Nova Patents
EP0245020B1

Photochromic articles

Abstract

This record has no abstract on file.

EP0245020B1, drawing sheet 1
Sheet 1 of 97

Term

Term ended

Expired 29 April 2007, 19.4 years ago.

  1. Priority
  2. Filed
  3. Granted
  4. Expired
  5. Today

29 claims: 37 independent, 0 dependent

  1. 1
    l. A plastic organic photochromic article comprising a plastics host material having a photochromic spiro-oxazine compound incorporated therein or applied thereto, characterised in that the photochromic spiro-oxazine compound which is incorporated in or applied to the plastics host material is a photochromic compound of the general formula (I):wherein n is an integer of l to 4, and m is l, 2 or 3, each of R l and R₂ independently represents (i) a hydrogen atom or an amine functionality of general formula -NR′R′′, wherein each of R′ and R′′ independently represents a hydrogen atom or an alkyl, cycloalkyl or phenyl group or a substituted derivative thereof, or an amine functionality which is a cycloheteroalkyl ring or a substituted cycloheteroalkyl ring which ring includes one or more heteroatoms, (ii) a group of formula -R, -OR, -SR, -COR, or -COOR wherein R represents H, alkyl, aryl or heteroaryl, (iii) -Hal, -CH₂Hal, -CH(Hal)₂, -C(Hal)₃ wherein Hal represents halogen, or (iv) -NO₂, -CN, -SCN, with the proviso that ring A is always substituted at the 6′ position by a group R₂ which is an amine-functionality as defined above;R₄ represents -H, alkyl, alkenyl, phenyl, phenylalkyl, mono-, di- or tri-substituted phenyl or alkoxy,    each of R₅ and R₆ independently represents -H, alkyl, alkenyl, phenyl, phenylalkyl such as benzyl, mono-, di- or tri-substituted phenyl, or R₅ and R₆ together represent an alicyclic ring including spiro carbons, norbornane, and adamantane,    R₃ represents a hydrogen atom, or an alkyl, aryl or heteroaryl group,    R₇ is as defined for R l and R₂ above, or is a ring system fused to ring A, which ring system may incorporate aromatic and/or alicyclic rings, the said ring system optionally carrying one or more substituents R₈, the substituent R₈ being as defined above for R l and R₂, and    Ring B may optionally contain one or more ring nitrogen atoms.
  2. 2
    A photochromic article according to Claim l, having incorporated therein or applied thereto a photochromic compound of the general formula (II) wherein each of R l , R₉ and R l0 independently represents (i) a hydrogen atom or an amine functionality of general formula -NR′R′′, where each of R′ and R′′ independently represents a hydrogen atom or an alkyl, cycloalkyl or phenyl group or a substituted derivative thereof, or an amine functionality which is a cycloheteroalkyl ring or a substituted cycloheteroalkyl ring, which ring includes one or more heteroatoms, (ii) a group of formula -R, -OR, -SR, -COR, or -COOR wherein R represents H, alkyl, aryl or heteroaryl, (iii) -Hal, -CH₂Hal, -CH(Hal)₂, -C(Hal)₃ wherein Hal represents halogen, or (iv) -NO₂ -CN, -SCN:with the proviso that the group (R₉)p always includes an amine-functionality as defined above at the 6′-position,    n is an integer of l to 4,    p is l or 2,    q is 1, 2 or 3, and    =X- and =Y- each independently represents or wherein R l0 is as defined above, and    R₃, R₄, R₅ and R₆ are as defined in claim l for formula (I).
  3. 3
    A photochromic article according to Claim 2, wherein the photochromic compound of general formula (II) is one in which n is l and R l is a hydrogen atom, or a 5-alkoxy substituent, preferably 5 methoxy, or a 5-halogen substituent, preferably a 5-chloro substituent;R₃ is a hydrogen atom;each of R₄, R₅ and R₆ is an alkyl group, preferably methyl;p is l and R₉ is a 6′-piperidino, 6′-morpholino, 6′-N-methylpiperazino, 6′-N-phenylpiperazino, 6′-tetrahydroisoquinolino, 6′-indolino, 6′-thiomorpholino, 6′-homopiperidino, 6′-(l,2,3,4,4a,9a-hexahydrocarbazolino, or 6′ aziridino substituent;q is l and R l0 is a hydrogen atom or an 9′-alkoxy substituent, preferably 9′-methoxy;X is -CH= or -N= located in the 7′ position;and Y is -CH= or -N=.
  4. 4
