Method for Light Stabilization of Two-Layer Uni-Lacquer Coatings

The present invention relates to the stabilization, by the addition of polyalkylpiperidine derivatives, of two-layer uni-lacquer coatings based on acrylic, alkyd and polyester resins, against the action of light and humidity, and also to the lacquers stabilized in this way.

It is already known from the two Japanese Patent Applications Sho 52-132050 and Sho 53-60942 that two-layer uni-lacquer coatings can be stabilized with conventional UV-absorbers. However, if good stabilization is to be ensured, these stabilizers must be used in relatively high concentrations and, moreover, in most cases they do not possess the desired lack of color which, because of the frequently varying layer thicknesses of the clear lacquers, is of extremely great importance in practice.

Typical degradation phenomena in two-layer lacquer coatings, especially crazing, blistering and delamination should, according to experience, best be prevented by UV-absorbers. However, it has now been found, surprisingly, that when light stabilizers based on polyalkylpiperidine derivatives are used excellent stabilization is achieved, even in considerably smaller concentrations, despite the lack of absorption in the near-UV range. Moreover, the requisite lack of colour is ensured by the polyalkylpiperidine derivatives.

The present invention therefore relates to the use of 2,2,6,6-tetraalkylpiperidine compounds or their acid addition salts or complexes with metal compounds, if desired together with further stabilizers, for stabilizing two-layer uni-lacquer coatings based on acrylic, alkyd or polyester resins, which, if desired, can be crosslinked with melamine/formaldehyde resins, epoxide resins or polyisocyanates, against the action of light, humidity and oxygen.

The 2,2,6,6-tetraalkylpiperidine compounds to be used according to the invention are generally known and are already employed against light degradation. They are preferably compounds which contain a group of the formula (I) ##STR1## in which R is hydrogen or methyl.

The light stabilizers to be used according to the invention include, in particular, the following compound categories:

(a) Light stabilizers of the formula (II) ##STR2## in which n is the numbers 1-4 and preferably 1 or 2, T is hydrogen or --CONH.sub.2, R is as defined under formula (I), R.sub.1 is hydrogen, oxyl, C.sub.1 -C.sub.18 alkyl, C.sub.3 -C.sub.8 alkenyl, C.sub.3 -C.sub.8 alkynyl, C.sub.7 -C.sub.12 aralkyl, C.sub.1 -C.sub.8 alkanoyl, C.sub.3 -C.sub.5 alkenoyl, glycidyl or a group --CH.sub.2 CH(OH)--Z, in which Z is hydrogen, methyl, ethyl or phenyl, and R.sub.1 is preferably hydrogen, C.sub.1 -C.sub.12 alkyl, allyl, benzyl, acetyl or acryloyl and R.sub.2, if n=1, is hydrogen, C.sub.1 -C.sub.18 alkyl, which can be interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic carboxylic acid, carbamic acid or phosphorus-containing acid or a monovalent silyl radical, preferably a radical of an aliphatic carboxylic acid having 2-18 C atoms, of a cycloaliphatic carboxylic acid having 5-12 C atoms or of an aromatic carboxylic acid having 7-15 C atoms, if n=2 is C.sub.1 -C.sub.12 alkylene, C.sub.4 -C.sub.12 alkenylene, xylylene, a divalent radical of an aliphatic, cycloaliphatic, araliphatic, aromatic or heterocyclic dicarboxylic acid, dicarbamic acid or phosphorus-containing acid or a divalent silyl radical, preferably a radical of an aliphatic dicarboxylic acid having 2-36 C atoms, of a cycloaliphatic or aromatic dicarboxylic acid having 8-14 C atoms or of an aliphatic, cycloaliphatic or aromatic dicarbamic acid having 8-14 C atoms, if n=3 is a trivalent radical of an aliphatic, cycloaliphatic, aromatic or heterocyclic tricarboxylic acid, of an aromatic tricarbamic acid or of a phosphorus-containing acid or a trivalent silyl radical and if n=4, is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

Any C.sub.1 -C.sub.12 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

C.sub.1 -C.sub.18 Alkyl R.sub.1 or R.sub.2 can be, for example, the groups listed above and, in addition, also, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

C.sub.3 -C.sub.8 Alkenyl R.sub.1 can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert.-butyl-2-butenyl.

C.sub.3 -C.sub.8 Alkynyl R.sub.1 is preferably propargyl.

C.sub.7 -C.sub.12 Aralkyl R.sub.1 is especially phenethyl or in particular benzyl.

