JP3069926B2 - 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 a treatment solution for imparting antifouling properties and hydrophilicity to hard contact lenses, non-hydrated soft contact lenses and hydrated soft contact lenses. The present invention relates to a contact lens treatment solution that can be used as a treatment agent.

[0002]

2. Description of the Related Art Contact lenses conventionally used are classified into non-water-containing ones and non-water-containing ones. Non-water-containing hard contact lenses and soft contact lenses are used. There is a lens. Non-water-containing lenses have advantages in terms of material stability and ease of care compared to water-containing lenses, and those containing methyl methacrylate as the main component and lenses using silicone rubber In recent years, hard oxygen-permeable hard contact lenses containing silyl-based methacrylate or fluorine-based methacrylate as a main component, which have further reduced the influence on the eyes, have come to be used.

[0003] However, non-water-containing lenses have problems such as lack of wearing due to their hydrophobic surface and influence on intraocular cells. Particularly, high oxygen permeable lenses use a large amount of silicon and fluorine components. Such lenses have strong hydrophobicity, and have the following drawbacks: a feeling of wearing, a decrease in adhesion to eyes, and a stain of proteins and lipids. Therefore, a method of performing a plasma treatment or a chemical treatment with an acidic or basic substance to hydrophilize a hydrophobic surface is known. However, in these methods, the hydrophilicity is maintained, the lens is modified by the treatment, and the treatment process is not performed. There is a problem in trouble. As another method, for example,
There is a method of immersing a contact lens in a solution containing a water-soluble polymer such as polyvinyl alcohol, hydroxyethyl cellulose, and polyvinylpyrrolidone disclosed in No. 48-37910. Further, there is a disadvantage that it is not effective in preventing contamination of proteins, lipids and the like.

[0004] In addition, a hydrous soft contact lens has a good wearing feeling unlike a non-hydrous soft contact lens, and has an advantage that is gentle to the eyes. However, it is a hydrogel lens containing 2-hydroxyethyl methacrylate, vinylpyrrolidone or the like as a main component, and there is a problem of hygiene such as adhesion of proteins and lipids, propagation of bacteria, etc. There was a problem that the strength was reduced. Therefore, it is usually necessary to perform sanitary management by boiling sterilization and using care products such as a bactericide and a cleaning solution.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a non-hydrated contact lens with surface hydrophilicity or a highly hydrated contact lens with high water content by a simple immersion treatment. Can improve the effect on the eyes,
Another object of the present invention is to provide a contact lens treatment solution capable of suppressing the adhesion and deposition of proteins and lipid stains.

[0006]

According to the present invention, the following general formula:

[0007]

Embedded image

Wherein R ₁ is a hydrogen atom or a methyl group. Y is

[0009]

Embedded image

[0010] n shows the integer of 1-20. R ₂ , R ₃ and R ₄ are the same or different groups, and represent an alkyl group having 1 to 8 carbon atoms or a hydroxyalkyl group. The present invention provides a contact lens treatment solution comprising a polymer containing, as a constituent, a compound having a phospholipid-like structure represented by the formula (1) and a solvent dissolving the polymer.

Hereinafter, the present invention will be described in more detail. In the treatment solution for a contact lens of the present invention, the compound used as an essential component is a (meth) acrylate monomer having a phospholipid polar group represented by the general formula (1). In the formula (1), Y is selected from the formula (4), and the higher the carbon number, the lower the hydrophilicity of the obtained polymer.
R ₂ , R ₃ and R ₄ are alkyl groups having a large number of carbon atoms.
Alkyl or hydroxyalkyl groups with low hydrophilicity and low carbon number increase the hydrophilicity of the polymer. When the alkyl group has more than 8 carbon atoms, the hydrophilicity decreases significantly and the polymerizability of the monomer decreases. Absent.

The monomer represented by the general formula (1) includes 2- (methacryloyloxy) ethyl 2'-
(Trimethylammonio) ethyl phosphate, 3- (methacryloyloxy) propyl 2 ′-(trimethylammonio) ethyl phosphate, 4- (methacryloyloxy) butyl 2 ′-(trimethylammonio) ethyl phosphate,
5- (methacryloyloxy) pentyl 2 '-(trimethylammonio) ethyl phosphate, 6- (methacryloyloxy) ethyl 2'-(trimethylammonio) ethyl phosphate, 2- (methacryloyloxy) ethyl
2 ′-(triethylammonio) ethyl phosphoric acid, 2-
(Methacryloyloxy) ethyl phosphoric acid, 2- (methacryloyloxy) ethyl 2 ′-(tributylammonio) ethyl phosphoric acid, 2- (methacryloyloxy) ethyl 2 ′-(tricyclohexylammonio) ethyl phosphoric acid,

