX 7.5 H 2 0, X = OH, halogen, C104 [sodalite]; Na 6 Al 6 Si 3 oO 7 2 5 24 H 2 0; Na 8 Al 8 Si 4 0
O
96 . 24 H 2 0; Na 1 6 Al 6 Si 24 0 80 . 16 H 2 0; Na 1 6 Al 1 6 Si 32 0 96 . 16 H 2 0; Na 5 6 Al 5 6 Sii 36 03 8 4 . 250 H 2 0 [zeolite Y], Na 8 6 Al 8 6 Sio 6
O
38 4 . 264 H 2 0 [zeolite X]; or the zeolites which can be prepared by partial or complete exchange of the Na atoms by Li atoms, K atoms, 10 Mg atoms, Ca atoms, Sr atoms or Zn atoms, for example (Na, K) ioAl1OSi 22
O
64 - 20 H 2 0 ; Ca 4
.
5 Na 3 [ (A10 2 ) 12 (SiO 2 ) 12] 30 H 2 0; K 9 Na 3 [(AlO 2
)
1 2 (SiO 2
)
1 2 ] . 27 H 2 0. Very particular preference is given to Na zeolite A and Na zeolite P. 15 The hydrotalcites and/or zeolites may be used in amounts of, for example, 0.1 to 20 parts by weight, expediently 0.1 to 10 parts by weight and in particular 0.1 to 5 parts by weight, based on 100 parts by weight of halogen-containing polymer. 20 Katoites Compounds suitable for the inventive stabilizer combinations from the group of the katoites can be 25 described by the general formula Ca 3 Al 2
(OH)
12 e mH 2 0, where m = 0-10. 30 The compounds mentioned may, if appropriate, have been surface-modified. They have a very particular crystal lattice, (known as hydrogarnet structure), which distinguishes them from other calcium aluminum hydroxy 35 compounds. This crystal lattice, together with lattice separations, is described in the article by C. Cohen-Addad and P. Ducros in Acta Cryst. (1967), 23, pages 220 to 225. By way of example, these materials - 25 may be prepared by a method based on German patent specification DE 2 424 763. Hydrocalumites 5 Compounds suitable for the inventive stabilizer combinations and derived from the group of the hydro calumites are described by the general formula: CaxAl (OH) 2 x+ 3 emH 2 0, 10 where x = 1 to 4 and m = from 0 to 8. Preferred compounds are those where, in the above 15 general formula, x = 2 or 3. Calcium aluminum hydroxy(hydrogen)phosphites 20 Suitable compounds from the group of the basic CHAPs, calcium aluminum hydroxyhydrogenphosphites, have the general formula CaxAl 2 (OH)2(x+2)HPO 3 emH 2 0, where x = from 2 to 8 and 25 m = from 0 to 12, or CaxAl 2 (OH) 2 (x+3-y> (HPO 3 ) yemH 2 0, where x = from 2 to 12, 2x+5 > y > 0 and 2 m = from 0 to 12, 30 with the exception y = 1, if x = from 2 to 8. Other examples of the hydrocalumites which via variation of the metal cation M and of the acid anions A or B of the general formula below 35 M 2+( 2 +x)A1+ (1yY) (OH) (6+z)A a[Br]l*mH20 and are described in detail in patent specification WO - 26 02/098964, pages 18-20. In one preferred embodiment, M is calcium, which may be present in a mixture with magnesium or zinc or magnesium and zinc. For the purposes of the preferred embodiment, the composition 5 is selected to be free from the heavy metal zinc. If a surface treatment is desired, the product may be modified accordingly using the methods and reagents known to the person skilled in the art. 10 Lithium layer-lattice compounds Lithium aluminum layer-lattice compounds have the general formula A LiaMII(b-2aAl(2+a)OH(4+2b)An
-
2 /emH 2 0 15 where MII is Mg, Ca or Zn and An is a selected anion of valency n or a mixture of anions and the indices are in the range 20 0 < a < (b-2)/2, 1 < b < 6 and m = from 0 to 30 with the proviso that b-2a > 2 or the general formula B 25 [Al 2 (Li(1-.xeMI Ix) (OH) 6 ]n(An~) 1 ,+ mH 2 0 where MII, A, m and n are as defined above and x complies with the condition 0.01 x < 1. 30 The preparation of the layer-lattice compounds mentioned is characterized by reacting lithium hydroxide, lithium oxide and/or its compounds capable of conversion to hydroxide, metal(II) hydroxides, metal(II) oxides and/or their compounds derived from 35 the metals mentioned and capable of conversion to hydroxides, and aluminum hydroxides and/or their compounds capable of conversion to hydroxides, and also acids and/or their salts or mixtures thereof with one another in an aqueous medium, at a pH of from 8 to 10 - 27 and at temperatures of from 20 to 2500C, and isolating the resultant solid product of the reaction. The reaction time is preferably 0.5 to 40 hours, in particular from 3 to 15 hours. 5 The product directly produced from the reaction described above can be isolated from the aqueous reaction medium by known processes, preferably via filtration. The product isolated from the reaction is 10 also worked up in a manner known per se, for example via washing of the filter cake with water and drying of the washed residue at temperatures of, for example, from 60 to 150'C, preferably at from 90 to 1200C. For the reaction with aluminum it is possible to use either 15 fine-particle, activated metal(III) hydroxide in combination with sodium hydroxide or to use an NaAlO2. Lithium, or one of the metal(II) compounds mentioned, may be used in the form of fine-particle lithium oxide or fine-particle lithium hydroxide, or a mixture 20 thereof, or in the form of fine-particle metal(II) oxide or fine-particle metal(II) hydroxide or a mixture thereof. The corresponding acid anions may be used at various concentrations, e.g. directly in the form of acid or else in the form of salt. 25 The reaction temperatures are preferably from about 20 to 2500C, more particularly from about 60 to 1800C. Catalysts or accelerators are not required. The water of crystallization of the substances may be removed 30 entirely or partially by heating. In their use as stabilizers, the dried layer-lattice compounds do not evolve water or any other gas at the usual processing temperatures of from 160 to 220 0 C for 35 PVC, and therefore no blistering defects occur in the moldings. The anion An in the above general formula can be sulfate, sulfite, sulfide, thiosulfate, peroxide, - 28 peroxosulfate, peroxodisulfate, hydrogenphosphate, hydrogenphosphite, carbonate, halides, nitrate, nitrite, hydrogensulfate, hydrogencarbonate, hydrogen sulfite, hydrogensulfide, dihydrogenphosphate, 5 dihydrogenphosphite, monocarboxylic anions, such as acetate and benzoate, amide, azide, hydroxide, hydroxylamine, hydroazide, acetylacetonate, phenolate, pseudohalides, halites, halates, perhalates, periodate, permanganate, dianions of dicarboxylic acids, e.g. 10 phthalate, oxalate, maleate or fumarate, bisphenolates, phosphate, pyrophosphate, phosphite, pyrophosphite, trianions of tricarboxylic acids, e.g. citrate, trisphenolates, and many others, or else a mixture thereof. Among these, preference is given to hydroxide, 15 carbonate, phosphite and maleate. To improve the dispersibility of the substances in halogen-containing thermoplastic polymer compositions, these may be surface-treated with a higher fatty acid, 20 e.g. stearic acid, with an anionic surfactant, with a silane coupling agent, with a titanate coupling agent, or with a glycerol ester of a fatty acid. The calcium aluminum hydroxides, calcium aluminum 25 hydroxohydrogenphosphites, aluminum hydroxides, calcium aluminum hydroxo(hydrogen)carbonates and lithium layer lattice compounds described above may be not only crystalline but also semicrystalline and/or amorphous. 