GB2295619A - Siloxanes containing piperidine triazine groups as stabilisers - Google Patents

Siloxanes containing piperidine triazine groups as stabilisers Download PDF

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GB2295619A
GB2295619A GB9524075A GB9524075A GB2295619A GB 2295619 A GB2295619 A GB 2295619A GB 9524075 A GB9524075 A GB 9524075A GB 9524075 A GB9524075 A GB 9524075A GB 2295619 A GB2295619 A GB 2295619A
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tert
bis
butyl
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Valerio Borzatta
Primo Carrozza
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Novartis AG
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Ciba Geigy AG
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/38—Polysiloxanes modified by chemical after-treatment
    • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
    • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
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    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08K5/49—Phosphorus-containing compounds
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
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Description

2295619 Piveridine triazine compounds containing silane groups as
stabilizers for organic materials The present invention relates to novel piperidine triazine compounds containing silane groups, to their use as light, heat and oxidation stabilizers for organic materials, especially synthetic polymers, and to organic materials thus stabilized.
The use of derivatives of 2,2,6,6-tetramethylpiperidine containing silane groups, such as those noted in US-A-4 177 186, US-A-4 859 759, US-A-4 895 885, US-A-4 946 880, US-A4 948 888, US-A-5 134 233, US-A-5 219 905, US-A5 321066, EP-A-162 524, EP-A- 182 415, EP-A-244 026, EP-A-343 717, EP-A388 32 1, EP-A-480 466, DD-A-234 682 and DD-A-234 683, as stabilizers for synthetic polymers, is known.
The present invention relates to novel compounds of formula (I) CH3 CH3 1 1 0- 0 - Si- CH3 1 1 CH3 1 h3C-.b' 1 CH3 (1 1 -"2)3 A (H3 N ' N (D N-Rl CH3 CH3 CH3 ANCH3 1 X 1 CH3 CH3 CH3 N CH3 1 K 2 R - N (I) R2 in which m + n is a number from 1 to 100 and n varies from zero to 90% of the sum of m + n, X is -0- or -NH-; R 1 is hydrogen, C 1 -C 1 salkyl, C2- COlkyl substituted in position 2, 3 or 4 by C 1 -C8alkoxy or by di(C1C4alkyl)amino; CS-CUCycloalkyl unsubstituted or substituted with 1, 2 or 3 C l-C4alkyls; C7-C9phertylalkyl unsubstituted or substituted on the phenyl with 1, 2 or 3 I- Cl-C4alkyls; or a group of formula (II); CH3 CH3 N-R2 -(11 CH3 CH3 (11) R2 is hydrogen, Cl-Cgalkyl, 0., OH, NO, CH2CN, Cl-CI8alkoxy, CS- CUCYCloalkoxy, GrC9phenylalkyl unsubstituted or substituted on the phenyl with 1, 2 or 3 Cl-C4alkyls; Cl-C8acyl; and A is C6-CI8alkyl.
Examples of alkyl with up to 18 carbon atoms are methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, isobutyl, t-butyl, pentyl, 2-pentyl, hexyl, heptyl, octyl, 2-ethylhexyl, t-oetyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
Examples Of C2-C4alkyl substituted with Cl-C8alkoxy, preferably ClC4alkoxy, in particular methoxy and ethoxy, are 2-methoxyethyl, 2ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-butoxypropyl, 3octoxypropyl and 4-methoxybutyl.
Examples Of C2-C4alkyl substituted by di(CI-C4alkyl)amino, preferably with dimethylamino or diethylamino, are 2-dimethylaminoethyl, 2diethylarninoethyl, 3-dirnethylarninopropyl, 3-diethylaminopropyl, 3-dibutylaminopropyl and 4-diethylaminobutyl.
Examples of Cl-CI8alkoxy are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, pentoxy, isopentoxy, hexoxy, heptoxy, octoxy, decyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy and octadecyloxy. Preferred examples are C6- CI2alkoxy, in particular heptoxy and octoxy.
Examples Of CS-CUCycloalkyl unsubstituted or substituted with 1, 2 or 3 Cl-C4alkyls, are cyclopentyl, methylcyclopentyl, dimethylcyclopentyl, cyclohexyl, methylcyclohexyl, dimethylcyclohexyl, trimethylcyclohexyl, t-butylcyclohexyl, cyclooctyl, cyclodecyl and cyclododecyl. Cyclohexyl unsubstituted or substituted with Cl-C4alkyl is preferred.
Examples Of C7-C9phenylalkyl unsubstituted or substituted on the phenyl with 1, 2 or 3 Cl-C4alkyls are benzyl, methylbenzyI, dimethylbenzyI, trimethylbenzyI, t-butylbenzyl and 1 1 2-phenylethyl. Benzyl is preferred.
Examples of CS-C12Cycloalkoxy are cyclopentoxy, cyclohexoxy, cycloheptoxy, cyclooctoxy, cyclodecyloxy and cyclododecyloxy. Cyclopentoxy and cyclohexoxy are preferred.
Examples of CI-C8acyl, which can be aliphatic or aromatic, are formyl, acetyl, propionyl, butyryl, isobutyryl, pentanoyl, hexanoyl, heptanoyl, octanoyl and benzoyl. CI-C8allcanoyl and benzoyl are preferred. Acetyl is especially preferred.
Those compounds of formula (1) are of interest in which m + n is a number from 1 to 100, n is e.g. zero or a number from 1 to 50 and can vary from zero to 50% of the sum of m + n The sum m + n may be, for example, also a number from 2 to 100, 4 to 100, 8 to 100, 2 to 70, 4 to 70 or 8 to 70. The variable n preferably varies from 10 to 50%, e.g. 20 to 50% or 30 to 50%, of the sum m + n. Furthermore, the variable m may be for example a number from 10 to 50 and the variable n may be for example a number from 0 to 50, 5 to 50 or 10 to 40.
The radical A may be for example C9-CIgalkyl, CIO-Clsalkyl or C12-CHalkyl.
Preferred meanings of R2 are hydrogen, Cl-C4alkyl, OH, C6-CUalkoxy, CSC8cycloalkoxy, benzyl or acetyl, in particular hydrogen or methyl.
Preferred compounds of formula (I) are those in which m + n is a number from 1 to 90 and n varies from zero to 90% of the sum m + n; X is -0- or NH-; R 1 is hydrogen, C 1 -C 12alkyl, CS-C7cycloalkyl, C7-C9phenylalkyl or a group of formula (H); and A is C6-CUalkyl.
Particularly preferred compounds of formula (1) are those in which m + n is a number from 1 to 80 and n varies from zero to 90% of the sum m + n; X is -0- or -NH-; R, is hydrogen, Cl-C8alkyl, cyclohexyl, benzyl or a group of formula (I1); and A 'S C8-C 12alkyl.
Compounds of formula (1) of special interest are those in which m + n is a number from 1 to 70 and n varies from zero to 50% of the sum m + n; X is -0- or -NH-; R, is hydrogen, C I -C4alkyl or a group of formula (I1); and A iS CS- C12alkyl.
Compounds of formula (1) of particular interest are those in which m + n is a number from 1 to 60 and n varies from zero to 50% of the sum m + n; X is -0- or -NH-; R, 'S Cl-COlkyl or a group of formula (H); and A iS C8-C 12alkyl.