2- (methacryloyloxy) propyl
2 ′-(trimethylammonio) ethyl phosphoric acid, 2-
(Methacryloyloxy) butyl 2 '-(trimethylammonio) ethyl phosphate, 2- (methacryloyloxy) pentyl 2'-(trimethylammonio) ethyl phosphate, 2- (methacryloyloxy) hexyl 2 '
-(Trimethylammonio) ethyl phosphate, 2- (methacryloyloxy) ethyl 2 '-(triphenylammonio) ethyl phosphate, 2- (methacryloyloxy)
Ethyl 2 '-(trimethanolammonio) ethylphosphate, 2- (vinyloxy) ethyl 2'-(trimethylammonio) ethylphosphate, 2- (allyloxy) ethyl2 '-(trimethylammonio) ethyl2'-
(Trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyl) oxy 2 '-(trimethylammonio) ethyl phosphate, 2- (p-vinylbenzoyloxy) ethyl 2'-(trimethylammonio) ethyl phosphate,

2- (styryloxy) ethyl 2'-
(Trimethylammonio) ethyl phosphate, 2- (p-vinylbenzyl) ethyl 2 ′-(trimethylammonio) ethyl phosphate, 2- (allyloxycarbonyl) ethyl 2 ′-(trimethylammonio) ethyl phosphate,
2- (vinylcarbonylamino) ethyl 2 '-(trimethylammonio) ethyl phosphate, 2- (allyloxycarbonylamino) ethyl 2'-(trimethylammonio) ethyl phosphate, 2- (vinyloxy) ethyl 2'-
(Trimethylammonio) ethylphosphoric acid, 2- (allyloxy) 2 ′-(trimethylammonio) ethylphosphoric acid, 2- (p-vinylbenzyl) ethyl2 ′-(trimethylammonio) ethylphosphoric acid,

2- (vinylbenzoyloxy) ethyl
2 ′ (trimethylammonio) ethyl phosphate, 2- (styryloxy) ethyl 2 ′-(trimethylammonio) ethylphosphate, 2- (allyloxycarbonyl) ethyl 2 ′-(trimethylammonio) ethylphosphate,
2- (vinyloxycarbonyl) ethyl 2 '-(trimethylammonio) ethyl phosphate, 2- (acryloylamino) ethyl 2'-(trimethylammonio) ethyl phosphate, 2- (allyloxycarbonylamino) ethyl 2 '-( Trimethylammonio) ethyl phosphate,
(Methacryloyloxy) methyloxy (methacryloyloxy) methyloxy 2 '-(trimethylammonio) ethylphosphoric acid, 2'-(trimethylammonio)
Ethyl phosphate, 2- (methacryloyloxy) ethyloxy 2 ′-(trimethylammonio) ethyl phosphate,

3- (methacryloyloxy) propyloxy 2 '-(trimethylammonio) ethyl phosphoric acid,
2- (methacryloyloxy) isopropyloxy
2 ′-(trimethylammonio) ethyl phosphoric acid, 4-
(Methacryloyloxy) butyloxy 2 ′-(trimethylammonio) ethylphosphoric acid and the like. The obtained polymer can exhibit water solubility or hydrophilicity, and such polymer adheres to the surface or surface layer of the contact lens. The deposition can impart hydrophilicity to the contact lens and prevent stains from adhering.

The general formula (1) used characteristically in the present invention:
The (meth) acrylate represented by can be synthesized by various known methods. For example, hydroxyalkyl (meth) acrylate and 2-chloro-2-oxo-1,3,
Reacting 2-dioxaphosphorane in the presence of an amine;
There is a method in which (2-oxo-1,3,2-dioxaphosphoroyloxy) alkyl (meth) acrylate is obtained and further reacted with a predetermined tertiary amine. Other methods include hydroxyalkyl (meth) acrylate and 2-
A method of reacting bromoethylphosphoryl dichloride with (meth) acryloyloxyalkyl-2′-bromoethylphosphoric acid, and further reacting the same with a predetermined tertiary amine, and the like are described. It is desirable to purify by a known method such as

The polymer used in the contact lens treatment solution of the present invention is represented by the following general formula (1):
Although it can be obtained by polymerization of an acrylate monomer, it can also be obtained by further copolymerizing with another copolymerizable vinyl monomer. As copolymerizable vinyl monomers, styrene, methylstyrene, chloromethylstyrene, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, (meth)
One or two of 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, etc. And at least one kind of mixed monomer.
It is preferably used in the range of 10,000 to 5 parts by weight based on 100 parts by weight of the acrylate. In this case, if the amount exceeds 10,000 parts by weight, the water-soluble and antifouling properties of the (meth) acrylate-based monomer of the general formula (1) do not sufficiently appear. Can not be demonstrated.

