FI78019B - AOTMINSTONE DELVIS TONADE KONTAKTLINSER OCH FOERFARANDE FOER DERAS FRAMSTAELLNING. - Google Patents

Abstract

Contact lenses comprising polymeric lens materials are coloured by reactive dyestuffs covalently bonded to monomer units of the polymer backbone, said dyestuffs being reactive dyes capable of forming ether linkages with cellulose, and being reactive with hydroxyl, amino, amido or mercapto groups present in a hydrogel polymer to form the covalent bond therewith. The invention is of particular interest in the area of "soft" contact lenses (hydrogel lenses).

Description

7801 9

Contact lenses, at least partially colored, and method of making them -

The invention relates to tinted contact lenses or lenses and to a method of making the same.

In particular, the invention relates to contact lenses made of polymeric lens materials in which reactive dyes are covalently bonded to the monomer units of the polymer backbone. The invention is of particular interest in the field of so-called hydrophilic or soft contact lenses, commonly referred to as hydrogel lenses.

Many of the known methods for preserving or dyeing plastic materials are unsuitable for dyeing contact lenses, especially hydrophilic contact lenses. For example, those methods in which a colorant is introduced into a plastic by dissolving or dispersing a color or pigment in a monomer precursor or polymer backbone cannot be used to make satisfactory water-absorbent materials. This is because water causes the toner to migrate inside the plastic and leak outside. In addition, this migration can be accelerated during heat sterilization treatments commonly used in the manufacture of hydrophilic lenses, since heat treatment in most cases expands the polymer body. Therefore, the most common method of making hard contact lenses, in which the lens blades are tinted or dyed, is not suitable for making soft lenses.

An alternative possibility for staining plastic materials is to use a printing, transfer or coating method. According to this method, the toner is adhered to the surface of the plastic. This method is also unsuitable for dyeing water-absorbent plastics used in the manufacture of hydrophilic contact lenses. If the plastic material dyed by this method is allowed to swell in water, the toner layer will not swell as much as the plastic itself. As a result, the toner will separate from the surface of the plastic. In any case, the simple transfer dyeing method does not eliminate the problem of runoff and is always limited by the physical bonding of the dye to the plastic surface.

10 A number of methods have been described in the literature for painting or printing a contact lens or part thereof, for example with a brush. For example, Contact Lens Forum, Vol. 3, March 1978, pp. 13-17 discloses a method of staining the surface of a lens by a chemical printing method. However, this method is not entirely satisfactory because the color tends to fade after several autoclave treatments.

The use of water-soluble dyes is also unsatisfactory, especially in the manufacture of soft contact lenses.

20 Water-soluble dyes run off during repeated heat sterilization treatments. In addition, water-soluble dyes, when in prolonged contact with the eye, permanently stain ocular tissue. Thus, the method described in the American Journal of Optometry and Physiological Optics, 25 Vol. 54, pp. 160-164 (1977), "Methods of Tinting Soileni Contact Lenses" does not provide a solution to the problems encountered in the manufacture of useful soft contact lenses.

In addition to the problems caused by the use of a hydrophilic plastic material in the manufacture of these lenses, there are additional complications caused by the dimensions of the lens itself.

Ordinary hard contact lenses, which are generally made from compositions whose main comonomer is methyl methacrylate, generally have a diameter smaller than the diameter of the cornea of the eye. In this case, it is possible to use a lens that is completely colored. In contrast, soft contact lenses generally have a larger diameter than the cornea. Because of this, the differences-5 would be supported by a uniformly colored soft contact lens clearly against the white sclera of the eye. A natural-looking contact lens should therefore have a tinted center and a bright outer part.

As can be seen from U.S. Patent 4,252,421, the manufacture of such lenses leads to assembly difficulties. Do not spill paint from the inside to the outside. Furthermore, the colored part and the clear part must be concentric and it must be possible to join them together easily during manufacture. Finally, it is essential that no color leaks into the tear fluid or sterilizing solution.

