Stabilized adhesive compositions containing highly soluble, red-shifted, photostable benzotriazole UV absorbers and laminated articles derived therefrom

• US 6,187,845 B1
• Filed: 05/03/1999
• Issued: 02/13/2001
• Est. Priority Date: 05/03/1999
• Status: Expired due to Term

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Ravichandran, Ramanathan, Renz, Walter, Suhadolnik, Joseph, Iyengar, Revathi, Wood, Mervin Gale Jr.
• Primary Examiner(s): Szekely, Peter A.
• Application Number:
  US09/303,583
• Time in Patent Office: 652 Days
• Field of Search: 524/91, 548/259
• US Class Current: 524/91
• CPC Class Codes: B32B 17/10678 comprising UV absorbers or stabilizers, e.g. antioxidants
• CPC Class Codes: B32B 17/10743 containing acrylate (co)polymers or salts thereof
• CPC Class Codes: C08K 5/3475 condensed with carbocyclic rings
• CPC Class Codes: C09J 11/06 organic
• CPC Class Codes: F24S 2025/601 by bonding, e.g. by using adhesives
• CPC Class Codes: F24S 23/82 characterised by the material or the construction of the reflector
• CPC Class Codes: Y02E 10/40 Solar thermal energy, e.g. solar towers

Abstract

Adhesive compositions are rendered stable against degradation caused by ultraviolet light through the incorporation of selected highly soluble, red-shifted, photostable benzotriazole UV absorbers which absorb light strongly in the 350 to 400 nm range. These UV absorbers exhibit excellent photostability and are highly soluble in adhesive formulations. The laminated articles derived from these compositions include, for example, solar control films, films and glazings, UV absorbing glasses and glass coatings, windscreens, retroreflective sheetings and signs, solar reflectors, optical films and the like.

Claims

1. A stabilized adhesive composition, suitable for use as an adhesive layer in a laminated article or multilayer construction, which comprises

(a) an adhesive resin selected from the group consisting of the

(i) polyurethanes;

(ii) polyacrylics;

(vi) poly(vinyl butyral);

(viii) polyacrylates;

(xi) poly(ethylenelvinyl acetate);

(xvii) polytvinyl acetate); and

(xx) polyesters; and

(b) an effective stabilizing amount of a benzotriazole of formula I, II or III

wherein

G₁ and G₁′

are independently hydrogen or halogen, G₂ and G₂′

are independently perfluoroalkyl of 1 to 12 carbon atoms;

or G₂′

is also hydrogen,

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 —

OH, —

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) _wOE₂₁where 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 pyrrolidine, piperidine, piperazine

or morpholine ring,

2. A composition according to claim 1 wherein the adhesive of component (a) is poly(vinyl butyral).

3. A composition according to claim 1 wherein the benzotriazole compound of formula I is

wherein

G₁is 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 phenylallyl 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;

is a compound of formula I wherein,

G₁ is hydrogen,

G₂ is CF₃—

,

E₁ is hydrogen or straight or branched alkyl of 1 to 24 carbon atoms,

E₂ is as defined above.

4. A composition according to claim 1 wherein the benzotriazole compound is a compound of formula IIA

wherein

G₁ is hydrogen,

G₂ is is CF₃—

E₁ is hydrogen, straight or branched alkyl of 1 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms,

E₅ is —

OE₆ or —

NE₇E₈, or

E₅ is

5. A composition according to claim 1 wherein the benzotriazole is a compound of formula IIIA

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.

6. A composition according to claim 1 wherein the benzotriazole 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 compound of formula I

wherein,

G₁ is hydrogen,

G₂ is CF₃—

,

E₁ is hydrogen, straight or branched alkyl of 1 to 24 carbon atoms or phenylalkyl of 7 to 15 carbon atoms, and

E₂ is as defined above.

7. A composition according to claim 1 wherein the benzotriazole is a compound of formula IIA

wherein

G₁ is hydrogen,

G₂ is CF₃—

,

E₁ is hydrogen, straight or branched alkyl of 1 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)_wOE₂₁where 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, piperidine, piperazine or morpholine ring.

8. A composition according to claim 1 wherein the benzotriazole is a compound of formula IIIA

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.

9. A composition according to claim 1 wherein the benzotriazole is

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

-cumyl-5-tert-octylphenyl)-2H-benzo-triazole;

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

(c) 5-trifluoromethyl-2-(2-bydroxy-3,5-di-tert-octylphenyl)-2H-benzotriazole;

(d) 2,2′

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

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

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

(f) 3-(5-trifluoromethyl-2H-benzotiazol-2-yl)-5-tert-butyl-4-hydroxy-hydrocinnamic acid;

(g) methyl 3-(5-trifluoromethyl-2H-benzottiazol-2-yl)-5-tert-butyl4-hydroxy-hydrocinnamate;

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

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

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

-cumyl-5-tert-butylphenyl)-2H-benzo-triazole;

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

-cumyl-5-nonylphenyl)-2H-benzotriazole;

(p) 5-trifluoromethyl-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-benzotriazole;

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

(s) 5-trifluoromethyl-2-(2-hydroxy-3,5-di-tert-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-trifluoromethyl-2-[2-hydroxy-5-(2-hydroxyethyl)phenyl]-2H-benzotriazole;

or

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

-cumylphenyl)-2H-benzotriazole.

10. A composition according to claim 9 wherein the benzotriazole is

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

-cumyl-5-tert-octylphenyl)-2H-benzo-triazole;

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

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

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

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

-cumyl-5-tert-butylphenyl)-2H-benzo-triazole;

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

or

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

-cumylphenyl)-2H-benzotriazole.

11. A composition according to claim 1 wherein the effective stabilizing amount of a benzotriazole of formula I, II or III is 0.1 to 20% by weight based on the adhesive.

12. A composition according to claim 1 wherein the adhesive of component (a) is selected from the group consisting of the pressure sensitive adhesives, the rubber-based adhesives, the solvent or emulsion based adhesives, the hot melt adhesives and natural-product based adhesives.

13. A composition according to claim 1 wherein the adhesive of component (a) is a polyacrylate.

14. A composition according to claim 1 which additionally contains from 0.01 to 10% by weight based on the adhesive of a coadditive which is selected from the group consisting of the antioxidants, other UV absorbers, hindered amines, phosphites or phosphonites, hydroxylamines, nitrones, benzofuran-2-ones, thiosynergists, polyamide stabilizers, metal stearates, nucleating agents, fillers, reinforcing agents, lubricants, emulsifiers, dyes, pigments, optical brighteners, flame retardants, antistatic agents and blowing agents.

15. A composition according to claim 14 wherein the amount of coadditive is from 0.025 to 5% by weight based on the adhesive.

16. A composition according to claim 15 wherein the amount of coadditive is from 0.1 to 3% by weight based on the adhesive.

17. A composition according to claim 1 which additionally contains optional coadditives selected from the group consisting of plasticizers, adhesion promoters, waxes, petroleum waxes, elastomers, tackifier resins, oils, resins, polymers, rosin, modified rosin, hydrocarbon resins, terpene resins, paraffin wax, microcrystalline wax, synthetic hard wax and/or polyethylene wax.