Examples of compounds of formula (I) are CH3 1 HSC--- S 1 CM3 Cr13 H9C4 N CH3 CH3 C1H3 U 0-1 0 So- CH k r103)26 NiN N - C4H9 CH CH3 CH CH3 CH3 N CH3 CH3 N CH3 1 1 k;M3 q;r'3 1 3 CooH 17) CH3 7 CH3 CH3 H3 CH3 C 1 ( 15 1 1 H3C- Si 0-& O-Si-CH 3 (k;r12)3 H 17 CH C8 3 NH 26 27 N'N N H,C, - N N C4 Hoo CH CH3 CH CH3 CH N ICH CHAM CH 1 3 3 1 3 H H CH3 C13 CH3 CH3 HP' i 0-1 1 o-si 0 - bl- (M3 H 1 1 c (CH2)3 3 3 1+2)3 H 6 (8"17 UH3 1 26 27 W'N N - C4H9 3A'J.1 C H CH3 L 3 CH35 CH3 CH L. ' 1 3 N CH3 CH3 N CH3 1 H H3 H3C Si- H3 H CH3 CH3 CH3 o - ki I O-si U - bi- UH3 t I I (CHi2)3 C; IH 1 8"17 CH3 NH 1 26 N!'N H9C4 - N N - C4H9 CH3 CH3 CH35(,,, CH3 CHj N CH3 CH3 N CH3 1 1 (;H3 UM3 27 CH 3 CH3 c 3 CH 3 1 1 H3C- Si v - 1 1 1 1 O-S si- c CH3 (( 1 H2)3 U 26 N '-N N - C4)19 CH CH3 CH CH3 CH N CH 3 CHAN CH 1 3 1 3 CH3 CH 3 Hq C4 -N 1 1 .;12" 25 CH3 27 3 9 fl,--, CH 3 1 H3C- Si 1 kIrl 3 CH3 1 H3Co- Si 1 L;M3 CH 3 H9C, - N CH3 H3 CH 3 0- 0JS -CH (U" 2)3 NH N ',N A /114 N kIl, N - C4H9 CH3 CH3 CH CH3 CH N AN CH 3 1 CH3 CH3 1 3 H H H9C, - N 3, 1 1 C12 H 25.;m 3 27 CH 3 H3 CH3 0 O-Si-CH (CH J3 1 0 N 'N N CHg CH CH3 CH 3 AM CH 3 CH3 N CH3 CH 3 N CH 3 1 1 k;m 3 k^ CH 3 H3 1 H 3 1 0 H3C- 5 0 C8H 17j kk 1 'r103 NH 39 N N N - CHg CH CH3 CH CH3 CH N CH AN CH 3 3 1 3 CH3 1 H H H9C, - N 1 1 C8H17 um 3 14 CH3 1 1 CH3 14 3 ? 1 CH3 CH 3 1 H3c- S' 1 CH 3 CH3 CH 3 1 1 HSC- Si O-Ri- (UM 2h NiN H9C, - N N CHg CH:5 CH 3 CH CH 3 CH3 N CH3 CHAN CH 1 3 f 3 CH 3 CH 3 1 CH3 1 H9C, - N 1 (CH2)3 NH N '- N "N'\ N - C4H9 CH CH3 CH 3 AN CH3 CH N CH 3 CH3 CH3 1 1 H H CH 3 H 3 1 c, HP- S () - si 1 1 Ul 3 (CH 2)3 1 U)2 N J'N N CH3 CH 3 H3C - N -- N CH 3 CH 3 CH CH 3 CH 3 N CH 3 1 k;m 3 and 6 CH3 CH3 N N-CH3 CH3 CH 3 CH CH3 CHAN 3 1 CH3 toM3 C HI 3 CH 3 o-si- U - Zw- um 12 H 25 1.0 m 3 14 CH3 CH 3 1 i _ 1 Zl- k;H3 C12H 25 m 3 14 H3 CH3 - c, 1 0 si- CH 1 1 C12H25 k1M3 27 CH3 CH 3 H3C- S1 1 CH3 CH3 CH3 HN - N CH3 CH3 CH CH3 CH N CH 3 1 3 1 (CH2)3 1 NH N '-N 26 CH3 CH3 N NH CH3 CH.
CH3 CH3 3A, CH3 N CH3 1 H 1.H3 CH 3 0 C12 H25 CH3 27 The compounds of the present invention can be prepared, for example, by reacting a compound of formula (III) CH3 C113 1 1 CH3 1 H3C_ S' U- NI 0 - IS'- UH3 M3 H +n 3 1 CH.4 (III) where m and n are as defined above, with the appropriate amounts of alkene capable of forming a group 1 kCH2)3 1 X N J, N /0 N \ RI-N N-R CH3 CH3 CH3., CH3 CH N CH CH3 N CH3 3 3 1 1 R2 R2 and a group Awhere R,, R2, X and A are as defined above, effecting the reaction of hydrosilylation in the presence of catalytic amounts of complex of Pt or Rh as described in EP-A-343 717 and EP-A-388 321 (Chemical Abstracts 115: 160 562f; Derwent 90-28449W38) and by Speier (LA. C.S. 79, 974, 1957).
The compounds of formula (M) are commercially available or they can be prepared according to known methods.
The alkenes capable of forming a group 1 (CH2)3 1 X N N 0 /-, N N-Rl CH3 CH3 CH CH3!> 3 CH3 N CH3 CH N CH3 1 1 RI-N R2 R2 are prepared, for example, as described in US-A-4 731393 or according to known methods, whereas the alkenes capable of forming a group A are commercially available.
The compounds of the present invention are very effective in improving the light, heat and oxidation resistance of organic materials, in particular synthetic polymers and copolymers, and are particularly suitable for stabilizing polypropylene fibres on account of their increased resistance to volatilization.
Examples of organic materials that can be stabilized are:
1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut- 1 -ene, poly-4-methylpent- 1 -ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbomene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high den- sity and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), branched low density polyethylene (BLDPE).
Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, preferably polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:
a) radical polymerisation (normally under high pressure and at elevated temperature).
b) catalytic polymerisation using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either n- or a-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(HI) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerisation medium. The catalysts can be used by themselves in the polymerisation or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups la, Ha and/or Ifla of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).
2. Mixtures of the polymers mentioned under 1), for example mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).
3. Copolymers of monoolefins and diolef ins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/butI -ene copolymers, propylene/isobutylene copolymers, ethylene/but- I -ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethyleneloctene copolymers, propylenelbutadiene copolymers, isobutylene/isoprene copolymers, ethylenelalkyl acrylate copolymers, ethylenelalkyl methacrylate copolymers, ethylenelvinyl acetate copolymers and their copolymers with carbon monoxide or ethylenelacrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbomene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylenelethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), L13PElethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylenelcarbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.
4. Hydrocarbon resins (for example CS-C9) including hydrogenated modifications thereof (e.g. tackifiers) and mixtures of polyalkylenes and starch.
5. Polystyrene, poly(p-methylstyrene), poly((x-methylstyrene).
6. Copolymers of styrene or cc-methylstyrene with dienes or acrylic derivatives, for example styrene/butadiene, styrene/acrylonitrile, styrene/alkyl methacrylate, styrene/butadiene/alkyl acrylate, styrene/butadiene/alkyl methacrylate, styrene/maleic anhydride, styrene/acrylonitrile/methyl acrylate; mixtures of high impact strength of styrene copolymers and another polymer, for example a polyacrylate, a diene polymer or an ethylene/propylene/diene terpolymer; and block copolymers of styrene such as styrene/butadiene/styrene, styrene/isoprene/styrene, styrene/ethylene/butylene/styrene or styrene/ethylene/propylene/ styrene.
7. Graft copolymers of styrene or (x-methylstyrene, for example styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadieneacrylonitrile copolymers; styrene and acrylonitrile (or methacrylonitrile) on polybutadiene; styrene, acrylonitrile and methyl methacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleimide on polybutadiene; styrene and maleimide on polybutadiene; styrene and alkyl acrylates or methacrylates on polybutadiene; styrene and acrylonitrile on ethylene/propylene/diene terpolymers; styrene and acrylonitrile on polyalkyl acrylates or polyalkyl methacrylates, styrene and acrylonitrile on acrylate/butadiene copolymers, as well as mixtures thereof with the copolymers listed under 6), for example the copolymer mixtures known as ABS, MBS, ASA or AES polymers.
8. Halogen -containing polymers such as polychloroprene, chlorinated rubbers, chlorinated and brominated copolymer of isobutylene-isoprene (halobutyl rubber), chlorinated or sulfochlorinated polyethylene, copolymers of ethylene and chlorinated ethylene, epichlorohydrin homo- and copolymers, especially polymers of halogen-containing vinyl compounds, for example polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, as well as copolymers thereof such as vinyl chloride/vinylidene chloride, vinyl chloride/vinyl acetate or vinylidene chloride/vinyl acetate copolymers.
