Benzotriazole UV absorbers having enhanced durability

• US 6,262,151 B1
• Filed: 07/12/2000
• Issued: 07/17/2001
• Est. Priority Date: 11/07/1996
• Status: Expired due to Fees

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Wolf, Jean-Pierre, Wood, Mervin G., Ravichandran, Ramanathan, Detlefsen, Robert E., Suhadolnik, Joseph, Debellis, Anthony, Iyengar, Revathi
• Primary Examiner(s): OSWECKI, JANE C
• Application Number:
  US09/614,527
• Time in Patent Office: 370 Days
• Field of Search: 524/89, 524/91, 524/94
• US Class Current: 524/89
• CPC Class Codes: B41M 5/124 using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
• CPC Class Codes: B41M 5/3375 Non-macromolecular compounds
• CPC Class Codes: B41M 5/392 Additives, other than colour forming substances, dyes or pigments, e.g. sensitisers, transfer promoting agents
• 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: C08K 5/3475 condensed with carbocyclic rings
• CPC Class Codes: C09D 7/48 Stabilisers against degradation by oxygen, light or heat
• CPC Class Codes: Y10S 430/132 Anti-ultraviolet fading

Abstract

Benzotriazole UV absorbers which are substituted at the 5-position of the benzo ring by an electron withdrawing group exhibit enhanced durability and very low loss rates when incorporated into automotive coatings. This is particularly the case when the 3-position of the phenyl ring is also substituted by phenyl or phenylalkyl such as α-cumyl. Compounds where the 5-position of the benzo ring are substituted by perfluoroalkyl such as trifluoromethyl are particularly of interest for both their enhanced durability and for their excellent solubility and excellent color properties in some thermoplastic compositions when the phenyl ring is substituted at the 3-position by hydrogen or tert-alkyl.

Claims

1. A composition stabilized against thermal, oxidative or light-induced degradation which comprises

(a) an organic material subject to thermal, oxidative or light-induced degradation, and

(b) an effective stabilizing amount of a compound of formula I, III or IV

wherein

G₁ is hydrogen or chloro,

G₂ is cyano, perfluoroalkyl of 1 to 12 carbon atoms or fluoro,

G₆ is perfluoroalkyl of 1 to 12 carbon atoms,

G₇ is hydrogen or perfluoroalkyl of 1 to 12 carbon atoms,

E₁ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight or branched chain alkenyl of 2 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms;

or E₁ is alkyl of 1 to 24 carbon atoms substituted by one or two hydroxy groups,

E₂ and E₂′

are independently 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, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by one to three alkyl of 1 to 4 carbon atoms;

or E₂ and E₂′

are independently said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more —

OH, —

OCOE₁₁, —

OE₄, —

NCO, —

NH₂, —

NHCOE₁₁, —

NHE₄ or —

N(E₄)₂, or mixtures thereof, where E₄ is straight or branched chain alkyl of 1 to 24 carbon atoms;

or said alkyl or said alkenyl interrupted by one or more —

O—

, —

NH—

or —

NE₄—

groups or mixtures thereof and which can be unsubstituted or substituted by one or more —

H, —

OE₄ or —

NH₂ groups or mixtures thereof;

n is 1 or 2,

when n is 1, E₅ is OE₆ or NE₇E₈, or

E₅ is —

PO(OE₁₂)₂, —

OSi(E₁₁)₃ or —

OCO—

E₁₁, or straight or branched chain C₁-C₂₄alkyl which is interrupted by —

O—

, —

S—

or —

NE₁₁ and which can be unsubstituted or substituted by —

OH or —

OCO—

E₁₁, C₅-C₁₂ cycloalkyl which is unsubstituted or substituted by —

OH, straight chain or branched C₂-C₁₈alkenyl which is unsubstituted or substituted by —

OH, C₇-C₁₅aralkyl, —

CH₂—

CHOH—

E₁₃ or glycidyl,

E₆ is hydrogen, straight or branched chain C₁-C₂₄alkyl which is unsubstituted or substituted by one or more OH, OE₄ or NH₂ groups, or —

OE₆ is —

(OCH₂CH₂)_wOH or —

(OCH₂CH₂)_wOE₂₁ where w is 1 to 12 and E₂₁ is alkyl of 1 to 12 carbon atoms,

E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by —

O—

, —

S—

or —

NE₁₁—

, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇ and E₈ together with the N atom are a pyrtolidine, piperidine, piperazine or morpholine ring,