U.S. Patent No. 4,252,421 discloses a method of making soft contact lenses comprising a tinted center and an outer lens element that is usually clear. The dyed center is formed from 20 tinted preforms, which in turn are polymerized from a monomer mixture comprising dye as a comonomer. The water-insoluble color is thus part of the polymer body. Alternatively, a water-insoluble color can be added to the mixture of comonomers and this combination polymerized, leaving the color inside the polymer backbone. Due to the insolubility of the dye, this does not cast or seep from the polymerized preform button. Two methods of making a contact lens are also described. According to the first method, the dyed preform is polymerized, placed in a mold and poured around it with a hydrogel-comonomer mixture, and this is polymerized. According to an alternative method, to form the lens, the bright outer part is first polymerized and a central hole is made in it. The dye-containing comonomer mixture is placed in a hole and polymerized.

35 This method suffers from a number of significant disadvantages.

4 7801 9

There are the same difficulties as in the method in which the water-insoluble color is merely placed inside the polymer body. In contrast to the uniform composition of a conventional hydrophilic contact lens, lenses made in accordance with U.S. Patent No. 4,252,421 are combinations of hard lens materials and soft or hydrogel lens materials. Furthermore, the manufacture of these lenses requires a number of separate manufacturing and polymerization steps. In addition, these types of lenses must be selected separately for each customer. For this reason, a contact lens dealer must maintain substantial inventory in order to be able to fulfill "recipes" and normally desired color desires. The use of a combination of hard and soft lenses would still generally result in the rim or corrugation of the lens edge ry-15 as it wets, causing discomfort to the wearer.

U.S. Patent No. 4,157,892 discloses a four-step process for dyeing a water-absorbent plastic. In the first step, a linker moo-20 isomer or polymer is prepared. The polymerization radical is introduced into the coupling agent to provide a polymerizable coupling monomer from which a coupling polymer can be prepared.

Either of the linkers obtained in the first step is copolymerized or polymerized with a water-absorbent plastic in the form of a monomer or polymer with a polymerization initiator to produce a water-absorbent plastic capable of developing color. The material thus prepared is formed into an intermediate having the same dimensions as the desired end product, such as a water-absorbing contact lens. Finally, the intermediate is colored by immersing the lens in an aqueous solution of the diazonium double salt acting as developer. Immersion is continued when-. . the intermediate swells, causing the diazo component to penetrate the plastic. The pH of the solution is then adjusted to an optimum of 35 to effect the coupling reaction and to allow the development of Azo Dye 5 7801 9 in the final product. The preparation of partially colored intermediates is possible by applying ultraviolet radiation to those parts of the plastic which are not intended to be colored, whereby the diazo-5 components in these parts decompose.

This method, on the other hand, has the disadvantage that it is very complex. The method of manufacturing the material, in which the color is later developed, has to be carried out as a series of separate steps, and care must be taken that the azo dye does not develop prematurely in the lens material. The azo dye precursor is dispersed in the lens material, which can lead to variations in color intensity due to the thickness of the lens material. In order to be able to offer tinted lenses to a large number of customers, 15 the broker would again have to maintain a large stock. Furthermore, it is clear that this method is only suitable for use with a specially prepared lens material that includes a connector. Therefore, it would not be possible to use the method of U.S. Patent No. 4,157,892 in conjunction with conventional hydrophilic lens materials currently in use. In addition, the use of the connectors described in this publication would be likely to result in inferior polymeric materials compared to materials currently used for this purpose.

The object of the invention is to avoid the problems associated with previously known methods. In particular, it is an object of the invention to provide a method for tinting or coloring contact lenses which can be carried out without complicated operations and special equipment.

It is a further object of the invention to provide a dyeing method for lenses which can be kept unstained in stock or which are already available and / or prescribed to customers.

It is a further object of the invention to provide a method of manufacturing a contact lens which appears to be completely natural to the eye, i.e. a lens having a central, colored corneal covering portion and bright peripheral covering portions of the sclera. In addition, it is an object of the invention to provide contact lenses which retain color for a long time and during repeated chemical and / or thermal sterilization treatments. It is a further object of the invention to manufacture contact lenses in a wide variety of colors and color combinations by mechanical means.

One object of the invention is to provide at least a partially colored contact lens comprising a copolymeric hydrogel material containing hydroxyl, amino, amido or mercapto groups, and characterized in that an ether, thioether, amino or via amido groups at least one reactive dye of general formula I or II as defined below.

