Stabilized adhesive compositions containing highly soluble, high extinction, photostable hydroxyphenyl-s-trianzine UV absorbers and laminated articles derived therefrom

• US 6,225,384 B1
• Filed: 04/17/2000
• Issued: 05/01/2001
• Est. Priority Date: 05/03/1999
• Status: Expired due to Term

• Current Assignee: CIBA Specialty Chemicals
• Original Assignee: CIBA Specialty Chemicals
• Inventors: Renz, Walter, Iyengar, Revathi, Suhadonlik, Joseph, Hayoz, Pascal, Ravichandran, Ramanathan, Wood, Mervin
• Primary Examiner(s): Cain, Edward J.
• Application Number:
  US09/551,033
• Time in Patent Office: 379 Days
• Field of Search: 524/100
• US Class Current: 524/100
• 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: B32B 2307/40 having particular optical properties light or UV resistant B32B2307/71
• CPC Class Codes: B32B 27/18 characterised by the use of special additives
• CPC Class Codes: B32B 7/12 using interposed adhesives or interposed materials with bonding properties
• CPC Class Codes: C09J 11/06 organic
• CPC Class Codes: C09J 11/08 Macromolecular additives

Abstract

Adhesive compositions are rendered stable against degradation caused by ultraviolet light through the incorporation of a highly soluble, high extinction, photostable hydroxyphenyl-s-triazine UV absorber or mixtures of s-triazine UV absorbers. An example of such compounds is 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α-cumylphenyl]-s-triazine (* denotes a mixture of octyloxy, nonyloxy and decyloxy groups). Such compounds exhibit high extinction, 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;

and

(b) an effective stabilizing amount of a highly soluble, high molar extinction and photostable s-triazine UV absorber of formula I, II, III, IV V or VI or a mixture thereof,

 

wherein

X and Y are independently phenyl, naphthyl, or said phenyl or said naphthyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof;

or X and Y are independently Z₁ or Z₂;

R₁ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, halogen, —

SR₃, —

SOR₃ or —

SO₂R₃;

or said alkyl, said cycloalkyl or said phenylalkyl substituted by one to three halogen, —

R₄, —

OR₅, —

N(R₅)₂, —

COR₅, —

COOR₅, —

OCOR₅, —

CN, —

NO₂, —

SR₅, —

SOR₅, —

SO₂R₅ or —

P(O)(OR₅)₂, morpholinyl, piperidinyl, 2,2,6,6-tetramethylpiperidinyl, piperazinyl or N-methylpiperidinyl groups or combinations thereof;

or said alkyl or said cycloalkyl interrupted by one to four phenylene, —

O—

, —

NR₅—

, —

CONR₅—

, —

COO—

, —

OCO—

or —

CO groups or combinations thereof;

or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above;

R₃ is alkyl of 1 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;

R₄ is aryl of 6 to 10 carbon atoms or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof;

cycloalkyl of 5 to 12 carbon atoms;

phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof;

or straight or branched chain alkenyl of 2 to 18 carbon atoms;

R₅ is defined as is R₄;

or R₅ is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms;

or R₅ is a group for formula

T is hydrogen, oxyl, hydroxyl, —

OT₁, alkyl of 1 to 24 carbon atoms, said alkyl substituted by one to three hydroxy;

benzyl or alkanoyl of 2 to 18 carbon atoms;

T₁ is alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkenyl of 2 to 24 carbon atoms, cycloalkenyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, a radical of a saturated or unsaturated bicyclic or tricyclic hydrocarbon of 7 to 12 carbon atoms or aryl of 6 o 10 carbon atoms or said aryl substituted by one to three alkyl of 1 to 4 carbon atoms;

R₂ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms;

or said alkyl or said cycloalkyl substitute by one to four halogen, epoxy, glycidyloxy, furyloxy, —

R₄, —

OR₅, —

N(R₅)₂, —

CON(R₅)₂, —

COR₅, —

COOR₅, —

OCOR₅, —

OCOC(R₅)═

C(R₅)₂, —

C(R₅)═

CCOOR₅, —

CN, —

NCO, or

 

or combinations thereof;

or said alkyl or said cycloalkyl interrupted by one to four epoxy, —

O—

, —

NR₅—

, —

CONR₅—

, —

COO—

, —

OCO—

, —

CO—

, —

C(R₅)═

C(R₅)COO—

, —

OCOC(R₅)═

C(R₅)—

, —

C(R₅)═

C(R₅)—

, phenylene or phenylene-G-phenylene in which G is —

O—

, —

S—

, —

SO₂—

, —

CH₂—

or —

C(CH₃)₂—

or combinations thereof, or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above;

or R₂ is —

SO₂R₃ or —

COR₆;

