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Benzotriazole UV absorbers having enhanced durability

  • US 5,977,219 A
  • Filed: 10/30/1997
  • Issued: 11/02/1999
  • Est. Priority Date: 10/30/1997
  • Status: Expired due to Fees
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Assignment
First Claim
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1. A coating composition, stabilized with a benzotriazole, which benzotriazole exhibits enhanced durability and a low loss rate when incorporated in said coating, which composition comprises(a) a resin selected from the group consisting of a thermoset acrylic melamine resin, an acrylic urethane resin, an epoxy carboxy resin, a silane modified acrylic melamine, an acrylic resin with carbamate pendant groups crosslinked with melamine or an acrylic polyol resin crosslinked with melamine containing carbamate groups, and(b) 0.01 to 5% by weight, based on resin solids, of a benzotriazole of formula A, B, C or D ##STR13## wherein G1, G2 or T is an electron withdrawing radical,G1 is hydrogen or halogen,G2 is halogen, nitro, cyano, R3 SO--, R3 SO2 --, --COOG3, CF3 --, --P(O)(C6 H5)2, --CO--G3, --CO--NH--G3, --CO--N(G3)2, --N(G3)--CO--G3, ##STR14## G3 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight of 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 4 alkyl of 1 to 4 carbon atoms,R1 is hydrogen, straight or branched chain alkyl of 1 to 24 carbon atoms, straight of 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 4 alkyl of 1 to 4 carbon atoms,R2 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 R2 is hydroxyl or --OR4 where R4 is straight or branched chain alkyl of 1 to 24 carbon atoms;

    or said alkyl substituted by one or more --OH, --OCO--R11, --OR4, --NCO or --NH2 groups or mixtures thereof;

    or said alkyl or said alkenyl interrupted by one or more --O--, --NH-- or --NR4 -- groups or mixtures thereof and which can be unsubstituted or substituted by one or more --OH, --OR4 or --NH2 groups or mixtures thereof;

    or R2 is --SR3, --NHR3 or --N(R3)2 ;

    or R2 is
    

    space="preserve" listing-type="equation">--(CH.sub.2).sub.m --CO--X--(Z).sub.p --Y--R.sub.15whereinX is --O-- or --N(R16)--,Y is --O-- or --N(R17)--,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(R16)-- and --N(R17)--, respectively,R15 is a group --CO--C(R18)═

