JPH0920873A - Polymer dye, method for producing the same, colored contact lens using the polymer dye, and method for producing the same - Google Patents

Abstract

(57) Abstract: A dye capable of uniformly and strongly coloring a lens and the like in one step, a method for producing the dye, a colored contact lens using the dye, and a method for easily producing the colored contact lens are provided. To provide. SOLUTION: A polymer dye consisting of a reaction product of a non-crosslinked polymer (A) and a reactive dye (B), and a non-crosslinked polymer (A) and a reactive dye (B) are present in the presence of a hydrophilic solvent. A method for producing the polymeric dye which is reacted under basic conditions, a colored contact lens comprising a polymer having the polymeric dye and a polymerizable monomer component as an essential component, and the polymeric dye are dissolved in the polymerizable monomer component. Then, a method for producing the colored contact lens, in which a polymerization reaction is performed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a polymeric dye, a method for producing the same, a colored contact lens using the polymeric dye, and a method for producing the same. More specifically, it does not require a pre-dyeing step, a post-dyeing step, a post-treatment step, etc., and can uniformly and strongly color the lens in one step. Especially, a colored contact lens such as a highly hydrous soft contact lens The present invention relates to a polymeric dye that can be preferably used for the production of the same, a method for producing the same, a colored contact lens using the polymeric dye, and a method for easily producing the colored contact lens.

[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 a contact lens, and 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 a hydrous soft contact lens dyed with such a 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 because of a structural problem of the diazonium salt which is an azo dye.

Further, JP-A-63-50581 describes a colored soft contact lens obtained by using a water-insoluble dye and a method for producing the same. 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, contact lenses are obtained by a dyeing method using 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 of 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, since the reactivity between the dye and the monomer is low, the coloring effect does not occur sufficiently without causing the reaction, and the monomer solution containing the unreacted dye remains to be polymerized, so that the polymerization There is a problem in that there are many treatment steps and the process is complicated, such that the unreacted dye must be removed after the completion, and the monomer solution in which the monomer and the dye have been previously reacted must be purified.

Further, since the reactive dye usually colors the contact lens by reacting with a hydroxyl group or the like to form a covalent bond, for example, as in the N-vinylpyrrolidone-based highly water-containing contact lens,
Those that do not have a group capable of reacting with a reactive dye such as a hydroxyl group are difficult to be colored by such a reactive dye.

Therefore, in one step, a dye capable of coloring a lens obtained from various raw materials easily and with or without a specific reactive group, a colored contact lens using the same, and a method for producing the same. Development is awaited.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned prior art, and does not require a pre-dyeing step, a post-dyeing step, a post-treatment step, etc. It is an object of the present invention to provide a dye capable of coloring the above lens and a method for producing the same, and a colored contact lens using the dye and a method for producing the same.

[0013]

Means for Solving the Problems The present invention is a polymer dye comprising a reaction product of a non-crosslinked polymer (A) and a reactive dye (B), a non-crosslinked polymer (A) and a reactive dye (B). And, a method for producing the polymer dye, characterized by reacting under basic conditions in the presence of a hydrophilic solvent, a colored contact lens comprising a polymer having the polymer dye and a polymerizable monomer component as essential components, The present invention also relates to a method for producing the colored contact lens, which comprises dissolving the polymer dye in a polymerizable monomer component and then performing a polymerization reaction.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the polymer dye of the present invention is composed of the reaction product of the non-crosslinked polymer (A) and the reactive dye (B).

Non-crosslinked polymer (A) used in the present invention
Include 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 through an ether group, a thioether group or an NC bond. There are polymers having at least one kind.

Examples of the non-crosslinked polymer (A) include a polymer comprising a reactive group-containing monomer, a copolymer of the reactive group-containing monomer and another monomer, polyvinyl alcohol, cellulose and the like.

