AU717186B2

AU717186B2 - Method for incorporating additives into an ophthalmic article by means of a fluid in supercritical state

Info

Publication number: AU717186B2
Application number: AU39462/97A
Authority: AU
Inventors: Gilles Baillet; Jean-Paul Cano; Jean-Francois Magne
Original assignee: Essilor International Compagnie Generale dOptique SA
Current assignee: EssilorLuxottica SA
Priority date: 1996-08-14
Filing date: 1997-08-08
Publication date: 2000-03-16
Anticipated expiration: 2017-08-08
Also published as: JP2000516270A; WO1998007054A1; DE69713509D1; EP0919003B1; AU3946297A; FR2752462A1; EP0919003A1; FR2752462B1; DE69713509T2

Description

'U

AJC/DD 1 B 1861/96 Method for incorporating additives in an ophthalmic article by means of a fluid in the supercritical state.

The present invention generally relates to a method for incorporating additives in an ophthalmic article made of organic glass by means of a fluid in the supercritical state.

The present invention more particularly relates to a method for incorporating additives, such as stabilizers, antioxidants, antiozonants, UV absorbers, plasticizers, dyes and pigments (photochromic substances and conventional dyes and pigments), in finished or semifinished ophthalmic articles made of transparent organic polymers by means of a fluid in the supercritical state, for example CO 2 in the supercritical state.

There exists a number of conventional methods for incorporating an additive, in particular a photochromic substance, in a substrate made of transparent organic polymers of an ophthalmic article.

A first conventional method consists in incorporating the various additives in the transparent and liquid monomer composition, in pouring the liquid monomer composition in which the additives are incorporated between the two parts of a mold and in then polymerizing the monomers in order to obtain the ophthalmic article comprising a substrate made of organic glass in which the desired additives are found enclosed. This technique exhibits a number of disadvantages. In particular, when the additives are photochromic pigments or UV absorbers, this method requires polymerization by the thermal route, since the presence of the UV absorber and/or of the photochromic pigments does not generally make possible, or only with great difficulty, a photochemical polymerization. Moreover, the incorporation of photochromic compounds in the case of the use of allylic monomers is virtually ruled out, the method requiring the use of a high concentration of initiator, long polymerization times and relatively high polymerization temperatures.

When the additive incorporated is a photochromic sub- 2 stance, there is a risk that the long polymerization times and the relatively high polymerization temperatures will cause degradation of the photochromic substance.

Moreover, it is not ruled out that degradation of the photochromic substance is generated by reaction of the latter with radicals originating from thermal or photochemical initiators.

Another conventional technique, used to incorporate conventional dyes in an ophthalmic article, consists in immersing the ophthalmic article, composed of a transparent polymer substrate, in an aqueous dispersion of insoluble dye particles and in heating at a temperature of the order of 90 0 C for a time sufficient to cause the dye particles to penetrate into the surface of the polymer substrate. This technique also exhibits a number of disadvantages. First of all, the dispersion has a limited lifetime and has to be discarded after a relatively short time, resulting in a significant loss of dye or requiring expensive stages for recovering the dye.

This method is not applied to all types of substrates or polymers and requires, for substrates which are the most resistant to dyeing, the use of an aggressive vector agent (for example phenol derivatives), which results in problems of discharges and risks of environmental pollution. Finally, the incorporation of the dye remains superficial, that is to say that the dye does not penetrate very far under the surface of the substrate, which does not make possible a core dyeing of the substrate.

A recently developed technique, more particularly for the introduction of photochromic substances into ophthalmic articles comprising a transparent polymer substrate, is the so-called "thermal transfer" technique.

This thermal transfer method is described, inter alia, in the documents US 4,286,957 and 4,880,667. In this technique, a surface of the transparent polymer substrate is coated with a layer of a varnish containing the photochromic substance to be incorporated. The substrate, thus T coated, is then treated thermally in order to cause the photochromic substance to migrate into the substrate.

-3- This method also exhibits a number of disadvantages. The heating time necessary to cause the photochromic substance to migrate is relatively long, of the order of hours. Only part of the photochromic substance is introduced into the substrate, so that there are not insignificant losses of photochromic substance. Finally, this method only makes possible a low depth of penetration of the photochromic substance into the substrate, of the order of 150 ym at most.

