Photochromic compositions and articles comprising siloxane, alkylene or substituted alkylene oligomers

• US 20070187656A1
• Filed: 04/29/2005
• Published: 08/16/2007
• Est. Priority Date: 04/30/2004
• Status: Abandoned Application

• Current Assignee: Advanced Polymerik Pty Ltd.
• Original Assignee: Polymers Australia Pty., Ltd.
• Inventors: Lewis, David, Evans, Richard, Malic, Nino, Davis, Thomas, Such, Georgina
• Application Number:
  US11/568,480
• Publication Number:
  US 20070187656A1
• Time in Patent Office: Days
• US Class Current: 252/582
• CPC Class Codes: C08F 220/1804 C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
• CPC Class Codes: C08G 63/66 Polyesters containing oxygen in the form of ether groups C08G63/42, C08G63/58 take precedence
• CPC Class Codes: C08G 63/695 containing silicon
• CPC Class Codes: C08G 64/183 containing polyether sequences
• CPC Class Codes: C08G 64/186 containing polysiloxane sequences
• CPC Class Codes: C08G 69/40 Polyamides containing oxygen in the form of ether groups C08G69/12, C08G69/32 take precedence
• CPC Class Codes: G02B 5/23 Photochromic filters

Abstract

This invention relations to a polymerizable composition for forming a photochromic article of glass transition temperature of at least 50 ° C. on curing, the composition comprising: (a) a polymerizable composition comprising a monomer component or resin formed therefrom; and (b) a photochromic dye monomer comprising a photochromic moiety and at least one oligomeric group having at least one group reactive with the monomer component during or following curing wherein the oligomer group comprises a multiplicity of monomer units selected from siloxane, alkylene and substituted alkylene.

Claims

1. A polymerizable composition for forming a photochromic article of glass transition temperature of at least 50°

C., on curing the composition comprising;

(a) a polymerizable composition comprising a monomer component; and

(b) a photochromic dye monomer comprising a photochromic moiety and at least one oligomeric group having at least one group reactive with the monomer component during curing wherein the oligomer group comprises a multiplicity of monomer units selected from siloxane, alkylene and substituted alkylene.

2. A polymerizable composition according to claim 1 wherein the photochromic dye monomer is of formula I:

(PC)_q-(L(R )_n)_m 

 

I

wherein;

PC is a photochromic moiety;

R is an oligomer;

m and n are independently selected integers from 1 to 3;

q is 1 or 2;

R is independently selected from oligomers comprising at least 3 monomeric units selected from the group consisting of alkylene, substituted alkylene and di-(hydrocarbyl)siloxane; and

wherein at least one oligomer R comprises at least one group which is reactive with the monomer composition on curing of the polymerizable composition.

3. A polymerizable composition according to claim 1 wherein the reactive group is selected from the group consisting of amino;

alkylamino (including mono and di-alkylamino);

halo hydroxyl;

thio;

mercapto;

epoxy;

carbamate;

alkylhalo;

unsaturated groups (such as acryloyl, methacryloyl, acryloyloxy, allyl allyloxy and methacryloyloxy), maleimides;

the group of formula —

SiX¹X²X³ wherein X¹, X² and X³ are independently selected from the group consisting of hydrogen, halogen, hydrocarbyl and hydrocarbyloxy and wherein at least one of X¹, X² and X³ is selected from hydrogen, halogen and hydrocarbyloxy;

dithioester (—

S—

C═

S—

R);

trithiocarbonate (—

S—

C═

S—

S—

R);

dithiocarbamate (—

S—

C═

S—

NRR);

xanthate (—

S—

C═

S—

O—

R);

carboxylic acids;

carboxylic esters; and

C₁ to C₆ alkyl substituted with a group selected from hydroxy, thio, amino, alkyl amino, carboxyl, (C₁ to C₆ alkoxy)carboxyl, acryloyl, methacryloyl, acryloyloxy and methacryloyloxy.

4. A polymerizable composition according claim 2 wherein said at least one reactive group comprises a radical capped radical group adapted to be reversibly cleaved from the compound under activating conditions to provide a reactive radical during curing of the composition.

5. A polymerisable composition according to claim 4 wherein the oligomer comprises reactive group selected from the group consisting of dithioesters (—

S—

C═

S—

R);

trithiocarbonates (—

S—

C═

S—

S—

R);

dithiocarbamates (—

S—

C═

S—

NRR);

xanthates (—

S—

C═

S—

O—

R);

carboxylic acids;

carboxylic esters and nitroxides.