Representative examples of the reactive group-containing monomer include, for example, 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and 3-hydroxyethyl (meth) acrylate.
Hydroxy group-containing monomers such as hydroxypropyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate, hydroxyethyl maleate, hydroxyethyl fumarate, vinylbenzyl alcohol and allyl alcohol; N, N-dimethylaminopropyl (meth) Amino group-containing monomers such as acrylamide, allylamine, (meth) acrylamide, (meth) acryloyloxyethylamine; N-isopropylallylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-hydroxyethyl (meth ) Imino group-containing monomers such as acrylamide may be used, and these may be used alone or in admixture of two or more.

Other monomers that can be used together with the reactive group-containing monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate,
Alkyl (meth) acrylates such as propyl (meth) acrylate and butyl (meth) acrylate; (meth)
Unsaturated nitriles such as acrylonitrile; aromatic olefins such as styrene; vinyl compounds such as vinyl propionate and vinyl acetate; alkyl (meth) such as N, N-dimethyl (meth) acrylamide and N, N-diethyl (meth) acrylamide Acrylamide; N-vinylpyrrolidone, α-methylene-N-methylpyrrolidone and other polymerizable group-containing lactams; methoxydiethylene glycol mono (meth) acrylate, methoxytriethylene glycol mono (meth) acrylate, methoxydipropylene glycol mono (meth) Examples thereof include alkoxypolyalkylene glycol mono (meth) acrylates such as acrylates, and these can be used alone or in admixture of two or more.

When the non-crosslinked polymer (A) is a copolymer of a reactive group-containing polymer and another monomer, the reactivity of the reactive dye (B) with the non-crosslinked polymer (A), the non-crosslinked polymer Considering the solubility of (A) in the hydrophilic solvent and the solubility of the obtained polymer dye in the polymerizable monomer component, the weight ratio of the reactive group-containing monomer to the other monomer (reactive group-containing monomer / other The monomer) is preferably 1/10 to 10/1.

Further, when the polymerizable non-crosslinked polymer (A) is used to obtain a polymerizable polymer dye having a polymerizable group in the molecule, for example, ethylene glycol di (meth) acrylate is used. , 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, 1,3- Crosslinkable monomers such as butylene glycol di (meth) acrylate, vinyl (meth) acrylate and allyl (meth) acrylate can be used as other monomers. These may be used alone or in combination of two or more.

When the crosslinkable monomer is used as another monomer, the amount of the crosslinked structure formed in the polymer dye due to the use of the crosslinkable monomer and at least the polymerizable group in one molecule of the polymer dye. Considering the introduction of one, the weight ratio of the reactive group-containing monomer and the crosslinkable monomer (reactive group-containing monomer / crosslinkable monomer)
Is preferably 100/10 to 100 / 0.1.

In the present invention, considering the reactivity with the reactive dye (B), the non-crosslinked polymer (A) is
Polymers based on 2-hydroxyethyl methacrylate and polyvinyl alcohol are preferred.

The polymer containing 2-hydroxyethyl methacrylate as a main component means a polymer obtained by polymerizing a polymerization component containing 50% by weight or more of 2-hydroxyethyl methacrylate. Further, among the polyvinyl alcohol, considering the solubility of the obtained polymer dye in the polymerizable monomer component and the prevention of elution from the colored polymer after polymerization,
Those having a low water solubility, for example, a low saponification degree of about 30 to 80 mol% are preferable.

Some of the polymeric dyes of the present invention are water-soluble, and even when such a water-soluble polymeric dye is used as a raw material for obtaining colored contact lenses, for example, a chain reaction occurs during the polymerization reaction. As the polymer dye enters the polymer skeleton composed of the polymerizable monomer component by migration,
For example, when the colored contact lens obtained is hydrated, the polymeric dye is difficult to elute, but the polymeric dye and the polymerizable monomer component are polymerized, and the polymeric dye is incorporated into the polymer skeleton composed of the polymerizable monomer component. In order to eliminate the risk of further elution of the polymer dye by incorporating or grafting to the polymer skeleton, the non-crosslinked polymer (A), for example, obtained by using the crosslinkable monomer as a polymerization component, It is preferable to use a polymer having a polymerizable group in its molecule.

