Copolymers and processing solutions for contact lenses

Abstract

To provide a treatment solution for soft contact lenses that can easily impart hydrophilicity and lubricity to the surface of soft contact lenses, and that exhibits excellent durability. [Solution] The copolymer (P) has a constituent unit (A) represented by the following formula (A), and a constituent unit (B) obtained by polymerizing a monomer having a polyalkylene glycol structure, and the molar ratio of the constituent unit (A) to the whole copolymer (P) is n A The molar ratio of the constituent unit (B) is 10-80 mol%, and n B A copolymer having a molecular weight of 20-90 mol% and a weight-average molecular weight of 10,000-2,000,000. TIFF2026081357000028.tif60132

Description

[Technical Field]

[0001] This invention relates to copolymers and processing solutions for contact lenses. [Background technology]

[0002] Conventionally, surface treatment agents containing phosphorylcholine group copolymers have been widely proposed to impart surface hydrophilicity, biocompatibility, antithrombotic properties, and other characteristics derived from the phosphorylcholine group to the surfaces of various materials. Their applications include hydrophilization treatment to make hydrophobic substrates hydrophilic, antifouling treatment of industrial filter surfaces, and surface treatment to suppress the adsorption of proteins and cells onto medical polymer materials. In recent years, they have been particularly used in soft contact lenses.

[0003] The comfort of wearing soft contact lenses is greatly influenced by the hydrophilicity and lubricity of the lens surface. Maintaining these properties in good condition for extended periods is crucial for sustained comfort throughout the day.

[0004] As a technology for maintaining the comfort of wearing lenses, for example, the technologies described in Patent Documents 1 and 2 are known. Patent Document 1 discloses a technology in which a soft contact lens is subjected to plasma treatment and hydrophilized treatment with zwitterionic groups. Patent Document 2 discloses a technology in which a soft contact lens containing reactive groups is chemically reacted and bonded with a hydrophilic polymer having reactive groups to hydrophilize the surface of the soft contact lens. These technologies impart hydrophilicity to the surface of the soft contact lens itself by treating it, and because the treatment process is complex, it requires highly controlled manufacturing equipment tailored to the treatment technology, which has been economically disadvantageous.

[0005] As a technology to solve such problems, for example, Patent Documents 3, 4, and 5 describe a technique that improves the wearing comfort of soft contact lenses by incorporating polyethylene glycol or cellulose-based polymers into a treatment solution for soft contact lenses to impart and enhance hydrophilicity to the surface of the soft contact lens.

[0006] Furthermore, phosphorylcholine group-containing polymers are known to have excellent properties such as being highly hydrophilic and highly moisturizing, as they possess a phospholipid-like structure derived from biological membranes. For example, Patent Document 6 discloses a technology that improves the wearing comfort of soft contact lenses by adding a copolymer of a phosphorylcholine group-containing monomer and butyl methacrylate to a treatment solution. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2010 / 092686 [Patent Document 2] International Publication No. 2001 / 074932 [Patent Document 3] International Publication No. 2009 / 032122 [Patent Document 4] International Publication No. 2012 / 098653 [Patent Document 5] International Publication No. 2008 / 060798 [Patent Document 6] U.S. Patent Application Publication No. 2009 / 0100801 [Overview of the project] [Problems that the invention aims to solve]

[0008] However, while contact lenses using the soft contact lens processing solutions described in Patent Documents 3, 4, 5, and 6 offer excellent comfort during the initial period of wear, the copolymer and its components do not adsorb sufficiently to the contact lens surface, resulting in only a temporary sustained good wearing comfort.

[0009] In view of the above problems, the present invention aims to provide a copolymer that can easily impart hydrophilicity and lubricity to the surface of soft contact lenses and maintain these properties for a long period of time, as well as a contact lens treatment solution using the same. [Means for solving the problem]

[0010] As a result of intensive studies, the present inventors have found that a novel copolymer obtained by copolymerizing at least two specific monomers can achieve the above object, and have completed the present invention.

[0011] That is, the present invention consists of the following [1] to [4]. [1]. A copolymer having structural units represented by the following formulas (A) and (B), wherein the molar ratio n of the structural unit represented by the following formula (A) to the whole copolymer A is 10 to 80 mol%, and the molar ratio n of the structural unit represented by the following formula (B) to the whole copolymer B is 20 to 90 mol%, and the weight average molecular weight is 10,000 to 2,000,000. [Chemical formula] [Chemical formula] [In the above formulas (A) and (B), R 1 and R 2 each independently represent a hydrogen atom or a methyl group. X in formula (A) is O or NR 3 , where R 3 is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 4 O in formula (B) represents an oxyalkylene group having 2 to 4 carbon atoms, R 4 O contains at least two oxyalkylene groups having different carbon numbers, and their addition forms may be either block or random, and p represents the average addition molar number of oxyalkylene groups, which is a number from 4 to 100.] [2]. The copolymer according to [1], wherein the copolymer has a structural unit represented by the following formula (C) or (D), and the total of the molar ratios n C and n D is more than 0 mol% and 50 mol% or less. [Chemical formula] [ka] [ka] [In the above formula (C), R 5 is H or a methylene group, R 6 is an alkyl group having 1 to 5 carbon atoms, or R 5 If it is a methylene group, the terminal is R 5 It is an alkylene group having 1 to 5 carbon atoms that is bonded to and forms a cyclic structure. In formula (D), R 7 is a hydrogen atom or a methyl group, and Y is O or NR 10 , here, R 10 is H or an alkyl group having 1 to 4 carbon atoms, and if Y is O, then E 1 This is a structure represented by equation (E), where Y is NR 10 In the case of E 1 R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms or a structure represented by formula (E). In formula (E), R 8 H or an alkyl group having 1 to 4 carbon atoms, R 9 [This is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.] [3] The copolymer according to [1] or [2], wherein the constituent unit (A) is a constituent unit derived from 2-(methacryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate. [4] A treatment solution for contact lenses containing 0.001 w / v% or more and 5.0 w / v% or less of the copolymer (P) described in any one of items [1] to [3]. [Effects of the Invention]

[0012] The copolymer of the present invention can impart excellent hydrophilicity and lubricity, as well as their persistence, to the surface of soft contact lenses. Therefore, the copolymer of the present invention is suitable as a treatment solution for soft contact lenses. [Brief explanation of the drawing]

[0013] [Figure 1]Figure 1 is a diagram illustrating wb and wf in a chromatogram (vertical axis: refractive index intensity, horizontal axis: retention time). [Modes for carrying out the invention]

[0014] The present invention will be described in detail below.

[0015] In this specification, "(meth)acrylate" means "acrylate or methacrylate," and the same applies to other similar terms. Furthermore, in this specification, alkyl groups may be linear or branched.

[0016] In this specification, "all day" refers to the period from the start of contact lens insertion to the end of contact lens insertion, assuming continuous wear of 8 to 16 hours. "Long duration" refers to the entire day's wear of contact lenses.

