FR2751648A1 - Cpds. used in mfr. of e.g. ophthalmic lenses - Google Patents

Abstract

Cpds. of formula (1), are claimed. R1, R2, R4, R6 = H, halogen, 1-12C linear or branched alkyl, 3-12C cycloalkyl or bicycloalkyl, 1-12C linear or branched alkoxy, 1-6C linear or branched haloalkyl or haloalkoxy, 1-12C linear or branched alkenyl or alkynyl, a methacryloyl or acryloyl, an epoxy of formula (i), where n = 1 to 3: 6-24C aryl or aryloxyl, 4-24C heteroaryl or heteroaryloxy and at least one heteroatom selected from sulphur, oxygen and nitrogen. The aryl or heteroaryl are opt. substd. by at least one substit. selected from a halogen, 1-6C linear or branched alkyl, 1-6C linear or branched alkoxy, 1-6C linear or branched haloalkyl or haloalkoxy, an NH2, an NHR where R = 1-6C linear or branched alkyl, a NR'R" where R' and R" may be identical or different, and are a 1-6C linear or branched alkyl, or together with the N atom to which they are bound form a 5-7 member ring which can comprises at least another heteroatom selected from oxygen, sulphur, and nitrogen; (The nitrogen is opt. substd. by a 1-6C linear or branched alkyl); a 1-4C aralkyl or heteroalkyl, an NH2, NHR, NR'R", CONH2, CONHR or CONR'R"; OCOR' or COOR' where R' = 1-6C linear or branched alkyl or a 3-12C cycloalkyl or bicycloalkyl or an aryl or heteroaryl; a polyether, polyamide, polycarbonate, polycarbamate, polyurea or polyester residue; R7, R8 = a 1-12C linear or branched alkyl, 3-12C cycloalkyl, an aryl or heteroaryl gp. as previously defined, the julolidin-9-yl gp.; or R7 and R8 together = an adamantyl, norbornyl, fluorenylidene or di(1-6C alkyl)anthracenylidene or spiro (5-6C alkyl) anthracenylidene or spiro (5-6C cycloalkyl) anthracenylidene; R3 and R5 = 1-6C linear or branched alkoxy.

Description

 The present invention relates to novel compounds of the naphthopyran type and having, in particular, photochromic properties. It also relates to photochromic compositions and ophthalmic articles (for example lenses) containing naphthopyrans.

 The photochromic compounds are capable of changing color under the influence of a poly- or monochromatic light (eg W) and to recover their initial color, when the light irradiation ceases, or under the influence of a light poly- or monochromatic different from the first, or under the influence of temperature and / or a poly- or monochromatic light different from the first.

 These photochromic compounds have applications in various fields, for example, for the manufacture of ophthalmic lenses, contact lenses, sunglasses, filters, camera optics or cameras or other optical and observation devices, glazings, decorative objects, display elements or even for the storage of information by optical inscription (coding).

In the field of ophthalmic optics, and in particular eyewear, a photochromic lens, comprising one or more photochromic compounds, must present
- high transmission in the dark or in the absence of sunlight,
a weak transmission (high colorability) under solar irradiation,
a suitable coloration and discoloration kinetics,
a shade acceptable by the consumer (preferably gray or brown) with, preferably, a maintenance of the hue chosen during the coloration and the discoloration of the lens,
a maintenance of the properties of the properties in a temperature range of 0-40 C,
- an important durability, because the objectives are sophisticated corrective lenses and therefore expensive.

 These lens characteristics are, in fact, determined by the active photochromic compounds, which must, in addition, be perfectly compatible with the organic or inorganic material constituting the lens.

 It should also be noted that obtaining a gray or brown hue may require the use of at least two photochromics of different colors, that is to say having wavelengths of maximum absorption. in the visible distinct. This association imposes other requirements on photochromic compounds. In particular, the staining and fading kinetics of the two or more associated active photochromic compounds must be substantially identical. It is the same for their stability over time and, also, for their compatibility with a plastic or mineral support.

Among the numerous photochromic compounds described in the prior art, mention may be made of the naphthopyrans described in patents US Pat. No. 3,567,605, US Pat. No. 3,627,690 and US Pat. No. 4,826,977.
US 5,200,116, US 5,458,814 and Research Disclosure No. 36144:

 These compounds claim to meet the specifications defined above. In fact, if these compounds do have one or more of the desired basic properties, such as high dark transmittance and high colorability under solar irradiation, all the compounds described to date do not have the complete combination of properties sought, necessary for the production of satisfactory articles, susceptible of industrial manufacture. If the prior art teaches how to modify the decolorization kinetics by the presence of methyl groups at R1 and R2, it does not teach how to modify the profile of the visible spectrum of the activated form (exposure to UV). The compounds of the prior art are generally orange or red with a main absorption band in the visible.

