JPH08194191A - Production of colored soft contact lens - Google Patents

Abstract

PURPOSE: To produce a fast colored soft contact lens reduced in the damage of the lens and without causing any change such as discoloration due to a boiling water sterilization, etc., by dipping a contact lens contg. a reacting dye in an aq. soln. contg. a cationic compd. to stick a color developing component to the contact lens base material. CONSTITUTION: A soln. contg. a reacting dye capable of forming a covalent bond with the hydroxyl, etc., in the monomer or polymer as a color developing component is infiltrated into or stuck to a swollen soft contact lens in a desired shape, and then the lens is dipped in an aq. soln. contg. a cationic compd. to stick the color developing component to the base material. In this case, the amt. of dye to be added is appropriately controlled to 0.001-2% of the polymerizable monomer or more preferably to 0.01-0.5%. When the concn. is too low, the color of the formed lens is too pale. Conversely, when the concn. is too high, the color is too dark, and the wearing of the lens is recognized by others, which is not favorable from the standpoint of beauty culture.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for coloring a water-containing soft contact lens. Further, the present invention relates to a method for producing a colored soft contact lens, which does not require the use of an alkali to fix the color-forming component and thus causes little damage to the lens and has strong dyeability.

[0002]

2. Description of the Related Art Colored soft contact lenses are
In addition to facilitating the presence and identification of the lens in the storage container, etc., it has the advantage of being easy to find if lost. It is also effective for protecting eyes from strong ultraviolet rays, preventing dazzling under direct sunlight, and improving the product image. However, due to the characteristics of the product, soft contact lenses are always used in a state where they are swollen with water and require disinfection treatment such as boiling, so a strong dyeing that prevents the dyeing agent from swelling or boiling with water is used. Wearability is required.

As a conventional technique, there are broadly classified into the coloring methods for soft contact lenses, that is, so-called pre-dyeing, in which a coloring agent or a pigment is added in the state of a liquid polymerizable monomer before the polymer is polymerized to perform coloring. There is so-called post-dyeing in which the produced colorless and transparent contact lens molded product is dyed to be colored.

As the dyeing, for example, (1) JP-A-49-
6939 discloses a method of adding a reactive dye capable of reacting with an acrylic acid-based monomer to a polymerization reaction system and then polymerizing the dye to obtain a colored contact lens.
In JP-A-3-50581, a water-insoluble dye is dissolved and dispersed in a polymerizable monomer in advance before polymerization to prepare a hydrogel molded product, which is swollen in water or a solution containing water. A method of obtaining a colored contact lens by depositing fine particles is also (3) JP-A-01-280464.
The publication discloses a method for obtaining a colored contact lens by using a specific polymerizable dye that is soluble in a vinyl-based monomer used for an ophthalmic lens and is copolymerizable with the polymerizable monomer. .

On the other hand, as the post-dyeing, for example, (4) Japanese Patent Laid-Open No. 63-50581 discloses a pre-dyeing method as well as a post-dyeing method. A water-insoluble dye is added to an organic solvent. A method of dissolving and then immersing a contact lens in this dyeing solution to dye the surface or the inside thereof is described in (5) JP-B-53-2692, in which a contact lens is printed or coated with a colored layer. A method for obtaining a colored contact lens is described in (6) JP-B-59-3.
No. 9553, Dye Handbook (edited by the Society of Synthetic Organic Chemistry, Maruzen (1970), p. 112) and the like disclose dyeing methods using vat dyes, and reduced water-soluble vat dyes are used in contact lenses. A method of obtaining a colored contact lens by insolubilizing it by permeating it and then oxidizing it, and (7) JP-A-58-46319 discloses a hydroxyl group, an amino group in a contact lens substrate,
A method for obtaining a colored contact lens using a reactive dye that is covalently bonded to an amide group or the like is disclosed.

[0006]

In the method (1), a reactive dye capable of directly reacting with a (meth) acrylic acid type monomer, which is a main raw material for contact lenses, is added to a polymerization reaction system of the monomer. It is a method of obtaining a colored contact lens free from elution and discoloration by adding and binding the monomer and the dye. However, this method may adversely affect the physical properties of the polymer by incorporating the reactive dye component in the main chain of the polymer. In the method (2), a water-insoluble dye is dissolved and dispersed in a polymerizable monomer to prepare a hydrogel molded product, which is swollen in water or a solution containing water, resulting in uneven coloring. There is a drawback that the transparency of the lens is deteriorated due to agglomeration or accelerated aggregation of precipitated particles. Further, in the method (3), since the polymerizable dye is copolymerized with the polymerizable monomer that serves as the skeleton of the ophthalmic lens, there is a risk of adverse effects such as polymerization inhibition during the polymerization process. It may cause a decrease.

