JPH0545613A - Contact lens having improved contamination resistance and its production - Google Patents

Abstract

PURPOSE:To improve contamination resistance of a contact lens comprising a polymer material having hydroxyl groups in the molecule by grafting a specified compd. or its functional deriv. onto the lens by use of esterification reaction. CONSTITUTION:To a lens material comprising a polymer material having hydroxyl groups in the molecule, polyethylene glycol monocarboxylic acid expressed by formula I or its functional deriv. is introduced by ester coupling. Or, polyethylene glycol dicarboxylic acid expressed by formula II or its functional deriv. is introduced by ester coupling. In both cases, after ester coupling, the material is swollen by hydration. In formulae I and II, n is an integer >=1 and R is a satd. or unsatd. hydrocarbon. Although the esterification is effected mainly on the surface of the lens substance, transparency and water-containing property of the contact lens can be maintained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel contact lens, and more specifically, the present invention relates to a water-containing soft contact lens which is transparent and has little dirt adhesion and is excellent in wearing feeling. Is.

[0002]

2. Description of the Related Art Contact lenses are essentially composed of hard contact lenses mainly composed of polymethyl methacrylate and oxygen permeable hard contact lenses mainly composed of a material obtained by copolymerizing alkyl methacrylate and siloxanyl methacrylate. There are two types, namely, a non-water-containing and hard type, and an essentially water-containing and flexible type mainly composed of polyhydroxyethyl methacrylate or polyvinylpyrrolidone.

The hard type lens is widely used due to its excellent optical and mechanical characteristics, but it has a drawback that it has a strong feeling of foreign matter in the early stage of wearing and the wearer has to get used to the pain. .. Water-containing type lenses have the advantages that they are easier to wear and easier to fit in the eye than hard-type lenses, but tear components are deposited inside the lens through the water contained in the lens material. Therefore, in addition to the usual washing with a surfactant, it is necessary to carry out a washing treatment using an enzyme that decomposes proteins and lipids, and the handling is complicated. Further, during handling, dirt from fingers may adhere.

As a means for improving such stain resistance, some techniques for copolymerizing a hydrogel-forming monomer with a fluorine-containing monomer have been disclosed. For example, in Japanese Examined Patent Publication No. 62-62323, trifluoroethyl methacrylate and hexafluoroisopropyl methacrylate are used as the fluorine-containing monomer, but the fluorine-containing monomer and the hydroxyl group-containing monomer are bulk polymerized. No proactive solution has been proposed for the tendency to become cloudy or opaque.

[0005]

SUMMARY OF THE INVENTION Under the circumstances described above, the present invention has been made for the purpose of providing a water-containing soft contact lens which is transparent, has little stain adhesion, and is excellent in wearing feeling. is there.

[0006]

The present inventors have taken into consideration biosafety, biocompatibility, economic efficiency, chemical reactivity, etc. in order to develop a water-containing soft contact lens having the above-mentioned preferable properties. As a result of intensive studies, a polyethylene glycol polycarboxylic acid represented by the formula HOOC—CH ₂ — (O—CH ₂ —CH ₂ ) _n —OR or functional derivatives and / or of the acid of the formula _{HOOC-CH 2 - (O-} CH 2 -CH 2) n -O-CH 2 COOH ( provided that Shikichu, n represents an integer of 1 or more, R represents a saturated Or an unsaturated hydrocarbon), the polyethylene glycol dicarboxylic acid or a functional derivative of the acid is ester-bonded to the polyethylene glycol dicarboxylic acid without impairing its transparency and water content. It is obtained led to the heading present invention the fact that considerably improved contact lens dyeing is obtained.