C.sub.1 -C.sub.8 Alkanoyl R.sub.1 is, for example, formyl, propionyl, butyryl or octanoyl, but preferably acetyl, and C.sub.3 -C.sub.5 alkenoyl R.sub.1 is especially acryloyl.

As a monovalent radical of a carboxylic acid, R.sub.2 is, for example, the radical of acetic acid, stearic acid, salicylic acid, methacrylic acid, maleic acid, benzoic acid or .beta.-(3,5-di-tert.-butyl-4-hydroxyphenyl)propionic acid.

As a divalent radical of a dicarboxylic acid, R.sub.2 is, for example, the radical of adipic acid, suberic acid, sebacic acid, phthalic acid, dibutylmalonic acid, dibenzylmalonic acid, butyl-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonic acid or bicycloheptenedicarboxylic acid.

As a trivalent radical of a tricarboxylic acid, R.sub.2 is, for example, the radical of trimellitic acid or of nitrilotriacetic acid.

R.sub.2 can also be radicals of di- and tri-carboxylic acids such as are prepared industrially by oligomerisation of higher molecular weight unsaturated fatty acids or by a Diels-Alder addition of acrylic acid onto linoleic acid. R.sub.2 can also be radicals which are formed by reacting mono-, di- and poly-epoxides, for example bisphenol A diglycidyl ether, butanediol diglycidyl ether, tris-glycidyl isocyanurate or 1,3-diglycidyl-4,4-dimethyl-hydantoin, with 4-hydroxy-1,2,2,6,6-pentamethylpiperidine.

As a tetravalent radical of a tetracarboxylic acid, R.sub.2 is, for example, a pyromellitic acid radical.

As a divalent radical of a dicarbamic acid, R.sub.2 is, for example, the radical of hexamethylenedicarbamic acid or of 2,4-toluylene-dicarbamic acid.

Examples of polyalkylpiperidine light stabilizers of this category are the following compounds:

(1) 4-Hydroxy-2,2,6,6-tetramethylpiperidine

(2) 1-Allyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

(3) 1-Benzyl-4-hydroxy-2,2,6,6-tetramethylpiperidine

(4) 1-(4-tert.-Butyl-2-butenyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine

(5) 4-Stearoyloxy-2,2,6,6-tetramethylpiperidine

(6) 1-Ethyl-4-salicyloyloxy-2,2,6,6-tetramethylpiperidine

(7) 4-Methacryloyloxy-1,2,2,6,6-pentamethylpiperidine

(8) 1,2,2,6,6-Pentamethylpiperidin-4-yl .beta.-(3,5-di-tert.-butyl-4-hydroxyphenyl)-propionate

(9) 1-Benzyl-2,2,6,6-tetramethyl-4-piperidinyl maleate

(10) Di-(2,2,6,6-tetramethylpiperidin-4-yl) adipate

(11) Di-(2,2,6,6-tetramethylpiperidin-4-yl) sebacate

(12) Di-(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) sebacate

(13) Di-1-allyl-(2,2,6,6-tetramethyl-piperidin-4-yl) phthalate

(14) 1-Propargyl-4-.beta.-cyanoethyloxy-2,2,6,6-tetramethylpiperidine

(15) 1-Acetyl-2,2,6,6-tetramethylpiperidin-4-yl acetate

(16) Tri-(2,2,6,6-tetramethylpiperidin-4-yl) trimellitate

(17) 1-Acryloyl-4-benzoyloxy-2,2,6,6-tetramethylpiperidine

(18) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl) dibutylmalonate

(19) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl) butyl-(3,5-di-tert.-butyl-4-hydroxybenzyl)-malonate

(20) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl) dibenzylmalonate

(21) Di-(1,2,3,6-tetramethyl-2,6-diethyl-piperidin-4-yl) dibenzyl-malonate

(22) Hexane-1',6'-bis-(4-carbamoyloxy-1-n-butyl-2,2,6,6-tetramethylpiperidine)

(23) Toluene-2',4'-bis-(4-carbamoyloxy-1-n-propyl-2,2,6,6-tetramethylpiperidine )

(24) Dimethyl-bis-(2,2,6,6-tetramethylpiperidin-4-oxy) silane

(25) Phenyl-tris-(2,2,6,6-tetramethylpiperidin-4-oxy) silane

(26) Tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphite

(27) Tris-(1-propyl-2,2,6,6-tetramethylpiperidin-4-yl) phosphate

(28) Bis-(1,2,2,6,6-pentamethylpiperidin-4-yl) phenylphosphonate

(29) Di-(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate

(30) Di-(1-benzyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

(31) Di-(1-allyl-2,2,6,6-tetramethylpiperidin-4-yl) sebacate

(31a) 2,2,6,6-Tetramethyl-4-hydroxy-4-carbamoyl-piperidine.

