JP7004205B2 - Treatment liquid for contact lenses - Google Patents

Description

The present invention relates to a treatment liquid for contact lenses containing a copolymer having a specific structure.

Contact lenses currently on the market are roughly divided into soft contact lenses and hard contact lenses. Compared to soft contact lenses, hard contact lenses supply more oxygen to the cornea and have many advantages such as being able to correct astigmatism, so demand for hard contact lenses is still high.

Although it is a hard contact lens with such excellent advantages, it is also known that various proteins and lipids contained in tears are easily adsorbed on the surface of the hard contact lens, and in some cases, due to the adsorption of proteins and lipids. It is said that the surface of a hard contact lens may become cloudy (Patent Document 1).

So far, for the purpose of preventing fogging of hard contact lenses, technological developments have been made to make the surface of hard contact lenses hydrophilic and suppress the adsorption of proteins, lipids, etc. on the surface of hard contact lenses. For example, a technique for suppressing the adsorption of proteins and lipids by subjecting hard contact lenses to plasma treatment to make the surface hydrophilic (Patent Document 2), or a cationic polymer compounded in a shipping solution for hard contact lenses to make hard contacts. Techniques for making the lens surface hydrophilic (Patent Document 3) and the like have been developed.

Surface hydrophilization using plasma treatment (Patent Document 2) can impart excellent hydrophilicity to hard contact lenses, but the surface treatment process is complicated and highly controlled equipment may be required. It may be economically disadvantageous. Regarding the technology for making the surface of hard contact lenses hydrophilic by blending a cationic polymer with the shipping liquid for hard contact lenses, although the method itself is simple, the hydrophilicity that can be imparted and its durability are not satisfactory. there were.

JP-A-7-218878 WO2010 / 092686 Japanese Patent Application Laid-Open No. 10-221654

A contact that can impart excellent surface hydrophilicity and surface wettability to the surface of hard contact lenses, and can impart anti-fog effect by having durable surface hydrophilicity and surface wettability that will not be washed away by scrubbing. No processing solution for lenses is known.

Therefore, an object of the present invention is to provide a treatment liquid for a contact lens that exhibits an excellent anti-fog effect by imparting durable surface hydrophilicity and surface wettability to the surface of the contact lens.

As a result of diligent research to solve the above problems, the present inventors have made the contact lens surface durable by a contact lens treatment liquid containing a copolymer having two different structural units in a specific ratio. It has been found that surface hydrophilicity and surface wettability can be imparted and an excellent anti-fog effect can be exhibited, and the present invention has been completed.

［式（１ａ）及び（１ｂ）中、Ｒ^１及びＲ^２はそれぞれ独立に水素原子又はメチル基であり、Ｒ^３、Ｒ^４及びＲ^５は、それぞれ独立に、水素原子又は炭素数１～８のアルキル基を示し、Ｘ^－はハロゲンイオンもしくは酸残基を示す。］
２．カルボン酸基を有するコンタクトレンズに適用する前項１に記載のコンタクトレンズ用処理液。
３．コンタクトレンズ用出荷液である前項１又は２に記載のコンタクトレンズ用処理液。
４．コンタクトレンズ用ケア用品である前項１又は２に記載のコンタクトレンズ用処理液。 That is, the treatment liquid for contact lenses of the present invention is as follows.
1. 1. It has structural units represented by the following formulas (1a) and (1b), and the molar ratio n _a : n _b of each structural unit is 15 to 99: 1 to 85, and the weight average molecular weight is 10,000 to 5. A treatment liquid for contact lenses containing 0.001 to 5.0 w / v% of the copolymer (P) of 000,000.

[In the formulas (1a) and (1b), R ¹ and R ² are independently hydrogen atoms or methyl groups, and R ³ , R ⁴ and R ⁵ are independently hydrogen atoms or carbon atoms 1 to 8, respectively. Indicates an alkyl group of, ^and X- indicates a halogen ion or an acid residue. ]
2. 2. The treatment liquid for contact lenses according to item 1 above, which is applied to contact lenses having a carboxylic acid group.
3. 3. The treatment liquid for contact lenses according to item 1 or 2 above, which is a shipping liquid for contact lenses.
4. The treatment liquid for contact lenses according to item 1 or 2 above, which is a care product for contact lenses.

By using the treatment liquid for contact lenses of the present invention for contact lenses, it is possible to impart durable surface hydrophilicity and surface wettability to the contact lens surface, thereby exhibiting an excellent anti-fog effect.

The treatment liquid for contact lenses of the present invention has structural units represented by the following formulas (1a) and (1b), and the molar ratio n _a : n _b of each structural unit is 15 to 99: 1 to 85. , A treatment liquid for contact lenses containing 0.001 to 5.0 w / v% of a copolymer (P) having a weight average molecular weight of 10,000 to 5,000,000.

In formulas (1a) and (1b), R ¹ and R ² are independently hydrogen atoms or methyl groups, and R ³ , R ⁴ and R ⁵ are independently hydrogen atoms or carbon atoms 1 to 8, respectively. It indicates an alkyl group, ^and X- indicates a halogen ion or an acid residue.

Hereinafter, the configuration of the present invention will be described.
In addition, in this specification, "(meth) acrylate" means "acrylate or methacrylate", and the same applies to other similar terms.
Further, in the present specification, when a preferable numerical range (for example, a range of concentration and weight average molecular weight) is described stepwise, each lower limit value and upper limit value can be combined independently. For example, in the description "preferably 10 or more, more preferably 20 or more, and preferably 100 or less, more preferably 90 or less", a combination of "preferable lower limit value: 10" and "more preferable upper limit value: 90" is used. Therefore, it can be set to "10 or more and 90 or less". Further, for example, even in the description of "preferably 10 to 100, more preferably 20 to 90", it can be similarly set to "10 to 90".

