Stabilization of photochromic systems

Abstract

Photochromic compositions are disclosed comprising a polymeric material, a photochromic dye, a hydroxyphenyl triazine UV absorber and, optionally, a further light stabilizer selected from the sterically hindered amines. These systems provide a reversible photochromic effect and show improved light stabilization and color fastness.

1 . Photochromic composition comprising 
 a) a polymeric material,    b) a photochromic dye and    c) a hydroxyphenyl triazine UV absorber (i) conforming to formula I, II, III, IV, V or (100)                          wherein    Y 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 Y is Z 1  or Z 2 ;      X is Z 1  or Z 2 ;    R 1  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, —SR 3 , —SOR 3  or —SO 2 R 3 ; or said alkyl, said cycloalkyl or said phenylalkyl substituted by one to three halogen, —R 4 , —OR 5 , —N(R 5 ) 2 , —COR 5 , —COOR 5 , —OCOR 5 , —CN, —NO 2 , —SR 5 , —SOR 5 , —SO 2 R 5  or —P(O)(OR 5 ) 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—, —NR 5 —, —CONR 5 —, —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;    R 3  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;    R 4  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;    R 5  is defined as is R 4 ; or R 5  is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms; or R 5  is a group for formula                          T is hydrogen, oxyl, hydroxyl, —OT 1 , alkyl of 1 to 24 carbon atoms, said alkyl substituted by one to three hydroxy; benzyl or alkanoyl of 2 to 18 carbon atoms;    T 1  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;    R 2  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 four halogen, epoxy, glycidyloxy, furyloxy, —R 4 , —OR 5 , —N(R 5 ) 2 , —CON(R 5 ) 2 , —COR 5 , —COOR 5 , —OCOR 5 , —OCOC(R 5 )═C(R 5 ) 2 , —C(R 5 )═CCOOR 5 , —CN, —NCO, or                          or combinations thereof; or said alkyl or said cycloalkyl interrupted by one to four epoxy, —O—, —NR 5 —, —CONR 5 —, —COO—, —OCO—, —CO—, —C(R 5 )═C(R 5 )COO—, —OCOC(R 5 )═C(R 5 )—, —C(R 5 )═C(R 5 )—, phenylene or phenylene-G-phenylene in which G is —O—, —S—, —SO 2 —, —CH 2 — or —C(CH 3 ) 2 — or combinations thereof, or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above; or R 2  is —SO 2 R 3  or —COR 6 ;    R 6  is straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 12 carbon atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms, —R 7 COOH or —NH—R 8 —NCO;    R 7  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                          R 1  and R 1 ′ are the same or different and are as defined for R 1 ;    R 2  and R 2 ′ are the same or different and are as defined for R 2 ;    X and X′ are the same or different and are as defined for X; Y and Y′ are the same or different and are as defined for 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—, —SO 2 —, —SO—E—SO—, —SO 2 —E—SO 2 —, —CH 2 —NH—E—NH—CH 2 — 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—R 8 —NHCO—, —CH 2 CH(OH)CH 2 O—R 9 —OCH 2 CH(OH)CH 2 —, —CO—R 10 —CO—, or —(CH 2 ) m —COO—R 11 —OOC—(CH 2 ) m —, where m is 1 to 3; or Q is                          R 9  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—, —SO 2 —, —CH 2 — or —C(CH 3 ) 2 —;    R 10  is alkylene of 2 to 10 carbon atoms; or said alkylene interrupted by one to four —O—, —S— or —CH═CH—; or R 10  is arylene of 6 to 12 carbon atoms;    R 11  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 —[(CH 2 ) m COO] 3 —R 12  where m is 1 to 3, and R 12  is an alkanetriyl of 3 to 12 carbon atoms;    when n is 4, Q is a group —[(CH 2 ) m COO] 4 —R 13  where m is 1 to 3, and R 14  is an alkanetetrayl of 4 to 12 carbon atoms;    Z 1  is a group of formula                          Z 2  is a group of formula                          where    r 1  and r 2  are 1;    R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22  and R 23  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 R 17  and R 18  or R 22  and R 23  together with the phenyl radical to which they are attached are a cyclic radical interrupted by one to three —O— or —NR 5 —;    x 2  is a number from 1 to 50;    A 1  is a group of the formula (101)                          or has one of the meanings given for T 10 ;    D 1  is C 4 -C 12  alkylene or said alkylene substituted by OH or interrupted by O or both substituted by OH and interrupted by O;    L 1  is C 1 -C 18 alkylene; C 5 -C 12 cycloalkylene; C 3 -C 18 alkenylene; or one of said residues substituted by phenyl, C 7 -C 11 alkylphenyl, C 5 -C 12 cycloalkyl, OH, halogen, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 18 alkenyloxy, COOH;    the R 50  are independently of each other H, OR 54  or OH, with the proviso that at least one of R 50  or R 53  is OH;    the R 54  are independently of each other hydrogen, C 1 -C 12 alkyl or a radical of formula —L 1 —CO—O—R 55 ;    R 55  is H, C 1 -C 18 alkyl, C 2 -C 12 hydroxyalkyl;    R 51  is hydrogen, C 1 -C 4 alkyl, Cl, phenyl or a group —OR 54 ;    R 52  is hydrogen or methyl;    R 53  is hydrogen, methyl, OH or OR 54 ; and    T 10  is the divalent acyl residue of an aliphatic or cycloaliphatic dicarboxylic acid of 13 to 60 carbon atoms;    and which contains at least one moiety of formula (101) and at least one moiety T 10 .    
     