[0017] Furthermore, when preferred numerical ranges (e.g., ranges for concentration or weight-average molecular weight) are described in steps in this specification, each lower and upper limit can be combined independently. For example, in the description "preferably 10 or more, more preferably 20 or more, and preferably 100 or less, and more preferably 90 or less," the "preferred lower limit: 10" and the "more preferred upper limit: 90" can be combined to get "10 or more and 90 or less." Similarly, in the description "preferably 10 to 100, more preferably 20 to 90," the range can be changed to "10 to 90."

[0018] Product forms of compositions containing the copolymer of the present invention include compositions applied directly to the eye and compositions used to process devices worn on the eye, such as contact lenses, and can be specifically described as follows. Specifically, examples include contact lens processing solutions. Furthermore, specific product forms of contact lens processing solutions of the present invention include contact lens packing solutions (contact lens shipping solutions), contact lens storage solutions, contact lens cleaning solutions, contact lens cleaning and storage solutions, contact lens disinfectants, contact lens insertion solutions, and the like.

[0019] In this specification, "shipping solution for soft contact lenses" refers to the solution that is sealed in packaging containers such as blister packages along with the soft contact lenses during distribution. Generally, soft contact lenses are used in a swollen state with an aqueous solution, so the lenses are sealed in packaging containers in a swollen state with the aqueous solution at the time of factory shipment so that they can be used immediately.

[0020] <Copolymer (P)> The copolymer (P) of the present invention contains constituent units represented by the following formulas (A) and (B), and the molar ratio of the constituent unit represented by the following formula (A) to the entire copolymer (P) is n A The molar ratio of the constituent unit represented by the following formula (B) to the entire copolymer (P) is 10-80 mol%, and n B The molecular weight is 20-90 mol%, and the weight-average molecular weight is 10,000-2,000,000.

[0021] [ka] [ka]

[0022] In formulas (A) and (B) above, R 1 and R 2 Each of these independently represents either a hydrogen atom or a methyl group. In formula (A), X is either O or NR 3 , here R3 R in formula (B) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. 4 O represents an oxyalkylene group with 2 to 4 carbon atoms, and R 4 O contains at least two oxyalkylene groups with different numbers of carbon atoms, and their addition can be either block or random; and p indicates the average number of moles of oxyalkylene groups added, and is a number between 4 and 100.

[0023] [Constituent units represented by formula (A)] The copolymer (P) used in the present invention has a structural unit represented by general formula (A). This structural unit is obtained by polymerizing a monomer having a phosphorylcholine structure represented by the following general formula (a) (hereinafter also referred to as "PC monomer"). By including structural units derived from the PC monomer in the copolymer (P), hydrophilicity can be imparted to soft contact lenses.

[0024] [ka] [ka]

[0025] In formulas (A) and (a) above, R 1 represents a hydrogen atom or a methyl group, and X is O or NR 3 , here R 3 This represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

[0026] The PC monomer is preferably 2-((meth)acryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate, and more preferably 2-(methacryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate represented by the following formula (a') (hereinafter also referred to as "2-methacryloyloxyethyl phosphorylcholine").

[0027] [ka]

[0028] Content (molar ratio n) of the constituent unit represented by formula (A) in copolymer (P) A The molar ratio n is 10-80 mol%, preferably 15-75 mol%, more preferably 25-65 mol%, and even more preferably 30-55%. A If the molar ratio is less than 10 mol%, the effect of improving the hydrophilicity of the soft contact lens surface cannot be expected. A If the amount exceeds 80 mol%, the content of the constituent unit represented by formula (B) decreases, reducing the adsorption force of the copolymer (P) to the soft contact lens surface, and resulting in insufficient persistence of good wearing comfort. Also, the molar ratio n A When the ratio is 80 mol% or less, the effect of improving the hydrophilicity and lubricity of the soft contact lens surface can be further enhanced by adjusting the ratio of the constituent units represented by formula (A) and the constituent units represented by formula (B).

[0029] [Constituent units represented by formula (B)] The copolymer (P) used in the present invention has a structural unit represented by the following formula (B). This structural unit is obtained by polymerizing a monomer represented by the following general formula (b), that is, a monomer having a polyalkylene glycol structure (hereinafter also referred to as "PAG monomer"). By including structural units derived from PAG monomers in copolymer (P), a good wearing comfort is maintained when the resulting soft contact lens is worn. Furthermore, by having both the structural unit represented by formula (A) and the structural unit represented by formula (B), the effect of improving the hydrophilicity and lubricity of the soft contact lens surface is further enhanced.

[0030] Furthermore, the copolymer (P) may contain a plurality of structural units represented by (B) below, each having different p values.

[0031] [ka] [ka]

[0032] In the above formulas (B) and (b), R 2 R represents a hydrogen atom or a methyl group. 4 O represents an oxyalkylene group with 2 to 4 carbon atoms, and R 4 O contains at least two oxyalkylene groups with different numbers of carbon atoms. Formula (b) is a polyalkylene glycol mono(meth)acrylate containing at least two of the following oxyalkylene groups: oxyethylene group (-CH2CH2O-), oxypropylene group (-CH(CH3)CH2O-, -CH2CH(CH3)O-), and oxybutylene group (-CH(CH2CH3)CH2O-, -CH2CH(CH2CH3)O-, -CH(CH3)CH(CH3)O-), and R 4 The addition of O can be in either block or random form, and p represents the average number of moles of oxyalkylene groups added, ranging from 4 to 100.

[0033] The oxyalkylene group in formulas (B) and (b) preferably has a form consisting of an oxyethylene group and an oxypropylene group, an oxyethylene group and an oxybutylene group, an oxypropylene group and an oxybutylene group, or an oxypropylene group, an oxyethylene group and an oxybutylene group, and more preferably has a form consisting of an oxyethylene group and an oxypropylene group.

[0034] Furthermore, regarding the number of moles of oxyethylene, oxypropylene, and oxybutylene groups added, the molar ratio of oxyethylene groups to the total number of moles of all oxyalkylene groups is 0-90%, preferably 40-90%, and more preferably 60-80%. The molar ratio of oxypropylene groups is 0-70%, more preferably 10-50%, and the molar ratio of oxybutylene groups is 0-70%, more preferably 0-30%. If the molar ratio of oxyethylene groups is greater than 90%, the relative ratios of oxypropylene and oxybutylene groups decrease, and the adsorption force to the contact lens surface decreases. On the other hand, if the proportions of oxypropylene and oxybutylene groups exceed 70%, the cohesive force between copolymers (P) becomes excessive, and the transparency of the resulting contact lens treatment solution and the contact lenses after treatment deteriorates.

[0035] The monomer represented by formula (b) is calculated from a chromatogram (vertical axis: refractive index intensity, horizontal axis: retention time) obtained by gel permeation chromatography (GPC) measurement using a differential refractometer. b and lol f The ratio w b / w f However, equation (1): 1.10≦w b / w f ≤2.50 (1) (In equation (1), the retention time at the maximum peak height (h) in the chromatogram is t h And, 1 / 10 of the maximum peak height (h 1 / 10 ) Two retention times t f and t b (However, t f <t b ) If we do this, w f is t h and t f The difference (t h -t f ) shows, and w b is t b and t h The difference (t b -t hThis demonstrates that it is preferable to satisfy the relationship between (see Figure 1).