(b) Light stabilizers of the formula (III) ##STR3## in which n is the number 1 or 2, R is as defined under formula I, R.sub.1 is as defined under (a), R.sub.3 is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.5 -C.sub.7 cycloalkyl, C.sub.7 -C.sub.8 aralkyl, C.sub.2 -C.sub.18 alkanoyl, C.sub.3 -C.sub.5 alkenoyl or benzoyl and R.sub.4, if n=1, is hydrogen, C.sub.1 -C.sub.18 alkyl, C.sub.5 -C.sub.7 cycloalkyl, C.sub.2 -C.sub.8 alkenyl, which is unsubstituted or substituted by a cyano, alkoxycarbonyl or carbamide group, glycidyl or a group of the formula --CH.sub.2 --CH(OH)--Z" or of the formula --CONH--Z", in which Z" is hydrogen, methyl or phenyl; and if n=2 is C.sub.2 -C.sub.12 alkylene, C.sub.6 -C.sub.12 arylene, xylylene, a --CH.sub.2 -CH(OH)--CH.sub.2 group or a group --CH.sub.2 --CH(OH)--CH.sub.2 --O--X--O--CH.sub.2 CH(OH)--CH.sub.2 --, in which x is C.sub.2 -C.sub.10 alkylene, C.sub.6 -C.sub.15 arylene or C.sub.6 -C.sub.12 cycloalkylene, or, with the proviso that R.sub.3 is not alkanoyl, alkenoyl or benzoyl, R.sub.4 can also be a divalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid or the group --CO--, or R.sub.3 and R.sub.4 together, if n=1, can be the imide radical of an aliphatic, cycloaliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

Any C.sub.1 -C.sub.18 alkyl substituents are as already defined under (a).

Any C.sub.5 -C.sub.7 cycloalkyl substituents are in particular cyclohexyl.

C.sub.7 -C.sub.8 Aralkyl R.sub.3 is especially phenethyl or in particular benzyl.

C.sub.2 -C.sub.18 Alkanoyl R.sub.3 is, for example, propionyl, butyryl, octanoyl, dodecanoyl, hexadecanoyl or octadecanoyl, but preferably acetyl, and C.sub.3 -C.sub.5 alkenoyl R.sub.3 is especially acryloyl.

As C.sub.2 -C.sub.8 alkenyl which is unsubstituted or substituted by a cyano, carbonyl or carbamide group, R.sub.4 is, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl, 2,2-dicyanovinyl, 1-methyl-2-cyano-2-methoxycarbonyl-vinyl or 2,2-diacetylaminovinyl.

Any C.sub.2 -C.sub.12 alkylene substituents are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

Any C.sub.6 -C.sub.15 arylene substituents are, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

C.sub.6 -C.sub.12 Cycloalkylene X is in particular cyclohexylene.

Examples of polyalkylpiperidine light stabilizers of this category are the following compounds:

(32) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylene-1,6-diamine

(33) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-hexamethylene-1,6-diacetamide

(34) 1-Acetyl-4-(N-cyclohexylacetamido)-2,2,6,6-tetramethylpiperidine

(35) 4-Benzylamino-2,2,6,6-tetramethylpiperidine

(36) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dibutyl-adipamide

(37) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-N,N'-dicyclohexyl-(2-hydroxyp ropylene)

(38) N,N'-Bis-(2,2,6,6-tetramethylpiperidin-4-yl)-p-xylylene-diamine

(39) The compound of the formula ##STR4## (40) 4-(Bis-2-hydroxyethyl)-amino-1,2,2,6,6-pentamethylpiperidine (41) 4-(3-Methyl-4-hydroxy-5-tert.-butyl-benzoic acid amido)-2,2,6,6-tetramethylpiperidine

(42) 4-Methacrylamido-1,2,2,6,6-pentamethylpiperidine

(43) Methyl .alpha.-cyano-.beta.-methyl-[N-(2,2,6,6-tetramethylpiperidin-4-yl)]-amino- acrylate.

(c) Light stablizers of the formula (IV) ##STR5## in which n is the number 1 or 2, R is as defined under formula (I), R.sub.1 is as defined under (a) and R.sub.5, if n=1, is C.sub.2 -C.sub.8 alkylene or hydroxyalkylene or C.sub.4 -C.sub.22 acyloxyalkylene and, if n=2, is the group (--CH.sub.2).sub.2 C(CH.sub.2 --).sub.2.