In the case of the incorporation of a photochromic substance, it is desirable to obtain the greatest possible penetration of this substance into the substrate. This is because the deep layers of photochromic substance act as a reservoir. Thus, as the surface layers of photochromic substance lose, under the effect of repeated UV irradiations, their photochromic characteristics, they are replaced by intact underlying layers of photochromic substance, which prolongs the lifetime of the photochromic ophthalmic article.

The document US-A-4,598,086 describes a method for impregnating a thermoplastic polymer with an impregnation material (namely a fragrance, a disinfecting or rat-killing agent or a pharmaceutical composition) by dissolving the impregnation material in a volatile blowing agent (for example, C0 2 maintained at or near supercritical conditions), causing the thermoplastic polymer to swell by bringing it into contact with the volatile blowing agent in the supercritical state or near supercritical state containing the impregnation material, and by reducing the pressure, so that the volatile blowing agent diffuses from the polymer.

The polymers act solely as support for an active product which must subsequently be released in a controlled way.

The document US-A-4,820,752 describes a method for infusing an additive into a polymer by dissolving the additive in a gaseous fluid solvent (for example C0 2 which has a boiling point below room temperature and a 3 density of at least 0.01 g/cm 3 by bringing the solution r0- \-av 1~ 4 of the additive and the fluid solvent into contact with a polymeric material for a time sufficient to enable at least part of the solution to be absorbed into the polymeric material, and by separating the fluid solvent from the polymeric material, leaving the infused additive therein.

Although this document envisages the use of a fluid in the supercritical state, this condition does not appear to be essential for the method described. Moreover, the only example using a fluid in the supercritical state relates to the incorporation of progesterone in a polyurethane substrate.

The document US-A-5,340,614 describes the impregnation in a polymer substrate of additives which are insoluble in a supercritical fluid which consists in bringing the polymer substrate, the impregnation additive and a liquid vehicle, such as water, into contact simultaneously in the presence of a supercritical fluid.

The document WO 95/20476 describes the treatment of ophthalmic lenses with a fluid in the supercritical state in order to remove incompletely polymerized materials therefrom.

It would thus be desirable to have available a method for incorporating additives in finished and semifinished ophthalmic articles containing a transparent polymer substrate which can be applied to all types of polymers which can be used for the manufacture of ophthalmic articles, which makes it possible to adjust at will the depth of penetration of the additives into the substrate and which in particular makes possible a core penetration of the additives, even into relatively thick substrates. In addition, this method should make possible short treatment times, should not degrade the additive, in particular should not harm the photochromic properties when the incorporated additive is a photochromic substance, and should not degrade the physical and optical properties nor the geometry of the polymer substrate of the ophthalmic article.

Thus, the method'must not harm in particular the 5 geometry of the polymer substrate, that is to say that it must not deform the polymer substrate to a point such that it will be necessary to reshape the ophthalmic article after the incorporation of the additive. In addition, the method must not harm the advantageous properties of the ophthalmic article, such as the resistance to scratching and to abrasion and the impact strength.

In addition, this method must make possible a homogeneous incorporation of the additive within the polymer substrate. The additive introduced must not be subject to a release phenomenon. Finally, the method must not detrimentally affect the resistance to ageing of the ophthalmic article.

According to the invention, a method for incorporating additives in a finished or semi-finished ophthalmic article comprising a transparent polymer substrate has been developed which comprises: the introduction of a fluid in the supercritical state into a reactor containing the ophthalmic article and the additive to be incorporated; the maintenance of the fluid in the supercritical state in the reactor, in the static state, for a predetermined period of time, in order to obtain the incorporation of the additive in the polymer substrate of the ophthalmic article to a predetermined depth; the removal of the fluid in the supercritical state; and the recovery of the ophthalmic article in which the additive has been incorporated.

