US 7,320,826 B2 | ||
Photochromic articles with reduced temperature dependency and methods for preparation | ||
Anil Kumar, Allegheny County, Pa. (US); Barry Van Gemert, Westmoreland County, Pa. (US); Forrest R. Blackburn, Allegheny County, Pa. (US); and Clara E. Nelson, Allegheny County, Pa. (US) | ||
Assigned to PPG Industries Ohio, Inc., Cleveland, Ohio (US) | ||
Filed on Mar. 20, 2003, as Appl. No. 10/393,174. | ||
Prior Publication US 2004/0191520 A1, Sep. 30, 2004 | ||
Int. Cl. B32B 17/10 (2006.01); B32B 27/20 (2006.01); B32B 27/36 (2006.01); B32B 33/00 (2006.01); G02C 7/10 (2006.01) |
U.S. Cl. 428—411.1 [428/423.1; 428/426; 428/457; 428/480; 428/500; 428/522; 428/537.1; 428/537.5; 428/913; 359/738; 351/163] | 56 Claims |
1. A photochromic article demonstrating consistent photochromic response over a broad temperature range comprising:
a) a substrate;
b) a temperature dependent reducing amount of at least one organic photochromic material associated with said substrate, said
photochromic material having a temperature dependent variable absorbance that changes from more absorbing to less absorbing
of radiation in its activating spectral absorbance as the temperature increases from 10° C. to 35° C.; and
c) at least one other organic photochromic material (c) associated with said substrate that is different from photochromic
material (b); said photochromic material (b) being used in a coating or film on the surface of the substrate and interposed
between photochromic material (c) and a source of activating radiation, wherein the substituent groups of photochromic material
(b) are chosen such that said photochromic article exhibits an activated optical density response loss of 50 percent or less
as measured in the Photochromic Temperature Dependence Test, said photochromic material (b) being chosen from:
(1) a naphthopyran compound represented by the following graphic formula I:
![]() (a) R1 and R2 are each independently chosen from:
(i) hydrogen, hydroxy, C1-C6 alkyl, C1-C8 haloalkyl, C3-C7 cycloalkyl, or the group, —C(O)W, wherein W is hydroxy, C1-C6 alkyl, C1-C6 alkoxy , di(C1-C6)alkylamino, morpholino or piperidino;
(ii) the group, —OR8 wherein R8 is C1-C6 alkyl, C1-C6 acyl, C1-C8 haloalkyl, phenyl(C1-C3)alkyl or the group —CH(R9)Q, wherein R9 is hydrogen or C1-C3 alkyl and Q is —COOR10, and R10 is hydrogen or C1-C3 alkyl;
(iii) the group —CH(R12)G, wherein R12 is hydrogen or C1-C6 alkyl, and G is —COOR11, wherein R11 is hydrogen or C1-C6 alkyl; or
(iv) the group T represented by the formula:
-Z[(OC2H4)x(OC3H6)y(OC4H8)z]Z′ or
—[(OC2H4)x(OC3H6)y(OC4H8)z]Z′
wherein -Z is —C(O)— or —CH2—, Z′ is C1-C3 alkoxy or a polymerizable group, x, y and z are each a number between 0 and 50, and the sum of x, y and z is between 2 and
50; or
(v) R1 and R2 together form R3 chosen from a substituted or unsubstituted spiro-carbocyclic ring containing 5 to 6 carbon atoms, said spiro-carbocyclic ring
being annellated with 0, 1 or 2 benzene rings, said substituents being hydrogen or C1-C6 alkyl;
(b) R4 and R7 are each independently chosen from hydrogen, provided that both are not hydrogen, the group T, —OR7′ wherein R7′ is chosen from C1-C6 alkyl, phenyl(C1-C6)alkyl or C1-C6 alkoxy(C1-C6)alkyl or R4 and R7 are each independently a nitrogen-containing group chosen from:
(i) —N(R15)R16 wherein R15 and R16 are each independently chosen from hydrogen, C1-C8 alkyl or R15 and R16 come together with the nitrogen atom to form a C3-C20 hetero-bicycloalkyl ring or a C4-C20 hetero-tricycloalkyl ring;
(ii) a nitrogen containing ring represented by the following graphic formula:
![]() wherein each Y is —CH2—, and X is chosen from —Y—, —O—, —S—, —S(O)—, —S(O2)—, —NH—, —N(R17)— or —N(aryl)-, wherein R17 is C1-C6 alkyl, said aryl is phenyl or naphthyl, m is the integer 1, 2 or 3, and p is the integer 0, 1, 2, or 3 and when p is O, X
is Y; or
(iii) a group represented by one of the following graphic formulae:
![]() (c) R5 and R6 are each independently chosen from hydrogen, C1-C6 alkyl, C1-C6 haloalkyl, the group T, —OR7′, described hereinbefore in (b) or nitrogen-containing group (b) (i), (ii) or (iii); and
(d) B and B′ are each independently chosen from:
(i) mono-T-substituted phenyl;
(ii) the unsubstituted, mono-, di-, or tri-substituted aryl groups, phenyl or naphthyl, each of said aryl substituents being
chosen from hydroxy, aryl, morpholino, C1-C8 alkoxy (C1-C8)alkoxy, aryl(C1-C6)alkyl, aryloxy, C1-C6 alkyl, C1C6 haloalkyl, C1-C6 alkoxy, acryloxy, methacryloxy, halogen, —CF3, —CN or —COOR11; wherein R11 is the same as described hereinbefore; or
(iii) mono-substituted phenyl, said substituent located at the para position being —(CH2)t— or —O—(CH2)t—, wherein t is the integer 1, 2, 3, 4, 5 or 6, said substituent being connected to an aryl group on another photochromic
material;