9. Polymers derived from cc,p-unsaturated acids and derivatives thereof such as polyacrylates, and polymethacrylates; polymethyl methacrylates, polyacrylamides and polyacrylonitriles, impact-modified with butyl acrylate.
10. Copolymers of the monomers mentioned under 9) with each other or with other unsaturated monomers, for example acrylonitrile/ butadiene copolymers, acrylonitrile/alkyl acrylate copolymers, acrylonitrile/alkoxyalkyl acrylate or acrylonitrile/vinyl halide copolymers or acrylonitrile/ alkyl methacrylate/butadiene terpolymers.
11. Polymers derived from unsaturated alcohols and arnines or the acyl derivatives or acetals thereof, for example polyvinyl alcohol, polyvinyl acetate, polyvinyl stearate, polyvinyl benzoate, polyvinyl maleate, polyvinyl butyral, polyallyl phthalate or polyallyl melamine; as well as their copolymers with olefins mentioned in 1) above.
12. Homopolymers and copolymers of cyclic ethers such as polyalkylene glycols, polyethylene oxide, polypropylene oxide or copolymers thereof with bisglycidyl ethers.
13. Polyacetals such as polyoxymethylene and those polyoxymethylenes which contain ethylene oxide as a comonomer; polyacetals modified with thermoplastic polyurethanes, acrylates, or MBS.
14. Polyphenylene oxides and sulfides, and mixtures of polyphenylene oxides with styrene polymers or polyamides.
15. Polyurethanes derived from hydroxyl-terminated polyethers, polyesters or polybutadienes on the one hand and aliphatic or aromatic polyisocyanates on the other, as well as precursors thereof.
16. Polyamides and copolyamides derived from diamines and dicarboxylic acids and/or from aminocarboxylic acids or the corresponding lactams, for example polyamide 4, poly- amide 6, polyamide 6/6, 6/10, 6/9, 6/12, 4/6, 12/12, polyamide 11, polyamide 12, aromatic polyamides starting from m-xylene diamine and adipic acid; polyamides prepared from hexamethylenediamine and isophthalic or/and terephthalic acid and with or without an elastomer as modifier, for example poly-2,4,4,-trimethylhexamethylene terephthalamide or poly-m-phenylene isophthalamide; and also block copolymers of the aforementioned polyamides with polyolefins, olefin copolymers, ionomers or chemically bonded or grafted elastomers; or with polyethers, e.g. with polyethylene glycol, polypropylene glycol or polytetramethylene glycol; as well as polyamides or copolyamides modified with EPDM or ABS; and polyamides condensed during processing (RIM polyamide systems).
17. Polyureas, polyimides, polyamide-imides, polyetherimids, polyesterimids, polyhydantoins and polybenzimidazoles.
18. Polyesters derived from dicarboxylic: acids and diols and/or from hydroxycarboxylic acids or the corresponding lactones, for example polyethylene terephthalate, polybutylene terephthalate, poly- 1,4dimethylolcyclohexane terephthalate and polyhydroxybenzoates, as well as block copolyether esters derived from hydroxyl-terminated polyethers; and also polyesters modified with polycarbonates or MBS.
19. Polycarbonates and polyester carbonates.
20. Polysulfones, polyether sulfones and polyether ketones.
21. Crosslinked polymers derived from aldehydes on the one hand and phenols, ureas and melarnines on the other hand, such as phenollformaldehyde resins, urealformaldehyde resins and melaminelforin aldehyde resins.
22. Drying and non-drying alkyd resins.
23. Unsaturated polyester resins derived from copolyesters of saturated and unsaturated dicarboxylic acids with polyhydric alcohols and vinyl compounds as crosslinking agents, and also halogen-containing modifications thereof of low flammability.
24. Crosslinkable acrylic resins derived from substituted acrylates, for example epoxy acrylates, urethane acrylates or polyester acrylates.
25. Alkyd resins, polyester resins and acrylate resins crosslinked with melamine resins, urea resins, isocyanates, isocyanurates, polyisocyanates or epoxy resins.
26. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic, heterocyclic or aromatic glycidyl compounds, e.g. products of diglycidyl ethers of bisphenol A and bisphenol F, which are crosslinked with customary hardeners such as anhydrides or amines, with or without accelerators.
27. Natural polymers such as cellulose, rubber, gelatin and chemically modified homologous derivatives thereof, for example cellulose acetates, cellulose propionates and cellulose butyrates, or the cellulose ethers such as methyl cellulose; as well as rosins and their derivatives.
28. Blends of the aforementioned polymers (polyblends), for example PP/EPDM, Polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PGABS, PBTP/ABS, PC/ASA, PC/PBT, PVC1CPE, PVC/acrylates, POWthermoplastic PUR, PC/thermoplastic PUR, POM/acrylate, POM/MBS, PPO/HIPS, PPO/PA 6.6 and copolymers, PA/HDPE, PA/PP, PA/PPO, PBT/PC/ABS or PBT/PET/PC.
29. Naturally occurring and synthetic organic materials which are pure monomeric compounds or mixtures of such compounds, for example mineral oils, animal and vegetable fats, oil and waxes, or oils, fats and waxes based on synthetic esters (e.g. phthalates, adipates, phosphates or trimellitates) and also mixtures of synthetic esters with mineral oils in any weight ratios, typically those used as spinning compositions, as well as aqueous emulsions of such materials.
30. Aqueous emulsions of natural or synthetic rubber, e.g. natural latex or latices of carboxylated styrenelbutadiene copolymers.
The compounds of the formula (I) are particularly suitable for improving the light stability, heat stability and oxidation stability of polyolefins, especially polyethylene and polypropylene.
The compounds of the formula (I) can be used in mixtures with organic materials in various proportions depending on the nature of the material to be stabilized, on the end use and on the presence of other additives.
In general, it is appropriate to use, for example, 0.01 to 5 % by weight of the compounds of the formula (I), relative to the weight of the material to be stabilized, preferably between 0.05 and 1 %.
In general, the compounds of the formula (I) can be added to the polymeric materials before, during or after the polymerization or crosslinking of the said materials.
The compounds of the formula (I) can be incorporated in the polymeric materials in the pure form or encapsulated in waxes, oils or polymers.
The compounds of the formula (I) can be incorporated in the polymeric materials by various processes, such as dry mixing in the form of powder, or wet mixing in the form of solutions or suspensions or also in the form of a masterbatch; in such operations, the polymer can be used in the form of powder, granules, solutions, suspensions or in the form of latices.
The materials stabilized with the products of the formula (I) can be used for the production of mouldings, films, tapes, monofflaments, fibres, surface coatings and the like.
If desired, other conventional additives for synthetic polymers, such as antioxidants, UV absorbers, nickel stabilizers, pigments, fillers, plasticizers, corrosion inhibitors and metal deactivators, can be added to the mixtures of the compounds of the formula (I) with the organic materials.
Particular examples of additives which can be used in admixture with the compounds of the formula (I) are:
1. Antioxidants 1. 1. Alkylated monophenols, for example 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl4,6-dimethylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-di- tert-butyl-4-n-butylphenol, 2,6-di-tert-butyl-4-isobutylphenol, 2,6- dicyclopentyl-4-methylphenol, 2-((x-rnethylcyclohexyl)-4,6-dimethylphenol, 2,6-dioctadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tertbutyl-4-methoxymethylphenol, nonylphenols which are linear or branched in the side chains, for example, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6(1'-methylundec-l'-yl)phenol, 2,4-dimethyl-6-(1'-methylheptadec-l'yl)phenol, 2,4-dimethyl-6-(Vmethyltridec-1'-yl)phenol and mixtures thereof.
1.2. Alkylthiomethylphenols, for example 2,4-dioctylthiomethyl-6-tertbutylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl6-ethylphenol, 2,6-di-dodecyithiomethyl-4-nonylphenol.