A specific implementation of the method according to the invention relates to a method for the photochromization of a finished or semi-finished ophthalmic article comprising a transparent polymer substrate which comprises: A. A first stage composed of: the insertion into a reactor of a transparent polymer substrate and of a plasticizer for the substrate, the introduction into the reactor of a fluid in 'i -6the supercritical state, Sthe maintenance of the fluid in the supercritical state in the reactor, in the static state, for a predetermined period of time, in order to obtain the incorporation of the plasticizer in the polymer substrate, and the removal of the supercritical fluid; and B. A second stage composed of: the insertion into the reactor containing the plasticized polymer substrate of one or more photochromic compounds, Sthe introduction of a fluid in the supercritical state, the maintenance of the fluid in the supercritical state in the reactor, in the static state, for a predetermined period of time, in order to obtain the incorporation of the photochromic compound or compounds in the plasticized polymer substrate of the ophthalmic article to a predetermined depth, the removal of the supercritical fluid, and the recovery of the ophthalmic article in which the photochromic compound or compounds are incorporated.

Materials are generally known in three states: solid, liquid and gaseous. Materials change from one to another of these states when the temperature and/or the pressure is/are varied. Now, there exists a point beyond which it is possible to change from the liquid state to the gaseous or vapor state without boiling or, conversely, without condensing, thus without changing: this point is known as the critical point.

A fluid in a state characterized either by a pressure and a temperature which are respectively higher than the critical pressure and the critical temperature, in the case of a pure body, or by a representative point (pressure, temperature) situated beyond the boundary of the critical points represented on a diagram (pressure, temperature), in the case of a mixture, is said to be in the supercritical state.

Carbon dioxide proves to be a particularly 7 advantageous fluid for being used as fluid in the supercritical state, because of its critical parameters (t C 31-C, PC 7.3 MPa), its absence of toxicity, its non-polluting nature and its low cost.

The use of CO 2 in the supercritical state as fluid in the supercritical state is thus recommended in the method according to the invention. The ophthalmic articles which can be treated by the method of the invention are finished or semi-finished articles comprising a transparent polymer substrate.

The finished ophthalmic articles are ophthalmic articles obtained in their definitive shape, generally by pouring polymerizable compositions between two molds exhibiting required surface geometries and then polymerizing. An article is then obtained, the two faces of which are in their final state.

It is often the case that semi-finished articles are manufactured which comprise, after molding, a single face with its final geometry, it being possible for the second face then to be surface-finished as required.

The ophthalmic articles according to the invention comprise, for example, spectacle lenses, sun or corrective lenses, hard or soft contact lenses and hydrogel contact lenses in the dry state.

The ophthalmic articles can also, before the treatment by the method of the invention, contain layers of abrasion-resistant varnish and layers for increasing the impact strength on one of the surfaces of the transparent polymer substrate.

The polymers of the transparent substrate of the ophthalmic articles which can be used in the method of the invention are all transparent polymers, copolymers and mixtures of the latter which are suitable for the formation of ophthalmic articles.

Mention may be made, among the polymers and copolymers which can be used in the present invention, of allylic polymers, polyol (allyl carbonate) polymers, polyacrylates, poly(alkyl acrylate)s, such as poly(methyl Smethacrylate)s or such as poly(ethoxy)bisphenol A 8 di(meth)acrylates, polyurethanes, polythiourethanes and polycarbonates.

The particularly recommended polymers and copolymers are polycarbonates, such as poly(4,4'-dioxyphenyl-2,2-propane carbonate), poly(ethoxy)bisphenol A dimethacrylate, polyethylene glycol dimethacrylate (PEG dimethacrylate), poly(methyl methacrylate) or poly(allyl carbonate)s, such as diethylene glycol bis(allyl carbonate) and its copolymers.

The polymers and copolymers used for the manufacture of ophthalmic articles are well known and are described, inter alia, in the documents WO 95/10790 and EP-Al-0,653,428.

The additives which can be incorporated in the polymer substrate of the ophthalmic articles by means of the method according to the invention comprise all additives generally used in polymer substrates of ophthalmic articles and in particular UV absorbers, infrared absorbers, materials for laser screens, stabilizers, antioxidants, plasticizers, dyes and pigments, such as conventional dyes and pigments, photochromic substances and their mixtures.

The additives which are particularly recommended with the process of the present invention are dyes and pigments and very especially photochromic substances.

Mention may be made, among the UV absorbers which can be used in the present invention, of benzophenones, dihydroxybenzophenones or benzotriazoles. Use may be made, among the stabilizing agents, of stericallyhindered amines.

Mention may be made, among the materials for laser screens, of porphyrin complexes, phthalocyanine derivatives and their mixtures. Such materials are described in the document US-A-4,657,345.