A wide variety of polymers are suitable for use in the manufacture of new lenses. The only requirement is that the monomers contain at least one functional group capable of reacting with the reactive dye either before or after polymerization.

The composition of the lens material itself may vary within wide limits, the only requirement being that the monomer mixture contains at least one component that produces a polymer containing the required extracorporeal functional groups. Particularly suitable monomers for this purpose are hydroxyalkyl esters of polymerizable unsaturated acids. Of these esters, hydroxyethyl methacrylate (HEMA) has been widely used; lenses made of such material are described, for example, in U.S. Patent Nos. 2,976,576 and Re 27,401.

In general, however, any material suitable for making contact lenses 35 may be used in the manufacture of the lenses of the invention, provided that at least one of the monomer components constituting the material contains an extracorporeal functional group that can react with the reactive dye molecule. Accordingly, the present invention can be used with a variety of known polymeric lens materials. This makes it possible to manufacture tinted contact lenses according to the invention from a large number of materials already available and from new contact lens materials which are only being developed or are being marketed.

In addition to hydroxyalkyl esters of unsaturated acids, the following monomer materials may represent typical examples of comonomers that can be used with monomers having the required functional groups: acrylic and methacrylic acids} alkyl and cycloalkyl acrylates and methacrylates; N- (1,1-dimethyl-3-oxobutyl) acrylamide; and heterocyclic N-vinyl compounds containing a carbonyl group functionally adjacent to the ring nitrogen, especially N-vinyl lactams such as N-vinylpyrrolidone. Furthermore, one or more crosslinking agents known in the art may be used to produce a polymeric material having optimal properties. Examples of such crosslinking agents include trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate (EDMA) and diethylene glycol bis-allyl carbonate.

Useful reactive dyes useful in this invention are commonly referred to as "ether-forming reactive dyes" because in this known class of dyes, the reactive group or groups react with cellulose to form an ether linkage as opposed to, e.g., ester linkages. Such ether-bonding reactive dyes are generally described in FIBER-REACTIVE DYES Chapter VI, W.F. Beech, SAF International Inc., 8 7801 9

New York (1970).

Reactive dyes of this species are believed to react with hydroxyl, amino, amido or mercapto-5 groups present in the hydrogel polymer network of contact lens materials primarily by nucleophilic addition reaction to form a covalent bond with them.

Several commercial dyes that are reactive via nucleophilic substitution are suitable for preparing the contact lenses of the invention. In addition, virtually any desired shade can be provided using a particular reactive dye or combination thereof.

Thus, dyes containing an activated double bond capable of attaching to a functional group outside the polymer backbone can be used in the invention. For example, an external backbone bond activated by a bridging group, such as -SO 2 - f -SO- or -CO-, is particularly suitable for use in the invention. Likewise, dyes having functional groups that can participate in addition reactions with double bonds outside the polymer backbone can be used.

Among the types of reactive dyes useful in the invention, the following general classes may be mentioned: dyes containing vinyl sulfone precursors, such as β-sulfatoethylsulfonyl, β-sulfatoethylsulfonamido, β-hydroxyethylsulfonyl and β-hydroxyethyl sulfonamides, and their β-hydroxyethyl sulfonamides; dyes containing acryloylamino, β-chloropropionylamino-30 and β-sulfatopropionylamino groups and their corresponding reactive groups; dyes containing β-phenylsulfonylpropionylamino groups; dyes containing β-sulfatato or β-chloroethylsulfamoyl groups; klooriasetyyliväriaineet; α-bromoacryloyl dyes and a large number of other reactive dyes, developed for dyeing natural and synthetic fibers, in particular cellulose and wool, and which act by a nucleophilic addition reaction. Although there are numerous examples of the use of reactive dyes in the dyeing of fibers used in clothing, these dyes have not been disclosed to date for use in the manufacture of tinted contact lenses.

Typical examples of commercial dyes suitable for use in the invention are: Dye-SO 2 "CH 2" 10 Cl 2 -O-SO 2 Na (Remazol), Dye-SC 2 NHCl 2 Cl 2 OSO 2 Na (Leva-fix), Dye-NH-OC -CH 2 CH 2 SO 2 CgHg (Solidazol), Dye NH-OC-CH-CH ~ Br (Lanasol), Dye NH-OC-C = CHo, Dye

Br Br ne-NHCH 2 OH (Calcobond).