It is easily inferred that such an esterification reaction mainly occurs on the surface of the lenticular material as in the invention described later, but nevertheless its transparency and water content are secured. That was something else. That is, the present invention is as follows. 1. Polyethylene glycol monocarboxylic acid represented by the formula HOOC—CH ₂ — (O—CH ₂ —CH ₂ ) _n —OR or a functional derivative of the acid is added to a lens-like material composed of a polymer having a hydroxyl group in the molecule. and / or the formula _{HOOC-CH 2 - (O-} CH 2 -CH 2) n -O-CH 2 COOH ( provided that Shikichu, n represents an integer of 1 or more, the hydrocarbon R is a saturated or unsaturated The contact lens is characterized in that a polyethylene glycol dicarboxylic acid or a functional derivative of the acid is ester-bonded. 2. Polyethylene glycol monocarboxylic acid or a functional derivative of the acid, and / or polyethylene glycol dicarboxylic acid or a functional derivative of the acid, and a solution in which an esterification catalyst is dissolved or dispersed in a reaction catalyst to form a hydroxyl group in the molecule. By processing a lens-shaped product comprising a polymer substance, a polyethylene-glycol monocarboxylic acid or a functional derivative of the acid and / or a polyethylene glycol dicarboxylic acid or a functional derivative of the acid is formed into a lens-shaped product. The method for producing a contact lens is characterized by hydrating and swelling after esterifying the hydroxyl groups in the molecule.

Examples of the polymer substance having a hydroxyl group in the molecule used in the present invention include various natural polymers and synthetic polymers. Specific examples of the natural polymer include cellulose. The synthetic polymer is a polymer containing a hydroxyl group-substituted unsaturated aliphatic compound as a main component, that is, a polymer composed of 50% by weight or more of a hydroxyl group-substituted unsaturated aliphatic compound, including polyvinyl alcohol and the like. Be done.

More specifically, the unsaturated aliphatic compound substituted with a hydroxyl group is 3-methyl-3-butene-1-.
All, 3-methyl-3-buten-2-ol, 2-methyl-1-penten-3-ol, 2-methyl-4-penten-2-ol and 4-methyl-1-pentene-
A hydroxyl group-substituted olefin such as 3-ol may be used, but a hydroxyl group-substituted unsaturated aliphatic ester as a preferable compound, and a glycol acrylate as a more preferable compound, for example, hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxymethyl. Methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and the like can be exemplified, and these are used alone or in combination of two or more. Among these, the most preferable ones are hydroxyethyl methacrylate and hydroxypropyl methacrylate. Is.

As a constituent component of the polymer, a vinyl lactam as exemplified by N-vinylpyrrolidone as a water content adjusting monomer and a dihydroxyalkyl methacrylate as exemplified by dihydroxypropyl methacrylate, etc. Examples of the property improving monomer include trifluoroethyl acrylate, hexafluoroisopropyl acrylate, hexafluorobutyl methacrylate, hexafluorobutyl acrylate, tetrafluoropropyl methacrylate, tetrafluoropropyl acrylate, octafluoropentyl methacrylate and octafluoropentyl acrylate. Examples of the dimensional stability improving monomer such as fluorine-containing unsaturated organic acid ester as described above include ethylene glycol dimethacrylate and polyethylene glycol. Call dimethacrylate, trimethylolpropane trimethacrylate, vinyl methacrylate, allyl methacrylate, triallyl isocyanurate, as divinylbenzene strength improved for monomer,
Known monomers such as cyclohexyl methacrylate are used as desired.

The polyethylene glycol monocarboxylic acid used in the present invention has a general formula of HOOC-CH _2-.
Indicated by _{(O-CH 2 -CH 2)} n -OR, n = 15
0, R = a saturated or unsaturated hydrocarbon having 1 to 20 carbon atoms is preferably used. In this case, the ester-bonded polyethylene glycol monocarboxylic acid residue corresponds to the binding molecular chain, that is, the graft chain.