Mention may be made, among the antioxidants which can be used in the present invention, of phenolic antioxidants, such as monophenols, bisphenols and thiobisphenols, phosphites, such as 4,6-di-tert-butylphenyl phosphite and triphenyl phosphite, or phosphines, such as 9 triphenylphosphine.

Mention may be made, among the plasticizers which can be used in the present invention, of linear or branched phthalates, such as the phthalates of Cg-C12 alcohols, in particular dioctyl phthalate (DOP), and isophthalates, such as diisodecyl phthalate (DIDP), diisononyl phthalate (DINP) and diisooctyl phthalate (DIOP), as well as benzyl butyl phthalate (BBP) and diisoundecyl phthalate (DIUP), or C 18

-C

30 fatty acid esters, such as adipates, sebacates and azelates.

Use may be made, among the conventional dyes and pigments, of all dyes and pigments which are conventional in coloring ophthalmic articles, such as, in particular, azo and anthraquinone pigments. Use is preferably made of lipophilic pigments.

Dyes which are particularly useful in the method of the present invention are photochromic substances.

These photochromic substances are well known in the art and are substances which, when they are irradiated by a light beam of appropriate wavelengths, change color and return to their original color as soon as the irradiation ceases. Mention may be made, among the photochromic substances which can be used, of benzopyran (chromene) derivatives, in particular naphthopyrans and preferentially diaryl[2H]naphthopyrans, and spirooxazine derivatives. Chromene derivatives are well known in the art and are described, inter alia, in United States Patent No.

US-3,567,605, International Applications No. 90/07507 and No. 91/00861 and European Patent Applications EP-0,246,114 and EP-0,401,958.

Spirooxazine derivatives are also well known and are described, inter alia, in numerous patents and patent applications, such as United States Patents US 5,139,707 and US 5,114,621 Guglielmetti and P. Tardieu) and European Patent Application EP-0,245,020.

Very clearly, the additives incorporated in the ophthalmic articles by the method of the present invention must not harm the optical properties of the S articles obtained.

As indicated above, an important characteristic of the method of the invention is that the additive is brought into contact with the ophthalmic article in a reactor in the static state in the presence of a fluid in the supercritical state.

Use may be made of any fluid in the supercritical state which is inert with respect to materials constituting the polymer substrate of the ophthalmic article and additive or additives to be introduced. Mention may be made, among the fluids which can be used according to the invention, of C02, NO 2 ethylene, ethane and chlorotrifluoromethane.

As indicated above, a particularly recommended fluid is carbon dioxide (C0 2 because it is nontoxic and inexpensive and it can be easily recycled.

The temperature and pressure conditions of the fluid in the supercritical state will very clearly depend on the critical point of the fluid and on the nature of the polymers of the substrate and of the additives to be incorporated. However, it is recommended that the temperature of the fluid in the supercritical state should be lower by 30°C or more, preferably lower by 50 0 C, than the glass transition temperature under normal conditions, of the polymer or polymers of the substrate of the ophthalmic article treated.

The duration of the treatment will very clearly depend on the temperature and pressure conditions of the fluid in the supercritical state, on the nature of the polymer substrate and of the additive to be incorporated, and on the amount and on the depth desired for the incorporation of the additive. In general, it has been found that a duration of 1 to 30 minutes, preferably of to 20 minutes and better still of the order of 10 to minutes was sufficient to obtain the desired incorporation.

Once the incorporation of the additive has been completed, the fluid in the supercritical state absorbed Sby the substrate is removed. This removal is carried out easily by bringing the substrate back to atmospheric 1 pressure, thus causing expansion of the gas.

The process according to the invention has many advantages. It does not use a solvent and consequently risks of pollution are avoided and the costs related to the possible removal and the possible reprocessing of solvents are eliminated. It makes possible efficient use of the amount of additives because they can be employed until the amount of additives initially introduced into the reactor has been completely exhausted, and consequently prevents additives from being lost and wasted.

This economic aspect of the method according to the invention is particularly advantageous for the incorporation of relatively expensive additives, such as photochromic substances. In addition, the method according to the invention makes it possible to adjust the amount and the depth of incorporation of the additive into the polymer substrate and, in particular, makes it possible to obtain a core incorporation, even in significantly thick substrates. Thus, it is possible to carry out incorporations of additives, in particular of photochromic substances and dyes, to depths of 10 mm, preferably of 1 to 2 mm.

