SK58293A3 - Composition on base of rigid solution and method of its preparation - Google Patents

Abstract

Composition on base of low-molecular and high-molecular tetramethylpiperidines, which consists of solid solution of component A, which is bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate or mixture of esters with general formula I, where R means stearoyl, palmitoyl, heptadecanoyl, myristoyl and oleoyl and of component B, which is compound with general formula II, where R/EXP_1/ means cyclohexylamino-, terc. octyl-amino- or morpholine group and M means the whole number from 3 to 50.

Description

The invention relates to a solid solution composition comprising a low-molecular-weight and a high-molecular-weight compound which comprises at least one of 2,2,6,6-ethers and piperidines. . They are mixed in the melt, process for its preparation, stabilization of the polymers by means of this composition and the polymeric and coating compositions containing it.

^5- fc ^av technique

It is known that low molecular weight compounds containing 2,2,6,6-tetraalkyl pylidyl groups (low molecular weight HALS) and high molecular weight compounds containing 2,2,6,6-tetrachloride pylidinyl groups (high molecular weight HALS), used alone, improve the weathering properties, such as the light fastness of polymeric materials.

SUMMARY OF THE INVENTION

We have now surprisingly found that when low-molecular HALS and high-molecular HALS are mixed together to form a solid solution thereof, the synergistic effect is significantly increased. A solid solution can be prepared by mixing the low molecular weight and high molecular weight HALS together, melting the mixture and cooling the melt to form a solid solution of low molecular weight and high molecular weight HALS.

The solid solution is an amorphous material in which the low molecular weight HALS is homogeneously dissolved in the high molecular weight HALS.

Based on this surprising finding, we have developed a solid solution (or molten mixture) composition of the invention. SUMMARY OF THE INVENTION The solid solution composition consists of component A, which is an alcoholic compound containing at least one 2,2,6,6-tetraalkyl per peridiryl group, and component B, which is a high molecular weight compound containing at least one 2,2,6,6-tetraalkylpiperidinyl group that has been melt blended.

The ratio of component A to B in the composition of the invention is 1: 1 to 1:20, more preferably 1: 1 to 1:10, most preferably 1: 2 to 1: 9, especially 1: 4.

Component A is a mono (non-oligomeric or polymeric) compound containing at least one (preferably one to four) 2,2,6,6-tetraalkylpiperidinyl groups.

Component B is an oligomeric or polymeric compound containing at least one 2,2,6,6-tetraalkylpiperidinyl group (preferably one to four) per repeating polymer unit.

Any 2,2,6,6-tetraalkylpiperidinyl group in this application is. preferably N-unsubstituted or N-substituted. Preferred N-substituted 2,2,6,6-tetraalkylpiperidinyl groups are N-acyl-substituted or N-alkylated 2,2,6,6-tetraalkylpiperidinyl groups. Acyl is preferably CO-C 1-6 alkyl and alkylated is C 1-6 alkylated, preferably methylated. Any 2,2,6,6-tetraalkylpiperidinyl group is preferably a 2,2,6,6-tetramethylpiperidinyl group.

The compounds representing component A have a molecular weight of 155 to 800, preferably 300 to 800.

The high molecular weight 2,2,6,6-tetraalkylpiperidinyl compounds (component B) have a molecular weight of more than 1000, more preferably 1000 to 20000, most preferably 1500 to 15000, in particular 2000 to 5000.

A more preferred component A is selected from compounds of formulas 1 to X, (1)

ο n

0 — C— (CH ₂ ) τ (II)

-NH- _(CH2)

(III)

CH ₃ CH ₃

R-N

CH ₃ CH _?

-NH-C-NH-C

(IV)

CH ₃ CH 3 (A)

CH ₃ CH ₃

R-N N-R-14

CH3 CH3

o Q ______ II

CH3 CH3

-CH = CH-C-O

N-R

CH ₃ CH ₃

CH ₃ CH ₃ (VI) (VII) (VIII) (IX) (X)

wherein n is a number from 1 to 4 inclusive, m is 1 to 4 (preferably 1 or 4, more preferably 1);

X 1 is oxygen or -N (R ₃ ) wherein R ₃ is hydrogen or C 1-4 alkyl;

R1 is a 1- to 4-group selected from carboxylic acid and amide;

R 10 is hydrogen, C 1-12 -alkyl or C 1-12 alkoxy;

R 11 is hydrogen or C 1-6 alkyl (preferably C 12 H 25);

R12 is hydrogen or -CH2CH2COQC1-14alkyl (preferably -CH2CH2COQC12H25 or -CH2CH2COOC14H2?):

R 13 is -O- (CH 2) 1-3 -COOC 1-12 ^{and 1} alkyl (preferably -O- (CH 2) 1-3 -COOC 1 -alkyl);