Also within the scope of the invention are dyes containing more than one reactive group capable of forming a covalent bond with hydroxyl, amino, amido or mercapto groups in the hydrogel polymer network of contact lens materials by a nucleophilic addition reaction.

The reactive dyes of the invention which are capable of forming a covalent bond with hydroxyl, amino, amido or mercapto groups in the hydrogel material of contact lenses are commonly found in D-R-C = CH_ (I) I 2

X

or D-R-CH-CHO (II) I I 2

X Y

wherein D is an organic dye residue; R is a divalent electron-withdrawing group capable of causing the removal of electrons from the carbon atoms in the groups of formulas I and II to activate “C = CH2 CH-CH2n2; X is hydrogen or halogen and Y is a leaving group; mixtures of the compounds of the formulas are also suitable.

The radical D can preferably be a radical of an azo, phthalocyanine, azomethine, nitro or anthraquinone dye.

The reactive dyes of formula II are depleted in the reaction medium HY to form intermediates of formula I which then react via nucleophilic addition.

The divalent group -R- is preferably directly attached to the aromatic ring carbon of D or is attached to it via an aliphatic group such as an alkylene group, e.g. a lower alkylene group. Most preferably, -R- is directly attached to the ring carbon of D.

Suitable divalent groups R include -CO-, -SO 2 -, -SO-, -NHCO-, -NHSO 2 -, -SO 2 NH- and the like. Most preferred -20 min is -R- -SO 2 ", -SO 2 NH-, -CO- or -NHCO-.

When X is halogen, it is most preferably chlorine or bromine.

Suitable leaving groups Y include -Cl, -Br, -OH, di-lower alkylamino, -OCH 2 n / * ^ Cl, -SO 2 -phenyl, -OSO 2 -Z *, where Z is cation, -OSO 3 R 1 or -OSO 2 R 2 wherein R 1 is alkyl, aryl, aralkyl or alkaryl.

When R 1 is alkyl, it is preferably containing 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, such as methyl, ethyl, isopropyl, butyl or the like. When R 1 is aryl, it is preferably phenyl or naphthyl. When R 1 is alkaryl, it is preferably lower alkyl substituted phenyl, such as tolyl or xynyl, and when R 1 is aralkyl, it is preferably Lower alkylene phenylphenyl, such as benzyl or phenethyl.

The reactive dyes of the formula I and II known per se form covalent bonds with the network of hydroxyl, amino, amido or mercapto groups of the hydrogel polymer in an aqueous medium of pH 9 or higher and at a temperature of at most 40 ° C. Due to the mild reaction conditions, these reactive dyes of formula (I) or (II) are capable of tinting hydrogel-lipilic lenses without significant degradation or alteration of the hydrogel substrate.

The invention provides new tinted lenses with exceptional color fastness and evenness. The toner can be applied to both pins of the lens or to just one surface. The lens can also be tinted only on a certain part. Thus, it is possible to easily manufacture lenses having, for example, a dyed center and clear edges or an annular, iridescent colored annular part. This method can also be used to examine lenses, such as showing a concave or convex surface of a flexible lens.

Although tinting or staining is performed by contacting one or both surfaces of the lens with an aqueous dye solution, the interior of the lens also tones or stains to some extent due to the diffusion of the dye during the reaction.

The covalent bond between the lens material and the reactive dye is generally formed by contacting the dye composition, e.g., as a slightly basic aqueous solution, with the lens material for a period of time sufficient to complete the reaction. When both surfaces of the lens need to be dyed, the lens is brought into contact with the reactive dye on its molar surfaces. The intensity of the color depends on the contact time as well as the reactivity of the color with the surface of the lens. If it is desired to add the toner only to one surface or to a certain part of the surface, the manufactured lens can be placed in a frame or mold and the reactive dye composition can be added only to a certain part or parts of the lens surface. Compared to the complex methods commonly used in the art, this simple mechanical operation represents a tremendous advance over known paddle methods.

Furthermore, if desired, deep and permanent stains can be provided, e.g., such that the light transmittance of the lens is 90% or less in the desired visible color range, as well as opacity-free lenses.