In the present invention, functional derivatives such as halides and acid anhydrides of the above polyethylene glycol monocarboxylic acid can also be used. As the polyethylene glycol monocarboxylic acid halide, polyethylene glycol monocarboxylic acid chloride is preferable from the viewpoints of handleability and safety at the time of remaining. As the polyethylene glycol monocarboxylic acid anhydride, a single acid anhydride obtained by dehydration condensation of two molecules of the polyethylene glycol monocarboxylic acid, or a mixed acid of the polyethylene glycol monocarboxylic acid and another carboxylic acid is used. Anhydrides can be used. In the latter case, in order to preferentially ester bond the desired polyethylene glycol monocarboxylic acid, as the other carboxylic acid, a carboxylic acid having a large steric hindrance, such as isobutyric acid or isovaleric acid, is a mixed acid anhydride. Or alkyl hydrogen carbonate (HOCO
₂ R, R is preferably a mixed acid anhydride using an alkyl group).

The polyethylene glycol dicarboxylic acid used in the present invention has a general formula of HOOC-CH _2-.
(O—CH ₂ —CH ₂ ) _n —O—CH ₂ COOH, where n = 1 to 150 is preferably used.
In this case, the ester-bonded polyethylene glycol dicarboxylic acid residue corresponds to the bonding molecular chain, that is, the graft chain.

As described above, not only polyethyleneglycol monocarboxylic acid but also polyethyleneglycol dicarboxylic acid can be used. In the latter case, before reacting with the hydroxyl group in the polymer constituting the lens, Polymerization of polyethylene glycol carboxylic acid may progress due to condensation and the like, and reactivity of esterification may decrease. Further, in the case of dicarboxylic acid, there is a possibility of forming a loop-shaped graft chain bonded at two positions, but as described later, it is preferable that only one end of the graft chain is bonded, and polyethyleneglycolcarboxylic acid More preferred are the monocarboxylic acids of

These polyethylene glycol carboxylic acids or functional derivatives thereof are contained in an amount of 0.5-50 mmol /
It is used at a low concentration of 1, and is advantageously used at a concentration of 1.0 to 10 mmol / l from the viewpoint of adhesion residue on contact lenses and economical efficiency. The ester bond to the contact lens is carried out by an esterification reaction with a hydroxyl group existing in the polymer constituting the lens, and a known low molecular weight alcohol and a low molecular weight carboxylic acid or a functional derivative of the acid. Can be applied. As processing conditions, keep the processing temperature low so as not to affect the physical properties of the contact lens,
It is preferable to shorten the processing time as much as possible. That is, conditions of a treatment time of 1 minute to 24 hours are used at a temperature of 5 ° C. or higher and 120 ° C. or lower of the boiling point of the reaction medium used, whichever is lower, preferably 15 ° C. or higher and 90 ° C.
Alternatively, a treatment temperature equal to or lower than the boiling point of the reaction medium used, whichever is lower, or a treatment time of 3 to 180 minutes is used. These conditions are also advantageous from the economical aspect.

It is preferable to use an esterification catalyst to accelerate the reaction. As the esterification catalyst, in the case of a carboxylic acid, a sulfuric acid, a mineral acid such as hydrochloric acid, an organic acid such as an aromatic sulfonic acid, a Lewis acid such as boron trifluoride etherate, a carbodiimide derivative such as dicyclohexylcarbodiimide, and a carbodiimide derivative and 4- A mixed catalyst or the like with dimethylaminopyridine and / or 4-pyrrolidinopyridine is used, and in the case of an acid halide,
To remove the by-product halide, pyridine, dimethylaniline, triethylamine, tetramethylurea,
Alternatively, metallic magnesium, etc.
A mixed catalyst with dimethylaminopyridine and / or 4-pyrrolidinopyridine is used, and in the case of an acid anhydride, sulfuric acid, p-toluenesulfonic acid, zinc chloride, sodium acetate, pyridine, 4-dimethylaminopyridine, Four
-Pyrrolidinopyridine or the like is used.