R is selected from the group consisting of hydrogen, oxygen, -OH, C 1-6 alkyl, C 1-6 alkoxy, -OCO-C 1-6 alkyl, -O-C 0 -phenyl, and -COR 5; wherein R 5 is -C (R ₃ ) = CH ₂ . phenyl, -CO-phenyl, -NR ₇ R _8, -CH ₂ C ₆ H _5, COO-C 1 - 1 ₂ alkyl or COOH; R 3 is hydrogen or C 1-4 alkyl; R 7 is hydrogen, C 1-12 alkyl, C _5-8 cycloalkyl, phenyl, phenylC 1-4 alkyl or C 1-12 alkylcenyl and R 8 is C 1-2 alkyl or hydrogen;

R 14 is C 1-6 alkyl, C 1-4 alkene or

CH ₃ ch ₃ - N, exp

U ch ₃ ch ₃

The most preferred component A is selected from compounds of formulas 1.11 and IV, especially compounds of formula Ia and II. Particularly preferred are compounds designated DASTIB 845, Tinuvin 770,

The specific compounds representing component A are selected from the following:

bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate (Tinuvin 770); bis (1,2,2,6,6-pentamethyl-4-piperidinyl) (3,5-di-tert-butyl-4-hydroxybenzoyl) butyl tert-butadiene;

bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate;

8-acetyl-3-dodecyl-7,7,9,9,9-tetramethyl-1,3,8-triazaspiro (4,5) decane-2,4-diene:

butanedioic acid bis (2,2,6,6-tetramethyl-4-piperidinyl) ester; tetraki with (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butenetetracarboxylate;

7-oxa-3,20-diazadispiro (5,1,11,2) heneicosene-20-propenoic acid, 2,2,4,4-tetramethyl-21-oxo, dodecyl ester;

N- (2,2,6,6-tetramethyl-4-piperidinyl) -N'-aminoxamide;

0-tert. and methyl-O- (1,2,2,6,6-pentamethyl-4-piperidinyl) morphine oxycarbonate;

beta-a 1 an n, N- (2,2,6,6-tetramethyl-4-piperidinyl) dodecyl ester: ethanediamine, N- (1-acetyl-2,2,6,6-tetramethylpiperid N-dodecyl:

3-dodecyl-1- (2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione;

3-dodecyl-1- (1,2,2,6,6-pentamethyl-4-piperidinyl) -pyrrolidin-2,5-dione:

3-dodecyl-1- (1-acetyl-2,2,6,6-tetramethyl-4-piperidinyl) pyrrolidine-2,5-dione (Sanduvor 3058):

4-Berizoxy oxyxy-2,2,6,6-tetramethyl per piperidine:

- d i t e r c. 4- (4-hydroxy-4-hydroxyphenylpropionyloxy) -2,2,6,6-tetramethylpiperidine; 4- (4-hydroxy-4-hydroxyphenylpropionyloxy) -4,4-tetramethylpiperidine;

2-Methyl-2- ('2, 2, 6, 6-tetramethyl-4-piperidinyl-amino) -N- (2', 2 ', 6', 6'-tetramethyl-4 ' -piperidinyl) propionyl amide;

1,2-bis (3,3,5,5-tetramethyl-2-oxo-piperazinyl) ethane;

4-oleoyloxy-2,2,6,6-tetramethylpiperidine;

Tiriuvin 123, a compound of formula

0-C - (CH ₂₎ 4 II of

Mixxim HALS 6? (ADK-STAB LA 67) and Mixxim HALS 62 (ADK-STAB LA 62), a compound of formula

CH ₂ -C00R 17

CH — COOR17 7

CH — COOR17 I ch -coor ₁₇

wherein each R 17 is C 13 H 27 or R 30 - wherein each R 30 is hydrogen or methyl;

Host n 20. compound of formula

wherein both R 30 are hydrogen (500 H) or both H 30 are -CH 3 (51 6 H)

OASTIB 845, product according to CS 229 069;

Goodrite 3150, a compound of formula

CH ₃ CH 3

404 9th compound of formula

NH

More preferably, the compounds representing component B are selected from the compounds of formulas XI to XIX:

II (xii)

R i c, NH (C H 3)

N (R 15) - (CH 2) 2 -N (R 3 d) - (CH2) 3-NHR 1 ₅

CH ₃ CH 3

H (xv) (XVI)

(XVIII) (known as ADK STAB LA-63 + LA-68) is hydrogen (LA-68) or -CH 3 (LA-63)

Hostavin N 30 wherein n is 1 to 4 and each R 30

where p is 4 to 30, m has the meaning of p R 11 is hydrogen k more preferably 4 to independently of p, or C 1-4 alk.vl, (XIX)