The polymer characteristically used in the present invention can be obtained by homopolymerization or copolymerization of the monomer. In this case, the polymer is obtained by a radical polymerization method using a general radical polymerization initiator. It can be performed by a known technique such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Benzoyl peroxide, lauroyl peroxide, diisopropyloxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butyl
Peroxydiisobutyrate, azobisisobutyronitrile, azobisdimethylvaleronitrile, persulfate and persulfate-bisulfite systems can be used.
The amount of the polymerization initiator to be used is 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of all the monomers.

The above polymerization or copolymerization is carried out under conditions in which the polymerization system is replaced with an inert gas such as nitrogen, carbon dioxide, helium or under an atmosphere at an appropriate time.
In the range of 100 ° C., the polymerization time is about 5 to 72 hours. The molecular weight of the polymer used in the contact lens treatment solution of the present invention obtained by radical polymerization varies depending on the polymerization temperature, the amount of the initiator used, the use of the degree of polymerization regulator, and the like, but the number average molecular weight is in the range of 1,000 to 300,000. In particular, from the viewpoint of solubility in a processing solution, viscosity of the processing solution and adhesion to a contact lens, those having a range of 2000 to 200,000 are more preferable.

The solvent used in the contact lens treatment solution of the present invention can dissolve the polymer and has no effect on the contact lens. Those that satisfy the condition that they can be achieved are used. Specifically, water,
Methanol, isopropanol, ethylene glycol,
Examples thereof include a mixture of one or more of polyethylene glycol, glycerin, ethylene glycol monomethyl ether, dimethyl sulfoxide, tetrahydrofuran, acetone and the like. The amount of the solvent used is in the range of 0.01 to 10% by weight of the polymer concentration, but if the amount is too small, the treatment effect cannot be sufficiently obtained. In the case of treatment, a contact lens is immersed in or brought into contact with the treatment solution at a temperature of 20 to 70 ° C., and further washed with water, physiological saline or an appropriate washing solution before wearing. This makes the contact lens hydrophilic,
Prevents contamination of proteins and lipids.

The treatment solution for contact lenses of the present invention can be used in combination with a surfactant, a bactericide, a preservative, and the like, if necessary, and can also be used as a detergent and a preservative.

[0023]

According to the contact lens treatment solution of the present invention, the phospholipid polar polymer can be attached to the lens by a simple operation of dipping or coating the contact lens and then rinsing the contact lens with water. The surface of the lens or the water-containing soft contact lens can be made hydrophilic and the water content can be improved, and the wearing feeling to the eye can be improved. Furthermore, since adhesion and deposition of stains such as proteins and lipids can be suppressed, it is also effective in preventing lens denaturation and improving eye safety.

[0024]

EXAMPLES Hereinafter, the present invention will be described in detail with reference to Reference Examples and Examples, but the present invention is not limited thereto. Reference Example 1 As a monomer, 40 parts by weight of 2- (methacryloyloxy) ethyl 2 '-(trimethylammonio) ethyl phosphate, 60 parts by weight of n-butyl methacrylate, 0.1 part by weight of azobisisobutyronitrile were mixed with ethanol / tetrahydrofuran (50 parts). / 50 mixture) Dissolve in 300 parts by weight, place in a prescribed glass tube, replace with nitrogen, seal, and place in a thermostat at 60 ° C for 12 hours.
Polymerized for hours.

After completion of the polymerization, the mixture was diluted with 50 ml of ethanol, and the resulting mixture was added dropwise to 1 liter of diethyl ether to precipitate a polymer. Next, the polymer obtained by suction filtration was dried under reduced pressure at room temperature for 12 hours to obtain a desired polymer. The obtained polymer was dissolved in ethylene glycol to prepare a treatment solution for contact lenses.

Reference Example 2 2- (methacryloyloxy) ethyl as a monomer
A contact lens treatment solution was prepared in the same manner as in Reference Example 1 except that 40 parts by weight of 2 '-(trimethylammonio) ethyl phosphoric acid, 60 parts by weight of 2-hydroxyethyl methacrylate, and 300 parts by weight of ethanol were used as a solvent. did.

