Highly compatible hydroxyphenyltriazine uv-absorbers

Abstract

The present invention relates to highly compatible hydroxyphenyltriazine UV-absorbers and to their use in protecting plants in green houses and the protection of foodstuffs, beverages, pharmaceuticals, cosmetics, personal care products, shampoos and the like from the deleterious effects of ultraviolet radiation. It has been found that certain highly compatible tris-arly-s.triazines are especially effective towards this end when incorporated in the containers or films in which such materials are stored.

1 . A compound hydroxyphenyltriazine of formula (I) or (Ib)  
       
         
           
           
               
               
           
         
       
       or an oligomeric or polymeric hydroxyphenyltriazine conforming to the formula (II)  
       -[A-L-D-L] x -  (II) 
       in which 
 x is a number from 1 to 50;  
 A is a group of the formula (IIIb)  
                     
 or has one of the meanings given for D, wherein formula (II) contains at least one A conforming to formula (IIIb);  
 D is a divalent residue containing 2 to 60 carbon atoms comprising an aliphatic, cycloaliphatic or aromatic hydrocarbon, or said aliphatic residue substituted by OH or interrupted by O or both substituted by OH and interrupted by O; and in case that D bonds to the carbon atom of L, D also comprises methylene or a direct bond;  
 L stands for an ester linkage group;  
 the R 1  are independently of each other H, OR 7 , with the proviso that at least one of R 1  or R 13  is OH;  
 the R 7  are independently of each other hydrogen, C 1 -C 12 alkyl or a radical of formula (III)  
                     
 wherein in formula (I) at least one of the R 7  is a radical of formula (III);  
 R 8  is hydrogen, C 1 -C 18 alkyl; C 5 -C 12 cycloalkyl; C 2 -C 18 alkenyl; phenyl; C 7 -C 11 phenylalkyl; C 7 -C 11 alkylphenyl; C 1 -C 18 alkyl substituted by phenyl, OH, halogen; C 1 -C 18 alkoxy, C 5 -C 2 cycloalkoxy, C 3 -C 18 alkenyloxy or COOH;  
 Y is —CO— or C 1 -C 12 alkylene;  
 R 9  , if Y is —CO—, is C 20 -C 60  alkyl, C 20 -C 60 alkyl substituted by OH and/or interrupted by O, or is  
 C 20 -C 60 alkenyl, or is a group of formula (IV)  
                     
 wherein m is a number from 1 to 20;  
 R 9 , if Y is alkylene, is C 20 -C 60 alkanoyl;  
 R 2 , R 3 , R 4 , R 5  and R 6  are independently of each other hydrogen, C 1 -C 38 alkyl which is unsubstituted or substituted by hydroxy or C 1 -C 8 alkoxy; or  
 C 1 -C 38 alkyl which is interrupted by an oxygen atom or a N(C 1 -C 8 )alkyl group; phenyl or C 7 -C 12 phenylalkyl which are unsubstituted or substituted by hydroxy or C 1 -C 8 alkyl;  
 R 10  is hydrogen, C 1  -C 4 alkyl, Cl, phenyl or a group —OR 7 ;  
 R 11  is hydrogen or methyl; R 13  is hydrogen, methyl, OH or OR 7 ;  
 R 14  and R 15  are independently hydrogen, C 1 -C 8 alkyl, Cl or a group OR 7 ;  
 R, 6  is is hydrogen, C 1 -C 8 alkyl, Cl or phenyl;  
 R 18  is hydrogen or C 1 -C 8 alkyl.  
 
     
     
         2 . A compound according to  claim 1  of formula (I), (Ia) or (Ib)  
       
         
           
           
               
               
           
         
       
       in which 
 the R 1  are independently of each other H, OR 7  or OH, with the proviso that at least one of R 1  or R 13  is OH;  
 the R 7  are independently of each other hydrogen, C 1 -C 12 alkyl or a radical of formula III  
                     
 wherein in formula I at least one of the R 7  is a radical of formula III;  
 R 8  is hydrogen, C 1 -C 8 alkyl; C 5 -C 12 cycloalkyl; C 2 -C 18 alkenyl; phenyl; C 7 -C 11 phenylalkyl; C 7 -C 11 alkylphenyl; C 1 -C 18 alkyl substituted by phenyl, OH, halogen; C 1 -C 18 alkoxy, C 5 -C 12 cycloalkoxy, C 3 -C 18 alkenyloxy or COOH;  
 R 9 , is C 20 -C 60  alkyl, C 20 -C 60 alkyl which is substituted in ω position with a OH group or C 20 -C 60 alkenyl or a group of formula (IV)  
                     
 wherein  
 m is a number from 1 to 20;  
 R 2 , R 3 , R 4 , R 5  and R 6  are independently of each other hydrogen, C 1 -C 38 alkyl which is unsubstituted or substituted by hydroxy or C 1 -C 8 alkoxy; or  
 C 1 -C 38 alkyl which is interrupted by an oxygen atom or a N(C 1 -C 18 )alkyl group; phenyl or C 7 -C 12 phenylalkyl which are unsubstituted or substituted by hydroxy or C 1 -C 8 alkyl;  
 n is a number from 1 to 38;  
 p is a number from 2 to 20; and  
 R 10  is hydrogen, C 1 -C 4 alkyl, Cl, phenyl or a group —OR 7 ;  
 R 10  is hydrogen or methyl;  
 R 12  is hydrogen, methyl or ethyl;  
 R 13  is hydrogen, methyl, OH or a group OR 7 ;  
 R 14  and R 15  are independently hydrogen, C 1 -C 8 alkyl, Cl or a group OR 7 ; and  
 R 16  is is hydrogen, C 1 -C 8 alkyl, Cl or phenyl.  
 