20, most preferably 4 to 10,

R? is-N (1-C 1 ₂ alkyl) 2, NHC 1 ~ - 1 ₂ alkyl, or morpholino,

R1 s is e

X is fHz-COOCOOCH-COO1

CH2-COOwhere each R30 is hydrogen (LA-63) or -CH3 (LA-63)

The specific compounds representing component B are selected from the following:

1,3,5-triazine-2,4,6-triamine-N ', N' '' - (ethanediyl bis [4,6-bis / butyl (1,2,2,6,6-pentamethyl) - 4-piperidinyl) amino] -1,3,5-1-thiazin-2-yl-imino-propanediyl} [N'N-dibutyl-N ', N-bis (1,2,2,6) 6-pentamethyl-4-piperidinyl) -;

pol y-methylpropyl-3-oxy- [4- (2,2,6,6-tetramethyl) piperidinyl] siloxane;

octadecene-N- (2,2,6,6-tetramethylpiperidin-4-N-malefinide and oxalic acid diamide copolymer);

poly (6-fluoropheno-s-triazin-2,4-diyl) (2,2,6,6-tetramethyl) 4-piperidinyl) -hexamethylene ((2 2,6,6-tetramethyl-4-piperidinyl) amino} polymeric reaction product of α1-methylstyrene, N- (2,2,6,6-tetramethylpiperidinyl-4) ma1 ei ni mi du and N-stearyl have melamine;

Chi rosssorb 905. defined in Cler. Abstracts, Reg. Nr

07 043-87-8-,

Chimassorb 944. compound of formula

Tinuvin 622 compound of formula

N- _(CH2)

-CH ₂ -CH 2

Ti nuvi n

079. compound of formula

J-CH - CH? -O-C

C2H5;

C 2 H 5 0 rn

Uvasi 1299 from Enichem, a compound of formula

Si = O ^from NH

Spinuvex A 36, a compound of formula

where n? is 2 to 20;

Lowilite 62, a compound of formula

—CH -

I

C = 0 /

'1 N H 3 7

and Dastib 1082, a compound of formula

wherein in the formulas p is 4 to 30 and m is 4 to 30.

The most preferred compounds representing component B are compounds of formula XI.

Particularly preferred as component B are compounds defined as Oastib 1082, Chimassorb 944 and Cyasorb 3346.

The ratio of the components A and B may be within the limits of the mutual solubility of the components. However, the preferred component A would preferably have δ

should be soluble in of 10 ž, k e B, a b y in the melt. d \ and / or a true solution. Preferably, when R is R where R 'is hydrogen, C1-6-alkyl, - 0 - C 1 - g a 1 k y 1 a 1 s b 0 ••• CO — C1 - g and 1 , more preferably, when R is R, where R 1 is hydrogen, -CH 3, -OCH3 or - COCH 3. Advantageously, 1 ' now R1 is R1 ¹ , where R η 'is - (CO) _n 1 R40 or

- (CO-CO-NH), R 4, wherein R 40 is C 1-22 alkyl or phenyl, unsubstituted or substituted with 1 to 3 groups selected from C 1-2 alkyl or C 1-22 ^and alkoxy groups.

For the avoidance of doubt, a carboxylic acid moiety is an acyl group, for example, -CO-C 1 -C 22 alkyl, CO-R 5 wherein R 5 is phenyl unsubstituted or substituted with 1 to 3 groups selected from C 1-22 ^and alkyl or C 1. -22 ^and alkoxy groups.

The solid solution compositions of the invention can be prepared by mixing 1 part by weight of component A with 1 to 20 parts by weight of component B, melting the mixture to form a solution, and cooling the solution to form a solid solution.

The mixture is melted at a temperature of 100 to 300 ° C, more preferably at a temperature of 150 to 250 ° C.

If a symbol appears more than once in a formula, its meanings unless otherwise indicated. are independent of each other. *

The compounds of formulas 1 to XIX are known or can be prepared by known methods.

Further, we have developed a polymeric composition according to the invention consisting of a polymeric material and a solid solution composition according to the invention.

The amount of solid solution composition present is 0.01 to 5, preferably 0.02 to 2%, based on the weight of the polymeric material.

Additional additives, including antioxidants, such as sterically shielded phenols, secondary aromatic amines, or thioethers, as described in Kunstoffe-Additive Gächter / Muller, 3rd edition, may be added to the polymer composition of the invention. 1SS0, p. 42-50, in the amounts recited in this reference; acid deactivators. such as sodium, magnesium or calcium stearate or lactate; h y d r o 't a i c i t, a k o x y 1 o a t e a b e h o y d o x y 1 o a n d e s; For V-ab orbers (e.g., ad 2- (2'-hydroxy oxenyl) -benzotriazoyl, 2-hydroxybenzothiophenones, 2-hydroxyphenyls 1-1, 3,5) -triazines, 1,3-bis- (2'-hydroxybenzoyl) -benzenesalicylates, cinnamate and ebodium (ni-oxoxalic acid) UV-quencher (e.g. 1 adbenzo) but bosubstituted benzoetes): antistatic agents, flame retardants, emollients, sheaths ficiculators, lubricants, metal deactivators, co-complexes, biocides, fungicides, nucleating agents, fillers, pigments, impact modifiers and others.