Specific examples of the product form of the treatment liquid for contact lenses of the present invention include the following. Specifically, shipping liquids for contact lenses (contact lens packaging liquids), care products for contact lenses (contact lens multipurpose agents), preservative liquids for contact lenses, cleaning liquids for contact lenses, cleaning preservative liquids for contact lenses, contacts. Examples include lens disinfectants, eye drops, contact lens wearing agents, and the like. Above all, it is preferable to use it as a shipping liquid for contact lenses or a care product for contact lenses.
In the present specification, the shipping solution for contact lenses is a solution that is enclosed in a packaging container such as a blister package together with contact lenses when the contact lenses are distributed. Since contact lenses are generally used in a state of being swollen with an aqueous solution, the lenses are enclosed in a packaging container in a state of being swollen with an aqueous solution at the time of shipment from the factory so that they can be used immediately.
Further, in the present specification, the care product for contact lenses is not particularly limited as long as it is a solution used for the care of contact lens products, and for example, a contact lens disinfectant solution, a cleaning solution, a preservative solution, a cleaning preservative solution, and disinfection. It refers to a cleaning storage solution, a mounting solution, and the like. That is, it can be used as a liquid that comes into contact with the contact lens before, during, or after wearing the contact lens.

<Copolymer (P)>
The copolymer (P) used in the treatment liquid for contact lenses of the present invention has _a hydrophilic monomer (number of moles na) represented by the following general formula (1a') and the following general formula (1b'). It is obtained by polymerizing a quaternary ammonium group-containing (meth) acrylic monomer (number of moles n _b ) represented by, and the molar ratio n _a : n _b of each constituent unit is 15 to 99: 1 to 85. Yes, the weight average molecular weight is 10,000 to 5,000,000.

In the general formula (1a'), R ¹ represents a hydrogen atom or a methyl group.

In the formula (1b'), R ² may be either a hydrogen atom or a methyl group, and is preferably a methyl group. R ³ , R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and the alkyl group may be linear, branched or cyclic. X ^- indicates a halogen ion or acid residue.

[Hydrophilic monomer represented by the general formula (1a')]
The copolymer (P) used in the present invention has a structural unit represented by the following general formula (1a). The structural unit is a hydrophilic monomer represented by the following general formula (1a'), that is, a monomer having a phosphorylcholine structure (hereinafter, also referred to as “hydrophilic monomer” or “PC monomer””. ) Is used for polymerization. By having the PC monomer as a constituent unit of the copolymer (P), hydrophilicity is imparted to the copolymer (P), and excellent hydrophilicity can be imparted to the surface of the contact lens.
The hydrophilic monomer in the copolymer (P) is 15 to 99 mol%.

In the general formulas (1a) and (1a'), R ¹ represents a hydrogen atom or a methyl group.

The PC monomer is 2- ((meth) acryloyloxy) ethyl 2- (trimethylammonio) ethyl phosphate, preferably 2- (methacryloyloxy) ethyl represented by the following general formula (1a ″). 2- (trimethylammonio) ethyl phosphate (hereinafter, also referred to as "2-methacryloyloxyethyl phosphorylcholine").

The content of the PC monomer in the copolymer (P) is 15 to 99 mol%. If the content is less than 15 mol%, the effect of improving the hydrophilicity on the contact lens surface cannot be expected, and if the content is more than 99 mol%, the copolymer (P) is electrically reciprocally attached to the contact lens. Adsorption and binding due to action cannot be expected.

From the above viewpoint, the content of the PC monomer in the copolymer (P) is preferably 50 to 99 mol%, more preferably 98 mol% or less.

[Quaternary ammonium group-containing (meth) acrylic monomer represented by the general formula (1b')]
The copolymer (P) used in the present invention has a structural unit represented by the following general formula (1b). The structural unit is also referred to as a quaternary ammonium group-containing (meth) acrylic monomer represented by the following general formula (1b') (hereinafter, also referred to as "quaternary ammonium group-containing (meth) acrylic monomer". ) Is used for polymerization. Since the copolymer (P) has a quaternary ammonium group-containing (meth) acrylic monomer as a constituent unit, the copolymer (P) has a positive charge. The cationic copolymer (P) has an excellent adsorption / binding ability to the contact lens surface by an electric action.

In the formula (1b) and the formula (1b'), R ² may be either a hydrogen atom or a methyl group, and is preferably a methyl group.

In formula (1b) and formula (1b'), R ³ , R ⁴ and R ⁵ independently represent hydrogen atoms or alkyl groups having 1 to 8 carbon atoms, and the alkyl groups are linear, branched and It may be circular. X ^- is a halogen ion or acid residue. The quaternary ammonium group-containing (meth) acrylic monomer (n _b ) in the copolymer (P) is 1 to 85 mol%.
Specifically, as R ³ , R ⁴ and R ⁵ , methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Examples thereof include an isopentyl group, an n-hexyl group, an isohexyl group, an n-heptyl group, an isoheptyl group, an n-octyl group, an isooctyl group, a cyclopyropyl group, a cyclobutyl group, a cyclopentyl group and a cyclohexyl group.
R ³ , R ⁴ and R ⁵ are preferably a methyl group, an ethyl group, a propyl group and an isopropyl group, and more preferably a methyl group.

In the formula (1b) and the formula (1b'), examples of X ⁻ include halogen ions such as fluorine ion, bromine ion and chlorine ion (chloride ion), and acid residues such as sulfate ion and methyl sulfate ion. .. It is preferably a halogen ion (particularly a chloride ion).