The contact lens obtained by the method (4), which is post-dyeing, tends to be discolored or fading due to the dye elution during use. Particularly, in the case of hydrous soft contact lenses which require boiling disinfection treatment of contact lenses. In this case, there is a drawback that the dye elutes and discolors during the disinfection process. Further, the method (5) has a drawback that the printing layer or coating layer on the lens surface is peeled off during use.
The method (6) is a method of dyeing a soft contact lens containing hydroxyethyl methacrylate as a main component using a water-soluble vat dye leuco body. However, the water-soluble vat dye leuco body used at this time needs to be stable in the air, and in order to make the dye insoluble for color development, an oxidation treatment such as immersing the lens in an oxidant aqueous solution is required. To do. The method (7) is a very effective method when the contact lens substrate has a hydroxyl group, an amino group, an amide group and the like. However, in this method, after immersing the lens in the dye solution for a certain period of time, the alkali solution is directly added to the dye solution and mixed to cause the reaction, so that it takes a long time to complete the reaction of the dye, The dye solution also has the drawback that it cannot be reused. Further, unreacted dye is often attached to the lens, and there is a problem that a step of removing the unreacted dye by washing with a surfactant solution or the like is necessary.

As a means for overcoming the above-mentioned drawbacks of the prior art, the inventors of the present invention disclosed in Japanese Patent Laid-Open No. 04-293010 in a dyeing method, a monomer as a coloring component in advance in a polymerizable monomer. Alternatively, after containing a reactive dye capable of forming a covalent bond with a hydroxyl group in the polymer and polymerizing this into a rod shape, the bar material is processed using a lathe to obtain a dry contact lens. , Swelling by swelling in an alkaline solution and at the same time covalently bonding the colored components to the contact lens material, and with a very simple process, it is a robust material that does not cause changes such as discoloration by boiling disinfection treatment etc. A method of making a tinted soft contact lens is disclosed. In the post-dyeing method, JP-A 03-259111 discloses that a soft contact lens in a swollen state is permeated with a dyeing agent containing a reactive dye capable of forming a covalent bond with a hydroxyl group or the like in a monomer or a polymer as a coloring component or After attaching
Disclosed is a method for producing a tough colored soft contact lens that does not cause a change such as discoloration even when it is boiled and disinfected by immersing it in an alkaline solution to form a covalent bond.

As a result of further intensive research thereafter, a colored soft contact lens having a strong dyeing property was produced without using an alkaline solution which may damage a general hydrous soft contact lens. I found a way to do it. The damage to a water-containing soft contact lens by an alkaline solution is specifically the action of hydrolysis to the polymer network that constitutes the lens, and this action reduces the mechanical strength and shape stability of the lens. Deterioration, fluctuation of water content, etc. will be caused.

Here, a method of manufacturing a contact lens will be described. The contact lens can be roughly classified into three types, and is manufactured by any one of a race cut method (cutting and polishing method), a molding method, and a spin casting method (centrifugal casting method). The race cut method is the most commonly used method for manufacturing contact lenses at present, and is a method for manufacturing a contact lens by cutting out a rod-shaped or button-shaped contact lens material with a lathe, cutting and polishing it. .
Although this method is suitable for manufacturing a wide variety of contact lenses having different shapes, it has a feature of high manufacturing cost. Currently, most hard contact lenses are manufactured by the lace cut method, and many manufacturers of soft contact lenses also use the lace cut method.

On the other hand, the molding method and the spin casting method are mostly used in the production of soft contact lenses. The molding method is a method of filling a mold having a lens-shaped space with a polymerizable monomer, and polymerizing this to manufacture a contact lens.The spin casting method is to cast the polymerizable monomer into a rotating mold and centrifugal force. This is a method of manufacturing a contact lens by utilizing that the raw material spreads thinly. These methods are disadvantageous when flexibly manufacturing a wide variety of contact lenses of different shapes, but in the case of soft contact lenses, BC (base curve: the surface where the contact lens contacts the cornea or its surface). These methods are applied because of the small number of types of molds required and the few types of molds required. Further, these methods are characterized in that contact lenses can be manufactured at low cost.

In the method for producing a colored soft contact lens of the present invention, a pre-produced contact lens molded product is dyed even in pre-dyeing, in which a dye is added in the state of a polymerizable monomer before the polymer is polymerized for coloring. Since it can also be applied to post-dyeing in which the coloring is performed, the application is possible even if any of the above manufacturing methods is selected.

That is, the present invention is to overcome the drawbacks of the prior art, and in the production of colored soft contact lenses, a reactive dye capable of forming a covalent bond with a hydroxyl group or the like in a monomer or a polymer is used as a coloring component in the lens. The contact lens containing the reactive dye is immersed in an aqueous solution containing a cationic compound to fix the coloring component to the contact lens base material, the damage to the lens is small, and the discoloration occurs even by boiling disinfection treatment. The object is to produce a robust tinted soft contact lens that does not cause a change in

[0014]

The method for producing a colored soft contact lens of the present invention comprises a swelled soft contact lens containing a reactive dye capable of forming a covalent bond with a hydroxyl group or the like in a monomer or a polymer as a coloring component. After permeating or adhering the dye solution into a desired shape, it is immersed in an aqueous solution containing a cationic compound to fix the color forming component to the contact lens substrate.

Further, a reactive dye capable of forming a covalent bond with a hydroxyl group or the like in the monomer or the polymer is previously contained in the polymerizable monomer as a color-forming component, and this is polymerized and processed into a contact lens shape, It is characterized in that it is immersed in an aqueous solution containing a cationic compound to cause it to swell and at the same time to fix the color-forming component to the contact lens substrate.