30 Fillers Fillers such as calcium carbonate, dolomite, wollastonite, magnesium oxide, magnesium hydroxide, silicates, china clay, talc, glass fibers, glass beads, 35 wood flour, mica, metal oxides or metal hydroxides, carbon black, graphite, rock flour, heavy spar, glass fibers, talc, kaolin and chalk are used. Preference is given to chalk (HANDBOOK OF PVC FORMULATING E. J. Wickson, John Wiley & Sons, Inc., 1993, pp. 393-449) - 29 and reinforcing agents (TASCHENBUCH der Kunststoff additive [Plastics Additives Handbook], R. Gachter & H. Miller, Carl Hanser, 1990, pp. 549-615). The fillers may be used in amounts of preferably at 5 least one part by weight, for example 5 to 200 parts by weight, expediently 10 to 150 parts by weight and in particular from 15 to 100 parts by weight, based on 100 parts by weight of PVC. 10 Metal soaps Metal soaps are primarily metal carboxylates, preferably of relatively long-chain carboxylic acids. Well-known examples of these are stearates and 15 laurates, and also oleates and salts of relatively short-chain aliphatic or aromatic alkanecarboxylic acids, such as acetic acid, propionic acid, butyric acid, valeric acid, hexanoic acid, sorbic acid; oxalic acid, malonic acid, succinic acid, glutaric acid, 20 adipic acid, fumaric acid, citric acid, benzoic acid, salicylic acid, phthalic acids, hemimellitic acid, trimellitic acid, pyromellitic acid. Metals which should be mentioned are: Li, Na, K, Mg, 25 Ca, Sr, Ba, Zn, Al, La, Ce and rare earth metals. Use is frequently made of so-called synergistic mixtures, such as barium/zinc stabilizers, magnesium/zinc stabilizers, calcium/zinc stabilizers or calcium/ magnesium/zinc stabilizers. The metal soaps may be used 30 either alone or in mixtures. An overview of common metal soaps is found in Ullmann's Encyclopedia of Industrial Chemistry, 5th Ed., Vol. A16 (1985), pp. 361 et seq. Besides the compounds mentioned, use may also be made of organoaluminum compounds, and of compounds 35 analogous to the abovementioned compounds, in particular aluminum tristearate, aluminum distearate, and aluminum monostearate, and also aluminum acetate and basic derivatives derived therefrom.
- 30 US 4,060,512 and US 3,243,394 give further explanations concerning the aluminum compounds which can be used and those which are preferred. 5 Besides the abovementioned compounds, use may also be made of organic rare earth compounds, in particular compounds analogous to the abovementioned compounds. The term rare earth compound means particularly compounds of the elements cerium, praseodymium, 10 neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, lanthanum and yttrium, particular preference being given to mixtures with cerium. Other preferred rare earth compounds are found in EP-A-0 108 023. 15 Examples of the amount of the metal soaps or their mixtures which may be used are from 0.001 to 10 parts by weight, advantageously from 0.01 to 8 parts by weight, particularly preferably from 0.05 to 5 parts by weight, based on 100 parts by weight of PVC. 20 Compounds of alkali metals and of alkaline earth metals For the purposes of the present invention, these are mainly the carboxylates of the acids described above, 25 but also corresponding oxides or, respectively, hydroxides or carbonates. Mixtures of these with organic acids are also possible. Examples are LiOH, NaOH, KOH, CaO, Ca(OH) 2 , MgO, Mg(OH) 2 , Sr(OH) 2 , Al(OH) 3 , CaCO 3 and MgCO 3 (and also basic carbonates, such as 30 magnesia alba and huntite), and also fatty-acid salts of Na and of K. In the case of alkaline earth metal carboxylates and Zn carboxylates it is also possible to use adducts of these with MO or M(OH) 2 (M = Ca, Mg, Sr or Zn), so-called "overbased" compounds. In addition to 35 the stabilizers according to the invention it is preferable to use alkali metal carboxylates, alkaline earth metal carboxylates and/or aluminum carboxylates.
- 31 Lubricants Examples of possible lubricants are: montan wax, fatty acid esters, (ox.) polyethylene waxes, polypropylene 5 waxes, (ox.) paraffin waxes, amide waxes, chloroparaffins, glycerol esters and alkaline earth metal soaps, and fatty ketones, and also the lubricants, or combinations of the lubricants, listed in EP 0 259 783, based on complex esters. Other 10 lubricants which may be used are mentioned in "Plastics Additives Handbook", Carl Hanser Verlag, 5th edition, 2001, pages 511-552. Plasticizers 15 Examples of organic plasticizers are those from the following groups: A) Phthalates: such as preferably di-2-ethylhexyl, 20 diisononyl and diisodecyl phthalate, also known by the common abbreviations DOP (dioctyl phthalate, di-2 ethylhexylphthalate), DINP (diisononyl phthalate), DIDP (diisodecyl phthalate). B) Esters of aliphatic dicarboxylic acids, in 25 particular esters of adipic, azelaic, and sebacic acid: preferably di-2-ethylhexyl adipate and diisooctyl adipate. C) Trimellitic esters, such as tri-2-ethylhexyl trimellitate, triisodecyl trimellitate (mixture), 30 triisotridecyl trimellitate, triisooctyl trimellitate (mixture), and also tri-C 6 -CB-alkyl, tri-C 6 -Cio-alkyl, tri-C 7
-C
9 -alkyl and tri-C 9
-C
1 1 -alkyl trimellitate. Common abbreviations are TOTM (trioctyl trimellitate, tri-2 ethylhexyl trimellitate), TIDTM (triisodecyl 35 trimellitate) and TITDTM (triisotridecyl trimellitate). D) Epoxy plasticizers: by way of example here, mention may be made of epoxidized unsaturated fatty acids, e.g. epoxidized soybean oil, epoxidized linseed oil, epoxidized sunflower oil, epoxidized rapeseed oil, - 32 epoxidized tallow oil, epoxidized olive oil. Other epoxidized fatty acid esters which may be mentioned are the variants based on the monoesters of fatty acids and on monohydric alcohols, disclosed in WO 02/060884 Al. 5 Other variants of epoxidized fatty acid esters are produced via transesterification of, for example, triacetin, described in DE-A-30 04 660. Among these are the epoxidized glyceride acetates, obtainable by transesterifying epoxidized fatty acid esters with 10 triacetin. The molar ratio here can be selected so that, if desired, the appropriate diglyceride monoacetates are quantitatively predominant. Detailed examples and processes are disclosed in patent specification WO 02/060884 Al. The preparation of other 15 derivatives, such as the monoglyceride diacetates, is also disclosed in US-A2-895 966. All of the mixtures as described actually mostly comprise complex mixtures derived from the transesterification reactions. E) Polymeric plasticizers: the commonest starting 20 materials for preparing polyester plasticizers are: dicarboxylic acids, such as adipic, phthalic, azelaic or sebacic acid; diols, such as 1,2-propanediol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol and diethylene glycol. 25 F) Phosphoric esters: a definition of these esters is given in the abovementioned "Taschenbuch der Kunststoffadditive" ["Plastics Additives Handbook"], Chapter 5.9.5, pp. 408-412. Examples of these phosphoric esters are tributyl phosphate, tri-2-ethyl 30 butyl phosphate, tri-2-ethylhexyl phosphate, tri chloroethyl phosphate, 2-ethylhexyl diphenyl phosphate, cresyl diphenyl phosphate, triphenyl phosphate, tricresyl phosphate and trixylenyl phosphate. Preference is given to tris(2-ethylhexyl) phosphate and 35 Reofos@ 50 and 95 (Ciba Spezialitstenchemie). G) Chlorinated hydrocarbons (paraffins) H) Hydrocarbons I) Monoesters, e.g. butyl oleate, phenoxyethyl oleate, tetrahydrofurfuryl oleate and alkylsulfonates.