After the reaction of the lens material with the reactive dye is completed, the unreacted dye can be removed using a suitable solvent. The solvent chosen for extraction or rinsing will, of course, depend on the solubility of the dye in question. The majority of the dyes currently used are lower alcohols, such as methanol, suitable solvents. After cleaning, the tinted lens is freed of solvent waste, e.g. by boiling it in boiling water.

For economic reasons, it is preferable to treat the material already polymerized with the dye preparation. However, it is also possible to treat the monomer, such as HEMA, with a reactive dye before polymerization, and then to polymerize the units consisting of the reactive dye and the monomer.

Due to the covalent bond formed between the polymeric material forming the contact lens and the reactive dye, the lenses of the invention have considerable color fastness in all kinds of sterilization treatments, such as chemical, enzymatic and thermal sterilization commonly used in contact lenses. Because the coloring material is applied directly to the surface or surfaces of the lens, the shade is independent of the thickness of the lens. This is in stark contrast to lenses made of plastic buttons in which the pigment is inside the polymer body, since in such a case the intensity of the tone is directly proportional to the thickness of the lens. This applies, for example, to contact lenses manufactured in accordance with U.S. Patent No. 4,157,872.

Since the method according to the invention makes it possible to add a coloring material at any time during the production of colored lenses, it is possible to tint the lenses even after an order for clear lenses has been delivered. In this case, it is not necessary to maintain a large stock of pre-dyed lenses, which is a considerable disadvantage in the manufacture of lenses tinted by known methods. After fitting conventional clear lenses, color can be added as a final step before delivery to the customer. Alternatively, the previously prescribed lenses may be subsequently tinted according to the applicant's wishes. Since the range of polymers useful in the invention is wide enough to cover almost all of the lens materials currently in use, the invention can be applied almost universally.

Another advantage of the method according to the invention is a considerable reduction in the manufacturing cost of the contact lenses according to the invention compared to the known methods for manufacturing lenses in which at least the center is colored. Suitable reactive dyes are readily available and the ease of adding these dyes to lens materials eliminates the need for complex polymerization methods and equipment.

Experiments on the oxygen permeability of lenses treated according to the invention have shown that the treatment does not cause significant changes in oxygen permeability, as can be seen from the following table:

Clear lenses Tinted lenses (blue)

Oxygen content (PT) Transmittance Oxygen content (P = 6.10) (maximum value (PT) la 587 nm) (pq = 6 ^ 10) 1. 1.68 68.3% 1.71 2. 1.47 23.0 % 1.50 3. 1.56 9.3% 1.51 4. 1.66 0.0% 1.60 * · Tested by technique presented by MF Re-fojo, F.J. Holly and F.L. Leong, Contd. Intraocular 5 Lens Med. J., 3 (4) (1977) 27.

An additional advantage of the lenses according to the invention is that most of the dyes used for tinting absorb ultraviolet radiation, especially at wavelengths which have been shown to be harmful to the eye, cf. e.g., 10 Optical Management, "Ultraviolet Radiation and the Ocular Media," January 1981, pp. 21-33. In particular, it has been suggested that ultraviolet radiation may be associated with cataracts.

The invention can be better understood in the light of the following examples: Example 1: Lens tinted completely blue on both sides

Prepare a solution stable for at least five weeks by dissolving 0,1 g of HO NH.

o ...:; 2 ... o m3s-o-c2 * 4-s- (Y ^ -NN- (> -s-c2h4-o-so3h 0 Nao / 'W \ o3 ». 0 15 7801 9 to 10 ml) 0.001 M HCl solution The clear HEMA lens is thoroughly soaked in 1.0 M sodium carbonate solution, then placed in 0.11 ml of stock solution, 4 ml of 1.0 M sodium-5 carbonate solution are added and the lens is left in the solution for 53 minutes. The tinted lens is then neutralized with buffered saline (pH = 7) The tinted lens is extracted using methanol as a solvent in an extractor until the dye molecules no longer dissolve, as can be readily determined, for example, by a spectrophotometer.

After extraction, the tinted lens is boiled in distilled water for one hour to remove residual methanol. The tinted lens is stored in buffered saline.