1.3. Hydroquinones and gi!ylated hydMuinones, for example 2,6-di-tertbutyl-4methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tertarnylhydroquinone, 2,6-diphenyl-4-octadecyloxyphenol, 2,6-di-tertbutylhydroquinone, 2,5-di-tert-butyl-4-hydroxyanisole, 3,5-di-tert-butyl4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate, bis-(3,5-ditert-butyl-4-hydroxyphenyl) adipate.
1.4. Tocopherols, for example a-tocopherol, P-tocopherol, -f-tocopherol, 8-tocopherol and mixtures thereof (Vitamin E).
1.5. Hydroxylated thiodiphenyl ethers, for example 2,2'-thiobis(6-tertbutyl-4-methylphenol), 2,2'-thiobis(4-octylphenol), 4,4'-thiobis(6-tertbutyl-3-methylphenol), 4,4'-thiobis(6-tert-butyl-2-methylphenol), 4,4'thiobis-(3,6-di-sec-amylphenol), 4,4'-bis-(2,6-dimethyl-4-hydroxyphenyl) disulfide.
1.6. Alkylidenebisphenols, for example 2,2'-methylenebis(6-tert-butyl-4methylphenol), 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'methylenebis[4-methyl-6-(ot-methylcyclohexyl)phenoll, 2,2-methylenebis(4methyl-6-cyclohexylphenol), 2,2-methylenebis(6-nonyl-4-methylphenol), 2, 2'-methylenebis(4,6-di-tert-butylphenol), 2,2-ethylidenebis(4,6-di-tertbutylphenol), 2,2'-ethylidenebis(6-tert-butyl-4-isobutylphenol), 2,2'rnethylenebis[6-(ot-methylbenzyl)-4-nonylphenoll, 2,2'-methylenebis[6-(cc, ct-dimethylbenzyl)4-nonylphenoll, 4,4'-methylenebis(2,6-di-tertbutylphenol), 4,4-methylenebis(6-tertbutyl-2-methylphenol), 1,1-bis(Stert-butyl-4-hydroxy-2-methylphenyl)butane, 2,6-bis(3tert-butyl-S-methyl2-hydroxybenzyl)-4-methylphenol, 1,1,3-tris(5-tert-butyl-4-hydroxy 2methylphenyl)butane, 1,1-bis(5-tert-butyl-4-hydroxy-2-methyl-phenyl)-3-ndodecylmercaptobutane, ethylene glycol bis[3,3-bis(3'-tert-butyl-4'hydroxyphenyl)butyrate], bis(3tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene, bis[2-(3'-tert-butyl-2'-hydroxy5'-methylbenzyl)6-tert-butyl-4-methylphenyllterephthalate, 1,1-bis-(3,5-dimethyl2hydroxyphenyl)butane, 2,2-bis-(3,5-di-tert-butyl-4-hydroxyphenyl)propane, 2,2-bis-(5tert-butyl-4-hydroxy2-methylphenyl)-4-n-dodecylmercaptobutane, 1,1,5,5-tetra-(5-tertbutyl-4-hydroxy2-methylphenyl)pentane.
1.7. 0-, N- and S-benzyl compounds. for example 3,5,3',5'-tetra-tertbutyl-4,4'-dihydroxydibenzyl ether, octadecyl-4-hydroxy-3,5dimethylbenzylmercaptoacetate, tridecyl-4hydroxy-3,5-di-tert-butylbenzylmercaptoacetate, tris(3,5-di-tert-butyl-4hydroxybenzyl)amine, bis(4-tert-butyl-3-hydroxy-2,6dimethylbenzyl)dithioterephthalate, bis(3,5-di-tertbutyl-4hydroxybenzyl)sulfide, isooctyl-3,5di-tert-butyl-4hydroxybenzylmercaptoacetate.
1.8. Hydroxybenzylated malonates. for example dioctadecyl-2,2-bis-(3,5-ditert-butyl-2hydroxybenzyl)-malonate, di-octadecyl-2-(3-tert-butyl-4hydroxy-5-methylbenzyl)-malonate, di-dodecyimercaptoethyl-2,2-bis-(3,5-ditert-butyl-4-hydroxybenzyl)malonat e, bis[4-(1,1,3,3tetrainethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydro xybenzy1)malonate.
1.9. Aromatic hydroxvbenzyl compounds for example 1,3,5-tris-(3,5-di-tertbutyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, 1,4-bis(3,5-di-tert-butyl4-hydroxybenzyl)-2,3,5,6tetramethylbenzene, 2,4,6-tris(3,5-di-tert-butyl4-hydroxybenzyl)phenol.
1. 10. Triazine Compounds. for example 2,4-bis(octylmercapto)-6-(3,5-ditert-butyl-4hydroxyanilino)- 1,3,5-triazine, 2-octylmercapto-4,6-bis(3,5di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine, 2-octylmercapto-4,6-bis(3, 5-di-tert-butyl-4-hydroxyphenoxy)1,3,5-triazine, 2,4,6-tris(3,5-di-tertbutyl-4-hydroxyphenoxy)-1,2,3-triazine, 1,3,5-tris(3,5-di-tert-butyl-4hydroxybenzyl)isocyanurate, 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6dimethylbenzyl)isocyanurate, 2,4,6-tris(3,5-di-tert-butyl-4hydroxyphenylethyl)-1,3,5-triazine, 1,3,5-tris(3,5-di-tert-butyl-4hydroxyphenylpropionyl)-hexahydro-1,3,5-tri azine, 1,3,5-tris(3,5dicyclohexyl-4-hydroxybenzyl)isocyanurate.
1. 11. Benzylphosphonates, for example dimethyl-2,5-di-tert-butyl-4hydroxybenzylphos- phonate, diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecy13,5-di-tertbutyl-4-hydroxybenzylphosphonate, dioctadecyl-Stert-butyl-4-hydroxy3-methylbenzylphosphonate, the calcium salt of the monoethyl ester of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.
1. 12. Acylaminophenols. for example 4-hydroxylauranilide, 4hydroxystearanilide, octyl N(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.
1. 13. Esters of 0-(3.5-di-tert-butyl-4-hydroxyphenyl)i)ropionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3thiapentadecanol, trimethylhexanediol, trimethylol propane, 4hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]- octane.
1. 14. Esters of D-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid with mono- or polyhydric alcohols, e.g. with methanol, ethanol, n-octanol, i-octanol, octadecanol, 1,6hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'-bis(hydroxyethyl)oxarnide, 3-thiaundecanol, 3thiapentadecanol, trimethy1hexanediol, trimethylolpropane, 4hydroxymethyl-l-phospha-2,6,7-trioxabicyclo[2.2.2]octane. 1. 15. Esters of 0-(3,5-dicyclohexyl-4-hydroxyphenyl)proi)ionic acid with
mono- or polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9- nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N, N'bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- I -phospha-2,6, 7-trioxabicyclo[2.2.2] octane.
1. 16. Esters of 3.5-di-tert-butyl-4-hydroxyphenyI acetic acid with monoor polyhydric alcohols, e.g. with methanol, ethanol, octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N'-bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylolpropane, 4-hydroxymethyl- I -phospha-2,6, 7-trioxabicyclo[2.2.2] octane.
1. 17. Amides of 0-(3,5-di-tert-butyl-4-hydroxylphenyl)propionic acid e.g. NNAis(3,5AP tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine, N, W-bis(3,5-di-tert-butyl- 4-hydroxyphenylpropionyl)trimethylenediamine, N,N'-bis(3,5-di-tert-butyl- 4-hydroxyphenylpropionyl)hydrazine.
