TW201900786A - Solution for silicone hydrogel contact lens and distribution solution including the same improving the surface hydrophilicity and surface lubricity of a silicone hydrogel contact lens - Google Patents

Abstract

This invention provides a solution for a silicone hydrogel contact lens, which may improve the surface hydrophilicity and surface lubricity of a silicone hydrogel contact lens. The solution for the silicone hydrogel contact lens contains a copolymer (P) having structural units represented by the following formulas (1a) to (1c) and a water-soluble polymer (Q), wherein the ratio na:nb:nc of the structural units in the copolymer (P) is 100:10-400:2-50. In the formulas (1a) to (1c) of [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3], R1, R2 and R5 are each independently hydrogen atom or a methyl group; R3 and R4 are each independently a hydrogen atom, a methyl group or an ethyl group, or bonded to each other to form a morpholinyl group; and R6 is a hydrocarbyl group having 12 to 24 carbon atoms.

Description

Acetone hydrogel contact lens solution and its delivery solution

This invention relates to a solution for an anthrone ketone hydrogel contact lens containing a specific polymer.

There are more than 10 million contact lens wearers in Japan, and the number of users has increased dramatically due to its simplicity and convenience. However, according to the report, the use of contact lenses has been progressing for a long time, especially in the case of young people, and it has been pointed out that this prolongation causes hypoxia and adverse effects on the cornea and the like (Non-Patent Document 1). Therefore, development of an anthrone hydrogel contact lens which incorporates an anthrone material excellent in oxygen permeability has been continuously performed.

According to the characteristics of the anthrone material, the anthrone ketone hydrogel contact lens has high hydrophobicity, so the surface hydrophilicity and surface lubricity are low, and the wearing feeling is poor. Therefore, research is being continuously conducted on a technique for improving the surface hydrophilicity and surface lubricity of an anthrone ketone hydrogel contact lens, and a delivery liquid for improving surface hydrophilicity and surface lubricity of an anthrone ketone hydrogel contact lens ( Patent Documents 1 to 3).

On the other hand, it is known to use 2-(methacryloxy)ethyl-2'-(trimethylammonio)ethyl phosphate (alias: 2-methacryloyloxyethylphosphocholine, Hereinafter, the copolymer obtained by abbreviating as MPC) can improve the wearing feeling of the contact lens (Patent Documents 4 to 6).

Prior technical literature

Patent Document 1: Patent Document 1: Japanese Patent Publication No. 2015-524090 Patent Document 2: Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei. No. Hei. No. Hei. No. Hei. U.S. Patent No. 5,461,333, Patent Document 6: International Publication No. 2013/128633

Non-Patent Literature Non-Patent Document 1: Walline J. J., 2013, Long-term Contact Lens Wear of Children and Teens, Eye&Contact Lens, 39, 283-289.

Technical problem to be solved by the present invention

However, the technical effects of the above Patent Documents 1 to 3 are limited. Further, even if the copolymers of the above Patent Documents 4 to 6 are applied to an anthrone hydrogel contact lens, the effect of improving the surface hydrophilicity and the surface lubricity is low, and therefore the effect of improving the lens wearing feeling is also limited. Therefore, there is a need for development of a technology that can give a better wearing feeling.

The technical problem of the present invention is to provide a solution for an anthrone hydrogel contact lens which can improve the surface hydrophilicity and surface lubricity of an anthrone ketone hydrogel contact lens.

Technical means to solve technical problems .

The inventors of the present application conducted intensive studies in order to solve the above technical problems, and as a result, found that an indole ketone hydrogel invisible can be improved by using a copolymer having three different structural units in a specific ratio in combination with a specific water-soluble polymer. The surface of the spectacles is hydrophilic and surface lubricated, thereby completing the present invention.

The solution for the fluorenone hydrogel contact lens of the present invention contains 0.001 to 1.0 w/v% of the copolymer (P) and 0.001 to 10.0 w/v% of the water-soluble polymer (Q). The copolymer (P) has a weight average molecular weight of 5,000 to 2,000,000 and has a structural unit represented by the following formulas (1a) to (1c). The water-soluble polymer (Q) is selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, alginic acid and salts thereof, hyaluronic acid and salts thereof, polyethylene glycol, hydroxypropylmethylcellulose, carboxyvinyl polymer, At least one polymer of the group consisting of hydroxyethyl cellulose, methyl cellulose, and a phospholipid polymer different from the copolymer (P). [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3]

In the formulae (1a) to (1c), R ¹ , R ² and R ⁵ are each independently a hydrogen atom or a methyl group, and R ³ and R ⁴ are each independently a hydrogen atom, a methyl group or an ethyl group, or are bonded to each other. The morpholinyl group is formed, and R ⁶ is a hydrocarbon group having 12 to 24 carbon atoms. The number ratio of structural units in the copolymer (P) is n _a : n _b : n _c is 100: 10 to 400: 2 to 50.