In the present invention, these catalysts may be used alone or in appropriate combination, but from the viewpoint of promoting the reaction smoothly and removing after the reaction, it is preferable to use a small amount of the one soluble in the reaction medium. Is preferred. From this point of view, a method for performing an esterification reaction of polyethylene glycol monocarboxylic acid with a mixed catalyst of a carbodiimide derivative such as dicyclohexylcarbodiimide and 4-dimethylaminopyridine and / or 4-pyrrolidinopyridine, and polyethyleneglycolcarboxylic acid A method in which an acid anhydride is subjected to an esterification reaction with 4-dimethylaminopyridine and / or 4-pyrrolidinopyridine is preferably used.

The reaction medium is required not to react with polyethylene glycol carboxylic acid or a functional derivative of the acid, not to deactivate the esterification catalyst, and not to cause morphological change in the lens-like material. Therefore, as the reaction medium, any solvent that satisfies the above requirements and that disperses or dissolves the polyethylene glycol carboxylic acid or the functional derivative of the acid and the esterification catalyst is used. A solvent that dissolves polyethylene glycol carboxylic acid or a functional derivative of the acid and an esterification catalyst is preferable in terms of uniformity of reaction, smoothness and removal after the reaction. Examples of such a reaction medium include n-hexane, n-heptane, cyclohexane, petroleum ether,
Hydrocarbons such as petroleum benzine, benzene and toluene, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate, ethyl acetate and propyl acetate, ethers such as ethyl ether, isopropyl ether and dioxane, 1,1,2 -Trichloro-1,2,2-trifluoroethane, trichlorofluoromethane, 1,1,
2,2-tetrachloro-1,2-difluoroethane,
1,1-dichloro-2,2,3,3,3-pentafluoropropane, 1,3-dichloro-1,1,2,2,3-
Examples thereof include chlorofluorocarbons such as pentafluoropropane. These reaction media can be used alone or in combination. From the viewpoint of safety to living organisms and removal after reaction, chlorofluorocarbons, especially 1,1,2-trichloro-1,2,2
A reaction medium containing 2-trifluoroethane is preferred,
A mixed solvent of 1,1,2-trichloro-1,2,2-trifluoroethane and dichloromethane is preferably used.

There are various methods for treating the lens-like material. That is, a treatment liquid in which a polyethylene glycol carboxylic acid or a functional derivative of the acid and an esterification catalyst are dispersed or dissolved in a reaction medium, a method of adding a lens-like material and stirring, a dipping tank filled with the treatment liquid A method of immersing the lens-shaped material, a method of circulating the processing liquid in a processing tank filled with the lens-shaped material, and the like can be adopted.

After the completion of the esterification reaction, the lens-like material (contact lens) is separated from the treatment liquid, and if the reaction reagent, the esterification catalyst, the side reaction product, etc. do not remain, they are omitted, but they are usually removed. To do this, cleaning is performed.
For this washing operation, immersion extraction or Soxhlet extraction is performed using a solvent used for the reaction or a solvent such as chloroform that does not cause a change in the shape of the contact lens. Finally, the residual solvent is removed by vacuum drying, blast drying or the like.

The amount of grafting varies depending on the treatment conditions, for example, the concentration of carboxylic acid in the treatment liquid, the concentration of catalyst, the reaction time, the reaction temperature and the like. When the contact lens obtained as described above is extracted with an aqueous alkaline solution, the ester bond is hydrolyzed and the polymeric carboxylic acid grafted to the lens is extracted. The amount of grafting can be determined by analyzing this.

The amount of polyethylene glycol carboxylic acid to be esterified in order to achieve the improvement of stain resistance which is the object of the present invention is preferably 0.2 μg / cm ² or more, and 1.0 μg / cm 2. More preferably, it is ² or more. A contact lens made of such a polymer compound having a molecular chain by an ester bond has markedly improved stain resistance without impairing the excellent transparency and strength of the polymer compound before the reaction treatment.