The reactive dye (B) used in the present invention is
For example, it reacts with a reactive group such as a hydroxyl group, an amino group, an imino group and a mercapto group in the non-crosslinked polymer (A) by nucleophilic addition to give an ether group, a thioether group or an N group.
Any material that forms a covalent bond via a -C bond may be used, for example, a natural fiber such as cotton, cellulose, or wool, or a synthetic fiber used for dyeing.

Typical examples of the reactive dye (B) include:
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. Reactive
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:

[0028]

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 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:

[0031]

Embedded image

The group represented by the formula:

[0033]

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[0034] 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:

[0036]

Embedded image

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

[0038]

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. Reactive
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. Reactive
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:

[0041]

[Chemical 6]

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

As the monofluorotriazine type reactive dye, for example, Cibacron F dye (Ciba-C
Geigy Co. (CIBA-GEIGY), Levaf
ixEN dye (F. Bayer)
General formula (IV) such as:

[0044]

Embedded image

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

[0046]

Embedded image

And a compound represented by

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:

[0049]

Embedded image

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

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

[0052]

Embedded image

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:

[0055]

Embedded image

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

Examples of the vinyl sulfone monochlorotriazine bifunctional reactive dyes include Sumifix.
General formula (VIII) such as Supra dye (Sumitomo Chemical Co., Ltd.):

[0058]

Embedded image

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 reactive dyes (B), the reactivity with the non-crosslinked polymer (A),
In addition, vinylsulfone type reactive dyes and dichlorotriazine type reactive dyes are preferable from the viewpoint of safety and fastness when obtaining a colored contact lens from the obtained polymer dye, and particularly C.I. I. Reactive Bla
ck 5, C.I. I. Reactive Blue 2
1, C.I. I. Reactive Orange 78,
C. I. Reactive Yellow 15, C.I.
I. Reactive Blue 19, C.I. I. Re
active Red 180, C.I. I. Reacti
ve Blue 4, C.I. I. Reactive Re
d 11, C.I. I. Reactive Yellow
86 and C.I. I. Reactive Blue 16
3 is preferred.

The mixing ratio of the non-crosslinked polymer (A) and the reactive dye (B) is such that the non-crosslinked polymer (A) and the reactive dye (B) are mixed in order to obtain a sufficiently high-concentration polymer dye.
It is desirable that the weight ratio (reactive dye (B) / non-crosslinked polymer (A)) is 1/50 or more, preferably 1/20 or more. Further, in order to improve the solubility of the obtained polymer dye in the polymerizable monomer component, it is desirable that the weight ratio is 2/1 or less, preferably 1/1 or less.

According to the production method of the present invention, a polymer dye can be obtained by reacting the non-crosslinked polymer (A) with the reactive dye (B) in the presence of a hydrophilic solvent under basic conditions. it can.

Non-crosslinked polymer (A) and reactive dye (B)
The reaction with is preferably carried out in a homogeneous aqueous solution, but the non-crosslinked polymer (A) preferably used in the present invention
Since many of them are insoluble in water, in order to improve the compatibility between the non-crosslinked polymer (A) and the reactive dye (B), the reaction between them is carried out in the presence of a hydrophilic solvent.

Examples of the hydrophilic solvent include dimethyl sulfoxide (hereinafter referred to as DMSO), amines such as triethylamine, amides such as hexamethylphosphoamide and dimethylformamide, methanol, ethanol, n-propanol, isopropanol, t-butanol and the like. Alcohol, water, etc. Among these, DMSO is preferable because the non-crosslinked polymer (A) is easily dissolved and is inactive to the reactive dye (B).

Among the hydrophilic solvents, reactive dyes (B) having, for example, hydroxyl group, amino group, imino group, etc.
A compound having a reactive group capable of reacting with, and having a high reactivity of such a reactive group may react with the reactive group of the solvent itself and the reactive dye (B). In this case, it is preferable to select a secondary alcohol or a tertiary alcohol having low reactivity.

The reaction between the non-crosslinked polymer (A) and the reactive dye (B) is promoted by being carried out under a basic condition, preferably pH 9 or higher, more preferably pH 9 or higher.
It is desirable to carry out the reaction at a temperature of 12 to 12 because of the reactivity of both.