6. A polymerizable composition according to claim 2 wherein at least one of the oligomers R comprises a terminal reactive group.

7. A polymerizable composition according to claim 2 wherein the at least one reactive group is a terminal unsaturated group selected from the group consisting of (meth)acryloyl, (meth)acryloyloxy, allyl and allyloxy.

8. A polymerizable composition according to claim 1 wherein at least one pendant oligomer group is selected from the group consisting of polyalkylene oligomers, substituted polyalkylene oligomers, polydialkylsilyloxy oligomers, polysilicene acid oligomers and derivatives thereof, poly(ZSi(OH)₃) oligomers and derivatives thereof, poly (ZSiCl₃) oligomers and derivatives thereof, poly(ZSi(Ome)₃) and mixtures thereof wherein Z is an organic group.

9. A polymerizable composition according to claim 8 wherein Z is selected from the group consisting of hydrogen, optionally substituted alkyl, haloalkyl, optionally substituted cycloalkyl, hydroxy, optionally substituted amino, alkoxy, aryloxy, optionally substituted aryl, carboxyl and derivatives thereof.

10. A polymerizable composition according to claim 1 wherein the oligomer comprises at least 3 monomeric units selected from the group consisting of di-(C₁ to C₆)alkylsilyloxy monomeric units C₁ to C₆ alkyl acrylate and C₁ to C₆ alkyl methacrylate monomeric units.

11. A polymerizable composition according to claim 1 wherein the oligomer includes at least 5 monomeric units selected from the group consisting of alkylenyloxy, perfluoroalkylene and C₁ to C₆ alkyl acrylate, C₁ to C₆ alkylmethacrylate and halogenated C₁ to C₆ alkyl acrylate or C₁ to C₆ alkylmethacrylates.

12. A polymerizable composition according to claim 1 wherein the at least one oligomer is selected from groups of formula II:

—

(X)_p(R¹)_q—

X¹R2 

 

II

wherein

X is selected from oxygen sulfur amino, substituted amino and C₁-C₄ alkylene;

X¹ is a bond or an attachment group for one or more reactive groups;

p is 0 or 1;

q is the number of monomer units;

R¹ which may be the same or different are selected from the group consisting of;

C₂ to C₄ alkylene, substituted C₂ to C₄ alkylene and di(C₁ to C₁₀) hydrocarbylsilyloxy; and

R² is selected from the group consisting of amino;

alkylamino (including mono and di-alkylamino);

halo hydroxyl;

thio;

mercapto;

epoxy;

carbamate;

alkylhalo;

unsaturated groups (such as acryloyl, methacryloyl, acryloyloxy, allyl allyloxy and methacryloyloxy), maleimides;

the group of formula -SiX¹X²X³ wherein X¹, X² and X³ are independently selected from the group consisting of hydrogen, halogen, hydrocarbyl and hydrocarbyloxy and wherein at least one of X¹, X² and X³ is selected from hydrogen, halogen and hydrocarbyloxy;

dithioester (—

S—

C═

S—

R);

trithiocarbonate (—

S—

C═

S—

S—

R);

dithiocarbamate (—

S—

C═

S—

NRR);

xanthate (—

S—

C═

S—

O—

R);

carboxylic acids;

carboxylic esters; and

C₁ to C₆ alkyl substituted with a group selected from hydroxy, thio, amino, alkyl amino, carboxyl, (C₁ to C₆ alkoxy)carboxyl, acryloyl, methacryloyl, acryloyloxy and methacryloyloxy.

13. A polymerisable composition according to claim 1 wherein the at least one oligomer comprises at least three substituted C₂ to C₄ alkylene units of formula III

wherein

R³ is selected from the group consisting of hydroxy, alkoxy, aryl, aryloxy, heterocyclic, arylalkyl, alkylaryl, carboxyl, nitrile, alkoxycarbonyl, substituted alkoxycarbonyl, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, carbaniloyl, alkylphenylaminocarbonyl, alkoxyphenylaminocarbonyl, acyl, substituted acyl and the groups of formula:

-L′

-(O)_q-(Z-O)_p-ZY; and

wherein

p is the number of (ZO) units and is preferably from 1 to 20 and more preferably 2 to 15, q is 0 or 1, Z is selected from the group consisting of C₂-C₄ alkylene, dialkylsilyl, diarylsilyl and diaryloxysilyl;

L′

is a bond or a linking group such as C₁ to C₆ alkylene, aryl, alkaryl and aralkyl; and

Y′

is a terminal group selected from the group consisting of hydrogen, alkyl, hydroxyl and alkoxy, alkoxyalkoxy, hydroxyalkoxy and aryloxy, tri-(C₁ to C₆ alkyl)silane, di(C₁ to C₆ alkyl)phenyl silane;

R³′

is hydrogen and R³ and R^3′

may together form a group of formula

wherein

X is selected from the group consisting of oxygen and the group NR⁷R⁸ wherein R⁷ and R⁸ are independently selected from the group of hydrogen, alkyl, aryl, substituted alkyl and substituted aryl; and

R⁴ is selected from the group consisting of hydrogen, halogen, alkyl, hydroxy, hydroxy alkyl, nitrile and alkoxy.