    A photochromic article according to Claim l or 2, wherein the photochromic spiro-oxazine compound is one or more of:-    6′-indolino-l,3,3-trimethylspiro[indoline-2,3′-3 H -naphtho[2,l- b ] [l,4]oxazine],    l,3,3-Trimethyl-6′-piperidinospiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4] oxazine],    9′-Methoxy-l,3,3-trimethyl-6′-piperidinospiro[indoline-2,3-3 H -naphtho[2,l- b ][l,4]oxazine],    5-Methoxy-l,3,3-trimethyl-6′-piperidinospiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    l,3,3-Trimethyl-6′-morpholinospiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    5-Methoxy-l,3,3-trimethyl-6′-morpholinospiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    9′-Methoxy-l,3,3-trimethyl-6′-morpholinospiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    5-Chloro-l,3,3-trimethyl-6′-morpholinospiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    l,3,3-Trimethyl-6′-thiomorpholinospiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    l,3,3-Trimethyl-6′-(N-methylpiperazino)spiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    l,3,3-Trimethyl-6′-(N-phenylpiperazino)spiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    6′-(l,2,3,4-Tetrahydroisoquinolino)-l,3,3-trimethylspiroindoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    6′-Homopiperidino-l,3,3-trimethylspiro[indoline-2,3′-3 H -naphtho[l,2- b ][l,4]oxazine],    6′-Aziridino-l,3,3-trimethylspiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    6′-Dimethylamino-l,3,3-trimethylspiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    6′-Diethylamino-l,3,3-trimethylspiro[indoline-2,3′-3 H -benzo[l,4]oxazine],    6′-Dimethylamino-l,3,3-trimethylspiro[indoline-2,3′-3 H -benzo[l,4]oxazine],    6′-Indolino-l,3,3-trimethylspiro[indoline-2,3′-3 H -pyrido[3,2-f][l,4]benzooxazine],    l,3,3-Trimethyl-6′-piperidinospiro[7-azaindoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine],    6′-Indolino-l,3,3-trimethylspiro[7-azaindoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine].
  5. 5
    A photochromic article according to any one of the preceding claims, wherein the plastics host material is an optically clear plastics selected from polymers of polyol(allyl carbonate)-monomers, polyacrylates, poly(alkylacrylates) such as polymethylmethacrylates, cellulose acetate, cellulose triacetate, cellulose acetate propionate, cellulose acetate butyrate, poly(vinyl acetate), poly(vinyl alcohol), polyurethanes, polycarbonates, polyethyl-eneterephthalate, polystyrene, poly(styrene-methyl-methacrylate) copolymers, poly(styreneacrylonitrile) copolymers, and polyvinylbutyral.
  6. 6
    A photochromic article according to any one of Claims l to 4, wherein the plastics host material is an optically clear polymer or copolymer of a methacrylate or acrylate of a linear or branched aliphatic or aromatic liquid polyol.
  7. 7
    A photochromic article according to Claim 6, wherein the plastics host material is a polymer or copolymer of triethylene glycol dimethacrylate, ethylene glycol dimethacrylate, l,3-butyleneglycol dimethacrylate or trimetholpropane trimethacrylate.
  8. 8
    A photochromic article according to Claim 5, wherein the plastics host material is a polymer or copolymer of diethylene glycol bis (allyl carbonate).
  9. 9
    A photochromic article according to any one of the preceding claims, wherein the amount of spiro-oxazine compound incorporated in the article is 0,05 to 5% by weight, based on the volume of the polymer host material.
  10. 10
    l0. A photochromic article according to any one of the preceding claims which is in the form of an optical lens.
  11. 12
    l2. A photochromic article according to any one of claims l to 9, the said article being incorporated in a window pane.
  12. 13
    l3. A photochromic article according to claim l2 in the form of a vehicle roof light.
  13. 14
    l4. A photochromic compound of the general formula (I):wherein n is an integer of l to 4, and m is l, 2 or 3, each of R l and R₂ independently represents (i) a hydrogen atom or an amine functionality of general formula -NR′R′′, wherein each of R′ and R′′ independently represents a hydrogen atom or an alkyl, cycloalkyl or phenyl group or a substituted derivative thereof, or an amine functionality which is a cycloheteroalkyl ring or a substituted cycloheteroalkyl ring which ring includes one or more heteroatoms, (ii) a group of formula -R, -OR, -SR, -COR, or -COOR wherein R represents H, alkyl, aryl or heteroaryl, (iii) -Hal, -CH₂ Hal, -CH(Hal)₂, -C(Hal)₃ wherein Hal represents halogen, or (iv) -NO₂, -CN, -SCN, with the proviso that ring A is always substituted at the 6′ position by a group R₂ which is an amine-functionality as defined above;R₄ represents -H, alkyl, alkenyl, phenyl, phenylalkyl, mono-, di- or