2-[2-Hydroxy-3,5-di-(.alpha. ,.alpha.-dimethylbenzyl)-phenyl]-2H-benzotriazole and stabilized compositions

• US 4,315,848 A
• Filed: 10/01/1980
• Issued: 02/16/1982
• Est. Priority Date: 05/10/1979
• Status: Expired due to Term

• Current Assignee: Ciba Specialty Chemicals Corp (BASF SE)
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Winter, Roland A. E., Dexter, Martin
• Primary Examiner(s): Kight, III, John
• Assistant Examiner(s): White, R. A.
• Application Number:
  US06/192,741
• Time in Patent Office: 503 Days
• Field of Search: 260/45.8 NP, 260/45.8 NT, 260/45.8 NZ
• US Class Current: 524/91
• CPC Class Codes: C07C 37/14 by addition reactions, i.e. reactions involving at least one carbon-to-carbon unsaturated bond
• CPC Class Codes: C07C 39/15 with all hydroxy groups on non-condensed rings , e.g. phenylphenol
• CPC Class Codes: C07D 249/20 with aryl radicals directly attached in position 2
• CPC Class Codes: C08K 5/3435 Piperidines
• CPC Class Codes: C08K 5/3475 condensed with carbocyclic rings
• CPC Class Codes: C08L 2666/36 Nitrogen-containing compounds
• CPC Class Codes: C09B 29/10 from coupling components containing hydroxy as the only directing group
• CPC Class Codes: C09D 133/06 of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
• CPC Class Codes: C09D 7/48 Stabilisers against degradation by oxygen, light or heat
• CPC Class Codes: Y10T 428/31935 Ester, halide or nitrile of addition polymer

Abstract

2-[2-Hydroxy-3,5-di-(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole exhibits outstanding efficacy in protecting organic substrates from light induced deterioration as well as good resistance to loss by volatilization or exudation during the high temperature processing of stabilized compositions. The combination of the benzotriazole UV absorber with a hindered amine light stabilizer is particularly efficacious in protecting thermoset and thermoplastic acrylic resin automotive finishes and enamels.

Claims

1. An automotive topcoat finish, lacquer or enamel composition exhibiting retention of gloss and resistance to delamination on weathering which comprises

(a) a thermoplastic acrylic resin or a thermoset acrylic resin,

(b) 0.1 to 5% by weight of resin of a compound of the formula ##STR27## wherein T₁ is hydrogen or chloro, T₂ and T₃ are independently the group ##STR28## where T₄ is hydrogen or lower alkyl, T₅ is tert-octyl or the group ##STR29## T₆ has the same meaning as T₅, with the proviso that one of T₅ and T₆ must be tert-octyl, but both cannot be tert-octyl, and

(c) 0.1 to 5% by weight of resin of a hindered amine light stabilizer.

2. A composition according to claim 1 containing 0.5 to 2% by weight of component (b) based on resin, and 0.5 to 2% by weight of component (c) based on resin.

3. A composition according to claim 1 wherein T₄ in component (b) is hydrogen.

4. A composition according to claim 1 wherein component (b) is 2-[2-hydroxy-3,5-di(α

,α

-dimethylbenzyl)-phenyl]-2H-benzotriazole.

5. A composition according to claim 1 wherein component (c) is a light stabilizer of the formula (II) ##STR30## in which n is a number from 1-4 inclusive;

R is hydrogen or methyl;

R₁ is hydrogen, oxyl, C₁ -C₁₈ alkyl, C₃ -C₈ alkenyl, C₁ -C₈ alkynyl, C₇ -C₁₂ aralkyl, C₁ -C₈ alkanoyl, C₃ -C₅ alkenoyl, glycidyl or a group --CH₂ --CH(OH)--Z wherein Z is hydrogen, methyl or phenyl; and

R₂ when n is 1 is hydrogen, C₁ -C₁₈ alkyl optionally interrupted by one or more oxygen atoms, cyanoethyl, benzyl, glycidyl, a monovalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic carboxylic acid, or of carbamic acid or of a phosphorus-containing acid, or a monovalent silyl radical;

R₂ when n is 2 is C₂ -C₁₂ alkylene, C₄ -C₁₂ alkenylene, xylylene, a bivalent radical of an aliphatic, cycloaliphatic, araliphatic or aromatic dicarboxylic acid, of dicarbamic acid or of a phosphorus-containing acid, or a bivalent silyl radical;

R₂ when n is 3 is a trivalent radical of an aliphatic, cycloaliphatic or aromatic tricarboxylic acid, of an aromatic tricarbamic acid or of a phosphorus-containing acid, or a trivalent silyl radical; and

R₂ when n is 4 is a tetravalent radical of an aliphatic, cycloaliphatic or aromatic tetracarboxylic acid.