Quaternary ammonium group-containing (meth) acrylic from the viewpoint of enhancing the adsorptivity and bondability to the contact lens surface of the copolymer (P) by the electrical interaction of the quaternary ammonium group-containing (meth) acrylic monomer. Preferable examples of the system monomer include 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride and the like.

A preferred combination of the monomers used in the copolymer (P) of the present invention is, for example, 2- (meth) acryloyloxyethyl phosphorylcholine, as a hydrophilic monomer represented by the general formula (1a'). The quaternary ammonium group-containing (meth) acrylic monomer represented by the formula (1b') is 2-hydroxy-3- (meth) acryloyloxypropyltrimethylammonium chloride.

The copolymer (P) of the present invention {particularly, the copolymer (P) in which each monomer is a combination thereof} forms a simple and strong bond to the contact lens surface by electrical interaction. However, durable surface hydrophilicity and surface wettability can be imparted.

[Other monomers]
The copolymer (P) may contain other monomers other than the hydrophilic monomer and the quaternary ammonium group-containing (meth) acrylic monomer as long as the effect of the present invention is not impaired. Although it is preferable, it is preferably composed of only the hydrophilic monomer and the quaternary ammonium group-containing (meth) acrylic monomer.

The other monomer may be, for example, a linear or branched alkyl (meth) acrylate, a cyclic alkyl (meth) acrylate, an aromatic group-containing (meth) acrylate, a styrene-based monomer, a vinyl ether monomer, or vinyl. Examples thereof include a polymerizable monomer selected from an ester monomer, a hydrophilic hydroxyl group-containing (meth) acrylate, an acid group-containing monomer, and a nitrogen-containing group-containing monomer.

Examples of the linear or branched alkyl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, and stearyl (meth) acrylate. And so on.
Examples of the cyclic alkyl (meth) acrylate include cyclohexyl (meth) acrylate.
Examples of the aromatic group-containing (meth) acrylate include benzyl (meth) acrylate and phenoxyethyl (meth) acrylate.
Examples of the styrene-based monomer include styrene, methylstyrene, chlorostyrene and the like.
Examples of the vinyl ether monomer include methyl vinyl ether and butyl vinyl ether.
Examples of the vinyl ester monomer include vinyl acetate and vinyl propionate.
Examples of the hydrophilic hydroxyl group-containing (meth) acrylate include polyethylene glycol (meth) acrylate, propylene glycol (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate and 4-hydroxy. Examples thereof include butyl (meth) acrylate.
Examples of the acid group-containing monomer include (meth) acrylic acid and styrene sulfonic acid (meth) acryloyloxyphosphonic acid.
Examples of the nitrogen-containing group-containing monomer include N-vinylpyrrolidone and the like.

When the copolymer (P) contains another monomer as a constituent unit, the molar ratio [ _na ] of the hydrophilic monomer (number of moles n _a ) and the other monomer (number of moles n _x ) / N _x ] is preferably 100/50 or less, with the hydrophilic monomer as 100. When the copolymer (P) contains another monomer as a constituent unit, it is based on a hydrophilic monomer, a quaternary ammonium group-containing (meth) acrylic monomer, and other monomers. It is preferable that the molar ratio of each constituent unit is n _a : n _b : n _x = 15 to 99: 1 to 85: 1 to 50.

[Weight average molecular weight of copolymer (P)]
The weight average molecular weight of the copolymer (P) is 10,000 to 5,000,000, preferably 50,000 or more, more preferably 100,000 or more, still more preferably 150,000 or more, and preferably. Is 4,000,000 or less, more preferably 3,000,000 or less, still more preferably 2,000,000 or less, still more preferably 1,500,000 or less, and particularly preferably 1,000,000 or less. .. For example, the weight average molecular weight of the copolymer (P) may be 15,000 to 800,000, 20,000 to 700,000, and 250,000 to 600,000.
When the weight average molecular weight is less than 10,000, the binding / adsorbing ability due to electrical interaction with the contact lens surface is lowered, and excellent hydrophilicity is imparted to the contact lens surface and the contact lens is subjected to this. It may not be possible to expect an excellent anti-fog effect. If the weight average molecular weight exceeds 5,000,000, the viscosity may increase and handling may become difficult.

The weight average molecular weight of the copolymer (P) is a value measured by gel permeation chromatography (GPC).

[Method for producing copolymer (P)]
The copolymer (P) can be produced by copolymerizing the above-mentioned monomers, and is usually a random copolymer, but an alternating copolymer in which each monomer is regularly arranged. It may be a block copolymer or a block copolymer, and may have a partially grafted structure.

Specifically, for example, a copolymer (for example, by radically polymerizing a mixture of the above-mentioned monomers in the presence of a radical polymerization initiator in an inert gas atmosphere such as nitrogen, carbon dioxide, argon, and helium) ( P) can be obtained.
The radical polymerization method can be carried out by a known method such as bulk polymerization, suspension polymerization, emulsion polymerization and solution polymerization. As the radical polymerization method, solution polymerization is preferable from the viewpoint of purification and the like. The copolymer (P) can be purified by a known purification method such as a reprecipitation method, a dialysis method, or an ultrafiltration method.
Examples of the radical polymerization initiator include an azo radical polymerization initiator, an organic oxide, a persulfated product and the like.
Examples of the azo radical polymerization initiator include 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis (2-diaminopropyl) dihydrochloride, and 2,2'-azobis. (2- (5-Methyl-2-imidazolin-2-yl) propane) dihydrochloride, 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobisisobutyramid dihydrate, Examples thereof include 2,2'-azobis (2,4-dimethylvaleronitrile) and 2,2'-azobisisobutyronitrile (AIBN).
Examples of the organic peroxide include t-butylperoxyneodecanate, benzoyl peroxide, diisopropylperoxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, and t-butylperoxyiso. Butyrate, lauroyl peroxide, t-butylperoxydecanate, succinate peroxide and the like can be mentioned.
Examples of the persulfated product include ammonium persulfate, potassium persulfate, sodium persulfate and the like.
These radical polymerization initiators may be used alone or in combination of two or more.
The amount of the polymerization initiator used is usually 0.001 to 10 parts by mass, preferably 0.02 to 5.0 parts by mass, and more preferably 0.03 to 3.% by mass with respect to 100 parts by mass of each monomer. It is 0 parts by mass.