- 33 J) Glycol esters, e.g. diglycol benzoates. K) Representatives of citric acid plasticizers Among these are the citric esters of the general 5 formula B, derived from 2-hydroxy-1,2,3-propanetri carboxylic acid as described in WO 02/094927 R1-O-C-(COOR) (CH 2
-COOR)
2 B 10 where each R is a straight-chain or branched alkyl radical having from 4 to 18 carbon atoms and R1 = H, or R1 = R2CO. If R1 is not H, R2 is a straight-chain or branched alkyl radical having from 1 to 10 carbon 15 atoms. Preferred alcohol components R used in the citric ester are C6-C14 alkanols, which may be branched or unbranched, and the alkanol radicals here may be identical or different. Compounds which may be listed as non-restricting 20 examples are triethyl citrate (Citrofol A I), tributyl citrate (Citrofol B I), triethyl acetylcitrate (Citrofol A II), tributyl acetylcitrate (Citrofol B II), tri-n-hexyl acetylcitrate, tri-n-hexyl n-butyryl citrate, tri-n-(hexyl/octyl/decyl) acetylcitrate and 25 tri-n-(octyl/decyl) acetylcitrate. L) Perhydrophthalic, perhydroisophthalic and perhydro terephthalic esters, and also perhydrogenated glycol benzoate and perhydrogenated diglycol benzoate esters. Preference is given to perhydrogenated diisononyl 30 phthalate (@Hexamoll DINCH - BASF) as described in DE 19.756.913, DE 19.927.977, DE 19.927.978 and DE 19.927.979. A definition of these plasticizers and examples of the 35 same are given in "Kunststoffadditive" ["Plastics Additives"], R. Guchter/H. Miller, Carl Hanser Verlag, 3rd Ed., 1989, Chapter 5.9.6, pp. 412 - 415, and in "PVC Technology", W. V. Titow, 4th Ed., Elsevier Publ., 1984, pp. 165-170. It is also possible to use mixtures - 34 of different plasticizers. Examples of the amount which may be used of the plasticizers are 5 to 20 parts by weight, expediently 5 10 to 20 parts by weight, based on 100 parts by weight of PVC. Rigid or semirigid PVC preferably comprises up to 10%, particularly preferably up to 5%, of plasticizer, or no plasticizer. 10 Pigments Suitable substances are known to the person skilled in the art. Examples of inorganic pigments are TiO 2 , pigments based on zirconium oxide, BaSO 4 , zinc oxide 15 (zinc white) and lithopones (zinc sulfide/barium sulfate), carbon black, carbon black-titanium dioxide mixtures, iron oxide pigments, Sb 2
O
3 , (Ti,Ba,Sb)0 2 , Cr 2 0 3 , spinels, such as cobalt blue and cobalt green, Cd(S,Se), ultramarine blue. Examples of organic 20 pigments are azo pigments, phthalocyanine pigments, quinacridone pigments, perylene pigments, diketo pyrrolopyrrole pigments and anthraquinone pigments. TiO 2 in micronized form is also preferred. A definition and further descriptions are found in the "Handbook of 25 PVC Formulating", E.J. Wickson, John Wiley & Sons, New York, 1993. Phosphites 30 Organic phosphites are known costabilizers for chlorine-containing polymers. Examples are trioctyl, tridecyl, tridodecyl, tritridecyl, tripentadecyl, trioleyl, tristearyl, triphenyl, tricresyl, trisnonyl phenol, tris-2,4-tert-butylphenyl or tricyclohexyl 35 phosphite. Other suitable phosphites are various mixtures of aryl dialkyl or alkyl diaryl phosphites, e.g. phenyl dioctyl, phenyl didecyl, phenyl didodecyl, phenyl - 35 ditridecyl, phenyl ditetradecyl, phenyl dipentadecyl, octyl diphenyl, decyl diphenyl, undecyl diphenyl, dodecyl diphenyl, tridecyl diphenyl, tetradecyl diphenyl, pentadecyl diphenyl, oleyl diphenyl, stearyl 5 diphenyl and dodecyl bis-2,4-di-tert-butylphenyl phosphite. It is also advantageous to use phosphites of various di- or polyols: examples are tetraphenyl dipropylene 10 glycol diphosphite, polydipropylene glycol phenyl phosphite, tetramethylolcyclohexanol decyl diphosphite, tetramethylolcyclohexanol butoxyethoxyethyl diphosphite, tetramethylolcyclohexanol nonylphenyl diphosphite, bisnonylphenyl ditrimethylolpropane 15 diphosphite, bis-2-butoxyethyl ditrimethylolpropane diphosphite, trishydroxyethyl isocyanurate hexadecyl triphosphite, didecyl pentaerythrityl diphosphite, distearyl pentaerythrityl diphosphite, bis-2,4-di-tert butylphenyl pentaerythrityl diphosphite, and also 20 mixtures of these phosphites and aryl/alkyl phosphite mixtures of empirical composition
(H
19
C
9
C
6
H
4 ) 0 1
.
5 P (OC 12
,
13
H
25
,
27 ) 1.5 or [C 8
H
17
-C
6
H
4 -0-1 2 P [i
C
8
H
17 0] , (H 19
C
9
C
6
H
4 ) 0 1
.
5 P (OC9, 11
H
19
,
23 ) 1.5 25 An example of the amount which may be used of the organic phosphites is from 0.01 to 10 parts by weight, advantageously from 0.05 to 5 parts by weight, and in particular from 0.1 to 3 parts by weight, based on 100 parts by weight of PVC. 30 Epoxidized fatty acid esters and other epoxy compounds The inventive stabilizer combination may also preferably comprise at least one epoxidized fatty acid 35 ester. Esters of fatty acids from natural sources (fatty acid glycerides) may especially be used here, examples being soy oil or rapeseed oil. However, it is also possible to use synthetic products, such as epoxidized butyl oleate. It is also possible to use - 36 epoxidized polybutadiene and polyisoprene, if appropriate also in partially hydroxylated form, or glycidyl acrylate and glycidyl methacrylate in the form of homo- or copolymer. These epoxy compounds may also 5 have been applied to an alumino salt compound; in this connection see also DE-A-4 031 818. Antioxidants 10 Alkylated monophenols, e.g. 2,6-di-tert-butyl-4-methyl phenol, alkylthiomethylphenols, e.g. 2,4-dioctylthio methyl-6-tert-butylphenol, alkylated hydroquinones, e.g. 2,6-di-tert-butyl-4-methoxyphenol, hydroxylated thiodiphenyl ethers, e.g. 2,2'-thiobis(6-tert-butyl-4 15 methylphenol), alkylidenebisphenols, e.g. 2,2' methylenebis(6-tert-butyl-4-methylphenol), benzyl compounds, e.g. 3,5,3' ,5'-tetra-tert-butyl-4,4'-di hydroxydibenzyl ether, hydroxybenzylated malonates, e.g. dioctadecyl 2,2-bis(3,5-di-tert-butyl-2-hydroxy 20 benzyl)malonate, hydroxybenzylaromatics, e.g. 1,3,5 tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-tri methylbenzene, triazine compounds, e.g. 2,4-bisoctyl mercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5 triazine, phosphonates and phosphonites, e.g. dimethyl 25 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, acyl aminophenols, e.g. 4-hydroxylauranilide, esters of beta- (3, 5-di-tert-butyl-4-hydroxyphenyl)propionic acid, of beta-(5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid, of beta-(3,5-dicyclohexyl-4-hydroxy 30 phenyl)propionic acid, esters of 3,5-di-tert-butyl-4 hydroxyphenylacetic acid with mono- or polyhydric alcohols, amides of beta- (3,5-di-tert-butyl-4-hydroxy phenyl)propionic acid, e.g. N,N'-bis (3,5-di-tert-butyl 4-hydroxyphenylpropionyl)hexamethylenediamine, vitamin 35 E (tocopherol), and derivatives. An example of the amount which may be used of the antioxidants is from 0.01 to 10 parts by weight, advantageously from 0.1 to 10 parts by weight, and in particular from 0.1 to 5 parts by weight, based on 100 - 37 parts by weight of PVC. UV absorbers and light stabilizers 5 Examples of these are: 2-(2'-hydroxyphenyl)benzo triazoles, such as 2-(2'-hydroxy-5'-methylphenyl) benzotriazole, 2-hydroxybenzophenones, esters