R^4′

is selected from the group consisting of hydrogen and halogen.

14. A polymerisable composition according to claim 13 wherein the monomeric unit of formula III form a block copolymer.

15. A polymerisable composition according to claim 14 wherein the oligomer comprises a group of formula V

wherein R³,R^3′

,R⁴ and R^4′

are as therein defined;

t is from 2 to 200;

w is from 0 to 500 and wherein the units may be present as blocks or randomly distributed.

16. A polymerizable composition according to claim 2 wherein the oligomer R is selected from the groups of the following formulae (i) to (vii):

wherein ∅

is alkyl or aryl and includes at least a portion of aryl groups; and

wherein X and R², R⁴, R^4′

and p are hereinbefore defined and x, v and y are the number of repeating units, and wherein at least one oligomer group is present

wherein the number of monomer units (x or y+v in the above examples) is at least 5 and

wherein the monomer units are distributed randomly or in block form.

17. A polymerizable composition according to claim 1 wherein the dye monomer is of formula IA or IB:

wherein;

X is a linking group for the oligomer;

X′

is bond or attachment group for the one more reactive groups and is preferably selected from the group consisting of C₁ to C₄ alkylene;

where Y is oxygen or sulphur;

w is the number of hydroxy or thiol groups at the terminal end of the oligomer and is preferably 1 to 3;

p is independently selected from 0 and 1;

PC is a photochromic moiety;

J is hydrogen or C₁ to C₄ alkyl (preferably hydrogen or methyl);

R is an oligomer;

R′

is hydrogen, C₁ to C₆ alkyl or substituted (C₁ to C₆) alkyl; and

R″

is hydrogen (C₁ to C₆) alkyl or substituted C₁ to C₆) alkyl.

18. A polymerizable composition according to claim 2 wherein the oligomer R is linked to the photochromic moiety (PC) by a linker group of any one of the formulae selected from VIIa to VIIp:

wherein n is from 1 to 3;

wherein in the formula VIIa to VIIp;

X which may be the same or different is as hereinbefore defined;

R¹¹ is selected from the group consisting of hydroxy, alkoxy, amino and substituted amino such as alkyl amino;

n is an integer from 1 to 3;

w is an integer from 1 to 4;

q is an integer from 0 to 15;

p which when there is more than one may be the same or different is 0 or 1; and

(R) shows the radial for attachment of oligomer R.

19. A polymerizable composition according to claim 1 wherein the monomer component comprises at least one crosslinking monomer.

20. A polymerizable composition according to claim 1 wherein the resulting polymer comprises at least one selected from the group consisting of polyester, urethanes, polycarbonates, polyamides, epoxies and thiolene polymers.

21. A polymerizable composition according to claim 1 wherein the polymerizable matrix comprises monomers selected from the group consisting of polyol(allyl carbonate) monomers, multifunctional acrylate and methacrylate monomers, acrylates, alkylacrylates such methylmethacrylate, cellulose acetate, cellulose triacetate, cellulose acetate propionate, nitrocellulose cellulose acetate butyrate, poly(vinyl acetate), vinylalcohol, vinylchloride, vinlylidene chloride, polyurethanes, polycarbonates, poly(ethylene-terephthalate), polystyrene, copoly(styrene-methylmethacrylate), copoly(styrene-acrylateonitrile), poly(vinylbutryal), and homopolymers and copolymers of diacylidene pentaerythritol, particularly copolymers with polyol(allylcarbonate) monomers, eg diethylene glycol bis(allyl carbonate), and acrylate monomers.

22. A polymerizable composition according to claim 1 wherein the photochromic moiety (PC) is selected from the group consisting of chromenes, spiropyrans;

spiro-oxazines, fulgides, fulgimides, anils, perimidinespirocyclohexadienones, stilbenes, thioindigoids, azo dyes and diarylethenes and diarylperfluorocyclopentenes.