[0036] W of monomer (b) b / w f If the ratio becomes less than 1.10, the bias towards the high molecular weight side in the molecular weight distribution of monomer (b) increases, the concentration of polymerizable functional groups decreases, and the polymerizability of monomer (b) may decrease. From the viewpoint of the polymerizability of monomer (b), w b / w f However, it is preferable that it be 1.20 or higher, and more preferably 1.30 or higher.

[0037] On the other hand, the w of monomer (b) b / w f If the ratio exceeds 2.50, the adsorption force of the copolymer (P) to the soft contact lens surface may decrease. Preferably w b / w f However, it is 2.00 or less, and more preferably 1.80 or less.

[0038] w b / w f The chromatogram (vertical axis: refractive index intensity, horizontal axis: retention time) used to calculate the chromatogram was obtained using the EcoSECGPC calculation program. The system used was an HLC-8320GPC (registered trademark) gel permeation chromatography (GPC) system, with SHODEXKF-G as the guard column and three SHODEXKF804L columns mounted in sequence. The column temperature was 40°C, tetrahydrofuran was flowed at a flow rate of 1 mL / min as the developing solvent, and 0.1 mL of a 0.1 wt% tetrahydrofuran solution of polyalkylene glycol mono(meth)acrylate was injected.

[0039] Content (molar ratio n) of the constituent unit represented by formula (B) in copolymer (P) BThe amount is 20 to 90 mol%, preferably 25 to 85 mol%, more preferably 35 to 75 mol%, and even more preferably 45 to 70 mol%. As described above, since the copolymer (P) used in the present invention has monomers represented by formula (B) as constituent units, the adsorption force of the copolymer (P) to the soft contact lens surface can be improved, resulting in good durability of wearing comfort.

[0040] The content (molar ratio n) of the constituent units represented by formula (B) B ) represents the content (molar ratio n) of the constituent units represented by formula (A). A It is preferable that the amount is greater than ). This further enhances the effect of improving the hydrophilicity and lubricity of the soft contact lens surface. Specifically, the molar ratio n A and molar ratio n B The ratio (n B / n A The value of ) is preferably 0.5 to 7.0, and more preferably 1.0 to 3.0.

[0041] In formula (B) above, p is 4 to 100, preferably 5 to 70, and more preferably 7 to 40. If p is less than 4, the adsorption force of the copolymer (P) to the soft contact lens surface decreases, and if it is greater than 100, the cohesive force between copolymers (P) increases, resulting in a deterioration of the transparency of the resulting contact lens treatment solution and the contact lenses after treatment.

[0042] Formula (b) can be produced by adding ethylene oxide, propylene oxide, and butylene oxide (preferably propylene oxide and ethylene oxide) to a starting material (e.g., 2-hydroxypropyl methacrylate) in the presence of a complex metal cyanide catalyst (hereinafter sometimes referred to as "DMC catalyst"). Specifically, the starting material and the DMC catalyst are added to a reaction vessel, and at least two of ethylene oxide, propylene oxide, and butylene oxide (hereinafter collectively referred to as "alkylene oxides having 2 to 4 carbon atoms") are added continuously or intermittently under stirring in an inert gas atmosphere to carry out addition polymerization. The alkylene oxides having 2 to 4 carbon atoms may be added under pressure or under atmospheric pressure.

[0043] The reaction temperature for adding a C2-C4 alkylene oxide to the starting material is preferably 50°C to 120°C, and more preferably 70°C to 90°C. If the reaction temperature is lower than 50°C, the reaction rate is very low, and if it is higher than 120°C, polymerization of polymerizable groups in the starting material and discoloration problems occur.

[0044] While any known DMC catalyst can be used in this invention, for example, the DMC catalyst described in Japanese Patent Application Publication No. 2022-130139 can be used.

[0045] A particularly preferred DMC catalyst is Zn(II)3[Co(III)(CN)6]2(H2O)4(tert-butyl alcohol)2.

[0046] The amount of DMC catalyst used is not particularly limited, but preferably 0.0001 to 0.1 parts by mass, and more preferably 0.001 to 0.05 parts by mass, per 100 parts by mass of the monomer represented by formula (b). The DMC catalyst may be added to the reaction system all at once at the beginning, or it may be added sequentially in portions. After the polymerization reaction is complete, the DMC catalyst is removed. The catalyst can be removed by known methods such as filtration, centrifugation, or treatment with synthetic adsorbents.

[0047] In reactions in which a C2-C4 alkylene oxide is added to a starting material, other additives may be used. For example, hydroquinone (HQ), hydroquinone monomethyl ether (MQ), 2,6-di-tert-butylhydroxytoluene (BHT), di-tert-butylhydroxyanisole (BHA), α-tocopherol, β-tocopherol, γ-tocopherol, etc., can be added to the reaction system as polymerization inhibitors. The polymerization inhibitor is preferably MQ and / or BHT, and more preferably BHT. The amount of polymerization inhibitor to be added is preferably 0.001 to 0.3 parts by mass per 100 parts by mass of the total of the starting material (e.g., 2-hydroxypropyl methacrylate) and the C2-C4 alkylene oxide. If this amount is less than 0.001 parts by mass, the function of the polymerization inhibitor will be insufficient, and gelation may occur during the addition of the C2-C4 alkylene oxide. If the amount of this additive is greater than 0.3 parts by mass, the purity of the resulting equation (1b') may decrease.

[0048] [Constituent units represented by formulas (C) and (D)] The copolymer (P) used in the present invention may include a constituent unit represented by the following formula (C) or (D). This constituent unit is obtained by polymerizing monomers represented by the following general formulas (c) and (d), respectively. By including (c) or (d) in the copolymer (P), the adsorption force of the copolymer (P) to soft contact lenses is more easily maintained depending on the type of contact lens, enabling a sustained good wearing comfort.

[0049] [ka] [ka]

[0050] [ka] [ka] [Chemical formula]

[0051] In the above formulas (C) and (c), R 5 is H or a methylene group, and R 6 is an alkyl group having 1 to 5 carbon atoms, or when R 5 is a methylene group, R 5 is an alkylene group having 1 to 5 carbon atoms that is bonded to R 7 and forms a cyclic structure. In formulas (D) and (d), R 10 is a hydrogen atom or a methyl group, and Y is O or NR 10 , where R 1 is H or an alkyl group having 1 to 4 carbon atoms. When Y is O, E 1 has the structure represented by formula (E). When Y is NR 10 , E 1 is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or the structure represented by formula (E). In formula (E), R 8 is H or an alkyl group having 1 to 4 carbon atoms, and R 9 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.

[0052] Examples of the monomer represented by formula (c) include N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylformamide, N-vinylacetamide, N-methyl-N-vinylacetamide, and the like. Examples of the monomer represented by formula (d) include N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-butyl(meth)acrylamide, N-tert-butyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, 2-(acetylamino)ethyl (meth)acrylate, 2-(stearamido)ethyl (meth)acrylate, 2-palmitamidoethyl (meth)acrylate, and the like.

[0053] If the copolymer (P) contains constituent units represented by (C) and (D), the content (molar ratio n) of the constituent unit represented by formula (C) in the copolymer (P) is... C ) and the content (molar ratio n) of the constituent units represented by formula (D) D The total of ) is preferably more than 0 moles and 50 mol% or less, and more preferably between 10 and 50 mol%.