C.sub.2 -C.sub.8 Alkylene or hydroxyalkylene R.sub.5 is, for example, ethylene, 1-methyl-ethylene, propylene, 2-ethyl-propylene or 2-ethyl-2-hydroxymethylpropylene.

C.sub.4 -C.sub.22 Acyloxyalkylene R.sub.5 is, for example, 2-ethyl-2-acetoxymethyl-propylene.

Examples of polyalkylpiperidine light stabilizers of this category are the following compounds:

(44) 9-Aza-8,8,10,10-tetramethyl-1,5-dioxaspiro[5.5]undecane

(45) 9-Aza-8,8,10,10-tetramethyl-3-ethyl-1,5-dioxaspiro[5.5]decane

(46) 8-Aza-2,7,7,8,9,9-hexamethyl-1,4-dioxaspiro[4.5]decane

(47) 9-Aza-3-hydroxymethyl-3-ethyl-8,8,9,10,10-pentamethyl-1,5-dioxaspiro[5.5]u ndecane

(48) 9-Aza-3-ethyl-3-acetoxymethyl-9-acetyl-8,8,10,10-tetramethyl-1,5-dioxaspir o[5.5]undecane

(49) 2,2,6,6-Tetramethylpiperidine-4-spiro-2'-(1',3'-dioxan)-5'-spiro-5"-(1",3" -dioxan)-2"-spiro-4'''-(2''',2''',6''',6'''-tetramethylpiperidine).

(d) Light stabilizers of the formulae (VA), (VB) and (VC) ##STR6## in which n is the number 1 or 2, R is as defined under formula (I), R.sub.1 is as defined under (a), R.sub.6 is hydrogen, C.sub.1 -C.sub.12 alkyl, allyl, benzyl, glycidyl or C.sub.2 -C.sub.6 alkoxyalkyl and R.sub.7, if n=1, is hydrogen, C.sub.1 -C.sub.12 alkyl, C.sub.3 -C.sub.5 alkenyl, C.sub.7 -C.sub.9 aralkyl, C.sub.5 -C.sub.7 cycloalkyl, C.sub.2 -C.sub.4 hydroxyalkyl, C.sub.2 -C.sub.6 alkoxyalkyl, C.sub.6 -C.sub.10 aryl, glycidyl or a group of the formula --(CH.sub.2).sub.m --COO--Q or of the formula --(CH.sub.2).sub.m --O--CO--Q, in which m is 1 or 2 and Q is C.sub.1 -C.sub.18 alkyl or phenyl, and if n=2 is C.sub.2 -C.sub.12 alkylene, C.sub.6 -C.sub.12 arylene, C.sub.4 -C.sub.12 alkenylene, a group --CH.sub.2 --CH(OH)--CH.sub.2 --O--X--O--CH.sub.2 --CH(OH)--CH.sub.2 --, in which X is C.sub.2 -C.sub.10 alkylene, C.sub.6 -C.sub.15 arylene or C.sub.6 -C.sub.12 cycloalkylene, or a group --CH.sub.2 CH(OZ')CH.sub.2 -(OCH.sub.2 --CH(OZ')CH.sub.2).sub.2 --, in which Z' is hydrogen, C.sub.1 -C.sub.18 alkyl, allyl, benzyl, C.sub.2 -C.sub.12 alkanoyl or benzoyl, and T.sub.1 and T.sub.2 independently of one another are hydrogen, C.sub.1 -C.sub.18 alkyl or C.sub.6 -C.sub.10 aryl which is unsubstituted or substituted by halogen or C.sub.1 -C.sub.4 alkyl, or C.sub.7 -C.sub.9 aralkyl, or T.sub.1 and T.sub.2 together with the C atom which bonds them form C.sub.5 -C.sub.7 cycloalkyl, pyrrolidinyl or piperidinyl, which are unsubstituted or substituted by C.sub.1 -C.sub.4 alkyl.

Any C.sub.1 -C.sub.12 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Any C.sub.1 -C.sub.18 alkyl substituents can be, for example, the groups listed above and, in addition, also, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Any C.sub.2 -C.sub.6 alkoxyalkyl substituents are, for example, methoxymethyl, ethoxymethyl, propoxymethyl, tert.-butoxymethyl, ethoxyethyl, ethoxypropyl, n-butoxyethyl, tert.-butoxyethyl, isopropoxyethyl or propoxypropyl.

