Compositions – Light transmission modifying compositions – Displaying color change
Reexamination Certificate
2001-10-09
2003-05-06
Tucker, Philip (Department: 1712)
Compositions
Light transmission modifying compositions
Displaying color change
C549S382000, C549S381000, C549S331000, C351S163000, C568S732000, C524S110000
Reexamination Certificate
active
06558583
ABSTRACT:
The present invention relates to novel naphthopyran-type compounds which are annelated in C
5
-C
6
with a dihydrobenzocycloheptatriene-type carbocycle, and which have, in particular, photochromic properties. The invention also relates to photochromic compositions and photochromic ophthalmic articles (lenses for example) which contain said naphthopyrans. The invention also covers the preparation of these novel compounds.
The photochromic compounds are capable of changing color under the influence of a poly- or mono-chromatic light (UV for example) and of returning to their initial color when the luminous irradiation ceases, or under the influence of temperature and/or a poly- or mono-chromatic light different from the first.
The photochromic compounds find applications in various fields, e.g. for the manufacture of ophthalmic lenses, contact lenses, solar protection glasses, filters, camera optics or photographic apparatus optics or other optical devices and observation devices, glazing, decorative objects, bill elements or even for information storage by optical inscription (coding).
In the field of ophthalmic optics, and in particular the spectacles trade, a photochromic lens which comprises one or more photochromic compounds must have:
a high transmission in the absence of ultraviolets,
a low transmission (high colorability) under solar irradiation,
adapted coloration and discoloration kinetics,
a tint acceptable to the consumer (grey or brown preferably) with preferably a maintenance of the chosen tint during the coloration and the discoloration of the lens,
a maintenance of the performances, the properties, within a temperature range of 0-40° C.,
a significant durability, since these objectives sought after are sophisticated corrective lenses and therefore expensive.
These lens characteristics are in fact determined by the active photochromic compounds which they contain; compounds which must furthermore be perfectly compatible with the organic or inorganic, even hybrid support which constitutes the lens.
Moreover, it is to be noted that obtaining a grey or brown tint may necessitate the use of at least two photochromes of different colors, i.e. having distinct maximal absorption wavelengths in the visible. This combination further imposes other requirements of the photochromic compounds. In particular, the coloration and discoloration kinetics of the (two or more) combined active photochromic compounds must be essentially identical. The same applies for their stability with time and also for their compatibility with a plastic, inorganic or hybrid inorganic-organic support.
Amongst the numerous photochromic compounds described in the prior art, benzopyrans and naphthopyrans may be cited which are described in patents or patent applications: U.S. Pat. Nos. 3,567,605, 3,627,690, 4,826,977, 5,200,116, 5,238,981, 5,411,679, 5,429,744, 5,451,344, 5,458,814, 5,651,923, 5,645,767, 5,698,141, 5,783,116, WO-A-95 05382, FR-A-2,718,447, WO-A-96 14596, WO-A-97 21698, which are of the reduced formulae below:
U.S. Pat. No. 5,645,767 describes naphthopyrans which have an indeno group linked to carbons 5 and 6 of the naphtho skeleton:
U.S. Pat. No. 5,783,116 describes naphthopyrans which have a non-substituted alicyclic group
Patent application WO 00/15628 of the Applicant describes naphthopyrans which have an alicyclic group which is substituted or fused with an aromatic:
These compounds claim to satisfy the specifications defined above. In reality, if these compounds really do have one or more of the basic properties sought after, such as a high transmission in the absence of ultraviolets and a high colorability under solar irradiation, none of the compounds described hitherto have the complete combination of the properties sought after which are necessary for the production of satisfactory articles.
In this context, it is to the credit of the inventors for having been interested in this type of derivative as a basis for the development of novel photochromes and for having proposed a novel family of molecules having particularly advantageous photochromic properties.