[0054] E in equation (d) above 1 A monomer having formula (E) can be synthesized, for example, by the esterification reaction of an alcohol having an amide structure at its terminus with (meth)acrylic acid or (meth)acrylic acid chloride, as described in Japanese Patent Application Publication No. 2017-160380.

[0055] [Other monomers] The copolymer (P) may also contain other polymerizable monomers other than the PC monomer, PAG monomer, or the constituent units represented by (c) or (d), as long as the effects of the present invention are not impaired. The proportion of the copolymer can be appropriately selected within a range that does not affect the effects of the present invention, but it is preferable that it consists only of the PC monomer and PAG monomer.

[0056] Other monomers include polymerizable monomers selected from, for example, linear or branched alkyl (meth)acrylates, cyclic alkyl (meth)acrylates, aromatic group-containing (meth)acrylates, styrene monomers, vinyl ether monomers, vinyl ester monomers, hydroxyl group-containing (meth)acrylates, carboxyl group-containing monomers, sulfonyl group-containing monomers, and the like.

[0057] Examples of linear or branched alkyl (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, ethylhexyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and the like. Examples of cyclic alkyl (meth)acrylates include cyclohexyl (meth)acrylate. Examples of aromatic group-containing (meth)acrylates include benzyl (meth)acrylate and phenoxyethyl (meth)acrylate. Examples of styrene monomers include styrene, methylstyrene, and chlorostyrene. Examples of vinyl ether monomers include methyl vinyl ether, propyl vinyl ether, butyl vinyl ether, triethylene glycol divinyl ether, and ethylene glycol monovinyl ether. Examples of vinyl ester monomers include vinyl acetate and vinyl propionate. Examples of hydrophilic hydroxyl group-containing (meth)acrylates include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and glycerol (meth)acrylate. Examples of carboxyl group-containing monomers and sulfonyl group-containing monomers include (meth)acrylic acid, styrene sulfonic acid, and (meth)acryloyloxyphosphonic acid.

[0058] [Weight-average molecular weight of copolymer (P)] The weight-average molecular weight of the copolymer (P) is 10,000 to 2,000,000, preferably 20,000 or more, more preferably 30,000 or more, even more preferably 40,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less, and even more preferably 300,000 or less.

[0059] If the weight-average molecular weight is less than 10,000, the adsorption force to the soft contact lens surface will decrease, and the sustained effect of the copolymer (P) on the soft contact lens surface may not be achieved. If the weight-average molecular weight exceeds 2,000,000, the viscosity may increase, making it difficult to handle.

[0060] The weight-average molecular weight of a copolymer (P) is the value obtained by gel permeation chromatography (GPC).

[0061] [Method for producing copolymer (P)] The copolymer (P) can be prepared by copolymerizing the monomers, and is usually a random copolymer, but may also be an alternating copolymer or a block copolymer in which each monomer is regularly arranged, and may have a graft structure in part.

[0062] Specifically, for example, a copolymer (P) can be obtained by radical polymerization of a mixture of the monomers in the presence of a radical polymerization initiator and under an inert gas atmosphere such as nitrogen, carbon dioxide, argon, and helium.

[0063] Radical polymerization can be carried out by known methods such as bulk polymerization, suspension polymerization, emulsion polymerization, and solution polymerization. Solution polymerization is preferred as the radical polymerization method from the viewpoint of purification. The copolymer (P) can be purified by general purification methods such as reprecipitation, dialysis, and ultrafiltration.

[0064] Examples of radical polymerization initiators include azo radical polymerization initiators, organic peroxides, and persulfur oxides. Examples of azo radical polymerization initiators include 2,2'-azobis(2-methylpropionamidine) dihydrochloride (V-50), 2,2'-azobis(2-diaminopropyl) dihydrochloride, 2,2'-azobis(2-(5-methyl-2-imidazolin-2-yl)propane) dihydrochloride, 4,4'-azobis(4-cyanovaleric acid), 2,2'-azobisisobutylamide dihydrate, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobisisobutyronitrile (AIBN). Examples of organic oxides include t-butylperoxyneodecanate (Perbutyl® ND), benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, t-butylperoxyisobutyrate, lauroyl peroxide, t-butylperoxydecanate, and succinate peroxide (succinyl peroxide). Examples of persulfur oxides include ammonium persulfate, potassium persulfate, and sodium persulfate. These radical polymerization initiators can be used individually or in combination of two or more. The amount of 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 3.0 parts by mass, per 100 parts by mass of the total of each monomer.

[0065] The polymerization reaction of 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 react itself. Examples include water, alcohol-based solvents, ketone-based solvents, ester-based solvents, linear or cyclic ether-based solvents, and nitrogen-containing solvents. Examples of alcohol-based solvents include methanol, ethanol, n-propanol, and isopropanol. Examples of ketone solvents include acetone, methyl ethyl ketone, and diethyl ketone. An example of an ester solvent is ethyl acetate. Examples of linear or cyclic ether solvents include ethyl cellosolve and tetrahydrofuran. Examples of nitrogen-containing solvents include acetonitrile, nitromethane, and N-methylpyrrolidone. Among these solvents, a mixed solvent of water and alcohol is preferred.

[0066] [Concentration of copolymer (P)] The processing solution for soft 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, more preferably 0.05 w / v% or more, and 5.0 w / v% or less, preferably 2.0 w / v% or less, and more preferably 1.0 w / v% or less. If the copolymer (P) concentration is less than 0.001 w / v%, the amount of copolymer (P) added is insufficient, and therefore, sufficient hydrophilicity, lubricity, and their persistence cannot be obtained. If it exceeds 5.0 w / v%, aseptic filtration performed during manufacturing may become difficult.

[0067] In this invention, "w / v%" refers to the mass of a certain component in 100 mL of solution, expressed in grams (g). For example, "the treatment solution of this invention contains 1.0 w / v% copolymer (P)" means that 100 mL of the solution contains 1.0 g of copolymer (P).

[0068] As solvents used in the processing solution of the present invention, water, alcohols such as ethanol, n-propanol, isopropanol, glycerol, and propylene glycol, and mixed solvents thereof can be used. Preferably, it is water or a mixed solvent of water and alcohol, and more preferably, it is water.

[0069] The water used in the contact lens processing solution of the present invention can be water that is typically used in the manufacture of pharmaceuticals and medical devices. Specifically, ion-exchanged water, purified water, sterile purified water, distilled water, and water for injection can be used.