of unsubstituted or substituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, 10 acrylates, nickel compounds, oxalamides, such as 4,4'-dioctyloxyoxanilide, 2,2'-dioctyloxy-5,5'-di-tert butyloxanilide, 2-(2-hydroxyphenyl)-1,3,5-triazines, such as 2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5 triazine, 2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(2,4 15 dimethylphenyl)-1,3,5-triazine, sterically hindered amines, such as bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate. 20 Blowing agents Examples of blowing agents are organic azo compounds and organic hydrazo compounds, tetrazoles, oxazines, isatoic anhydride, and also soda and sodium bicarbonate. Preference is given to azodicarbonamide 25 and sodium bicarbonate and also mixtures of these. Definitions and examples of impact modifiers and processing aids, gelling agents, antistats, biocides, metal deactivators, optical brighteners, flame 30 retardants, antifogging agents, and compatibilizers, are described in "Kunststoffadditive" ["Plastics Additives"], R. Gschter/H. MUller, Carl Hanser Verlag, 3rd edn., 1989, "Plastics Additives Handbook" H. Zweifel, Carl Hanser Verlag, 5th edn., 2001 and in 35 "Handbook of Polyvinyl Chloride Formulating" E.J. Wilson, J. Wiley & Sons, 1993, and also in "Plastics Additives" G. Pritchard, Chapman & Hall, London, 1st edition, 1998. Impact modifiers are also described in detail in - 38 "Impact Modifiers for PVC", J.T. Lutz/ D.L. Dunkelberger, John Wiley & Sons, 1992. The invention further provides compositions which 5 comprise a chlorine-containing polymer and comprise an inventive stabilizer mixture. The amount used of the compounds of the general formulae (I) in these compositions, in order to achieve 10 stabilization in the chlorine-containing polymer, is advantageously from 0.01 to 10 parts by weight, preferably from 0.05 to 5 parts by weight, in particular from 0.1 to 2 parts by weight, based on 100 parts by weight of PVC. 15 The amount used of the compounds of the general formulae (II) in these compositions, in order to achieve stabilization in the chlorine-containing polymer, is advantageously from 0.01 to 10 parts by 20 weight, preferably from 0.05 to 5 parts by weight, in particular from 0.1 to 2 parts by weight, based on 100 parts by weight of PVC. The amount used of the compounds of the general 25 formulae (III) in these compositions, in order to achieve stabilization in the chlorine-containing polymer, is advantageously from 0.01 to 10 parts by weight, preferably from 0.05 to 5 parts by weight, in particular from 0.1 to 2 parts by weight, based on 100 30 parts by weight of PVC. An example of the amount which may be used of the perchlorate salt is from 0.001 to 5 parts by weight, advantageously from 0.01 to 3 parts by weight, 35 particularly preferably from 0.01 to 2 parts by weight, based on 100 parts by weight of PVC. Examples of the chlorine-containing polymers to be stabilized are: - 39 polymers of vinyl chloride, of vinylidene chloride, vinyl resins whose structure contains vinyl chloride units, such as copolymers of vinyl chloride and vinyl esters of aliphatic acids, in particular vinyl acetate, 5 copolymers of vinyl chloride with esters of acrylic or methacrylic acid and with acrylonitrile, copolymers of vinyl -chloride with diene compounds and with unsaturated dicarboxylic acids or anhydrides of these, such as copolymers of vinyl chloride with diethyl 10 maleate, diethyl fumarate or maleic anhydride, postchlorinated polymers and copolymers of vinyl chloride, copolymers of vinyl chloride and vinylidene chloride with unsaturated aldehydes, ketones and others, such as acrolein, crotonaldehyde, vinyl methyl 15 ketone, vinyl methyl ether, vinyl isobutyl ether and the like; polymers of vinylidene chloride and copolymers of the same with vinyl chloride and with other polymerizable compounds; polymers of vinyl chloroacetate and of dichlorodivinyl ether; chlorinated 20 polymers of vinyl acetate, chlorinated polymeric esters of acrylic acid and of alpha-substituted acrylic acid; polymers of chlorinated styrenes, such as dichlorostyrene; chlorinated rubbers; chlorinated polymers of ethylene; polymers and postchlorinated 25 polymers of chlorobutadiene and copolymers of these with vinyl chloride, chlorinated natural or synthetic rubbers, and also mixtures of the polymers mentioned with themselves or with other polymerizable compounds. For the purposes of this invention, PVC includes 30 copolymers with polymerizable compounds, such as acrylonitrile, vinyl acetate or ABS, where these may be suspension polymers, bulk polymers or else emulsion polymers. Preference is given to a PVC homopolymer, also in combination with polyacrylates. 35 Other possible polymers are graft polymers of PVC with EVA, ABS or MBS. Other preferred substrates are mixtures of the abovementioned homo- and copolymers, in particular vinyl chloride homopolymers, with other - 40 thermoplastic or/and elastomeric polymers, in particular blends with ABS, MBS, NBR, SAN, EVA, CPE, MBAS, PMA, PMMA, EPDM or with polylactones, in particular from the group consisting of ABS, NBR, NAR, 5 SAN and EVA. The abbreviations used for the copolymers are familiar to the skilled worker and have the following meanings: ABS: acrylonitrile-butadiene styrene; SAN: styrene-acrylonitrile; NBR: acrylonitrile-butadiene; NAR: acrylonitrile-acrylate; 10 EVA: ethylene-vinyl acetate. Other possible polymers are in particular styrene-acrylonitrile copolymers based on acrylate (ASA) . A preferred component in this context is a polymer composition which comprises, as components (i) and (ii), a mixture of 25-75% by weight 15 of PVC and 75-25% by weight of the copolymers mentioned. Components of particular importance are compositions made from (i) 100 parts by weight of PVC and (ii) 0-300 parts by weight of ABS and/or SAN modified ABS and 0-80 parts by weight of the copolymers 20 NBR, NAR and/or EVA, but in particular EVA. For the purposes of the present invention it is also possible to stabilize in particular recycled materials of chlorine-containing polymers, specifically the polymers described in more detail above, which have been 25 degraded by processing, use or storage. Recycled material from PVC is particularly preferred. The compounds which may be used concomitantly according to the invention, and also the chlorine-containing 30 polymers, are well known to the skilled worker and are described in detail in "Kunststoffadditive" ["Plastics Additives"], R. Guchter/H. Mudller, Carl Hanser Verlag, 3rd edn., 1989; in DE 197 41 778 and in EP-A 99 105 418.0 of 03.17.1999, which are incorporated 35 herein by way of reference. The inventive stabilizer system for chlorine-containing polymer compositions is represented by non-plasticized or plasticizer-free, or substantially plasticizer-free - 41 compositions. The inventive compositions are particularly suitable in the form of unplasticized formulations for hollow 5 articles (bottles), packaging foils (thermoforming foils), blown foils, crash-pad foils (automobiles), pipes, foams, heavy profiles (window frames), thin-wall profiles, construction profiles, external cladding, fittings, office foils, and apparatus casings 10 (computers, household devices) . Preferred other compositions in the form of plasticized formulations are suitable for wire sheathing, cable insulation, decorative foils, roof sheeting, foams, agricultural sheeting, hoses, sealing profiles, office foils, and 15 sheeting for air-supported structures. Examples of use of the inventive compositions in the form of plastisols are synthetic leather, flooring, textile coatings, wallcoverings, metal coatings (coil 20 coatings), and underbody protection for motor vehicles. Examples of sintered-PVC uses of the inventive compositions are slush, metal coatings and coil coatings, and Luvitherm foils in the EPVC sector. 