JP4457237B1 - Contact lens solution - Google Patents
Contact lens solution Download PDFInfo
- Publication number
- JP4457237B1 JP4457237B1 JP2009177807A JP2009177807A JP4457237B1 JP 4457237 B1 JP4457237 B1 JP 4457237B1 JP 2009177807 A JP2009177807 A JP 2009177807A JP 2009177807 A JP2009177807 A JP 2009177807A JP 4457237 B1 JP4457237 B1 JP 4457237B1
- Authority
- JP
- Japan
- Prior art keywords
- group
- contact lens
- alkyl
- solution
- methacrylate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000882 contact lens solution Substances 0.000 title claims abstract description 36
- 229920000642 polymer Polymers 0.000 claims abstract description 45
- 150000001875 compounds Chemical class 0.000 claims abstract description 40
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 6
- 125000006165 cyclic alkyl group Chemical group 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- -1 alkyl methacrylate Chemical compound 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 28
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 230000000249 desinfective effect Effects 0.000 claims description 10
- 238000004659 sterilization and disinfection Methods 0.000 claims description 8
- 125000004663 dialkyl amino group Chemical group 0.000 claims description 7
- 230000001954 sterilising effect Effects 0.000 claims description 7
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- 239000002563 ionic surfactant Substances 0.000 claims description 5
- WIYVVIUBKNTNKG-UHFFFAOYSA-N 6,7-dimethoxy-3,4-dihydronaphthalene-2-carboxylic acid Chemical compound C1CC(C(O)=O)=CC2=C1C=C(OC)C(OC)=C2 WIYVVIUBKNTNKG-UHFFFAOYSA-N 0.000 claims description 4
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical group CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims 1
- 125000001421 myristyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims 1
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims 1
- 230000003373 anti-fouling effect Effects 0.000 abstract description 25
- 230000002045 lasting effect Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 35
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 27
- 238000004140 cleaning Methods 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000178 monomer Substances 0.000 description 14
- 230000002209 hydrophobic effect Effects 0.000 description 13
- 230000000844 anti-bacterial effect Effects 0.000 description 12
- 229920001577 copolymer Polymers 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 239000003945 anionic surfactant Substances 0.000 description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 229960003237 betaine Drugs 0.000 description 7
- 150000001767 cationic compounds Chemical class 0.000 description 7
- 230000008859 change Effects 0.000 description 7
- 238000013329 compounding Methods 0.000 description 7
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 6
- 108090000790 Enzymes Proteins 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 229940088598 enzyme Drugs 0.000 description 6
- 230000003993 interaction Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000003204 osmotic effect Effects 0.000 description 6
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 6
- 239000003755 preservative agent Substances 0.000 description 6
- 108091005804 Peptidases Proteins 0.000 description 5
- 102000035195 Peptidases Human genes 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 238000007654 immersion Methods 0.000 description 5
- 239000002736 nonionic surfactant Substances 0.000 description 5
- 239000002689 soil Substances 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 4
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- 229920002413 Polyhexanide Polymers 0.000 description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 125000002091 cationic group Chemical group 0.000 description 4
- 239000000645 desinfectant Substances 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 4
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 4
- 230000002335 preservative effect Effects 0.000 description 4
- 235000018102 proteins Nutrition 0.000 description 4
- 102000004169 proteins and genes Human genes 0.000 description 4
- 108090000623 proteins and genes Proteins 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 235000002639 sodium chloride Nutrition 0.000 description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 3
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 description 3
- 239000012591 Dulbecco’s Phosphate Buffered Saline Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 230000002411 adverse Effects 0.000 description 3
- 239000002280 amphoteric surfactant Substances 0.000 description 3
- 230000036760 body temperature Effects 0.000 description 3
- 239000006172 buffering agent Substances 0.000 description 3
- 239000003093 cationic surfactant Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 125000001453 quaternary ammonium group Chemical group 0.000 description 3
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 2
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- 239000004471 Glycine Substances 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910021538 borax Inorganic materials 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
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- 229960003333 chlorhexidine gluconate Drugs 0.000 description 2
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Abstract
【課題】コンタクトレンズに持続性のある親水性と防汚性を付与できるコンタクトレンズ用溶液を提供することにある。
【解決手段】下記構造式で表される高分子化合物を含むことを特徴とするコンタクトレンズ用溶液。
【化１】
式中、Ｒ１は水素原子又はメチル基を示し、Ｒ２は炭素数１〜２３の直鎖、分岐鎖もしくは環状のアルキル基を示し、Ｒ３〜Ｒ６はそれぞれ炭素数１〜８の直鎖もしくは分岐鎖のアルキル基を示し、ｍ及びｎは１〜４の整数であり、Ｘ、Ｙ、Ｚは正の整数である。
【選択図】なしAn object of the present invention is to provide a contact lens solution capable of imparting a lasting hydrophilic property and antifouling property to a contact lens.