It is considered that such an effect is due to the esterification reaction mainly occurring on the lens surface in the present invention, and the chemical and physical properties inside the lens are maintained. In addition, the amount of esterification on the surface is sufficient to improve the physicochemical and biochemical properties of the surface, but it is a trace amount that does not adversely affect the permeability and transparency of water and substances. It is also thought to be because.

One rationale for this effect is probably
Advance In Polymer Science
e, 57 (1984) p. It is presumed to be the same as that given below for 103 and below. Briefly summarized, on a surface grafted with hydrophilic grafts, the water-containing graft chains act as if a ciliary body is present on the lens surface, allowing access of proteins to the material's parenchymal surface. Although it interferes and prevents its adsorption, the idea is that small molecules such as water have no preventive effect and easily slip through, but it is not clear.

To suppress the adsorption of proteins as described above,
It is preferable that one end is bound and the other end is free to move, rather than a state where the grafted chain is bound to the polymer at two or more positions and the chain movement is suppressed. It is considered that this is because the free graft chain shields the substantial surface of the lens-like material made of a polymeric substance and suppresses protein adsorption.

The hydrous soft contact lens is autoclave sterilized before shipping, but this does not impair the excellent properties of the contact lens of the present invention. In addition, it goes without saying that the present invention also includes a lens that is used by directly contacting the eyeball in addition to a normal contact lens, such as an intraocular lens.

[0027]

EXAMPLES The present invention will be described in more detail by way of examples, which should not be construed as limiting the invention thereto. In addition, each physical property etc. were calculated | required as follows. (1) Moisture content When dried, the dimensions are 11.9 mm diameter and 0.08 m center thickness.
The weight (Wω) after hydration and swelling of the lens of m and the weight (Wd) after re-drying were measured, and the water content (Wc) was calculated from the following equation.

Wc (%) = [(Wω−Wd) × 100] / Wω (2) Tensile strength Power at hydration swelling is −3.00D, base curve 8.
A strip sample having a width of about 1.5 mm was obtained from a lens having a center thickness of about 0.1 mm by 60 mm by using a single-edged razor.

While holding the sample piece in the clip-type grip, it was submerged in physiological saline adjusted to 25 ° C., and a tensile test was conducted in the solution. Test conditions: Operation Autograph AGS-50B [Shimadzu Corporation] Load cell 2 kg Tensile speed 100 mm / min After sample breakage, sample pieces were collected and the dimensions of the fracture surface were measured using a projector and calculated. Calculate the area of fracture by
The tensile strength was calculated from the breaking load and the breaking area recorded by the operation. (3) Transparency The lens used for the measurement of tensile strength was visually observed by holding it in a strong light flux (spot illumination in which a condenser lens was connected to a light source) to make the background black. (4) Grafting amount A contact lens was placed in a sample bottle, an aqueous sodium hydroxide solution was added, and the mixture was shaken at 50 ° C. for 2 hours. The alkali extract thus obtained was separated and neutralized with hydrochloric acid. After freeze-drying, the residue was redissolved in 1,4-dioxane, 7-anthryldiazomethane (Funakoshi Yakuhin Co., Ltd.) was added and reacted, and a fluorescence detector (Soma Optical, S-3350) was used. The analysis was carried out by a high-performance liquid clastography [LC-4A manufactured by Shimadzu Corporation] provided. (5) Contamination resistance After immersing the lens in distilled water for 24 hours, immersing one lens in 5 ml of 4g / dl bovine albumin solution, and after 24 hours, washing with physiological saline for 10 minutes, 1% dodecyl Bovine albumin is desorbed in 1 ml of sodium sulfonate (SDS) phosphate buffer, and the supernatant is measured by BCA Protein Assay (using a measurement kit manufactured by Pierce Inc., USA).