The synthesis of the copolymer (P) can be carried out in the presence of a solvent. The solvent is not particularly limited as long as it dissolves each monomer composition and does not adversely affect the reaction. For example, water, an alcohol solvent, a ketone solvent, an ester solvent, a linear solvent or a cyclic solvent is used. Examples thereof include an ether solvent and a nitrogen-containing solvent.
Examples of the alcohol solvent include methanol, ethanol, n-propanol, isopropanol and the like.
Examples of the ketone solvent include acetone, methyl ethyl ketone, diethyl ketone and the like.
Examples of the ester solvent include ethyl acetate.
Examples of the linear or cyclic ether solvent include ethyl cell solve, tetrahydrofuran and the like.
Examples of the nitrogen-containing solvent include acetonitrile, nitromethane, N-methylpyrrolidone and the like.
Among these solvents, a mixed solvent of water and alcohol is preferable.

[Concentration of copolymer (P)]
The treatment liquid for contact lenses of the present invention has a copolymer (P) concentration of 0.001 w / v% or more, preferably 0.01 w / v% or more, and more preferably 0.02 w / v% or more. Yes, and it is 5.0 w / v% or less, preferably 4.0 w / v% or less, more preferably 3.0 w / v% or less, still more preferably 2.0 w / v% or less. For example, the treatment liquid for contact lenses of the present invention may have a copolymer (P) concentration of 0.02 w / v% to 1.5 w / v%.
When the concentration of the copolymer (P) is less than 0.001 w / v%, the amount of the copolymer (P) added is small, so that an excellent antifogging effect can be obtained by imparting excellent hydrophilicity to the contact lens. I can't. If it exceeds 5.0 w / v%, it is economically disadvantageous because the effect commensurate with the blending amount cannot be obtained.

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

[Other ingredients]
The treatment liquid for contact lenses of the present invention may further contain the following components in addition to the copolymer (P), if necessary.

[solvent]
Water can be used as the solvent for the treatment liquid for contact lenses of the present invention, but alcohols such as ethanol, n-propanol, and isopropanol can be used in addition to water.
As the water used for the treatment liquid for contact lenses of the present invention, water used for manufacturing pharmaceuticals and medical devices can be usually used. Specifically, ion-exchanged water, purified water, sterile purified water, distilled water, and water for injection can be used.

[Buffering agent]
The treatment liquid for contact lenses of the present invention may contain a buffer. When the treatment liquid for contact lenses of the present invention contains a buffer, the pH and osmotic pressure can be adjusted, and the wearing feeling when wearing contact lenses can be further improved.
In the present invention, from the viewpoint of obtaining the above effects, one or more selected from a phosphate buffer solution and a borate buffer solution can be used as a buffering agent.
In the present specification, the phosphate buffer is referred to as disodium hydrogen phosphate, sodium dihydrogen phosphate, anhydrous sodium dihydrogen phosphate, potassium dihydrogen phosphate, dipotassium hydrogen phosphate, hydrochloric acid, sodium hydroxide, and hydroxylation. It is a buffer solution made of potassium or the like, and the borate buffer solution is a buffer solution made of boric acid, borosand, hydrochloric acid, sodium hydroxide, potassium hydroxide or the like.
The concentration of the buffering agent in the treatment liquid for contact lenses of the present invention is preferably 0.0001 to 15.0 w / v%, more preferably 0.001 to 10.0 w / v%, still more preferably 0.01 to 0.01. It is 5.0 w / v%.
In particular, when one or more selected from a phosphate buffer solution and a borate buffer solution is used as the buffering agent, the concentration thereof is preferably 0.001 to 10 as the total of the components of the phosphate buffer solution and the borate buffer solution. It is 0 w / v%, more preferably 0.01 to 5.0 w / v%, and even more preferably 0.1 to 5.0 w / v%.

[Additive]
The treatment liquid for contact lenses of the present invention may further contain an additive, if necessary.
Examples of the additive include those used in conventional contact lens applications, such as vitamins, amino acids, sugars, refreshing agents, inorganic salts, organic acid salts, acids, bases, and antioxidants. Agents, stabilizers, preservatives and the like can be mentioned.

Examples of vitamins include flavin adenine dinucleotide sodium, cyanocobalamin, retinyl acetate, retinol palmitate, pyridoxine hydrochloride, panthenol, sodium pantothenate, calcium pantothenate and the like.
Examples of amino acids include aspartic acid and salts thereof, aminoethyl sulfonic acid and the like.
Examples of the saccharide include glucose, mannitol, sorbitol, xylitol, trehalose and the like.
Examples of the refreshing agent include menthol and camphor.
Examples of the inorganic salts include sodium chloride, potassium chloride, magnesium chloride, calcium chloride 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 the like.
Examples of the base include trishydroxymethylaminomethane and monoethanolamine.
Examples of the antioxidant include tocopherol 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, chlorobutanol, polyhexanide hydrochloride and the like.
Further, from the viewpoint of moisturizing contact lenses and improving the wearing feeling, polyethylene glycol, poloxamer, sodium alginate, hydroxypropylmethyl cellulose, hydroxyethyl cellulose, sodium hyaluronate, sodium chondroitin sulfate and the like may be used.