Furthermore, a polymerizable monomer containing a reactive dye capable of forming a covalent bond with a monomer or a hydroxyl group in the polymer as a color forming component is polymerized and contacted using a resin mold for manufacturing a contact lens. After the lens shape is formed, it is immersed in an aqueous solution containing a cationic compound to fix the color forming component to the contact lens substrate.

The present invention will be described in detail below. Examples of reactive dyes used as coloring components include (1) dyes having a chlorotriazinyl group, (2) as disclosed in Dye Handbook (edited by the Society of Synthetic Organic Chemistry, Maruzen (1970), p. 880). Dyes with vinyl / sulfone groups,
(3) Examples thereof include dyes having an alkyl sulfate group. Specifically, CAI Reactive Blue 19
(C.I. Reactive Blue 19), CI Reactive Blue 27 (C.I. Reactive
e Blue 27), CII Reactive Blue 2
8 (CI Reactive Blue 28), CI Reactive Violet 5 (CI Reac
active Violet 5), CI Reactive Black 5 (CI Reactive Black)
5), CI Reactive Black 14 (C.I.R.
eactive Black 14) and the like.

The concentration of the dye used varies depending on the type of the dye, the intended coloring concentration, and the like. Further, in the case of pre-dyeing in which a dye is added in the state of a polymerizable monomer before the polymer is polymerized for coloring, This is also different from the case of post-dyeing, in which the produced contact lens molded product is dyed and colored.

Here, a method for manufacturing a colored soft contact lens by dyeing will be described. For dyeing,
The above reactive dye is dispersed and dissolved in a polymerizable monomer that is a raw material of a lens, and the resultant is polymerized to form a contact lens shape according to the various production methods described above. The contact lens in a dry state thus obtained It is desirable to immerse the component in an aqueous solution containing a cation compound to swell the contact lens and at the same time fix the color forming component to the contact lens substrate. At this time, the addition amount of the dye is appropriately 0.001 to 2% with respect to the polymerizable monomer, and more preferably 0.01 to 0.5%. If the usage concentration is too low, the color will be too light when used as a lens and does not make sense of coloring.On the contrary, if the usage concentration is too high, the color will be too dark and can be discriminated by others when worn, which is preferable for beauty. Absent.

To manufacture a rod-shaped or button-shaped contact lens material, a polymerizable monomer in which a reactive dye is dispersed and dissolved is injected into a glass tube or a polypropylene or polytetrafluoroethylene tube or a sheet-shaped void, Usually, it is suitable to carry out by irradiation with active energy rays such as heating or irradiation with ultraviolet rays in the presence of a polymerization initiator. Also, after this, when the polymer shrinks due to polymerization shrinkage or heat of polymerization, in order to eliminate this,
It is desirable to perform heat annealing. As a specific polymerization initiator used for this purpose, a radical polymerization initiator is desirable, and examples thereof include benzoyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxy-2-ethylhexanoate and t-butyl peroxide. Oxypivalate, t-butylperoxydiisobutyrate, t
-Butyl peroxyisopropyl carbonate, lauroyl peroxide, azobisisobutyronitrile, azobis (2,4-dimethylvaleronitrile) and the like are used. Further, in the case of irradiation with active energy rays, a photopolymerization initiator such as benzoin ether or a sensitizer is used if necessary. The amount of these initiators used is preferably 0.001 to 2% by weight based on the monomers used.
However, since some of these initiators decompose specific reactive dye components, an appropriate initiator must be selected and used according to the type of reactive dye used.

The bar material thus obtained is used to form a contact lens by a lace cut method. next,
By dipping this dry contact lens in an aqueous solution containing a cationic compound, the lens is swollen and at the same time the lens material and the coloring component are fixed.

In the production of a colored soft contact lens using the molding method, a polymerizable monomer in which a reactive dye is dispersed and dissolved is filled in a mold generally used as a resin mold for manufacturing a contact lens and heated. It is suitable to carry out thermal polymerization or to carry out photopolymerization by irradiating ultraviolet rays. As a manufacturing method using the resin mold for manufacturing a contact lens used in the present invention, for example, two types can be mentioned, and a space formed when a male mold and a female mold are combined is filled with a polymerizable monomer. A method for producing a contact lens, or filling the space formed when a male mold and a female mold are combined with a polymerizable monomer and polymerizing this, and then removing the female mold while the two molds are still in agreement. In this state, the male mold is attached to the lathe for lens cutting, and the FC (front curve: the surface opposite to the surface where the contact lens contacts the cornea, or the curvature of that surface) of the lens is cut to manufacture the contact lens. It can be applied to any of the methods. The latter method is also called the blank molding method, and it has the advantage of the molding method that it is possible to manufacture contact lenses with less variation in quality at low cost, and the race-cut method that can flexibly manufacture a wide variety of contact lenses with different shapes. By combining this method with the coloring technique of the present invention, it becomes possible to more efficiently produce a high-quality colored soft contact lens.