25 The stabilizers may advantageously be incorporated by the following methods: in the form of an emulsion or dispersion (an example of a possible form being that of a paste-like mixture, and an advantage of the inventive combination in that supply form being the stability of 30 the paste); in the form of a dry mixture during the mixing of added components or polymer mixtures; via direct addition to the processing apparatus (e.g. calender, mixer, kneader, extruder, or the like), or in the form of a solution or melt or flakes or 35 granules/pellets in dust-free form in the form of a one-pack system. The inventive stabilized PVC likewise provided by the invention can be prepared in a manner known per se, and - 43 formulations, and for plasticized formulations. For further details in this connection, see "Kunststoffhandbuch PVC" [Plastics handbook PVC], vol. 2/2, W. Becker/H. Braun, 2nd edn., 1985, Carl Hanser 5 Verlag, pages 1236-1277. The examples below illustrate the invention but do not restrict the same. As in the rest of the description, data relating to parts and percentages are based on 10 weight. Examples The composition of test formulations as in the tables 15 is given below. The data are in parts by weight, based on 100 parts of PVC resin. A laboratory extruder was used to extrude strips in accordance with the formulations, starting from the 20 respective dry mixtures. To produce the strips, the PVC powder mixtures and the additives mentioned were prepared by the conventional hot/cold mixing technique and homogenized and plastified in a twin-screw extruder. 25 The extrusion parameters are as follows: Weber CE-3, conical twin screw: screw rotation rate 13 rpm, temperature control in individual zones: barrel section in zone 1: 170'C, zone 2 at 165'C, zone 3 at 170'C, and 30 zone 4 at 180'C. The die temperature was adjusted to 190'C. Die geometry: 50 x 2 mm. Initial color was determined as yellowness index (YI) to ASTM D1925-70. The results are given in the tables 35 below. Low YI values mean good stabilization. Long-term stability was further determined via determination of thermal stability to DIN VDE 0472. Here, the test piece was heated to 200'C in a glass - 44 tube in an oil bath, the bottom of which had been sealed by fusion (AR glass from Peco-Laborbedarf GmbH, Darmstadt), and the time at which visible red coloration of the universal pH indicator paper was 5 observed (corresponding to pH of 3) was determined. The stability of the PVC was further determined via the dehydrochlorination test (DHC test), carried out by a method based on DIN 53381, sheet 3. Here, the time 10 required for the dehydrochlorination curve to rise to a conductivity of 200 pS/cm was measured at 1800C. Example 1 A 1 A 2 A 3 A 4 A 5 A 6 A 7 PVC (Shin Etsu 6704) 100 100 100 100 100 100 100 Compound 1 --- --- --- --- --- --- 0.1 Zeolite A 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Calcium stearate 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Marklube 367 0.6 0.6 0.6 0.6 0.6 0.6 0.6 Licowax PE 520 0.6 0.6 0.6 0.6 0.6 0.6 0.6 AC 629 A 0.1 0.1 0.1 0.1 0.1 0.1 0.1 1,3-Dimethyl-4- --- 0.1 0.2 --- --- 0.1 0.1 aminouracil TEA ---- 0.1 0.2 0.1 0.1 Test results Color measurement Yellowness Index red- 31 26 73 73 27 23 extruded strip/ violet initial color 15 PVC Shin Etsu 6704, K value 67 (ex Shin Etsu) Compound 1 = mixture composed of 9% NaClO 4 , 45% CaCO 3 , 40% CaSiO 3 , 6% H 2 0 Marklube 367 = paraffin wax (ex Crompton) 20 Licowax PE 520 = polyethylene wax (ex Clariant) AC 629 A = oxidized polyethylene wax (ex Honeywell) TEA = triethanolamine in the form of commercially - 45 available product 1,3-dimethyl-4-aminouracil in the form of commercially available product 5 From the table it can be seen that the inventive composition A6 has surprising stabilizer action when compared with the comparative mixtures. This clearly meets an objective of this invention, improvement of initial color. For assessment of processing properties, 10 the initial color of the test specimen is especially important for providing sufficient processing stability. Even small differences in the YI value here are relevant. The particular effect of a combination of compounds of the structure (I) with compounds of the 15 structure (II) is seen to be significant here. The compound of the formula (I), used alone, does not have a satisfactory effect on the initial color of the PVC, as shown by the comparative examples A 4 and A 5. Synergistic action is only released in combination with 20 a compound of formula (II) , as shown in example A6. It can also be seen that the stabilization of the polymer via use of alkanolamines in combination with uracils can be still further raised via addition of perchlorates, as stated in inventive example A7. 25 Example 2 A 4 A 5 B 1 B 2 B 3 PVC (Shin Etsu 6704) 100 100 100 100 100 Compound 1 --- --- --- --- -- Zeolite A 1.0 1.0 1.0 1.0 1.0 Calcium stearate 0.4 0.4 0.4 0.4 0.4 Marklube 367 0.6 0.6 0.6 0.6 0.6 Licowax PE 520 0.6 0.6 0.6 0.6 0.6 AC 629 A 0.1 0.1 0.1 0.1 0.1 N,N'-Dimethyl-N- --- --- 0.1 0.2 0.1 cyanoacetylurea TEA 0.1 0.2 --- 0.1 - 46 Test results Color measurement Yellowness Index 73 73 36 30 28 extruded strip/ initial color PVC Shin Etsu 6704, K value 67 (ex Shin Etsu) Compound 1 = mixture composed of 9% NaClO 4 , 45% CaCO 3 , 40% CaSiO 3 , 6% H 2 0 5 Marklube 367 = paraffin wax (ex Crompton) Licowax PE 520 = polyethylene wax (ex Clariant) AC 629 A = oxidized polyethylene wax (ex Honeywell) TEA = triethanolamine in the form of commercially available product 10 From the table it can be seen that the inventive composition B3 has improved stabilizer action when compared with the comparative mixtures. This clearly meets an objective of this invention, improvement of 15 initial color. For assessment of processing properties, the range of initial color of the test specimen is especially important. The particular effect of a combination of compounds of the structure (I) with compounds of the structure (III) is seen to be 20 significant here. Example 3/1 The following formulations were roll-milled at 180'C 25 for 5 minutes on mixing rolls. The milled sheet formed was used to produce a pressed sheet at 180'C in a preheated multi-daylight sheet press. Pressed sheet thickness: 1 mm, press time: 1 minute. Yellowness index was determined to ASTM D1925-70. Low YI values mean 30 good stabilization and, respectively, initial color. High percentages mean good transparency.
