JPH0643407A - Contact lens treating solution - Google Patents

Abstract

PURPOSE:To ensure high water containability by incorporating a polymer obtd. by polymerizing a fumaric diester monomer having a specified phospholipid polar group with a vinyl monomer and a solvent which dissolves the polymer. CONSTITUTION:This contact lens treating soln. contains a polymer obtd. by homopolymerizing a fumaric diester monomer represented by formula I or copolymerizing it with other copolymerizable vinyl monomer and a solvent which dissolves the polymer as essential components. In the formula I, each of R1 and R2 is 1-20C alkyl, alkenyl, hydroxyalkyl or a group represented by formula II and at least one of R1 and R2 is a group represented by the formula II. In the formula II, R3 is a group represented by formula III or IV [where (n) is an integer of 1-8] and R4 is 1-8C alkyl, aryl or hydroxyalkyl.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a treatment solution for contact lenses, and more specifically, it imparts hydrophilicity, stain resistance and the like to hard contact lenses, non-water-containing soft contact lenses and water-containing soft contact lenses. The present invention relates to a treatment solution for contact lenses.

[0002]

2. Description of the Related Art Contact lenses include non-hydrous contact lenses and hydrous contact lenses. Non-hydrous contact lenses include hard contact lenses and soft contact lenses, and hydrous contact lenses include soft contact lenses. . Non-hydrous contact lenses are superior to hydrous contact lenses in terms of stability of lens materials and ease of care. As the non-hydrous contact lens, those containing methyl methacrylate as a main component, those using silicon rubber, etc. have been conventionally known, and more recently, silyl methacrylate, fluorine methacrylate, etc., which have further reduced the effects on the eyes. High-oxygen permeable hard contact lenses containing as a main component have been used.

However, the non-hydrous contact lens has a problem in that the lens surface is hydrophobic, so that the feeling of wearing is poor and the cells in the eye are affected. In particular, the above-mentioned high oxygen-permeable hard contact lens contains a large amount of silicon, fluorine, etc. as the main components, and thus has strong hydrophobicity and poor adhesion to the eye, resulting in poor wearing comfort and adhesion of proteins and lipids. There is a problem such as doing.

Therefore, in order to impart hydrophilicity to the hydrophobic surface of the contact lens, there are used methods such as plasma treatment and chemical treatment with an acidic / basic substance. In this method, the hydrophilicity is maintained. There are problems that it is difficult, the contact lens is modified by chemical treatment, and the treatment process is complicated.

As another method for imparting hydrophilicity to the surface of a contact lens, for example, in Japanese Patent Publication No. 48-37910, the contact lens is dipped in a solution containing a water-soluble polymer such as polyvinyl alcohol, hydroxyethyl cellulose, polyvinylpyrrolidone. Although a method has been proposed, the method has a problem that the degree of hydrophilicity is limited depending on the type of contact lens, and further, the adhesion of proteins, lipids and the like cannot be sufficiently prevented.

On the other hand, the hydrous contact lens is superior to the non-hydrous contact lens in wearing feeling, but since it is a hydrogel lens containing 2-hydroxyethyl methacrylate, vinylpyrrolidone and the like as main components, There are hygiene problems such as protein and lipid adhesion, and further bacterial growth. There is also a problem that the mechanical strength is lowered when the water content of the lens is increased.

Therefore, in normal use, it is necessary to perform complicated hygiene management such as boiling sterilization treatment, protein removal treatment, care with a disinfectant and a cleaning solution, and such a contact lens can be easily performed. It is desired to develop a treatment solution for use.

[0008]

An object of the present invention is to impart hydrophilicity to the surface of a non-hydrous contact lens by a simple dipping treatment method, while imparting high hydrousity to a hydrous contact lens. In addition, it is to provide a treatment solution for contact lenses, which can suppress the adhesion and deposition of proteins and lipids.

[0009]

According to the present invention, a fumaric acid diester monomer represented by the following general formula 2 (hereinafter referred to as fumaric acid diester monomer 1) can be copolymerized alone or with another copolymer. Provided is a contact lens treatment solution containing as an essential component a polymer obtained by polymerization with a vinyl monomer and a solvent capable of dissolving the polymer.

