JPH08327954A - Production of colored contact lens - Google Patents

Abstract

PURPOSE: To provide a method capable of easily producing a contact lens which is uniformly and firmly colored in one process. CONSTITUTION: A colored contact lens is produced by mixing a polymerizable component (A) containing monomers which can form covalent bonds with a reactive dye (B), the reactive dye (B) and an alkali soln. (C) and polymerizing the polymerizable component (A) while effecting the reaction of the polymerizable component (A) and the reactive dye (B).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing colored contact lenses. More specifically, it does not require a pre-dyeing step, a post-dyeing step, a post-treatment step, etc., and a uniformly and strongly colored contact lens can be easily obtained in one step, especially a colored hydrous soft contact lens, etc. The present invention relates to a method that can be preferably used for manufacturing the colored contact lens of

[0002]

2. Description of the Related Art Coloring a contact lens is not only effective for protecting the wearer's eyes from strong light rays, that is, for preventing glare, but also makes the lens easy to see and when dropped. It is an effective means for achieving various purposes such as improvement in handling such as easy discovery, improvement in product image, and easy identification of products.

Conventionally, various methods have been proposed for coloring contact lenses, for example, a method of dyeing a contact lens using a vat dye has been attempted. However, according to such a method, since the vat dye is physically fixed to the contact lens, for example, when the hydrous soft contact lens dyed with the vat dye is sterilized by boiling,
The vat dye may be eluted.

Further, Japanese Patent Publication No. 53-3420 discloses that
There is described a method of obtaining a colored contact lens by synthesizing a polymer compound from a coupler monomer having a polymerizable group introduced therein, molding the contact lens, and then immersing the contact lens in an aqueous solution containing a diazonium salt. However, such a method requires a plurality of steps, and the colored contact lens obtained by such a method is not so good in light resistance due to a structural problem of the diazonium salt which is an azo dye.

Further, Japanese Patent Application Laid-Open No. 63-50581 describes a method for producing a colored soft contact lens using a water-insoluble dye. However, according to such a production method, the water-insoluble dye is not chemically bound to the polymer which is the material of the soft contact lens and is merely dispersed, so that the obtained colored highly water-containing soft If the contact lens is sterilized by boiling, the water-insoluble dye may be eluted.

In addition to these, there is a method of dyeing a contact lens with a reactive dye which is generally called a post-dyeing method or a pre-dyeing method.

Examples of the post-dyeing method include US Pat. No. 4,468,229 and US Pat. No. 4,8.
There is a method for producing a dyed contact lens described in Japanese Patent No. 91,046. However, in these production methods, the contact lens is immersed in the dye solution for a certain period of time, and then the alkali treatment is performed to fix the dye to the contact lens. Since unreacted dye may remain, the unreacted dye must be removed with a surfactant or the like, and there are problems that the treatment process is complicated and the cost is increased.

As the above-mentioned dyeing method, for example, a method for dyeing a contact lens described in US Pat. No. 5,151,106 and a method for producing a dyed contact lens described in US Pat. No. 5,292,350. and so on. However, in these methods, a monomer for obtaining a contact lens and a dye are mixed and polymerized, and then post-treatment with an alkali compound is performed to fix the dye to the contact lens. For example, the dye may be exposed to the heat during the polymerization of the monomer before it reacts with the polymer that is the material of the contact lens, and its activity may be lost. Even if alkali treatment is performed later, the dye does not sufficiently adhere to the contact lens and is eluted.

In addition to the above, as a dyeing method,
For example, there is a contact lens coloring method described in JP-A-6-235887. In this coloring method, a monomer for obtaining a contact lens and a dye are reacted in advance to obtain a purified monomer solution, and then the monomer is further mixed. And polymerize. However,
In such a coloring method, the reactivity between the dye and the monomer is low, and the monomer solution containing the unreacted dye is to be subjected to the polymerization, so the unreacted dye must be removed after the completion of the polymerization. In addition, there is a problem in that there are many treatment steps and the process is complicated, such as purification of a monomer solution in which a monomer and a dye are reacted in advance.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and it is uniformly and strongly colored without the need for a pre-dyeing step, a post-dyeing step, a post-treatment step and the like. It is an object of the present invention to provide a method capable of easily obtaining a contact lens in one step.

[0011]

In the present invention, a polymerization component (A) containing a monomer capable of forming a covalent bond with a reactive dye (B), a reactive dye (B) and an aqueous alkaline solution (C) are mixed. Then, the polymerization component (A) is polymerized, and at the same time, the polymerization component (A) and the reactive dye (B) are reacted with each other.