(2) a naphthopyran compound represented by the following graphic formula II:
![]() R1, R2, R4, B and B′ are the same groups described hereinbefore in (1) (a), (b) and (d); R3′ is —OR8′, wherein R8′ is C1-C6 alkyl or phenyl(C1-C3)alkyl; or R3′ is chosen from hydrogen, C1-C6 alkyl or C1-C6 haloalkyl;
(3) a naphthopyran compound represented by graphic formula III:
![]() R1, R2, R4, B and B′ are the same groups described hereinbefore in (1) (a), (b) and (d); each R22 is independently chosen from hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, C1-C6 haloalkyl or —OR8′, which was described hereinbefore in (2), and n is the integer 0, 1, 2, or 3;
(4) a naphthopyran compound represented by the following graphic formula IV:
![]() (a) R23 is —C(O)L, or —C(R27) (R28)OR11, wherein L is —OR11, —N(R15)R16, (2-(2-hydroxyethoxy)ethoxy) or an unsubstituted, mono-substituted or di-substituted heterocyclic ring chosen from 1-indolinyl,
morpholino, piperidino, 1-pyrrolidyl or 1-piperazinyl, said heterocyclic ring substituents being C1-C6 alkyl; R11, R15, and R16 are the same as described hereinbefore in (1) (a) (iii) and (b) (i); R27 and R28 are each independently chosen from C1-C6 alkyl, C3-C7 cycloalkyl, C1-C6 haloalkyl or phenyl;
(b) R24 is hydrogen, C1-C6 alkyl, C3C7 cycloalkyl, mono- or di- (C1-C6)alkylaryl, mono- or di-(C1-C6)alkoxyaryl, C1-C6 haloalkyl, phenyl or naphthyl;
(c) R25 and R26 are each independently chosen from hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, C1-C6 haloalkyl, the group T, described hereinbefore in (1) (a) (iv) —OR8′, described hereinbefore in (2) or said nitrogen-containing group (1) (b) (i), (ii), or (iii) described hereinbefore or R25 and R26 together form one of the following graphic formulae:
![]() wherein J and K are each independently chosen for each occurrence in each formula from oxygen or the group —N(R15)—, R15, R19 and R20, are the same groups described hereinbefore in (1) (b) (i) and (iii); and
(d) B and B′ are the same roups described hereinbefore in (1) (d);
(5) a naphthopyran represented by the following graphic formula V:
![]() (a) R22 and n are the same as described hereinbefore in (3); R29 is hydroxy, C1-C6 alkyl, C3-C7 cycloalkyl, C1-C6 haloalkyl, aryl, mono(C1-C6)alkoxyaryl, di(C1-C6)alkoxyaryl, mono(C1-C5)alkylaryl, di(C1-C6)alkylaryl, haloaryl, di(C1-C6)alkylaminoaryl, the group T described hereinbefore in (1) (a) (iv), —OR8′ described hereinbefore in (2), or said nitrogen-containing group (1) (b) (i), (ii) or (iii) described hereinbefore;
(b) R30 is hydrogen or R23 described hereinbefore in (4) (a); and
(c) B and B′ are the same groups described hereinbefore in (1) (d);
(6) a naphthopyran compound represented by the following graphic formula VI:
![]() (a) R31 is hydrogen or R29 described hereinbefore in (5) (a);
(b) R32 is C1-C6 alkyl, C1-C6 alkoxy or C1-C6 haloalkyl, n is the same as described hereinbefore in (3); and
(c) B and B′ are the same groups described hereinbefore in (1) (d); and
(7) a naphthopyran represented by the following graphic formula VII:
![]() each R22 and n are the same as described hereinbefore in (3); R23 and R24 are the same as described hereinbefore in (4) (a) and (b); B and B′ are the same as described hereinbefore in (1) (d);
(8) a naphthopyran represented by the following graphic formula VIII:
![]() (a) R33 and R34 together form an oxo group or R33 is hydrogen and R34 is hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, allyl, phenyl, mono- or di-substituted phenyl, benzyl, mono-substituted benzyl, linear or branched C3-C12 alkenyl, C1-C6 alkoxy carbonyl (C1-C6) alkyl, methacryloxy(C1-C6)alkyl, acryloxy(C1C6)alkyl, C1-C4 acyloxy(C1-C6)alkyl, each of said phenyl or benzyl substituents being C1-C6 alkyl, C1-C6 alkoxy, morpholino, di(C1-C6)alkylamino, chioro or fluoro;
(b) each R35 is independently chosen for each occurrence from C1-C6 alkyl, C1-C6 alkoxy, chloro, fluoro, phenyl, C3-C7 cycloalkyl, di(C1-C6)alkylamino, morpholino, thiomorpholino, piperidino, pyridyl, N—(C1-C6)alkyl piperizino or N-phenyl piperizino, and s is the integer 0, 1 or 2;
(c) D is oxygen or —N(R36)—, wherein R36 is hydrogen, C1-C6 alkyl, C3-C7 cycloalkyl, C1-C5 acyl or phenyl;
(d) E is oxygen, —N(R36)— or —C(R37) (R38)—, wherein R37 and R38 are each independently chosen from hydrogen, C1-C6 alkyl or C3-C7 cycloalkyl, with the proviso that when E is —C(R37) (R38)—, D is oxygen; and
(e) M and M′ are each chosen from the urisubstituted, mono—, di- or tri-substituted aryl group, phenyl or naphthyl; each of
said aryl substituents being chosen from hydroxy, phenyl, morpholino, naphthylaryl(C1-C6)alkyl, aryloxy, C1-C6 alkyl, C1-C6 chloroalkyl, C1-C6 fluoroalkyl, C1-C6 alkoxy, acryloxy, methacryloxy, bromo, chloro or fluoro; or
(9) mixtures thereof.
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