[0070] [Other ingredients] In addition to the polymer (P), the contact lens treatment solution of the present invention may contain other components as needed, such as vitamins, amino acids, sugars, viscosity modifiers, cooling agents, inorganic salts, organic acid salts, acids, bases, antioxidants, stabilizers, and preservatives. Examples of vitamins include flavin adenine dinucleotide sodium, cyanocobalamin, retinyl acetate, retinyl palmitate, pyridoxine hydrochloride, panthenol, sodium pantothenate, and calcium pantothenate. Examples of amino acids include aspartic acid or its salts, and aminoethylsulfonic acid. Examples of sugars include glucose, mannitol, sorbitol, xylitol, and trehalose. Examples of viscosity-enhancing agents include hydroxypropylmethylcellulose and hydroxyethylcellulose. Examples of cooling agents include menthol and camphor. Examples of inorganic salts include sodium chloride, potassium chloride, disodium hydrogen phosphate, sodium dihydrogen phosphate, anhydrous sodium dihydrogen phosphate, potassium dihydrogen phosphate, and dipotassium hydrogen phosphate. Examples of organic acid salts include sodium citrate. Examples of acids include phosphoric acid, citric acid, sulfuric acid, acetic acid, hydrochloric acid, and boric acid. Examples of bases include potassium hydroxide, sodium hydroxide, borax, trishydroxymethylaminomethane, and monoethanolamine. Examples of antioxidants include tocopherol acetate and dibutylhydroxytoluene. Examples of stabilizers include sodium edetate, glycine, and taurine. Examples of preservatives include benzalkonium chloride, chlorhexidine gluconate, potassium sorbate, methylparaben, ethylparaben, propylparaben, isopropylparaben, butylparaben, isobutylparaben, polyhexanide hydrochloride, and sulfamexazole.

[0071] [pH of contact lens treatment solution] From the viewpoint of improving wearing comfort, the pH of the contact lens treatment solution of the present invention is preferably 3.0 to 8.0, more preferably 3.5 to 7.8, even more preferably 4.0 to 7.6, and even more preferably 4.5 to 7.5. In this specification, the pH of the contact lens treatment solution refers to the value measured according to the pH measurement method in accordance with the 18th edition of the Japanese Pharmacopoeia, General Test Methods 2.54.

[0072] [Osmotic pressure and osmotic pressure ratio of contact lens treatment solution] From the viewpoint of improving wearing comfort, the osmotic pressure of the contact lens treatment solution of the present invention is preferably 200 to 400 mOsm, more preferably 225 to 375 mOsm, even more preferably 230 to 350 mOsm, and even more preferably 240 to 340 mOsm. 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. In this specification, the osmotic pressure of the contact lens treatment solution refers to the value measured according to the osmotic pressure measurement method (osmolality measurement method) of General Test Methods 2.47 of the 18th edition of the Japanese Pharmacopoeia, and the osmotic pressure ratio refers to the value obtained by dividing the obtained osmotic pressure by the osmotic pressure of 0.9 mass% physiological saline solution (286 mOsm).

[0073] [Method for manufacturing a treatment solution for soft contact lenses] The soft contact lens treatment solution of the present invention can be manufactured by a general method for manufacturing contact lens solutions. For example, it can be manufactured by mixing and stirring a polymer (P), a solvent and other components as needed. The resulting soft contact lens treatment solution may be subjected to sterile filtration or other operations as needed. [Examples]

[0074] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited thereto. The copolymers used in the examples and comparative examples are as follows.

[0075] <Synthesis of compound I represented by formula (b)> [Synthesis Example 1-1] Into a 5 L autoclave equipped with a thermometer, a pressure gauge, a safety valve, a nitrogen gas injection tube, a stirrer, a vacuum exhaust pipe, a cooling coil, and a steam jacket, 500 g of 2-hydroxypropyl methacrylate (HPMA), 0.07 g of a DMC catalyst, and 1.0 g of 2,6-di-tert-butylhydroxytoluene (BHT) were charged. After nitrogen substitution, the temperature was raised to 80°C, and 403 g of propylene oxide (PO) was dropped from the nitrogen gas injection tube under the condition of 0.3 MPa or less. When the changes in the pressure and temperature in the reaction tank over time were measured, after 5 hours, the pressure in the reaction tank decreased rapidly. Then, while maintaining the temperature in the reaction tank at 80°C, a mixture of 262 g of PO and 870 g of ethylene oxide (EO) was gradually dropped from the nitrogen gas injection tube under the condition of 0.5 MPa or less. After the addition was completed, the reaction was carried out at 80°C for 1 hour, the reaction mixture was extracted from the reaction layer, and the reaction mixture was filtered to remove solids, whereby 2 moles of PO was added to HPMA, and then a liquid substance of the monomer of formula (b) in which 1.3 moles of PO and 5.7 moles of EO were randomly added was obtained. When the molecular weight distribution was confirmed by GPC, w b / w f was 1.59. The structure was 1 confirmed by 1H NMR. The DMC catalyst used was synthesized by the procedure described in JP-A-2022-130139.

[0076] [Synthesis of Compound II Represented by Formula (b)] [Synthesis Example 1-2] 520g of HPMA, 0.08g of DMC catalyst, and 1.0g of BHT were charged into a 5L autoclave equipped with a thermometer, pressure gauge, safety valve, nitrogen gas inlet, stirrer, vacuum exhaust pipe, cooling coil, and steam jacket. After nitrogen purging, the temperature was raised to 80°C, and 19g of PO4 was added dropwise from the nitrogen gas inlet under conditions of 0.3 MPa or less. The changes in pressure and temperature in the reaction vessel over time were measured, and after 5 hours, the pressure in the reaction vessel decreased sharply. Subsequently, while maintaining the temperature in the reaction vessel at 80°C, 1111g of EO mixture was gradually added dropwise from the nitrogen gas inlet under conditions of 0.5 MPa or less. After the addition was complete, the reaction was allowed to proceed at 80°C for 1 hour, the reaction mixture was removed from the reaction bed, and the reaction mixture was filtered to remove the solid, yielding a monomer liquid of formula (b) in which 2 moles of PO were added to HPMA, followed by the addition of 7 moles of EO. The molecular weight distribution was confirmed by GPC, and w b / w f It was 1.75. The structure is 1 This was confirmed by 1H NMR.

[0077] <(d) represents the synthesis of MAEM> [Synthesis Examples 1-3] In a 250 mL flask fitted with a thermometer, gas inlet, stirrer, and dropping funnel, 9.28 g of 2-acetamidoethanol and 100 mL of anhydrous dichloromethane were added. After thoroughly replacing the flask with argon gas, 13.15 g of triethylamine was added. The system was then cooled to -15°C, and 11.29 g of methacrylate chloride was slowly added dropwise from the dropping funnel while monitoring the thermometer to maintain a temperature of approximately -9°C. After the addition was complete, the mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered to remove precipitates, and the filtrate was washed sequentially with water, saturated sodium bicarbonate aqueous solution, and saturated sodium chloride aqueous solution. After drying with sodium sulfate, the mixture was concentrated under reduced pressure using a rotary evaporator to obtain an oily substance. Further purification was performed by silica gel chromatography using hexane and ethyl acetate as eluents to obtain the example compound 2-(acetylamino)ethyl methacrylate. The structure is 1 This was confirmed by 1H NMR. Furthermore, 2-(acetylamino)ethyl methacrylate (MAEM) was synthesized according to the procedure described in Japanese Patent Publication No. 2017-160380.

[0078] <Copolymer (P)> In the examples, copolymers 1 to 6 shown below were used as the polymers for implementation.