The above-described solid solution composition can be incorporated into the polymeric material to be stabilized by known methods. Of particular note is the mixing of compositions with thermoplastic polymers in the melt, for example, in a melt mixer or in the molding of shaped articles including films, films, tubes, packaging, bottles, fibers and foams by extrusion, injection, blow molding, spinning or wire coating.

It is not necessary that the polymer material be completely polymerized prior to mixing with the solid solution compositions of the invention. The solid solution may be mixed with a monomer, a prepolymer or a precondensate, and the polymerization reaction is carried out subsequently. This will obviously be an advantageous method of incorporating solid solutions into thermosets that cannot be melt mixed.

Polymeric materials that may stabilize with the composition of the invention include homopolymers, copolymers, and polymeric blends of the following types:

cellulose acetate, cellulose acetate butyrate, cellulose acetopropionate, cresol-formaldehyde resins, carboxymethylcellulose, cellulose nitrate, cellulose propiorate, casein plastics, cellulose nitrate, cellulose triacetate, ethylcellulose, epoxy resins, cellulose 1 amine n-formaldehyde resins, polyamide, polyamideimide, polyacrylonitrile, 1. polybut-1-ene. polybut-2-ene, polybutyl acrylate, poly (butylene terephthalate), polycarbonate, poly (chlorotriene, polyphenylene ether, lystyrene, polysulfone, fluoroethylene), poly (diallyl phthalate), polyethylene, chlorinated polyethylene, polyether ether, polyether ether, polyether ether, polyether , pol y (ethyl ether). polytetrafluoroethylene, phenolform 1 dehydroxy resins, polyirnide, polyisobutylene, polyisocyanurate, polymethacrylic acid; polymethyl methacrylate, poly (4-methylpent-1-ene), poly (alpha-methylstyrene), polyoxymethylene, polyacetal, polypropylene polyphenylene sulfide, polyphenylene sulfone, poly (polyurethane), polyvinyl acetate, polyvinyl alcohol, polyvinylchloride, polyvinylchloride polyvinylidene fluoride, polyvinylidene chloride, polyvinylfluoride, polyvinyl chloride, polyvinyl formamide, polyvinylcarbazole, polyvinylpyrrolidone, silicone polymers, saturated polyesters, urea-formaldehyde resins, polyunsaturated polymers, polyacrylate, polyacrylate, polyacrylate, polyacrylate, polyacrylate, resins and silicone resins.

Examples of suitable copolymers:

acrylonitrile / butadiene / acrylic acid, acrylonitrile / butadiene / styrene, acrylonitrile / methyl methacrylate, acrylonitrile / styrene / acrylic ester, acrylonitrile / ethylene propylene diene / styrene, acrylonitrile 1 / chlorinated polyethylene / styrene, ethylene / propylene, ethylene / propylenediene, ethylene / vinyl acetate, ethylene / vinyl alcohol, ethylene / tetrafluoroethylene, tetrafluoroethylene / hexafluoropropopylene, polymethylene amide / methacrylate / butadiene / methanesulfonamide / methacrylate / butadiene / methanesulfonamide canane, styrene / butadiene, styrene / maleic anhydride, styrene / alpha-methyl styrene, vinylchloride / ethylene / methacrylate, vinyl chloride / ethylene / vinyl acetate. vinyl chloride / methyl methacrylate, vinyl chloride / octyl acetate, vinyl chloride / vinyl acetate, vinyl chloride or vinyl chloride.

Even more preferred polymeric materials include plastic materials. for example polyethylene, polypropylene, ethylene / propylene copolymers, polyides, polyester, polyamide, polyurethane, polyecrylonitrile, ABS, acrylate, styrene and acrylonitrile terpolymers, styrene / acrylonitrile and styrene / butadiene. They may be used

9 also other plastic materials such as polybutylene, polystyrene, chlorinated polyethylene, polycarbonate, polymethylmethacrylate, polyphenylene oxide and polypropylene oxide, polyacetals, phenol form of the 1 -dehyde resin. and epoxy resins. Preferred plastic materials are polypropyl arrays, polyethylene, ethylene / propylene copolymers and ABS.

The most suitable polymeric materials whose properties can be improved by the composition of the invention are polyolefins such as polyethylene (for example, high density polyethylene, low density polyethylene, linear low density polyethylene or medium density polyethylene), polybutylene, poly-4-methylpentene, and copolymers thereof.