[0012]

FUNCTIONS AND EXAMPLES As described above, the method for producing a colored contact lens of the present invention comprises a polymerizable component (A) and a reactive dye (B) containing a monomer capable of forming a covalent bond with the reactive dye (B). And an aqueous alkaline solution (C) are mixed to polymerize the polymerization component (A), and at the same time, the polymerization component (A) and the reactive dye (B) are reacted. That is, according to the present invention, a polymerization component containing a polymerizable monomer having a specific reactive group for obtaining a contact lens, a reactive dye as a color forming component and an alkaline aqueous solution are mixed to polymerize the polymerization component. At the same time, reacting the reactive group in the polymerizable monomer and the polymer obtained from the polymerization component with the reactive dye,
A uniform and strongly colored contact lens can be obtained very easily by only one step of chemically fixing the reactive dye to the polymer which is the material of the contact lens.

The polymerization component (A) used in the present invention contains a monomer (hereinafter referred to as a monomer (A)) capable of forming a covalent bond with the reactive dye (B).

As the monomer (A), a reactive group such as a hydroxyl group, an amino group, an imino group or a mercapto group which can react with the reactive dye (B) to form a covalent bond via an ether group is used. I have things that I have.

Typical examples of the monomer (A) include 2-hydroxyethyl (meth) acrylate and 4
A hydroxyl group-containing monomer such as hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, hydroxyethyl maleate, hydroxyethyl fumarate, vinylbenzyl alcohol, allyl alcohol; N, N-dimethylaminopropyl (meth) acrylamide, allylamine, (meth) acrylamide,
Amino group-containing monomer such as (meth) acryloyloxyethylamine; N-isopropylallylamide, N-
Examples thereof include imino group-containing monomers such as methyl (meth) acrylamide, N-ethyl (meth) acrylamide, and N-hydroxyethyl (meth) acrylamide, and these can be used alone or in admixture of two or more.

The content of the monomer (A) in the polymerization component (A) is sufficient to react with the reactive dye (B) so that the polymer used as a material for the colored contact lens is colored in a desired color. Is preferably adjusted to 5% by weight or more, especially 10% by weight or more.

The monomer (A) may be contained in the polymerization component (A) in an amount of 100% by weight. For example, the polymerization component (A) may contain a monomer other than the monomer (A) described later. In this case, the total amount of the other monomer and the monomer (A) may be 100% by weight.

In the present invention, the polymerization component (A) may contain, in addition to the above-mentioned monomer (A), if necessary, other monomers in order to impart desired properties to the colored contact lens obtained. Can be made.

For example, when it is desired to improve the mechanical properties of the obtained colored contact lens or to adjust the water content, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl is used. Alkyl (meth) acrylates such as (meth) acrylate; unsaturated nitriles such as (meth) acrylonitrile; aromatic olefins such as styrene; hydrophobic monomers such as vinyl compounds such as vinyl propionate and vinyl acetate, alone or in combination with 2 A mixture of two or more species can be used.

The content of the above-mentioned hydrophobic monomer in the polymerization component (A) is 5% by weight or more, in particular, so that the effect of improving the mechanical properties by using such a monomer is sufficiently exhibited. It is preferably adjusted to 10% by weight or more, and in order to prevent the decrease of water content and the development of plasticity, it is preferably adjusted to 50% by weight or less, and particularly 40% by weight or less.

Further, when it is desired to impart flexibility to the obtained colored contact lens, for example, alkyl (meth) s such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide.
Acrylamide; polymerizable group-containing lactams such as N-vinylpyrrolidone and α-methylene-N-methylpyrrolidone; methoxydiethylene glycol mono (meth) acrylate, methoxytriethylene glycol mono (meth)
The flexibility-imparting monomers such as acrylate and alkoxypolyalkylene glycol mono (meth) acrylate such as methoxydipropylene glycol mono (meth) acrylate can be used alone or in combination of two or more.

Polymerization component (A) of the flexibility-imparting monomer
The content in the above is such that the effect of imparting flexibility by using such a monomer is sufficiently expressed.
It is preferable to adjust to 10% by weight or more, especially 20% by weight or more, and in order to prevent deterioration of mechanical strength, it is preferable to adjust to 80% by weight or less, especially 60% by weight or less. .

When it is desired to form a crosslinked structure in the polymer constituting the obtained colored contact lens, for example, ethylene glycol di (meth) is used.
Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate,
1,4-butylene glycol di (meth) acrylate,
Crosslinkable monomers such as 1,3-butylene glycol di (meth) acrylate may be used alone or in combination of two or more.