Among these other components, it is preferable to add sodium chloride or potassium chloride, which are inorganic salts, from the viewpoint of adjusting the osmotic pressure of the treatment liquid for contact lenses to a suitable range. Inorganic salts can also be used as a physiological saline solution (for example, ISO physiological saline solution) together with a buffer.
Polyethylene glycol, sodium alginate, poloxamer, hydroxypropylmethylcellulose, hydroxyethylcellulose, hyaluronic acid from the viewpoint of further enhancing the effect of imparting durable surface hydrophilicity and surface wettability of the contact lens treatment liquid, that is, the antifog effect. It is preferable to add sodium or sodium chondroitin sulfate.

When the treatment liquid for contact lenses of the present invention contains an additive, the concentration thereof is preferably 0.001 to 10.0 w / v%, more preferably 0.001 to 7. It is 0w / v%.
In particular, when the treatment liquid for contact lenses of the present invention contains sodium chloride, the concentration thereof is preferably 0.01 to 1.5 w / v%, more preferably 0.05 to 1.3 w / v%, still more preferably. Is 0.1 to 1.0 w / v%.
On the other hand, when the treatment liquid for contact lenses of the present invention contains potassium chloride, the concentration thereof is preferably 0.01 to 4.0 w / v%, more preferably 0.05 to 3.5 w / v%, and further. It is preferably 0.1 to 3.0 w / v%.

[Manufacturing method of treatment liquid for contact lenses]
The treatment liquid for contact lenses of the present invention can be produced by a general method for producing a treatment liquid for contact lenses, in which the copolymer (P) and, if necessary, other components are mixed and stirred. The obtained treatment liquid for contact lenses may be subjected to operations such as aseptic filtration and autoclave, if necessary.

[PH of treatment liquid for contact lenses]
From the viewpoint of improving the wearing feeling, the pH of the treatment liquid for contact lenses of the present invention is preferably 3.0 to 8.0, more preferably 3.5 to 7.8, and even more preferably 4.0 to 7. 6, more preferably 4.5 to 7.5.
The pH of the contact lens treatment solution in the present specification refers to a value measured according to the 17th revised Japanese Pharmacopoeia General Test Method 2.54 pH measurement method.

[Osmotic pressure and osmotic pressure ratio of treatment liquid for contact lenses]
The osmotic pressure of the treatment liquid for contact lenses of the present invention is preferably 200 to 400 mOsm, more preferably 225 to 375 mOsm, still more preferably 230 to 350 mOsm, still more preferably 240 to 340 mOsm, from the viewpoint of improving the wearing feeling. .. The osmotic pressure ratio is preferably 0.7 to 1.4, more preferably 0.7 to 1.3, and even more preferably 0.8 to 1.2.
The osmotic pressure of the treatment liquid for contact lenses in the present specification refers to a value measured according to the 17th revised Japanese Pharmacy General Test Method 2.47 osmotic pressure measurement method (osmolal concentration measurement method), and the osmotic pressure ratio can be obtained. It refers to the value obtained by dividing the osmotic pressure value by the osmotic pressure value (286 mOsm) of 0.9 mass% physiological saline.

[Contact lenses and their constituents]
Any contact lens can be used as a contact lens using the treatment liquid for contact lenses of the present invention. Specifically, it can be used for soft contact lenses, hard contact lenses, intraocular lenses and the like, and among them, it is preferably used for hard contact lenses, and hard contact lenses having a water content of less than 10% are particularly preferable.

The material used for the hard contact lens is not particularly limited, and can be appropriately selected and used from the known materials used for the conventional hard contact lens. Examples of the material used for the hard contact lens include those made of a copolymer containing components such as a fluorine-containing (meth) acrylate, a silicon-containing (meth) acrylate, a crosslinked monomer, and a hydrophilic monomer.
Examples of the fluorine-containing (meth) acrylate include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,2,2', 2', 2'-hexafluoroisopropyl (meth) acrylate, 2, 2,3,3,4,4,4-heptafluorobutyl (meth) acrylate, 2,2,3,3,4,5,5,6,6,7,7,8,8,8- Pentadecafluorooctyl (meth) acrylate, 2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluorononyl (meth) acrylate, etc. Fluoroalkyl (meth) acrylate and the like can be mentioned.
Examples of the silicon-containing (meth) acrylate include tris (trimethylsiloxy) silylpropyl (meth) acrylate, heptamethyltrisiloxanylethyl (meth) acrylate, pentamethyldisiloxanyl (meth) acrylate, and isobutylhexamethyltri. Syroxanyl (meth) acrylate, methyldi (trimethylsiloxy)-(meth) acrylic oxymethylsilane, n-propyl octamethyltetrasiloxanylpropyl (meth) acrylate, pentamethyldi (trimethylsiloxy)-(meth) acrylicoxymethylsilane , T-butyltetramethyldisiloxanyl ethyl (meth) acrylate and other siloxanyl (meth) acrylates, as well as trimethylsilyl (meth) acrylate, phenyldimethylsilylmethyl (meth) acrylate and the like.
Examples of the crosslinked monomer include alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and diethylene glycol di (meth) acrylate, or trimethylolpropane tri (meth) acrylate, pentaerythritol tetra or tri (meth) acrylate. Examples thereof include bifunctional or higher monomers such as.
Examples of the hydrophilic monomer include hydroxyl group-containing (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth) acrylate, acrylic acid, and methacrylic acid. Examples thereof include unsaturated carboxylic acids such as itaconic acid, fumaric acid, maleic acid and silicic acid, (meth) acrylamides such as acrylamide, methacrylic acid, dimethylacrylamide and diethylacrylamide, vinylpyridine and vinylpyrrolidone.

