Compositions stabilized with 5-thio-substituted benzotriazole UV-absorbers

• US 5,516,914 A
• Filed: 11/01/1993
• Issued: 05/14/1996
• Est. Priority Date: 02/12/1991
• Status: Expired due to Term

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: Ciba-Geigy Corporation (Novartis Ag)
• Inventors: Ravichandran, Ramanathan, Stevenson, Tyler A., Holt, Mark S., Winter, Roland A. E., von Ahn, Volker H.
• Primary Examiner(s): Higel, Floyd D.
• Application Number:
  US08/146,331
• Time in Patent Office: 925 Days
• Field of Search: 548/259, 548/307.1, 524/91, 524/99, 526/259
• US Class Current: 548/259
• CPC Class Codes: C07D 249/20 with aryl radicals directly attached in position 2
• CPC Class Codes: C07F 9/65188 condensed with carbocyclic rings or carbocyclic ring systems
• CPC Class Codes: C08F 220/387 and containing nitrogen and oxygen
• CPC Class Codes: C08K 5/3475 condensed with carbocyclic rings
• CPC Class Codes: C08K 5/378 containing heterocyclic rings

Abstract

2-(2-Hydroxyphenyl)-2H-benzotriazole UV-absorbers substituted at the 5-position of the benzo ring by a thioether group exhibit enhanced absorption in the near visible range (over 350 nm) allowing said compounds to be particularly effective in protecting polymer systems which are prone to degradation caused by actinic irradiation with wavelengths over 350 nm.

Claims

1. A compound of formula A ##STR9## wherein R₁ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight of branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms,

R₂ is

View Dependent Claims (2)

2. The compounds according to claim 1 which are

(s) an isomeric mixture of 3-[3-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamoyloxy]-2-hydroxypropyl methacrylate and 2-[3-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamoyloxy]-3-hydroxypropyl methacrylate.

3. A stabilized composition which comprises

(a) an organic material subject to degradation by exposure to the deleterious effects of actinic radiation, and

(b) an effective stabilizing amount of a compound of formula A, B or C ##STR11## wherein R₁ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight of branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms or phenylalkyl of 7 to 15 carbon atoms,

R₂ is straight or branched alkyl chain of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, hydroxyl, --OR₄ where R₄ is straight or branched chain alkyl of 1 to 24 carbon atoms;

or said alkyl substituted by one or more --OH, --OCO--R₁₁, --OR₄, --NCO or --NH₂ groups or mixtures thereof;

or said alkyl or said alkenyl interrupted by one or more --O--, --NH-- or --NR₄ -- groups or mixtures thereof and substituted by one or more --OH, --OR₄ or --NH₂ groups or mixtures thereof;

or R₂ is

space="preserve" listing-type="equation">--(CH.sub.2).sub.m --CO--X--(Z).sub.p --Y--R.sub.15

wherein

X is --O-- or --N(R₁₆)--,

Y is --O-- or --N(R₁₇)--,

Z is C₂ -C₁₂ -alkylene, C₄ -C₁₂ -alkylene interrupted by one to three nitrogen atoms, oxygen atoms or is C₃ -C₁₂ -alkylene, butenylene, butynylene, cyclohexylene or phenylene, each substituted by a hydroxyl group,

m is zero, 1 or 2,

p is 1, or p is also zero when X and Y are --N(R₁₆)-- and --N(R₁₇)--, respectively,

R₁₅ is a group --CO--C(R₁₈)═

C(H)R₁₉ or, when Y is --N(R₁₇)--, forms together with R₁₇ a group --CO--CH═

CH--CO--, wherein R₁₈ is hydrogen or methyl, and R₁₉ is hydrogen, methyl or --CO--X--R₂₀, wherein R₂₀ is hydrogen, C₁ -C₁₂ -alkyl or a group of the formula ##STR12## wherein the symbols R₁, R₃, X, Z, m and p have the meanings defined above, and R₁₆ and R₁₇ independently of one another are hydrogen, C₁ -C₁₂ -alkyl, C₃ -C₁₂ -alkyl interrupted by 1 to 3 oxygen atoms, or is cyclohexyl or C₇ -C₁₅ aralkyl, and R₁₆ together with R₁₇ in the case where Z is ethylene, also forms ethylene,

n is 1 or 2,

when n is 1, R₅ is Cl, OR₆ or NR₇ R₈, or

R₅ is --PO(OR₁₂)₂, --OSi(R₁₁)₃ or --OCO--R₁₁, or straight or branched chain C₁ -C₂₄ alkyl which is interrupted by --O--, --S-- or --NR₁₁ and which can be unsubstituted or substituted by --OH or --OCO--R₁₁, C₅ -C₁₂ cycloalkyl which is unsubstituted or substituted by --OH, straight chain or branched C₂ -C₁₈ alkenyl which is unsubstituted or substituted by --OH, C₇ -C₁₅ aralkyl, --CH₂ -CHOH--R₁₃ or glycidyl,

