Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1997-11-14
2002-06-25
Higel, Floyd D. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S381000, C549S456000, C549S472000, C549S473000, C546S258000, C544S344000, C525S420000, C525S437000, C525S450000, C525S452000, C525S461000
Reexamination Certificate
active
06410754
ABSTRACT:
This application is a 371 of PCT/FR96/00429 field Mar. 21, 1996.
TECHNICAL FIELD
The present invention relates to novel compounds of the spiropyran type which have photochromic properties in particular. It further relates to the photochromic compositions and ophthalmic articles (e.g. lenses) containing these spiropyrans.
PRIOR ART
Photochromic compounds are capable of changing color under the influence of polychromatic or monochromatic light (e.g. UV) and of reverting to their initial color when the light irradiation ceases, or under the influence of a different polychromatic or monochromatic light from the first, or under the influence of temperature and/or a different polychromatic or monochromatic light from the first.
These photochromic compounds have applications in a variety of fields, for example for the manufacture of ophthalmic lenses, contact lenses, sunglasses, filters, lenses for moving or still cameras or for other optical and observation devices, glazing, decorative objects or display elements, or alternatively for the storage of information by optical recording (coding).
In the field of ophthalmic optics and particularly glasses, a photochromic lens comprising one or more photochromic compounds must have, over a wide temperature range (−20° C. to +50° C.), a high transmission in the dark or in the absence of sunlight, a low transmission (high colorability) under solar irradiation, fast coloration and decolorization kinetics, an appreciable durability with an optimal efficacy, and a pleasant tint acceptable to-the consumer (preferably gray or brown).
These lens characteristics are in fact determined by the active photochromic compounds, which must also be perfectly compatible with the organic or inorganic substrate of which the lens is made. It should furthermore be noted that, to obtain a gray or brown tint, it may be necessary to use at least two photochromic compounds of different colors, i.e. with different maximum absorption wavelengths in the visible (&lgr;
max
). This association also makes other demands on the photochromic compounds. In particular, the coloration and decolorization kinetics of the two types of active photochromic compounds in association must be substantially identical. The same applies to their stability over time and also to their compatibility with a plastic or inorganic substrate.
The benzopyrans and naphthopyrans forming the subject of the invention according to U.S. Pat. No. 3,567,605 may be mentioned among the numerous photochromic compounds described in the prior art. When subjected to temperatures of the order of −30 or −40° C., these compounds change from a colorless state to a yellow-orange or even red tint under high energy activating irradiation of the UV type. These compounds revert to the colorless state when the temperature is raised (≧0° C.) and/or when they are irradiated in the visible. The thermal and kinetic conditions of the photochromism peculiar to these compounds seem a priori to be rather incompatible with common ophthalmic applications.
These compounds also have relatively low &lgr;
max
values in the visible.
In the case of photochromic compounds of the pyran type, high energy radiation (UV) allows the opening of the pyran ring and hence the conjugation of double bonds. This ring opening causes the appearance of an absorbance in the visible whose &lgr;
max
, colorability Ao and &lgr;
max
peak height and area are characteristic.
Patent application EP 0 562 915 discloses novel heterocyclic chromenes which are useful as photochromic compounds in the field of ophthalmic optics. These compounds are benzopyrans or chromenes substituted by two phenyls, which themselves are optionally substituted. These photochromic compounds are presented as having a colorability in the red region (&lgr;
max
=438-510 nm) and as being usable with photochromic compounds whose &lgr;
max
is situated in the blue (≈600 nm). It has been found, however, that these known compounds are still capable of improvement as regards their colorability and their photochemical stability.
More recently, U.S. Pat. No. 5,238,281 has disclosed novel photochromic compounds of the naphthopyran type substituted in the 5-, 8- and 9-positions of the naphthyl moiety. According to the assignee, these substitutions, and more particularly the one in the 8-position of a naphthopyran which is itself substituted in the 3-position by two phenyl groups, effects an increase in the photochromic sensitivity, said increase supposedly being related to a bathochromic modification of the activating UV spectrum. This specific substitution of the naphthyl is also said to be the cause of a bathochromic change in the visible absorption spectrum of the activated compound (exposed to UV). The two phenyl substituents on the pyran ring are structurally independent. The &lgr;
max
values in the visible of the photochromic compounds according to this US patent range from 432 nm to 543 nm.
Despite all these improvements, these naphthopyrans have the disadvantage of possessing an insufficient colorability and a &lgr;
max
(visible) which is rather incompatible with the most commonly available complementary photochromic compounds for obtaining satisfactory tints and colorabilities.
Furthermore, patent applications WO 95/00 504 and WO-A-95/05 382 and U.S. Pat. No. 5,395,567 describe diphenylnaphthopyrans or diphenylheterobenzopyrans in which the two phenyl radicals, bonded to the 2-position of the pyran ring, are bridged by a direct a bond or the following groups:
&Parenopenst;CH
2
&Parenclosest;
n=1à3
, —O—, —S— ou &Parenopenst;CH═CH&Parenclosest;
In WO 95/00 504 the bridging is proposed in order to reduce the rate of diffusion of these products in a polymeric matrix.
The products in which the bridging is formed by a direct bond are photochemically unstable. Those with the following bridging:
—O—
have a low colorability.
In this state of the art, one of the essential objects of the present invention is to provide novel compounds, particularly photochromic compounds, which belong to the spiropyran family and do not exhibit the disadvantages of the known photochromic compounds of the same type. In particular, the invention relates to spiropyrans possessing:
a high colorability,
a high sensitivity to the activating irradiation which causes the opening of the pyran ring (, e.g. in the UV with large peak height and area),
an absence of coloration or a very weak coloration in the non-activated (non-exposed) state,
an intense coloration after activation: large peak height and area at &lgr;
max
in the visible,
&lgr;
max
in the visible which, in association with at least one other photochromic compound of complementary &lgr;
max
. in the visible, permits a substantial coverage of the visible spectrum,
high coloration/decolorization rates,
suitability for photochromism over a wide and extensive temperature range (−20° C. to +50° C.),
long durability (of the optimal efficacy), it also being necessary for these spiropyrans to be easy to prepare.
Another object of the invention relates to the use of the photochromic compounds in the field of ophthalmic optics and particularly for their use in and/or on ophthalmic lenses, i.e., in terms of the invention, lenses for glasses (sunglasses), contact lenses and lenses for optical devices, inter alia.
Within the framework of the use of the above-mentioned photochromic compounds, another object of the invention is to provide compositions which comprise said photochromic compounds and are intended for example for use in the coating of ophthalmic lenses or as constituent chromogenic agents of said lenses.
Another object of the invention is to provide the photochromic compound in the form of polymers and/or crosslinking agents.
Another object of the invention is to provide an organic polymeric or copolymeric matrix and/or an inorganic matrix containing the above-mentioned photochromic compounds in polymeric or non-polymeric form.
Another object of the invention relates to the ophthalmic articles, for e
Chan You-Ping
Soula Gerard
Flamel Technologies
Lydon James C.
Sackey Ebenezer
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