The content of the crosslinkable monomer in the polymerization component (A) is such that the effect of forming a crosslinked structure by using such a monomer and improving the mechanical strength of the colored contact lens is sufficiently exhibited. 0.1 to
It is preferable to adjust the content to be not less than 0.3% by weight, especially not less than 0.3% by weight, and in order to prevent the colored contact lens from becoming too brittle, not more than 5% by weight, especially not more than 2% by weight. It is preferable to adjust.

In the present invention, considering the water content and mechanical strength of the obtained colored contact lens and the dyeability with the reactive dye (B), the polymerization component (A) is 2-hydroxyethyl methacrylate, N. , N
-Preferably consisting of dimethyl acrylamide and methyl methacrylate.

The reactive dye (B) used in the present invention is
It reacts with a reactive group such as a hydroxyl group, an amino group, an imino group and a mercapto group in the monomer (A) and the polymer obtained from the polymerization component (A) by nucleophilic addition, and forms a covalent bond through an ether group. Any of those used for dyeing natural fibers such as cotton, cellulose and wool, and synthetic fibers can be used.

Typical examples of the reactive dye (B) are:
For example, vinyl sulfone type reactive dyes; monochlorotriazine type reactive dyes, dichlorotriazine type reactive dyes, monofluorotriazine type reactive dyes and other halotriazine type reactive dyes; trichloropyrimidine type reactive dyes, fluoromethylchloropyrimidine type dyes. Halopyrimidine-type reactive dyes such as reactive dyes; haloquinoxarine-type reactive dyes such as dichloroquinoxaline-type reactive dyes and the like among these reactive dyes such as vinyl sulfone monochlorotriazine difunctional reactive dyes. Examples thereof include bifunctional reactive dyes in which two or more reactive groups are combined.

Examples of the vinyl sulfone type reactive dyes include C.I. I. Reactive Black
5, C.I. I. Reactive Black 14,
C. I. Reactive Blue 19, C.I. I.
Reactive Blue 20, C.I. I. Reac
live Blue 21, C.I. I. Reactive
Blue 27, C.I. I. Reactive Blue
28, C.I. I. Reactive Blue 37,
C. I. Reactive Blue 38, C.I. I.
Reactive Orange 7, C.I. I. Rea
ctive Orange 14, C.I. I. React
iv Orange 15, C.I. I. Reactiv
e Orange 16, C.I. I. Reactive
Orange 23, C.I. I. Reactive Or
age 24, C.I. I. Reactive Oran
ge 78, C.I. I. Reactive Yellow
13, C.I. I. Reactive Yellow 1
4, C.I. I. Reactive Yellow 15,
C. I. Reactive Yellow 17, C.I.
I. Reactive Yellow 23, C.I. I.
Reactive Yellow 24, C.I. I. Re
active Yellow 37, C.I. I. Reac
seven Yellow 42, C.I. I. Reacti
ve Red21, C.I. I. Reactive Red
22, C.I. I. Reactive Red 23, C.I.
I. Reactive Red 34, C.I. I. Rea
ctive Red 35, C.I. I. Reactive
Red 36, C.I. I. Reactive Red
49, C.I. I. Reactive Red 50, C.I.
I. Reactive Red 63, C.I. I. Rea
ctive Red64, C.I. I. Reactive
Red 180, C.I. I. ReactiveViole
t 4, C.I. I. Reactive Violet
5, C.I. I. General formula (I) such as Reactive Brown 16:

[0029]

Embedded image

(Wherein D ¹ is a dye residue, A is a direct bond or an alkylene group having 1 to 10 carbon atoms, R ¹ is a divalent electron withdrawing group which can be activated by causing electron withdrawing of a carbon atom, X
Is a hydrogen atom or a halogen atom, and Z is a hydrogen atom or a leaving group).

Examples of the dye residue represented by D ¹ in the above general formula (I) include azo dyes, phthalocyanine dyes, azomethine dyes, nitro dyes, anthraquinone dyes, formazan dyes, oxazine dyes, indigoid dyes and phenylmethane dyes. Dyes, xanthene dyes, acridine dyes, azine dyes, thiazine dyes, nitroso dyes,
Residues such as benzoquinone dyes, naphthoquinone dyes, naphthalimide dyes and perinone dyes can be mentioned. Also R ¹
Examples of the divalent electron withdrawing group represented by
₂ -, - SO ₂ NH- and the like. Examples of the halogen atom represented by X include a chlorine atom and a bromine atom. Further, as the leaving group represented by Z, for example, -Cl, -Br, -OH, a formula:

[0032]

Embedded image

The group represented by the formula:

[0034]

Embedded image

[0035] In the group represented by the general formula: -OSO ₃ ^- E ⁺
(In the formula, E represents Na or K) and the like.