By way of comparison, the thermal transfer process only makes it possible to incorporate photochromic substances to depths of the order of 150 pm.

The method according to the invention also makes it possible to incorporate additives, in particular photochromic substances and dyes, in polymer substrates regarded until now as difficult or even impossible to color, such as polycarbonate substrates or substrates coated with an abrasion-resistant and/or impact-resistant layer.

The following examples illustrate the present invention without, however, limiting it.

The incorporation of the additives was carried out in a laboratory device represented diagrammatically in Figures 1 and 2.

The device represented in Figure 1 comprises a

CO

2 source connected to a pump 2 which is itself connected to a high-pressure tubular reactor 3 placed in an oven 4.

Valves make it possible to isolate the CO 2 source from the pump 2 and the reactor 3.

As is seen in Figure 2, the reactor 3 comprises a tubular body 5, the two ends of which are closed by plates made of sintered glass 6 and 7 and stoppers 8 and 9. The stopper 8 is provided with means for introducing

CO

2 and is connected to the pump 2. Inside the tubular body 5 of the reactor, a transparent polymer substrate for an ophthalmic article is placed between two cotton pads 12, 13, while an additive 11 or a mixture of additives intended to be incorporated in the substrate is placed in the reactor, next to the substrate 10, between the cotton pad 13 and a third cotton pad 14.

When operating, CO 2 is introduced from the source 1 into the reactor 3 and brought to the pressure greater than the critical pressure and heated by means of the oven to a desired temperature greater than the critical temperature. The CO 2 is maintained under the chosen supercritical conditions, in the static state, in the reactor 3 for a predetermined time necessary for the incorporation of the additive. At the end of the incorporation, the CO 2 is removed from the reactor and from the substrate by returning the pressure and the temperature to ambient pressure and temperature (generally normal pressure and temperature or close to normal) and by allowing the CO 2 to discharge from the substrate under these ambient pressure and temperature conditions. The substrate incorporating the additive is then recovered.

EXAMPLES 1 to 3 Three test specimens, with a thickness of 1 mm, of a polymer substrate obtained by polymerization of the following polymerizable composition, described in Patent Application WO 95/10790, were treated in the reactor described above.

Base ingredients Parts by weight Ethoxybisphenol A dimethacrylate containing 2.5 ethoxy units 43.5 Poly(ethylene glycol) with a molecular mass of 600, terminated at both ends by methacrylate 21.0 1,3-Diisopropenylbenzene 2-Phenoxyethyl methacrylate 20.5 Poly(ethylene glycol) with a molar mass of 200, containing a benzoate ending at both ends 8.7 Triphenyl phosphite 0.3 Diethyl pyrocarbonate 0.15 Initiator Diisopropyl peroxydicarbonate 00-tert-Butyl O-2-ethylhexyl mono-peroxycarbonate The polymerizable composition is poured into a flat-sheet mold. The mold is placed in a circulating air oven and the composition is cured by using the following curing cycle.

Cumulative hours Temperature of the oven °C 0 34 24 36 32 44 34 46 36 48 38 54 42 58 44 64 46 69 48 49 105 49.5 130 50.5 130 (end of the cycle) The polymerisate is allowed to cool in the oven back to approximately 80 0 C and is then withdrawn from the oven and removed from the mold.

The additive to be incorporated was a mixture of photochromic substances comprising 55% by weight of a compound of formula: H3 H3

CH

3

C

3

H

7 described in Patent Application WO 90/12819 ("blue" dye), and 45% by weight of a compound of formula: 15 described in Patent Application WO 90/17071 ("orange" dye) 100 mg of the above mixture was placed in the reactor.

The operating conditions for the supercritical

CO

2 were as follows: P 20 MPa T Density Pc02 0.6 g/cm 3 Each of the test specimens of Examples 1 to 3 was subjected to a different treatment time, namely 5, 15 and minutes respectively.

The test specimens obtained are virtually colored to the core.

The degree of impregnation of the photochromic substances into the substrate was monitored by UV spectroscopy. The results are represented in Figures 3 and 4, which respectively represent the absorption curves of the colorless form and of the colored form of the test specimens of Examples 1 to 3.