Among the components constituting these hard contact lenses, acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, and silica acid, from the viewpoint of efficiently adsorbing and binding the copolymer (P) to the surface of the hard contact lens. It is preferable to use a hard contact lens having a carboxylic acid group containing unsaturated carboxylic acids such as skin acid. Above all, it is particularly preferable to use a hard contact lens containing acrylic acid and methacrylic acid.

When acrylic acid and methacrylic acid are contained in a hard contact lens using the treatment liquid for contact lenses of the present invention, the amount thereof may be any, but is preferably 0.1 to 50 w / v%, more preferably 0.5 to 0.5 to 50 w / v%. It is 30 w / v%, more preferably 1 to 15 w / v%.

Hereinafter, the treatment liquid for contact lenses of the present invention will be specifically described with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited thereto. The copolymers and polymers used in Examples and Comparative Examples are as follows.

<Copolymer (P)>
As the copolymer (P), the following copolymers (1) to (4) were used.

Copolymer (1)
2-Methylloyloxyethyl phosphorylcholine as the hydrophilic monomer represented by the general formula (1a), 2-hydroxy-3 as the quaternary ammonium group-containing (meth) acrylic monomer represented by the general formula (1b) -Using methacryloyloxypropyltrimethylammonium chloride, 2-methacryloyloxyethylphosphorylcholine 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride copolymer (copolymer composition (molar ratio) 70/30, weight average molecular weight: 450 000) was obtained.

Copolymer (2)
2-Methylloyloxyethyl phosphorylcholine as the hydrophilic monomer represented by the general formula (1a), 2-hydroxy-3 as the quaternary ammonium group-containing (meth) acrylic monomer represented by the general formula (1b) -Using methacryloyloxypropyltrimethylammonium chloride, 2-methacryloyloxyethylphosphorylcholine 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride copolymer (copolymer composition (molar ratio) 90/10, weight average molecular weight: 310 000) was obtained.

Copolymer (3)
2-Methylloyloxyethyl phosphorylcholine as the hydrophilic monomer represented by the general formula (1a), 2-hydroxy-3 as the quaternary ammonium group-containing (meth) acrylic monomer represented by the general formula (1b) -Using methacryloyloxypropyltrimethylammonium chloride, 2-methacryloyloxyethylphosphorylcholine 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride copolymer (copolymer composition (molar ratio) 60/40, weight average molecular weight: 500 000) was obtained.

Copolymer (4)
2-Methylloyloxyethyl phosphorylcholine as the hydrophilic monomer represented by the general formula (1a), 2-hydroxy-3 as the quaternary ammonium group-containing (meth) acrylic monomer represented by the general formula (1b) -Using methacryloyloxypropyltrimethylammonium chloride, 2-methacryloyloxyethylphosphorylcholine 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride copolymer (copolymer composition (molar ratio) 15/85, weight average molecular weight: 456 000) was obtained.

<Measurement of weight average molecular weight>
5 mg of the obtained polymer was dissolved in 1 g of a 0.1 mol / L sodium sulfate aqueous solution and measured. Other measurement conditions are as follows.
Column: PLgel-mixed-C
Mobile phase: Methanol / chloroform mixed solution (80/20, V / V)
Standard substance: Polyethylene glycol Detector: Differential refractometer RI-8020 (manufactured by Tosoh Corporation)
Calculation method of weight average molecular weight: Molecular weight calculation program (GPC program for SC-8020)
Flow rate: 1.0 mL / min
Injection volume: 100 μL
Column oven: 40 ° C
Measurement time: 60 minutes

<Comparative polymer>
The following polymers (A), (B), (C) and (D) were used as comparative polymers of the copolymer (P).

Polymer (A)
A 2-methacryloyloxyethyl phosphorylcholine homopolymer (weight average molecular weight 200,000) was used.

Polymer (B)
A commercially available polydimethyldimethylenepyrosodinium solution (40% solution) (Polyquaternium-6, ME Polymer H40W (product name) manufactured by Toho Chemical Industry Co., Ltd., weight average molecular weight 250,000) was used.

Polymer (C)
A 2-methacryloxyethyl phosphorylcholine-methacrylic acid copolymer (molar ratio; 2-methacryloyloxyethylphosphorylcholine: methacrylic acid = 3: 7) (weight average molecular weight 288,000) was used.

Polymer (D)
2-Methylloyloxyethyl phosphorylcholine as the hydrophilic monomer represented by the general formula (1a), 2-hydroxy-3 as the quaternary ammonium group-containing (meth) acrylic monomer represented by the general formula (1b) -Using methacryloyloxypropyltrimethylammonium chloride, 2-methacryloyloxyethylphosphorylcholine 2-hydroxy-3-methacryloxypropyltrimethylammonium chloride copolymer (copolymer composition (molar ratio) 99.5 / 0.5, weight) Average molecular weight: 425,000) was used.