[0030]

Example 1 To 250 ml of toluene, 28.4 g of polyethylene glycol dicarboxylic acid having an average molecular weight of polyethylene glycol of 3700 and 0.08 g of paratoluenesulfonic acid were added to prepare a treatment liquid. 80 wt% of hydroxyethyl methacrylate (hereinafter referred to as HEMA), 19.8 wt% of hydroxypropyl methacrylate (hereinafter referred to as HPMA), and ethylene glycol dimethacrylate (hereinafter referred to as EGDMA) 0.2 were added to the treatment liquid. A copolymer obtained by polymerizing a monomer mixture in weight% is formed into a lens shape by a known cutting and polishing process (center thickness: 0.08 mm, diameter: 11.9 mm) 10
The sheets were immersed for 60 minutes with occasional agitation.

The treated lens-like material was immersed in the same solvent as the treatment solution for 30 minutes, dried under reduced pressure at room temperature, and immersed in a physiological saline solution at 70 ° C. for 16 hours to hydrate and swell,
I got a soft contact lens. The evaluation results are shown in Table 4.

[0032]

Example 2 A soft contact lens was obtained in the same manner as in Example 1 except that 110 ml of toluene, 18.8 g of polyethylene glycol dicarboxylic acid having an average molecular weight of 7800 in the polyethylene glycol portion, and 140 ml of pyridine were used. The evaluation results are shown in Table 4.

[0033]

Example 3 250 ml of toluene, 0.45 g of polyethylene glycol dicarboxylic acid chloride having a polyethylene glycol portion having an average molecular weight of 980, and 4-dimethylaminopyridine (hereinafter referred to as DMAP) 0.007
g, and a soft contact lens was obtained in the same manner as in Example 1 except that 1 ml of pyridine was used. The evaluation results are shown in Table 4.

[0034]

Example 4 140 ml of toluene, 0.19 g of polyethylene glycol dicarboxylic acid chloride having a polyethylene glycol portion having an average molecular weight of 400, and pyridine 11
A soft contact lens was obtained in the same manner as in Example 1 except that 0 ml was used. The evaluation results are shown in Table 4.

[0035]

Example 5 250 ml of toluene, 0.26 g of ethoxypolyethylene glycol carboxylic acid chloride having an average molecular weight of 106 in the polyethylene glycol portion, 4-pyrrolidinopyridine (hereinafter referred to as PP) 0.022 g,
A soft contact lens was obtained in the same manner as in Example 1 except that 1 ml of pyridine was used. The evaluation results are shown in Table 4.

[0036]

EXAMPLE 6 1,1,2-trichloro-1,2,2-trifluoroethane - dichloromethane mixed solvent (dichloromethane 5 wt%) 250 ml, alkoxy polyethylene of glycol monocarboxylic acid [C ₁₃ H ₂₇ - (OCH ₂ C
H _{2) 7} -OCH ₂ COOH] 0.10g, DMAP
A soft contact lens was obtained in the same manner as in Example 1 except that 0.004 g was used. The evaluation results are shown in Table 4.

[0037]

Example 7 Benzene 250 ml, alkoxy polyethylene of glycol monocarboxylic acid [C ₁₂ H ₂₅ - (OCH
₂ CH _{2) 10} -OCH ₂ COOH] 0.35 g, DMA
A soft contact lens was obtained in the same manner as in Example 1 except that 0.005 g of P and 0.10 g of dicyclohexylcarbodiimide (hereinafter referred to as DCC) were used. The evaluation results are shown in Table 4.

[0038]

EXAMPLE 8 1,1,2-trichloro-1,2,2-trifluoroethane - dichloromethane mixed solvent (dichloromethane 5 wt%) 250 ml, alkoxy polyethylene of glycol monocarboxylic acid [C ₁₂ H ₂₅ - (OCH ₂ C
H _{2) 4.5} -OCH ₂ COOH] 0.33g, DCC
A soft contact lens was obtained in the same manner as in Example 1 except that 0.15 g was used. The evaluation results are shown in Table 4.