In order to react the non-crosslinked polymer (A) with the reactive dye (B) under basic conditions, it is preferable to add a basic substance to both reaction systems.

Typical examples of the basic substance include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as calcium hydroxide; alkali metals such as sodium carbonate and potassium carbonate. Metal carbonates; alkaline earth metal carbonates such as calcium carbonate; alkali metal phosphates such as sodium phosphate and potassium phosphate; alkaline earth metal phosphates such as calcium phosphate; bases such as pyridine, triethylamine and dimethyl sulfoxide Examples of the solvent include organic solvents. Among these, hydroxides, carbonates and phosphates of alkali metals and alkaline earth metals are preferred from the viewpoint of having a large effect of promoting the reaction between the non-crosslinked polymer (A) and the reactive dye (B). Particularly preferred is sodium hydroxide.

The amount of the basic substance used may be adjusted in consideration of the effect of promoting the reaction between the non-crosslinked polymer (A) and the reactive dye (B). 100 parts in total with functional dye (B) (parts by weight, the same applies hereinafter)
0.1 part or more, preferably 1 part or more, and 50
It is desirable that the amount is not more than 10 parts, preferably not more than 10 parts.

In the present invention, since the reaction between the non-crosslinked polymer (A) and the reactive dye (B) is further promoted, the non-crosslinked polymer (A) previously dissolved in the hydrophilic solvent is used. And the reactive dye (B) dissolved in a basic aqueous solution such as an aqueous solution of the basic substance are preferably reacted.

Further, since the reactive dye (B) used in the present invention has the optimum dyeing temperature depending on its type, it is sufficiently and surely reactive with the non-crosslinked polymer (A) in the shortest possible time. In order to react with the dye (B), it is preferable to carry out the reaction of both in the range of the optimum dyeing temperature of the reactive dye (B).

Table 1 shows the types of reactive dyes (B) and their optimum dyeing temperatures when the above-exemplified reactive dyes (B) are used.

[0074]

[Table 1]

The reaction time between the non-crosslinked polymer (A) and the reactive dye (B) is not particularly limited, and it depends on the types of the non-crosslinked polymer (A) and the reactive dye (B) and the reaction temperature. The time may be set so that both can react sufficiently.

The reaction product thus obtained by reacting the non-crosslinked polymer (A) with the reactive dye (B) was precipitated by salting out and dissolved in, for example, methanol, DMSO, dimethylformamide, triethylamine or the like. Then, the polymer dye of the present invention can be obtained by re-precipitation purification with ethyl acetate, acetone, hexane, tetrahydrofuran or the like.

Further, when a polymerizable polymer dye having a polymerizable group in its molecule is to be prepared, for example, a hydroxyl group in the polymer dye is reacted with (meth) acrylic acid chloride or crosslinked. It is possible to react the non-crosslinked polymer (A) having a polymerizable group obtained by using a reactive monomer with the reactive dye (B).

The non-crosslinked polymer (A) having a polymerizable group in its molecule, which is obtained by using, for example, a crosslinkable monomer as one polymerization component, has a difference in reactivity of the polymerizable group of the crosslinkable monomer. It is polymerized in a state where the polymerizable group is left by utilizing it. Further, the portion of the crosslinkable monomer that has been crosslinked without leaving a polymerizable group is methanol, DM used when the obtained reaction product is dissolved.
Since it does not dissolve in SO or the like, if purified by filtration, even if a polymer having a crosslinkable structure is partially contained in the polymer having a polymerizable group, the polymer having the crosslinked structure is separated and the polymerizable group is removed. Only the non-crosslinked polymer (A) that it has can be subjected to the reaction with the reactive dye (B).
Thus, from the reaction product obtained by reacting the non-crosslinked polymer (A) having a polymerizable group with the reactive dye (B),
Polymerizable polymeric dyes can be obtained.

The weight average molecular weight of the polymer dye of the present invention is not particularly limited even when the colored contact lens obtained by using the polymer dye having no polymerizable group in the molecule is boiled. In order to eliminate the risk of elution itself, it is desirable that the amount is 10,000 or more, preferably 100,000 or more. Further, in order to prevent the polymer dye from being dissolved in a polymerizable monomer component or a solvent to carry out polymerization to obtain a colored contact lens, it does not take a long time to obtain a weight average molecular weight of the polymer dye. Is 5
It is desirable that it is 10 million or less, preferably 10 million or less.