     
     
         3 . A compound according to  claim 1  conforming to formula (I) or (II), wherein the R 7  are independently of each other hydrogen, C 1 -C 12 alkyl or a radical of formula (III)  
       
         
           
           
               
               
           
         
       
       wherein in formula (I) at least one of the R 7  is a radical of formula (III); 
 R 8  is hydrogen or C 1 -C 8 alkyl;  
 Y is —CO— or C 1 -C 2 alkylene;  
 R 9 , if Y is —CO—, is C 20 -C 60  alkyl, C 20 -C 60 alkyl substituted by OH and/or interrupted by O, or is a group of formula (IV)  
                     
 wherein m is a number  
 from 2 to 12;  
 R 9  , if Y is alkylene, is C 20 -C 60 alkanoyl;  
 R 2 , R 3 , R 4 , R 5  and R 6  are independently of each other hydrogen, C 1 -C 18 alkyl or C 4 -C 12 hydroxyalkyl or C 4 -C 12 alkoxyalkyl;  
 R 10  is hydrogen or a group —OR 7 ;  
 R 11  and R 18  independently are hydrogen or methyl;  
 R 13  is hydrogen, OH or methyl.  
 
     
     
         4 . A compound according to  claim 1  conforming to the formula (IIa)  
       
         
           
           
               
               
           
         
       
       in which 
 x is a number from 1 to 20;  
 the number y is at least 1 and ranges from (x+z−1) to (x+z+1);  
 z is a number from 0 to 20; and  
 R 12  is hydrogen or C 1 -C 8 alkyl;  
 R 18 is hydrogen or C 1 -C 8 alkyl;  
 Y is —CO— or C 1 -C 12 alkylene;  
 if Y is —CO—, D′ is C 2 -C 38 alkylene or C 4 -C 60 alkylene interrupted by O; and T is the divalent acyl residue of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid of 2 to 12 carbon atoms;  
 if Y is alkylene, D′ is the divalent acyl residue of an aliphatic, cycloaliphatic or aromatic dicarboxylic acid of 2 to 12 carbon atoms; and T is C 2 -C 38 alkylene or C 4 -C 60 alkylene interrupted by O,  
 and all other symbols are as defined in  claim 1 .  
 
     
     
         5 . A compound according to  claim 3  wherein R 1  is OH; 
 R 7  is hydrogen or methyl or a radical of formula (III)  
                     
 R 8  is hydrogen or C 1 -C 4 alkyl;  
 R 10  is hydrogen, methyl or a group —OR 7 ;  
 R 11  and R 18  are hydrogen;  
 R 13  is hydrogen, OH or methyl.  
 
     
     
         6 . Compound obtainable by reacting a tris-aryl-triazine of the formula V  
       
         
           
           
               
               
           
         
       
       wherein all symbols are as defined in  claim 4 , provided that R 12  is hydrogen in case that Y is alkylene, if Y is —CO—, with a diol HO-D′-OH, optionally in presence of a compound of the formula R 12 —O-T-O—R 12 ; and 
 if Y is alkylene, with a diester R′ 12 —O-D′-O—R′ 12 , where R′ 12  is hydrogen or C 1 -C 8 alkyl, optionally in presence of a diol of the formula HO-T-OH.  
 
     
     
         7 . A composition protected against the permeation of ultraviolet radiation comprising 
 (a) an organic polymer material, and    (b) at least one compound of formula (I), (II) or (Ib) or a mixture thereof according to  claim 1 .    
     
     
         8 . A composition according to  claim 7  which is a plastic container or film or sheet which protects against the deleterious effects of ultraviolet radiation and wherein component (a) is a clear or lightly colored plastic material.  
     
     
         9 . A plastic container or film according to  claim 8  which is a food packaging material or a greenhouse film.  
     
     
         10 . A composition according to  claim 7  wherein the clear or lightly colored plastic is a polyolefin, a polyester, a polyvinylalcohol, a polyvinylacetate, a polycarbonate, a polyamide, an acrylic (co)polymer, or acryl-butadiene-styrene terpolymer a polyamide.  
     
     
         11 . A plastic container or film according to  claim 8  wherein the thickness of the film is from 10 μm m to 100 μm and the thickness of the plastic container is from 200 μm to 1000 μm.  
     
     
         12 . A composition according to  claim 7  wherein component (b) is present in an amount of from 0.005% to 10% by weight of component (a).  
     
     
         13 . A plastic container or film or sheet according to  claim 8  which is a multilayer construction of 2 to 7 polymer layers containing the compound of formula (I), (II) or (Ib) or a mixture thereof in at least 1 layer.  
     
     
         14 . A plastic container or film according to  claim 8  which contains an additional additive selected from phenolic antioxidants, sterically hindered amines, phosphites, phosphonites, flame retardants and iron based oxygen absorbers.  
     
     
         15 . Use of a compound of formula (I), (II) or (Ib) or a mixture thereof according to  claim 1 , incorporated into a clear or lightly colored plastic container or film, for content protection of a greenhouse or packaged foodstuff, beverages, pharmaceuticals, cosmetics or personal care products, from the deleterious effects of ultraviolet radiation.  
     
     
         16 . Method of protecting the content of a greenhouse or a package of foodstuffs, beverages, pharmaceuticals, cosmetics, or personal care products from the deleterious effects of ultraviolet radiation, which method comprises shielding said content under a plastic container or film which contains incorporated a compound of formula (I), (II) or (Ib) or a mixture thereof according to  claim 1.