[0010]

[Chemical 2]

The present invention will be described in more detail below.

The treatment solution for contact lenses of the present invention comprises
A polymer obtained by polymerizing a fumaric acid diester monomer having a specific phospholipid polar group alone or with another copolymerizable vinyl monomer, and a solvent for dissolving the polymer are contained as essential components.

In the present invention, the fumaric acid diester used as a raw material monomer of the polymer used as the essential component is the fumaric acid diester monomer 1 represented by the general formula 1. In the fumaric acid diester monomer 1, when n exceeds 8, or when the carbon number of R ₄ exceeds 8, hydrophilicity and polymerizability are lowered, and R ₁ or R ₂ has 20 carbon atoms. In the case of an alkyl group, an alkenyl group, or a hydroxyalkyl group exceeding the above range, the hydrophobicity becomes high and it cannot be used.

Specific examples of the fumaric acid diester monomer 1 include 2- (isopropyl fumaroyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphoric acid and 3- (t-butyl fumaroyloxy). ) Propyl-2 '-(trimethylammonio) ethyl phosphoric acid, 2
-(Cyclohexylfumaroyloxy) ethyl-2'-
(Trimethylammonio) ethyl phosphoric acid, 3- (isopropylfumaroyloxy) propyl-2 ′-(trimethylammonio) ethylphosphoric acid, 4- (sec-butylfumaroyloxy) butyl-2 ′-(trimethylammonio) ethylphosphoric acid Acid, 2- (isopropylfumaroyloxy) ethyl-2 '-(triethylammonio) ethylphosphoric acid, 2- (cyclohexylfumaroyloxy) ethyl-2'-(tributylammonio) ethylphosphoric acid, 2-
(T-butyl fumaroyloxy) ethyl-2 ′-(tri-2 ″ -hydroxyethylammonio) ethyl phosphoric acid,
2- (Isopropylfumaroyloxy) ethoxyethyl-2 '-(trimethylammonio) ethylphosphoric acid and the like can be preferably mentioned.

To prepare the fumaric acid diester monomer 1, for example, a fumaric acid derivative such as a hydroxyalkyl-alkyl fumaric acid diester and 2-chloro-2-oxo-1,3,2-dioxaphosphorane. With a phosphorane compound such as trimethylamine in the presence of a tertiary amine such as trimethylamine at 0 to 50 ° C. for 1 to 10 hours,
Obtained by obtaining a monophosphorane fumarate derivative, and then reacting the obtained monophosphorane fumarate derivative with a tertiary amine such as a trialkylamine at a reaction temperature of 30 to 100 ° C. for a reaction time of 3 to 48 hours. it can. Further, the obtained product can be purified by a known method such as recrystallization or column chromatography.

In the present invention, other copolymerizable vinyl monomers that can be copolymerized with the fumaric acid diester monomer 1 include, for example, styrene, nucleus-substituted methylstyrene, α-methylstyrene, nucleus-substituted chloro. Styrene, vinyl acetate, vinyl propionate, vinyl pivalate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid, (meth) acrylic acid amide, 2-hydroxyethyl (meth ) Acrylate, ethyl vinyl ether, n-butyl vinyl ether, N-vinyl pyrrolidone, vinyl chloride, vinylidene chloride, ethylene, propylene, isobutylene, acrylonitrile and the like can be preferably mentioned. When used, they can be used alone or as a mixture.

When the other copolymerizable vinyl monomer is used, the amount used is the fumaric acid diester monomer 1 described above.
It is desirable to use in the range of 5 to 10,000 parts by weight with respect to 100 parts by weight. The use range is 10,000
If the amount exceeds 5 parts by weight, water solubility, antifouling property, etc. are not sufficiently exhibited, and if the amount is less than 5, the effect of copolymerization cannot be exhibited, which is not preferable.