The polymer dye of the present invention exerts an excellent effect that a lens or the like can be colored uniformly and firmly in one step, and therefore, it is suitably used for manufacturing a colored contact lens or the like. be able to.

The colored contact lens of the present invention is composed of a polymer containing the above-mentioned polymer dye and a polymerizable monomer component as essential components.

The polymerizable monomer component used in the present invention is not particularly limited as long as it is one that is usually used in the preparation of contact lenses, and it is appropriately selected according to the desired properties of the contact lens, and the amount thereof is used. Can be adjusted and used.

As the polymerizable monomer component, for example, a hydroxyl group-containing monomer, an amino group-containing monomer, an imino group-containing monomer, etc., which are exemplified as the monomer constituting the polymer or copolymer that can be used in the non-crosslinked polymer (A), etc. Reactive group-containing monomers, and hydrophobic monomers such as alkyl (meth) acrylates, unsaturated nitriles, aromatic olefins, and vinyl compounds; alkyl (meth) acrylamides, polymerizable group-containing lactams,
Examples thereof include flexibility-imparting monomers such as alkoxypolyalkylene glycol mono (meth) acrylate; other monomers such as crosslinkable monomers, and these can be used alone or in admixture of two or more.

The use ratio of the polymer dye and the polymerizable monomer component may be adjusted so that the obtained contact lens can be colored as desired. For example, a polymer may be used depending on the purpose of use of the colored contact lens. It is preferable to appropriately adjust the amount of the dye used.

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 amount of the polymeric dye used is the total amount of the polymerizable monomer component 1
It is desirable to adjust to 0.5 parts or more, preferably 0.8 parts or more, and 5 parts or less, preferably 3 parts or less with respect to 00 parts.

Further, in order to improve the handling property, for example, when the colored contact lens is dropped or when the colored contact lens is displaced in the pupil, it is easy to find it, the amount of the polymeric dye used is Total amount of polymerizable monomer components 10
It is desirable to adjust to 0.01 part or more, preferably 0.05 part or more, and 1 part or less, preferably 0.8 part or less with respect to 0 part.

According to the production method of the present invention, the types and blending amounts of the polymer dye and the polymerizable monomer component are appropriately adjusted,
A colored contact lens can be obtained by mixing these to dissolve the polymer dye in the polymerizable monomer component, and then performing a polymerization reaction and molding.

As a method of the above-mentioned polymerization reaction, for example, a radical polymerization initiator is added when mixing the polymer dye and the polymerizable monomer component, and then, for example, in a thermostat or thermostatic chamber, if necessary, for example, stepwise. For example, a method of completing the polymerization by heating to about 30 to 150 ° C. for about 1 to 100 hours can be adopted, and the polymerization reaction may be performed by a usual bulk polymerization method or solution polymerization method.

A typical example of the radical polymerization initiator is 2,2-azobis (4-methoxy-2,4).
-Dimethylvaleronitrile), 2,2-azobis (2,2
4-dimethylvaleronitrile), 2,2-azobisisobutyronitrile, 2,2-azobis (2-methylbutyronitrile), 2,2-azobis (2-methylpropionamide) dihydrochloride, 1, Azo compounds such as 1-azobis (cyclohexane-1-carbonitrile), 1-[(1-cyano-1-methylethyl) azo] formamide, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile; Examples thereof include peroxides such as benzoyl peroxide, t-butyl hydroperoxide and cumene peroxide.

The amount of the radical polymerization initiator used is usually adjusted to about 0.01 to 3 parts, preferably about 0.03 to 1 part, relative to 100 parts of the polymerizable monomer component (A). It is desirable to do.

Thus, the polymer constituting the colored contact lens of the present invention can be obtained by carrying out the polymerization reaction of the component comprising the polymeric dye and the polymerizable monomer component. In the present invention, the type of the polymeric dye used The composition of the obtained polymer changes depending on the.