C.sub.3 -C.sub.5 Alkenyl R.sub.7 is, for example, 1-propenyl, allyl, methallyl, 2-butenyl or 2-pentenyl.

C.sub.7 -C.sub.9 Aralkyl R.sub.7, T.sub.1 and T.sub.2 is especially phenethyl or in particular benzyl, and C.sub.5 -C.sub.7 cycloalkyl R.sub.7, T.sub.1 and T.sub.2 (T.sub.1 and T.sub.2 together with the C atom which bonds them) is in particular cyclohexyl.

C.sub.2 -C.sub.4 Hydroxyalkyl R.sub.7 is, for example, 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C.sub.6 -C.sub.10 Aryl R.sub.7, T.sub.1 and T.sub.2 is especially phenyl or .alpha.- or .beta.-naphthyl, which are unsubstituted or substituted by halogen or C.sub.1 -C.sub.4 alkyl.

C.sub.2 -C.sub.12 alkylene R.sub.7 is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

C.sub.4 -C.sub.12 Alkenylene R.sub.7 is especially 2-butenylene, 2-pentenylene or 3-hexenylene.

C.sub.6 -C.sub.12 Arylene R.sub.7 is, for example, o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

C.sub.2 -C.sub.12 Alkanoyl Z' is, for example, propionyl, butyryl, octanoyl or dodecanoyl but preferably acetyl.

C.sub.2 -C.sub.10 Alkylene, C.sub.6 -C.sub.15 arylene or C.sub.6 -C.sub.12 cycloalkylene X is as defined under (b).

Examples of polyalkylpiperidine light stabilizers of this category are the following compounds:

(50) 3-Benzyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione

(51) 3-n-Octyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione

(52) 3-Allyl-1,3,8-triaza-1,7,7,9,9-pentamethylspiro[4.5]decane-2,4-dione

(53) 3-Glycidyl-1,3,8-triaza-7,7,8,9,9-pentamethylspiro[4.5]decane-2,4-dione

(53a) 2-iso-Propyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxo-spiro[4.5]decane

(53b) 2-Butyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane

(53c) 2-Isopropyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4.5]decane

(53d) 2-Butyl-7,7,9,9-tetramethyl-1-oxa-4,8-diaza-3-oxospiro[4.5]decane

or the compounds of the following formulae: ##STR7## (e) Light stabilizers of the formula (VI) ##STR8## in which n is the number 1 or 2 and R.sub.8 is a group of the formula ##STR9## in which R is as defined under formula (I), R.sub.1 is as defined under (a), Y is --O-- or --NR.sub.11 --, A is C.sub.2 -C.sub.6 alkylene or --(CH.sub.2).sub.3 --O-- and p is the numbers 0 or 1, R.sub.9 is the groups R.sub.8, NR.sub.11 R.sub.12, --OR.sub.13, --NHCH.sub.2 OR.sub.13 or --N(CH.sub.2 OR.sub.13).sub.2, and R.sub.10, if n=1, is the groups R.sub.8 or R.sub.9, and if n=2, is the group --Y--D--Y--, in which D is C.sub.2 -C.sub.6 alkylene which can be interrupted by --N(R.sub.11)--, and R.sub.11 is C.sub.1 -C.sub.12 alkyl, cyclohexyl, benzyl or C.sub.1 -C.sub.4 hydroxyalkyl or a group of the formula ##STR10## R.sub.12 is C.sub.1 -C.sub.12 alkyl, cyclohexyl, benzyl or C.sub.1 -C.sub.4 hydroxyalkyl, R.sub.13 is hydrogen, C.sub.1 -C.sub.12 alkyl or phenyl and R.sub.14 is hydrogen, C.sub.1 -C.sub.12 alkyl, cyclohexyl, benzyl or phenyl, or R.sub.11 and R.sub.12 together are C.sub.4 -C.sub.5 alkylene or oxaalkylene, or R.sub.11 and R.sub.12 are each a group of the formula ##STR11##

Any C.sub.1 -C.sub.12 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethylhexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Any C.sub.1 -C.sub.4 hydroxyalkyl substituents are, for example, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 2-hydroxybutyl or 4-hydroxybutyl.

C.sub.2 -C.sub.6 Alkylene A is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene.

C.sub.4 -C.sub.5 Alkylene or oxaalkylene formed by R.sub.11 and R.sub.12 together is, for example, tetramethylene, pentamethylene or 3-oxa-pentamethylene.