- 47 C 1 C 2 C 3 C 4 C 5 C 6 C 7 Evipol SH 5730 100 100 100 100 100 100 100 Paraloid BTA III/N2 5 5 5 5 5 5 5 Paraloid K 120N 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Paraloid K 175 0.5 0.5 0.5 0.5 0.5 0.5 0.5 E wax 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Loxiol G 16 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Epox. soybean oil 3.0 3.0 3.0 3.0 3.0 3.0 3.0 NaP/H 2 0 0.6 0.6 0.6 0.6 0.6 0.6 0.6 TEA 0.2 0.4 --- --- 0.2 0.2 0.2 1,3-Dioctyl-4-amino- --- --- 0.1 0.3 0.1 0.2 0.2 uracil Mark CH 300 0.5 Color measurement on 1 mm pressed sheets Yellowness Index YI 43.8 36.1 83.1 54.4 24.4 18.4 14.8 Transparency 90.5 91.1 78.0 89.9 92.3 93.1 92.9 Evipol SH 5730 PVC, K value 57 (ex EVC) Paraloid K 175/K 120N = acrylate processing aid (ex Rohm & Haas) 5 Paraloid BTA III/N2 = methacrylate-butadiene-styrene modifier (ex Rohm & Haas) E wax = ester wax/montan wax (ex Clariant) Loxiol G 16 = fatty acid partial ester (ex Henkel) NaP/H 2 0 = 30% strength sodium perchlorate solution in 10 water Mark CH 300 = mixed aryl/alkyl phosphite (ex Crompton) TEA = triethanolamine in the form of commercially available product 15 From the table it can be seen that the inventive composition C 5 provides an improvement in stabilizer action when compared with the comparative mixtures. It can also be seen that stabilization of the polymer via use of alkanolamines in combination with uracils can be 20 still further raised via addition of phosphites, as - 48 stated in inventive example C 7. Example 3/2 5 The formulations were roll-milled at 1800C for 5 minutes on mixing rolls. The milled sheet formed was used to produce a pressed sheet at 180'C in a preheated multi-daylight sheet press. Pressed sheet thickness: 1 mm, press time: 1 minute. Yellowness index was 10 determined to ASTM D1925-70. Low YI values mean good stabilization and, respectively, initial color. High percentages mean good transparency. C 1 C 2 C 8 C 9 C 10 C 11 C 12 Evipol SH 5730 PVC 100 100 100 100 100 100 100 Paraloid BTA III/N2 5 5 5 5 5 5 5 Paraloid K 120N 0.5 0.5 0.5 0.5 0.5 0.5 0.5 Paraloid K 175 0.5 0.5 0.5 0.5 0.5 0.5 0.5 E wax 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Loxiol G 16 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Epox. soybean oil 3.0 3.0 3.0 3.0 3.0 3.0 3.0 NaP/H 2 0 0.6 0.6 0.6 0.6 0.6 0.6 0.6 TEA 0.2 0.4 --- --- 0.2 0.2 0.2 1,3-Dimethyl-4-amino- --- --- 0.1 0.3 0.1 0.2 0.2 uracil Phosphite Mark CH 300 0.5 Color measurement on 1 mm pressed sheets Yellowness Index YI 43.8 36.1 55.7 24.1 16.3 14.2 11.6 Transparency 90.5 91.1 88.8 91.1 92.8 92.5 92.6 15 Evipol SH 5730 PVC, K value 57 (ex EVC) Paraloid K175/K 120N = acrylate processing aid (ex Rohm & Haas) Paraloid BTA III/N2 = methacrylate-butadiene-styrene modifier (ex Rohm & Haas) 20 E wax = ester wax/montan wax (ex Clariant) - 49 Loxiol G 16 = fatty acid partial ester of glycerol (ex Henkel) NaP/H 2 0 = 30% strength sodium perchlorate solution in water 5 Phosphite Mark CH 300 = mixed aryl/alkyl phosphite (ex Crompton) TEA = triethanolamine in the form of commercially available product 10 From the table it can be seen that the inventive compositions C 10 and C 11 provide an improvement in stabilizer action when compared with the comparative mixtures. It can also be seen that stabilization of the polymer via use of alkanolamines in combination with 15 uracils can be still further raised via addition of phosphites, as stated in inventive example C 12. Example 4 20 The following formulations were roll-milled at 180'C for 5 minutes on mixing rolls. The milled sheet formed was used to produce a pressed sheet at 180'C in a preheated multi-daylight sheet press. Pressed sheet thickness: 1 mm, press time: 1 minute. Yellowness index 25 was determined to ASTM D1925-70. Low YI values mean good stabilization and, respectively, initial color. High percentages mean good transparency. The Congo Red value was determined at 2000C to DIN 473/811/3/2. High minute values mean good thermal stability of the test 30 specimen. The time taken to reach conductivity of 200 pS/cm was measured. The higher the value from this dehydrochlorination test (DHC), the better the stabilization.
- 50 D 1 D 2 D 3 D 4 D 5 D 6 D 7 D 8 PVC (Evipol SH 100 100 100 100 100 100 100 100 7020) DEHP 20 20 20 20 20 20 20 20 Epox. soybean oil 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 NaP/BDG 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 AC 629 A 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 TEA 0.2 0.4 --- --- 0.2 -- Diethanolsoyamine --- 0.2 0.4 0.2 1,3-Dibutyl-4- --- --- 0.2 0.3 0.1 --- --- 0.1 aminouracil Color measurement on 1 mm pressed sheets Yellowness Index 17.4 14.7 15.8 12.2 9.7 15.7 13.9 9.1 YI Transparency 96.7 95.9 97.3 97.4 97.3 97.6 97.6 98.1 Congo Red 17 28 10 10 21 10 22 17 DHC [200OS/cm] 117 152 88 93 128 89 129 115 Evipol 7020 PVC, K value 70 (ex EVC) DEHP = di-2-ethylhexyl phthalate in the form of commercially available product 5 NaP/BDG = 30% strength sodium perchlorate solution in butyl diglycol TEA = triethanolamine in the form of commercially available product Diethanolsoyamine = bis(2-hydroxyethyl)soyamine in the 10 form of commercially available product 1,3-Dibutyl-4-aminouracil AC 629 A = oxidized polyethylene wax (ex Honeywell) From the table it can be seen that the inventive 15 compositions D5 and D8 have improved stabilizer action when compared with the comparative mixtures.
- 51 Example 5 The formulations were roll-milled at 180'C for 5 minutes on mixing rolls. The milled sheet formed was 5 used to produce a pressed sheet at 180'C in a preheated multi-daylight sheet press. Pressed sheet thickness: 1 mm, press time: 1 minute. Yellowness index was determined to ASTM D1925-70. Low YI values mean good stabilization and, respectively, initial color. High 10 percentages mean good transparency. E 1 E 2 E 3 E 4 E 5 E 6 E 7 E 8 E 9 E 10 E 11 Evipol SH 100 100 100 100 100 100 100 100 100 100 100 7020 PVC DEHP 47 47 47 47 47 47 47 47 47 47 47 Epox. 3 3 3 3 3 3 3 3 3 3 3 soybean oil Loxiol G 71 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 S Calcium 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 stearate NaP/BDG --- --- --- --- --- --- --- --- 0.5 0.5 0.5 1,3-Dioctyl- 0.2 0.2 0.2 0.2 0.2 0.2 0.2 4-amino uracil TEA --- 0.2 0.2 0.2 Diethanol- 0.2 0.2 0.2 soyamine TIPA 0.2 0.2 0.2 Color measurement on 1 mm pressed sheets Yellowness 66.3 56.1 24.3 13.9 87.2 18.2 72.5 17.0 10.2 9.6 9.6 Index YI b value 21.9 23.4 14.2 10.7 23.9 10.7 30.4 10.1 5.7 5.6 5.8 Transparency,74.7 85.2 97.5 97.8 66.4 97.8 84.6 97.9 96.5 96.8 97.6 - 52 Evipol SH 7020 PVC, K value 70 (ex EVC) DEHP = di-2-ethylhexyl phthalate in the form of commercially available product NaP/BDG = 30% strength sodium perchlorate solution in 5 butyl diglycol Loxiol G 71 S = multicomponent ester lubricant (ex Henkel) TEA = triethanolamine in the form of commercially available product 10 Diethanolsoyamine = ES-2 in the form of commercially available product TIPA = triisopropanolamine in the form of commercially available product 15 From the table it can be seen that the inventive compositions E4, E6, and E8 provide an improvement in stabilizer action when compared with the comparative mixtures. It can also be seen that stabilization of the polymer can be still further raised via addition of 20 perchlorate, as stated in inventive examples E9, E10, and Ell.