A contact lens solution comprising a polymer compound represented by the following structural formula.
[Chemical 1]
In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a linear, branched, or cyclic alkyl group having 1 to 23 carbon atoms, and R 3 to R 6 are each a straight chain having 1 to 8 carbon atoms. A chain or branched alkyl group is shown, m and n are integers of 1 to 4, and X, Y and Z are positive integers.
[Selection figure] None
Description
本発明は、コンタクトレンズ用溶液に関する。詳しくは、コンタクトレンズ表面に親水性及び防汚性を付与できる洗浄剤や保存剤並びに洗浄保存剤として効果的なコンタクトレンズ用溶液に関する。 The present invention relates to a contact lens solution. Specifically, the present invention relates to a cleaning agent and a preservative that can impart hydrophilicity and antifouling properties to the contact lens surface, and a contact lens solution that is effective as a cleaning preservative.
コンタクトレンズを快適かつ適切に装用するためには、専用の洗浄剤や保存剤を用いた定期的なケアが必要である。従来のコンタクトレンズ用溶液は、装用によりレンズ表面に付着したタンパク質、脂質等を洗浄により除去することを主目的とし、コンタクトレンズの装用感を向上させる効果は少なかった。 In order to wear contact lenses comfortably and appropriately, regular care using special cleaning agents and preservatives is necessary. Conventional contact lens solutions are mainly intended to remove proteins, lipids and the like adhering to the lens surface by wearing, and have little effect on improving the wearing feeling of contact lenses.
装用感を向上させる手段としては、コンタクトレンズ自体の表面を親水性化する方法と、レンズ表面を親水性化できる専用溶液で処理する方法が知られている。例えば、レンズ自体の表面を親水性化する方法としては、親水性高分子をレンズ材料の表面にグラフトする処理が挙げられる。この方法は表面の親水性化と共に汚れ付着の防止に対しても有効ではあるが、繰り返しの装用による経時的な性能の低下が課題となっている。 As means for improving the wearing feeling, a method of making the surface of the contact lens itself hydrophilic and a method of treating with a special solution capable of making the lens surface hydrophilic are known. For example, as a method for making the surface of the lens itself hydrophilic, a treatment of grafting a hydrophilic polymer onto the surface of the lens material can be mentioned. Although this method is effective for making the surface hydrophilic and preventing the adhesion of dirt, the deterioration of performance over time due to repeated wearing is a problem.
一方、専用溶液で処理する方法としては、ポリビニルアルコールやポリビニルピロリドン、ポリオキシエチレンポリオキシプロピレンブロックポリマー等の水溶性高分子を含有する溶液での処理が挙げられる。しかし、ポリビニルアルコールやポリビニルピロリドンは、高い親水性を有し、疎水性の高いレンズ表面とは反発し合うので、持続性のある親水性を付与することはできない。ポリオキシエチレンポリオキシプロピレンブロックポリマーは、親水性部位と疎水性部位を有する非イオン性高分子であり、溶液のｐＨや共存するイオン性成分の影響を受け難く、その上任意のＨＬＢ（親水性／疎水性のバランス）を設定できるため一般的に利用されている。しかし、親水性部位であるポリオキシエチレンの保水力と、疎水性部位であるポリオキシプロピレンのレンズ表面への吸着力とは相反する関係にあるため、その水濡れ性の持続的効果には限界がある。 On the other hand, the method of treating with a dedicated solution includes treatment with a solution containing a water-soluble polymer such as polyvinyl alcohol, polyvinyl pyrrolidone, or polyoxyethylene polyoxypropylene block polymer. However, since polyvinyl alcohol and polyvinyl pyrrolidone have high hydrophilicity and repel each other with a highly hydrophobic lens surface, it is impossible to impart sustained hydrophilicity. The polyoxyethylene polyoxypropylene block polymer is a nonionic polymer having a hydrophilic part and a hydrophobic part, and is hardly affected by the pH of the solution or coexisting ionic components, and also has an arbitrary HLB (hydrophilic property). / Hydrophobicity balance), which is generally used. However, since the water retention capacity of polyoxyethylene, which is a hydrophilic site, and the adsorption capacity of polyoxypropylene, which is a hydrophobic site, to the lens surface are in conflict, there is a limit to the sustained effect of its water wettability. There is.