As a concrete manufacturing method, a required amount of the polymerizable monomer containing a coloring component is discharged onto the concave surface of the resin type female mold, and the convex surface of the male mold matches the concave surface. In this way, the contact lenses are obtained by superimposing them and heating them for thermal polymerization or by irradiating with ultraviolet rays to perform photopolymerization. After that, when distortion occurs in the polymer due to polymerization shrinkage or polymerization heat, heat annealing may be performed to eliminate the distortion. When cutting the FC side to form a contact lens shape, after hardening, attach the male mold to the lens cutting lathe via the attachment with both molds still in agreement or with the female mold removed The contact lens is obtained by cutting the FC side of the lens.

The dry contact lens thus obtained is swollen with water or physiological saline and then immersed in an aqueous solution containing a cationic compound to fix the color-forming component to the lens substrate to obtain a colored soft contact lens. However, at this time, by immersing the dry contact lens in an aqueous solution containing a cationic compound as it is, swelling of the soft contact lens and fixing of the coloring component are carried out at the same time, and further release from the resin mold for manufacturing the contact lens. By performing the molding, the steps can be omitted and the colored soft contact lens can be efficiently manufactured. At this time, it is the temperature of the aqueous solution containing the cationic compound used for fixing the color-forming component. The higher the liquid temperature, the faster the fixing reaction.
On the contrary, since the damage to the lens becomes large, it is necessary to set it in consideration of the balance between the speed of the sticking reaction and the damage to the lens. Generally, room temperature to 70 ° C is suitable, and more preferably 30 to 50 ° C.

Further, since the soft contact lens generally contains a considerable amount of unreacted monomer, it is necessary to remove it. However, the colored soft contact lens is immersed in an aqueous solution containing a cationic compound. The unreacted monomer can be extracted at the same time by heating by heating.

As the cationic compound used for the fixing reaction of the color-forming component, those generally known as cationic surfactants are desirable, for example, quaternary ammonium salts,
Examples thereof include alkylamine salts, alkylpyridinium salts and alkylimidazolinium salts. More specifically, octadecyltrimethylammonium chloride, cetyltrimethylammonium chloride, dodecyltrimethylammonium chloride, benzalkonium chloride, benzethonium chloride, octadecyldimethylbenzylammonium chloride, polyoxyethylenedodecylmonomethylammonium chloride, octadecylamine acetate, tetradecylamine. An acetic acid salt etc. are mentioned and it can be used as 1 type or a mixture of 2 or more types. Among them, the quaternary ammonium salt is known to have a cleaning effect and a bactericidal effect, and can be said to be particularly suitable as a substance used for a medical device such as a contact lens.

The concentration of the cation compound used varies depending on the type of dye or cation compound used, but is 0.0
1-10% is suitable, and more preferably 0.05-5.
% Is appropriate. If the concentration of the cationic compound is too low, it takes a long time for the reaction, and the reaction does not proceed completely, so that the unreacted dye may remain. On the contrary, if the concentration of the cation compound is too high, the cation compound may be adsorbed on the lens, requiring long washing with water after the fixing treatment,
Further, it may cause damage such as strength reduction to the lens, which is not preferable.

Next, a method of manufacturing a colored soft contact lens by post-dyeing will be described. In case of post-dyeing,
A soft contact lens prepared in advance is permeated or adhered with a dye solution containing the above-mentioned reactive dye in a desired shape, and then immersed in an aqueous solution containing a cationic compound to fix the color forming component to the contact lens substrate. Is desirable. At this time, the dye concentration in the dye solution is 0.001 to 1
0% is suitable, and more preferably 0.002 to 2% is suitable. If the usage concentration is too low, the color will be too light when used as a lens and does not make sense of coloring.On the contrary, if the usage concentration is too high, the color will be too dark and can be discriminated by others when worn, which is preferable for beauty. Absent.

If necessary, a dyeing auxiliary agent can be added to the dyeing solution used in the case of post-dyeing. The dyeing aid is used to help permeation or adhesion of the reactive dye into the lens, and examples thereof include sodium sulfate and sodium chloride. By using this auxiliary agent, it is possible to easily and uniformly color the composition.

Further, when a letter or a symbol is applied on the contact lens by marking, the dye solution can be used as an ink for marking. In this case, it is desirable to add a surfactant to the dye solution.
Surfactants are very effective in suppressing the bleeding that tends to occur when marking a water-containing soft contact lens. Since water-containing soft contact lenses are swollen with water or physiological saline, if a water-soluble dye solution is used for marking, the dye solution diffuses from the mark area to the surrounding area, which causes bleeding. As a result, clear coloring cannot be obtained. However, by adding an appropriate amount of a surfactant to the dye solution, bleeding at the time of marking does not occur and clear coloring can be obtained. As the surfactant to be used, any of hydrocarbon type, silicon type and fluorine type can be used. Examples of hydrocarbon surfactants include polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether acetate, N-acyl amino acid salt. , Alkyl sulfocarboxylates, sucrose fatty acid esters and the like, and these are selected and used.

As a coloring method using the dye solution, a batch dipping method, a screen printing method, a transfer method and the like which are generally used can be used, but it is necessary to adjust the viscosity of the dye solution according to each method. . In the case of marking, bleeding of characters, symbols, etc. can be suppressed by adjusting the viscosity. The viscosity is adjusted by adding a thickening agent to the dye solution, and the type and the addition amount are determined according to the coloring method, and examples thereof include sodium alginate, starch, carboxymethylcellulose, polyvinylpyrrolidone, and polyethylene glycol. ,
Examples thereof include glycerin.