<Adjusting the concentration of the copolymer (1) to the copolymer (4) and the polymer (A) to the polymer (D)>
The copolymers (1) to the copolymer (4) and the polymers (A) to the polymer (D) are described below in advance for the purpose of facilitating handling when used in Examples and Comparative Examples. The concentration was adjusted.
Copolymer (1) to Polymer (4), Polymer (A), Polymer (C) and Polymer (D): (Co) polymer using each (co) polymer and purified water. Was adjusted to a concentration of 5 w / v%.
Polymer (B): The polymer (B) was a 40 w / v% solution and was used as it was.

<Buffers, additives and water>
[ISO saline solution containing buffer and water]
The following solutions were used as buffers, additives and solvents for the treatment liquid for contact lenses of the present invention.
(Preparation of ISO saline solution)
ISO18369-3: 2006, Optics-Contact Lenses Part3: Measurement Methods. According to the above, ISO physiological saline solution was prepared.
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 volume of 1000 mL, and filtered. An ISO physiological saline solution was obtained.
Sodium chloride is manufactured by Kishida Chemical Co., Ltd., sodium hydrogen phosphate twelve hydrate is manufactured by Wako Pure Chemical Industries, Ltd., sodium dihydrogen phosphate dihydrate is manufactured by Wako Pure Chemical Industries, Ltd., and water is ion-exchanged water. Was used.

<Contact lenses>
Examples and Comparative Examples include commercially available Seed Super HiO2 (manufactured by Seed Co., Ltd., hard contact lens, lens material: silicon-containing methacrylate compound, fluorine-containing methacrylate compound, MMA (methyl methacrylate), MAA (methacrylic acid), etc. EGDMA (ethylene glycol dimethacrylate)) was purchased and used.

<Pretreatment of contact lenses>
Contact lenses were pretreated and prepared according to the following procedure.
(1) 10 mL or more of ISO physiological saline was put into a 15 mL centrifuge tube, the contact lens was taken out from the package, put into the 15 mL centrifuge tube, and shaken for 2 hours.
(2) Remove the ISO saline solution in the centrifuge tube, add 10 mL or more of the ISO saline solution again, and shake overnight.
(3) The contact lens was taken out from the 15 mL centrifuge tube, the water was lightly wiped off, and the contact lens was placed in a newly prepared 15 mL centrifuge tube. Further, 10 mL or more of the Example or Comparative Example was added and shaken for 2 hours.
(4) The liquid of Example or Comparative Example was removed from the 15 mL centrifuge tube, 10 mL or more of the liquid of a new Example or Comparative Example was added again, and an autoclave (121 ° C., 20 minutes) treatment was performed.
(5) The contact lens was taken out and transferred to a contact lens case. At the same time, the liquid of the example or the comparative example was filled in the contact lens case.
(6) It was used for the WBUT test of contact lenses and the contact angle test of contact lenses.

<WBUT (Water Breaking Up Time) test and contact angle test of contact lenses>
A WBUT test of contact lenses was performed according to the following procedure.
(1) The contact lens was picked up from the contact lens case with tweezers and slowly pulled up.
(2) Time measurement was started from the time when the pulled contact lens was pulled up to a height where it did not come into contact with the liquid surface.
(3) When the liquid film formed on the surface of the contact lens was cut off, the time was recorded and used as WBUT (before scrubbing).
(4) The liquid remaining on the surface of the contact lens was removed, and the contact angle (before scrubbing) of the surface of the hard contact lens was measured using a contact angle device (DropMaster500, manufactured by Kyowa Interface Science Co., Ltd.).
(5) Before scrubbing After the measurement was completed, the contact lens was placed on the index finger, and scrubbing was performed 20 times using the thumb and index finger.
(6) After scrubbing, the contact lens was immersed in the ISO saline solution using tweezers.
(7) The operations of (2), (3) and (4) were performed again, and the WBUT (after scrubbing) and the contact angle (after scrubbing) were measured.

For WBUT measurement and contact angle measurement, each measurement is repeated 3 times, and the average value of each is WBUT (before scrubbing), WBUT (after scrubbing), contact angle (before scrubbing) and contact angle (after scrubbing). ) Was evaluated.
The larger the value of WBUT, the better the hydrophilicity, and the smaller the value of the contact angle, the better the hydrophilicity.
WBUT: It was judged to have surface hydrophilicity in 3 seconds or more, excellent surface hydrophilicity in 5 seconds or more, and extremely excellent surface hydrophilicity in 7 seconds or more.
Contact angle: It was judged to have surface wettability at 70 ° or less, excellent surface wettability at 60 ° or less, and extremely excellent surface wettability at 55 ° or less.
Anti-fog if it has surface hydrophilicity, excellent surface hydrophilicity or extremely excellent surface hydrophilicity, and surface wettability, excellent surface wettability or extremely excellent surface wettability before and after scrubbing. It was judged to have an effect (durable surface hydrophilicity and surface wettability).

(Example 1)
To about 80 mL of ISO physiological saline, 2 mL of a 5 w / v% solution of the copolymer (1) was added, and the mixture was stirred and dissolved. A treatment solution for contact lenses was prepared by adding an ISO physiological saline solution so that the total volume was 100 mL, and this was used as Example 1 (the pure content concentration of the copolymer (1) was 0.1 w / v). %).
A WBUT test of a contact lens and a contact angle test of a contact lens were performed using Example 1. The results are shown in Table 1.

(Examples 2 to 6 and Comparative Examples 1 to 6)
Treatment solutions for contact lenses of Examples 2 to 6 and Comparative Examples 1 to 6 were prepared in the same manner as in Example 1 except that the formulations shown in Tables 1 and 2 were followed.
A WBUT test of a contact lens and a contact angle test of a contact lens were performed using each of the prepared Examples and Comparative Examples. The results are shown in Tables 1 and 2.