 It is the merit of the Applicant to have found, in a surprising way, that the presence of at least two alkoxy groups, at R3 to R6, allowed obtaining photochromes having two intense absorption bands in the visible and at high Xmax. The compounds of the invention thus cover a part of the visible spectrum (400 to 700 nm).

dans laquelle
- R1 à R6 sont identiques ou différents et représentent: .1' hydrogène,
un groupement alkyle, alcoxy, cycloalkyle, alcényle, alcynyle , aryle, alkylaryle, hétéroaryle, aryloxyle ou aralkyle, ledit groupement étant éventuellement halogéné,
un halogène, de préférence F, Br, C1,
un groupement amine,
-OCOR, -COOR, avec R = H, alkyle et/ou cycloalkyle et/ou aryle,
un reste de (poly)éther, (poly)amide, (poly)carbonate, (poly)carbamate, (poly)urée ou (poly)ester,
- R7 et R8 sont identiques ou différents et représentent un groupement
(poly)aromatique (par exemple phényle ou naphthyle, substitué ou non),
(poly)hétéroaromatique (par exemple furanyle, thiényle, pyridyle, benzofuranyle, substitué ou non)
cycloalkyle (par exemple cyclopropyle), ou bien
- les deux groupements R7 et R8 peuvent être liés pour former ensemble un groupement adamantyle, norbornyle, fluorénylidène ou dialkylanthracénylidène, éventuellement substitué.Thus, the present invention relates to compounds, in particular photochromic compounds, of general formula (I) below

in which
R 1 to R 6 are identical or different and represent:
an alkyl, alkoxy, cycloalkyl, alkenyl, alkynyl, aryl, alkylaryl, heteroaryl, aryloxyl or aralkyl group, said group being optionally halogenated,
a halogen, preferably F, Br, C1,
an amine group,
-OCOR, -COOR, with R = H, alkyl and / or cycloalkyl and / or aryl,
a residue of (poly) ether, (poly) amide, (poly) carbonate, (poly) carbamate, (poly) urea or (poly) ester,
- R7 and R8 are identical or different and represent a grouping
(poly) aromatic (for example phenyl or naphthyl, substituted or unsubstituted),
(poly) heteroaromatic (e.g. furanyl, thienyl, pyridyl, benzofuranyl, substituted or unsubstituted)
cycloalkyl (for example cyclopropyl), or
the two groups R7 and R8 may be linked to form together an optionally substituted adamantyl, norbornyl, fluorenylidene or dialkylanthracenylidene group.

characterized in that at least two of the groups R3 to
R6 are C1-C6 alkoxy groups.

 Among the possible substituents for the compounds of the formula (I) according to the invention, it is necessary to envisage groups comprising and / or forming at least one function capable of polymerization and / or crosslinking, preferably selected from the list next alkenyl - advantageously vinyl, methacryloyl, acryloyl, acryloxyalkyl, methacryloxyalkyl or epoxy.

 Thus, the photochromic compounds according to the invention may be monomers, of different or different natures, capable of reacting with each other or with other comonomers, to form homopolymers and / or copolymers, carrying a photochromic functionality and possessing mechanical properties of macromolecules. It follows that one of the objects of the present invention is formed by those homopolymers or copolymers comprising (co) monomers and / or by reticulates, at least partly constituted by photochromic compounds (I) according to the invention. .

 In the same vein, the aforementioned compounds (I) may be crosslinking agents provided with reactive functions capable of allowing bridging between photochromic or non-photochromic polymer chains. The reticles, which can thus be obtained, are also part of the present invention.

In a particularly preferred manner, the alkoxy groups are methoxys. Preferred compounds of the invention have the following formulas (I1 to I4)

 where R7 and R8 are (poly) aromatic or (poly) heteroaromatic groups optionally substituted by one or more C1-C5 alkoxys, amines or C1-C6 alkyl or C6-C12 aryl groups.

 It is the merit of the Applicant to have disclosed these compounds, because they have particularly advantageous photochromic properties. Specifically, they are endowed with high colorability with two bands of absorption in the visible with high Xmax.

 These compounds are, moreover, perfectly stable and compatible with matrices of organic polymer or mineral material, both in the form included in the matrix and in the form of coating.