23. A polymerizable composition according to claim 2 wherein the photochromic moiety (PC) is selected from the group consisting of naphthopyrans, benzopyrans, indenonaphthopyrans, phenanthro- pyrans, spiro(benzindoline) naphthopyrans, spiro(indoline)- benzopyrans, spiro(indoline) naphthopyrans, spiroquinopyrans, spiro(indoline)pyrans, spiro(indoline) naphthoxazines, spiro(indoline)pyridobenzoxazines, spiro(benzindoline)pyrido-benzoxazines, spiro(benzindoline)naphthoxazines, spiro(indoline)-benzoxazines, fulgides and fulgimides.

24. The polymerizable composition of claim 3 wherein the monomer component comprises diethylene glycol bis(allyl carbonate).

25. A polymerizable composition according to claim 1 wherein the monomer comprises at least one selected from the group consisting allyl diglycol carbonate monomer(s), polycarbonates forming monomers, monomers for forming polyurea urethanes and polyfunctional isocyanate(s) and polythiol or polyepisulfide monomer(s).

26. A polymerizable composition according to claim 1 wherein the photochromic compound comprises one or more reactive terminal groups comprising active hydrogen groups (such as hydroxyl, amine and alkylamine) and the monomer composition comprises a polyisocyanate or epoxy crosslinking monomer.

27. A polymerizable composition according to claim 13 which forms a polymer having a Tg of at least 70°

C. on curing.

28. A polymerizable composition according to claim 1 wherein the fade half life is changed by at least 20% compared with the corresponding composition in the absence of the oligomer.

29. A polymerizable composition according to claim 1 wherein the fade half life is reduced by at least 40% compared with the corresponding composition comprising the photochromic compound without the oligomer.

30. A polymerizable composition according to claim 1 wherein t¾

is at least 40% reduced compared with the corresponding composition wherein the photochromic compound does not contain the oligomer.

34. A photochromic compound according to claim 28 wherein the oligomer R is selected from the groups of the following formulae (i) to (vii):

wherein ∅

is alkyl or aryl and includes at least a portion of aryl groups

wherein X, X′ and

R² and p are hereinbefore defined and x, v and y are the number of repeating units, and alkyl is C₁ to C₂₀ alkyl, preferably C₁ to C₁₀ alkyl such as methyl, ethyl, propyl, butyl, pentyl or hexyl.

35. A photochromic article according to claim 34 wherein the number of monomer units (x or y+v in the above examples) is at least 5.

36. A process for preparing a photochromic article comprising:

(a) forming a polymerizable composition according to claim 1;

(b) casting the photopolymerizable composition or applying it as a coating to a substrate; and

(c) polymerizing the polymerizable composition to provide a polymeric matrix incorporating a photochromic monomeric unit comprising a photochromic moiety covalently tethered to the matrix polymer via an oligomer comprising at least 7 monomeric units selected from the group consisting of alkylenyloxy, fluoroalkylenyloxy (particularly perfluoroalkylenyloxy), fluoroalkylene (particularly perfluoroalkylene) and di-(hydrocarbyloxy)siloxane.

31. A photochromic article having a Tg of at least 50°

C. comprising a polymeric matrix formed from a monomer composition comprising a photochromic monomer comprising a photochromic moiety which is tethered to the polymer via a pendant oligomer comprising at least 3 monomeric units selected from the group consisting of alkylene, substituted alkylene and di-(hydrocarbyloxy)siloxane.

32. A photochromic article according to claim 31 wherein the photochromic dye monomeric unit is of formula I:

(PC)_q-(L(R )_n)_m

wherein;

PC is a photochromic moiety;

R is an oligomers;

m and n are independently selected integers from 1 to 3;

q is 1 or 2;

R is independently selected from oligomers comprising and least 7 monomeric units selected from the group consisting of alkylene, substituted alkylene, alkylenyloxy, fluoroalkylenyloxy (particularly perfluoroalkylenyloxy), fluoroalkylene (particularly perfluoroalkylene) and di-(hydrocarbyloxy)siloxane; and

wherein at least one oligomers R comprise a group which is covalently incorporated into the polymeric matrix.