The cation compound used for the fixing reaction of the color forming component is the same as that used in the pre-dyeing, but its concentration may be different between the pre-dyeing and the post-dyeing, so that the optimum concentration is set. There is a need. The temperature of the aqueous solution containing the cationic compound at this time is also the same as in the case of the dyeing, preferably room temperature to 70 ° C, more preferably 30 to 50 ° C.

As the contact lens raw material monomer applicable to the colored soft contact lens of the present invention, for example, 2-hydroxyethyl methacrylate (HEMA),
2,3-dihydroxypropyl methacrylate, N, N
-Dimethylacrylamide, (meth) acrylic acid, etc. are applied, and are applied to soft contact lenses made of a polymer obtained by polymerizing these polymerizable monomers alone or with other polymerizable monomers that are raw materials for contact lenses. it can. That is, it can be applied to almost all hydrous soft contact lenses in which a hydroxyl group, an amino group, an amide group and the like are present in a polymer substrate.

Further, examples of the polymerizable monomer copolymerizable with the above-mentioned hydrophilic monomer are generally used radically polymerizable compounds such as vinyl group, allyl group,
It is a compound containing one or more acryl groups or methacryl groups in the molecule, and is a substance that is usually used as a composition component of a soft contact lens material. Specifically, alkyl (meth) acrylate, siloxanyl (meth) acrylate, fluoroalkyl (meth) acrylate, polyethylene glycol (meth) acrylate, (meth) acrylic acid ester of polyhydric alcohol, vinyl (meth)
Examples thereof include (meth) acrylic acid esters such as acrylates, styrene derivatives, N-vinyl lactams, vinyl compounds such as (polyvalent) vinyl carboxylates, and the like.

[0035]

In the method for producing a colored soft contact lens according to the present invention, a contact lens containing a reactive dye is immersed in an aqueous solution containing a cationic compound to fix the color-forming component to the contact lens substrate, so that damage to the lens is prevented. It is not necessary to use a large alkali, and a colored soft contact lens having a strong dyeing property can be manufactured.

[0036]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto.

(Example 1) 97 parts by weight of 2-hydroxyethyl methacrylate, 2 parts by weight of ethylene glycol dimethacrylate, C.I. I. Reactive Blue
28 0.05 parts by weight and 0.05 parts by weight of azobis (2,4-dimethylvaleronitrile) were mixed well, and this mixture was placed in a glass sealed tube, the inside was replaced with nitrogen, and degassing was repeated to perform sealing under vacuum. did. This sealed tube is heated in warm water at 30 ° C for 10
Heating at 40 ° C for 5 hours, 50 ° C for 5 hours, 60 ° C for 3 hours, 70 ° C for 3 hours, and further 2 hours at 100 ° C in an atmospheric furnace.
Polymerization was performed by heating for a time to obtain a bar material. The obtained bar material was cut by a lace cut method to obtain a dry contact lens. The lens was swollen by immersing the lens in a 2% benzalkonium chloride aqueous solution set at room temperature for 20 minutes, and at the same time, the color forming component was fixed to the lens substrate. After that, the lens was thoroughly washed with a large amount of water and further boiled in physiological saline for 30 minutes. The obtained soft contact lens was uniformly colored blue, and no damage such as a decrease in mechanical strength or deterioration of shape stability was observed on the lens by the fixing treatment by immersing it in an aqueous solution containing a cationic compound. .

Next, the following test was conducted on this soft contact lens to confirm its durability.

(1) Light resistance test: 0.9% physiological saline and one colored soft contact lens were placed in a transparent glass vial (capacity: 20 cc), and this was put into a Sunshine Weather Meter manufactured by Suga Test Instruments Co., Ltd. Then, the lens was exposed to light for 80 hours to perform a light resistance test. The fading was evaluated by measuring the light transmittance before and after the light resistance test using a spectrophotometer manufactured by Hitachi, Ltd., and the discoloration was evaluated by visual comparison with a control lens which was not treated. went.

(2) Boiling resistance test: 0.9% physiological saline and one colored soft contact lens were placed in a transparent glass vial (capacity: 20 cc), and this was placed in a 100 ° C. atmosphere constant temperature bath. A boiling resistance test was conducted by continuous heating for up to 200 hours. The fading was evaluated by measuring the light transmittance before and after the boiling resistance test using a spectrophotometer manufactured by Hitachi, Ltd., and the evaluation of the discoloration was made by visual comparison with a non-treated control lens. Went by.

As a result of the above durability test, no abnormality such as fading or discoloration was observed in any of the tests.

Comparative Example 1 By the same method as in Example 1, a dry colored contact lens was obtained. This lens was immersed in pure water instead of a 2% benzalkonium chloride aqueous solution for swelling, and the subsequent treatment was carried out in the same manner as in Example 1 to obtain a swollen soft contact lens.

As a result of carrying out the same durability test as in Example 1 on this lens, clear discoloration was recognized in the boiling resistance test.