R₆ is straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 12 carbon atoms, phenoxy, alkyl amino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms, —

R₇COOH or —

NH—

R₈—

NCO;

R₇ is alkylene of 2 to 14 carbon atoms or phenylene;

R₈ is alkylene of 2 to 24 carbon atoms, phenylene, tolylene, diphenylmethane or a group

R₁, R₁′ and

R₁″

are the same or different and are as defined for R₁;

R₂, R₂′ and

R₂″

are the same or different and are as defined for R₂;

X, X′

, Y and Y′

are the same or different and are as defined for X and Y;

t is 0 to 9;

L is straight or branched alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene substituted or interrupted by cyclohexylene or phenylene;

or L is benzylidene;

or L is —

S—

, —

S—

S—

, —

S—

E—

S—

, —

SO—

, —

SO₂—

, —

SO—

E—

SO—

, —

SO₂—

E—

SO₂—

, —

CH₂—

NH—

E—

NH—

CH₂—

or

E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene interrupted or terminated by cycloalkylene of 5 to 12 carbon atoms;

n is 2, 3 or 4;

when n is 2;

Q is straight or branched alkylene of 2 to 16 carbon atoms;

or said alkylene substituted by one to three hydroxy groups;

or said alkylene interrupted by one to three —

CH═

CH—

or —

O—

;

or said alkylene both substituted and interrupted by combinations of the groups mentioned above;

or Q is xylylene or a group —

CONH—

R₈—

NHCO—

, —

CH₂CH(OH)CH₂O—

R₉—

OCH₂CH(OH)CH₂—

, —

CO—

R₁₀—

CO—

, or —

(CH₂)_m—

COO—

R₁₁—

OOC—

(CH₂)_m—

, where m is 1 to 3;

or Q is

R₉ is alkylene of 2 to 50 carbon atoms;

or said alkylene interrupted by one to ten —

O—

, phenylene or a group -phenylene-G-phenylene in which G is —

O—

, —

S—

, —

SO₂—

, —

CH₂—

or —

C(CH₃)₂—

;

R₁₀ is alkylene of 2 to 10 carbon atoms, or said alkylene interrupted by one to four —

O—

, —

S—

or —

CH═

CH—

;

or R₁₀ is arylene of 6 to 12 carbon atoms;

R₁₁ is alkylene of 2 to 20 carbon atoms or said alkylene interrupted by one to eight —

O—

;

when n is 3, Q is a group —

[(CH₂)_mCOO]₃—

R₁₂ where m is 1 to 3, and R₁₂ is an alkanetriyl of 3 to 12 carbon atoms;

when n is 4, Q is a group —

[(CH₂)_mCOO]₄—

R₁₃ where m is 1 to 3, and R₁₄ is an alkanetetrayl of 4 to 12 carbon atoms;

Z₁ is a group of formula

Z₂ is a group of formula

 

where

r₁ and r₂ are independetly of each other 0 or 1;

R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are independently of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl;

or R₁₇ and R₁₈ or R₂₂ and R₂₃ together with the phenyl radical to which they are attached are a cyclic radical interrupted by one to three —

O—

or —

NR₅—

; and

with the proviso that the s-triazine of formula I, II, III, IV, V or VI or a mixture thereof exhibits enhanced durability and low loss of absorbance when exposed to actinic radiation as witnessed by an absorbance loss of less than 0.5 absorbance units after exposure for 1050 hours or less than 0.7 absorbance units after exposure for 1338 hours in a Xenon Arc Weather-Ometer.

2. A composition according to claim 1 wherein the s-triazine of component (b) is of formula I where

X and Y are the same or different and are phenyl or said phenyl substituted by one to three alkyl of 1 to 6 carbon atoms, halogen, hydroxy or alkoxy of 1 to 12 carbon atoms; or Z₁ or Z₂;

R₁ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, phenylalkyl of 7 to 15 carbon atoms or halogen;

R₂ is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms or cycloalkyl of 5 to 12 carbon atoms;

or said alkyl or said cycloalkyl substituted by one to three —

R₄, —

OR₅, —

COOR₅, —

OCOR₅ or combinations thereof;

or said alkyl or cycloalkyl interrupted by one to three epoxy, —

O—

, —

COO—

, —

OCO—

or —

CO—

;