From the results of Tables 1 and 2, regarding the WBUT test, in Examples 1 to 6, the WBUT evaluation (before scrubbing) 5.1 to 15.4 and the WBUT evaluation (after scrubbing) 3.1 to 5 It became 3.3. On the other hand, in Comparative Examples 1 to 6, the WBUT evaluation (before scrubbing) was 2.1 to 3.6, and the WBUT evaluation (after scrubbing) was 0.5 to 0.6.
Regarding the contact angle test, in Examples 1 to 6, the contact angle evaluation (before scrubbing) was 45.1 to 56.0, and the contact angle evaluation (after scrubbing) was 54.7 to 70.0. rice field. On the other hand, in Comparative Examples 1 to 6, the contact angle evaluation (before scrubbing) was 60.7 to 81.2, and the contact angle evaluation (after scrubbing) was 92.8 to 94.6.
From the above, the contact lenses treated with the treatment liquids for contact lenses containing the copolymers (1) to (4) showed surface hydrophilicity and surface wettability, respectively, before and after scrubbing. Therefore, it was confirmed that the treatment liquid for contact lenses containing the copolymers (1) to (4) can impart an anti-fog effect (durable surface hydrophilicity and surface wettability).

(Examples 7 to 13)
The contact lens treatment liquids of Examples 7 to 13 were prepared in the same manner as in Example 1 except that the formulations shown in Table 3 were followed. The WBUT test of the contact lens and the contact angle test of the contact lens were performed using each of the prepared examples. The results are shown in Table 3.

Sodium chloride is manufactured by Otsuka Pharmaceutical Co., Ltd., potassium chloride is manufactured by Nichiiko Co., Ltd., boric acid is manufactured by Wako Pure Chemical Industries, Ltd. Company-made, sodium dihydrogen phosphate manufactured by Wako Pure Chemical Industries, Ltd., polyethylene glycol manufactured by Macrogor 4000 (manufactured by Nichiyu Co., Ltd.), poroxamar by Unilube 70DP-950B (manufactured by Nichiyu Co., Ltd.), sodium alginate manufactured by Wako Jun Yakuhin Kogyo Co., Ltd., hydroxypropylmethyl cellulose manufactured by 60SH-50, Shinetsu Chemical Industry Co., Ltd., hydroxyethyl cellulose manufactured by SE900, Daicel FineChem Co., Ltd., chondroitin sodium sulfate manufactured by Sigma Aldrich Japan, and sodium hyaluronate manufactured by Sigma Aldrich. Made by Japan, ion-exchanged water was used as the water.

From the results in Table 3, for the WBUT test, the WBUT evaluation (before scrubbing) was 7.2 to 18.9, and the WBUT evaluation (after scrubbing) was 5.8 to 12.3, showing high WBUT values.
The contact angle test was 41.1 to 48.5 for contact angle evaluation (before scrubbing) and 52.3 to 58.9 for contact angle evaluation (after scrubbing).
From the above, the contact lenses treated with the treatment liquid for contact lenses containing the copolymers (1) to (4) and the additive showed excellent surface hydrophilicity and surface wettability before and after scrubbing, respectively. Therefore, it was confirmed that the treatment liquid for contact lenses containing the copolymers (1) to (4) and the additive can impart an anti-fog effect (durable surface hydrophilicity and surface wettability).

Contact lenses, especially hard contact lenses containing carboxylic acids such as methacrylic acid, tend to adsorb lipids and proteins. Lipids and proteins adsorbed on the surface of contact lenses cause contact lens wearers to feel cloudy.
By containing the cationic copolymer (P), the treatment liquid for contact lenses of the present invention electrically interacts with the carboxylic acid group on the surface of the contact lens and suppresses the adsorption of the cationic protein. ..
Further, the treatment liquid for contact lenses of the present invention imparts durable surface hydrophilicity and surface wettability to the contact lens surface, and suppresses the adsorption of hydrophobic lipids.
As is clear from the results in Tables 1 to 3, the treatment liquid for contact lenses of the present invention containing the cationic copolymer (P) has surface hydrophilicity that can withstand scrubbing against the contact lens surface. The surface wettability, that is, the anti-fog effect could be imparted.
Further, the treatment liquid for contact lenses of the present invention has durability when it contains polyethylene glycol, sodium alginate, poroxamar, hydroxypropylmethyl cellulose, hydroxyethyl cellulose, sodium hyaluronate or sodium chondroitin sulfate as other components (additives). Certain surface hydrophilicity and surface wettability, that is, anti-fog effect, was further enhanced.

By using the treatment liquid for contact lenses of the present invention for contact lenses, surface hydrophilicity and surface wettability can be imparted to the contact lens surface, whereby an excellent anti-fog effect can be exhibited.

Claims (4)

It is composed of only the structural units represented by the following formulas (1a) and (1b), the molar ratio na: nb of each structural unit is 15 to 99: 1 to 85, and the weight average molecular weight is 10,000 to 5, A treatment liquid for contact lenses containing 0.001 to 5.0 w / v% of a copolymer (P) of 1,000,000.

[In the formulas (1a) and (1b), R ¹ and R ² are independently hydrogen atoms or methyl groups, and R ³ , R ⁴ and R ⁵ are independently hydrogen atoms or carbon atoms 1 to 8, respectively. Indicates an alkyl group of, ^and X- indicates a halogen ion or an acid residue. ]

The treatment liquid for contact lenses according to claim 1, wherein the contact lens is a hard contact lens.
The treatment liquid for contact lenses according to any one of claims 1 or 2 , which is a shipping liquid for contact lenses.
The treatment liquid for contact lenses according to any one of claims 1 or 2 , which is a care product for contact lenses.