The solid solution compositions of the invention are particularly suitable for use in polyolefins and copolymers thereof prepared using catalysts known as Generation II to Generation V, which may or may not be (preferably not) subjected to a catalyst removal operation.

Catalyst removal refers to a process wherein, in order to completely remove catalyst residues from polymerized polyolefins, polyolefins are treated with compounds that react with the catalyst residues to inactivate or solubilize the residues, for example, with alcohols or water, and then inactivated or solubilized. The recovered catalyst residues are removed by physical means such as filtration, washing and centrifugation.

Thus, in the case of suspension polymerization, the process of separating the resulting polymer from a dispersion medium such as a solvent or liquefied monomer does not fall under the above definition of the catalyst residue removal process, although the catalyst dissolved in the dispersion medium can be removed in the separation process. The addition of a small amount of catalyser poisons, such as ethers, alcohols, ketones, esters and water, to the resulting polymer suspension with a gas, such as steam or nitrogen, to remove dispersed rhodium, also does not fall under the above definition of the catalyst residue removal process.

0 na

P o d C? e n & r o c o k k k a t t 1 1 1 1 1 m m m m The base of the base of the body with organoalutinium from one body to the body or to the body of the body. cl.

Generation 11 of catalysts is understood to mean Generation 1 of catalysts deposited on or-g and n oration. e J is 1 or not based on an organic chromium compound deposited on SiO2.

Generation III catalysts are understood to be Ziegler-type complex catalysts supported on a halogen-containing magnesium compound.

Generation IV catalyst means Generation III catalyst with a silane donor.

Generation V of a catalyst is understood to mean a bis-indenyl organotitanium compound. deposited on alumina or bis-cyclopentadienylthiohalide, activated and aluminum alkyl by apprentices.

Subsequent generations of highly specific catalysts particularly suitable for the production of high stereoregular polyolefins. which are currently under development are also within the meaning of the invention. these generations of catalytic systems. Examples of such high stereoregular polyolefins are syndiotactic polypropylene. isotactic stereoblock polymers, isotactic polypropylene, containing spherical defects distributed along the polymer chain (so-called anisotactic polypropylene) or stereoiregular stereoblock polymers.

In view of the rapid progress in the development of a new generation of catalyst systems (e.g. metallocene catalysts), the commercial importance of these polymers with new ones. very interesting, in fact, it is not. However, in later generations, they may have an adverse effect on the polymer if they contain metals of t. 4. and g, groups of the periodic system analogous to the older generations of catalysts, and if not physically removed and remain present in the polymer, even in deactivation, e.g.

These generations of catalysts are described in the Iwe Ifth Annual Interantion C1 Materials on the State and the Controlled Degradation of Polymers, Lucerne, Switzerland, 21-23 May 1990, p. 181-196, as well as in R. MijlKaupta's New Ideas in Polyolefin Catalysts and Influence on Polymer Stability. The contents of this work are incorporated by reference and Table 1 on page 184, describing Generation Catalysts at:

and b u i k and I

Catalysts development

Generáci a Activity-Stereore-Technology Ti catalysts gu 1 ar i ta zétora (&) Insoluble. (g PP / g Ti) in heptane)

I. TiCU / AlRs 40 0.01 45 remove increase TiCl ₃ / AlEt ₂ Cl 30 0, 1 92 metal catalyst and atacti PP remove increase II. Mg (OEt ₂ ) / T and C14 / ΑΊR ₃ 40000 50 metal catalyst without removing it SiO ₂ / Cp ₂ Cr 40000 HDPE catalyst residues J 11 .Mod.TiCl ₃ cat. 5000 1 95 tora (in particular HDPE / LLDPE) without cleaning MgCl ₂ / TiCl 4 / AlEt ₃ 20000 10 92 -ester donor IV. MgCl ₂ / TiCl / AlR ₃ 40000 18 99 without cleaning -silary donor V. Bis-indenyl-TiR ₂ 40000 150 99 without extrusion new PP, narrow to (A1CH ₃ O) ₂ MWD

where R is an organic group, HDPE is a high density polyethylene, L.LDPE is a linear enrichment of totriety polyethylene, Cp is cyclopentadiene, Et is ethyl, PP is polypropylene, MWD is the molar-time distribution in solution, but I) t. i.

The compositions of the invention may be added before. or after polymerization in solid or molten form, preferably as a liquid concentrate containing 10 to 80% by weight of the composition and 90 to 80% by weight of the composition. 20% by weight of the solvent or up to 80% (preferably 40 to 70 as masterbatch containing the compositions by weight) and up to 20% (preferably 60 to 30%) by weight of a solid polymer identical or compatible with the polymer to be stabilized.