Examples of polyalkylpiperidine light stabilizers of this category are the compounds of the following formulae: ##STR12## (f) Light stabilizers of the formula (VII) ##STR13## in which n is the number 1 or 2, R is as defined under formula (I) and R.sub.14, if n=1, is C.sub.4 -C.sub.18 alkyl, C.sub.7 -C.sub.12 aralkyl, the group --CO--R.sub.15 or C.sub.1 -C.sub.4 alkyl substituted by --CN, --COOR.sub.16, --OH, --OCOR.sub.17 or ##STR14## in which R.sub.15 is C.sub.1 -C.sub.12 alkyl, C.sub.2 -C.sub.4 alkenyl or phenyl, R.sub.16 is C.sub.1 -C.sub.18 alkyl and R.sub.17 is C.sub.1 -C.sub.18 alkyl, C.sub.2 -C.sub.10 alkenyl, cyclohexyl, benzyl or C.sub.6 -C.sub.10 aryl, or, if n=2, R.sub.14 is C.sub.4 -C.sub.12 alkylene, 2-but-1,4-enylene, xylylene, the group --(CH.sub.2).sub.2 --OOC--R.sub.18 --COO--(CH.sub.2).sub.2 -- or the group --CH.sub.2 --OOC--R.sub.19 --COO--CH.sub.2 --, in which R.sub.18 is C.sub.2 -C.sub.10 alkylene, phenylene or cyclohexylene and R.sub.19 is C.sub.2 -C.sub.10 alkylene, xylylene or cyclohexylene.

Any C.sub.1 -C.sub.12 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl or n-dodecyl.

Any C.sub.1 -C.sub.18 alkyl substituents can be, for example, the groups listed above and, in addition, also, for example, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Any C.sub.2 -C.sub.10 alkylene groups are, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene or decamethylene.

C.sub.4 -C.sub.18 Alkyl R.sub.14 is, for example, n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, 1,1-dimethyl-2-tert.-butylethyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

As C.sub.1 -C.sub.4 alkyl substituted by --CN, R.sub.14 is, for example, cyanomethyl, cyanoethyl, 3-cyano-n-propyl or 4-cyano-n-butyl.

C.sub.4 -C.sub.12 Alkylene R.sub.14 is, for example, 2,2-dimethylpropylene, tetramethylene, hexamethylene, octamethylene, decamethylene or dodecamethylene.

C.sub.7 -C.sub.12 Aralkyl R.sub.14 is especially phenethyl or p-methyl-benzyl or in particular benzyl.

C.sub.2 -C.sub.4 Alkenyl R.sub.15 is, for example, vinyl, 1-propenyl, allyl, methallyl or 2-butenyl.

C.sub.2 -C.sub.10 Alkenyl R.sub.17 is, for example, the groups listed for alkenyl R.sub.15 and, in addition, also, for example, crotyl, 2-hexenyl, 2-octenyl or 2-decenyl.

C.sub.6 -C.sub.10 Aryl R.sub.17 is, for example, phenyl which is unsubstituted or substituted in the o-position or p-position by methyl, ethyl, isopropyl, n-butyl or tert.-butyl.

Examples of polyalkylpiperidine light stabilizers of this category are the following compounds:

(64) Bis-[.beta.-(2,2,6,6-tetramethylpiperidino)-ethyl] sebacate

(65) n-Octyl .alpha.-(2,2,6,6-tetramethyl-piperidino)-acetate

(66) 1,4-Bis-(2,2,6,6-tetramethylpiperidino)-2-butene.

(g) Light stabilizers of the formula (VIII) ##STR15## in which B is --N(R.sub.21)-- or --O--, E is C.sub.1 -C.sub.3 alkylene, the group --CH.sub.2 --CH(R.sub.22)--O--, in which R.sub.22 is hydrogen, methyl or phenyl, the group --(CH.sub.2).sub.3 --NH-- or a single bond, R is hydrogen or methyl, R.sub.1 is as defined under a), R.sub.20 is hydrogen or C.sub.1 -C.sub.18 alkyl and R.sub.21 is hydrogen, C.sub.1 -C.sub.18 alkyl, C.sub.5 -C.sub.7 cycloalkyl, C.sub.7 -C.sub.12 aralkyl, cyanoethyl, C.sub.6 -C.sub.10 aryl, the group --CH.sub.2 --CH(R.sub.22)--OH, in which R.sub.22 is as defined above, a group of the formula ##STR16## or a group of the formula ##STR17## in which G can be C.sub.2 -C.sub.6 alkylene or C.sub.6 -C.sub.12 arylene, or R.sub.21 is a group --E--CO--NH--CH.sub.2 --OR.sub.20.