     
         2 . A composition according to  claim 1  comprising 
 a) a polymeric material containing a photochromic dye and    c) a stabilizer combination of 
 i) a hydroxyphenyl triazine UV absorber and  
 ii) at least one further light stabilizer selected from the sterically hindered amines.  
   
     
     
         3 . Composition according to  claim 1 , which is an optical device, an architectural or vehicle glazing, a greenhouse film, a coating, or a construction element, in particular an ophthalmic lense.  
     
     
         4 . Composition according to  claim 1 , wherein component (a) is selectected from polyolefines, polycarbonate, polyesters, styrene polymers or copolymers, polyacrylates, cellulose esters, polyvinylalcohol, polyurethanes; in particular from polyethylene, polypropylene, polyethylene terephthalate, polystyrene, high impact polystyrene, polyvinylbutyrate, styrene-methacrylate, styrene-acrylonitrile, glycole modified polyethyleneterephtalate, polycarbonate, polymethylmethacrylate, polyvinylbutyral, ethylene-vinyl acetate copolymer, ethylene-butyl acrylate copolymer, and blends thereof.  
     
     
         5 . Composition according to  claim 1  containing a photochromic dye selected from the naphthopyranes, benzopyranes, spiropyranes or spirooxazines as component (b) in an amount of 0.001 to 10% by weight, with respect to the total weight of the polymeric material (a).  
     
     
         6 . Composition of  claim 2  wherein the sterically hindered amine (ii) is a compound comprising at least one radical of the formula IX, X and/or XI  
       
         
           
           
               
               
           
         
       
       in which 
 G is hydrogen or methyl, and  
 G 1  and G 2  are hydrogen, methyl or together are oxygen, and having a molecular weight of 400 g/mol or higher.  
 
     
     
         7 . Composition of  claim 1  which is a 2- or multilayer system wherein the UV absorber (i) is enriched in an upper layer containing no photochromic dye, while a lower layer contains the dye (b) and optionally the sterically hindered amine (ii).  
     
     
         8 . Composition of  claim 1  wherein the polymeric material (a) contains 0.001 to 10% by weight of the stabilizer component (c) comprising a ratio of UVA component (i) to sterically hindered amine component (ii) in the range 0.01 to 100 parts (i) per 1 part (ii).  
     
     
         9 . Composition of  claim 1  comprising as component (d) at least one further additive selected from antioxidants, phosphites and phosphonites, processing stabilizers, fillers, pigments, dyes, clarifiers, modifiers, acid scavengers, flame retardants, further light stabilizers.  
     