Comparative Example 2 By the same method as in Example 1, a dry colored contact lens was obtained. This lens was immersed in a 2% sodium hydroxide aqueous solution instead of the 2% benzalkonium chloride aqueous solution to swell, and the subsequent treatment was carried out in the same manner as in Example 1 to obtain a colored soft contact lens.

As a result of carrying out the same durability test as in Example 1 on this lens, no abnormality such as fading or discoloration was observed, but the lens was typified by deterioration of mechanical strength and deterioration of shape stability. Damage was observed.

Example 2 60 parts by weight of 2,3-dihydroxypropyl methacrylate, butyl methacrylate 2
0 parts by weight, N, N-dimethylacrylamide 17 parts by weight, diethylene glycol dimethacrylate 2 parts by weight,
C. I. 190.02 parts by weight of Reactive Blue and 0.05 parts by weight of t-butylperoxy-2-ethylhexanoate were mixed well, the mixture was put in a glass sealed tube, and the inside was replaced with nitrogen and deaeration was repeated, It was sealed under vacuum. This sealed tube is heated at 30 ° C. in warm water for 10 hours, 40
5 hours at ℃, 5 hours at 50 ℃, 3 hours at 60 ℃, 70 ℃
For 3 hours, and further heated at 100 ° C. for 2 hours in an atmospheric furnace to carry out polymerization to obtain a bar material. The obtained bar material was cut by a lace cut method to obtain a dry contact lens. The lens was swollen by immersing this lens in a 2% benzethonium chloride aqueous solution having a liquid temperature set at 70 ° C. for 5 minutes, and at the same time, the color forming component was fixed to the lens substrate. Further, the unreacted monomer in the contact lens was extracted by holding the state as it was for 2 hours. Then, the lens was thoroughly washed with a large amount of water. The obtained soft contact lens was uniformly colored blue, and no damage such as a decrease in mechanical strength or deterioration of shape stability was observed on the lens by the fixing treatment by immersing it in an aqueous solution containing a cationic compound. . Further, as a result of performing a durability test on this lens in the same manner as in Example 1, no abnormality such as discoloration or discoloration was observed in any test.

Example 3 As the polymerizable monomer, 2-
97 parts by weight of hydroxyethyl methacrylate, 2 parts by weight of ethylene glycol dimethacrylate, C.I. I. Rea
0.05 parts by weight of ctive Blue 28, 2,
The mixture was thoroughly mixed with 0.5 part by weight of 4,6-trimethylbenzoyldiphenylphosphine oxide, and the mixture was deaerated and replaced with nitrogen. This mixture
The cavity formed when a male mold having a BC optical surface with a curvature of 7.21 mm and a female mold having a FC optical surface with a curvature of 7.70 mm was filled, and an 80 W / cm high pressure mercury lamp was filled in the cavity. It was irradiated with ultraviolet rays at a distance of 15 cm for 200 seconds and cured. The obtained contact lens in a dry state was swollen in pure water, and then immersed in a 3% cetyltrimethylammonium chloride aqueous solution whose liquid temperature was set to 50 ° C. for 5 minutes to fix the color forming component to the lens substrate. After that, the lens was thoroughly washed with a large amount of water and further boiled in physiological saline for 30 minutes. The BC of the obtained soft contact lens is 8.60 mm and the power is −
It had a 3.00 D and was uniformly colored blue. Also,
No damage such as a decrease in mechanical strength or deterioration of shape stability was observed on the lens due to the fixing treatment by immersing the lens in an aqueous solution containing a cationic compound. Further, as a result of performing a durability test on this lens in the same manner as in Example 1, no abnormality such as discoloration or discoloration was observed in any of the tests.

Example 4 As the polymerizable monomer, 2,
70 parts by weight of 3-dihydroxypropyl methacrylate,
28 parts by weight of methyl methacrylate, 1 part by weight of ethylene glycol dimethacrylate, C.I. I. Reactive
Violet 5 0.02 parts by weight, azobis (2,
0.2 parts by weight of 4-dimethylvaleronitrile) was mixed well, and the mixture was deaerated and replaced with nitrogen. This mixture is filled into a cavity formed when a male mold and a female mold for the blank molding method having a BC optical surface curvature of 7.25 mm are combined, and the mixture is put into a hot-air circulating constant temperature bath. And heated at 60 ° C. for 10 hours and 90 ° C. for 5 hours. After curing, remove the female mold from the male mold and attach the male mold to which the semi-finished lens product is bonded to the lathe for lens cutting,
After cutting the FC side of the lens with a curvature of 7.70 mm, the FC side surface was polished. The obtained contact lens is kept at a liquid temperature of 40
By dipping in a 2% benzalkonium chloride aqueous solution set at 0 ° C. for 10 minutes, the coloring component was fixed to the lens base material and at the same time the lens was swollen and released. After that, the lens was thoroughly washed with a large amount of water and further boiled in physiological saline for 30 minutes. The soft contact lens thus obtained had a BC of 8.60 mm, a power of -3.00 D, and was uniformly colored in purple. Further, no damage such as a decrease in mechanical strength or deterioration of shape stability was observed on the lens due to the fixing treatment by immersing it in an aqueous solution containing a cationic compound. Further, as a result of performing a durability test on this lens in the same manner as in Example 1, no abnormality such as discoloration or discoloration was observed in any of the tests.