The polymer used as an essential component in the present invention is a polymer obtained by polymerizing the fumaric acid diester monomer 1 alone or with another copolymerizable vinyl monomer. There is no particular limitation as long as it has a monomer unit. The number average molecular weight of the polymer varies depending on the polymerization temperature, the amount of the polymerization initiator used, the use of the polymerization degree modifier, and the like, and is not particularly limited, but is preferably in the range of 1000 to 300,000, and particularly to the solvent described below. 200, the viscosity of the treatment solution for contact lenses, the adhesion to the contact lens surface, etc.
The range of 0-200000 is preferable. If the number average molecular weight is less than 1000, the tackiness is reduced, and
If it exceeds 00, the viscosity becomes high and the operability deteriorates.
Not preferable.

To prepare the polymer, for example, bulk polymerization of the fumaric acid diester monomer 1 or the fumaric acid diester monomer and the other copolymerizable vinyl monomer in the presence of a radical polymerization initiator. It can be easily obtained by radical polymerization or copolymerization by a known polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization, etc., particularly solution polymerization, non-aqueous suspension polymerization and bulk polymerization. preferable.
As the radical polymerization initiator, benzoyl peroxide,
Lauroyl peroxide, diisopropylperoxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxyisobutyrate, azobisdimethylvaleronitrile, azobisisobutyronitrile, peroxy Sulfates or persulfates-hydrogen sulfite can be preferably used. The amount of the radical polymerization initiator used is preferably 0.01 to 10 parts by weight, and particularly preferably 0.1 to 5 parts by weight, based on 100 parts by weight of all the raw material monomers used.

To carry out the polymerization, nitrogen, carbon dioxide,
The polymerization can be carried out by substituting the polymerization system with an inert gas such as helium or under an atmosphere, preferably at a polymerization temperature of 30 to 100 ° C., preferably at a polymerization time of 5 to 72 hours. . At this time, a polymer having a narrow molecular weight distribution can be obtained by further performing a fractionation operation.

The solvent used as an essential component in the present invention dissolves the above-mentioned polymer, does not affect the contact lens such as denaturation and deformation, and is miscible with water, and a simple operation such as dipping and washing. With respect to the contact lens, if hydrophilicity, antifouling property, etc. can be imparted,
It is not particularly limited. Specific examples of the solvent include water, methanol, ethanol, isopropanol, ethylene glycol, polyethylene glycol, glycerin, ethylene glycol monomethyl ether, dimethyl sulfoxide, tetrahydrofuran, acetone, and the like.
They can be used alone or as a mixture.

In the present invention, the blending ratio of the polymer and the solvent is such that the polymer is preferably in the range of 0.01 to 10% by weight based on the whole treatment solution of the present invention. Is preferred. When the blending ratio of the polymer is less than 0.01% by weight, the contact lens cannot be sufficiently imparted with hydrophilicity and antifouling property, which is not preferable.

In order to use the treatment solution for contact lenses of the present invention, the treatment solution for contact lenses is preferably heated to 20 to 70 ° C. and used by immersing or contacting the contact lens with the treatment solution. be able to. After the treatment, the contact lens can be put into a wearable state by rinsing the contact lens with water, physiological saline, or an appropriate washing solution.

Furthermore, the treatment solution for contact lenses of the present invention can be used in combination with a surfactant, a bactericide, an antiseptic, etc., if necessary, and can also be used as a cleaning agent or a preservation solution.

[0025]

The contact lens treatment solution of the present invention contains a polymer having a specific polar group of phospholipids as an essential component, so that the contact lens can be protected from hydrophilicity and proteins / lipids by a simple operation. It can impart stain resistance, and is useful for improving the feeling of wearing and preventing denaturation of contact lenses.

[0026]

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

[0027]

Example 1 (A) Preparation of Treatment Solution for Contact Lens 2- (Isopropylfumaroyloxy) ethyl-2′-
5 g of (trimethylammonio) ethyl phosphoric acid, 5 g of vinyl acetate and 0.1 g of azobisisobutyronitrile were dissolved in 30 g of ethanol and sealed in a glass tube. The glass tube was replaced with nitrogen and then sealed, and the raw material monomer in the glass tube was polymerized at 60 ° C. for 12 hours to obtain a polymer. The polymer obtained was treated with ethanol / diethyl ether (3/7) 10
The precipitate was purified by reprecipitation using 0 g and dried. 2 g of the obtained dried product was dissolved in 98 g of ethylene glycol to obtain a treatment solution for contact lenses.