1. 18. Ascorbic acid (vitamin Q 1. 19. Aminic antioxidants, for example N,N'-di-isopropyl-p- phenylenediamine, N,M-disecbutyl-p-phenylenediarnine, N,N'-bis(1,4dimethylpentyl)-p-phenylenediamine, N,Wbis(l-ethyl-3-methylpentyl)-pphenylenediamine, N,N'-bis(l-methylheptyl)-p-phenylenediamine, N,N'dicyclohexyl-p-phenylenediamine, N,N'-diphenyl-p-phenylenediamine, N,N'-bis(2-naphthyl)-p-phenylenediamine, N-isopropyl-N'-phenyl-pphenylenediarnine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N(Pmethylheptyl)-W-phenyl-p- phenylenediamine, N-cyclohexyl-N'-phenyl-p-phenylenediamine, 4-(ptoluenesulfamoyl)diphenylamine, N,N'-dimethyl-N,N'-di-sec-butyl-pphenylenediamine, diphenylamine, N-allyldiphenylamine, 4isopropoxydiphenylamine, N-phenyl-l-naphthylamine, N-(4tert-octylphenyl)l-naphthylamine, N-phenyl-2-naphthylamine, octylated diphenylamine, for example p,p'-di-tert-octyldiphenylamine, 4-n-butylaminophenol, 4butyrylaminophenol, 4-nonanoylamino-phenol, 4-dodecanoylaminophenol, 4octadecanoylaminophenol, bis(4-methoxyphenyl)amine, 2,6-di-tert-butyl-4dimethylaminomethylphenol, 2,4'-diaininodiphenylmethane, 4,4'diaminodiphenylmethane, N,N,N',N'-tetramethyl-4,4'-diaminodiphenylmethane, 1,2-bis[(2-methylphenyl)amino]ethane, 1,2-bis(phenylamino)propane, (otolyl)biguanide, Bis[4-(I',3'-dimethylbutyl)phenyllamine, tert-octylated N-phenyl- I -naphthylamine, a mixture of mono- and dialkylated tertbutyl/tert-octyldiphenylamines, a mixture of mono- and dialkylated nonyldiphenylamines, a mixture of mono- and dialkylated dodecyldiphenylamines, a mixture of mono- and dialkylated isopropyl/isohexy1diphenylamines, a mixture of mono- und dialkylated. tert-butyldiphenylamines, 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine, phenothiazine, a mixture of mono- und dialkylated tert-butyl/tertoctylphenothiazines, a mixture of mono- und dialkylated tertoctylphenothiazines, N-allylphenothiazin, N,N,N,N'-tetraphenyl-1,4diaminobut-2-ene, N,Nbis(2,2,6,6-tetramethyl-piperid-4-ylhexamethylenediamine, bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate, 2,2,6, 6-tetramethylpiperidin-4-one, 2,2,6,6-tetramethylpiperidin-4-ol.
2. UV absorbers and light stabilisers 2.1. 2-(2'-Hydroxyphenyl)benzotriazoles, for example 2-(2'-hydroxy-S'methylphenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'hydroxyphenyl)benzotriazole, 2-(5'-tert-butyl2hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-S'-(1,1,3,3tetramethylbutyl)phenyl)benzotriazole, 2-(3',5'-di-tert-butyl-2'hydroxyphenyl)-5-chloro-benzotriazole, 2-(Y-tert-butyl2'-hydroxy-5'methylphenyl)-5-chloro-benzotriazole, 2-(3'-sec-butyl-5'-tert-butyl2'hydroxyphenyl)benzotriazole, 2-(2'-hydroxy-4'octyloxyphenyl)benzotriazole, 2-(3 di-tert-amyl-2'hydroxyphenyl)benzotriazole, 2-(3',5'-bis-(ot,ct-dimethylbenzyl)2'hydroxyphenyl)benzotriazole, mixture of 2-(3'-tert-butyl-2'-hydroxy-5'(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butylS'-[2-(2-ethylhexyloxy)-carbonylethyll-2'-hydroxyphenyl)-5-chlorobenzotriazole, 2-(3'-tert-butyl-2'-hydroxy-5'(2methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole, 2-(3'-tert-butyl2'-hydroxy-S'-(2methoxycarbonylethyl)phenyl)benzotriazole, 2-(3'-tertbutyl-2'-hydroxy-5'-(2-octyloxycarbonylethyl)phenyl)benzotriazole, 2-(3'tert-butyl-5'-[2-(2-ethylhexyloxy)carbonylethyl] -Thydroxyphenyl)benzotriazole, 2-(3'-dodecyl-2'-hydroxy-5'methylphenyl)benzotriazole, and 2-(Y- tert- butyl- 2'-hydroxy-5'-(2isooctyloxycarbonylethyl)phenyl ben zotri- ,Y- azole, 2,2'-methylene-bis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazole-2ylphenol l; the transesterification product of 2-[3'-tert-butyl-5'-(2methoxycarbonylethyl)-2'-hydroxyphenyl]-2H-benzotriazole with polyethylene glycol 300; [R-CH2CH2-COO(CH2)ATwhere R = 3-tert-butyl-4'hydroxy-5'-2H-benzotriazol-2-ylphenyl.
2.2. 2-Hydroxybenzophenones for example the 4-hydroxy, 4-methoxy, 4c"loxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and Thydroxy-4,4'-dimetboxy derivatives.
2.3. Esters of substituted and unsubstituted benzoic acids. as for example 4-tertbutylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoyl resorcinol, bis(4tert-butylbenzoyl) resorcinol, benzoyl resorcinol, 2,4-di-tertbutylphenyl 3,5-di-tert-butyl4- hydroxybenzoate, hexadecyl 3,5-di-tert-butyl-4-hydroxybenzoate, octadecyl 3,5-di-tertbutyl-4-hydroxybenzoate, 2-methyl-4,6-di-tert-butylphenyl 3,5di-tert-butyl-4-hydroxy- benzoate.
2.4. Acrylates, for example ethyl cc-cyano-o,p-diphenylacrylate, isooctyl cc-cyano-p,p-diphenylacrylate, methyl cc-carbomethoxycinnamate, methyl otcyano-o-methyl-p-methoxycinnamate, butyl (x-cyano-o-methyl-p-methoxycinnamate, methyl cc-carbomethoxy-p- methoxycinnamate and N-(0-carbomethoxy-o-cyanovinyl)-2-methylindoline.
2.5. Nickel compounds, for example nickel complexes of 2,2'-thio-bis-[4(1,1,3,3-tetramethylbutyl)phenoll, such as the 1: 1 or 1:2 complex, with or without additional ligands such as n-butylarnine, triethanolamine or NcyclobexyIdiethanolamine, nickel dibutyldithiocarbamate, nickel salts of the monoalkyl esters, e.g. the methyl or ethyl ester, of 4hydroxy-3,5-di-tert-butylbenzylphosphonic acid, nickel complexes of ketoximes, e.g. of 2-hydroxy-4-methylphenyl undecylketoxime, nickel complexes of 1-phenyl-4-1auroyl-5hydroxypyrazole, with or without additional ligands.
2.6. Sterically hindered amines, for example bis(2,2,6,6-tetramethyl-4piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)succinate, bis(1, 2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(l-octyloxy-2,2,6,6tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl4-piperidyl) nbutyl-3,5-di-tert-butyl-4-hydroxybenzyimalonate, the condensate of lQhydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensate of N,N'-bis(2,2,6,6-tetramethyl-4piperidyl)hexamethylenediamine and 4-tert-octYlamino-2,6-dichloro-1,3,5-triazine, tris(2,2,6,6-tetramethyl-4piperidyl)nitrilotriacetate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butane-tetracarboxylate, 1,1'-(1,2-ethane- diyl)bis(3,3,5,5-tetramethylpiperazinone), 4-benzoyl-2,2,6,6- tetramethylpiperidine, 4stearyloxy-2,2,6,6-tetramethylpiperidine, bis(1,2, 2,6,6-pentamethylpiperidyl)-2-n-butyl2-(2-hydroxy-3,5-di-tertbutylbenzyl)malonate, 3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4. 5]decan-2,4-dion, bis(l-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate, bis(loctyloxy-2,2,6,6-tetramethylpiperidyl)succinate, the condensate of N, N'-bis-(2,2,6,6-tetramethyl-4-piperidyl)hexarnethylenediamine and 4morpholino-2,6-dichloro- 1,3,5-triazine, the condensate of 2-chloro-4,6bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyI)-1,3,5-triazine and 1,2bis(3-aminopropylamino)ethane, the condensate of 2-chloro-4,6-di-(4nbutylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triaz ine and 1,2-bis(3-aminopropylamino)ethane, 8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8triazaspiro[4.5]decane-2,4dione, 3-dodecyl-l-(2,2,6,6-tetramethyl-4piperidyl)pyffolidin-2,5-dione, 3-dodecyl-l(1,2,2,6,6-pentamethyl-4piperidyl)pyrrolidine-2,5-dione, a mixture of 4-hexadecyloxyand 4stearyloxy-2,2,6,6-tetramethylpiperidine, a condensation product of N,N'bis(2,2,6,6-tetramethyl-4-piperidyl)hexamethylenediamine and 4cyclohexylamino-2,6-dichloro- 1,3,5-triazine, a condensation product of 1, 2-bis(3-aminopropylamino)ethane and 2,4,6-trichloro- 1,3,5-triazine as well as 4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [13650496-6]); N-(2,2,6,6-tetramethyl-4-piperidyl)-n-dodecylsuccinimid, N(1,2,2, 6,6-pentamethyl-4-piperidyl)-n-dodecylsuccinimid, 2-undecyl-7,7,9,9tetramethylI-oxa-3,8-diaza-4-oxo-spiro[4,5]decane, a reaction product of 7,7,9,9-tetramethyl-2-cycloundecyl-l-oxa-3,8-diaza-4-oxospiro [4,5]decane und epichlorohydrin.
