JP3206117B2 - Treatment solution for contact lenses - Google Patents

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 particularly to imparting hydrophilicity, antifouling property, etc. to hard contact lenses, non-hydrous soft contact lenses, and hydrous soft contact lenses. A treatment solution for a contact lens.

[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 material and ease of care. As the non-water-containing contact lens, those containing methyl methacrylate as a main component, those using silicon rubber, and the like have been conventionally known, and more recently, silyl-based methacrylate, fluorine-based methacrylate, and the like, in which the influence on the eyes is further reduced. A high oxygen permeable hard contact lens mainly composed of is used.

[0003] However, the non-water-containing contact lens has a problem that the surface of the lens is hydrophobic, so that the feeling of wearing is poor and there is an effect on intraocular cells. In particular, the high oxygen permeable hard contact lens contains a large amount of silicon, fluorine, and the like as a main component, and thus has a high hydrophobicity and a low adhesiveness to the eyes. Problem.

In order to impart hydrophilicity to the hydrophobic surface of the contact lens, a method of performing a plasma treatment, a chemical treatment with an acidic / basic substance, or the like has been used. There are problems such as difficulty, denaturation of the contact lens due to chemical treatment, and complicated processing steps.

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

On the other hand, a hydrous contact lens is more excellent in wearing feeling than a non-hydrous contact lens, but is a hydrogel-like lens containing 2-hydroxyethyl methacrylate, vinylpyrrolidone and the like as a main component. There are hygiene problems such as attachment of proteins and lipids and further propagation of bacteria. There is also a problem that increasing the water content of the lens lowers the mechanical strength.

Therefore, in normal use, it is necessary to perform complicated sanitary control such as boiling sterilization, protein removal, care with a bactericide and a cleaning solution, and such a contact lens can easily perform such treatment. There is a demand for the development of treatment solutions.

[0008]

SUMMARY OF THE INVENTION It is an object of the present invention to impart hydrophilicity to the surface of a non-hydrous contact lens by a simple immersion treatment method, while imparting high hydrousity to a hydrous contact lens. Another object of the present invention is to provide a contact lens treatment solution capable of suppressing 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 used alone or in another copolymer. Provided is a contact lens treatment solution containing, as essential components, a polymer obtained by polymerizing a vinyl monomer and a solvent that dissolves the polymer.

[0010]

Embedded image

Hereinafter, the present invention will be described in more detail.

The contact lens treatment solution of the present invention comprises:
It contains, as essential components, 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 dissolving the polymer.

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 R ₄ has more than 8 carbon atoms, hydrophilicity and polymerizability decrease, and R ₁ or R ₂ has 20 carbon atoms. In the case of an alkyl group, an alkenyl group or a hydroxyalkyl group which exceeds the above, the hydrophobicity becomes high and cannot be used.

Examples of the fumaric acid diester monomer 1 include, for example, 2- (isopropylfumaroyloxy) ethyl-2 '-(trimethylammonio) ethylphosphate, 3- (t-butylfumaroyloxy) ) Propyl-2 '-(trimethylammonio) ethylphosphoric acid, 2
-(Cyclohexylfumaroyloxy) ethyl-2'-
(Trimethylammonio) ethylphosphoric 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,
(T-butylfumaroyloxy) ethyl-2 ′-(tri-2 ″ -hydroxyethylammonio) ethylphosphoric acid,
Preferable examples include 2- (isopropylfumaroyloxy) ethoxyethyl-2 ′-(trimethylammonio) ethylphosphoric acid.

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 By reacting with a phosphorane compound such as tertiary amine such as trimethylamine at 0 to 50 ° C. for 1 to 10 hours,
A monophosphorane fumarate derivative is obtained, and then the obtained monophosphorane fumarate derivative is reacted 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 which can be copolymerized with the fumaric acid diester monomer 1 include, for example, styrene, nucleus-substituted methylstyrene, α-methylstyrene, nucleus-substituted chloromethane. Styrene, vinyl acetate, vinyl propionate, vinyl pivalate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic acid, (meth) acrylamide, 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 exemplified. When used, they can be used alone or as a mixture.

When the other copolymerizable vinyl monomer is used, the amount used is the above-mentioned fumaric acid diester monomer 1
It is desirable to use 5 to 10,000 parts by weight based on 100 parts by weight. The use range is 10,000
When the amount is more than 5 parts by weight, water solubility, antifouling property and the like are not sufficiently exhibited. On the other hand, when the amount is less than 5, the effect by copolymerization cannot be exerted.

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. It is not particularly limited 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 polymerization initiator used, the use of a polymerization degree regulator and the like, and is not particularly limited, but is preferably in the range of 1,000 to 300,000, and particularly to the solvent described below. Solubility, viscosity of contact lens treatment solution, adhesion to contact lens surface, etc.
The range of 0 to 200,000 is preferred. When the number average molecular weight is less than 1,000, the tackiness is reduced and 3000
If it exceeds 00, the viscosity increases and the operability deteriorates.
Not preferred.