权利要求:
Claims (26)
[1] 1. A stabilizer mixture for stabilizing chlorine containing polymers, encompassing at least 5 a) one alkanolamine of the formula (I) b) one uracil of the formula (II) where, for the alkanolamine of the formula (I) 10 R2 RL - (CHR )-CHR -O -H n x = 1, 2 or 3; y = 1, 2, 3, 4, 5 or 6; 15 n = from 1 to 10; R and R2 = independently of one another H, C 1 -C 22 alkyl, CHR 3 a)y-CHR 3 b-O-)n-H, -[-(CHR 3 a) y-CHRab 0-]n-CO-R 4 , C 2 -C 2 0 -alkenyl, C 2 -C 1 8 -acyl, C 4 -CB-cyclo alkyl, where this may have OH substitution in the 20 -position, C 6 -Cio-aryl, C 7 -Cio-alkaryl or C7-C1O aralkyl, or, if x = 1, R and R2 may also, together with the N, form a closed ring having from 4 to 10 members, composed of carbon atoms and, where appropriate, of up to 2 heteroatoms, or if x = 2, 25 R may also be C 2 -C 18 -alkylene which, at both P-carbon atoms, may have OH substitution and/or have interruption by one or more 0 atoms and/or by one or more NR2 groups, or be dihydroxy substituted tetrahydrodicyclopentadienylene, 30 dihydroxy-substituted ethylcyclohexanylene, dihydroxy-substituted 4,4'-(bisphenol A dipropyl ether)ylene, isophoronylene, dimethylcyclo hexanylene, dicyclohexylmethanylene or 3,3'-di methyldicyclohexylmethanylene, and if x = 3, R' - 54 may also be trihydroxy-substituted (tri-N-propyl isocyanurate)triyl; R 3 a and R 3 b = independently of one another C 1 -C 2 2 alkyl, C 2 -C 6 -alkenyl, C 6 -Cio-aryl, H or CH 2 -X-R 5 , 5 where X = 0, S, -0-CO- or -CO-O-; R = C 1 -Ci-alkyl/alkenyl or phenyl; and R 5 = H, Ci-C 22 -alkyl, C 2 -C 22 -alkenyl or C 6 -Co-aryl; and for the uracil of the formula (II) 0 RI N I (II), N NH 2 10 R 2 R1 and R2, independently of one another, are C1-C24-alkyl, which may have interruption by -C02 and/or by 1 or more oxygen atoms, and/or may have 15 substitution by one or more OH groups, or are C3-C24-alkenyl, branched or unbranched, or are C5-C8-cycloalkyl, unsubstituted or substituted with from 1 to 3 C1-C4-alkyl, C1-C4-alkoxy, or C5-C8-cycloalkyl groups, or with hydroxy groups, 20 or with Cl atoms, or are C7-C9-phenylalkyl, unsubstituted or substituted on the phenyl ring with from 1 to 3 Cl-C4-alkyl, Cl-C4-alkoxy, or C5-C8-cycloalkyl groups, or with hydroxy groups, or with Cl atoms, and R1 or R2 may also be 25 hydrogen, and Y is S or 0.
[2] 2. A stabilizer mixture for stabilizing chlorine containing polymers, encompassing at least 30 a) one reaction product of a mono- or polyfunctional epoxide and of ammonia or of a mono- or polyfunctional dialkyl(aryl)- or monoalkyl(aryl)amine of the formula (I) as claimed in claim 1 and 35 b) one uracil of the formula (II) as claimed in - 55 claim 1.
[3] 3. A stabilizer mixture for stabilizing chlorine containing polymers, encompassing at least 5 a) one alkanolamine of the formula (I) as claimed in claim 1 b) one cyanoacetylurea of the formula (III) 10 formula (III) Y I I CO-CH 2 -CN R-NH-C-N R, where Y is oxygen or sulfur, and 15 R2 is Cl-C24-alkyl, which may have interruption by -CO 2 - and/or by oxygen atoms, and/or may have substitution by from 1 to 3 OH groups, or is C3-C24-alkenyl, C7-C1O-phenylaikyl, C5-C8-cycloalkyl, C7-ClO-alkylphenyl, phenyl 20 or naphthyl, where in each case the aromatic radical may have substitution by -OH, Cl-C12 alkyl and/or OC1-C4-alkyl, and R1 is as defined for R2, or R1 is hydrogen. 25
[4] 4. A stabilizer mixture for stabilizing chlorine containing polymers, encompassing at least a) one reaction product of a mono- or polyfunctional epoxide and of ammonia or of a 30 mono- or polyfunctional dialkyl(aryl)- or monoalkyl(aryl)amine of the formula (I), and b) a cyanoacetylurea of the formula (III) as claimed in claim 3. 35
[5] 5. The stabilizer mixture as claimed in claim 2 and 4, where the polyfunctional epoxide is - 56 dicyclopentadiene diepoxide, vinylcyclohexene diepoxide, bisphenol A diglycidyl ether, or tris glycidyl isocyanurate, and the dialkylamine is diethanolamine or diisopropanolamine, and the 5 monoalkylamine is monoethanolamine or monoiso propanolamine.
[6] 6. The stabilizer mixture as claimed in any of claims 1 to 5, where, in the compound with the 10 general formula (I), R 3 a and R 3 b, independently of one another, are H or CH 3 and y = 1.
[7] 7. The stabilizer mixture as claimed in any of 15 claims 1 to 6, where, in the compound with the general formula (I), R1 = R 2 = CH 2 -CHR 3 -OH.
[8] 8. The stabilizer mixture as claimed in any of 20 claims 1 to 7, where the compounds of the general formula (I) are tris(2-hydroxy-l-propyl)amine, tris(2-hydroxyethyl)amine, bis(2-hydroxyethyl) 2-hydroxy-l-propyl)amine, or alkyl/alkenyl-bis (2-hydroxyethyl)amine, alkyl/alkenyl(2-hydroxy 25 1-propyl)amine, N-(2-hydroxyhexadecyl)diethanol amine, N-(2-hydroxy-3-octyloxypropyl)diethanol amine, N-(2-hydroxy-3-decyloxypropyl)diethanol amine, or a mixture thereof. 30
[9] 9. The stabilizer mixture for stabilizing chlorine containing polymers, as claimed in any of claims 1 to 8, also encompassing at least one perchlorate salt. 35
[10] 10. The stabilizer mixture as claimed in any of claims 1 to 9, where the perchlorate salt is a compound of the formula M(ClO 4 )n, where M is Li, Na, K, Mg, Ca, Sr, Ba, Zn, Al, La, Ce, or a hydrotalcite layer-lattice cation, or an organic - 57 onium cation; n is 1, 2 or 3, as appropriate for the valency of M, or if a hydrotalcite layer lattice cation is present 0 < n 1. 5
[11] 11. The stabilizer mixture as claimed in any of claims 1 to 10, where, in the perchlorate salt, M = Na or K, and n = 1.
[12] 12. The stabilizer mixture as claimed in any of 10 claims 1 to 11, also comprising an anhydrous hydrotalcite or a zeolite.
[13] 13. The stabilizer mixture as claimed in any of claims 1 to 12, which also, if appropriate, 15 comprises metal soaps, and/or, if appropriate, comprises another substance from the group of the polyols and disaccharide alcohols, salts of the hydroxycarboxylic acids, glycidyl compounds, hydrotalcites, aluminosilicates of alkali metals 20 or of alkaline earth metals, hydroxides/oxides of alkali metals or of alkaline earth metals, or the corresponding (hydrogen)carbonates or carboxylates, and fillers/pigments, plasticizers, antioxidants, light stabilizers, optical 25 brighteners, lubricants and epoxidized fatty acid esters.
[14] 14. The stabilizer mixture as claimed in any of claims 1 to 13, where a phosphite is also present, 30 and/or possible reaction products of phosphite with the component of formula (I) or with the perchlorate salt are present.
[15] 15. The stabilizer mixture as claimed in any of 35 claims 1 to 14, where the additional phosphite is distearyl pentaerythrityl diphosphite, triphenyl phosphite, trisnonylphenyl phosphite, phenyl didecyl phosphite, poly(dipropylene glycol) phenyl phosphite, tetraphenyl dipropylene glycol - 58 diphosphite, tetraisodecyl dipropylene glycol diphosphite, trisdipropylene glycol phosphite, decyl diphenyl phosphite, trioctyl phosphite, trilauryl phosphite or nonylphenyli. 5 C 12 /C 13 5 alkyli. 5 phosphite.
[16] 16. A composition, comprising a chlorine-containing polymer and the stabilizer mixture as claimed in any of claims 1 to 15. 10
[17] 17. The composition as claimed in any of claims 1 to 16, characterized in that it comprises, based on 100 parts by weight of chlorine-containing polymer, from 0.01 to 10 parts by weight of the 15 compound of the general formula (I) and from 0.01 to 10 parts by weight of the compound of the general formula (II).
[18] 18. The composition as claimed in any of claims 1 20 to 16, characterized in that it comprises, based on 100 parts by weight of chlorine-containing polymer, from 0.01 to 10 parts by weight of the compound of the general formula (I) and from 0.01 to 10 parts by weight of the compound of the 25 general formula (III).
[19] 19. The composition as claimed in claim 17 or 18, characterized in that it also comprises, based on 100 parts by weight of chlorine-containing 30 polymer, from 0.001 to 5 parts by weight of the perchlorate salt.
[20] 20. The composition as claimed in claim 19, characterized in that it also comprises, based on 35 100 parts by weight of chlorine-containing polymer, from 0.05 to 5 parts by weight of a phosphite.
[21] 21. A process for stabilizing chlorine-containing - 59 polymers via addition of the stabilizer mixture as claimed in any of claims 1 to 15 to a chlorine containing polymer. 5
[22] 22. The process for stabilizing chlorine-containing polymers as claimed in claim 21, characterized in that the chlorine-containing polymer is plasticized PVC. 10
[23] 23. The process for stabilizing chlorine-containing polymers as claimed in claim 21, characterized in that the plasticized PVC serves for production of floorcoverings, motor vehicle components, plasticized foils, hoses, injection moldings, or 15 wire sheathing.
[24] 24. The process for stabilizing chlorine-containing polymers as claimed in claim 21, characterized in that the chlorine-containing polymer is 20 unplasticized PVC.
[25] 25. The process for stabilizing chlorine-containing polymers as claimed in claim 21, characterized in that the chlorine-containing polymer serves for 25 production of foils (among which is Luvitherm), or of PVC pipes, or of profiles.
[26] 26. A consumer item, comprising PVC, which has been stabilized via the stabilizer mixture as claimed 30 in any of claims 1 to 15.