Examples of the monochlorotriazine type reactive dye include C.I. I. Reactive Red
3, C.I. I. Reactive Red 4, C.I. I.
Reactive Red 7, C.I. I. Reacti
ve Red 12, C.I. I. Reactive Re
d 13, C.I. I. Reactive Red 15,
C. I. Reactive Red 16, C.I. I. R
active Red 24, C.I. I. Reacti
ve Red 29, C.I. I. Reactive Re
d 31, C.I. I. Reactive Red 32,
C. I. Reactive Red 33, C.I. I. R
active Red 42, C.I. I. Reacti
ve Red 43, C.I. I. Reactive Re
d 45, C.I. I. Reactive Red 46,
C. I. Reactive Red 58, C.I. I. R
active Red 59, C.I. I. Reacti
ve Violet 1, C.I. I. Reactive
Violet 2, C.I. I. Reactive Blu
e 2, C.I. I. Reactive Blue 3,
C. I. Reactive Blue 5, C.I. I. R
active Blue 7, C.I. I. Reacti
ve Blue 13, C.I. I. Reactive B
lue 14, C.I. I. Reactive Blue
15, C.I. I. Reactive Blue 25,
C. I. Reactive Blue 26, C.I. I.
Reactive Blue 39, C.I. I. Reac
liveBlue 40, C.I. I. Reactive
Blue 41, C.I. I. Reactive Blue
46, C.I. I. Reactive Green 5,
C. I. Reactive Green 8, C.I. I.
Reactive Brown 1, C.I. I. Reac
seven Brown 2, C.I. I. Reactive
Brown 7, C.I. I. Reactive Bro
wn 8, C.I. I. Reactive Brown
9, C.I. I. Reactive Brown 11, C.I.
I. Reactive Brown 14, C.I. I. R
active Black 1, C.I. I. React
ive Black 3, C.I. I. Reactive
Black 8, C.I. I. Reactive Blac
k 10, C.I. I. Reactive Black 1
1, C.I. I. General formula (II) such as Reactive Black 13:

[0037]

[Chemical 4]

(Wherein D ² is a dye residue and R ² is

[0039]

Embedded image

And the like).

Examples of the dichlorotriazine type reactive dyes include C.I. I. Reactive Blue
1, C.I. I. Reactive Blue 4, C.I.
I. Reactive Blue 9, C.I. I. Rea
ctive Blue 31, C.I. I. Reactiv
e Blue 32, C.I. I. Reactive Bl
ue 33, C.I. I. Reactive Blue 1
63, C.I. I. Reactive Red 1, C.I.
I. Reactive Red 2, C.I. I. Reac
seven Red 5, C.I. I. Reactive R
ed 6, C.I. I. Reactive Red 8,
C. I. Reactive Red 11, C.I. I. R
active Yellow 1, C.I. I. Reac
seven Yellow 4, C.I. I. Reactiv
e Yellow 7, C.I. I. Reactive Y
ellow 22, C.I. I. Reactive Yel
low86, C.I. I. Reactive Orange
1, C.I. I. Reactive Orange 4,
C. I. Reactive Orange 18, C.I.
I. Reactive Violet 8, C.I. I. R
active Violet 9, C.I. I. Reac
live Violet 10, C.I. I. Reacti
ve Green 6, C.I. I. Reactive G
reen 7, C.I. I. Reactive Brown
10, C.I. I. Reactive Black 9,
C. I. General formula (III) such as Reactive Black 18:

[0042]

[Chemical 6]

Examples thereof include compounds represented by the formula (wherein D ² represents a dye residue).

Examples of the monofluorotriazine type reactive dyes include Cibacron F dyes (Ciba-C
Geigy Co. (CIBA-GEIGY), Levaf
ixEN dye (F. Bayer)
General formula (IV) such as:

[0045]

[Chemical 7]

(Wherein D ² is a dye residue and R ³ is

[0047]

Embedded image

And the like.

Examples of the trichloropyrimidine type reactive dye include C.I. I. Reactive Yell
ow 11, C.I. I. Reactive Red 1
7, C.I. I. Reactive Red 19, C.I.
I. Reactive Red 20, C.I. I. Reac
seven Red 39, C.I. I. ReactiveB
lue 8, C.I. I. Reactive Blue 1
7, C.I. I. Reactive Blue 18, C.I.
I. Reactive Blue 43, C.I. I. Re
active Brown 5, C.I. I. Reacti
ve Black 4, C.I. I. Reactive B
General formula (V) such as rack 6:

[0050]

[Chemical 9]

Examples thereof include compounds represented by the formula (wherein D ² represents a dye residue).