To prepare the polymer, for example, the fumaric acid diester monomer 1 or the fumaric acid diester monomer and the other copolymerizable vinyl monomer are subjected to bulk polymerization in the presence of a radical polymerization initiator. , Suspension polymerization, solution polymerization, emulsion polymerization, etc., by known polymerization methods, such as by performing radical polymerization or copolymerization, etc., can be easily obtained, in particular, solution polymerization, non-aqueous suspension polymerization, bulk polymerization, etc. preferable.
Benzoyl peroxide, as the radical polymerization initiator,
Lauroyl peroxide, diisopropylperoxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxyisobutyrate, azobisdimethylvaleronitrile, azobisisobutyronitrile, Sulfate or persulfate-bisulfite can be preferably used. The amount of the radical polymerization initiator to be used is preferably 0.01 to 10 parts by weight, 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 replacing 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 for 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 separation 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 water-miscible. As long as it can impart hydrophilicity, antifouling property, etc. to the contact lens at
There is no particular limitation. As the solvent, specifically, for example, water, methanol, ethanol, isopropanol, ethylene glycol, polyethylene glycol, glycerin, ethylene glycol monomethyl ether, dimethyl sulfoxide, tetrahydrofuran, acetone and the like can be preferably mentioned.
They can be used alone or as a mixture.

In the present invention, the mixing ratio of the polymer and the solvent is such that the polymer is preferably in the range of 0.01 to 10% by weight with respect to the entire treatment solution of the present invention. Is preferred. If the blending ratio of the polymer is less than 0.01% by weight, it is not preferable because hydrophilicity and antifouling property cannot be sufficiently imparted to the contact lens.

In order to use the treatment solution for a contact lens of the present invention, the treatment solution for a contact lens is preferably heated to 20 to 70 ° C., and the contact lens is immersed or contacted 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 using water, physiological saline, or an appropriate cleaning solution.

Furthermore treatment of contact lenses inventive solution may optionally surfactants, fungicides, can also have use in combination with a preservative such as detergents, may also be used as a preservation solution.

[0025]

The contact lens treatment solution of the present invention contains a polymer having a specific phospholipid polar group as an essential component, so that the contact lens can be easily treated to prevent hydrophilicity and prevent proteins and lipids. Stain can be imparted, which is useful for improving the feeling of wearing and preventing denaturation of contact lenses.

[0026]

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

[0027]

Example 1 (A) Preparation of Contact Lens Treatment Solution 2- (Isopropylfumaroyloxy) ethyl-2′-
5 g of (trimethylammonio) ethylphosphoric 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. After replacing the glass tube with nitrogen, the glass tube was sealed, and the raw material monomer in the glass tube was polymerized at 60 ° C. for 12 hours to obtain a polymer. The obtained polymer 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 types 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 poured into a glass tube, and nitrogen replacement and degassing were repeated. To 100 ° C. over 50 hours, and the raw material monomer in the glass tube was cured by heating to obtain a colorless and transparent polymer. 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 Tris (trimethylsiloxy) silylpropyl methacrylate 40 g, trifluoroethyl methacrylate 30
g, 10 g of methyl methacrylate, 15 g of triethylene glycol dimethacrylate and 5 g of methacrylic acid were used in the same manner as in the above (1) hard contact lens to prepare a test piece.

(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 glycol dimethacrylate were used.

(C) Measurement of hydrophilicity and antifouling property of the contact lens treatment solution The contact lens treatment solution was filled in a contact lens storage case, and the contact lens test pieces of (1) to (3) were placed in the storage case. After immersion for a minute, the contact lens test piece was washed with water, and the hydrophilicity and antifouling property of the test piece were measured according to the following methods. Table 1 shows the results.

A) Measurement of Hydrophilicity After the test piece surface was dried, the water contact angle on the test piece surface was measured by an appropriate water liquid 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, the sample was taken out of the physiological saline, washed with physiological saline, and the protein adhered to the test piece surface was peeled off using a surfactant, and a protein quantification reagent “ Micro BCA (mi
cro BCA) '' (trade name, manufactured by PIERSC)
The amount of protein in the solution was measured.

[0034]

Example 2 Except that 9 g of 2- (isopropyl fumaroyloxy) ethyl-2 '-(trimethylammonio) ethyl phosphoric 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 treatment solution for contact lenses was prepared, and for each of the test pieces, the hydrophilicity and antifouling property of the obtained treatment solution were measured. Table 1 shows the measurement results.

[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 as a solvent. In the same manner as described above, a treatment solution for contact lenses was prepared, and for each of the test pieces, the hydrophilicity and antifouling property of the obtained treatment solution were measured. Table 1 shows the measurement results.

[0036]

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

[0037]

Comparative Example 2 The oxygen-permeable hard contact lens (2) prepared in Example 1 was treated without any treatment.
The hydrophilicity and antifouling property were measured. Table 1 shows the measurement results.

[0038]

[Table 1]

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-3-191320 (JP, A) JP-A-5-107512 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02C 1/00-13/00

Claims (1)

(57) [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 dissolving the polymer are essential. A treatment solution for contact lenses contained as a component. Embedded image