Effect of the invention

The solution for the fluorenone hydrogel contact lens of the present invention can easily impart excellent surface hydrophilicity and surface lubricity to the fluorenone hydrogel contact lens, and thus can improve the wearing feeling of the fluorenone hydrogel contact lens.

The solution for an anthrone ketone hydrogel contact lens of the present invention contains a copolymer (P) and a water-soluble polymer (Q). Hereinafter, the "solution for an anthrone ketone hydrogel contact lens of the present invention" will be simply referred to as "a solution of the present invention".

The copolymer (P) used in the solution of the present invention has at least three structural units, namely, a PC structural unit, a guanamine structural unit, and a hydrophobic structural unit. The copolymer (P) may comprise a plurality of PC structural units, may also comprise a plurality of guanamine structural units, and may also comprise a plurality of hydrophobic structural units.

The above PC structural unit is represented by the following formula (1a). The PC structural unit imparts hydrophilicity and hydrogel forming ability to the copolymer (P) and improves lubricity. [Chemical Formula 4]

In the formula (1a), R ¹ is a hydrogen atom or a methyl group.

In the synthesis of the copolymer (P), the PC structural unit can be obtained from a monomer containing a phosphonium choline-like group represented by the following formula (1a') (hereinafter referred to as a PC monomer). [Chemical Formula 5]

In the formula (1a'), X represents a monovalent organic group having a polymerizable functional group containing an unsaturated bond.

From the viewpoint of availability, the PC monomer is preferably 2-((meth)acryloxy)ethyl-2'-(trimethylammonium)ethyl phosphate, further preferably the following formula 2-(Methethyloxy)ethyl-2'-(trimethylammonio)ethyl phosphate represented by (1a''). [Chemical Formula 6]

The PC monomer can be produced by a known method. For example, it can be produced by a method in which a hydroxyl group-containing polymerizable monomer and 2-bromoethylphosphonium dichloride are reacted in the presence of a tertiary base, as shown in JP-A-54-63025, and A method of reacting a compound thus obtained with a tertiary amine; or a reaction of a hydroxyl group-containing polymerizable monomer with a cyclic phosphorus compound, as shown in JP-A-58-154591, etc., to obtain a cyclic compound A method in which a tertiary amine is used to carry out a ring opening reaction.

The above guanamine structural unit is represented by the following formula (1b). The guanamine structural unit can polymerize the copolymer (P) and improve the adhesion of the solution of the present invention to an fluorenone hydrogel contact lens. [Chemical Formula 7]

In the formula (1b), R ² is a hydrogen atom or a methyl group. R ³ and R ⁴ are each independently a hydrogen atom, a methyl group or an ethyl group, or are bonded to each other to form a morpholinyl group.

Copolymer (P), the terms n _a is 100, the number n _b n _a number with a PC Amides structural units the structural unit ratio n _a: n _b is 100: 10 to 400, preferably 100:30~250. When the ratio of the number n _b of the indoleamine structural units to the number n _a of the PC structural units is too large, there is a possibility that the aseptic filtration performed when preparing the solution of the present invention becomes difficult. On the other hand, when the ratio is too small, the solution of the present invention has insufficient adhesion to the fluorenone hydrogel contact lens, and the effect of improving lubricity cannot be expected.

In the synthesis of the copolymer (P), the decylamine structural unit can be obtained from a monomer represented by the following formula (1b'), that is, a (meth) acrylamide or a (meth) acrylamide derivative. [Chemical Formula 8]

R ² , R ³ and R ⁴ in the formula (1b') have the same meanings as R ² , R ³ and R ⁴ in the formula (1b), respectively. Specific examples of the monomer represented by the formula (1b') include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, and N-propylene.醯 morpholine and the like.