Examples of the fluoromethyl chloropyrimidine type reactive dye include Levafix PN dye (manufactured by F. Bayer) and Drim.
arene K dye (manufactured by Sandoz)
General formula (VI) such as:

[0053]

[Chemical 10]

Examples thereof include compounds represented by the formula (wherein D ² represents a dye residue).

Examples of the dichloroquinoxaline type reactive dyes include C.I. I. Reactive Yell
ow 25, C.I. I. Reactive Yellow
26, C.I. I. Reactive Yellow 2
7, C.I. I. Reactive Red 37, C.I.
I. Reactive Red 38, C.I. I. Rea
ctive Red 40, C.I. I. Reactive
Red 41, C.I. I. Reactive Blue
29, C.I. I. Reactive Blue34,
C. I. General formula (VII) such as Reactive Blue 44:

[0056]

[Chemical 11]

Examples thereof include compounds represented by the formula (wherein D ² represents a dye residue).

As the vinyl sulfone monochlorotriazine bifunctional reactive dye, for example, Sumixix
General formula (VIII) such as Supra dye (Sumitomo Chemical Co., Ltd.):

[0059]

[Chemical 12]

Examples thereof include compounds represented by the formula (wherein D ² represents a dye residue).

The above general formulas (II), (III),
(IV), (V), (VI), (VII) and (VI
Examples of the dye residue represented by D ² in II) include azo dyes, phthalocyanine dyes, azomethine dyes, nitro dyes, anthraquinone dyes, formazan dyes, oxazine dyes, indigoid dyes, phenylmethane dyes, xanthene dyes, acridine dyes. , Azine dye, thiazine dye, nitroso dye, benzoquinone dye,
Residues such as naphthoquinone dyes, naphthalimide dyes, and perinone dyes can be mentioned.

In the present invention, among the above reactive dyes (B), vinyl sulfone type dyes are used from the viewpoint of safety and fastness when chemically fixed to a polymer which is a material of a colored contact lens. Reactive dyes and dichlorotriazine type reactive dyes are preferable, and C.I. I. Re
active Black 5, C.I. I. Reacti
ve Blue 21, C.I. I. Reactive O
range 78, C.I. I. Reactive Yel
low 15, C.I. I. Reactive Blue
19, C.I. I. Reactive Red 180,
C. I. Reactive Blue 4, C.I. I. R
active Red 11, C.I. I. Reacti
ve Yellow 86 and C.I. I. Reacti
ve Blue 163 is preferred.

The amount of the reactive dye (B) to be used may be an amount suitable for performing desired coloring on the obtained contact lens, and it is preferably adjusted appropriately according to the purpose of use of the colored contact lens. .

For example, when it is desired to impart an effect of making the color of the pupil stand out to a colored contact lens,
The reactive dye (B) is used in an amount of 0.05 parts or more, especially 0.07 parts or more, and 0.5 parts or less with respect to 100 parts (parts by weight, the same below) of the total amount of the polymerization component (A). It is preferable to adjust the amount to 0.3 parts or less.

In order to improve the handling property, for example, when the colored contact lens is dropped or when the colored contact lens is misaligned in the pupil, the handling amount of the reactive dye (B) is used. Is the total amount of the polymerization component (A) 1
0.001 parts or more to 00 parts, 0.01 especially
It is preferable to adjust the amount to be not less than 0.1 part and not more than 0.1 part, especially not more than 0.08 part.

Alkaline aqueous solution (C) used in the present invention
Has an action of making the reaction system of the polymerization component (A) and the reactive dye (B) alkaline to promote the reaction of both, and is inactive to the polymerization itself of the polymerization component (A). is there.

In the present invention, since the alkaline aqueous solution (C) is used, the polymerization component (A) and the reactive dye (B) are simultaneously reacted during the polymerization of the polymerization component (A). When the polymerization proceeds and the polymerization of the polymerization component (A) is completed, the coloring is also completed, and the colored contact lens can be manufactured in only one step.

Typical examples of the alkaline aqueous solution (C) include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; sodium carbonate, potassium carbonate and the like. Alkali metal carbonates; calcium carbonate and other alkaline earth metal carbonates; sodium phosphate, potassium phosphate and other alkali metal phosphates; calcium phosphate and other alkaline earth metal phosphates; pyridine, triethylamine, dimethyl sulfoxide, etc. Examples thereof include aqueous solutions of basic solvents. Among them, aqueous solutions of hydroxides, carbonates and phosphates of alkali metals and alkaline earth metals are preferred because they have a large effect of promoting the reaction between the polymerization component (A) and the reactive dye (B). A sodium hydroxide aqueous solution is particularly preferable.