15 The transmittance of a tinted lens at 600 nm is 68%.

Example 2: A lens completely tinted to aquamarine on both sides

Prepare a stable stock solution stable for at least three weeks by dissolving 0,1 g of the formula ^^^ (so2nh— 'so2ch2ch2-o-so3h) 1

CuPhc - (SO 2 NH 2) 0 * '' ^ ^ "" ^ (SO 3 h) 2_3 in 10 ml of 0.001 M HCl solution. A lens soaked for 10 minutes in 1.0 M sodium carbonate is placed in 1 ml of stock solution. Add 4 ml of 1.0 M sodium carbonate solution and soak the lens for the desired time. The methods of washing, extracting and rinsing the lenses are the same as in Example 1.

The transmittances of tinted lenses at 670 nm are 80% and 70% after two and four hours of soaking.

16 7801 9

Example 3: Brown tinted lens on both sides Three storage solutions are required for this method, each of which remains stable for at least three weeks 5.

A) 0.0512 g of the formula

j) /._N OH

H-SO -0-C H -S— · (> -N-Nn χ A ^ HCOCHj "· = · · ♦ ·

O I II I

NaO 3 S / ^ N · ^ dye in 5 ml of 0.001 M HCl solution.

B) 0.0574 g of the formula

OCH-j OH

0 I J I 6 (H / t <) -SO 0 Na h-o3s-o-c2h4-s- <> -n = n- <10 s CH3 ch3 in 5 ml of 0.001 M HCl solution.

10 C) 0.0291 g of the formula

jj ... OH NH2 ... J

H-0 S-O-C H -S ~ (/ N y \

Il »s · · · ·« s · 11

o IMI O

NaO;} S / N · ^ No ^ a dye in 5 ml of 0.001 M HCl solution.

Lens soaked for 10 minutes in 1.0 M nat-. : 0.18 ml of stock solution A, 0.12 ml of stock solution B and 0.2 ml of stock solution. . 15 grams of solution C. Add 1 ml of 1.0 M sodium carbonate solution and allow to stand for one hour. The transmittances of the tinted lens at 400, 490 and 605 nm are 17,780,015 45%, 51% and 60%.

Example 4; Lens tinted completely green on both sides

A lens soaked in 1.0 M sodium-5 carbonate solution for 10 minutes is placed in 0.18 ml of solution C and 0.12 ml of solution B prepared according to Example 3. Add 1 ml of 1.0 M sodium carbonate solution and allow the lens to remain in solution for 30 minutes. The transmittances of the tinted lens at 580 10 and 385 nm are 64% and 58%, respectively.

Example 5: Lens tinted on one side with bright edges The tinting methods are the same as in Examples 1-4. The only difference is that the clear lens is in the frame. The appropriate dye solution is placed in the frame and the lens is not dipped in the dye-quadrant solution. The final steps of the method are the same as in Example 1.

The manufacture of a frame suitable for the manufacture of a partially tinted lens is mechanically simple. Seu-20 describes one type of frame that has been found to be useful in making clear-edge lenses:

The frame has three interconnecting parts. The bottom is the cup into which the lens is placed. The diameter of the curved surface of the dish 25 corresponds to the diameter of the lens to be tinted. The top acts as a reservoir for the toner solution and has an elastic edge. The elastic edge forms a seal on the surface of the lens at the edge of the area to be tinted. The third part acts as a housing for the tank-seal combination.

30 The frame is placed in the press to hold the combination firmly in place during dyeing.

A lens soaked for 10 minutes in 1.0 M sodium carbonate is placed in a dish. The tank part of the frame is placed in place and fastened with a clamp. The solution is filled with a solution of the desired concentration of dye and 18 7801 9 sodium carbonate solution. The solution is allowed to contact the lens of the lens until the desired shade is achieved. Water is passed through the tank until all the dye residues have been removed. The lens is then removed from the fashion.