E₅ is —

X—

(Z)_p—

Y—

E₁₅

wherein

X is —

O—

or —

N(E₁₆)—

,

Y is —

O—

or —

N(E₁₇)—

,

Z is C₂-C₁₂-alkylene, C₄-C₁₂-alkylene interrupted by one to three nitrogen atoms, oxygen atoms or a mixture thereof, 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(E₁₆)— and

—

N(E₁₇)—

, respectively,

E₁₅ is a group —

CO—

C(E₁₈)═

C(H)E₁₉ or, when Y is —

N(E₁₇)—

, forms together with E₁₇ a group —

CO—

CH═

CH—

CO—

), wherein E₁₈ is hydrogen or methyl, and E₁₉ is hydrogen, methyl or —

CO—

X—

E₂₀, wherein E₂₀ is hydrogen, C₁-C₁₂-alkyl or a group of the formula

wherein the symbols E₁, G₂, X, Z, m and p have the meanings defined above, and E₁₆ and E₁₇ independendy of one another are hydrogen, C₁-C₁₂-alkyl, C₃-C₁₂-alkyl interrupted by 1 to 3 oxygen atoms, or is cyclohexyl or C₇-C₁₅aralkyl, and E₁₆ together with E₁₇ in the case where Z is ethylene, also forms ethylene,

when n is 2, E₅ is one of divalent radicals —

O—

E—

O—

or —

N(E₁₁)—

E₁₀—

N(E₁₁)—

,

E₉ is C₂-C₈alkylene, C₄-C₈alkenylene, C₄alkynylene, cyclohexylene, straight or branched chain C₄-C₁₀alkylene which is interrupted by —

O—

or by —

CH₂—

CHOH—

CH₂—

O—

E₁₄—

O—

CH₂—

CHOH—

CH₂—

,

E₁₀ being straight or branched chain C₂-C₁₂alkylene which may be interrupted by —

O—

, cyclohexylene, or

or E₁₀ and E₁₁ with the two nitrogen atoms form a piperazine ring,

E₁₄ is straight or branched chain C₂-C₈alkylene, straight or branched chain C₄-C₁₀alkylene which is interrupted by —

O—

, cycloalkylene, arylene or

where E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms or E₇ and E₈ together are alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3-methyliminopentamethylene,

E₁₁ is hydrogen, straight or branched chain C₁-C₁₈alkyl, C₅-C₁₂cycloalkyl, straight or branched chain C₂-C₁₈alkenyl, C₆-C₁₄aryl or C₇-C₁₅aralkyl,

E₁₂ is straight or branched chain C₁-C₁₈alkyl, straight or branched chain C₃-C₁₈alkenyl, C₅-C₁₀cycloalkyl, C₆-C₁₆aryl or C₇-C₁₅aralkyl,

E₁₃ is H, straight chain or branched C₁-C₁₈alkyl which is substituted by —

PO(OE₁₂)₂, phenyl which is unsubstituted or substituted by OH, C₇-C₁₅aralkyl or —

CH₂OE₁₂,

L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, α

,α

,α

′

,α

′

-tetramethyl-m-xylylene or cycloalkylidene, and

with the proviso that when G₂ is CF₃ and E₁ is hydrogen, E₂ is not methyl.

2. A composition according to claim 1 wherein component (b) is a compound of formula I

wherein

G₁ is hydrogen,

G₂ is cyano, CF₃— or fluoro,

E₁ is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,

E₂ 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, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms;

or E₂ is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more —

OH, —

OCOE₁₁, —

OE₄, —

NCO, —

NH₂, —

NHCOE₁₁, —

NHE₄ or —

N(E₄)₂, or mixtures thereof, where E₄ is straight or branched chain alkyl of 1 to 24 carbon atoms;

or said alkyl or said alkenyl interrupted by one or more —

O—

, —

NH—

or —

NE₄—

groups or mixtures thereof and which can be unsubstituted or substituted by one or more —

OH, —

OE₄ or —

NH₂ groups or mixtures thereof;

or

is a compound of formula I wherein,

G₁ is hydrogen,

G₂ is CF₃-or fluoo,

E₁ is hydrogen or straight or branched alkyl of 4 to 24 carbon atoms, and

E₂ is as defined above.