In the present invention, as described above, the polymerization component (A), the reactive dye (B) and the alkaline aqueous solution (C) are mixed to polymerize the polymerization component (A). It is preferred that the amount of water present in the system is small. That is, when the polymerization component (A) is polymerized while a large amount of water is present in the mixed system, white turbidity may occur when the obtained polymer is made to contain water.
Therefore, the amount of the alkaline aqueous solution (C) used is 100 parts by weight of the total amount of the polymerization component (A) in consideration of this fact and the effect of promoting the reaction between the polymerization component (A) and the reactive dye (B). It is preferable to adjust to 1 part or more, especially 2 parts or more, 8 parts or less, and especially 5 parts or less.

As described above, the alkaline aqueous solution (C) is required to make a mixed system of the three components alkaline to produce a desired reaction promoting effect, as described above. It is preferably 10 or more, and more preferably 11 or more.

According to the production method of the present invention, the polymerization component (A),
After appropriately adjusting the types and blending amounts of the reactive dye (B) and the alkaline aqueous solution (C), these are mixed and polymerized with the polymerization component (A), and the polymerization component (A) and the reactive dye (B) are mixed. A colored contact lens can be obtained by simultaneously advancing the reaction and the step of forming.

As the above-mentioned polymerization method, for example, a radical polymerization initiator is added when the polymerization component (A), the reactive dye (B) and the aqueous alkaline solution (C) are mixed, and then, for example, in a thermostat or a thermostatic chamber. Then, if necessary, for example, a method of completing the polymerization by heating stepwise for about 1 to 100 hours can be adopted.

According to the production method of the present invention, since the polymerization of the polymerization component (A) and the reaction of the polymerization component (A) with the reactive dye (B) proceed simultaneously, the radical polymerization initiator is Those which are involved in the polymerization but do not affect the reaction between the polymerization component (A) and the reactive dye (B) are used. Examples of such a radical polymerization initiator include 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2-azobis (2,4-dimethylvaleronitrile) and 2,2-azobisiso. Butyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2-methylpropionamide) dihydrochloride, 1,1-azobis (cyclohexane-1-carbonitrile), 1- Azo compounds such as [(1-cyano-1-methylethyl) azo] formamide and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; benzoyl peroxide, t
Examples include peroxides such as butyl hydroperoxide and cumene peroxide. Among these, azo compounds are preferable in consideration of the optimum dyeing temperature of the reactive dye (B) as described later.

In the present invention, the polymerization component (A)
Since the polymerization of (1) and the reaction of the polymerization component (A) with the reactive dye (B) are carried out at the same time, it is necessary to consider the kind of the reactive dye (B) and the polymerization temperature. That is, since the reactive dye (B) has an optimum dyeing temperature depending on its type, in order to make the reactive dye (B) react sufficiently and surely in the shortest possible time, such reaction is required. It is preferable to polymerize the polymerization component (A) within the range of the optimum dyeing temperature of the functional dye (B).

Thus, it is preferable to set the polymerization temperature of the polymerization component (A) in accordance with the optimum dyeing temperature of the reactive dye (B), and further radical polymerization having a half-life of the temperature adapted to the polymerization temperature. It is preferable to select and use an initiator.

For example, when the above-exemplified reactive dye (B) is used, the kind of the reactive dye (B),
Table 1 shows the optimum dyeing temperature and the type of the optimum radical polymerization initiator for each of the reactive dyes (B). The abbreviations in Table 1 indicate the following radical polymerization initiators.

V-70: 2,2-azobis (4-methoxy-2,4-dimethylvaleronitrile) V-65: 2,2-azobis (2,4-dimethylvaleronitrile) V-60: 2,2 -Azobisisobutyronitrile V-59: 2,2-azobis (2-methylbutyronitrile) V-50: 2,2-azobis (2-methylpropionamide) dihydrochloride V-40: 1,1 -Azobis (cyclohexane-1-carbonitrile) V-30: 1-[(1-cyano-1-methylethyl) azo] formamide V-19: 2-phenylazo-4-methoxy-2,4-
Dimethyl valeronitrile

[0078]

[Table 1]

The amount of the radical polymerization initiator used is usually about 0.01 to 3 parts per 100 parts of the polymerization component (A),
It is preferable to adjust the amount to be about 0.03 to 1 part.