    C(H)R19 or, when Y is --N(R17)--, forms together with R17 a group --CO--CH═

    CH--CO--, wherein R18 is hydrogen or methyl, and R19 is hydrogen, methyl or --CO--X--R20, wherein R20 is hydrogen, C1 -C12 -alkyl or a group of the formula ##STR15## wherein the symbols R1, R3, X, Z, m and p have the meanings defined above, and R16 and R17 independently of one another are hydrogen, C1 -C12 -alkyl, C3 -C12 -alkyl interrupted by 1 to 3 oxygen atoms, or is cyclohexyl or C7 -C15 aralkyl, and R16 together with R17 in the case where Z is ethylene, also forms ethylene,n is 1 or 2,when n is 1, R5 is Cl, OR6 or NR7 R8, orR5 is --PO(OR12)2, --OSi(R11)3 or --OCO--R11, or straight or branched chain C1 -C24 alkyl which is interrupted by --O--, --S-- or --NR11 and which can be unsubstituted or substituted by --OH or --OCO--R11, C5 -C12 cycloalkyl which is unsubstituted or substituted by --OH, straight chain or branched C2 -C18 alkenyl which is unsubstituted or substituted by --OH, C7 -C15 aralkyl, --CH2 --CHOH--R13 or glycidyl,R6 is hydrogen, straight or branched chain C1 -C24 alkyl which is unsubstituted or substituted by one or more OH, OR4 or NH2 groups, or --OR6 is --(OCH2 CH2)w OH or --(OCH2 CH2)w OR21 where w is 1 to 12 and R21 is alkyl of 1 to 12 carbon atoms,R7 and R8 are independently hydrogen, alkyl of 1 to 18 carbon atoms, straight or branched chain C3 -C18 alkyl which is interrupted by --O--, --S-- or --NR11 --, C5 -C12 cycloalkyl, C6 -C14 aryl or C1 -C3 hydroxylalkyl, or R7 and R8 together with the N atom are a pyrrolidine, piperidine, piperazine or morpholine ring,when n is 2, R5 is one of divalent radicals --O--R9 --O-- or --N(R11)--R10 --N(R11)--,R9 is C2 -C8 alkylene, C4 -C8 alkenylene, C4 alkynylene, cyclohexylene, straight or branched chain C4 -C10 alkylene which is interrupted by --O-- or by --CH2 --CHOH--CH2 --O--R14 --O--CH2 --CHOH--CH2 --,R10 being straight or branched chain C2 -C12 alkylene which may be interrupted by --O--, cyclohexylene, or ##STR16## or R10 and R11 with the two nitrogen atoms form a piperazine ring,R14 is straight or branched chain C2 -C8 alkylene, straight or branched chain C4 -C10 alkylene which is interrupted by --O--, cycloalkylene, arylene or ##STR17## where R7 and R8 are independently hydrogen, alkyl of 1 to 18 carbon atoms or R7 and R8 together are alkylene of 4 to 6 carbon atoms, 3-oxapentamethylene, 3-iminopentamethylene or 3-methyliminopentamethylene,R11 is hydrogen, straight or branched chain C1 -C18 alkyl, C5 -C12 cycloalkyl, straight or branched chain C3 -C8 alkenyl, C6 -C14 aryl or C7 -C15 aralkyl,R12 is straight or branched chain C1 -C18 alkyl, straight or branched chain C3 -C18 alkenyl, C5 -C10 cycloalkyl, C6 -C16 aryl or C7 -C15 aralkyl,R13 is H, straight chain or branched C1 -C18 alkyl which is substituted by --PO(OR12)2, phenyl which is unsubstituted or substituted by OH, C7 -C15 aralkyl or --CH2 OR12,R3 is alkyl of 1 to 20 carbon atoms, hydroxyalkyl of 2 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 or 1,1,2,2-tetrahydroperfluoroalkyl where the perfluoroalkyl moiety is of 6 to 16 carbon atoms,L is alkylene of 1 to 12 carbon atoms, alkylidene of 2 to 12 carbon atoms, benzylidene, p-xylylene or cycloalkylidene, andT is --SO--, --SO2 --, --SO--E--SO--, --SO2 --E--SO2 --, --CO--, --CO--E--CO--, --COO--E--OCO--, --CO--NG3 --E--NG3 --CO-- or --NG3 --CO--E--CO--NG3 --,where E is alkylene of 2 to 12 carbon atoms, cycloalkylene of 5 to 12 carbon atoms, or alkylene interrupted or terminated by cyclohexylene of 8 to 12 carbon atoms,which benzotriazole exhibits enhanced durability and low loss rate values when the coating is exposed to actinic radiation as witnessed by a loss of less than 0.22 absorbance units after exposure for 1200 hours, or less than 0.27 absorbance units after 1500 hours exposure, or less than 0.40 absorbance units after 2500 hours exposure in a Xenon-Arc Weather-Ometer, andwith the proviso that the benzotriazole is not(a) 5-n-dodecylsulfonyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole(b) 5-benzenesulfinyl-2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole;

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

    (d) 5,5'"'"'-sulfonylbis[2-(2-hydroxy-3,5-di-tert-butylphenyl)-2H-benzotriazole];

    (e) 5-benzenesulfonyl-2-[2-hydroxy-3-tert-butyl-5-(2-octyloxycarbonylethyl)-phenyl]-2H-benzotriazole;

    (f) 5-benzenesulfonyl-2-[2-hydroxy-3-tert-butyl-5-(3-hydroxypropyl)phenyl]-2H-benzotriazole;

    (g) 3-(5-benzenesulfonyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamic acid;

    (h) 3-(5-benzenesulfonyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamamide;

    (i) an isomeric mixture of 3-[3-(5-benzenesulfonyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamoyloxy]-2-hydroxypropyl methacrylate and 2-[3-(5-benzenesulfonyl-2H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyhydrocinnamoyloxy]-3-hydroxypropyl methacrylate;

     or(j) 5-benzenesulfonyl-2-{2-hydroxy-3-tert-butyl-5-[2-(ω

    -hydroxy-octa(ethyleneoxy)-carbonylethyl]phenyl}-2H-benzotriazole.

      

    

  

  
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