6. A composition according to claim 5 where in the light stabilizer of Formula II

n is the number 1 or 2;

R is hydrogen or methyl;

R₁ is hydrogen, C₁ -C₁₂ alkyl, allyl, benzyl, acetyl or acryloyl; and

R₂ when n is 1 is 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; and

R₂ when n is 2 is 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.

7. A composition according to claim 1 wherein compound (c) is a light stabiliser of the formula (III) ##STR31## in which n is the number 1 or 2;

R is hydrogen or methyl;

R₁ is hydrogen, oxyl, C₁ -C₁₈ alkyl, C₃ -C₈ alkenyl, C₃ -C₈ alkynyl, C₇ -C₁₂ aralkyl, C₁ -C₈ alkanoyl or C₃ -C₅ alkenoyl;

R₃ is hydrogen, C₁ -C₁₂ alkyl, C₅ -C₇ cycloalkyl, C₇ -C₈ aralkyl, C₂ -C₁₈ alkanoyl, C₃ -C₅ alkenoyl or benzoyl; and

R₄ when n is 1 is hydrogen, C₁ -C₁₈ alkyl, C₅ -C₇ cycloalkyl, C₂ -C₈ alkenyl which is unsubstituted or substituted by a cyano, carbonyl or carbamide group, or it is glycidyl, a group of the formula --CH₂ --CH(OH)--Z or of the formula --CONH--Z wherein Z is hydrogen, methyl or phenyl;

or R₄ when n is 2 is C₂ -C.sub. 12 alkylene, C₆ -C₁₂ arylene, xylylene, a --CH₂ --CH(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 bivalent radical of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid or dicarbamic acid, or can also be the group --CO--;

or R₃ and R₄ together when n is 1 can be the cyclic radical of an aliphatic or aromatic 1,2- or 1,3-dicarboxylic acid.

8. A composition according to claim 1 wherein component (c) is a light stabiliser of the formula (IV) ##STR32## in which n is the number 1 or 2;

R is hydrogen or methyl;

R₁ is hydrogen, oxyl, C₁ -C₁₈ alkyl, C₃ -C₈ alkenyl, C₃ -C₈ alkynyl, C₇ -C₁₂ aralkyl, C₁ -C₈ alkanoyl or C₃ -C₅ alkenoyl; and

R₅ when n is 1 is C₂ -C₈ alkylene or hydroxyalkylene or C₄ -C₂₂ acyloxyalkylene; and

R₅ when n is 2 is the group (--CH₂)₂ C(CH₂ --)₂.

9. A composition according to claim 1 wherein component (c) is a light stabiliser of the formula (V) ##STR33## in which n is the number 1 or 2;

R is hydrogen or methyl;

R₁ is hydrogen, oxyl, C₁ -C₁₈ alkyl, C₃ -C₈ alkenyl, C₃ -C₈ alkynyl, C₇ -C₁₂ aralkyl, C₁ -C₈ alkanoyl or C₃ -C₅ alkenoyl;

R₆ is hydrogen, C₁ -C₁₂ alkyl, allyl, benzyl, glycidyl or C₂ -C₆ alkoxyalkyl; and

R₇ when n is 1 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)_m --COO--Q or of the formula --(CH₂)_m --O--CO--Q wherein m is 1 or 2, and Q is C₁ -C₄ alkyl or phenyl;

or R₇ when n is 2 is C₂ -C₁₂ alkylene or C₆ -C₁₂ arylene, 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 a group --CH₂ CH(OZ'"'"')CH₂ --(OCH₂ --CH(OZ'"'"')CH₂)₂ -- wherein Z'"'"' is hydrogen, C₁ -C₁₈ alkyl, allyl, benzyl, C₂ -C₁₂ alkanoyl or benzoyl.