Equally good results can be obtained, for example, by using dyes having the following structural formulas: R VH2c „„ A A A / S03Na • · · ·

I II II I

• · ·. · ^ / \ / \ F • · · 8 Ah— ^ / · • s ·

NS02CH2CH20S03H

f »-Cu- <j> ljlHCOCH ^ • m · · · f \ f \ / ^ • N.-n = N- · · ·

\ / I II I

· = * · * Y *

Ao.C_H.OSO-H NaoV N / Ν · κ SO, Na 2 2 4 3 3 J

v .tvh3

Β038-0-0Λ802-J

icH3 Äh3

?B

H03S-O-C2H4SO2 "· ^ ^» - N = N— ^ · NrNHCO0CH3 * "*" /% / \ /

Na03S N ·

Claims (7)

7801 9 Many of these dyes are readily available commercially and these types of dyes have been known in the art for many years. These examples are intended to be illustrative only of the invention and are not intended to limit its scope. The claims; A contact lens comprising at least a partially colored contact lens comprising a copolymeric hydrogel material containing hydroxyl, amino, amido or mercapto groups, characterized in that at least one reactive dye is covalently bonded to the polymer backbone via ether, thioether, amino or amide groups, the formula is DRC = CH 2 (I) X or dr-ch-ch 2 (11) X Y wherein D is an organic dye residue; R is a divalent organic, electron withdrawing group capable of effecting the removal of an electron from carbon atoms in the groups of formulas (I) and (II) C = CH 2 or CH-CH 2 to activate them; X is hydrogen or halogen; and Y is a leaving group. 2. A contact according to claim 1, which comprises a reactive reactive compound having a hydrogel bar copolymer or a formulation of DRC-CH3 (A) X or DR-CH-CH2- (B) X and D, R and X har de i patentkravet l angivna betydel-sena. Contact lens according to Claim 1, characterized in that the reactive dye residue bound to the copolymeric hydrogel has the formula DRC-CH 3 (A) X or DR-CH-CH 2 - (B) X in which D, R and X have the same meaning as in claim 1. 3. A contact lens according to claim 2, which comprises an azo, phthalocyanine, azomethine, nitro or anthraquinone salt. Contact lens according to Claim 2, characterized in that D is a residue of an azo, phthalocyanine, azomethine, nitro or anthraquinone dye. 4. A contact lens according to claim 3, which is R--CO-, -SO2-, -SO-, -NHCO- or -NHSO2-. Contact lens according to Claim 2, characterized in that R is -CO-, -SO 2 -, -SO-, NHCO- or -nhso 2 -. 5. A contact lens according to claim 1, which comprises a rotating device and a clear ring shape. Contact lens according to Claim 1, characterized in that it has a colored center and a clear annular edge. 6. For use in the manufacture of contact lenses according to claims 1-3, which comprises reacting the contact material with a reactor in the form of a reactor with a temperature of up to 40 ° C and having a reactive temperature. Process for the preparation of a contact lens according to Claims 1 to 5, characterized in that the reaction of the lens material with at least one reactive dye of the formula I or II is carried out at a temperature of at most 40 ° C and the unreacted dye is removed from the lens material. Process according to Claim 6, characterized in that the reaction is carried out in an aqueous medium having a pH of at least 9. Method according to Claim 6, characterized in that the lens material is in the form of a contact lens. A method according to claim 6, characterized in that the reactive dye is added to only a part of said lens. Process according to Claim 6, characterized in that the reactive dye has the formula 7801 9 d-r-c = ch 2 X or D-R-CH-CH 0 I x y in which D, R, X and Y have the same meaning as in Claim 1. Process according to Claim 10, characterized in that D is a residue of an azo, phthalocyanine, azomethine, nitro or anthraquinone dye. Process according to Claim 10, characterized in that R is -CO-, -SO 2 -, -SO-, -NHCO- or -NHSO 2 -. Process according to Claim 10, characterized in that the leaving group Y is Cl, Br, OH, di-alkylamino, SO 2 -phenyl, OSO 3 'Z +, in which Z + is a cation, OSO 3 R 11 or OSO 2 R 2, in which R 2 is alkyl , aryl, aralkyl or alkaryl. 1. A contact glass having contact with a hydroxyl-, amino-, amido- or mercapto group-containing copolymer of a hydrogelmaterial, a rotatable mixture, a reactant and a reactive solvent, with the formula DRC = CH2 (I) X or DR- CH-CH2- (II) XY i flashes with organic acid; 22 7801 9 R is a divalent organic, electronically withdrawing group, a single electron is represented by a chelate atom in the group C = CH2 or CH-CH2 * form I and II, active substance, X is a halogen or a halogen a group that is covalently attached to a polymeric group having an ether, thioether, amino or amide group. 7. A patent according to claim 6, which provides for the reaction of water and water