2.7. Oxamides, for example 4,4'-dioctyloxyoxanilide, 2,2'diethoxyoxanilide, 2,T-dioctyloxy-5,5'-di-tert-butoxanilide, 2,2'didodecyloxy-5,5'-di-tert-butoxanilide, 2-ethoxy-2'ethyloxanilide, N,N'bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'-ethoxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert-butoxanilide and mixtures of ortho- and para-methoxy-disubstituted oxanilides and mixtures of o- and p-ethoxy-disubstituted oxanilides.
2.8. 2-(2-Hydroxvphenyl)- 1,35-triazines, for example 2,4,6-tris(2hydroxy-4-octyloxyphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-octyloxyphenyl)4,6-bis(2,4-dimethylphenyl)1,3,5-triazine, 2-(2,4-dihydroxyphenyl)-4,6bis(2,4-dimethylphenyl)- 1,3,5-triazine, 2,4bis(2-hydroxy-4propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy4octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)- 1,3,5-triazine, 2-(2hydroxy-4-tridecyloxyphenyl)4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2[2-hydroxy-4-(2-hydroxy-3-butyloxy-propoxy) phenyl] -4,6-bis(2,4-dime thyl)- 1,3,5-triazine, 2-[2-hydroxy-4-(2-hydroxy-3-octyloxy-pro py loxy) phenyl] -4,6- bis(2,4-dimethyl)-1,3,5-triazine, 2-[4-(dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxy-phenyll-4,6-bis(2,4-dimethylphenyl)-1,3,5t hazine, 2[2-hydroxy-4-(2-hydroxy-3-dodecyloxy-propoxy)phenyl]-4,6-bis(2, 4-dimethyl phenyl)1,3,5-triazine, 2-(2-hydroxy-4-hexyloxy)phenyl-4,6diphenyl-1,3,5-triazine, 2-(2hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5triazine, 2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxy-propoxy)phenyll-1,3, 5-triazine, 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl- 1,3,5triazine.
3. Metal deactivators, for example N,N'-diphenyloxamide, N-salicylal-N'salicyloyl hydrazine, N,M-bis(salicyloyl) hydrazine, N,N-bis(3,5-di-tertbutyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylarnino-1,2,4triazole, bis(benzylidene)oxalyl dihydrazide, oxanilide, isophthaloyl dihydrazide, sebacoyl bisphenylhydrazide, N,M-diacetyladipoyl dihydrazide, N,M-bis(salicyloyl)oxalyl dihydrazide, N,N'-bis(salicyloyl)thiopropionyl dihydrazide.
4. Phosphites and Dhosphonites. for example triphenyl phosphite, diphenyl alkyl phosphites, phenyl dialkyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)-pentaerythritol diphosphite, diisodecyloxypentaerythritol diphosphite, bis(2,4-di-tertbutyl-6-methylphenyl)pentaerythritol diphosphite, bis(2,4,6-tris(tertbutylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl) 4,4'-biphenylene diphosphonite, 6isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-1,3,2-dioxaphospho. cin, 6-fluoro-2,4,8,10tetra-tert-butyl-12-methyl-dibenz[d,g]-1,3,2dioxaphospho cin, bis(2,4-di-tert-butyl-6methylphenyl)methylphosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.
5. Hydroxylamines, for example, N,N-dibenzyIhydroxylarnine, N,NdiethyIkydroxylamine, N,N-dioctylhydroxylarnine, N,Ndilaurylhydroxylarnine, N,N-ditetradecylhydroxylamine, N,Ndihexadecylhydroxylarnine, N,N-dioctadecylhydroxylarnine, N-hexadecyl-Noctadecylhydroxylamine, N-heptadecyl-N-octadecylhydroxylamine, N,Ndialkylhydroxylamine derived from hydrogenated tallow amine.
6. Nitrones, for example, N-benzyPalpha-phenyl-nitrone, N-ethyPalphamethyl-nitrone, N-octyPalpha-heptyl-nitrone, N-lauryl-alpha-undecylnitrone, N-tetradecyl-alpha-tridecyl-nitrone, N-hexadecyl-alphapentadecyl-nitrone, N-octadecyl-alpha-heptadecyl-nitrone, N-hexadecylalpha-heptadecyl-nitrone, N-ocatadecyl-alpha-pentadecyl-nitrone, Nheptadecyl-alpha-heptadecyl-nitrone, N-octadecyl-alpha-hexadecyl-nitrone, nitrone derived from N,N-dialkylhydroxylarnine derived from hydrogenated tallow amine.
7. Thiosynergists, for example, dilauryl thiodipropionate or distearyl thiodipropionate.
8. Peroxide scavenpers, for example esters of P-thiodipropionic acid, for example the lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole, zinc dibutyldithiocarbamate, dioctadecyl disulfide, pentaerythritol tetmbs(pdodecylmercapto)propionate.
9. Polyamide stabilisers, for example, copper salts in combination with iodides andlor phosphorus compounds and salts of divalent manganese.
10. Basic co-stabilisers. for example, melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali metal salts and alkaline earth metal salts of higher fatty acids for example calcium stearate, zinc stearate, magnesium behenate, magnesium stearate, sodium ricinoleate and potassium palmitate, antimony pyrocatecholate or tin pyrocatecholate.
11. Nucleating agents, for example, inorganic substances such as talcum, metal oxides such as titanium dioxide or magnesium oxide, phosphates, carbonates or sulfates of, preferably, alkaline earth metals; organic compounds such as mono- or polycarboxylic: acids and the salts thereof, e. g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid, sodium succinate or sodium benzoate; polymeric compounds such as ionic copolymers ("ionomers").
12. Fillers and reinforcing agents, for example, calcium carbonate, silicates, glass fibres, glass bulbs, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite, wood flour and flours or fibers of other natural products, synthetic fibers.
13. Other additives, for example, plasticisers, lubricants, emulsifiers, pigments, rheology additives, catalysts, flow-control agents, optical brighteners, flameproofing agents, antistatic agents and blowing agents.
14. Benzofuranones and indolinones, for example those disclosed in US-A-4 325 863, US-A-4 338 244, US-A-5 175 312, US-A-5 216 052, US-A-5 252 643, DE-A-4 316 611, DE-A-4 316 622, DE-A-4 316 876, EP-A-0 589 839 or EP-A-0 591 102 or 3-[4-Q-acet- 1 1 i oxyethoxy)phenyll-5,7-di-tert-butyl-benzofuran-2-one, 5,7-di-tert-butyl-3[4-(2-stearoyloxyethoxy)phenyllbenzofuran-2-one, 3,3'-bis[5,7-di-tertbutyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-onel, 5,7-di-tert-butyl-3(4-ethoxyphenyl)benzofuran-2-one, 3-(4acetoxY-3,5-dimethylphenyl)-5,7-ditert-butyl-benzofuran-2-one, 3-(3,5-dimethy1-4-pivaloyloxyphenyl)-5,7-ditert-butyl-benzofuran-2-one.