The above hydrophobic structural unit is represented by the following formula (1c). The hydrophobic structural unit can improve the adsorption of the copolymer (P) on the fluorenone hydrogel contact lens, improve the physical cross-linking gel formation ability based on the hydrophobic interaction, and improve the lubricity. [Chemical Formula 9]

In the formula (1c), R ⁵ is a hydrogen atom or a methyl group, and R ⁶ is a hydrocarbon group having 12 to 24 carbon atoms. Specific examples of the hydrocarbon group include dodecyl group, octadecyl group, behenyl group and the like.

In the copolymer (P), when na is converted to 100, the ratio n _a : n _c of the number of PC structural units to the number of hydrophobic structural units n _a : n _c is 100: 2 to 50, preferably 100: 5 ~25. N _c the number of hydrophobic structural unit ratio is too small relative to the number of PC n _a structural unit, the lubricating effect is insufficient duration. On the other hand, when the ratio is too large, the hydrophilicity of the copolymer (P) is lowered, so that the solubility in an aqueous solution is lowered, and it may become difficult to prepare a solution for an fluorenone hydrogel contact lens.

In the synthesis of the copolymer (P), the hydrophobic structural unit can be obtained from a hydrophobic monomer represented by the following formula (1c'). [Chemical Formula 10]

R ⁵ and R ⁶ in the formula (1c') are synonymous with R ⁵ and R ⁶ in the formula (1c), respectively. Specific examples of the hydrophobic monomer represented by the formula (1c') include lauryl (meth)acrylate, octadecyl (meth)acrylate, and behenyl (meth)acrylate (methyl). A linear alkyl acrylate or the like.

The copolymer (P) may further contain any structural unit other than the above PC structural unit, guanamine structural unit, and hydrophobic structural unit, within a range not impairing the effects of the present invention. Copolymer (P), the number n of the structural unit 100 in terms of _a number n _a structural unit PC arbitrary ratio n _{e a} n: n _e is preferably 100: 50 or less.

Any of the above structural units may be, for example, a linear or branched alkyl (meth)acrylate other than a monomer selected from the formulae (1a'), (1b'), and (1c'), (methyl a cycloalkyl acrylate, an aromatic group-containing (meth) acrylate, a styrene monomer, a vinyl ether monomer, a vinyl ester monomer, a hydrophilic hydroxyl group-containing (meth) acrylate A polymerizable monomer of an acid group-containing monomer, a nitrogen group-containing monomer, an amino group-containing monomer, and a cationic group-containing monomer.

The copolymer (P) has a weight average molecular weight of 5,000 to 2,000,000, preferably 100,000 to 1,500,000. When the weight average molecular weight is less than 5,000, the adsorption force of the copolymer (P) on the surface of the fluorenone hydrogel contact lens is insufficient, and improvement in lubricity may not be expected. When the weight average molecular weight is more than 2,000,000, the viscosity is increased, and there is a possibility that the operation becomes difficult.

The copolymer (P) can be produced, for example, by copolymerization of the above monomers in accordance with the method described in International Publication No. 2013/128633. Although the copolymer (P) is usually a random copolymer, it may be an alternating copolymer or a block copolymer in which each structural unit is regularly arranged, or may have a graft structure in a part.

The solution of the present invention contains 0.001 to 1.0 w/v% of the copolymer (P) in water, alcohol (methanol, ethanol, n-propanol, isopropanol or the like) or a mixed solvent thereof. The concentration of the copolymer (P) is preferably from 0.002 to 1.0 w/v%, more preferably from 0.003 to 1.0 w/v%, still more preferably from 0.005 to 1.0 w/v%. When the concentration of the copolymer (P) is less than 0.001 w/v%, sufficient surface hydrophilicity and surface lubricity improving effect cannot be obtained. If it is more than 1.0 w/v%, since the effect equivalent to the blending amount cannot be obtained, it is economically disadvantageous.

Further, in the present invention, "w/v%" represents the mass of a component in a 100 ml solution in grams (g). For example, "the solution of the present invention contains 1.0 w/v% of the copolymer (P)" means that 100 ml of the solution contains 1.0 g of the copolymer (P).

The above water-soluble polymer (Q) is selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, alginic acid and salts thereof, hyaluronic acid and salts thereof, polyethylene glycol, hydroxypropylmethylcellulose, carboxyvinyl polymer At least one polymer selected from the group consisting of hydroxyethyl cellulose, methyl cellulose, and a phospholipid polymer different from the above copolymer (P). These polymers may be used alone or in combination of two or more. Further, in the present invention, the "phospholipid polymer" means a polymer containing a PC structural unit and a hydrophobic structural unit.