[0079] MPC: 2-Methacryloyloxyethyl phosphorylcholine (product of NOF Corporation) Compound I: Polyethylene glycol-polypropylene glycol monomethacrylate (random adduct of PO and EO (PO / EO = 3.3 / 5.7 mol), p ≈ 10, w) b / w f =1.59 (combined using synthesis example 1-1) Compound II: Polyethylene glycol-polypropylene glycol monomethacrylate (a block adduct of PO and EO (PO / EO = 2.0 / 7.0 mol), p ≈ 10, w) b / w f =1.75 (combined using synthesis example 1-2) MAEM: 2-(acetylamino)ethyl methacrylate (synthesized in Synthesis Examples 1-3) NVP: N-vinylpyrrolidone (a product of Fujifilm Wako Pure Chemical Industries, Ltd.) Table 1 summarizes the corresponding formulas for the compounds used. [Table 1]

[0080] <Measurement of weight-average molecular weight> One mg of the obtained copolymer was dissolved in one g of mobile phase and measured. Other measurement conditions are as follows. Columns: SB-802.5 HQ + SB-806MN HQ + SB-G Mobile phase: 20 mM phosphate buffer (pH 7.0) Standard substance: polyethylene glycol / oxide Measuring instrument: HLC-8320GPC (manufactured by Tosoh Corporation) Method for calculating weight-average molecular weight: Molecular weight calculation program (EcoSEC Date Analysis) Flow rate: 0.5 mL per minute Injection volume: 100μL Column oven: 45℃ Measurement time: 90 minutes

[0081] <Polymerization of copolymer for example> [Example 1-1] 0.90 g of MPC and 4.18 g of compound I (synthesized in Synthesis Example 1-1) were dissolved in 14.4 g of water and 14.4 g of ethanol. The mixture was placed in a 100 mL four-necked flask, and nitrogen was blown in at a flow rate of 0.2 L / min for 30 minutes (MPC:Compound I = 30:70 (molar ratio)). 0.51 g of perbutyl® ND (PB-ND, manufactured by NOF Corporation) was added at 55°C and the mixture was stirred for 3 hours. The temperature was then raised to 75°C and the polymerization reaction was carried out for a further 2 hours. After the reaction was complete, 14.4 g of water was added, and distillation was carried out for 1 hour. The resulting reaction solution was purified by dialysis to obtain a polymer solution (copolymer 1). The weight-average molecular weight was confirmed by GPC and was 32,100.

[0082] [Examples 1-2] 2.20 g of MPC and 2.92 g of compound I were dissolved in 14.5 g of water and 14.5 g of ethanol, and the mixture was placed in a 100 mL four-necked flask. Nitrogen was blown in at a flow rate of 0.2 L / min for 30 minutes (MPC:compound I = 60:40 (molar ratio)). 0.51 g of PB-ND was added at 55°C and the mixture was stirred for 3 hours. Then, the temperature was raised to 75°C and the polymerization reaction was carried out for a further 2 hours. After the reaction was complete, 14.5 g of water was added and distillation was carried out for 1 hour. The resulting reaction solution was purified by dialysis to obtain a polymer solution (copolymer 2). The weight-average molecular weight was confirmed by GPC and was 150,500.

[0083] [Examples 1-3] 1.70 g of MPC, 5.64 g of Compound I, and 0.66 g of MAEM (synthesized in Synthesis Example 1-3) were dissolved in 16.0 g of water and 16.0 g of ethanol. The mixture was placed in a 100 mL four-necked flask, and nitrogen was blown in at a flow rate of 0.2 L / min for 30 minutes (MPC:Compound I:MAEM = 30:50:20 (molar ratio)). 0.40 g of PB-ND was added at 55°C and the mixture was stirred for 3 hours. The temperature was then raised to 75°C and the polymerization reaction was carried out for a further 2 hours. After the reaction was complete, 16.0 g of water was added, and the mixture was distilled for 1 hour. The resulting reaction solution was purified by dialysis to obtain a polymer solution (copolymer 3). The weight-average molecular weight was confirmed by GPC and was 190,500.

[0084] [Examples 1-4] 2.20 g of MPC, 2.63 g of compound I, and 0.33 g of NVP were dissolved in 14.6 g of water and 14.6 g of ethanol. The mixture was placed in a 100 mL four-necked flask and nitrogen was blown in at a flow rate of 0.2 L / min for 30 minutes (MPC:Compound I:NVP = 50:30:20 (molar ratio)). 0.52 g of PB-ND was added at 55°C and the mixture was stirred for 3 hours. Then, the temperature was raised to 75°C and the polymerization reaction was carried out for a further 2 hours. After the reaction was complete, 14.6 g of water was added and distillation was carried out for 1 hour. The resulting reaction solution was purified by dialysis to obtain a polymer solution (copolymer 4). The weight-average molecular weight was confirmed by GPC and was 100,500.

[0085] [Examples 1-5] 0.50 g of MPC, 4.31 g of compound I, and 0.39 g of MAEM were dissolved in 14.7 g of water and 14.7 g of ethanol. The mixture was placed in a 100 mL four-necked flask and nitrogen was blown in at a flow rate of 0.2 L / min for 30 minutes (MPC:Compound I:MAEM = 15:65:20 (molar ratio)). 0.52 g of PB-ND was added at 55°C and the mixture was stirred for 3 hours. The temperature was then raised to 75°C and the polymerization reaction was carried out for a further 2 hours. After the reaction was complete, 14.7 g of water was added and distillation was carried out for 1 hour. The resulting reaction solution was purified by dialysis to obtain a polymer solution (copolymer 5). The weight-average molecular weight was confirmed by GPC and was 29,500.

[0086] [Examples 1-6] 0.90 g of MPC and 4.22 g of Compound II (synthesized in Synthesis Example 1-2) were dissolved in 14.5 g of water and 14.5 g of ethanol. The mixture was placed in a 100 mL four-necked flask, and nitrogen was blown in at a flow rate of 0.2 L / min for 30 minutes (MPC:Compound II = 30:70 (molar ratio)). 0.51 g of PB-ND was added at 55°C and the mixture was stirred for 3 hours. The temperature was then raised to 75°C and the polymerization reaction was carried out for a further 2 hours. After the reaction was complete, 14.5 g of water was added, and the mixture was distilled for 1 hour. The resulting reaction solution was purified by dialysis to obtain a polymer solution (copolymer 6). The weight-average molecular weight was confirmed by GPC and was 98,500.

[0087] <Copolymer for comparative example> In the comparative examples, the following homopolymers 1 and 2, copolymers 7 and 8, and PVP K30 (polyvinylpyrrolidone K30) were used as comparative polymers.

[0088] <Polymerization of copolymer for comparative example> [Comparative Example 1-1] 5.00 g of MPC was dissolved in 14.2 g of water and 14.2 g of ethanol, and the mixture was placed in a 100 mL four-necked flask. Nitrogen was blown in at a flow rate of 0.2 L / min for 30 minutes. 0.50 g of PB-ND was added at 55°C and the mixture was stirred for 3 hours. Then, the temperature was raised to 75°C and the polymerization reaction was carried out for a further 2 hours. After the reaction was complete, 14.2 g of water was added and distillation was carried out for 1 hour. The resulting reaction solution was purified by dialysis to obtain a polymer solution (homopolymer 1). The weight-average molecular weight was confirmed by GPC and was 300,000.

