Stabilization of coatings with N-hydroxy hindered amines

Claim 2

A stabilized ambient curable or acid catalyzed thermosetting coating composition containing an effective stabilizing amount of a hydroxyl substituted hindered amine compound containing the group where R is hydrogen or methyl.

Claim 3

A composition of claim 1, which contains hindered amine derivative corresponding to one of the formulae A-M wherein R is hydrogen or methyl, m is 1-4, when m is 1, R₁ is hydrogen, C₁-C₁₈ alkyl optionally interrrupted by one or more oxygen atoms, C₂-C₁₂ alkenyl, C₆-C₁₀ aryl, C₇-C₁₂ aralkyl, glycidyl, a monovalent acyl radical of an aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic or carbamic acid; or R₁ is a group wherein x is 0 or 1, or is a group wherein y is 2-4; when m is 2, R₁ is C₁-C₁₂ alkylene, C₄-C₁₂ alkenylene, xylylene, a divalent acyl radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic or dicarbamic acid; or R₁ is a group wherein D₁ and D₂ are independently hydrogen, C₁-C₈ alkyl, phenyl, benzyl or 3,5-di-tert.butyl-4-hydroxybenzyl and D₃ is an alkyl or alkenyl radical containing up to 18 carbon atoms; when m is 3, R₁ is a trivalent acyl radical of an aliphatic, unsaturated aliphatic, cycloaliphatic, or aromatic tricarboxylic acid; when m is 4, R₁ is a tetravalent acyl radical of a saturated or unsaturated aliphatic or aromatic tetracarboxylic acid; p is 1, 2 or 3, R₃ is hydrogen, C₁-C₁₂ alkyl, C₅-C₇ cycloalkyl, C₇-C₉ aralkyl, C₂-C₁₈ alkanoyl, C₃-C₅ alkenoyl or benzoyl; when p is 1, R₄ is hydrogen, C₁-C₁₈ alkyl, C₅-C₇ cycloalkyl, C₂-C₈ alkenyl unsubstituted or substituted by cyano, carbonyl or carbamide group, aryl, aralkyl, or it is glycidyl, a group of the formula -CH₂-CH(OH)-Z or -CONH-Z wherein Z is hydrogen, methyl or phenyl; or R₄ is a group of formula I or a group of the formula with h as 0 or 1; or R₃ and R₄ together are alkylene of 4 to 6 carbon atoms or 2-oxo-­alkylene or the cyclic acyl radical of an aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid, when p is 2, R₄ is C₂-C₁₂ alkylene, C₆-C₁₂ arylene, xylylene, a -CH₂CH(OH)-CH₂- group, or a group -CH₂-CH(OH)-CH₂-O-X-O-CH₂-CH(OH)-CH₂- wherein X is C₂-C₁₀ alkylene, C₆-C₁₅ arylene or C₆-C₁₂ cycloalkylene; or, provided that R₃ is not alkanoyl, alkenoyl or benzoyl, R₄ can also be a divalent acyl radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or can be the group -CO- or R₄ is a group of formula II where T₈ and T₉ are independently hydrogen, alkyl of 1 to 18 carbon atoms or a group of formula I, or T₈ and T₉ together are alkylene of 4 to 6 carbon atoms or 3-oxapentamethylene; when p is 3, R₄ is 2,4,6-triazinetriyl, n is 1 or 2 and when n is 1, R₅ and R′₅ are independently