 In solution or in a polymer matrix, the compounds according to the invention are colorless or slightly colored in the initial state and rapidly develop an intense coloration under a light W (365 nm) or a solar-type light source. Finally, they quickly recover their initial color when irradiation ceases.

 The compounds of the invention can be obtained by condensation of a suitably substituted 1-naphthol derivative and a propargyl alcohol derivative. This synthetic route is conventional and is described for example in the references cited above.

This reaction can be carried out in solvents such as toluene or tetrahydrofuran in the presence of an acidic catalyst such as para-toluenesulphonic acid, chloroacetic acid or acidic alumina.

The 1-naphthol derivatives for their part are obtained by methods adapted from the literature (see, for example, US Patent 5,200,116 and Sibi et al., J. Org Chem 1986, vol 51, p 271-273). Examples of naphthol derivatives synthesizable by these methods are

 As regards the applications of the compounds according to the present invention, it should be noted that they can be used as photochromic material dispersed in the mass of a polymer matrix. They can also be used in solution.

 A photochromic solution can be obtained by solubilizing the compound in an organic solvent, such as toluene, dichloromethane, tetrahydrofuran or ethanol. The solutions obtained are generally colorless and transparent. Exposed to sunlight, they develop a strong color and return to the colorless state when they are placed in an area of least exposure to solar radiation or, in other words, when they are no longer subjected to UV. In general, a very low concentration of product (of the order of 0.01 to 5 W) is sufficient to obtain an intense coloration.

 The most interesting applications are those in which the photochromic is dispersed uniformly within or on the surface of a polymer, copolymer or mixture of polymers. The implementation methods that can be envisaged are very varied. Among those known to those skilled in the art, there may be mentioned, for example, the diffusion in the (co) polymer, from a suspension or solution of photochromic, in a silicone oil, in an aliphatic hydrocarbon or aromatic, in a glycol, or from another polymer matrix. The diffusion is commonly carried out at a temperature of 50 to 2000C for a period of 15 minutes to a few hours, depending on the nature of the polymer matrix.

Another implementation technique consists in mixing the photochromic in a formulation of polymerizable materials, depositing this mixture on a surface or in a mold and then performing the polymerization. These and other processing techniques are described in the article by CRANO et al. In a variant of the invention, it is also possible to graft photochromic substances onto (co) polymers. Another object of the invention is formed by the (co) polymers grafted with at least one of the photochromics described above.

By way of examples of preferred polymeric materials for optical applications of the photochromic compounds according to the invention, mention may be made of the following products
poly (mono-, di-, tri-, tetra-) acrylate or optionally halogenated alkyl, cycloalkyl, aryl or arylalkyl poly (mono-, di-, tri-, tetra-) methacrylate or comprising at least one ether and / or ester and / or carbonate and / or carbamate and / or thiocarbamate and / or urea and / or amide groups; polystyrene, polycarbonate (eg bisphenol-A polycarbonate, poly (diallyl diethylene glycol carbonate), polyepoxy, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinyl polymers, cellulose acetate, cellulose triacetate, acetate cellulose propionate or polyvinyl butyral,
copolymers of two or more types of monomers or polymer mixtures referred to above, preferably polycarbonate-polyurethane, poly (meth) acrylatepolyurethane, polystyrene-poly (meth) acrylate or else polystyrene-polyacrylonitrile, advantageously a mixture of polyester and polycarbonate or poly (meth) acrylate.

 The amount of photochromic used depends on the degree of darkening desired. In the usual way, an amount of between 0.001 and 20 wt.

The photochromic compounds according to the invention may be used alone or as a mixture with other products to form a composition which may be in solid or liquid form, for example in solution or in dispersion, as already indicated above. These compositions, which constitute another subject of the invention, may comprise one or more compounds (I) according to the invention and other complementary photochromic compounds making it possible to obtain dark, for example gray or brown, colors desired by the in applications such as ophthalmic or solar eyewear. These additional photochromic compounds may be those known to those skilled in the art and described in the literature, for example chromenes (US 3,567,605, US 5,238,981, WO 94/2850, EP 562 915), spiropyrans or naphtospiropyrans (US 5,238,981) and spiroxazines (CRANO et al., "Applied Photochromic Polymer Systems, Ed. Blackie & Son Ltd, 1992, Chapter 2
These compositions according to the invention may also comprise
non-photochromic dyes for adjusting the hue,
and / or one or more stabilizers, for example an antioxidant
- and / or one or more anti-UV,
and / or one or more antiradicals,
and / or deactivators of photochemically excited states.