R₆ is hydrogen, straight or branched chain C₁ -C₂₄ alkyl which is unsubstituted or substituted by one or more OH, OR₄ or NH₂ groups, or --OR₆ is --(OCH₂ CH₂)_w OH or --(OCH₂ CH₂)_w OR₂₁ where w is 1 to 12 and R₂₁ is alkyl of 1 to 12 carbon atoms,

R₇ and R₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C₃ -C₁₈ alkyl which is interrupted by --O--, --S-- or --NR₁₁, C₅ -C₁₂ cycloalkyl, C₆ -C₁₄ aryl or C₁ -C₃ hydroxylalkyl, or R₇ and R₈ together with the N atom are a pyrrolidine, piperidine, piperazine or morpholine ring,

when n is 2, R₅ is one of divalent radicals --O--R₉ --O-- or --N(R₁₁)--R₁₀ --N(R₁₁)--,

R₉ is C₂ -C₈ alkylene, C₄ -C₈ alkenylene, C₄ alkynylene, cyclohexylene, straight or branched chain C₄ -C₁ alkylene which is interrupted by --O-- or by --CH₂ --CHOH--CH₂ --O--R₁₄ --O--CH₂ --CHOH--CH₂ --,

R₁₀ being straight or branched chain C₂ -C₁₂ alkylene uninterrupted or interrupted by --O--, cyclohexylene, or ##STR13## or R₁₀ and R₁₁ with the two nitrogen atoms form a piperazine ring,

R₁₄ is straight or branched chain C₂ -C₈ alkylene, straight or branched chain C₄ -C₁₀ alkylene which is interrupted by --O--, cycloalkylene, arylene or ##STR14## where R₇ and R₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms or R₇ and R₈ together are alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3-methyliminopentamethylene,

R₁₁ is hydrogen, straight or branched chain C₁ -C₁₈ alkyl, C₅ -C₁₂ cycloalkyl, straight or branched chain C₃ -C₈ alkenyl, C₆ -C₁₄ aryl or C₇ -C₁₅ aralkyl,

R₁₂ is straight or branched chain C₁ -C₁₈ alkyl, straight or branched chain C₃ -C₁₈ alkenyl, C₅ -C₁₀ cycloalkyl, C₆ -C₁₆ aryl or C₇ -C₁₅ aralkyl,

R₁₃ is H, straight chain or branched C₁ -C₁₈ alkyl which is substituted by --PO(OR₁₂)₂, phenyl which is unsubstituted or substituted by OH, C₇ -C₁₅ aralkyl or --CH₂ OR₁₂,

R₃ is alkyl of 8 to 20 carbon atoms, alkenyl of 3 to 18 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, aryl of 6 to 10 carbon atoms or said aryl substituted by one or two alkyl of 1 to 4 carbon atoms or 1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6 to 16 carbon atoms, and

space="preserve" listing-type="equation">T is --S--, --S--S-- or --S--E--S--,

where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms.

4. A composition according to claim 3 wherein the organic material is a synthetic resin.

5. A composition according to claim 4 wherein the synthetic resin is selected from the group consisting of the polystyrenes, graft copolymers of styrene, polyphenylene oxides, polyphenylene sulfides, polyurethanes, polyureas, polyimides, polyamide-imides, aromatic polyesters, polycarbonates, polysulfones, polyethersulfones, polyetherketones, alkyd resins, aminoplast resins and epoxy resins.

6. A composition according to claim 5 wherein the synthetic resin is an epoxy resin.

7. A composition according to claim 3 wherein the compound of component (b) is 5-n-dodecylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

8. A composition according to claim 3 wherein the compound of component (b) is 5-phenylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

9. A composition according to claim 3 wherein the compound of component (b) is 5-phenylthio-2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole.

10. A composition according to claim 3 wherein the compound of component (b) is 5-n-octylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole.

11. A composition according to claim 3 wherein the compound of component (b) is 5-phenylthio-2-(2-hydroxy-3,5-di-α

-cumylphenyl)-2H-benzotriazole.

12. A composition according to claim 3 wherein the compound of component (b) is 5-phenylthio-2-{2-hydroxy-3-tert-butyl-5-[2-(ω

-hydroxy-octa(ethyleneoxy)carbonylethyl]phenyl}-2H-benzotriazole;

ω

-hydroxy-poly(ethyleneoxy) 3-(5-phenylthio-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;

or poly(ethyleneoxy) bis[3-(5-phenylthio-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate)].

13. A composition according to claim 3 wherein the organic material is a coating system consisting of a lower layer of resin which contains an inorganic or organic pigment or mixture thereof and an upper clear layer of resin, and

(b) an effective stabilizing amount of a compound of formula A or B which is in either the upper resin or lower resin or in both resin layers.