3. A composition according to claim 1 wherein the compound of formula III is a compound of formula IIIA

wherein

G₁ is hydrogen,

G₂ is is CF₃—

or fluoro,

E₁ is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms,

E₅ is —

OE₆ or —

NE₇E₈, or

E₅ is —

X—

(Z)_p—

Y—

E₁₅

wherein

X is —

O—

or —

N(E₁₆)—

,

Y is —

O—

or —

N(E₁₇)—

,

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

m is 0, 1,2or3,

p is 1, or p is also zero when X and Y are —

N(E₁₆)— and

—

N(E₁₇)—

, respectively,

E₁₅ is a group —

CO—

C(E₁₈)═

C(H)E₁₉ or, when Y is —

N(E₁₇)—

, forms together with E₁₇ a group —

CO—

CH═

CH—

CO—

, wherein E₁₈ is hydrogen or methyl, and E₁₉ is hydrogen, methyl or —

CO—

X—

E₂₀, wherein E₂₀ is hydrogen, C₁-C₁₂-alkyl or a group of the formula

4. A composition according to claim 3 wherein component (b) is a compound of formula IV

wherein

G₆ is CF₃,

G₇ is hydrogen or CF₃,

E₂ and E₂′

are independently 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, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and

L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene, α

,α

,α

′

,α

′

-tetramethyl-m-xylylene or cycloalkylidene.

5. A composition according to claim 2 wherein component (b) is a compound of formula I

wherein

G₁ is hydrogen,

G₂ is CF₃—

,

E₁ is phenylalkyl of 7 to 15 carbon atoms, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 4 alkyl of 1 to 4 carbon atoms,

E₂ 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, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms;

or E₂ is said alkyl of 1 to 24 carbon atoms or said alkenyl of 2 to 18 carbon atoms substituted by one or more —

OH, —

OCOE₁₁, —

NH₂ or —

NHCOE₁₁, or mixtures thereof, or said alkyl or said alkenyl interrupted by one or more —

O— and

which can be unsubstituted or substituted by one or more —

OH, or is a cosmpound of formula I wherein,

G₁ is hydrogen,

G₂ is CF₃—

,

E₁ is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, and

E₂ is as defined above.

6. A composition according to claim 3 wherein the compound of formula III is a compound of formula IIIA

wherein

G₁ is hydrogen,

G₂ is CF₃—

,

E₁ is hydrogen, straight or branched alkyl of 4 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms,

E₅ is —

OE₆ or —

NE₇E₈ where

E₆ is hydrogen, straight or branched chain C₁-C₂₄alkyl which is unsubstituted or substituted by one or more OH groups, or —

OE₆ is —

(OCH₂CH₂)_wOH or —

(OCH₂CH₂)_wOE₂₁ where w is 1 to 12 and E₂₁ is alkyl of 1 to 12 carbon atoms, and

E₇ and E₈ are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C₃-C₁₈alkyl which is interrupted by —

O—

, —

S—

or —

NE₁₁—

, C₅-C₁₂cycloalkyl, C₆-C₁₄aryl or C₁-C₃hydroxylalkyl, or E₇ and E₈ together with the N atom are a pyrrolidine, pipeidine, piperazine or morpholine ring.

7. A composition according to claim 3 wherein component (b) is a compound of formula IV

wherein

G₆ is CF₃,

G₇ is hydrogen or CF₃,

E₂ and E₂′

are independently 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, phenyl, or said phenyl or said phenylalkyl substituted on the phenyl ring by 1 to 3 alkyl of 1 to 4 carbon atoms; and

L is methylene.

8. A composition according to claim 3 wherein component (b) is

(a) 5-trifluoromethyl-2-(2-hydroxy-3-α

-cumyl-5-tert-ctylphenyl)-2H-benzotriazole;

(b) 5-trifluoromethyl-2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

(c) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tertoctylphenyl)-2H-benzotriazole;

(d) 2,2′

-methylene-bis[6-(5-trifluoromethyl-2H-benzotriazol-2-yl)-4-tert-octylphenol];

(e) methylene-2-[4-tert-ctyl-6-(2H-benzotriazol-2-yl)phenol]2′

-[4-tert-octyl-6-(5-trifluoromethyl-2H-benzotriazol-2-yl)phenol];

(f) 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid;

(g) methyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;

(h) isooctyl 3-(5-trifluoromethyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamate;

(i) 5-trifluoromethyl-2-[2-hydroxy-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

(j) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acryloyloxypropyl)phenyl]-2H-benzotriazole;

(k) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacryloyloxypropyl)phenyl]-2H-benzotriazole;

(l) 5-trifluoromethyl-2-[2-hydroxy-5-(3-acrylylaminopropyl)phenyl]-2H-benzotriazole;

(m) 5-trifluoromethyl-2-[2-hydroxy-5-(3-methacrylylaminopropyl)phenyl]-2H-benzotriazole;

(n) 5-trifluoromethyl-2-(2-hydroxy-3-α

-cumyl-5-tert-butylphenyl)-2H-benzotriazole;

(o) 5-trifluoromethyl-2-(2-hydroxy-3-α

oumyl-5-nonylphenyl)2H-benzotriazole;