Examples of the polyvinylpyrrolidone include polyvinylpyrrolidone K25, polyvinylpyrrolidone K30, and polyvinylpyrrolidone K90. Examples of the polyvinyl alcohol include a complete saponified product of a polyvinyl alcohol, a partially saponified product, and the like. Examples of the alginic acid and salts thereof include alginic acid and sodium alginate. Examples of the hyaluronic acid and the salt thereof include sodium hyaluronate and the like. Examples of the polyethylene glycol include macrogol 200, macrogol 300, macrogol 400, macrogol 600, macrogol 1500, macrogol 1540, macrogol 4000, macrogol 6000, macrogol 20000, macrogol 35000, and the like. Examples of the hydroxypropylmethylcellulose include Hypromylose (2208), Hypromello (2906), and Hypromello (2910). Examples of the carboxyvinyl polymer include HIVISWAKO 105 manufactured by Wako Pure Chemical, Ltd., and the like. Examples of the hydroxyethyl cellulose include HEC Daicel SP400 manufactured by DAICEL FINECHEM LTD. Examples of the methyl cellulose include METOLOSE SM-15 manufactured by Shin-Etsu Chemical Co., Ltd., and the like. Examples of the phospholipid polymer include a copolymer (q) and the like which will be described later.

The copolymer (q) has a weight average molecular weight of 10,000 to 5,000,000, and has a PC structural unit represented by the above formula (1a) and a hydrophobic structural unit represented by the following formula (1d). The copolymer (q) may comprise a plurality of PC structural units or may comprise a plurality of hydrophobic structural units. [Chemical Formula 11]

In the formula (1d), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a hydrocarbon group having 1 to 24 carbon atoms. The hydrocarbon group may be a linear hydrocarbon group, a branched hydrocarbon group or a cyclic hydrocarbon group, and may also be a saturated hydrocarbon group, an unsaturated hydrocarbon group or an aromatic hydrocarbon group. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, a butyl group, a dodecyl group, a tridecyl group, an octadecyl group, an ethylhexyl group, a cyclohexyl group, an isobornyl group, and an allyl group. Benzyl and the like.

Copolymer (q), the number n _a structural unit PC and the hydrophobic structural unit number of the ratio n _a n _d: n _d is 10: 90 ~ 90: 10, preferably 50: 50 to 90: 10, more preferably 70:30~90:10.

The copolymer (q) may contain any structural unit other than the above PC structural unit and hydrophobic structural unit, within a range not impairing the effects of the present invention. Any structural unit in the copolymer (q) may be the same as any of the above structural copolymers (P). Copolymer (q), the terms n _a is 100, the number n _a structural unit PC with an arbitrary number of structural units of the ratio n _a n _f: n _f is preferably 100: 10 or less.

The copolymer (q) can be produced by the same method as the copolymer (P).

The solution of the present invention contains 0.001 to 10.0 w/v% of a water-soluble polymer (Q). The concentration of the water-soluble polymer (Q) is preferably from 0.002 to 9.5 w/v%, more preferably from 0.002 to 9.0 w/v%, still more preferably from 0.003 to 8.0 w/v%, particularly preferably 0.005. 7.0w/v%.

In addition to the copolymer (P), the water-soluble polymer (Q), and the solvent, the solution of the present invention may further contain an additive as needed. The additive may be an additive used in a solution for contact lens or the like, and examples thereof include vitamins, amino acids, sugars, cooling agents, inorganic salts, organic acid salts, acids, bases, antioxidants, and stabilizers. Agents, preservatives, etc.

Examples of the vitamins include flavin adenine dinucleotide sodium, cyanocobalamin, vitamin A acetate, vitamin A palmitate, pyridoxine hydrochloride, panthenol, sodium pantothenate, and calcium pantothenate. Examples of the amino acid include aspartic acid and a salt thereof, aminoethanesulfonic acid, and the like. Examples of the saccharide include glucose, mannitol, sorbitol, xylitol, trehalose, and the like. Examples of the cooling agent include menthol and camphor. Examples of the inorganic salt include sodium chloride, potassium chloride, sodium hydrogen phosphate, anhydrous sodium dihydrogen phosphate, and the like. Examples of the organic acid salt include sodium citrate and the like. Examples of the acid include phosphoric acid, citric acid, sulfuric acid, acetic acid, and boric acid. Examples of the base include potassium hydroxide, sodium hydroxide, trishydroxymethylaminomethane, monoethanolamine, and borax. Examples of the antioxidant include tocopheryl acetate and dibutylhydroxytoluene. Examples of the stabilizer include sodium edetate, glycine, and the like. Examples of the preservative include benzalkonium chloride, chlorhexidine gluconate, potassium sorbate, and polyhexylamine hydrochloride.