In the present invention, as described above, when the polymerization component (A), the reactive dye (B) and the aqueous alkaline solution (C) are mixed, for example, a radical polymerization initiator is added to carry out polymerization and The reaction can proceed,
For example, a part of the polymerization component (A), the reactive dye (B) and the alkaline aqueous solution (C) are mixed to start the reaction between the polymerization component (A) and the reactive dye (B), and then the rest. The polymerization component (A) and the radical polymerization initiator may be blended to proceed polymerization and reaction.

Thus, simultaneously with the polymerization of the polymerization component (A),
A colored contact lens can be obtained by reacting the polymerization component (A) with the reactive dye (B) and completing the polymerization and the reaction to form a colored polymer obtained. For such molding, a molding method commonly used by those skilled in the art is adopted. For example, a processing method by cutting, polishing, etc. (mechanical processing method), a molding method using a mold (molding method), and the mechanical processing method. It can be appropriately selected and used from among the methods in combination with the molding method.

In the mechanical processing method, the polymerization and the reaction are carried out in a suitable mold or container, and for example, a rod-shaped, block-shaped or plate-shaped polymer is obtained, and then mechanical processing such as cutting or polishing is performed. This is a method of processing to form a desired contact lens shape.

In the molding method, a molding die (mold) having a shape corresponding to a desired contact lens shape is prepared, polymerization and reaction are carried out in this mold to obtain a molded product, and finishing processing is carried out if necessary. Is a method of applying.

In the method combining the mechanical processing method and the molding method, first, a molding die having a shape corresponding to at least one surface of a desired contact lens shape is prepared,
Polymerization and reaction are carried out in this mold, and then mechanical processing is carried out so as to obtain the other surface of the contact lens to obtain the contact lens.

From the colored contact lens thus obtained, for example, to obtain a water-containing colored soft contact lens, distilled water, physiological saline, an aqueous solution whose osmotic pressure or pH is appropriately adjusted is used. The colored contact lens may be hydrated by immersion.

According to the production method of the present invention, a uniformly and strongly colored contact lens can be easily obtained in one step without a dyeing step, a post-dyeing step, a post-treatment step and the like. The colored contact lens does not fade or discolor even when exposed to sunlight for a long period of time or subjected to continuous boiling treatment, and the original colored state is maintained.

Next, the method for producing the colored contact lens of the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

Example 1 95.5 parts of 2-hydroxyethyl methacrylate, 0.4 parts of ethylene glycol dimethacrylate, 0.1 part of 2,2-azobisisobutyronitrile, 2N aqueous sodium hydroxide solution (pH 13.8) 5 parts and C.I. I. Rea
After mixing 0.03 parts of ctive Blue 19, it was transferred to a polypropylene test tube having an inner diameter of 20 mm, and polymerization and reaction were carried out in the test tube at 40 ° C. for 20 hours to obtain a rod-shaped colored polymer.

The colored polymer thus obtained was subjected to cutting / polishing to form a contact lens, and then immersed in distilled water for hydration to prepare a colored hydrous soft contact lens.

Visual observation of the obtained colored hydrous soft contact lens revealed that it was transparent and the entire lens had a uniform blue color.

This colored hydrous soft contact lens was immersed in water in a vial bottle, the vial bottle was tightly capped, allowed to stand outdoors for 1 month and exposed to sunlight, and then the colored hydrous soft contact lens was taken out. When the surface was visually observed, no discoloration or discoloration was observed, and it remained a uniform blue color before exposure.

The colored hydrous soft contact lens obtained was immersed in physiological saline and continuously boiled for 120 hours, and then the colored hydrous soft contact lens was taken out and the surface thereof was visually observed. No discoloration or discoloration was observed, and the color remained the uniform blue color before the treatment.

Example 2 N, N-dimethylacrylamide 46 parts, methyl methacrylate 30 parts, 2-hydroxyethyl methacrylate 20 parts, ethylene glycol dimethacrylate 0.5
Part, 2,2-azobis (2,4-dimethylvaleronitrile) 0.1 part, 2N sodium hydroxide aqueous solution (pH 1
3.8) 4 parts and C.I. I. Reactive Blu
After mixing 0.02 part of e4, transfer to a polypropylene test tube with an inner diameter of 20 mm,
Polymerization and reaction at 30 ° C. for 30 hours gave a rod-shaped colored polymer.

The colored polymer thus obtained was subjected to cutting / polishing to form a contact lens, which was then immersed in distilled water for hydration to prepare a colored hydrous soft contact lens.

Visual observation of the obtained colored hydrous soft contact lens revealed that it was transparent and the entire lens had a uniform blue color.

This colored hydrous soft contact lens was immersed in water in a vial bottle, the vial bottle was tightly stoppered, allowed to stand outdoors for one month and exposed to sunlight, and then the colored hydrous soft contact lens was taken out. When the surface was visually observed, no discoloration or discoloration was observed, and it remained a uniform blue color before exposure.