(p) 5-trfluormethyl-2-[2-hydroxy-3-α

-cumyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

(q) 5-trifluoromethyl-2-[2-hydroxy-3-α

-cumyl-5-(3-hydroxypropyl)phenyl]-2H-benzo triazole;

(r) 5-trifluoromethyl-2-(2-hydroxy-3,5ditert-amylphenyl)-2H-benzotriazole;

(s) 5-trifluoromethyl-2-(2-hydroxy-3,5-ditert-butylphenyl)-2H-benzotriazole;

(t) 5-trifluoromethyl-2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;

(u) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl)-2H-benzotriazole;

(v) 5-trifluoromethyl-2-[2-hydroxy-3-tert-butyl-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

(w) 5-tiitluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

(x) 5-trifluoromethyl-2-(2-hydroxy-3,5di-α

-cumylphenyl)-2H-benzotriazole;

or

(y) 5-fluoro-2-(2-hydroxy-3,5-di-α

-cumylphenyl)-2H-benzotriazole.

9. A composition according to claim 1 wherein the organic material is a natural, semi-synthetic or synthetic polymer or a polymer blend or a copolymer.

10. A composition according to claim 9 wherein the polymer is a polyolefin, polycarbonate, a styrenic, ABS, a nylon (polyamide), a polyester, a polyurethane, a polyacrylate, a rubber modified styrenic, poly(vinyl chloride), poly(vinyl butyral), polyacetal (polyoxymethylene), poly/ethylene/1,4-cyclohexylenedimethylene terephthalate (PETG) or an ethylene/acrylic acid copolymer or salts thereof.

11. A composition according to claim 10 wherein the polymer is a polyester.

12. A composition according to claim 11 wherein the polyester is poly(ethylene terephthalate), poly(butylene terephthalate) or poly(ethylene naphthalenedicarboxylate), or copolymer poly(ethylene/1,4-cyclohexylenedimethylene terephthalate) PETG.

13. A composition according to claim 9 wherein the polymer is a thermoplastic polymer.

14. A composition according to claim 10 wherein the polymer is is a polyolefin or polycarbonate.

15. A composition according to claim 14 wherein the polymer is polyethylene or polypropylene.

16. A composition according to claim 15 wherein the polymer is polypropylene.

17. A composition according to claim 1 which additionally contains an effective stabilizing amount of at least one other UV absorber selected from the group consisting the benzotriazoles, the s-triazines, hydroxy-benzophenones, the α

-cyanoacrylates, the oxanilides and benzoates.

18. A composition according to claim 17 wherein the other 2-hydroxyphenyl-2H-benzotriazole is selected from the group consisting of

2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole;

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

2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole;

2-(2-hydroxy-5-tert-octylphenyl)-2H-benzotriazole;

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

5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotriazole;

2-(2-hydroxy-3-sec-butyl-5-tert-butylphenyl)-2H-benzotriazole;

2-(2-hydroxy-4-octyloxyphenyl)-2H-benzotriazole;

2-(2-hydroxy-3-dodecyl-5-methylphenyl)-2H-benzotriazole;

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

2-[2-hydroxy-3,5-di(α

,α

-dimethylbenzyl)phenyl]-2H-benzotriazole;

[2-hydroxy-3-(α

,α

-dimethylbenzyl)-5-tert-octylphenyl]-2H-benzotriazole;

2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-ocma(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole; and

2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H- benzotniazole.

19. A composition according to claim 18 wherein the other benzotriazole is

2-(2-hydroxy-3,5-di-tert-amylphenyl)-2H-benzotriazole;

2-[2-hydroxy-3,5-di(α

,α

-dimethylbenzyl)phenyl]-2H-benzotriazole;

2-[2-hydroxy-3-(α

,α

-dimethylbenzyl)-5-tert-octylphenyll-2H-benzotriazole;

2-{2-hydroxy-3-tert-butyl-5-[2-(omega-hydroxy-octa(ethyleneoxy)carbonyl)ethyl]-phenyl}-2H-benzotriazole;

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

5-chloro-2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-2H-benzotnazole;

2-(2-hydroxy-5-tert-ctylphenyl)-2H-benzotriazole;

or

2-{2-hydroxy-3-tert-butyl-5-[2-(octyloxy)carbonyl)ethyl]phenyl}-2H-benzotriazole.

20. A composition according to claim 1 which also contains an effective stabilizing amount of a hindered amine.

21. A composition according to claim 10 wherein the polymer is a copolymer of ethylene/acrylic acid or an alkali metal, alkaline earth metal or transition metal salt thereof.