First, when a polymer dye having no polymerizing property, that is, a dye having no polymerizable group capable of undergoing a polymerization reaction with the polymerizable monomer component is used, the polymerizable monomer component alone is used. Polymerization reaction becomes a polymer,
The obtained polymer is a polymer mixture of a polymer dye and a polymer composed of a polymerizable monomer component.

On the other hand, when a polymerizable polymer dye, that is, a dye having a polymerizable group capable of undergoing a polymerization reaction with the polymerizable monomer component in its molecule, is used as the polymer dye, it is combined with the polymerizable monomer component. Polymerization reaction occurs with the polymer dye, and the polymer dye is incorporated into the main chain of the polymer composed of the polymerizable monomer component, or the polymer dye is graft-copolymerized with the polymer composed of the polymerizable monomer component. The obtained polymer is one kind of polymer.

Thus, a colored contact lens can be obtained by completing the polymerization reaction of the component consisting of the polymer dye and the polymerizable monomer component and molding the obtained colored polymer. 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 reaction are carried out in an appropriate mold or container, and a polymer such as 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 the 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 thus-obtained colored contact lens, 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.

In the present invention, by using a polymer dye, a uniformly and strongly colored contact lens can be easily obtained in one step without using a pre-dyeing step, a post-dyeing step, a post-treatment step and the like. The colored contact lens obtained can be, for example, exposed to sunlight for a long period of time or subjected to a continuous boiling treatment without fading or discoloring and having an original colored state. It will be maintained.

[0100]

EXAMPLES Next, the polymer dye of the present invention and a method for producing the same, and a colored contact lens using the polymer dye and a method for producing the same will be described in more detail with reference to Examples. It is not limited to the examples only.

Example 1 (Production of polymer dye) 100 g of 2-hydroxyethyl methacrylate, DMS
500 g of O and 0.5 g of 2,2-azobis (2,4-dimethylvaleronitrile) were mixed and polymerized with stirring at 50 ° C. for 1 hour and then at 70 ° C. for 1 hour to obtain a non-crosslinked polymer solution. 1000 g of water and DMSO
500 g, 5 g of sodium hydroxide and C.I. I. Rea
Add to a mixed solution of 20 g of ctive Blue 4 and mix, mix at pH 11 for 1 hour at 40 ° C., then 60 ° C.
After reacting for 1 hour, a reaction product was obtained.

The obtained reaction product was precipitated by salting out, dissolved in methanol and then purified with ethyl acetate to obtain a polymer dye (hereinafter referred to as PHRB4).

The molecular weight of the thus obtained polymer dye was measured by gel permeation chromatography (GPC) using a GPC analyzer (manufactured by Shimadzu Corporation, column: S).
hodex Asahipak GF-510 HQ
(Manufactured by Showa Denko KK), solvent: dimethylformamide,
When measured using a molecular weight standard: pullulan, the weight average molecular weight (hereinafter referred to as Mw) was 4 million and the number average molecular weight (hereinafter referred to as Mn) was 1 million.

Example 2 (Production of Polymer Dye) 50 g of polyvinyl alcohol (saponification degree: 50 mol%, polymerization degree: 600), 300 g of water and DMSO10.
After dissolving in 0 g of mixed solvent, C.I. I. React
ive Red 180 5g and sodium carbonate 5
g, mix and stir at pH 11 at 50 ° C. for 1 hour,
Then, the reaction product was obtained by reacting at 80 ° C. for 1 hour.

The obtained reaction product was precipitated by salting out, dissolved in methanol and purified with ethyl acetate to obtain a polymer dye (hereinafter referred to as PVARR180).

Example 3 (Production of Polymerizable Polymer Dye) 100 g of 2-hydroxyethyl methacrylate, 3 g of allyl methacrylate, 500 g of DMSO and 0.5 g of 2,2-azobis (2,4-dimethylvaleronitrile) were mixed and stirred. While at 50 ℃ for 2 hours, then at 60 ℃ 1
Polymerization reaction was carried out for a period of time to obtain a solution of a non-crosslinked polymer having a polymerizable group (unreacted allyl group) in its molecule. This was mixed with 2000 g of water, 1000 g of DMSO, 5 g of sodium hydroxide and C.I. I. Reactive Blue
21 Add to 30 g of mixed solution and mix to pH 11
The reaction product was obtained by reacting at 40 ° C. for 1 hour and then at 60 ° C. for 1 hour.