R₄ is aryl of 6 to 10 carbon atoms or said aryl substituted by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof;

cycloalkyl of 5 to 12 carbon atoms;

phenylalkyl of 7 to 15 carbon atoms or said phenylalkyl substituted on the phenyl ring by one to three halogen, alkyl of 1 to 8 carbon atoms, alkoxy of 1 to 8 carbon atoms or combinations thereof;

R₅ is defined as is R₄;

or R₅ is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms;

Z₁ is a group of formula

Z₂ is a group of formula

 

where

r₁ and r₂ are each 1; and

R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are independently of one another hydrogen, hydroxy, cyano, alkyl of 1 to 20 carbon atoms, alkoxy of 1 to 20 carbon atoms, phenylalkyl of 7 to 15 carbon atoms, cycloalkyl of 5 to 12 carbon atoms, cycloalkoxy of 5 to 12 carbon atoms, halogen, haloalkyl of 1 to 5 carbon atoms, sulfo, carboxy, acylamino of 2 to 12 carbon atoms, acyloxy of 2 to 12 carbon atoms, or alkoxycarbonyl of 2 to 12 carbon atoms or aminocarbonyl.

3. A composition according to claim 1 wherein the s-triazine of component (b) is of formula II where

X is phenyl, naphthyl or said phenyl or said naphthyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof;

or X is Z₁;

R₁ and R₁′

are independently as defined for R₁; and

R₂ and R₂′

are independently as defined for R₂.

4. A composition according to claim 1 wherein the s-triazine of component (b) is of formula IIII where

R₁, R₁′

and R₁″

are independently as defined for R₁; and

R₂, R₂′ and

R₂″

are independently as defined for R₂.

5. A composition according to claim 1 wherein the s-triazine of component (b) is of formula VI where

X and Y are independently phenyl or said phenyl substituted by one to three alkyl of 1 to 6 carbon atoms, by halogen, by hydroxy or by alkoxy of 1 to 6 carbon atoms or by mixtures thereof;

or X and Y are independently Z₁, or Z₂; and

L is straight or branched alkylene of 1 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms or alkylene substituted or interrupted by cyclohexylene or phenylene.

6. A composition according to claim 1 wherein the s-triazine of component (b) is of formula I where

X and Y are the same or different and are phenyl or said phenyl substituted by one to three alkyl of 1 to 6 carbon atoms;

Z₁ or Z₂;

R₁ is hydrogen or phenylalkyl of 7 to 15 carbon atoms;

R₂ is hydrogen, straight or branched chain alkyl of 1 to 18 carbon atoms;

or said alkyl substituted by one to three —

R₄, —

OR₅ or mixtures thereof;

or said alkyl interrupted by one to eight —

O—

or —

COO—

;

R₄ is aryl of 6 to 10 carbon atoms;

R₅ is hydrogen;

Z₁ is a group of formula

Z₂ is a group of formula

 

where

r₁ and r₂ are each 1; and

R₁₄, R₁₅, R₁₆, R₁₇, R₁₈, R₁₉, R₂₀, R₂₁, R₂₂ and R₂₃ are each hydrogen.

7. A composition according to claim 1 wherein the s-triazine UV absorber of component (b) is

(1) 2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine;

(2) 2-phenyl-4-[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-6-[2-hydroxy-4-(3-sec-amyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;

(3) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-benzyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;

(4) 2,4-bis(2-hydroxy-4-butyloxyphenyl)-6-(2,4-di-butyloxyphenyl)-s-triazine;

(5) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α

-cumylphenyl]-s-triazine;

(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups)

(6) methylenebis-{2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-butyloxy-2-hydroxypropoxy)phenyl]-s-triazine}, methylene bridged dimer mixture bridged in the 3;

5′

, 5;

5′ and

3;

3′

positions in a 5;

4;

1 ratio;

(7) 2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine;

(8) 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-hexyloxy-5-α

-cumylphenyl)-s-triazine;

(9) 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-octyloxyphenyl)-s-triazine, CYASORB®

1164, Cytec;

(10) 2-(2,4,6-trimethylphenyl)-4,6-bis[2-hydroxy-4-(3-butyloxy-2-hydroxypropyloxy)-phenyl]-s-triazine;

(11) 2,4,6-tris[2-hydroxy-4-(3-sec-butyloxy-2-hydroxypropyloxy)phenyl]-s-triazine;

or

(12) the mixture prepared by the reaction of 2,4,6-tris(2,4-dihydroxyphenyl)-s-triazine and isooctyl α

-bromopropionate.