The test specimens were irradiated with a Xenon lamp, 0.9 mW/cm 2 73 klux (visible), for 15 minutes (coloring phase).

Irradiation is then stopped. A decoloring phase takes place.

The variation in the percentage of transmission of the test specimen during the two phases is measured by being placed at the wavelength kma corresponding to the maximum absorption of each of the photochromic substances.

The kinetic study of the photochromic substances was carried out at 23 0 C at the wavelength corresponding to the absorption maximum of each of the substances.

The results are shown in Tables I and II and in Figures 5 and 6.

16 TABLE I ("Blue" dye) Time in Time in of trans- Absorbance minutes seconds mission 0.0 0 100.1 0.000 0.2 12 74.7 0.127 30 52.8 0.277 60 37.1 0.430 1.2 72 33.9 0.470 1.4 84 31.5 0.502 1.6 96 29.8 0.525 1.8 108 28.5 0.545 120 27.5 0.560 300 22.1 0.657 10.0 600 20.2 0.694 15.0 900 19.5 0.709 15.5 930 31.2 0.505 16.0 960 41.9 0.377 17.0 1020 57.9 0.237 17.5 1050 63.4 0.198 18.0 1080 67.8 0.169 19.5 1170 76.1 0.118 20.0 1200 77.9 0.108 20.5 1230 79.5 0.100 21.0 1260 80.8 0.093 21.5 1290 81.9 0.087 22.0 1320 82.9 0.081 22.5 1350 83.7 0.077 23.0 1380 84.6 0.073 23.5 1410 85.2 0.070 24.0 1440 85.8 0.066 24.5 1470 86.4 0.063 25.0 1500 86.9 0.061 30.0 1800 90.5 0.043 35.0 2100 92.5 0.034 -17 Time in Time in of trans- Absorbanice minutes seconds Mission Coloration sec. 45.2 T1/2__ Decoloration sec. 69.9 _T1/ measurement at 230C, 0.9 mW/cm 2 73 klux at X 620 nm 18 TABLE II ("Orange" dye) Time in Time in %of trans- Absorbance minutes seconds mission 0.0 0 100.1 -0.001 0.2 12 89.5 0.048 30 78.0 0.108 60 67.1 0.173 1.2 72 64.2 0.193 1.4 84 61.9 0.208 1.6 96 59.9 0.223 1.8 108 58.1 0.236 120 56.8 0.246 300 46.2 0.335 10.0 600 41.7 0.380 15.0 900 40.1 0.396 15.5 930 46.2 0.335 16.0 960 50.9 0.293 17.0 1020 58.4 0.234 17.5 1050 61.4 0.212.

18.0 1080 64.0 0.194 19.5 1170 70.5 0.152 20.0 1200 72.1 0.142 20.5 1230 73.8 0.132 21.0 1260 75.2 0.124 21.5 1290 76.4 0.117 22.0 1320 77.7 0.110 22.5 1350 78.8 0.104 23.0 1380 79.8 0.098 23.5 1410 80.6 0.094 24.0 1440 81.4 0.089 24.5 1470 82.2 0.085 25.0 1500 82.9 0.081 30.0 1800 87.5_ 0.058 35.0 2100 89.7 0.047 -19- Time in Time in %of trans- Absorbance minutes seconds mission Coloration sec. 76.1 Decoloration sec. 173.3 T1/ 2 measurement at 230C, 0.9 mW/cm 2 73 klux at X 490 nm 20 Example 4 The same photochromic substances as in Examples 1 to 3 were incorporated in a polycarbonate substrate (thermoplastic Polycarbonate from the Company Dalloz).

A plasticizer, dioctyl phthalate, was initially incorporated by using the same equipment as above and the following conditions: P 20 MPa T Density Pco2 0.6 g/cm 3 Duration: 15 minutes.

The photochromic substances are then incorporated in the same way with the following operating conditions: P 20 MPa T Duration: 15 minutes.

The amounts of plasticizer and of photochromic substances incorporated are determined by weighing. The same amount, approximately 1% by weight, of plasticizer and of photochromic substances was incorporated.

Example The primary dyes shown below are incorporated in a substrate with a refractive index of 1.6, sold by the Company Essilor under the name Ormil® (material regarded as exhibiting serious difficulties in coloring), by using the equipment described above and the following reaction conditions for the supercritical CO 2 P 40 MPa T 120°C Density Pco 2 0.75 g/cm 3 The duration of treatment is 10 minutes. An intense coloring of the material is obtained.