C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl, C₇-C₁₂ aralkyl, or R₅ is also hydrogen, or R₅ and R'₅ together are C₂-C₈ alkylene or hydroxyalkylene or C₄-C₂₂ acyloxyalkylene; when n is 2, R₅ and R′₅ together are (-CH₂)₂C(CH₂-)₂; R₆ is hydrogen, C₁-C₁₂ alkyl, allyl, benzyl, glycidyl or C₂-C₆ alkoxyalkyl; when n is 1, R₇ is hydrogen, C₁-C₁₂ alkyl, C₃-C₅ alkenyl, C₇-C₉ aralkyl, C₅-C₇ cycloalkyl, C₂-C₄ hydroxyalkyl, C₂-C₆ alkoxyalkyl, C₆-C₁₀ aryl, glycidyl, a group of the formula -(CH₂) t -COO-Q or of the formula -(CH₂) t -O-CO-Q wherein t is 1 or 2, and Q is C₁-C₄ alkyl or phenyl; or when n is 2, R₇ is C₂-C₁₂ alkylene, C₆-C₁₂ arylene, a group -CH₂CH(OH)-CH₂-O-X-O-CH₂­-CH(OH)-CH₂- wherein X is C₂-C₁₀ alkylene, C₆-C₁₅ arylene or C₆-C₁₂ cycloalkylene, or a group -CH₂CH(OZ′)CH₂-(OCH₂-CH(OZ′)CH₂)₂- wherein Z′ is hydrogen, C₁-C₁₈ alkyl, allyl, benzyl, C₂-C₁₂ alkanoyl or benzoyl; Q₁ is -N(R₈)- or -O-; E is C₁-C₃ alkylene, the group -CH₂-CH(R₉) -O- wherein R₉ is hydrogen, methyl or phenyl, the group -(CH₂)₃-NH- or a direct bond; R₁₀ is hydrogen or C₁-C₁₈ alkyl, R₈ is hydrogen, C₁-C₁₈ alkyl, C₅-C₇ cycloalkyl, C₇-C₁₂ aralkyl, cyano­ethyl, C₆-C₁₀ aryl, the group -CH₂-CH(R₉)-OH wherein R₉ has the meaning defined above; or R₈ is a group of the formula I or a group of the formula wherein G is C₂-C₆ alkylene or C₆-C₁₂ arylene, or R₈ is a group -E-CO-NH-CH₂-OR₁₀; T₃ is ethylene or 1,2-propylene, or is the repeating structural unit derived from an alpha-olefin copolymer with an alkyl acrylate or methacrylate; k is 2 to 100; T₄ has the same meaning as R₄ when p is 1 or 2, T₅ is methyl, T₆ is methyl or ethyl, or T₅ and T₆ together are tetramethylene or pentamethylene; M and Y are independently methylene or carbonyl; T₇ is the same as R₇; T₁₀ and T₁₁ are independently alkylene of 2 to 12 carbon atoms, or T₁₁ is a group of formula II; e is 2, 3 or 4 and T₁₂ is a group -N(R₅)-(CH₂) d -N(R₅)- or      -NH(CH₂) a - (CH₂) b - [(CH₂) c - ] f H where a, b and c are independently 2 or 3, d is 2 to 10 and f is 0 or 1; T₁₃ is the same as R₄ with the proviso that T₁₃ cannot be hydrogen when n is 1; E₁ and E₂, being different, each are -CO- or -N(E₅)-, and E₅ is hydrogen, C₁-C₄ alkyl or C₄-C₂₂-alkoxycarbonylalkyl; E₃ is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl, said phenyl or said naphthyl substituted by chlorine or by alkyl of 1 to 4 carbon atoms, or phenylalkyl of 7 to 12 carbon atoms, or said phenylalkyl substituted by alkyl of 1 to 4 carbon atoms, and E₄ is hydrogen, alkyl of 1 to 30 carbon atoms, phenyl, naphthyl or phenylalkyl of 7 to 12 carbon atoms, or E₃ and E₄ together are polymethylene of 4 to 17 carbon atoms, or said polymethylene substituted by up to four alkyl groups of 1 to 4 carbon atoms.