 These additives can make it possible to improve the durability of said compositions.

 According to another of its aspects relating to the application of photochromic compounds (I), the present invention also relates to ophthalmic articles, such as ophthalmic or solar eyewear, comprising at least one compound according to the invention and or at least one (co) polymer formed, at least in part, of repeating units derived from compounds of formula (I), and / or at least one composition comprising compounds (I), according to the invention, as defined above, and / or at least one matrix, as defined above, of organic polymer material or mineral material or hybrid organic mineral material incorporating at least one compound of the invention.

 In practice, the articles more particularly targeted by the present invention are ophthalmic lenses or photochromic lenses, glazing (windows for buildings, for locomotion machines, motor vehicles), optical devices, decorative items, sun protection articles, storage of information, etc ...

 The present invention will be better understood in the light of the following examples, of synthesis and photochromic validation of compounds of the general formula (I).

EXAMPLES
SYHTHESIS AND PROPERTIES OF PHOTOCHROMIC COMPOUNDS 1-3
ACCORDING TO THE INVENTION
Example 1 Synthesis of the compound (1)
Step 1: 5,7-Dimethoxy-3-methyl-1-naphthol is synthesized from N-diethyl-3,5-dimethoxybenzamide and 3-bromo-2-methylpropene according to the method described by Sibi et al. (J. Org Chem 1986, vol 51, p271-273).

 Step 2: The bis (para-methoxyphenyl) propargyl alcohol is obtained by reaction of lithium acetylide (diamine complex) with 4,4'-dimethoxybenzophenone in DMSO followed by hydrolysis and extraction with toluene.

 Step 3: The compound obtained from step 1 (2 g) is reacted with that obtained from step 2 (2.23 g) in 30 ml of toluene in the presence of a catalytic amount of paratoluene sulphonic acid. at 250C for 2 hours. The medium is then washed with water containing 10 W of sodium bicarbonate, evaporated to dryness and then the photochrome separated by chromatography on a silica column, eluting with a heptane / diisopropyl ether mixture. In this way, 100 mg of compound C1 is obtained in the form of a white powder. 1H NMR confirms the structure of the product. In solution in THF, the color of the solution changes from colorless to violet in the sun and fades quickly in the dark.

Example 2 Synthesis of Compound 2
Compound 2 is obtained analogously to that used for compound 1 from 5,7-dimethoxy-3-methyl-1-naphthol and (3,4-dimethoxyphenyl-4'-methoxyphenyl) propargyl alcohol.

Example 3 Synthesis of Compound 3
Compound 3 is obtained analogously to that used for compound 1 from 5,7-dimethoxy-3-methyl-1-naphthol and (6-methoxynaphthyl-4H-methoxyphenyl) propargyl alcohol.

Example 4 Incorporation of the Compounds in a Polyacrylate
General procedure: 10 -4 moles of each of the compounds are solubilized in 100 g of tetraethoxylated bisphenol A dimethacrylate (sold under the name DIACRYL 121 by AKZO) also containing 40 mg of 2,2'-azobis (2-methylbutyronitrile). The solution is then degassed, inerted with argon, and then poured into a glass lens mold 8 cm in diameter and 2 mm thick. The mold is then placed in an oven at 70 ° C for 12 hours.

After demolding, a transparent and rigid lens is obtained. Under solar irradiation, the glass rapidly develops an intense violet color and becomes colorless in the dark. The photochromic characteristics are given in Table 1 below. By way of comparison, the characteristics of the compound C1 of the prior art are given in Table 1 below.

After 15 minutes of exposure to a Xenon lamp, the UV-visible spectrum is recorded and the Xmax of the two main bands and their absorbance are measured.

Structures of Compounds 1 to 3 According to the Invention and Comparative Example C1

Comparntzf i
Tableau 1

Compound I Compound 2 Compound 3

Compare i
Table 1

<tb><SEP> band <SEP> 1 <SEP> band <SEP> 2 <SEP> absorbances
<tb> compound <SEP> Amax <SEP> Amax <SEP> band <SEP> 1 /
<tb><SEP> (absorbance) <SEP> (absorbance) <SEP> band <SEP> 2
<tb> Example <SEP> 440 <SEP> nm <SEP> (1.0) <SEP> 552 <SEP> nm <SEP> (0.9) <SEP> 1,2
<tb> Example <SEP> 444 <SEP> nm <SEP> (1,0) <SEP> 552 <SEP> (0,9) <SEP> 1,2
<tb><SEP> 2
<tb> Example <SEP> 444 <SEP> nm <SEP> (1,0) <SEP> 556 <SEP> (0,9) <SEP> 1,2
<tb><SEP> 3
<tb><SEP> Cl * <SEP> 422 <SEP> nm <SEP> (0.6) <SEP> 502 <SEP> nm <SEP> (0.9) <SEP> 0.7
<Tb>
* described in Research Disclosure No. 36.144
The results clearly demonstrate that the compound according to the invention
has higher Xmax (bathochromic effect),
is more colorable and
has a higher band 1 / band 2 absorbance ratio compared to the analogous compound having no methoxy (C1) on the naphthyl ring of the naphthopyran.