Further, the colored hydrous soft contact lens thus obtained was immersed in physiological saline and subjected to a continuous boiling treatment for 120 hours, and then the colored hydrous soft contact lens was taken out and the surface thereof was visually observed. No discoloration or discoloration was observed, and the color remained the uniform blue color before the treatment.

Example 3 1 part of 2-hydroxyethyl methacrylate, 4 parts of 0.5N aqueous sodium hydroxide solution (pH 13.5) and C.I.
I. Mix 0.06 parts of Reactive Blue 4 and stir for 2 hours at 30 ° C. and 2 hours at 50 ° C. and mix 2
-Hydroxyethyl methacrylate and C.I. I. Reac
The reaction with tive Blue 4 was started. Then, 46 parts of N, N-dimethylacrylamide, 19 parts of 2-hydroxyethyl methacrylate, 29 parts of methyl methacrylate, 0.5 part of ethylene glycol dimethacrylate and 0.1 part of 2,2-azobis (2,4-dimethylvaleronitrile). After adding and mixing, the inner diameter is 20 mm
Was transferred to a polypropylene test tube of No. 1 and polymerized and reacted in the test tube at 30 ° C. for 30 hours to obtain a rod-shaped colored polymer.

The colored polymer thus obtained was subjected to cutting and polishing to form a contact lens, which was then immersed in distilled water for hydration to prepare a colored hydrous soft contact lens.

When the obtained colored hydrous soft contact lens was visually observed, it was transparent and the whole lens had a uniform blue color.

This colored hydrous soft contact lens was immersed in water in a vial bottle, the vial bottle was tightly stoppered, allowed to stand outdoors for 1 month and exposed to sunlight, and then the colored hydrous soft contact lens was taken out. When the surface was visually observed, no discoloration or discoloration was observed, and it remained a uniform blue color before exposure.

The colored hydrous soft contact lens thus obtained was immersed in physiological saline and subjected to a continuous boiling treatment for 120 hours, and then the colored hydrous soft contact lens was taken out and the surface thereof was visually observed. No discoloration or discoloration was observed, and the color remained the uniform blue color before the treatment.

From the results of Examples 1 to 3, according to the production method of the present invention, even when exposed to sunlight for a long period of time or subjected to continuous boiling treatment, there is no discoloration or discoloration. It can be seen that the water-containing soft contact lens colored in 1 can be obtained very easily in one step.

[0104]

According to the manufacturing method of the present invention, a uniformly and strongly colored contact lens can be easily obtained in one step without a dyeing step, a post-dyeing step, a post-treatment step, etc. The manufacturing method of the invention can be preferably used particularly for obtaining a colored hydrous soft contact lens.

Further, the colored contact lens obtained by the production method of the present invention, even when exposed to sunlight for a long period of time or subjected to continuous boiling treatment,
The original colored state is maintained without fading or discoloration.

Claims (6)

[Claims] 1. A polymerization component (A) containing a monomer capable of forming a covalent bond with the reactive dye (B), the reactive dye (B) and an aqueous alkaline solution (C) are mixed to obtain the polymerization component (A). A method for producing a colored contact lens, characterized in that the polymerization component (A) and the reactive dye (B) are reacted at the same time as the polymerization of (1). 2. The coloring according to claim 1, wherein the monomer capable of forming a covalent bond with the reactive dye (B) is at least one of a hydroxyl group-containing monomer, an amino group-containing monomer, an imino group-containing monomer and a mercapto group-containing monomer. How to make contact lenses. 3. The method for producing a colored contact lens according to claim 1, wherein the polymerization component (A) is composed of 2-hydroxyethyl methacrylate, N, N-dimethylacrylamide and methyl methacrylate. 4. The method for producing a colored contact lens according to claim 1, wherein the reactive dye (B) is a vinyl sulfone type reactive dye or a dichlorotriazine type reactive dye. 5. The reactive dye (B) is C.I. I. React
ive Black5, C.I. I. Reactive B
lue 21, C.I. I. Reactive Orange
78, C.I. I. Reactive Yellow 1
5, C.I. I. Reactive Blue 19, C.I.
I. Reactive Red 180, C.I. I. Rea
ctive Blue 4, C.I. I. Reactive
Red 11, C.I. I. Reactive Yellow
w 86 and C.I. I. Reactive Blue
The method for producing a colored contact lens according to claim 1, 2 or 3, which is at least one of 163. 6. The method for producing a colored contact lens according to claim 1, wherein the pH of the alkaline aqueous solution (C) is 9 or more.