(Example 5) C. I. Reactive
Blue 19 0.01 g, anhydrous sodium sulfate 0.
5 g was dispersed and dissolved in 200 cc of pure water to prepare a dye solution, which was kept at 40 ° C in a water bath. HEM with a water content of 38%
A water-containing soft contact lens containing A as a main component was sandwiched between jigs and immersed in the above dye solution for 10 minutes. Remove the lens from the dye solution, then 2% with the liquid temperature set to 40 ° C
The color-forming component was fixed to the lens substrate by immersing in a benzalkonium chloride aqueous solution for 10 minutes. Then, the lens was thoroughly washed with a large amount of water, and then boiled in physiological saline for 30 minutes. The obtained soft contact lens was uniformly colored blue, and no damage such as a decrease in mechanical strength or deterioration of shape stability was observed on the lens by the fixing treatment by immersing it in an aqueous solution containing a cationic compound. . Further, as a result of performing a durability test on this lens in the same manner as in Example 1, no abnormality such as discoloration or discoloration was observed in any test.

(Example 6) C. I. Reactive
Yellow 17 0.01 g, C.I. I. React
0.005 g of ive Blue 28 and 0.5 g of anhydrous sodium sulfate were dispersed and dissolved in 200 cc of pure water to prepare a dye solution, which was kept at 40 ° C. in a water bath. Water content 38
% Of 2,3-dihydroxypropylmethacrylate and methylmethacrylate were copolymerized, and the hydrous soft contact lens was sandwiched between jigs and immersed in the dye solution for 5 minutes. Remove the lens from the dye solution and then apply a solution temperature of 40
The color-forming component was fixed to the lens substrate by immersing it in a 2% benzethonium chloride aqueous solution set at 0 ° C. for 10 minutes. Then, the lens was thoroughly washed with a large amount of water, and then boiled in physiological saline for 30 minutes. The obtained soft contact lens is uniformly colored in green, and no damage such as reduction in mechanical strength or deterioration of shape stability is observed on the lens due to the fixing treatment by immersing in an aqueous solution containing a cationic compound. It was In addition, this lens is the first embodiment.
As a result of performing a durability test in the same manner as above, no abnormality such as fading or discoloration was observed in any of the tests.

(Example 7) C. I. Reactive
Blue 19 0.2 g, anhydrous sodium sulfate 0.2
g, and 0.05 g of SILWET L-7604 (silicon-based surfactant, manufactured by Nippon Unicar Co., Ltd.) in pure water 4
Disperse and dissolve in g. Separately, 4 g of a thickener prepared by dissolving 2 g of sodium alginate in 30 g of pure water was added to prepare a marking ink. HEM with a water content of 38%
One piece of the water-containing soft contact lens containing A as a main component was taken out, water on the surface was wiped off well, and then the piece was attached so as to match the mark portion of the screen provided with the desired mark mold. The screen used for this has a thickness of 64 μm,
Mesh opening 270 mesh, opening area 33%
This is a polyester screen. Next, thickness 1m
After fixing the soft contact lens by sandwiching it with the glass plate of m, apply 1 drop of dyeing solution on the dyeing part of the screen,
It was left at room temperature for 5 minutes. Remove the glass plate, remove the soft contact lens from the screen, then the liquid temperature 40 ℃
The color-developing component was fixed to the lens substrate by immersing it in the 3% cetyltrimethylammonium chloride aqueous solution set for 5 minutes. Then, the lens was thoroughly washed with a large amount of water, and then boiled in physiological saline for 30 minutes.

The obtained soft contact lens is dyed with a clear blue symbol, and the mechanical strength of the lens is lowered and the shape stability is deteriorated by the fixing treatment by immersing it in an aqueous solution containing a cationic compound. No damage was observed. Further, as a result of performing a durability test on this lens in the same manner as in Example 1, no abnormality such as discoloration of the colored portion was observed in any of the tests.

(Example 8) Reactive dye C.I. I. Reac
0.3 g of active black 5, 0.5 g of anhydrous sodium sulfate, 0.2 g of Fluorad FC-430 (fluorine-based surfactant, manufactured by Sumitomo 3M Limited) and 10 g of glycerin are dispersed and dissolved in 50 cc of pure water to perform inkjet marking. Used as ink. Water content 38
%, 2,3-dihydroxypropylmethacrylate and methylmethacrylate were copolymerized, and one water-containing soft contact lens was taken out, the surface water was wiped off well, and the glass was pasted on a glass plate having a thickness of 5 mm. Next, after drawing desired characters on the soft contact lens using an ink jet device filled with the above ink, the desired characters are printed at room temperature for 3 days.
Let stand for a minute. The soft contact lens was peeled off from the glass plate and subsequently immersed in a 3% cetyltrimethylammonium chloride aqueous solution set at a liquid temperature of 40 ° C. for 15 minutes to fix the color forming component to the lens substrate. After that, the lens is thoroughly washed with a large amount of water and then in saline.
Boiled for 1 minute.