33. A photochromic article according to claim 31 wherein the photochromic moiety (PC) is selected from the group consisting of:

(a) spiro-oxazines of formula III

 

in the general formula III, R³, R⁴ and R⁵ may be the same or different and are each an alkyl group, a cycloalkyl group, a cycloarylalkyl group, an alkoxy group, an alklyleneoxyalkyl group, an alkoxycarbonyl group, a cyano, an alkoxycarbonylalkyl group, an aryl group, an arylalkyl group, an aryloxy group, an alkylenethioalkyl group, an acyl group, an acyloxy group or an amino group, R⁴ and R⁵ may together form a ring, and R³, R⁴ and R⁵ may optionally each have a substituent(s);

(b) chromenes of formula XX or XX(d)

wherein

B and B′

are optionally substituted phenylaryl and heteroaryl; and

R²², R²³ and R²⁴ are independently selected from hydrogen;

halogen;

C₁ to C₃ alkyl;

the group L(R)_n; and

the group of formula COW wherein W is OR25, NR²⁶R²⁷,

piperidino or morpholino wherein R²⁵ is selected from the group consisting of C₁ to C₆ alkyl, phenyl, (C₁ to C₆ alkyl)phenyl, C₁ to C₆ alkoxyphenyl, phenyl C₁ to C₆ alkyl (C₁ to C₆ alkoxy)phenyl, C₁ to C₆ alkoxy C₂ to C₄ alkyl and the group L(R)_n;

R₂₆ and R₂₇ are each selected from the group consisting of C₁ to C₆ alkyl, C₅ to C₇ cycloalkyl, phenyl, phenyl substituted with one or two groups selected from C₁ to C₆ alkyl and C₁ to C₆ alkoxy and the group L(R)_n;

R²² and R²³ may optionally from a carboxylic ring of 5 or 6 ring members optionally fused with an optionally substituted benzene and wherein at least one of the substituents selected from the group of substituents consisting of B and B′

, R²², R²³, R²⁴, R²⁵, R²⁶ and R²⁷ is the group L(R)_n;

fulgides and fulgimides of formula XXX;

wherein

Q is selected from the group consisting of optionally substituted aromatic, optionally substituted heteroaromatic (where said aromatic/heteroaromatic may be mono or polycyclic aromatic/heteroaromatic);

R³⁰ is selected from the group consisting of a C₁ to C₄ alkyl, C₁ to C₄ alkoxy phenyl, phenoxy mono- and di(C₁-C₄) alkyl substituted phenyl or phen(C₁ to C₄);

A′

is selected from the group consisting of oxygen or ═

N—

R³⁶, in which

R³⁶ is C₁-C₄ alkyl or optionally substituted phenyl;

R³⁴ and R³⁵ independently represents a C₁ to C₄ alkyl, phenyl or phen(C₁ to C₄) alkyl or one of and R³⁴ ,R³⁵ is hydrogen and the other is one of the aforementioned groups, or R³⁴R³⁵=represents an adamantylidine group;

wherein at least one of Q, R³⁰, R³⁴, R³⁵ and R³⁶ comprises the group L(R)_n;

azo dyes of formula XL

wherein;

R⁴⁰ and R⁴¹ are independently selected from the group consisting of hydrogen;

C₁ to C₆ alkyl;

C₁ to C₆ alkoxy;

-NR⁴²R⁴³ wherein R⁴² and R⁴³ are as defined for R²⁶ and R²⁷;

aryl (such as phenyl) aryl substituted with one or more substituents selected from C₁ to C₆ alkyl and C₁ to C₆ alkoxy, substituted C₁ to C₆ alkyl wherein the substituent is selected from aryl and C₁ to C₆ alkoxy, substituted C₁ to C₆ alkoxy wherein the substituent is selected from C₁ to C₆ alkoxy aryl and aryloxy; and

diarylperfluorocyclopentenes of the following formula

wherein

substituted aromatic, optionally substituted heteroaromatic (where said aromatic/heteroaromatic may be mono or polycyclic aromatic/heteroaromatic);

R³⁴,R³⁵,R³⁶,R³⁷ independently represents a C₁ to C₄ alkyl, phenyl or phen(C₁ to C₄) alkyl or one of and R³⁴,R³⁵,R³⁶,R³⁷ is hydrogen and the others is one of the aforementioned groups,; and

wherein at least one of Q , R³⁴,R³⁵ , R³⁶ and R³⁷comprises the group L(R)_n.

37. A polymerizable composition for forming a photochromic article of glass transition temperature of at least 50°

C. on curing, the composition comprising;

(a) a polymerizable composition comprising a monomer component or resin formed therefrom; and

(b) a photochromic dye monomer comprising a photochromic moiety and at least one oligomeric group having at least one group reactive with the monomer component during or following curing wherein the oligomer group comprises a multiplicity of monomer units selected from siloxane, alkylene and substituted alkylene.