Any C.sub.1 -C.sub.18 alkyl substituents are, for example, methyl, ethyl, n-propyl, n-butyl, sec.-butyl, tert.-butyl, n-hexyl, n-octyl, 2-ethyl-hexyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

Any C.sub.7 -C.sub.12 aralkyl substituents are, for example, phenethyl or especially benzyl.

C.sub.3 -C.sub.8 Alkenyl R.sub.1 can be, for example, 1-propenyl, allyl, methallyl, 2-butenyl, 2-pentenyl, 2-hexenyl, 2-octenyl or 4-tert.-butyl-2-butenyl.

C.sub.3 -C.sub.8 Alkynyl R.sub.1 is preferably propargyl. C.sub.1 -C.sub.8 Alkanoyl R.sub.1 is, for example, formyl, propionyl, butyryl, or octanoyl, but preferably acetyl, and C.sub.3 -C.sub.5 akenoyl R.sub.1 is in particular acryloyl.

C.sub.5 -C.sub.7 Cycloalkyl R.sub.21 is in particular cyclohexyl.

C.sub.6 -C.sub.10 Aryl R.sub.21 is in particular phenyl or .alpha.- or .beta.-naphthyl, which are unsubstituted or substituted by halogen or C.sub.1 -C.sub.4 alkyl. C.sub.1 -C.sub.3 Alkylene E is, for example, methylene, ethylene or propylene.

C.sub.2 -C.sub.6 Alkylene G is, for example, ethylene, propylene, 2,2-dimethylpropylene, tetramethylene or hexamethylene and C.sub.6 -C.sub.12 arylene G is o-, m- or p-phenylene, 1,4-naphthylene or 4,4'-diphenylene.

Examples of polyalkylpiperidine light stabilizers of this category are the following compounds:

(67) N-Hydroxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-urea

(68) N-Methoxymethyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-urea

(69) N-Methoxymethyl-N'-n-dodecyl-N'-2,2,6,6-tetramethylpiperidin-4-yl-urea

(70) O-(2,2,6,6-Tetramethylpiperidin-4-yl)-N-methoxymethyl-urethane.

(h) Polymeric compounds in which the recurring structural unit contains a polyalkylpiperidine radical of the formula (I), especially polyesters, polyethers, polyamides, polyamines, polyurethanes, polyureas, polyaminotriazines, poly(meth)acrylates, poly(meth)acrylamides and their copolymers which contain such radicals.

Examples of polyalkylpiperidine light stabilizers of this category are the compounds of the following formulae, in which m is the numbers 2 to about 200. ##STR18## (i) Compounds which contain, in their molecule, at least one 2-(2'-hydroxyphenyl)-benztriazole group or 2-hydroxybenzophenone group and at least one polyalkylpiperidine group.

Examples of polyalkylpiperidine light stabilizers of this category are the compounds of the following formulae: ##STR19##

It is also possible to use polyalkylpiperidine derivatives of categories (a)-(i) which enter into chemical bonds with the binder of the lacquer. This is the case if the polyalkylpiperidine derivative possesses a reactive group suitable for this purpose, for example a glycidyl group or a methylol group.

Examples of such compounds are the polyalkylpiperidine derivatives of category (g) which contain methylol groups or methylol-ether groups.

If the polyalkylpiperidine compounds are basic compounds, they can form salts with acids. Suitable acids for this purpose are, for example, inorganic acids or organic carboxylic, sulfonic, phosphonic or phosphinic acids, for example hydrochloric acid, boric acid, phosphoric acid, acetic acid, salicylic acid, toluenesulfonic acid or benzenephosphonic acid.

The polyalkylpiperidine compounds can form complexes with complex-forming metal compounds, for example with zinc-II acetate, cobalt-II acetylacetonate, nickel-II acetylacetonate, aluminium-III acetylacetonate, nickel-II benzoate or aluminum-III benzoylacetonate.

The customary stoving lacquers which are based on acrylic, alkyd or polyester resins, which, if desired, can be crosslinked with melamine/formaldehyde resins, epoxide resins or polyisocyanates, and which are described, for example in H. Wagner and H. F. Sarx, Lackkunstharze (Synthetic Lacquer Resins) can be used to prepare the two-layer uni-lacquer coatings stabilized according to the invention against light, humidity and oxygen.