Claim 4

A composition according to claim 2, which contains a hindered amine derivative of formula A, B, G-K or M wherein R is hydrogen and T₅ and T₆ are methyl.

Claim 5

A composition according to claim 2, which contains a hindered amine derivative of formula A wherein R is hydrogen, m is 1, 2 or 4 and when m is 1, R₁ is an acyl radical of an aliphatic carboxylic acid having 12-18 C atoms or of an aromatic carboxylic acid having 7-15 C atoms and when m is 2, R₁ is a divalent acyl radical of an aliphatic dicarboxylic acid having 4-18 C atoms or of an aromatic dicarboxylic acid having 8-14 C atoms or R₂ is a group wherein D₁ is C₁-C₈ alkyl or 3,4-di-tert.butyl-4-hydroxybenzyl and D₂ is D₁ or hydrogen, and when m is 4, R₁ is tetravalent acyl radical of a butane- or pentane-tetracarboxylic acid.

Claim 6

A composition of claim 1, containing di(1-hydroxy-2,2,6,6-tetra­methylpiperidin-4-yl) sebacate.

Claim 7

A composition of claim 1, containing 1-hydroxy-2,2,6,6-tetramethyl­piperidin-4-yl stearate.

Claim 8

A composition of claim 1, containing di-(1-hydroxy-2,2,6,6-tetra­methylpiperidin-4-yl) diethylmalonate.

Claim 9

A composition of claim 1, containing di-(1-hydroxy-2,2,6,6-tetra­methylpiperidin-4-yl) isophthalate.

Claim 10

A composition of claim 1, containing tetrakis (1-hydroxy-2,2,6,6-­tetramethyl-4-piperidyl) 1,2,3,4-butane-tetracarboxylate.

Claim 11

A composition of claim 1, containing the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4′-hexamethylenebis­(amino-1-hydroxy-2,2,6,6-tetramethylpiperidine).

Claim 12

A composition according to claim 1, wherein the hindered amine derivative is contained in an amount of 0.1 to 10 % by weight, based on resin solids.

Claim 13

A composition according to claim 1, which additionally contains a UV absorber selected form the group consisting of benzophenones, benz­triazoles, acrylic acid derivatives, aryl-s-triazines, organic nickel compounds and oxanilides.

Claim 14

A composition according to claim 12, which contains a benzotriazole UV absorber selected from the group consisting of 2-[2-hydroxy-3,5-di-­(alpha,alpha-dimethylbenzyl)-phenyl]-2H-benzotriazole, 2-(2-hydroxy-­3,5-di-tert-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-alpha,-alpha-­dimethylbenzyl-5-tert-octylphenyl)-2H-benzotriazole, 2-(2-hydroxy-3-tert-­octyl-5,alpha,alpha-dimethylbenzylphenyl)-2H-benzotriazole, 2-(2-hydroxy-­5-tert-octylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-­(omega-hydroxy-octa(ethyleneoxy)-carbonyl)-ethylphenyl]-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole, 5-chloro-2-[2-­hydroxy-3,5-di(alpha,alpha-dimethylbenzyl)-phenyl-2H-benzotriazole, 5-chloro-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3-tert.butyl-5-(2-octyloxycarbonylethyl)-phenyl]-5-chloro-­2H-benzotriazole, 2-(2-hydroxy-3-sec.dodecyl-5-methyl-phenyl)-2H-benzo­triazole and hexamethylene di[β-(3-tert.butyl-4-hydroxy-5-[2-benzo­triazolyl]-phenyl)-propionate].

Claim 15

A coating composition according to claim 1, which is an ambient curable system based on an alkyd resin, thermoplastic acrylic resin, acrylic alkyd resin, polyester resin, or said resins modified with silicones, isocyanates, epoxides, isocyanurates, ketimines or oxazolidines, or the system is based on a cellulose ester or on an epoxide resin.

Claim 16

A coating composition according to claim 1, which is an acid catalyzed thermosetting system based on a hot crosslinkable acrylic, polyester, polyurethane, polyamide or alkyd resin.

Claim 17

A composition according to claim 1, which is an enamel for industrial finishes.

Claim 18

A composition according to claim 1, which is a refinishing enamel for automobiles.