[0039]

[Examples 9 to 11] 1,1,2-trichloro-1,2,
To 250 ml of a 2-trifluoroethane-dichloromethane mixed solvent (dichloromethane 5% by weight), alkoxypolyethyleneglycol monocarboxylic acid [C ₁₂ H _25- (O
_{CH 2 CH 2) 4.5 -OCH 2} COOH ], DMAP,
Using DCC, soft contact lenses were obtained in the same manner as in Example 1 under the conditions shown in Table 1 below. The evaluation results are shown in Table 4.

[0040]

[Table 1]

[0041]

Examples 12 to 14 1,1,2-trichloro-1,
To 250 ml of a 2,2-trifluoroethane-acetone mixed solvent (acetone 12.5% by weight), methoxypolyethylene glycol monocarboxylic acid [CH _3- (OCH ₂
CH ₂ ) ₇ —OCH ₂ COOH], PP and DCC were used to obtain a soft contact lens in the same manner as in Example 1 under the following conditions. The evaluation results are shown in Table 4.

[0042]

[Table 2]

[0043]

Examples 15 to 17 Soft contact lenses were prepared in the same manner as in Example 1 under the conditions shown in Table 3 below using 250 ml of ethyl acetate and polyethylene glycol dicarboxylic acid having an average molecular weight of 400 in the polyethylene glycol portion, DMAP and DCC. Obtained. The evaluation results are shown in Table 4.

[0044]

[Table 3]

[0045]

Comparative Example 1 A copolymer obtained by polymerizing a monomer mixture of 80% by weight of HEMA, 19.8% by weight of HPMA and 0.2% by weight of EGDMA and a lens shape by known cutting and polishing (center thickness: 0). 0.08 mm, diameter 11.9
10 mm) were immersed in a physiological saline solution at 70 ° C. for 16 hours to be hydrated and swollen to obtain a soft contact lens. The evaluation results are shown in Table 4.

[0046]

Example 18 HEMA 95.5% by weight, EGDMA
A soft contact lens was obtained in the same manner as in Example 1 except that a copolymer obtained by polymerizing 0.5% by weight of a monomer mixture was used. The evaluation results are shown in Table 4.

[0047]

Example 19 HEMA 70% by weight, dihydroxypropyl methacrylate (hereinafter referred to as DHPMA) 2
0% by weight, cyclohexyl methacrylate (hereinafter referred to as CH
It is referred to as MA. ) A soft contact lens was obtained in the same manner as in Example 1 except that a copolymer obtained by polymerizing a monomer mixture of 5% by weight and 5% by weight of octafluoropentyl methacrylate (hereinafter referred to as 8FM) was used. It was The evaluation results are shown in Table 4.

[0048]

[Table 4]

[0049]

EFFECTS OF THE INVENTION The contact lens of the present invention is unlikely to be soiled with proteins and the like, and is unlikely to cause clouding of the lens or deterioration of visual acuity even if it is worn for a long time, and can be worn comfortably for a long time.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 22, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

It is easily inferred that such an esterification reaction mainly occurs on the surface of the lenticular material as will be discussed later, but nevertheless its transparency and water content are secured. That was something else. That is, the present invention is as follows. 1. Polyethylene glycol monocarboxylic acid represented by the formula HOOC—CH ₂ — (O—CH ₂ —CH ₂ ) _n —OR or a functional derivative of the acid is added to a lens-like material composed of a polymer having a hydroxyl group in the molecule. and / or the formula _{HOOC-CH 2 - (O-} CH 2 -CH 2) n -O-CH 2 COOH ( provided that Shikichu, n represents an integer of 1 or more, the hydrocarbon R is a saturated or unsaturated The contact lens is characterized in that a polyethylene glycol dicarboxylic acid or a functional derivative of the acid is ester-bonded. 2. Polyethylene glycol monocarboxylic acid or a functional derivative of the acid, and / or polyethylene glycol dicarboxylic acid or a functional derivative of the acid, and a solution in which an esterification catalyst is dissolved or dispersed in a reaction catalyst to form a hydroxyl group in the molecule. By processing a lens-shaped product comprising a polymer substance, a polyethylene-glycol monocarboxylic acid or a functional derivative of the acid and / or a polyethylene glycol dicarboxylic acid or a functional derivative of the acid is formed into a lens-shaped product. The method for producing a contact lens is characterized by hydrating and swelling after esterifying the hydroxyl groups in the molecule.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