14. A composition according to claim 13 wherein component (b) is

5-phenylthio-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole,

5-phenylthio-2-[2-hydroxy-3-tert-butyl-5-(β

-octyloxycarbonylethyl)phenyl]-2H-benzotriazole, 5-phenylthio-2-{2-hydroxy-3-tert-butyl-5-[2-(ω

-hydroxyocta(ethyleneoxy)-carbonylethyl]phenyl}-2H-benzotriazole, ω

-hydroxy-poly(ethyleneoxy) 3-(5-phenylthio-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, or

poly(ethyleneoxy) bis[3-(5-phenylthio-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate)].

15. A composition according to claim 14 wherein component (b) is

5-phenylthio-2-{2-hydroxy-3-tert-butyl-5-[2-(ω

-hydroxyocta(ethyleneoxy)-carbonylethyl]phenyl}-2H-benzotriazole, ω

-hydroxy-poly(ethyleneoxy) 3-(5-phenylthio-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate, or

poly(ethyleneoxy) bis[3-(5-phenylthio-benzotriazol-2-yl)-5-tert-butyl4-hydroxyhydrocinnamate)].

16. A composition according to claim 13 which additionally contain a UV absorber selected from the group consisting of the benzophenones, benzotriazoles, cyanoacrylic acid derivatives, hydroxyaryl-s-triazines, organic nickel compounds and oxanilides present in either the upper or lower resin layer or in both layers.

17. A composition according to claim 13 which additionally contains an effective stabilizing amount of a phenolic antioxidant in either the upper or lower resin layer or in both layers.

18. A composition according to claim 13 which additionally contains an effective stabilizing amount of a hindered amine in either the upper or lower resin layer or in both layers.

19. A composition according to claim 13 which additionally contains an effective stabilizing amount of a phosphite or phosphonite in either the upper or lower resin layer or in both layers.

20. A composition according to claim 12 which additionally contains a UV absorber selected from the group consisting of 2-[2-hydroxy-3,5-di--(α

,α

-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(ω

-hydroxy-octa(ethyleneoxy)carbonyl)ethylphenyl]-2H-benzotriazole, 2-[2-hydroxy-3-tert-butyl-5-(2-octyloxycarbonylethyl)phenyl]-2H-benzotriazole, 4,4'"'"'-dioctyloxyoxanilide, 2,2'"'"'-dioctyloxy-5,5'"'"'-di-tert-butyloxanilide, 2,2'"'"'-didodecyloxy-5,5'"'"'-di-tert-butyloxanilide, 2-ethoxy-2'"'"'ethyloxanilide, 2,6-bis(2,4-dimethylphenyl)-4-(2-hydroxy-4-octyloxyphenyl-s-triazine, 2,6-bis(2,4-dimethylphenyl)-4-(2,4-dihydroxyphenyl)-s-triazine, 2,4-bis(2,4-dihydroxyphenyl)-6-(4-chlorophenyl)-s-triazine, 2,6-bis(2,4-dimethylphenyl)-4-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropanoxy)phenyl]-s-triazine, and 2,2'"'"'-dihydroxy-4,4'"'"'-dimethoxybenzophenone.

21. A composition according to claim 14 which additionally contains a hindered amine selected from the group consisting of bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(1,2,2,6,6-pentamethylpiperidin-4-yl) sebacate, di(1,2,2,6,6-pentamethylpiperidin-4-yl) (3,5-di-tert-butyl-4-hydroxybenzyl)butylmalonate, the polycondensation product of 1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the polycondensation product of 2,4-dichloro-6-tert-octylamino-s-triazine and 4,4'"'"'-hexamethylenebis(amino-2,2,6,6-tetramethylpiperidine), N,N'"'"',N",N'"'"'"-tetrakis[(4,6-bis(butyl-(2,2,6,6-tetramethyl-piperidin-4-yl)amino)-s-triazine-2-yl]-1,10-diamino-4,7-diazadecane, di-(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, di-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) succinate, 1-octyloxy-2,2,6,6-tetramethyl-4-hydroxy-piperidine, poly-{[6-tert-octylamino-s-triazin-2,4-diyl][2-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino-hexamethylene-[4-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)imino], or 2,4,6-tris[N-(1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl)-n-butylamino]-s-triazine.

22. A composition according to claim 3 wherein the organic material is an enamel of high solids content used for an industrial finish.

23. A composition according to claim 3 wherein the organic material is used as a coil coating.

24. A composition according to claim 3 wherein the organic material is used as a penetrating wood finish.

25. A composition according to claim 3 wherein the organic material is used as a film-forming wood finish.

26. A methacrylate copolymer obtained by the addition polymerization of the isomeric mixture of 3-[3-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamoyloxy]-2-hydroxypropyl methacrylate and 2-[3-(5-phenylthio-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamoyloxy]-3-hydroxypropyl methacrylate.

27. A stabilized composition which comprises

(a) an organic material subject to degradation by exposure to the deleterious effects of actinic radiation, and

(b) an effective stabilizing amount of a copolymer according to claim 26.