tri-substituted phenyl or alkoxy,    each of R₅ and R₆ independently represents -H, alkyl, alkenyl, phenyl, phenylalkyl such as benzyl, mono-, di- or tri-substituted phenyl, or R₅ and R₆ together represent an alicyclic ring including spiro carbons, norbornane, and adamantane,    R₃ represents a hydrogen atom, or an alkyl, aryl or heteroaryl group,    R₇ is as defined for R l and R₂ above, or is a ring system fused to ring A, which ring system may incorporate aromatic and/or alicyclic rings, the said ring system optionally carrying one or more substituents R₈, the substituent R₈ being as defined above for R l and R₂, and    ring B may optionally contain one or more ring nitrogen atoms.
  14. 15
    l5. A photochromic compound according to Claim l4, having the general formula (II) wherein each of R l , R₉ and R l0 independently represents (i) a hydrogen atom or an amine functionality of general formula -NR′R′′, where each of R′ and R′′ independently represents a hydrogen atom or an alkyl, cycloalkyl or phenyl group or a substituted derivative thereof, or an amine functionality which is a cycloheteroalkyl ring or a substituted cycloheteroalkyl ring, which ring includes one or more heteroatoms, (ii) a group of formula -R, -OR, -SR, -COR, or -COOR wherein R represents H, alkyl, aryl or heteroaryl, (iii) -Hal, -CH₂Hal, -CH(Hal)₂, -C(Hal)₃ wherein Hal represents halogen, or (iv) -NO₂, -CN, -SCN:with the proviso that the group (R₉) p always includes an amine-functionality as defined above at the 6′-position,    n is an integer of l to 4,    p is l or 2,    q is l, 2 or 3, and    =X- and =Y- each independently represents or wherein R l0 is as defined above, and    R₃, R₄, R₅ and R₆ are as defined in claim l4 for formula (I).
  15. 16
    l6. A photochromic compound according to Claim l5, wherein n is l and R l is a hydrogen atom, or a 5-alkoxy substituent, preferably 5-methoxy, or a 5-halogen substituent, preferably a 5-chloro substituent;R₃ is a hydrogen atom;each of R₄, R₅ and R₆ is an alkyl group, preferably methyl;p is l and R₉ is a 6′-piperidino, 6′-morpholino, 6′-N-methylpiperazino, 6′-N-phenylpiperazino, 6′-tetrahydroisoquinolino, 6′-indolino, 6′-thiomorpholino, 6′-homopiperidino, 6′-(l,2,3,4,4a,9a-hexahydrocarbazolino), or 6′-aziridino substituent;q is l and R l0 is a hydrogen atom or an 9′-alkoxy substituent, preferably 9′-methoxy;X is -CH= or -N= located in the 7′ position;and Y is -CH= or -N=.
  16. 17
    l7. A photochromic compound according to Claim l4 or l5, which is any one of the following compounds:-    6′-Indolino-l,3,3-trimethylspiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4] oxazine];l,3,3-Trimethyl-6′-piperidinospiro[indoline-2,3′-3 H -naphth[2,l- b ][l,4] oxazine];9′-Methoxy-l,3,3-trimethyl-6′-piperidinospiro[indoline-2,3-3 H naphtho [2,l- b ][l,4] oxazine];5-Methoxy-l,3,3-trimethyl-6′-piperidinospiro[indoline-2,3′-3 H -naphtho [2,l- b ][l,4] oxazine];l,3,3-Trimethyl-6′-morpholinospiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4] oxazine];5-Methoxy-l,3,3-trimethyl-6′-morpholinospiro[indoline-2,3′-3 H -naphtho [2,l- b ][l,4] oxazine];9′-Methoxy-l,3,3-trimethyl-6′-morpholinospiro[indoline-2,3′-3 H -naphtho [2,l- b ][l,4] oxazine];5-Chloro-l,3,3-trimethyl-6′-morpholinospiro[indoline-2,3′-3 H -naphtho [2,l- b ][l,4] oxazine];l,3,3-Trimethyl-6′-thiomorpholinospiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4] oxazine];l,3,3-Trimethyl-6′-(N-methylpiperazino)spiro[indoline-2,3′-3 H -naphtho [2,l- b ][l,4] oxazine];l,3,3-Trimethyl-6′-(N-phenylpiperazino)spiro[indoline-2,3′-3 H -naphtho [2,l- b ][l,4] oxazine];6′-(l,2,3,4-Tetrahydroisoquinolino)-l,3,3-trimethylspiro[indoline-2,3′-3 H -naphtho [2,l- b ][l,4] oxazine];6′-Homopiperidino-l,3,3-trimethylspiro[indoline-2,3′-3 H -naphtho[l,2- b ][l,4] oxazine];6′-Aziridino-l,3,3-trimethylspiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4] oxazine];6′-Dimethylamino-l,3,3-trimethylspiro[indoline-2,3′-3 H -naphtho[2,l- b ][l,4] oxazine];6′-Dimethylamino-l,3,3-trimethylspiro[indoline-2,3′-3 H -benzo[l,4]oxazine];6′-Diethylamino-l,3,3-trimethylspiro[indoline-2,3′-3 H -benzo[l,4]oxazine];6′-Indolino-l,3,3-trimethylspiro[indoline-2,3′-3 H -pyrido[3,2-f][l,4] benzooxazine];l,3,3-Trimethyl-6′-piperidinospiro[7-azaindoline-2,3′-3 H -naphtho[2,l- b ][l,4]oxazine];6′-Indolino-l,3,3-trimethylspiro[7-azaindoline-2,3′-3 H -naphtho[2,l- b ][l,4] oxazine].
Independent claims16