The compounds of the invention can also be used as stabilizers, especially as light stabilizers, for almost all materials known in the art of photographic reproduction and other reproduction techniques as e.g. described in Research Disclosure 1990, 31429 (pages 474 to 480).
Several examples of the preparation and use of the compounds of formula (I) are given in order to give a more detailed illustration of the present invention; these examples are given solely for illustrative purposes and do not imply any restriction.
Example 1: Preparation of a polysiloxane of the formula CH3 H3 CH3 CH3 1 1 1 H3C- S' O-S' 0 - Si- CH3 CH3 (H2)3 CBH17 CH 1 j 3 0 26)27 1 N''N C4H9 H9C4 - N CH3nCH3 CH'S"CH3 CH3 CH3 CH3 CH3 CH3 CH3 44.5 g (77.8 mmol) of 2-allyloxy-4,6-bis[N-(1,2,2,6,6-pentamethyl-4piperidyl)butylamino]-1,3,5-triazine are dissolved in 50 ral of xylene and 2 Mg Of Ptc12(styrene)2 are added.
The solution is heated to 1400C and to it is slowly added, while stirring, a solution of 10 g (3 mmol) of trimethyl-silyl terminated polymethy1hydrosiloxane (possessing 53 Si-H units) in 150 ml of xylene. The reaction is maintained at 140'C for 3 hours. It is cooled to 70T and, while still stirring, 15 g (133.9 mmol) of I-octene and a further 2 mg of PtC'2(styrene)2 are added.
11- The mixture is heated for 6 hours while stirring at 1001C and the solvent and the excess of 1-octene are removed by vacuum distillation (140'00.1 mbar).
A white solid with m.p. 75-790C is obtained. NMR and IR analysis confirms the expected structure.
Example 2: Preparation of a polymethylsiloxane of the formula CH3 O-S 1 (C12)3 26 W'N 1 1 H9C4 - N N N - C4H9 CH&.1 CH3 CH CH3 ,..I h..
CH3 N CH3 CH3 N CH3 1 1 H H CH3 CH3 O-S 0 - Si- CH3 1 1 C8H17)27;"3 CH3 1 H3C"S"I 1 CH3 Using a procedure analogous to that described in Example 1, 43.2 g (77.7 mmol) of 2-allylainino-4,6-bis[N-(2,2,6,6-tetramethyl-4piperidyl)butylaminol-1,3,5 -triazine are reacted with 10 g of trimethylsilyl terminated polymethylhydrosiloxane (possessing 53 Si-H units) and with 15 g (133.9 mmol) of 1-octene in the presence of 4 mg of Ptc12(styreneh in xylene.
After removing the solvent and the excess of 1-octene by vacuum distillation (140Cl 1 mbar), a solid with m.p. 110- 1 15T is obtained. NMR and IR analysis confirms the expected structure.
Example 3: Preparation of a polymethylsiloxane of the formula CH CH c 3 1 3 1 H3 H3C- ' 0 - S.
1 1 1 CH3 (CH2)3 CH17 0 si j 26)2 W'N H9C4 - N N - C4H9 CH CH3 CH3f CH3 CH:>?NCH3 CH3 N CH3 1 1 H H CH3 1 U-bl- UM 1 1-;M3 7 3 - Using a procedure analogous to that described in Example 1, 43.4 g (77.8 mmol) of 2-allyloxy-4,6-bis[N-(2,2,6,6-tetramethyl-4piperidyl)butylamino]-1,3,5-tria zine are reacted with 10 g (3mmol) of trimethylsilyl terminated polymethylhydrosiloxane (possessing 53 SPH units) and with 15 g (133.9 mmol) of 1-octene in the presence of 4 ing of PtC12(styrene)2 in xylene.
After removing the solvent and the excess of 1-octene by vacuum distillation (140T/1 mbar), a solid with m.p. 90-95T is obtained.
NMR and IR analysis confirms the expected structure.
Example 4: Preparation of a polymethylsiloxane of the formula H3 CH3 CH3 1 1 H3C'S' O-S -S 0 CH3 (H2)3 C8H17 t NH 26 1 W'N H9C4 - N N - C4H9 CH3,,,hCH3 CH CH3 CH3 N CH3 CH3 N CH3 1 1 CH3 UH3 CH3 1 O-Si-CH3. 1 LAI 3 7 Using a procedure analogous to that described in Example 1, 45.5 g (77.8 mmol) of 2-allylamino-4,6-bis[N-(1,2,2,6,6-pentamethyl-4piperidyl)butylaminol-1,3,5-t riazine are reacted with 10 g (3 mmol) of trimethylsilyl terminated polymethylhydrosiloxane (possessing 53 Si-H units) and with 15 g (133.9 mmol) of 1-octene in the presence of 4 mg Of Ptc12(styrene)2 in xylene.
After removing the solvent and the excess of 1-octene by vacuum distillation (140T/1 mbar), a solid with m.p. 94-980C is obtained. NMR and IR analysis confirms the expected structure.
Example 5: Light-stabilizing action in polypropylene fibres.
2.5 g of each of the compounds given in Table 1, 1 g of tris(2,4-di-tbutylphenyl) phosphite, 0.5 g of calcium monoethyl 3,5-di-t-butyl-4hydroxybenzylphosphonate, 1 g of calcium stearate and 2.5 g of titanium dioxide are mixed in a slow mixer with 1000 g of polypropylene powder possessing a melt index = 12 g/10 min (measured at 2300C and 2.16 kg). The mixtures are extruded at 200-230C to give polymer granules which are then converted into fibres using a pilot-type apparatus (OLeonardSumirago (VA) Italy) and operating under the following conditions:
extruder temperature head temperature draw ratio linear density 200-230T 255-260T 1:33 11 dtex per filament The fibres thus prepared are exposed, after mounting on white cardboard, in a model 65WR Weather-0-Meter (ASTM D2565-85) with a black panel temperature of 6VC The residual tenacity is measured on samples taken after various times of exposure to light by means of a constant-speed tensometer, and the exposure time in hours (T50) needed to halve the initial tenacity is then calculated.
For comparison, fibres prepared under the same conditions as stated above, but without addition of the stabilizers according to the present invention, are also exposed.
Table 1 shows the results obtained.
Table 1:
Stabilizer without stabilizer Compound of Example 1 Compound of Example 2 T50 hoursI _L__ 150 2540 2680 C

Claims (14)

WHAT IS CLAIMED IS:
1. A compound of formula (I) CH3 1 CH3 1 1131- ""- -0- S1 1 1 UH3 1 M2)3 X N 1 N (D Rl-N CH3 CH3 CH3 N CH3 1 K2 in which m + n is a number from 1 to 100 and n varies from zero to 90% of the sum of m + n; X is -0- or -NH-; R 1 is hydrogen, C 1 -C 18alkyl, C2- C4alkyl substituted in position 2, 3 or 4 by C 1 -CSalkoxy or by di(C1- C4alkyl)amino; CS-C12CYCloalkyl unsubstituted or substituted with 1, 2 or 3 C l-C4alkyls; C7-C-9phenylalkyl unsubstituted or substituted on the phenyl with 1, 2 or 3 C l-C4alkyls; or a group of formula (H); N-Rl CH3 CH3 0 CH3 ANCH3 1 R2 (I) 1 U"3 CH3 CH3 IN-R2 I CH3 CH3 (11) R2 is hydrogen, C,-CSalkyl, 0., OH, NO, CH2CN, C,-C18alkoxy, C5- CUCYCloalkoxy, C7-C9phenylalkyl unsubstituted or substituted on the phenyl with 1, 2 or 3 Cl-C4alkyls; or Cl-C8acyl; and A is C6-CI8alkyl.
2. A compound of formula (I) according to claim 1, in which R2 is hydrogen, Cl-C4alkyl. OH, C6-CI2alkoxy, C5-C8cycloalkoxy, benzyl or acetyl.