Claims (14)

 1 - Photochromic compounds of the following general formula (I)

R6 are C1-C6 alkoxy groups.  characterized in that at least two of the groups R3 to  the two groups R7 and R8 together form an adamantyl, norbornyl, fluorenylidene or dialkylanthracenylidene group,  (poly) cycloalkyl; or  (poly) heteroaromatic substituted or unsubstituted,  (poly) aromatic substituted or unsubstituted,  - R7 and R8 are identical or different and represent a grouping  or a remainder of (poly) ether, (poly) amide, (poly) carbonate, (poly) carbamate, (poly) urea or (poly) ester,  -OCOR, -COOR, where R = H, alkyl and / or cycloalkyl and / or aryl  an amine group  a halogen,  an alkyl, alkoxy, cycloalkyl, alkenyl, alkynyl, aryl, alkylaryl, heteroaryl, aryloxyl or aralkyl group, said group being optionally halogenated,  R1 to R6 are identical or different and represent: hydrogen  in which,  2 - Compounds according to claim 1, characterized in that R3 and R5 are alkoxy groups.  3 - Compounds according to claim 1, characterized in that R3 and R5 are methoxys groups.  4 - Compounds according to any one of claims 1 to 3, characterized in that the groups R1 to R6 which are not alkoxy groups are hydrogen atoms or alkyl groups.  5 - Compounds according to claim 1, characterized in that they respond to the structures (I1) to (I4) following.

wherein R7 and R8 are as defined in claim 1.  6 - Compounds according to any one of claims 1 to 5, characterized in that R7 and R8 are aromatic or polyaromatic groups optionally substituted with at least one C1-C5 alkoxy group, C1-C5 alkyl, C2-C12 amine, aryl in C6 to C12, or CF3.  7 - Compounds according to claims 1 to 6, characterized in that the groups R1. at R8 of the formulas (I) and (I1) to (I4) according to the invention, comprise and / or form at least one polymerizable and / or crosslinkable reactive group, chosen from the following: alkenyl, methacryloyl, acryloyl, acryloxyalkyl, methacryloxyalkyl and epoxy.  8 - (Co) polymer and / or crosslink obtained by polymerization and / or crosslinking of at least one monomer consisting of at least one photochromic compound according to claim 7.  9 - Photochromic composition, characterized in that it comprises  at least one compound according to any one of claims 1 to 7 and / or at least one (co) polymer according to claim 8,  and optionally at least one other photochromic compound and / or at least one dye and / or at least one stabilizer.  10 - Matrix (co) polymer, characterized in that it comprises  at least one compound according to any one of claims 1 to 7,  and / or at least one composition according to claim 9.  11 - Matrix according to claim 10, characterized in that the (co) polymer is chosen from the following  poly (mono-, di-, tri- or tetra-) acrylate or optionally halogenated alkyl, cycloalkyl, aryl or arylalkyl poly (mono-, di-, tri- or tetra-) methacrylate or at least one an ether and / or ester and / or carbonate and / or carbamate and / or thiocarbamate and / or urea and / or amide group; polystyrene, polycarbonate, polyepoxy, polyurethane, polythiourethane, polysiloxane, polyacrylonitrile, polyamide, aliphatic or aromatic polyester, vinyl polymers, cellulose acetate, cellulose triacetate, cellulose acetate propionate or polyvinyl butyral,  copolymers of two or more types of monomers or polymer mixtures referred to above.  12 - Ophthalmic or solar article comprising  at least one compound according to any one of claims 1 to 7,  and / or at least one copolymer according to claim 8  and / or at least one composition according to claim 9.  13 - Article according to claim 12, characterized in that it consists of a lens.  14 - Glazing and / or optical device comprising  at least one compound according to any one of claims 1 to 7  and / or at least one (co) polymer according to claim 8  and / or at least one composition according to claim 9  and / or at least one matrix according to claim 10 or 11.