The compositions of the invention may also be incorporated into the polymer to be stabilized by other known methods. Each method comprises dry blending the compositions of the invention with a polymer or applying them to a polymer particle, for example, a bead, in the form of a liquid melt, solution or suspension / dispersion. Particularly important is the compounding of the compounds with the thermoplastic polymers in the melt, for example in a melt mixer or during the production of shaped articles, including films, tubes, fibers and foams by extrusion, injection molding, blow molding, rotary casting, spinning or wire coating. The compositions of the invention are particularly suitable for use in polypropylene and polyethylene products of each type.

We have further developed a method for stabilizing polyurethane, acrylic, alkyd and / or polyester resin coatings (crosslinked with melamine-formaldehyde resins, epoxy resins or polyisocyanates, if necessary) against the degradation effects of heat and light by incorporating the above described solid solution compositions, optionally together with an acid catalyst or a compound capable of releasing the acid catalyst into the resin.

Furthermore, we have developed a coating composition according to the invention based on polyurethane, acrylic, alkyd or polyester resins (if desired, they can be cross-linked with melamine formaldehyde resins, epoxy resins or polyisocyanates), containing the above-described solid solution compositions optionally together with an acid catalyst. or a compound capable of releasing an acid catalyst. A suitable concentration of the solid solution composition of the invention in the polymeric material used is 0.01 to 8% by weight, preferably 0.02 to 1% by weight, and results in an apparent improvement in the light and weather stability of the organic pigments in the baked coatings, cracks and gloss loss due to weathering. It has also been found in metallic coatings into which the compositions of the invention have been incorporated that excellent long-term stability of the translucent topcoat of bilayer metallic coatings is achieved. In such coatings, the solid solution composition may be added to the metallic primer, the translucent topcoat, or both, preferably only to the top translucent coat. The surface to be treated may be treated with a primer, as is conventional in the art of coatings.

Other antioxidants may also be added to the polymer material before, during or after (but prior to polymerization) addition of the composition of the invention.

Examples of suitable antioxidants include benzofuran-2-ones, indolin-2-ones and sterically shielded phenols, sulfur and phosphorus containing compounds, and mixtures thereof.

Suitable sterically shielded phenols include: beta- (4-hydroxy-3,5-di-tert-butylphenyl) propioriyl stearate, methanetretraks- [methylene-3- (3 ', 5'-di-tert-butyl-4)]. -hydroxyphenyl1) for p-ionate,

1,3,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane,

1,3,5-tris- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) -1,3,5-triazinyl-2,4,6- (1H, 3H, 5H) -trione , bis- (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) diol terephthalate, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate t, beta- (4-hydroxy-3,5-di-tert-butylphenyl) propionic acid triester with 1,3,4-tris- (2-hydroxyethyl) -5-triazinyl-2,4,6- (1H) (3H, 5H) -trione,

...;? 4 g Ί glycol ester of Bis - s '3,3-bis (' ¹ -h 4 Hydroxy-3-tert. Butyl-phenylpropan-1 yl) mas ove..i kyselinyl 1, -1, -1 3.5 R 1-ethyl-2,4,6 -1 R -is- (3,5-di-1-tert-butyl-4-hydroxybenzyl) benzene. é n,

2,2 ' -methylene-bis - (4-methyl-6-tert-butylphenyl) terephthane,

4,4-methylene-bis - (2,6-di-tert-butyl phenol),

4,4'-butylidin-bis- (tert-butylmethacresol),

2,2'-methyl-en-bis- (4-methyl-6-tert-butyl) phenol,

1,3,5-tris- (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanuret and 1,1,3-tri- (5-tert-butyl-4-hydroxy-2-methylphenyl) butane.

Sulfur-containing antioxidant co-stabilizers that may be used preferably include di-tridecyl-3,3-thiodipropionate, distearyl-3,3-thiodipropionate, di-lauryl-3,3-thiodipropiorate, methane tetrakis (methylene-3-hexylthiopropionate) , methane tetrakis (methylene-3-dodecyl thiopropionate) and dioctadecyl disulfide.

Phosphorus-containing co-stabilizers which may be used preferably include trinonylphenylphosphite, 4,9-distearyl-3,5,8,10-tetraoxadiphosphaspiroundecane, tri- (2,4-di-tert-butylphenyl) phosphite. tri 1aurylphosphite, bis- (2,6-di-tert-butyl-4-methylphenyl) pentaerythrityldiphosphite. bis- (2,4-di-tert-butylphenyl) pentaervetyldithiophosphite, distearylpentaerythritylphosphine and tetrakis- (2,4-di-tert-butylphenyl) -4,4'-biphenylene phosphite .