The lacquers are applied by the conventional twocoat process, for example by spraying the undercoat lacquer containing the pigment in a layer thickness of 20-30.mu. onto coil-coated sheet metal, onto which a commercially available filler had previously been baked in a layer thickness of 20-30.mu., and, after air-drying for about 5 minutes, applying the topcoat lacquer wet-in-wet in a layer thickness of 35-40.mu.. After further air-drying for about 15 minutes, the lacquer is baked at 80.degree.-150.degree. C., depending on the nature of the crosslinking agent, for about 30 minutes.

The amount of polyalkylpiperidine derivative added is 0.01 to 5% by weight, based on the solvent-free binder, and preferably 0.5 to 1% by weight. The lacquers can contain the customary organic solvents or can be dissolved or dispersed in water or can be free from solvent.

The polyalkylpiperidine derivative to be used for stabilization according to the invention can be incorporated either only into the unpigmented topcoat lacquer or both into the unpigmented topcoat lacquer and into the undercoat lacquer containing pigment. Preferably, the light stabilizer is incorporated in the unpigmented topcoat lacquer. Topcoat lacquers based on acrylic/melamine resins are preferred. When preparing acrylic resins or acrylic-modified alkyd resins, polymerisable polyalkylpiperidine derivatives (for example compounds 7 and 42) can be copolymerised in the resin.

Incorporation into the lacquer binder can, however, also be effected by a polycondensation reaction during the preparation or in some cases during baking of the melamine, alkyd or polyester resins. Examples of co-condensable polyalkylpiperidine derivatives are compounds 1 and 63 and also 1-hydroxyethyl-4-hydroxy-2,2,6,6-tetramethylpiperidine or the compounds of the formulae ##STR20##

Incorporation by a polyaddition reaction can take place, for example, via the reaction of free carboxyl groups in the acrylic resin with glycidyl groups of the polyalkylpipeidine derivative. These carboxyl groups can be incorporated, for example, by the copolymerisation of acrylic acid.

In these cases there is the additional advantage that the light stabilizers are not removable by extraction or migration, so that their action is very longlasting.

In order to achieve maximum stability to light, it can be advantageous additionally to use other conventional light stabilizers. Examples of these are UV-absorbers of the type comprising the benzophenones, oxalanilides, benztriazoles or acrylic acid derivatives, or metal-containing light stabilizers, for example organic nickel compounds.

In the case of such combinations, the sum of all of the light stabilisers is 0.02 to 5% by weight and preferably 0.5 to 2% by weight, based on the lacquer resin.

Further additives which can be contained in the lacquer are antioxidants, for example those of the type comprising sterically hindered phenol derivatives or organic phosphorus compounds, for example phosphites, phosphonites or phosphines, plasticizers, flow control agents, curing accelerators, for example organic Co salts, Mn salts or Zr salts, thickeners, dispersing agents or adhesion improvers.

The stabilization according to the invention is particularly suitable for lacquer coatings on vehicles.

The following examples describe the use, according to the invention, of polyalkylpiperidine derivatives in two-layer uni-lacquer coatings. Parts and percentages are by weight.

dissolved in a solvent mixture consisting of 44% of xylene, 26% of petroleum ether and 30% of butyl acetate.

A commercially available filler (Standox filling primer) is first sprayed in a layer thickness of 30.mu. onto coil-coated sheet aluminium and is baked for 15 minutes at 175.degree. C. The pigmented undercoat lacquer is then sprayed on in a layer thickness of about 30.mu. and, after air-drying for 5 minutes, the unpigmented topcoat lacquer is applied wet-in-wet in a layer thickness of 35-40.mu.. The lacquer is then baked for 30 minutes at 130.degree. C.

The metal sheets thus obtained are stored for four weeks under standard climatic conditions (23.degree. C./50% relative atmospheric humidity) and then subjected to weathering in a QUV apparatus according to ASTM G53-77.

When the tests described below were carried out, the light stabilizer indicated in column II of the tables 1, 2 and 3 given below (the stabilisers being numbered in accordance with the examples mentioned in the description in the case of the polyalkylpiperidine compounds to be used according to the invention) was added, in each case in the amount indicated in % (based on the lacquer resin) in column I of the said tables, to the topcoat lacquer before the latter was applied.

The change in the blue-yellow value (.DELTA. BYV) is a measure of the yellowing of the lacquers. It is determined by calculation from the photometrically determined colour coordinates. The corresponding values are listed in column III of Tables 1, 2 and 3 given below.

The gloss values determined after weathering for 1,200 hours and in accordane with ASTM D 523 are listed in column IV of Tables 1, 2 and 3 given below.

After weathering, the metal sheets were examined for cloudiness, crazing, blistering and delamination. The findings are listed in column V of Tables 1, 2 and 3 given below.