[0089] [Comparative Example 1-2] 5.10 g of compound I was dissolved in 14.5 g of water and 14.5 g of ethanol, and the mixture was placed in a 100 mL four-necked flask. Nitrogen was blown in at a flow rate of 0.2 L / min for 30 minutes. 0.51 g of PB-ND was added at 55°C and the mixture was stirred for 3 hours. Then, the temperature was raised to 75°C and the polymerization reaction was carried out for a further 2 hours. After the reaction was complete, 14.5 g of water was added and distillation was carried out for 1 hour. The resulting reaction solution was purified by dialysis to obtain a polymer solution (homopolymer 2). The weight-average molecular weight was confirmed by GPC and was 20,000.

[0090] [Comparative Examples 1-3] 3.30 g of MPC and 1.91 g of MAEM were dissolved in 14.8 g of water and 14.8 g of ethanol, and the mixture was placed in a 100 mL four-necked flask. Nitrogen was blown in at a flow rate of 0.2 L / min for 30 minutes (MPC:MAEM = 50:50 (molar ratio)). 0.52 g of PB-ND was added at 55°C and the mixture was stirred for 3 hours. Then, the temperature was raised to 75°C and the polymerization reaction was carried out for a further 2 hours. After the reaction was complete, 14.8 g of water was added and distillation was carried out for 1 hour. The resulting reaction solution was purified by dialysis to obtain a polymer solution (copolymer 7). The weight-average molecular weight was confirmed by GPC and was 53,600.

[0091] [Comparative Examples 1-4] 3.50 g of MPC and 1.54 g of 2-hydroxyethyl methacrylate (HEMA) were dissolved in 14.3 g of water and 14.3 g of ethanol, and the mixture was placed in a 100 mL four-necked flask. Nitrogen was blown in at a flow rate of 0.2 L / min for 30 minutes (MPC:HEMA = 50:50 (molar ratio)). 0.50 g of PB-ND was added at 55°C and the mixture was stirred for 3 hours. Then, the temperature was raised to 75°C and the polymerization reaction was carried out for a further 2 hours. After the reaction was complete, 14.3 g of water was added and distillation was carried out for 1 hour. The resulting reaction solution was purified by dialysis to obtain a polymer solution (copolymer 8). The weight-average molecular weight was confirmed by GPC and was 356,000.

[0092] <Test contact lenses used for evaluation> Lens A: One Day Fine UV Plus soft contact lens (product of Seed Co., Ltd.) Lens B: AQUAFORCE UV soft contact lens (a product of Aime Co., Ltd.)

[0093] <Preparation of physiological saline solution> Physiological saline solution was prepared based on the reference (ISO 18369-3:2017, Ophthalmic Optics-Contact Lenses Part3:Measurement Methods). 8.3g of sodium chloride, 5.993g of sodium hydrogen phosphate dodecahydrate, and 0.528g of sodium dihydrogen phosphate dihydrate were weighed out, dissolved in water to make 1000mL, and filtered to obtain physiological saline solution.

[0094] <Preparation of treatment solution for soft contact lenses> <Example 2-1> A solution of copolymer 1 was dissolved in a predetermined amount of physiological saline to prepare a 5 wt% polymer solution as shown in Table 2 below. Furthermore, 2 g of the polymer solution and 98 g of physiological saline were mixed to prepare a contact lens treatment solution as shown in Table 2 below. The hydrophilicity, lubricity, and durability of test contact lenses treated with this contact lens treatment solution were evaluated. The evaluation results are shown in Table 2 below.

[0095] <Examples 2-2 to 2-9> The hydrophilicity, lubricity, and durability of test contact lenses treated with a contact lens treatment solution prepared according to the same procedure as in Example 1, except for the use of the polymers shown in Tables 2 and 3 below, were evaluated. The evaluation results are shown in Tables 2 and 3 below.

[0096] <Comparative Examples 2-1 to 2-5> The hydrophilicity, lubricity, and durability of test contact lenses treated with a contact lens treatment solution prepared according to the same procedure as in Example 1, except for the polymers and PVP K30 shown in Table 4 below, were evaluated. The evaluation results are shown in Table 4 below.

[0097] <Hydrophilicity Evaluation> In the examples and comparative examples, the surface hydrophilicity of the soft contact lenses was evaluated according to the following procedure. 〇 Evaluation of surface hydrophilicity, simulating the initial wear of soft contact lenses. (1) Add 10 mL of physiological saline to a 15 mL conical tube, immerse 5 test contact lenses removed from the blister pack, and shake at room temperature for 6 hours using a roller mixer at a rotation speed of 50 rpm. (2) The test contact lenses were removed and each lens was placed in a 10 mL glass vial to which 5 mL of the soft contact lens treatment solution prepared individually was added. (3) Sterilized at 121°C for 20 minutes. (4) The test contact lenses were removed from the glass vials, and the time until the water film on the lens surface was broken (BUT) was measured with a stopwatch and evaluated according to the following criteria.

[0098] 〇 Evaluation of surface hydrophilicity of soft contact lenses, assuming the end of wear. (1) Add 10 mL of physiological saline to a 15 mL conical tube, immerse 5 test contact lenses removed from the blister pack, and shake at room temperature for 6 hours using a roller mixer at a rotation speed of 50 rpm. (2) The test contact lenses were removed and each lens was placed in a 10 mL glass vial to which 5 mL of the soft contact lens treatment solution prepared individually was added. (3) Sterilized at 121°C for 20 minutes. (4) Add 2 mL of physiological saline to one well of a 12-well plate, immerse one test contact lens removed from a glass vial, and shake at 80 rpm for 4 hours at 37°C using a shaker. (5) The test contact lenses were removed from the 12-well plate, and the time until the water film on the lens surface broke off (BUT) was measured with a stopwatch and evaluated according to the following criteria.

[0099] In evaluations simulating the end of wear, the actual tear volume and blinking frequency throughout the day are taken into consideration, and the condition of the contact lens after 12 hours of continuous wear is simulated.

[0100] The evaluation criteria are as follows: 4 points: 20 seconds or more 3 points: 15 seconds or more 2 points: 10 seconds or more, less than 15 seconds 1 point: 5 seconds or more, less than 10 seconds 0 points: Less than 5 seconds

[0101] <Lubricity Evaluation> In the examples and comparative examples, the lubricity of the contact lenses was evaluated according to the following procedure. Lubricity evaluation simulating the initial wear of soft contact lenses. (1) Add 10 mL of physiological saline to a 15 mL conical tube, immerse 5 test contact lenses removed from the blister pack, and shake at room temperature for 6 hours using a roller mixer at a rotation speed of 50 rpm. (2) The test contact lenses were removed and each lens was placed in a 10 mL glass vial to which 5 mL of the soft contact lens treatment solution prepared individually was added. (3) Sterilized at 121°C for 20 minutes. (4) The test contact lenses were removed from the glass vials, and the coefficient of friction in physiological saline solution was measured using a nanotribometer NTR3 (probe material: polypropylene, load: 2mN, travel distance: 1.00mm, speed: 0.1mm / s), and evaluated according to the following criteria.