Other additives that may be added to the polymer compositions of the invention include aminoaryl of the compound, UV-stabilizers and antistatic agents, agents, flame retardants, fading agents, nucleating agents, metal deactivators, biocides, impact modifiers, fillers, pigments. and fungicides.

Preferred aminoaryl compounds include N, N'-dinaphthyl-p-phenylene amide at N, N'-hexarboxy-3- (3,5-di-tert-butyl-4-h). ydroxyphenyl) propionamide.

Preferred UV stabilizers include UV absorbers (e.g.

- (2'-hydroxyphenyl) benzotriazoles, 2-hydroxybenzophenones, 1,3-bis- (2'-hydroxybenzoyl) benzenesulfonylates, cinnamonates and oxides of oxoic acid, UV-quenchers such as benzoates and substituted benzoates and light stabilizers shielded amine bases (for example, N-unsubstituted, N-alkyl or N-acyl-substituted 2,2,6,6-tetraalkylpiperidine compounds) that do not fall within the scope of the invention.

It is preferred to add a compound of formula XX to the composition of the invention,

wherein R 30 is C6-22.alkyl or C6-22alkoxy, R 31 and R 32 are independently selected from hydrogen, Cl-aalkyl, C 1 - 1 ^and 1 2 alkoxy, C 1 -12 ^N alkylthio, phenoxy and phenylthio, provided wherein only one of R 31 and R 32 is alkylthio, phenoxy or phenylthio and R 33 is hydrogen or C 1-6 alkyl.

Solid solutions are also suitable for coatings containing organic polymers, especially powder coatings such as microsuspensions.

The solid solution compositions of the invention may be added to the coatings at any stage of the coating. production and can be added in solid form.

The solid solution compositions of the invention are added to the powder coatings prior to firing or curing.

The composition of the invention may also be used in photopolymer substrates containing photoinitiators prior to photopolymerization.

Examples are shown

The invention is illustrated by the following examples, all of which are incorporated herein by reference.

Components A and B listed in Table 1 were used to prepare solid solution compositions.

Table 1

component Title temperature melting [oC] A-1. 1 Dastib 845 28 - 32 A-1. 2 T i n u v n n 0 0 81 - 83 B-1. 1 Dastib 1082 172 - 85 8-1.2 Chimassorb 944 1 1 6 - 130 B-1.3 Cyasorb UV 3346 112 - 125

Example 1 g of B-1.1 was homogenized for 5 min in a Brabender mixer at 110 ° C, and 35 rpm. Then 5 g of A-1.1 was added, the mixture was homogenized for 2 min, an additional 10 g of B-1.1 was added, the speed was increased to 50 rpm, the whole mixture was homogeneous for 1 and 10 min and finally cooled. A solid solution composition according to the invention, listed in Table 2 under the designation S3, was obtained. Similarly, the other compositions of the invention listed in Table 2 were prepared.

Table 2

No. ingredients ratio Melting point [° C] S1 B-1.1 10:90 122-139 S2 B-1.1 15:85 106-115 S 3 B-1.1 20:80 90 - 99

No Z Ί 0 b ratio T ep 101 and 10 pennies (' ⁰ C] S 4 A-1.1: B-1 1 25:75 77 - 8 5 S 5 A-1.1: B-1 1 30/70 64 - 6 9 S 6 A-2.1: 8-1 1 10:90 132 - 141 37 A-2.1: B-1 1 25:75 91-103 S 8 A-2.1: 8-1 . 2 20:80 75 - 83 S9 A-1.1: B-1 . 2 10:90 85 - 9 5 S10 A-1. 1: 8-1 . 2 25:75 45 - 55 S11 A-1.1: B-1 .3 10:90 80 - 90 S12 A-1.1: B-1 • 3 15:85 79 - 89 S13 A-1.1: B-1 . 2 20:80 50 - 7 6

For comparison, simple mixtures were prepared from the same ingredients used in the same proportions. For example, a simple 30:10 mixture of 8-1.1 and A-1.1 has the designation M1. Similarly, M2 is a grain corresponding to solid solution S2 and so on.

Example 2

Light and thermal stabilization of polypropylene.

100 parts of polypropylene powder (1TT230 ⁰ c / 2, 16 k? = 10.4 g / 10 min) was heated for 10 min in a Brabender under nitrogen atmosphere at 190 ° C with 0.1 part of 4-methyl- 2,6-di-tert. butyl phenol, 0.15 parts of calcium stearate and 0.2 parts of the solid solution composition according to the invention, or 0.2 parts of a simple mixture corresponding to said composition, 0.12 mm thick foils intended for the determination of the world were pressed from the homogenized mixture and a 0.5 mm thick film intended to determine the thermostabilizing effect. Foil samples of 0.12 mm thickness were exposed in a Xenotest 450 at a black panel temperature of 45 ° C and the absorbance of carbonyl (/C0) was measured by IC-spectrophotometer. Foil samples of 0.5 mm thickness were exposed in an air oven heated to 135 ° C and the time to embrittlement (Tb) was recorded.