The obtained soft contact lens was dyed with clear black characters, and the fixing treatment by immersing it in an aqueous solution containing a cationic compound resulted in a decrease in mechanical strength and deterioration in shape stability of the lens. No damage was observed. Further, as a result of performing a durability test on this lens in the same manner as in Example 1, no abnormality such as discoloration of the colored portion was observed in any of the tests.

(Example 9) C. I. Reactive
Blue 19 0.01 g and anhydrous sodium sulfate 0.
5 g was dispersed and dissolved in 200 cc of pure water to prepare a dye solution, which was kept at 40 ° C in a water bath. HEM with a water content of 38%
A water-containing soft contact lens containing A as a main component was sandwiched between jigs and immersed in the above dye solution for 3 minutes. The lens was taken out of the dye solution and then immersed in a 2% benzalkonium chloride aqueous solution set at a liquid temperature of 40 ° C. for 5 minutes to fix the color forming component to the lens substrate. Then, the lens was thoroughly washed with a large amount of water to obtain a soft contact lens in which the entire lens was uniformly colored blue.

One piece of the colored soft contact lens dyed by the above method was taken out in a swollen state, and after wiping off the surface water well, it was made to match the letter part of the screen provided with the desired letter pattern. I stuck it. The screen used for this is a stainless steel screen having a thickness of 55 μm, a mesh opening of 400 mesh, and an opening area of 41%. Next, a soft contact lens was sandwiched and fixed by a glass plate having a thickness of 1 mm, 1 drop of the marking ink prepared in the same manner as in Example 7 was applied on the dyed portion of the screen, and then left at room temperature for 5 minutes. did. The glass plate was removed, the soft contact lens was peeled off from the screen, and then the color developing component was fixed to the lens substrate by immersing the soft contact lens in a 3% aqueous solution of cetyltrimethylammonium chloride for 15 minutes. Then, the lens was thoroughly washed with a large amount of water, and then boiled in physiological saline for 30 minutes.

In the obtained soft contact lens, the entire lens was lightly colored blue, and dark blue characters were clearly dyed on the peripheral portion of the lens. Further, no damage such as a decrease in mechanical strength or deterioration of shape stability was observed on the lens due to the fixing treatment by immersing it in an aqueous solution containing a cationic compound. Further, as a result of performing a durability test on this lens in the same manner as in Example 1, no abnormality such as fading of the colored portion was observed in any of the tests.

[0058]

Industrial Applicability In the method for producing a colored soft contact lens according to the present invention, a reactive dye capable of forming a covalent bond with a hydroxyl group in a monomer or a polymer is present in the lens as a coloring component, and a contact containing this reactive dye is provided. Since the coloring component is fixed to the contact lens substrate by immersing the lens in an aqueous solution containing a cationic compound, it is not necessary to use an alkali that causes a great damage to the lens,
Moreover, it is possible to manufacture a tough colored soft contact lens that does not undergo changes such as discoloration due to boiling disinfection treatment and the like.

[0059]

Claims (9)

[Claims] 1. A swelled soft contact lens is permeated or adhered to a desired shape with a dye solution containing a reactive dye capable of forming a covalent bond with a hydroxyl group in a monomer or a polymer as a color-forming component, and then cation is adsorbed on the cation. A method for producing a colored soft contact lens, which comprises immersing a color-forming component in a contact lens substrate by immersing it in an aqueous solution containing a compound. 2. A polymerizable monomer previously containing a reactive dye capable of forming a covalent bond with a hydroxyl group or the like in the monomer or polymer as a color-forming component, polymerized and processed into a contact lens shape, and then a cation. 1. A method for producing a colored soft contact lens, which comprises immersing a colored component in a water solution containing a compound to cause swelling and at the same time fixing a coloring component to a contact lens substrate. 3. A polymerizable monomer containing a monomer or a reactive dye capable of forming a covalent bond with a hydroxyl group in the polymer as a color forming component is polymerized into a contact lens shape using a resin mold for producing a contact lens. A method for producing a colored soft contact lens, which comprises immersing a coloring component on a contact lens substrate by immersing it in an aqueous solution containing a cationic compound. 4. A polymerizable monomer containing a reactive dye capable of forming a covalent bond with a monomer or a hydroxyl group in a polymer as a color-forming component is filled in a space formed when a male mold and a female mold are combined. After polymerizing, the male mold is attached to the lathe for lens cutting with both molds still matching or with the female mold removed, and the front curve side of the lens is cut to form the contact lens shape. A method for producing a colored soft contact lens, which comprises immersing a coloring component in a contact lens material by immersing it in an aqueous solution containing a cationic compound. 5. The coloring software according to claim 3 or 4, wherein the coloring component is fixed to the contact lens material at the same time as being swollen and released from the mold by immersing in a water solution containing a cationic compound. Contact lens manufacturing method. 6. An unreacted monomer contained in the lens is extracted by immersing it in an aqueous solution containing a cationic compound to fix the color forming component to the contact lens material. A method for producing the colored soft contact lens described. 7. The method for producing a colored soft contact lens according to claim 1, wherein the reactive dye contains a vinyl sulfone group. 8. The method for producing a colored soft contact lens according to claim 1, wherein the reactive dye contains a chlorotriazinyl group. 9. The method for producing a colored soft contact lens according to claim 1, wherein the cationic compound is a quaternary ammonium salt.