[0102] Lubricity evaluation simulating the end of soft contact lens wear. (1) Add 10 mL of physiological saline to a 15 mL conical tube, immerse 5 test contact lenses removed from the blister pack, and shake at room temperature for 6 hours using a roller mixer at a rotation speed of 50 rpm. (2) The test contact lenses were removed and each lens was placed in a 10 mL glass vial to which 5 mL of the soft contact lens treatment solution prepared individually was added. (3) Sterilized at 121°C for 20 minutes. (4) Add 2 mL of physiological saline to one well of a 12-well plate, immerse one test contact lens removed from a glass vial, and shake at 80 rpm for 4 hours at 37°C using a shaker. (5) Test contact lenses were removed from the 12-well plate, and the coefficient of friction was measured using a nanotribometer NTR3 (probe material: polypropylene, load: 2mN, travel distance: 1.00mm, speed: 0.1mm / s), and evaluated according to the following criteria.

[0103] In evaluations simulating the end of wear, the actual tear volume and blinking frequency throughout the day are taken into consideration, and the condition of the contact lens after 12 hours of continuous wear is simulated.

[0104] The evaluation criteria are as follows: 4 points: Less than 0.30 3 points: 0.30 or higher, less than 0.5 2 points: 0.50 or higher, less than 1.0 1 point: 1.0 or higher, less than 1.5 0 points: 1.5 or higher

[0105] <Sustainability Assessment> In the examples and comparative examples, the durability was evaluated based on the hydrophilicity and lubricity evaluation results, according to the following criteria. ◎: In both evaluations, the scores for the initial and final wear periods are the same. ○: In either evaluation, the score for both the initial and final estimated wear time decreased by 1 point, or in both evaluations, the score for both the initial and final estimated wear time decreased by 1 point. △: In either evaluation, the score for both the initial and final assessments decreased by 2 points. ×: In both evaluations, the score for the initial and final estimated wear decreased by 2 points, or in either evaluation, the score for the initial and final estimated wear decreased by 3 points or more.

[0106] <Wearing comfort evaluation> Regarding the examples and comparative examples, the wearing comfort was evaluated based on the following criteria, using the evaluation results of hydrophilicity and lubricity assumed at the end of wearing. Excellent wearing comfort: Hydrophilicity: 4, Lubricity: 4 Hydrophilicity: 4, Lubricity: 3 Hydrophilicity: 3, Lubricity: 4 Comfortable to wear: Hydrophilicity: 3, Lubricity: 3 : Hydrophilicity: 2, Lubricity: 3 : Hydrophilicity: 3, Lubricity: 2 : Hydrophilicity: 2, Lubricity: 2 Unsatisfactory wearing comfort: Other than the above

[0107] [Table 2]

[0108] [Table 3]

[0109] [Table 4]

[0110] <Rating> The contact lens treatment solutions of Examples 2-2, 2-4, 2-5, and 2-9 were able to impart excellent hydrophilicity and lubricity to the surface of soft contact lenses, both at the start and end of wear, and these properties were very long-lasting. In other words, the contact lens treatment solutions of Examples 2-2, 2-4, 2-5, and 2-9, with their excellent hydrophilicity and lubricity and their long-lasting properties, can provide soft contact lenses with excellent comfort for extended periods. The contact lens treatment solutions of Examples 2-7 and 2-8 were able to impart good hydrophilicity and good lubricity to the surface of soft contact lenses at both the start and end of wear, and these properties were very long-lasting. In other words, the contact lens treatment solutions of Examples 2-7 and 2-8, with their good hydrophilicity, good lubricity and their long-lasting properties, can provide soft contact lenses with a comfortable wearing experience for extended periods. The contact lens treatment solutions of Examples 2-1, 2-3, and 2-6 were able to impart good hydrophilicity and good lubricity to the surface of soft contact lenses at both the start and end of wear, and these properties were also well-lasting. In other words, the contact lens treatment solutions of Examples 2-1, 2-3, and 2-6 can provide soft contact lenses with good hydrophilicity and lubricity and their persistence, resulting in a comfortable wearing experience for extended periods. The contact lens treatment solution in Comparative Example 1-1 showed good hydrophilicity at the start of wear compared to each of the examples, but its persistence was significantly inferior. Although the contact lens treatment solutions in Comparative Examples 1-2 exhibited good hydrophilicity as expected at the start of wear, their lubrication was insufficient, resulting in an unsatisfactory wearing experience. Although the contact lens treatment solutions in Comparative Examples 1-3 exhibited good hydrophilicity as expected at the start of wear, their lubrication was insufficient, and their durability and wearing comfort were also unsatisfactory. Although the contact lens treatment solutions in Comparative Examples 1-4 exhibited good hydrophilicity as expected at the start of wear, their lubricity was insufficient, and their durability was significantly poor. While the contact lens treatment solutions in Comparative Examples 1-5 provided good comfort at the start of wear, their durability was significantly inferior. [Industrial applicability]

[0111] By using the soft contact lens treatment solution of the present invention on soft contact lenses, it is possible to provide soft contact lenses with excellent wearing comfort throughout the day (for extended periods).

Claims

1. The copolymer (P) has constituent units represented by the following formulas (A) and (B), and the molar ratio of the constituent unit represented by the following formula (A) to the entire copolymer (P) is n. Ａ The molar ratio of the constituent unit represented by the following formula (B) to the entire copolymer (P) is 10 to 80 mol%, and n Ｂ A copolymer having a molecular weight of 20 to 90 mol% and a weight-average molecular weight of 10,000 to 2,000,000. 【Chemistry 1】 【Chemistry 2】 [In formulas (A) and (B) above, R １ and R ２ Each of these independently represents a hydrogen atom or a methyl group. In formula (A), X is O or NR ３ Here, R ３ R in formula (B) is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ４ O represents an oxyalkylene group with 2 to 4 carbon atoms, R ４ O contains at least two oxyalkylene groups with different numbers of carbon atoms, and their addition configuration can be either block or random; and p indicates the average number of moles of oxyalkylene groups added, and is a number between 4 and 100.

2. The copolymer (P) has a structural unit represented by the following formula (C) or (D), and the molar ratio n of the structural unit represented by the following formula (C) or (D) to the whole copolymer (P) Ｃ and n Ｄ The total of which is more than 0 mol% and 50 mol% or less. The copolymer according to claim 1 【Transformation 3】 【Chemistry 4】 【Transformation 5】 [In formula (C) above, R ５ is H or a methylene group, R ６ is an alkyl group having 1 to 5 carbon atoms, or R ５ If it is a methylene group, the terminal is R ５ It is an alkylene group having 1 to 5 carbon atoms that is bonded to and forms a cyclic structure. In formula (D), R ７ is a hydrogen atom or a methyl group, and Y is O or NR １０ Here, R １０ is H or an alkyl group having 1 to 4 carbon atoms, and if Y is O, then E １ This is a structure represented by equation (E), where Y is NR １０ In the case of E １ R is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a structure represented by formula (E). In formula (E), R ８ H or an alkyl group having 1 to 4 carbon atoms, R ９ [This is a hydrogen atom or an alkyl group having 1 to 18 carbon atoms.]

3. The copolymer according to claim 1, wherein the constituent unit (A) is a constituent unit derived from 2-(methacryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate.

4. A treatment solution for contact lenses containing 0.001 w / v% or more and 5.0 w / v% or less of the copolymer (P) described in any one of claims 1 to 3.

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