Thus, according to a first of its aspects, the present invention relates to compounds of the following formula (I):
in which:
R
1
and R
2
, which are identical or different, independently represent:
hydrogen,
a linear or branched alkyl group comprising 1 to 12 carbon atoms,
a cycloalkyl group comprising 3 to 12 carbon atoms,
an aryl or heteroaryl group comprising in its basic structure 6 to 24 carbon atoms or 4 to 24 carbon atoms respectively and at least one heteroatom selected from sulphur, oxygen and nitrogen; said basic structure being optionally substituted with at least one substituent selected from the whole of the substituents given below:
a halogen, and notably fluorine, chlorine and bromine,
a hydroxy,
a linear or branched alkyl group comprising 1 to 12 carbon atoms,
a linear or branched alkoxy group comprising 1 to 12 carbon atoms, or a silyloxy group,
a haloalkyl or haloalkoxy group corresponding to the (C
1
-C
12
) alkyl or alkoxy groups above respectively which are substituted with at least one halogen atom, and notably a fluoroalkyl group of this type,
a phenoxy or naphthoxy group optionally substituted with at least one linear or branched alkyl or alkoxy group comprising 1 to 12 carbon atoms,
a linear or branched alkenyl or alkynyl group comprising 2 to 12 carbon atoms, and notably a vinyl group or an allyl group,
an —NH
2
group,
an —NHR group, R representing a linear or branched alkyl group comprising 1 to 6 carbon atoms, or a phenyl group optionally substituted with at least one linear or branched alkyl group comprising 1 to 6 carbon atoms,
a
group, R′ and R″, which are identical or different, representing independently a linear or branched alkyl group comprising 1 to 6 carbon atoms, or a phenyl group optionally substituted with at least one linear or branched alkyl group comprising 1 to 6 carbon atoms, or representing together with the nitrogen atom to which they are bound a 5- to 7-membered ring which can comprise at least one other heteroatom selected from oxygen, sulphur and nitrogen, said nitrogen being optionally substituted with an R∴′ group, which is a linear or branched alkyl group comprising 1 to 6 carbon atoms,
a methacryloyl group or an acryloyl group;
and/or said basic structure being optionally annelated with an aromatic or non-aromatic cyclic group, which can comprise at least one heteroatom selected from the group comprising: oxygen, sulphur or nitrogen, which comprises one or two annelated rings; the ring(s), which is (are) independently aromatic or non-aromatic, and which is (are) 5- to 7-membered, being optionally substituted with at least one substituent selected from those listed above;
an aralkyl or heteroaralkyl group, the alkyl group of which, which is linear or branched, comprises 1 to 4 carbon atoms and the aryl part or heteroaryl part of which has the same definition as that given above for the aryl or heteroaryl group; or
said two substituents R
1
and R
2
together form an adamantyl, norbomyl, fluorenylidene, di(C
1
-C
6
)alkylanthracenylidene, or spiro(C
5
-C
6
)cycloalkylanthracenylidene group; said group being optionally substituted with at least one of the substituents listed above for R
1
, R
2
where R
1
and R
2
represent an aryl or heteroaryl group;
R
3
, which are identical or different, independently represent:
a hydroxy,
a halogen, and notably fluorine, chlorine or bromine,
a linear or branched alkyl group comprising 1 to 12 carbon atoms (advantageously 1 to 6 carbon atoms),
a cycloalkyl group comprising 3 to 12 carbon atoms,
a linear or branched alkoxy group comprising 1 to 12 carbon atoms (advantageously 1 to 6 carbon atoms), or a silyloxy group,
a haloalkyl, halocycloalkyl, or haloalkoxy group corresponding to the alkyl, cycloalkyl, alkoxy groups above respectively, which are substituted with at least one halogen atom, notably selected from fluorine, chlorine and bromine,
a linear or branched alkenyl or alkynyl group
Breyne Olivier
Chan You-Ping
Patrick Jean
Chen Siwen
Corning Incorporated
Schaeberle Timothy M.
Tucker Philip
LandOfFree
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