The obtained reaction product was precipitated by salting out, dissolved in methanol and purified with ethyl acetate to obtain a polymerizable polymer dye having a polymerizable group in its molecule (hereinafter referred to as PHRB21). I got it.

When the Mw and Mn of the obtained polymer dye were measured in the same manner as in Example 1, the Mw was 3 million and the Mn was 800,000.

Example 4 (Production of Polymerizable Polymer Dye) 50 g of 2-hydroxyethyl methacrylate, 50 g of acrylamide, 600 g of DMSO and 0.4 g of 2,2-azobis (2,4-dimethylvaleronitrile) were mixed and stirred. While conducting a polymerization reaction at 50 ° C. for 1 hour and then at 70 ° C. for 1 hour, a water-soluble non-crosslinked polymer solution was obtained. 1000 g of water, 5 g of sodium hydroxide,
C. I. 20 g of Reactive Blue 19 and C.I. I. Reactive Yellow 15
Add to a mixed solution of 30 g and mix, and adjust to pH 11 at 50
The reaction product was obtained by reacting at 70 ° C. for 1 hour and then at 70 ° C. for 1 hour.

The obtained reaction product was precipitated by salting out, dissolved in methanol, reprecipitated with ethyl acetate, dried under reduced pressure, and dried with N, N-dimethylacetamide 300.
g. While stirring this solution at 20 ° C., 2.5 g of methacrylic acid chloride was added, and reaction was carried out for 4 hours with 1 g of pyridine as a catalyst. Then add this solution to 1,4
-By reprecipitation in dioxane, a polymerizable polymer dye having a polymerizable group in its molecule (hereinafter referred to as PHGRE).
It's called EN).

When the Mw and Mn of the obtained polymer dye were measured in the same manner as in Example 1, the Mw was 5 million and the Mn was 1.2 million.

Example 5 (Production of Colored Hydrous Soft Contact Lens) 95.5 parts of 2-hydroxyethyl methacrylate, 0.4 part of ethylene glycol dimethacrylate, 0.1 part of 2,2-azobisisobutyronitrile and PVARR1
After 80 parts of 0.3 parts were mixed and the PVARR180 was dissolved, the PVARR180 was transferred to a polypropylene test tube having an inner diameter of 20 mm, and a polymerization reaction was carried out at 40 ° C. for 20 hours in the test tube to obtain a rod-shaped colored polymer.

The colored polymer thus obtained is subjected to cutting and polishing to form a contact lens, which is then immersed in distilled water for hydration to prepare a colored hydrous soft contact lens (water content: 38% by weight). did.

When the colored hydrous soft contact lens obtained was visually observed, it was transparent and the whole lens was red in 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 red color before exposure.

The colored hydrous soft contact lens thus 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 at all, and it remained a uniform red color before the treatment.

Example 6 (Production of colored hydrous soft contact lens) 48 parts of N, N-dimethylacrylamide, 31 parts of methyl methacrylate, 20 parts of 2-hydroxyethyl methacrylate, 0.8 parts of ethylene glycol dimethacrylate.
Part, 2,2-azobis (2,4-dimethylvaleronitrile) 0.08 part, water 4 parts and PHRB4 0.2 part are mixed, and after dissolving such PHRB4, the inner diameter 20
It was transferred to a polypropylene test tube of mm, and a polymerization reaction was carried out in the test tube at 30 ° C. for 30 hours to obtain a rod-shaped colored polymer.

The colored polymer thus obtained is subjected to cutting / polishing to form a contact lens, which is then immersed in distilled water for hydration to prepare a colored hydrous soft contact lens (water content: 60% by weight). did.

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 sealed, left 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.