10. A composition according to claim 1 wherein component (c) is a light stabilizer of the formula (VI) ##STR34## in which n is the number 1 or 2;

and R₈ is a group of the formula ##STR35## in which R and R₁ are as defined under the formula (II), Y is --O-- or --NR₁₁ --, A is C₂ -C₆ alkylene; and

m is the number 0 or 1;

R₉ is the groups R₈, NR₁₁ R₁₂, --OR₁₃, --NHCH₂ OR₁₃ or --N(CH₂ OR₁₃)₂ ;

R₁₀ when n is 1 is the groups R₈ or R₉ ; and

R₁₀ when n is 2 is the group --Y--Q--Y-- wherein Q is C₂ -C₆ alkylene optionally interrupted by --N(R₁₄)--;

R₁₁ is C₁ -C₁₂ alkyl, cyclohexyl, benzyl or C₁ -C₄ hydroxyalkyl, or a group of the formula ##STR36## R₁₂ is C₁ -C₁₂ alkyl, cyclohexyl, benzyl, C₁ -C₄ hydroxyalkyl;

R₁₃ is hydrogen, C₁ -C₁₂ alkyl or phenyl; and

R₁₄ is hydrogen or the group --CH₂ OR₁₃ ;

or R₁₁ and R₁₂ together are C₄ -C₅ alkylene or oxaalkylene, or R₁₁ and R₁₂ are each a group of the formula ##STR37##

11. A composition according to claim 1 wherein component (c) is a light stabiliser of the formula (VII) ##STR38## in which n is the number 1 or 2;

R is hydrogen or methyl; and

R₁₄ when n is 1 is C₄ 14 C₁₈ alkyl, C₇ -C₁₂ aralkyl, the group --CO--R₁₅, or C₁ -C₄ alkyl which is substituted by --CN, --COOR₁₆, --OH, --OCOR₁₇ or ##STR39## wherein R₁₅ is C₁ -C₁₂ alkyl, C₂ -C₄ alkenyl or phenyl, R₁₆ is C₁ -C₁₈ alkyl, R₁₇ is C₁ -C₁₈ alkyl, C₂ -C₁₀ alkenyl, cyclohexyl, benzyl or C₆ -C₁₀ aryl;

or R₁₄ when n is 2 is C₄ 14 C₁₂ alkylene, 2-butenylene-1,4, xylylene, the group --(CH₂)₂ --OOC--R₁₈ --COO--(CH₂)₂ -- or the group --CH₂ --OOC--R₁₉ --COO--CH₂ -- wherein R₁₈ is C₂ -C₁₀ alkylene, phenylene or cyclohexylene, and R₁₉ is C₂ -C₁₀ alkylene, xylylene or cyclohexylene.

12. A composition according to claim 1 wherein component (c) is a light stabiliser of the formula (VIII) ##STR40## in which Q is --N(R₃)-- or --O--;

E is C₁ -C₃ alkylene, the group --CH₂ --CH(R₄)--O-- wherein R₄ is hydrogen, methyl or phenyl, the group --(CH₂)₃ --NH-- or a single bond;

R is hydrogen or methyl;

R₁ is hydrogen, C₁ -C₁₈ alkyl, C₃ -C₈ alkenyl, C₃ -C₈ alkynyl, C₇ -C₁₂ aralkyl, C₁ -C₈ alkanoyl, C₃ -C₅ alkenoyl or glycidyl;

R₂ is hydrogen or C₁ -C₁₈ alkyl;

R₃ is hydrogen, C₁ -C₁₈ alkyl, C₅ -C₇ cycloalkyl, C₇ -C₁₂ aralkyl, cyanoethyl, C₆ -C₁₀ aryl, the group --CH₂ --CH(R₄)--OH wherein R₄ has the meaning defined above, a group of the formula ##STR41## or a group of the formula ##STR42## wherein G can be C₂ -C₆ alkylene or C₆ -C₁₂ arylene;

or R₃ is a group --E--CO--NH--CH₂ --OR₂.

13. A composition according to claim 1 wherein component (c) is bis-(2,2,6,6-tetramethyl-4-piperidyl)sebacate.

14. A composition according to claim 1 wherein component (c) is bis(1,2,2,6,6-pentamethyl-4-piperidyl)2-n-butyl-2-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.