Among these additives, sodium chloride and potassium chloride are preferred in terms of improving the surface hydrophilicity and surface lubricity of the fluorenone hydrogel contact lens. In the solution of the present invention, the concentration of sodium chloride is not particularly limited, but is preferably 0.01 to 1.5 w/v%, more preferably 0.1 to 1.3 w/v%, still more preferably 0.2 to 1.0 w/v%. The concentration of potassium chloride is not particularly limited, but is preferably 0.01 to 1.5 w/v%, more preferably 0.02 to 1.3 w/v%, still more preferably 0.05 to 1.0 w/v%.

In order to further improve the surface hydrophilicity and surface lubricity of the fluorenone hydrogel contact lens, it is preferred to use both sodium chloride and potassium chloride. When used at the same time, the quality of sodium chloride: potassium chloride is preferably from 1:1 to 50:1, more preferably from 2:1 to 40:1, further preferably from 3:1 to 30:1.

The solution of the invention can be used in any type of fluorenone hydrogel contact lens. In particular, it can be preferably used for tris(trimethylformamoxy)carbamylpropyl methacrylate, tris(trimethylformamoxy)carbamylpropylvinylcarbamate or An fluorenone hydrogel contact lens obtained by using methyl bis(trimethylformamoxy)carbomethoxypropyl glycerol methacrylate as an anthrone monomer.

Specific product forms of the solution of the present invention include a distribution liquid for an anthrone ketone hydrogel contact lens, a care product for an anthrone ketone hydrogel contact lens, a preservation solution for an anthrone ketone hydrogel contact lens, and an anthrone water. A cleaning solution for a gel contact lens, a cleaning and preservation solution for an anthrone ketone hydrogel contact lens, a disinfectant for a contact lens, and the like. Among them, it is preferably used as a dispensing liquid, a care product or a preservation solution for an fluorenone hydrogel contact lens, and is particularly preferably used as a dispensing liquid. In the present specification, the distribution liquid for the fluorenone hydrogel contact lens refers to a solution in which the oxime ketone hydrogel contact lens product is immersed at the time of shipment.

Example

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited thereto.

<Copolymer (P)>

In the examples and the comparative examples, the copolymers (p-1) to (p-4) shown below were used as the copolymer (P). Further, the copolymers (p-1) to (p-4) were prepared by the method described in the examples of International Publication No. 2013/128633.

Copolymer (p-1): 2-methylpropenyloxyethylphosphocholine represented by formula (1a''), N,N-dimethylpropenylamine represented by formula (1b'), and formula ( A copolymer of octadecyl methacrylate represented by 1c') (copolymerization composition ratio n _a :n _b :n _c =100:90:10, weight average molecular weight 1,000,000).

Copolymer (p-2): 2-methylpropenyloxyethylphosphocholine represented by formula (1a''), N,N-dimethylpropenylamine represented by formula (1b'), and formula ( A copolymer of octadecyl methacrylate represented by 1c') (copolymerization composition ratio n _a : n _b : n _c = 100 / 223/10, weight average molecular weight 1,200,000).

Copolymer (p-3): 2-methylpropenyloxyethylphosphocholine represented by formula (1a''), N,N-dimethylpropenylamine represented by formula (1b'), and formula ( A copolymer of octadecyl methacrylate represented by 1c') (copolymerization composition ratio n _a :n _b :n _c =100/34/9, weight average molecular weight 700,000).

Copolymer (p-4): 2-methylpropenyloxyethylphosphocholine represented by formula (1a''), N,N-dimethylpropenylamine represented by formula (1b'), and formula ( A copolymer of lauryl methacrylate represented by 1c') (copolymerization composition ratio n _a : n _b : n _c = 100 / 80 / 20, weight average molecular weight 1,000,000).

<Comparative polymer>

In the comparative examples, the homopolymers (A) to (C) shown below were used as the comparative polymer.