8. A composition according to claim 7 wherein the s-triazine UV absorber of component (b) is

the s-triazine UV absorber of component (b) is

(1) 2,4-bis(4-biphenylyl)-6-(2-hydroxy-4-octyloxycarbonylethylideneoxyphenyl)-s-triazine;

(5) 2,4-bis(2,4-dimethylphenyl)-6-[2-hydroxy-4-(3-nonyloxy*-2-hydroxypropyloxy)-5-α

-cumylphenyl]-s-triazine;

(* denotes a mixture of octyloxy, nonyloxy and decyloxy groups);

(7) 2,4,6-tris(2-hydroxy-4-isooctyloxycarbonylisopropylideneoxyphenyl)-s-triazine;

or

(12) the mixture prepared by the reaction of 2,4,6-tris(2,4-dihydroxyphenyl)-s-triazine and isooctyl α

-bromopropionate.

9. A composition according to claim 1 wherein the effective stabilizing amount of a s-triazine of formula I, II, III, IV, V or VI or a mixture thereof is 0.1 to 20% by weight based on the adhesive.

10. A composition according to claim 1 wherein the 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.

11. A composition according to claim 1 wherein the adhesive composition is present in a laminated or multilayer construction.

12. A composition according to claim 11 wherein the laminated or multilayer construction is selected from the group consisting of

(a) retroreflective sheets and signs and conformable marking sheets;

(b) solar control films of various construction;

(c) corrosion resistant silver mirrors and solar reflectors;

(d) reflective print labels;

(e) UV absorbing glasses and glass coatings;

(f) electrochromic devices;

(g) films/glazings;

(h) windscreens and intermediate layers; and

(I) optical films.

13. A composition according to claim 12 wherein the laminated or multilayer construction is selected from the group consisting of

(a) retroreflective sheets and signs and conformable marking sheets;

(b) solar control films of various construction;

(e) UV absorbing glasses and glass coatings;

(g) films/glazings; and

(h) windscreens and intermediate layers.

14. A composition according to claim 13 wherein the laminated or multilayer construction is selected from the group consisting of

(b) a solar control films of various construction;

and

(h) windscreens and intermediate layers.

15. A composition according to claim 1 wherein the adhesive of component (a) is a resin selected from the group consisting of

(i) polyurethanes;

(ii) polyacrylics;

(iii) epoxys;

(iv) phenolics;

(v) polyimides;

(vi) poly(vinyl butyral);

(vii) polycyanoacrylates;

(viii) polyacrylates;

(ix) ethylene/acrylic acid copolymers and their salts (ionomers);

(x) silicon polymers;

(xi) poly(ethylene/vinyl acetate);

(xii) atatic polypropylene;

(xiii) styrene-diene copolymers;

(xiv) polyamides;

(xv) hydroxyl-terminated polybutadiene;

(xvi) polychloroprene;

(xvii) poly(vinyl acetate);

(xviii) carboxylated styrene/butadiene copolymers;

(xix) poly(vinyl alcohol); and

(xx) polyesters.

16. A composition according to claim 1 wherein the adhesive is a resin selected from the group consisting of the polyurethanes, acrylics, epoxy resins, phenolics, polyimides, poly(vinyl butyral), polyolefins, polyacrylates, thermosets, vinyl polymers, styrene polymers and cyanoacrylates.

17. A composition according to claim 1 wherein the adhesive of component (a) is a resin selection from the group consisting of

poly(vinyl butyral), ethylene/vinyl acetate copolymers, polyacrylics, polyacrylates, natural rubber, polycyanoacrylates, poly(vinyl alcohol), styrene/butadiene rubber, phenolics, urea-formaldehyde polymers, epoxy resins, vinyl polymers, polyurethanes and styrene block copolymers.

18. A composition according to claim 17 wherein the adhesive of component (a) is a resin selected from the group consisting of

poly(vinyl butyral), ethylene/vinyl acetate copolymers, polyacrylics, polyacrylates, natural rubber, polycyanoacrylates, poly(vinyl alcohol), styrene/butadiene rubber, phenolics, vinyl polymers, polyurethanes and styrene block copolymers.

19. A composition according to claim 18 wherein the adhesive of component (a) is a polyacrylate.

20. 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.

21. A composition according to claim 20 wherein the amount of coadditive is from 0.025 to 5% by weight based on the adhesive.

22. A composition according to claim 21 wherein the amount of coadditive is from 0.1 to 3% by weight based on the adhesive.

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