Claim 19

18 A compound corresponding to the formulae A′ or B′ wherein R is hydrogen or methyl; m is 1-4; when m is 1, R₁ is wherein x is 0 or 1 and R₄ independently are C₁-C₈alkyl, or with y is 2-4; when m is 2, R₁ is wherein D₁ and D₂ are independently C₁-C₈alkyl, C₆-C₁₀aryl, C₇-C₁₂aralkyl or 3,5-di-t.butyl-4-hydroxybenzyl and D₂ is also hydrogen, D₃ is C₁-C₁₈­alkyl or C₂-C₁₈alkenyl, and D₄ is C₅-C₁₂cycloalkylene; when m is 3, R₁ is a trivalent acyl radical of an aliphatic, unsaturated aliphatic, cycloaliphatic or aromatic tricarboxylic acid having up to 20 C-atoms; when m is 4, R₁ is a tetravalent acyl radical of a saturated or un­saturated aliphatic or aromatic tetracarboxylic acid having up to 20 C-atoms; n is 1 or 2; when n is 1, R₂ and R₃ are independently hydrogen, C₁-C₁₂alkyl, C₂-C₁₂­alkenyl or C₇-C₁₂aralkyl; and when n is 2, R₂ and R₃ together are (-CH₂)₂C(CH₂-)₂.

Claim 20

18 A compound corresponding to the formulae A′ or B′ wherein R is hydrogen or methyl; m is 1-4; when m is 1, R₁ is wherein x is 0 or 1 and R₄ independently are C₁-C₈alkyl, or with y is 2-4; when m is 2, R₁ is wherein D₁ and D₂ are independently C₁-C₈alkyl, C₆-C₁₀aryl, C₇-C₁₂aralkyl or 3,5-di-t.butyl-4-hydroxybenzyl and D₂ is also hydrogen, D₃ is C₁-C₁₈­alkyl or C₂-C₁₈alkenyl, and D₄ is C₅-C₁₂cycloalkylene; when m is 3, R₁ is a trivalent acyl radical of an aliphatic, unsaturated aliphatic, cycloaliphatic or aromatic tricarboxylic acid having up to 20 C-atoms; when m is 4, R₁ is a tetravalent acyl radical of a saturated or un­saturated aliphatic or aromatic tetracarboxylic acid having up to 20 C-atoms; n is 1 or 2; when n is 1, R₂ and R₃ are independently hydrogen, C₁-C₁₂alkyl, C₂-C₁₂­alkenyl or C₇-C₁₂aralkyl; and when n is 2, R₂ and R₃ together are (-CH₂)₂C(CH₂-)₂.

Claim 21

A compound of claim 18, wherein R is hydrogen.

Claim 22

A compound of formula A′ of claim 18, wherein m is 2, R₁ is D₁ is C₁-C₈alkyl or 3,5-di-t.butyl-4-hydroxybenzyl and D₂ is D₁ or hydrogen.

Claim 23

A compound of formula A′ of claim 18, wherein R is hydrogen, m is 1, 2 or 4 and when m is 1, R₁ is a group when m is 2, R₁ is a group wherein D₁ is C₁-C₄alkyl or 3,5-di-t-butyl-4-hydroxybenzyl and D₂ is D₁ or hydrogen and D₄ is cyclohexylene, and when m is 4, R₁ is the tetravalent acyl radical of a butanetetra­carboxylic acid.

Claim 24

Di-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) methylmalonate according to claim 18.

Claim 25

Di-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) n -butylmalonate according to claim 18.

Claim 26

Di-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) diethylmalonate according to claim 18.

Claim 27

Di-(1-hydroxy-2,2,6,6-tetramethylpiperidin-4-yl) 2-(4-hydroxy-3,5-­di- tert -butylbenzyl)-2- n -butylmalonate according to claim 18.

Claim 28

Tetrakis(1-hydroxy-2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butane­tetracarboxylate according to claim 18.

Claim 29

Use of a compound of claim 18 as stabilizer for organic materials against actinic degradation.

Claim 30

Use according to claim 27 as stabilizer for organic polymers.

Claim 31

Use according to claim 27 as stabilizer for photographic layers.