Reference Example 3 2- (methacryloyloxy) ethyl as a monomer
A contact lens treatment solution was prepared in the same manner as in Reference Example 1, except that 90 parts by weight of 2 '-(trimethylammonio) ethyl phosphoric acid, 10 parts by weight of styrene, and 300 parts by weight of ethanol were used as a solvent.

Example 1 A general contact lens was prepared according to the following recipe. Inject 99 parts by weight of methyl methacrylate, 1 part by weight of diethylene glycol dimethacrylate, and 0.2 parts by weight of azobisisobutyronitrile as a monomer into a test tube glass mold. Heat curing was performed. Heat to 50-100 ° C in a thermostat
The temperature was raised over time. After the polymerization was completed, the cured product was taken out of the mold, and the obtained polymer was colorless and transparent. The obtained polymer was cut and polished by a usual processing method to prepare a test piece having a predetermined shape.

This was immersed in the contact lens storage case filled with the solution of Reference Example 1 together with the holder for 30 minutes, then taken out of the holder and washed thoroughly with tap water to subject the contact lens to a hydrophilic treatment. Was. After hydrophilization, the following physical properties were evaluated. Table 1 shows the results.

Example 2 An oxygen-permeable hard contact lens was prepared according to the following recipe. As monomers, except that 40 parts by weight of tris (trimethylsiloxy) silylpropyl methacrylate, 30 parts by weight of trifluoroethyl methacrylate, 10 parts by weight of methyl methacrylate, and 15 parts by weight of triethylene glycol dimethacrylate, and 5 parts by weight of methacrylic acid, A contact lens was prepared in the same manner as in Example 1, and the contact lens was subjected to a hydrophilic treatment. After hydrophilization, the following physical properties were evaluated. Table 1 shows the results.

Example 3 In a soft contact lens, a hydrophilic treatment of a contact lens was performed in the same manner as in Example 1, except that 99 parts by weight of 2-hydroxyethyl methacrylate and 1 part by weight of ethylene glycol dimethacrylate were used as monomers. Was done. After hydrophilization, the following physical properties were evaluated. Table 1 shows the results.

Examples 4 to 6 Each contact lens was subjected to a hydrophilizing treatment in the same manner as in Example 1 using the solution of Reference Example 2. After hydrophilization, the following physical properties were evaluated. Table 1 shows the results. Examples 7 to 9 Each contact lens was subjected to a hydrophilization treatment in the same manner as in Example 1 using the solution of Reference Example 3. After hydrophilization, the following physical properties were evaluated. Table 1 shows the results.

Comparative Example 1 A contact lens was subjected to a hydrophilization treatment in the same manner as in Example 1 using an aqueous solution of polyvinyl alcohol (degree of saponification: about 88%). After hydrophilization, the following physical properties were evaluated. Table 1 shows the results. Comparative Example 2 The physical properties of the contact lenses that were not subjected to the hydrophilic treatment were evaluated. Table 1 shows the results.

The contact angles and antifouling properties in the table were measured by the following methods. (I) Contact Angle After drying the surface, the contact angle of the contact lens after hydrophilization was measured by a water droplet method. (II) Antifouling property Albumin 0.39% (w / v), lysozyme 0.17% (w / v)
v), contact lenses are immersed in 0.105% (w / v) saline solution of γ-globulin (2 weeks, 35 ° C.)
Thereafter, the protein was washed with physiological saline, the protein was separated from the contact lens with a surfactant, a reagent for protein quantification was injected into the solution, and the amount of protein adsorbed on the contact lens was measured.

[0035]

[Table 1] Note) HCL: Hard contact lens GPH: Oxygen permeable hard contact lens SCL: Soft contact lens EG: Ethylene glycol PVA: Polyvinyl alcohol.

──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Shinji Nakata 2-26-2 Kasuga, Tsukuba, Ibaraki Prefecture (72) Inventor Takeo Matsumoto 2-14-9, Higashi, Tsukuba, Ibaraki Prefecture (72) Inventor Yasumi Koinuma, Tsukuba, Ibaraki Prefecture 32-16-1-102 Ichihigashi Arai (56) References JP-A-63-240938 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) G02C 13/00 C09K 3/00 112

Claims (1)

(57) [Claims] 1. A compound of the general formula And R ₁ represents a hydrogen atom or a methyl group. And Y is Indicates one of n shows the integer of 1-20. R ₂ , R ₃ and R ₄ are the same or different groups, and represent an alkyl group having 1 to 8 carbon atoms or a hydroxyalkyl group. A contact lens treatment solution comprising a polymer containing, as a constituent, a compound having a phospholipid-like structure represented by the formula (1) and a solvent dissolving the polymer.