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同族专利:

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公开号 | 公开日

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BR0317050B1|2013-11-26|

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EP1583796B1|2007-10-24|

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WO2004065470A2|2004-08-05|

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CA2505345A1|2004-08-05|

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AU2003292262B2|2009-04-02|

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EP1583796A2|2005-10-12|

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PT1583796E|2007-11-08|

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MXPA05007586A|2006-02-22|

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BR0317050A|2005-10-25|

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JP4711284B2|2011-06-29|

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KR101039285B1|2011-06-07|

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CN1742046A|2006-03-01|

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AT376570T|2007-11-15|

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CA2505345C|2011-06-28|

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US7358286B2|2008-04-15|

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KR20050101179A|2005-10-20|

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DE10301675A1|2004-07-29|

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JP2006513298A|2006-04-20|

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DK1583796T3|2008-02-18|

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DE50308475D1|2007-12-06|

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US20060052497A1|2006-03-09|

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ES2294332T3|2008-04-01|

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WO2004065470A3|2005-02-24|

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CN100532439C|2009-08-26|

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BRPI0317050B8|2018-08-28|

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法律状态:
2007-03-15| TC| Change of applicant's name (sec. 104)|Owner name: CHEMTURA VINYL ADDITIVES GMBH Free format text: FORMER NAME: CROMPTON VINYL ADDITIVES GMBH |

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2009-07-30| FGA| Letters patent sealed or granted (standard patent)|

优先权:

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申请号 | 申请日 | 专利标题

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DE10301675A|DE10301675A1|2003-01-17|2003-01-17|Stabilizer mixtures for chloropolymer, e.g. PVC, e.g. for flooring, vehicle part, foil, pipe, molding, wire covering or profile, contain alkanolamine or reaction product with epoxide and aminouracil or cyanoacetylurea|

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DE10301675.9||2003-01-17||

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PCT/EP2003/014691|WO2004065470A2|2003-01-17|2003-12-20|Stabilizer system for stabilizing pvc|

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