[0046]

Example 18 HEMA 99.5 % by weight, EGDMA
A soft contact lens was obtained in the same manner as in Example 1 except that a copolymer obtained by polymerizing 0.5% by weight of a monomer mixture was used. The evaluation results are shown in Table 4. ─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 22, 1991

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0007

[Correction method] Change

[Correction content]

It is easily inferred that such an esterification reaction mainly occurs on the surface of the lenticular material as will be discussed later, but nevertheless its transparency and water content are secured. That was something else. That is, the present invention is as follows. 1. Polyethylene glycol monocarboxylic acid represented by the formula HOOC—CH ₂ — (O—CH ₂ —CH ₂ ) _n —OR or a functional derivative of the acid is added to a lens-like material composed of a polymer having a hydroxyl group in the molecule. and / or the formula _{HOOC-CH 2 - (O-} CH 2 -CH 2) n -O-CH 2 COOH ( provided that Shikichu, n represents an integer of 1 or more, the hydrocarbon R is a saturated or unsaturated The contact lens is characterized in that a polyethylene glycol dicarboxylic acid or a functional derivative of the acid is ester-bonded. 2. Polyethylene glycol monocarboxylic acid or a functional derivative of the acid, and / or polyethylene glycol dicarboxylic acid or a functional derivative of the acid, and a solution in which an esterification catalyst is dissolved or dispersed in a reaction catalyst to form a hydroxyl group in the molecule. By processing a lens-shaped product comprising a polymer substance, a polyethylene-glycol monocarboxylic acid or a functional derivative of the acid and / or a polyethylene glycol dicarboxylic acid or a functional derivative of the acid is formed into a lens-shaped product. The method for producing a contact lens is characterized by hydrating and swelling after esterifying the hydroxyl groups in the molecule.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0046

[Correction method] Change

[Correction content]

[0046]

Example 18 HEMA 99.5 % by weight, EGDMA
A soft contact lens was obtained in the same manner as in Example 1 except that a copolymer obtained by polymerizing 0.5% by weight of a monomer mixture was used. The evaluation results are shown in Table 4.

Claims (2)

[Claims] 1. A polyethylene glycol monocarboxylic acid represented by the formula HOOC—CH ₂ — (O—CH ₂ —CH ₂ ) _n —OR or a lens thereof comprising a polymeric substance having a hydroxyl group in the molecule. functional derivatives of acid and / or the formula _{HOOC-CH 2 - (O-} CH 2 -CH 2) n -O-CH 2 -COOH ( although Shikichu, n represents an integer of 1 or more, R represents a saturated or A contact lens characterized by having an ester bond of a polyethylene glycol dicarboxylic acid or a functional derivative of the acid. 2. Polyethyleneglycol monocarboxylic acid or a functional derivative of the acid, and / or polyethyleneglycol dicarboxylic acid or a functional derivative of the acid,
Also, by treating a lens-like material comprising a polymer having a hydroxyl group in the molecule with a solution prepared by dissolving or dispersing an esterification catalyst in a reaction medium, polyethyleneglycol monocarboxylic acid or a functional derivative of the acid, and And / or a polyethylene glycol dicarboxylic acid or a functional derivative of the acid is esterified to a hydroxyl group in a molecule constituting the lens-like material, and then hydrated and swollen.