The colored hydrous soft contact lens thus 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 7 (Production of colored hydrous soft contact lens) N-vinylpyrrolidone 75 parts, methyl methacrylate 2
After mixing 5 parts, 1 part of vinyl methacrylate, 0.1 part of 2,2-azobisisobutyronitrile and 0.1 part of PHRB21 to dissolve such PHRB21, the mixture was transferred to a polypropylene test tube having an inner diameter of 20 mm, and Polymerization reaction was carried out at 45 ° C. for 20 hours in a test tube to obtain a rod-shaped colored polymer.

The colored polymer thus obtained is subjected to cutting and polishing to form a contact lens, which is then immersed in distilled water for hydration to prepare a colored hydrous soft contact lens (water content: 75% by weight). did.

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 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 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 8 (Production of colored hydrous soft contact lens) N-vinylpyrrolidone 75 parts, methyl methacrylate 2
5 parts, vinyl methacrylate 1 part, 2,2-azobisisobutyronitrile 0.1 part and PHGREEN 0.2
After mixing the parts to dissolve the PHGREEN,
The product was transferred to a polypropylene test tube having an inner diameter of 20 mm, and a polymerization reaction was carried out in the test tube at 45 ° C. for 20 hours to obtain a rod-shaped colored polymer.

The colored polymer thus obtained is subjected to cutting / polishing to form a contact lens, which is then immersed in distilled water for hydration to prepare a colored hydrous soft contact lens (water content: 75% by weight). did.

Visual observation of the obtained colored hydrous soft contact lens revealed that it was transparent and the entire lens had a uniform green 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 brown or discoloration was observed, and it remained a uniform green color before exposure.

The colored hydrous soft contact lens 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. However, no brown or discoloration was observed, and the green color remained uniform before the treatment.

From the results of Examples 5 to 8, by using the polymer dye of the present invention, fading or discoloration occurs even when exposed to sunlight for a long period of time or subjected to continuous boiling treatment. It can be seen that a uniformly and strongly colored water-containing soft contact lens free of color can be obtained very easily in one step.

[0133]

The polymeric dye of the present invention is capable of uniformly and firmly coloring a lens or the like in one step without using a pre-dyeing step, a post-dyeing step, and a post-treatment step. The method for producing a colored contact lens of the present invention using is particularly suitable for obtaining a colored highly hydrous soft contact lens.

In addition, the colored contact lens of the present invention comprises
For example, 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 discoloring.

Claims (11)

[Claims] 1. A polymeric dye comprising a reaction product of a non-crosslinked polymer (A) and a reactive dye (B). 2. The polymer dye according to claim 1, wherein the non-crosslinked polymer (A) is a polymer having at least one reactive group of a hydroxyl group, an amino group, an imino group and a mercapto group. 3. The polymer dye according to claim 1, wherein the non-crosslinked polymer (A) is a polymer having 2-hydroxyethyl methacrylate as a main component or polyvinyl alcohol. 4. The polymer dye according to claim 1, 2 or 3, 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 polymer dye according to claim 1, which is at least one of 163. 6. The method for producing a polymeric dye according to claim 1, wherein the non-crosslinked polymer (A) and the reactive dye (B) are reacted in the presence of a hydrophilic solvent under basic conditions. 7. The method for producing a polymeric dye according to claim 6, wherein the non-crosslinked polymer (A) previously dissolved in a hydrophilic solvent is reacted with the reactive dye (B) dissolved in a basic aqueous solution. 8. The method for producing a polymeric dye according to claim 6, wherein the hydrophilic solvent is dimethyl sulfoxide. 9. The method for producing a polymeric dye according to claim 6, 7 or 8, wherein the non-crosslinked polymer (A) and the reactive dye (B) are reacted at a pH of 9 or higher. 10. A colored contact lens comprising a polymeric dye comprising a reaction product of a non-crosslinked polymer (A) and a reactive dye (B) and a polymer containing a polymerizable monomer component as an essential component. 11. A method in which a polymer dye comprising a reaction product of a non-crosslinked polymer (A) and a reactive dye (B) is dissolved in a polymerizable monomer component and then a polymerization reaction is carried out. Item 10. A method for producing a colored contact lens according to Item 10.