Homopolymer (A): 2-methylpropenyl oxyethylphosphocholine homopolymer (weight average molecular weight: 200,000) obtained by the method described in the examples of JP-A-8-333421.

Homopolymer (B): Commercially available N,N-dimethyl methacrylamide homopolymer (poly(N,N-dimethyl methacrylate) manufactured by Sigma-Aldrich Japan, DDMAT Terminated (product name) , number average molecular weight 10,000).

Homopolymer (C): Commercially available lauryl methacrylate homopolymer (polylauryl methacrylate (product name) manufactured by Sigma-Aldrich Japan, weight average molecular weight: 470,000).

<Water-soluble polymer (Q)>

In the examples and the comparative examples, the following polymers were used as the water-soluble polymer (Q).

Polyvinylpyrrolidone: polyvinylpyrrolidone K90 manufactured by Wako Pure Chemical, Ltd.

Polyvinyl alcohol: GOHSENOL EG-05 manufactured by The Nippon Synthetic Chemical Industry Co., Ltd.

Alginate: sodium alginate manufactured by Wako Pure Chemical, Ltd.

Hyaluronate: sodium hyaluronate manufactured by Sigma-Aldrich Co. LLC.

Polyethylene glycol: Macrogol 4000 manufactured by NOF CORPORATION.

Hydroxypropyl methylcellulose: METOLOSE 60SH-50 manufactured by Shin-Etsu Chemical Co., Ltd.

Carboxyvinyl polymer: HIVISWAKO 105 manufactured by Wako Pure Chemical, Ltd.

Hydroxyethyl cellulose: HEC Daicel SP400 manufactured by DAICEL FINECHEM LTD.

Methylcellulose: METOLOSE SM-15 manufactured by Shin-Etsu Chemical Co., Ltd.

Copolymer (q-1): a copolymer of 2-methylpropenyloxyethylphosphocholine and butyl methacrylate represented by the formula (1a'') (described in the examples of JP-A-11-035605) The method was carried out by polymerization, and the copolymerization composition ratio was na: nd = 80:20, and the weight average molecular weight was 600,000).

Copolymer (q-2): a copolymer of 2-methylpropenyloxyethylphosphocholine and butyl methacrylate represented by the formula (1a'') (described in the examples of JP-A-2004-196868) The method was carried out by polymerization, and the copolymerization composition ratio was na: nd = 30:70, and the weight average molecular weight was 142,000).

<Evaluation of Surface Lubricity of Anthrone Hydrogel Contact Lens>

In the examples and comparative examples, the surface lubricity of the fluorenone hydrogel contact lens was evaluated in accordance with the following procedure. Preparation of ISO saline and pretreatment of contact lenses were performed prior to evaluation.

(Preparation of ISO saline)

ISO saline was prepared according to ISO 18369-3:2006, Ophthalmic Optics-Contact Lenses Part 3: Measurement Methods. Specifically, 8.3 g of sodium chloride, 5.993 g of sodium hydrogen phosphate dodecahydrate, and 0.528 g of sodium dihydrogen phosphate dihydrate were dissolved in water to make a total amount of 1000 mL, and filtration was carried out to obtain ISO physiology. brine.

(pre-treatment of contact lenses)

Follow the steps below to perform pre-treatment on the contact lenses.

(1) Add 10 mL or more of ISO physiological saline to a 15 mL centrifuge tube, and take out one fluorenone hydrogel contact lens from the blister pack (USAN: balafilcon A, product name: Medalist Fresh fit comfort moist, FDA classification: Class III, constituent monomers: TrisVC, NVP), was added to the centrifuge tube and shaken for 2 hours.

(2) Remove the ISO saline in the centrifuge tube, and add more than 10 mL of ISO saline again, and shake for one night.

(3) The above contact lens is taken out from the centrifuge tube, and the liquid is gently wiped off and then loaded into the contact lens case. 1 mL of each of the solutions of the examples and the comparative examples described later was added thereto, and subjected to autoclaving (121 ° C, 20 minutes).

(surface lubricity evaluation)

The surface lubricity of the contact lens pretreated as described above was evaluated by sensory evaluation. The surface lubricity was evaluated in 10 levels, and the score when the evaluation was "the most excellent lubricity" was 10, and the score when the evaluation was "completely lubricious" was 1. The average value of the scores when the six sensory evaluations were performed three times was referred to as "surface lubricity" and is shown in Tables 1 to 7. The case where the average value is 7.5 or more is referred to as "excellent surface lubricity", and the case where 8.5 or more is described is "excellent in surface lubricity".