The results of both measurements are summarized in Table 3.

Table 3

Stabi1 i zátor And CO after 4560 h Tb [days] S1 0107 151 ml 0205 22 S2 0051 358 M2 0186 319 S3 0.045 - M 3 0138 - S4 0051 272 M4 0.060 142 S5 507 M5 108

Example 3

Light stabilization of polypropylene fibers.

100 parts of polypropylene. Iene (ITT230 · c / 2.16 · kg ~ 3.2 g / 10 min) was dry mixed with 0.1 part 4-methyl-2,6-di-tert-butyl phenol, 0.1 part stearate calcium, 0.05 part of 2,5-dimethyl-2,5-di-tert. butyl peroxyhexene and 0.2 parts solid solution composition of calcium stearate, 0.05 parts of 2,5-dimethyl-2,5-di-tert-butyl peroxyhexery and 0.2 parts of the solid solution composition of the invention or 0, 2 parts of a simple mixture corresponding to said composition. The dry blend was then extruded in a laboratory screw extruder to granulate from which 6.7 dtex fibers were prepared using a laboratory extruder. The fiber samples were exposed in a Xenotest 450 at a black panel temperature of 45 ° C and their strength was measured. As a criterion for assessing the degree of light degradation of the samples, the time to decrease their strength to 50% of the original value (T50) was chosen.

The results are shown in Table 4.

Table 4

sample T50 Ch] ARE YOU 1010 M1 940 S3 800 M3 480 S4 920 M4 410 S9 1010 M9 410 36 740 M6 300 S7 800 phi? 410 S8 800 M8 410

Example 4

Light stabilization of polyethylene.

100 parts of high density polyethylene powder (gotι got; µl 2.1 g / 10 µm) were homogenized for 10 min in a Brabender under nitrogen atmosphere at 160 ° C with 0.1 part stearate calcium and 0.2 parts of the solid solution composition according to the invention or with 0.2 parts of a simple mixture corresponding to said composition, 0.12 mm thick films were compressed from the homogenized mixture and samples were exposed in the apparatus

Xenotest 450 at 45 ° C black panel temperature and carbonyl absorbance was measured at regular intervals by IC spectrophotometer. As a criterion for evaluating the degree of light degradation of the samples, the time to decrease the carbonyl absorbance (Aco) to 0.5 was chosen.

The results are shown in Table 5.

Table 5

Stab i 1 insulator A 5 o = 0.5 µ h] S8 6380 M 8 4810 S9 6040 M9 5810 513 6040 M13 5200 A-1.1 2880 A-2.1 5221 B-1. 2 5890

1

Claims (11)

What is claimed is: 1. A solid solution composition comprising: component A which is an alcoholic compound comprising at least one 2,2,6,6-tetraalkylpiperidine group; and component B, wherein: is a high molecular weight compound containing at least one 2,2,6,6-tetraalkylpiperidinyl group, both components being melt blended. A composition according to claim 1, comprising component A and component B in a ratio of 1: 1 to 1:20. The composition of claim 1 or claim 2, wherein component A comprises one to four 2,2,6,6-tetraalkylpiperidinyl groups. Composition according to any one of the preceding claims, characterized in that the compound representing component A has a molecular weight of 155 to 800. Composition according to any one of the preceding claims, characterized in that component B is an oligomeric or polymeric compound containing one to four 2,2,6,6-tetraalkylpiperidinyl groups per repeating polymer unit. Composition according to any one of the preceding claims, characterized in that the compound representing component B has a molecular weight of 1000 to 20,000. Composition according to claim 1, characterized in that it consists of component A and component B. as defined in the examples. • J í. A process for the preparation of a solid solution composition as defined in claim 1, characterized in that 1 part by weight of component A as defined in claim 1 is mixed with 1 to 20 parts by weight of component B as defined in claim 1, is melted to form a solution and cooling the solution to give a solid solution. A polymer composition comprising a polymer material and a solid solution composition as defined in any one of claims 1 to 7. IN 10. A process for stabilizing a coating composition based on polyurethane, acrylic, alkyd and / or polyester resins, optionally crosslinked with melamine-formaldehyde resins, epoxy resins or polyisocyanates, against the degradation effects of light and heat, characterized in that the composition comprises a solid solution base according to any one of claims 1 to 7, preferably together with an acid catalyst or a compound capable of releasing an acid catalyst. 11. Coating composition based on polyurethane, acrylic, alkyd and / or polyester resins, optionally crosslinked with h, mel amine-form idedehyde resins. epoxy resins or polyisocyanates, characterized in that it comprises a solid solution composition according to any one of claims T to 7.