(B) Preparation of Contact Lens Test Piece On the other hand, the following three kinds of test pieces were prepared as contact lenses. (1) Hard contact lens 99 g of methyl methacrylate, 1 g of diethylene glycol dimethacrylate and 0.2 g of azobisisobutyronitrile were injected into a glass tube, nitrogen substitution-deaeration was repeated, and the glass tube was sealed at 30 ° C. To 100 ° C over 50 hours, the raw material monomer in the glass tube was heat-cured, and a colorless transparent polymer was obtained. The obtained polymer was cut and polished by a usual processing method to prepare a contact lens test piece having a predetermined shape.

(2) Oxygen-permeable hard contact lens 40 g of tris (trimethylsiloxy) silylpropyl methacrylate, 30 of trifluoroethyl methacrylate
g, 10 g of methyl methacrylate, 15 g of triethylene glycol dimethacrylate, and 5 g of methacrylic acid were used to prepare a test piece in the same manner as in the above (1) hard contact lens.

(3) Soft Contact Lens A test piece was prepared in the same manner as in (1) Hard Contact Lens except that 99 g of 2-hydroxyethyl methacrylate and 1 g of ethylene glycolide dimethacrylate were used.

(C) Measurement of Hydrophilicity and Antifouling Property of Contact Lens Treatment Solution The above contact lens treatment solution was filled in a contact lens storage case, and the contact lens test pieces of (1) to (3) above were used. After soaking for a minute, it was washed with water, and the hydrophilicity and antifouling property of the contact lens test piece were measured according to the following methods. The results are shown in Table 1.

A) Measurement of hydrophilicity After the surface of the test piece was dried, the water contact angle on the surface of the test piece was measured by a water solution method. The smaller the contact angle, the higher the hydrophilicity.

B) Measurement of Antifouling Property The test piece was immersed in a physiological saline solution containing 0.39% by weight of albumin, 0.17% by weight of lysozyme and 0.105% by weight of globulin at 35 ° C. for 2 weeks. After that, it is taken out from the physiological saline, and then washed with physiological saline, and the protein adhering to the surface of the test piece is peeled off using a surfactant, and in the obtained solution, a protein quantification reagent " Micro BAC (mi
cro BCA) '' (product name, manufactured by PIERSC),
The amount of protein in the solution was measured.

[0034]

Example 2 Except that 9 g of 2- (isopropylfumaroyloxy) ethyl-2 ′-(trimethylammonio) ethylphosphoric acid and 1 g of styrene were used as raw material monomers, and 98 g of ethylene glycol / water (50/50) was used as a solvent. In the same manner as in Example 1, a contact lens treatment solution was prepared, and the hydrophilicity and antifouling property of the obtained treatment solution were measured for each of the test pieces. The measurement results are shown in Table 1.

[0035]

Example 3 Example 1 was repeated except that 5 g of 2- (t-butylfumaroyloxy) ethyl-2 ′-(tributylammonio) ethylphosphoric acid and 5 g of vinyl acetate were used as raw material monomers, and 98 g of ethylene glycol was used as a solvent. A treatment solution for contact lenses was prepared in the same manner as above, and the hydrophilicity and antifouling property of the obtained treatment solution were measured for each of the test pieces. The measurement results are shown in Table 1.

[0036]

Comparative Example 1 In the same manner as in Example 1 except that 100 g of an aqueous solution of polyvinyl alcohol (saponification degree: 88%) was used.
The hard contact lens test piece of (1) prepared in Example 1 was treated and the hydrophilicity and antifouling property were measured. The measurement results are shown in Table 1.

[0037]

Comparative Example 2 The oxygen-permeable hard contact lens of (2) prepared in Example 1 was subjected to no treatment,
The hydrophilicity and antifouling property were measured. The measurement results are shown in Table 1.

[0038]

[Table 1]

Claims (1)

[Claims] 1. A polymer obtained by polymerizing a fumaric acid diester monomer represented by the following general formula 1 alone or with another copolymerizable vinyl monomer, and a solvent for dissolving the polymer are essential. A treatment solution for contact lenses containing as a component. [Chemical 1]