3. A compound of formula (I) according to claim 1, in which R2 is hydrogen or methyl.
4. A compound of formula (I) according to any of claims 1 to 3, in which m + n is a number from 1 to 90 and n varies from zero to 90% of the sum m + n; X is -0- or -NH-; R, is hydrogen, Cl-C12alkyl, CS-C7CYCloalkyl, C7C9phenfialkyl or a group of formula (11); and A is C6-C12alkyl.
5. A compound of formula (I) according to any of claims 1 to 3, in which m + n is a number from 1 to 80 and n varies from zero to 90% of the sum m + n; X is -0- or -NH-; R, is hydrogen, Cl-C8alkyl, cyclohexyl, benzyl or a group of formula CII); and A 'S C8-C 12alkyl.
6. A compound of formula (I) according to any of claims 1 to 3, in which m + n is a number from 1 to 70 and n varies from zero to 50% of the sum of m + n; X is -0- or -NH-; R, is hydrogen, Cl-C4alkyl or a group of formula (II); and A 'S C8-C 12alkyl.
7. A compound of formula (I) according to claim 1, having the formula CH3 1 CH3 CH3 1 H3C- Si 0 kk 1 H2)3 U)26 H9C, - N N '-N /1 N N - CHg CH CH3 CH CH3 CH N CH AN CH 3 1 3 CH3 1 3 CH3 CH3 CH CH3 0- 0 S- CH 3 )27 - CH3 1 1 CaH 17 CH3 1 H3C- S' 1 UM3 H9C4 - N CH3 U (CH2)3 1 NH N ' N ",,N 26 N C4H9 CH CH3 CH3, CH3 CH:::5 N1CH ú N CH 1 3 CH 3 1 3 H H H 3 CH3 c, 1 O-
S U - N-,M 1 1 CaH 17) 27 CH3 CH H c 3 3 1 H3 a - (O-S- 0 - S.
H3C- S 1 CH3 P12)3 26 W' N H9C4 - N - C4H9 CH3: CH3 CH CH3 CH3 ' N 1 CH3 CH3 N CH3 1 1 H 1 CeH17 J_ H CH3 1 U - Ibl- LAI 1 M3 7 H CH c CH3 3 g 3 1 H3 1 H3c- S 0-si U - "3 1 1 1 1 H3 0 (H2)3 C8H17) H9C4 - N a NH 1 W- N CH3> CH3 CH35ú,,, CH3 C CH hNCH CH N CH 3 1 3 3 3 CH3 3 9 7 M3 CH 3 1 HSCS' 1 CH3 CH 3 CH 3 CH 3 CH 3 0 o-si -55-CH (k'r'2)3 k;l2H25 CH 1 3 0 J26 27 H9C, - N N "-L N /11,1 N l\ N - CHg CH t:. h.. CH3 CH AM CH3 CH3 N CH3 CH. CH3 1 1 k^ CH3 CH3 H3 CH3 CH3 1 c, 0- 1 - 1 NH (CH 2)3 1 N '-N H9C, N N - CHg CH3!:l( CH3 CH CH 3 3 3 C H N CH CH N CH.1 1 3 3 H H 1 1 C12H25 'M3 27 CH3 CH 3 CH3 CH3 H3C- 5 0 - 1 CH 3 H9C4 - N 1 ki 1 2J3 U 39 NiN N C4H9 CH CH3 CH3 CH3 CH3 N CH3 CH3 ANCH3 1 1 CH3 CH3 1 .;8 m 17 3, 3 ' 1 UM 3 14 k;t13 L; m 3 CH 3 k;M3 CH H CH 1 1 1 3 1. 3 3 H3C- Si U N 0 1 1 1 2J3 C H C' H - 0, kCH 1 '8 17 3 1 N 9 N ',N H N - CHg CH 'CH3 CH CH3 C3 kAN CH H N CH 3 CH3 3 1 1 H H H9C4 - N 14 CH CH CH CH3 3 1 3 3 l 0- si H30-5)39 0 - S'- CH3 (c;r'2)3 1 0 H9C4 - N N '-N N - CHg CH CH3 CH,, CH3 CH3 N CH3 CH3 -N CH3 1 1 t'M3 CH3 CH3 1 CH3 CH3 1 1 1 CH3 1 1 1'12H25 14 CH3 CH3 1 H.4re- S' -0-si 0- )39 12H25)14 (CH2)3 C 1 NH N '-L N 0,,,oN l\ H9C4 - N N - CHg CH CH3 CH CH 3 CH N CH AN CH 3 1 3 CH3 3 H H CH3 CH3 H3 CH3 0- 0 0 - Si- CH3 CH3 C12H25;'r13 U)26 27 CH3 CH3 H3C-N - N CH3 CH3 CH 5L CH3 CH3 N CH3 1 'r'3 or N "-L N CH3 1 CH3 i H30- S' 1 0 1 (A13 CH3 CH3 HN -- N CH3 CH.
CH 3.1 CH3 CH3 N CH3 CH3 CH3 N N CHS CH- ACH3 3 CH CH3 AN CH CH3 1 3 F';H3 1 (C J3 1 N N '-N N CH3 CH3 N NH CH3 CH3 CH <N CH3 CH3 1 CH3 H CH3 CH3 1. Sli CH3 0 O-S 1 1 C12H25 kM3 7 8. A compound of formula (1) according to any of claims 1 to 3, in which m + n Is a number from 1 to 60 and n varies from zero to 50% of the sum of m + n X is -0- or -NW; R, is Cl-C4alkyl or a group of formula (H); and A 'S C8- CUalkyl.
9. A composition which contains an organic material susceptible to degradation induced by light, heat or oxidation and at least one compound of formula (I) according to claim 1.
10. A composition according to claim 9, wherein the organic material is a synthetic polymer.
11. A composition according to claim 10 which contains other conventional additives for synthetic polymers, in addition to the compounds of formula (I).
12. A composition according to claim 9, wherein the organic material is polyethylene or polypropylene.
13. A method for stabilizing an organic material against degradation induced by light, heat or oxidation, which comprises incorporating into said organic material at least one compound of formula (I) according to claim 1.
14. A composition according to claim 9 substantially as hereinbefore described with reference to Example 5.
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Cited By (6)

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Publication number Priority date Publication date Assignee Title
US6538055B1 (en) 1999-04-27 2003-03-25 Ciba Specialty Chemicals Corporation Polysilane stabitizers containing sterically hindered amine groups
EP1943293A1 (en) * 2005-10-14 2008-07-16 Nor-X Industry AS Light protective additive based on organic/ inorganic hybrid polymer, method for its manufacture and use thereof
EP1943293A4 (en) * 2005-10-14 2012-07-04 Nor X Industry As Light protective additive based on organic/ inorganic hybrid polymer, method for its manufacture and use thereof
CN102268264A (en) * 2010-06-02 2011-12-07 Jsr株式会社 Liquid crystal orientation agent, liquid crystal orientation film and forming method of liquid crystal orientation film, liquid crystal display element and poly organo-silicon epoxide
CN102268264B (en) * 2010-06-02 2016-02-03 Jsr株式会社 The formation method of liquid crystal aligning agent, liquid crystal orientation film, liquid crystal orientation film, liquid crystal display device and polyorganosiloxane compounds
US8937122B2 (en) 2011-02-04 2015-01-20 Adeka Coporation Compound having hindered amine backbone, and resin composition

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TW303380B (en) 1997-04-21
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NL1001781A1 (en) 1996-05-30
GB2295619B (en) 1997-02-19
JPH08225650A (en) 1996-09-03
ITMI942429A0 (en) 1994-11-30
FR2727419B1 (en) 1997-12-12
CA2163956A1 (en) 1996-05-31
ITMI942429A1 (en) 1996-05-30
ES2102329A1 (en) 1997-07-16
BE1009749A3 (en) 1997-07-01
NL1001781C2 (en) 1997-03-25
IT1271133B (en) 1997-05-26
KR960017676A (en) 1996-06-17
ES2102329B1 (en) 1998-04-01
DE19544114A1 (en) 1996-06-05

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