<Evaluation of surface hydrophilicity of anthrone ketone hydrogel contact lenses>

In the examples and comparative examples, the surface hydrophilicity of the fluorenone hydrogel contact lens was evaluated in accordance with the following procedure. Further, the ISO physiological saline used for the evaluation of the surface hydrophilicity was prepared in the same manner as the above-described ISO physiological saline used for the evaluation of the surface lubricity.

(1) Take one fluorenone hydrogel contact lens from the blister pack (USAN: balafilcon A, product name: Medalist Fresh fit comfort moist (manufactured by BLJ Company, Ltd.), FDA classification: class III, constituting monomer :TrisVC, NVP), loaded into the contact lens case. At this time, the dispensing liquid in the blister pack was not added to the contact lens case.

(2) 1 mL of ISO physiological saline was added to the contact lens case, and fully immersed to reconcile the above contact lenses with ISO physiological saline.

(3) The ISO saline was removed, 1 mL of new ISO saline was again added, and fully immersed to reconcile the contact lenses with ISO saline.

(4) The ISO saline was removed, and 1 mL of each of the solutions of the examples and the comparative examples described later was added to the contact lens case, and subjected to autoclaving (121 ° C, 20 minutes).

(5) The contact lens was taken out, and the time (BUT) until the water film on the surface of the lens was broken was measured with a code table. This BUT was referred to as "surface hydrophilicity" and is shown in Tables 1-7. The case where the BUT was 10 seconds or longer was referred to as "excellent surface hydrophilicity", and the case where the BUT was 15 seconds or more was referred to as "the surface hydrophilicity was particularly excellent".

<Deformation inhibition evaluation of anthrone ketone hydrogel contact lens>

In the examples and comparative examples, the evaluation of the deformation inhibition of the fluorenone hydrogel contact lens was carried out in accordance with the following procedure. Further, an anthrone ketone hydrogel contact lens was prepared in the same manner as the steps (1) to (4) of the surface hydrophilicity evaluation described above before the evaluation was carried out.

(1) The prepared fluorenone hydrogel contact lens was taken out and allowed to stand on a Teflon (registered trademark) sheet for 10 minutes at 20 ° C and 40% RH.

(2) Visually confirming the deformation of the contact lens, and benchmarking with A (nearly observed deformation), B (observation of deformation in a part of the contact lens), or C (large deformation observed in the contact lens) Evaluation. The evaluation results are shown in Tables 1 to 7. In addition, the case of the B evaluation of the deformability evaluation is described as "the deformation can be suppressed", and the case of the A evaluation is described as "the deformation can be significantly suppressed".

<Preparation of solution for ketone ketone hydrogel contact lens>

The solutions for the anthrone ketone hydrogel contact lenses of Examples 1 to 23 and Comparative Examples 1 to 15 were prepared as follows.

(Example 1)

To about 80 g of ISO physiological saline, 0.1 g of a copolymer (p-1) and 0.1 g of polyvinylpyrrolidone (polyvinylpyrrolidone K90 manufactured by Wako Pure Chemical, Ltd.) were added and stirred to dissolve. The ISO physiological saline was added thereto in such a manner that the total amount became 100 mL, and the mixture was filtered and sterilized to prepare a solution for the sterile fluorenone hydrogel contact lens of Example 1. That is, the solution of Example 1 was composed of the components shown in Table 1 and ISO physiological saline, and these components were contained in the concentration (w/v%) shown in Table 1. The appearance, properties and evaluation results of the solution are shown in Table 1.

(Examples 2 to 18 and Comparative Examples 1 to 15)

Prepared solutions of sterile fluorenone hydrogel contact lenses of Examples 2 to 18 and Comparative Examples 1 to 15 were prepared in the same manner as in Example 1 except that the components of the types and amounts shown in Tables 1 to 6 were used. . That is, the solutions of Examples 2 to 18 and Comparative Examples 1 to 15 were composed of the components shown in Tables 1 to 6 and the ISO physiological saline, and these components were contained in the concentrations (w/v%) shown in Tables 1 to 6. . The appearance, properties and evaluation results of the solution are shown in Tables 1 to 6. Further, since the components in Comparative Example 8 were not dissolved, the evaluation of surface lubricity and surface hydrophilicity was not performed.