     
         10 . Process of stabilizing a photochromic system containing a photochromic dye in a polymer matrix against colour fading induced by irradiation, which process comprises incorporation of a hydroxyphenyl triazine UV absorber (i) and optionally a sterically hindered amine light stabilizer into the polymer matrix and/or into a polymer layer covering said polymer matrix, 
 wherein the hydroxyphenyl triazine UV absorber (i) is of formula I, II, III, IV, V or (100)                          wherein    Y 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 Y is Z 1  or Z 2 ;      X is Z 1  or Z 2 ;    R 1  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, —SR 3 , —SOR 3  or —SO 2 R 3 ; or said alkyl, said cycloalkyl or said phenylalkyl substituted by one to three halogen, —R 4 , —OR 5 , —N(R 5 ) 2 , —COR 5 , —COOR 5 , —OCOR 5 , —CN, —NO 2 , —SR 5 , —SOR 5 , —SO 2 R 5  or —P(O)(OR 5 ) 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—, —NR 5 —, —CONR 5 —, —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;    R 3  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;    R 4  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;    R 5  is defined as is R 4 ; or R 5  is also hydrogen or straight or branched chain alkyl of 1 to 24 carbon atoms, alkenyl of 2 to 24 carbon atoms; or R 5  is a group for formula                          T is hydrogen, oxyl, hydroxyl, —OT 1 , alkyl of 1 to 24 carbon atoms, said alkyl substituted by one to three hydroxy, benzyl or alkanoyl of 2 to 18 carbon atoms;    T 1  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;    R 2  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 four halogen, epoxy, glycidyloxy, furyloxy, —R 4 , —OR 5 , —N(R 5 ) 2 , —CON(R 5 ) 2 , —COR 5 , —COOR 5 , —OCOR 5 , —OCOC(R 5 )═C(R 5 ) 2 , —C(R 5 )═CCOOR 5 , —CN, —NCO, or                          or combinations thereof; or said alkyl or said cycloalkyl interrupted by one to four epoxy, —O—, —NR 5 —, —CONR 5 —, —COO—, —OCO—, —CO—, —C(R 5 )═C(R 5 )COO—, —OCOC(R 5 )═C(R 5 )—, —C(R 5 )═C(R 5 )—, phenylene or phenylene-G-phenylene in which G is —O—, —S—, —SO 2 —, —CH 2 — or —C(CH 3 ) 2 — or combinations thereof, or said alkyl or said cycloalkyl both substituted and interrupted by combinations of the groups mentioned above; or R 2  is —SO 2 R 3  or —COR 6 ;    R 6  is straight or branched chain alkyl of 1 to 18 carbon atoms, straight or branched chain alkenyl of 2 to 12 carbon atoms, phenoxy, alkylamino of 1 to 12 carbon atoms, arylamino of 6 to 12 carbon atoms, —R 7 COOH or —NH—R 8 —NCO;    R 7  is alkylene of 2 to 14 carbon atoms or phenylene;    R 8  is alkylene of 2 to 24 carbon atoms, phenylene, tolylene, diphenylmethane or a group                          R 1  and R 1 ′ are the same or different and are as defined for R 1 ;    R 2  and R 2 ′ are the same or different and are as defined for R 2 ;    X and X′ are the same or different and are as defined for X; Y and Y′ are the same or different and are as defined for 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—, —SO 2 —, —SO—E—SO—, —SO 2 —E—SO 2 —, —CH 2 —NH—E—NH—CH 2 — 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—R 8 —NHCO—, —CH 2 CH(OH)CH 2 O—R 9 —OCH 2 CH(OH)CH 2 —, —CO—R 10 —CO—, or —(CH 2 ) m —COO—R 11 —OOC—(CH 2 ) m —, where m is 1 to 3; or Q is                          R 9  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—, —SO 2 —, —CH 2 — or —C(CH 3 ) 2 —;    R 10  is alkylene of 2 to 10 carbon atoms; or said alkylene interrupted by one to four —O—, —S— or —CH═CH—; or R 10  is arylene of 6 to 12 carbon atoms;    R 11  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 —[(CH 2 ) m COO] 3 —R 12  where m is 1 to 3, and R 12  is an alkanetriyl of 3 to 12 carbon atoms;    when n is 4, Q is a group —[(CH 2 ) m COO] 4 —R 13  where m is 1 to 3, and R 14  is an alkanetetrayl of 4 to 12 carbon atoms;    Z 1  is a group of formula                          Z 2  is a group of formula                          where    r 1  and r 2  are 1;    R 14 , R 15 , R 16 , R 17 , R 18  , R 19 , R 20 , R 21 , R 22  and R 23  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 R 17  and R 18  or R 22  and R 23  together with the phenyl radical to which they are attached are a cyclic radical interrupted by one to three —O— or —NR 5 —;    x 2  is a number from 1 to 50;    A 1  is a group of the formula (101)                          or has one of the meanings given for T 10 ;    D 1  is C 4 -C 12  alkylene or said alkylene substituted by OH or interrupted by O or both substituted by OH and interrupted by O;    L 1  is C 1 -C 18 alkylene; C 5 -C 12 cycloalkylene: C 3 -C 18 alkenylene; or one of said residues substituted by phenyl, C 7 -C 11 alkylphenyl, C 5 -C 12 cycloalkyl, OH, halogen, C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 18 alkenyloxy, COOH;    the R 50  are independently of each other H, OR 54  or OH, with the proviso that at least one of R 50  or R 53  is OH;    the R 54  are independently of each other hydrogen, C 1 -C 12 alkyl or a radical of formula —L 1 —CO—O—R 55 ;    R 55  is H, C 1 -C 18 alkyl, C 2 -C 12 hydroxyalkyl;    R 51  is hydrogen, C 1 -C 4 alkyl, Cl, phenyl or a group —OR 54 ;    R 52  is hydrogen or methyl;    R 53  is hydrogen, methyl, OH or OR 54 ; and    T 10  is the divalent acyl residue of an aliphatic or cycloaliphatic dicarboxylic acid of 13 to 60 carbon atoms;    and which contains at least one moiety of formula (101) and at least one moiety T 10 .    
     
     
         11 . (canceled)