21 Structure of the primary dyes 0 HCH3 DISPERSE BLUE C CI 61505 0 NHCH 2

CH

2

OH

HC N DISPERSE YELLOW 3 CI 11855

HO

ON N -ONC- 2-C H DISPERSE RED 13

H

2 C1 11115 Example 6 Test specimens comprising a substrate composed of the material sold by the Company Essilor under the name Orma® (diethylene glycol bis(allyl carbonate) polymer), provided with an abrasion-resistant coating with a thickness of 3 im (varnish described in Example 3 of the document EP-A-0,614,957), a coating which is virtually impossible to color, are subjected to a treatment for incorporation of the dye "Disperse Red 13", as in the preceding examples, with the following conditions for the supercritical CO 2 P 40 MPa T 120°C Density Pco 2 0.75 g/cm 3 The duration of treatment is 10 minutes. A coloring of the test specimen is obtained.

Example 7 Contact lenses made of poly(methyl methacrylate) (PMMA), with a thickness of 160 Am, were treated as described above in order to incorporate the dye "Disperse Red 13" therein. The optical parameters of the lenses, U/ the supercritical CO, and treatment conditions, and the 22 results are shown in Table III below.

Example No.

7 optical parameters of the lens power or diameter -1.75 7.70 8.50 TABLE III supercritical C0 2 T p p (KPa) (g/cm) 60 8.5 0.217 Duration of the treatment (min) 10 Coloring red transmission TV Observations "Comprises /ccmprising" when used in this specification is taken to specify the presence of stated features, integers, steps or ccmponents but does not preclude the presence or addition of one or more other features, integers, steps, components or groups thereof.

C C C C Ce C C e esee e

CC..

*C.C

C C C

CC

CCCC

Claims

2. Method according to Claim I, characterized in that the additive is chosen from the group composed of plasticizers, antioxidants, dyes, photochromic sub- stances, UV absorbers and their mixtures.
3. Method for the photochromization of a finished or semi-finished ophthalmic article comprising a transparent polymer substrate which comprises: A. A first stage composed of: 9 the insertion into a reactor of a transparent polymer substrate and of a plasticizer for the substrate, Sthe introduction into the reactor of a fluid in the supercritical state, Sthe maintenance of the fluid in the supercritical state in the reactor, in the static state, for a predetermined period of time, in order to obtain the incorporation of the plasticizer in the polymer substrate, and Sthe removal of the supercritical fluid; and B. A second stage composed of: Sthe insertion into the reactor containing the plasticized polymer substrate of one or more photochromic compounds, Sthe introduction of a fluid in the super- 24 critical state, 0 the maintenance of the fluid in the super- critical state in the reactor, in the static state, for a predetermined period of time, in order to obtain the incorporation of the photochromic compound or compounds in the plasticized polymer substrate of the ophthalmic article to a predetermined depth, the removal of the supercritical fluid, and the recovery of the ophthalmic article in which the photochromic compound or compounds are incorporated.
4. Method according to any of Claims 1 to 3, charac- terized in that the polymers of the transparent substrate are chosen from allylic polymers, polyol (allyl carbonate) polymers, polyacrylates, poly(alkyl acrylate)s, vinyl polymers, polyurethanes, polythio- urethanes or polycarbonates. Method according any one of Claims 1 to 4, characterized in that the temperature of the fluid in the supercritical state is lower by at least 30°C than the glass transition temperature, under normal conditions, of the polymer or polymers of the substrate.
6. Method according to Claim 5, characterized in that the temperature of the fluid in the supercritical state is lower by 50 0 C than the glass transition tempera- ture, under normal conditions, of the polymer or polymers of the substrate.
7. Method according to any one of the preceding claims, characterized in that the duration of maintenance of the fluid in the supercritical state in the reactor is between 1 and 30 minutes, preferably 5 to 20 minutes.
8. Method according to any one of the preceding claims, characterized in that the fluid in the super- critical state is carbon dioxide.
9. Method according to any one of the preceding claims, characterized in that the ophthalmic article is a spectacle lens. Method according to any one of the preceding claims, characterized in that the ophthalmic article is a contact lens.