(Reference example 1)

Using the solution prepared in the above Example 1, a soft contact lens different from the above fluorenone hydrogel contact lens (USAN: etafilcon A, product name: 1day ACUVUE, FDA classification: class IV, constituent monomer: 2-HEMA The surface lubricity, surface hydrophilicity, and deformation inhibition of MAA) were evaluated. The results are shown in Table 6 as Reference Example 1.

(Examples 19 to 23)

Separate ketone ketone hydrogel contact lens solutions of Examples 19 to 23 consisting of the components shown in Table 7 and water were separately prepared. That is, the solutions of Examples 19 to 23 contained aqueous solutions of the respective components at the concentrations (w/v%) shown in Table 7. The appearance, properties and evaluation results of the solution are shown in Table 7. [Table 1] [Table 2] [table 3] [Table 4] [table 5] [Table 6] [Table 7]

As is apparent from Tables 1 to 7, in the examples using the solution for the fluorenone hydrogel contact lens of the present invention, excellent surface lubricity and surface hydrophilicity were obtained. In particular, it is understood that the combination of the copolymer (p-1) and the polyvinylpyrrolidone or the copolymer (q-1) has a high effect of improving the surface lubricity and surface hydrophilicity of the fluorenone hydrogel contact lens. The solution of the examples can be preferably used as a dispensing solution.

Industrial applicability

Since the solution for the fluorenone hydrogel contact lens of the present invention imparts excellent surface hydrophilicity and surface lubricity to the fluorenone hydrogel contact lens, it is possible to provide an fluorenone hydrogel contact lens excellent in wearing feeling.

no.

no.

Claims (5)

A solution for an fluorenone hydrogel contact lens comprising 0.001 to 1.0 w/v% of a copolymer (P) and 0.001 to 10.0 w/v% of a water-soluble polymer (Q), the copolymer (P) having The weight average molecular weight of 5,000 to 2,000,000 has a structural unit represented by the following formulas (1a) to (1c), and the number ratio of the structural units in the copolymer (P) is n _a : n _b : n _c is 100 :10~400:2~50, [Chemical Formula 1] [Chemical Formula 2] [Chemical Formula 3] In the formulae (1a) to (1c), R ¹ , R ² and R ⁵ are each independently a hydrogen atom or a methyl group, and R ³ and R ⁴ are each independently a hydrogen atom, a methyl group or an ethyl group, or are bonded to each other. And forming a morpholinyl group, R ⁶ is a hydrocarbon group having 12 to 24 carbon atoms, and the water-soluble polymer (Q) is selected from the group consisting of polyvinylpyrrolidone, polyvinyl alcohol, alginic acid and salts thereof, hyaluronic acid and salts thereof At least one of a group consisting of polyethylene glycol, hydroxypropyl methylcellulose, carboxyvinyl polymer, hydroxyethyl cellulose, methyl cellulose, and a phospholipid polymer different from the copolymer (P) A polymer. The solution for an anthrone ketone hydrogel contact lens according to claim 1, wherein the water-soluble polymer (Q) is the phospholipid polymer having a weight average molecular weight of 10,000 to 5,000,000 and having the formula (1a) a structural unit represented by the following formula (1d), wherein the number ratio of the structural units in the phospholipid polymer n _a : n _d is 10:90 to 90:10, [Chemical Formula 4] In the formula (1d), R ⁷ is a hydrogen atom or a methyl group, and R ⁸ is a hydrocarbon group having 1 to 24 carbon atoms. The solution for an anthrone ketone hydrogel contact lens according to claim 1 or 2, further comprising 0.01 to 1.5 w/v% of sodium chloride and/or 0.01 to 1.5 w/v% of chlorine. Potassium. The solution for an anthrone ketone hydrogel contact lens according to claim 1 or 2, wherein the fluorenone hydrogel contact lens has a structural unit derived from an anthrone monomer, wherein the fluorenone monomer is Freely selected tris(trimethylformamoxy)carbamylpropyl methacrylate, tris(trimethylformamoxy)carbamidopropylvinylcarbamate, and methyldi(3) At least one of the group consisting of methylformyloxy)carbamylpropyl glycerol methacrylate. A dispensing liquid for contact lenses, which is composed of a solution for an anthrone ketone hydrogel contact lens according to any one of claims 1 to 4.