Radiation imagery chemistry: process – composition – or product th – Imaging affecting physical property of radiation sensitive... – Radiation sensitive composition or product or process of making
Reexamination Certificate
1999-09-09
2003-01-14
Angebranndt, Martin (Department: 1756)
Radiation imagery chemistry: process, composition, or product th
Imaging affecting physical property of radiation sensitive...
Radiation sensitive composition or product or process of making
C430S019000, C549S381000, C549S382000, C252S586000, C524S110000
Reexamination Certificate
active
06506538
ABSTRACT:
The present invention relates to novel annelated naphthopyran-type compounds 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 naphthopyrans.
The photochromic compounds are capable of changing colour under the influence of a poly- or monochromatic light (UV for example) and of returning to their initial colour when the luminous irradiation ceases, or under the influence of temperature and/or a poly- or monochromatic 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 colourability) 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 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 colours, 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 or inorganic support.
Amongst the numerous photochromic compounds described in the prior art, benzopyrans or 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, WO-A-95 05382, FR-A-2,718,447, WO-A-96 14596, and WO-A-97 21698 which are of the reduced formula below:
The U.S. Pat. No. 5,645,767 describes naphthopyrans which have an indeno group linked to carbons 5 and 6 of the naphtho skeleton:
The U.S. Pat. No. 5,651,923 describes naphthopyrans having a naphthofurano or benzo group linked to carbons 5 and 6 of the naphtho skeleton.
The U.S. Pat. No. 5,783,116 describes naphthopyrans having a non-substituted alicyclic group.
These known compounds A, B, C, D, E claim to satisfy the specifications defined supra. 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 colourability 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 particular, none of these compounds is intrinsically grey or brown and the necessity of using an additional photochrome in order to obtain one of these two tints does subsist.
The photochromic compounds according to U.S Pat. No. 5,645,767 are obtained from substituted or non-substituted benzophenones, which are allowed to react with a succinic acid ester, such as the dimethyl ester, in the presence of toluene and potassium tert-butoxide. A half-ester is thus produced which is successively converted into acetoxynaphthalene and then into carboxynaphthol which is cyclised to obtain a naphthol fused with a benzofuranone residue. The reaction of this latter compound with a propargylic alcohol in the presence of DBSA leads to a naphthopyran fused with an indenone ring. The indene homologue of this naphthopyran can be obtained by starting from a precursor having a reduced ketone function. This carbon of the indene can be substituted in various ways.
As for the naphthopyrans fused with benzo or naphthofuran residues according to U.S. Pat. No. 5,657,923, they are prepared by reaction of a naphthol fused with an indenone ring or a naphthofuran ring, on the one hand, and with a propargylic alcohol on the other. The naphthol fused with an indenone ring is obtained for example as described in U.S. Pat. No. 5,645,767; while the naphthol fused with a naphthofuran ring originates from a reaction between a naphthoquinone and a 1,3-dihydroxynaphthalene, with or without subsequent methylation of at least one hydroxy.
In this context, it is to the credit of the inventors for having been interested in the above-mentioned naphthopyrans and for having selected, within this family of naphthopyrans fused in C
5
-C
6
with at least one carbocycle, a group of specific molecules having particularly advantageous photochromic properties.
The present invention thus relates, according to a first of its aspects, to the compounds of formula (I):
in which:
R
1
and R
2
are identical or different and independently represent:
hydrogen,
a linear or branched alkyl group which comprises 1 to 12 carbon atoms,
a cycloalkyl group which comprises 3 to 12 carbon atoms,
an aryl or heteroaryl group which comprises 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 group,
a linear or branched alkyl group which comprises 1 to 12 carbon atoms,
a linear or branched alkoxy group which comprises 1 to 12 carbon atoms,
a haloalkyl or haloalkoxy group corresponding respectively to the (C
1
-C
12
) alkyl or alkoxy groups above which are substituted with at least one halogen atom, and notably a fluoroalkyl group of this type,
a phenoxy or naphthoxy group optionally substituted by at least one linear or branched alkyl or alkoxy group which comprises 1 to 6 carbon atoms,
a linear or branched alkenyl group which comprises 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 which comprises 1 to 6 carbon atoms,
a:
group,
R′ and R″, which are identical or different, independently representing a linear or branched alkyl group which comprises 1 to 6 carbon atoms, a phenyl group optionally substituted by at least one linear or branched alkyl or alkoxy group which comprises 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,
an aralkyl or heteroaralkyl group, the alkyl group, which is linear or branched, comprising 1 to 4 carbon atoms, and the aryl and heteroaryl groups having the definitions given above, or
said two substituents R
1
and R
2
together form an adamantyl, norbornyl, fluorenylidene, di(C
1
-C
6
)alkylanthracenylidene or spiro(C
5
-C
6
)cycloalkylanthracenylidene group; said group being
Breyne Olivier
Chan You-Ping
Jean Patrick
Angebranndt Martin
Corning S.A.
Nwaneri Angela N.
Rogalskyj Peter
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