他の専用溶液で処理する方法としては、例えば、特定の両性界面活性剤とイオン性界面活性剤を組合せた技術（特許文献１参照）、リン脂質極性基を有する（メタ）アクリレートを含む溶液を用いる方法等が開示されている（特許文献２参照）。いずれもコンタクトレンズに付着した汚れを洗浄除去すると共に、レンズ表面に親水性と防汚性の付与を目的とするが、その持続的な効果は期待できず装用感の改善という点で満足できるものではなく、また、殺菌や消毒効果の有効性についても課題がある。 As a method of treating with other dedicated solution, for example, a technique combining a specific amphoteric surfactant and an ionic surfactant (see Patent Document 1), a solution containing a (meth) acrylate having a phospholipid polar group A method to be used is disclosed (see Patent Document 2). Both are intended to clean and remove the dirt adhering to the contact lens, and to impart hydrophilicity and antifouling properties to the lens surface. However, there are also problems regarding the effectiveness of the sterilization and disinfection effects.
例えば、特許文献２で用いられるリン脂質極性基を有する（メタ）アクリレートは、ホスホリルコリン構造を有する両性高分子化合物であるが、中性付近（ｐＨ６．５以上）では、わずかに陰イオン性を示し、ｐＨの上昇に伴って陰イオン性が強まると考えられる。そのため、通常のコンタクトレンズ溶液に適するｐＨ領域（ｐＨ６．５〜７．５）の水溶液中に、殺菌や消毒効果を示す陽イオン性化合物を共存させる場合には、その効果が低下する。この両性高分子化合物を減量したり、ｐＨを酸性側にすることで、陽イオン性化合物の効果への影響は抑制できるが、親水性と防汚性、及び眼に対する安全性において有効ではない。すなわち、特許文献２で用いられる両性高分子化合物をコンタクトレンズ用溶液に用いるには課題を有する。 For example, (meth) acrylate having a phospholipid polar group used in Patent Document 2 is an amphoteric polymer compound having a phosphorylcholine structure, but exhibits a slight anionic property near neutrality (pH 6.5 or higher). It is believed that anionicity increases with increasing pH. Therefore, when a cationic compound exhibiting a bactericidal or disinfecting effect is coexisted in an aqueous solution having a pH range (pH 6.5 to 7.5) suitable for a normal contact lens solution, the effect is reduced. By reducing the amount of the amphoteric polymer compound or making the pH acidic, the effect on the effect of the cationic compound can be suppressed, but it is not effective in terms of hydrophilicity, antifouling properties, and eye safety. That is, there is a problem in using the amphoteric polymer compound used in Patent Document 2 for the contact lens solution.
また、三級アミノ基や四級アンモニウム基を有する陽イオン性の化合物を配合して、洗浄性と同時に防汚性を付与する発明（特許文献３及び４参照）や疎水性モノマーと親水性モノマーとの共重合体を調製してレンズ表面に水膜を形成する発明が開示されている（特許文献５参照）。 In addition, a cationic compound having a tertiary amino group or a quaternary ammonium group is blended to provide an antifouling property as well as a detergency (see Patent Documents 3 and 4), a hydrophobic monomer and a hydrophilic monomer An invention is disclosed in which a water film is formed on the lens surface by preparing a copolymer (see Patent Document 5).
特許文献３及び４では、正電荷を帯びた三級アミノ基系や四級アンモニウム基系高分子によって、レンズ表面に防汚性が付与されるため、タンパク質汚れの付着や蓄積を抑制できるが、レンズ表面に親水性を付与して装用感を向上させることは配慮されていない。 In Patent Documents 3 and 4, antifouling is imparted to the lens surface by a positively charged tertiary amino group-based polymer or quaternary ammonium group-based polymer, so that adhesion and accumulation of protein stains can be suppressed. It is not considered to improve the wearing feeling by imparting hydrophilicity to the lens surface.
また、特許文献５の場合、疎水性モノマーと親水性モノマー更に第三成分として殺菌性モノマーを用いた共重合体によってレンズ表面に親水性と防汚性を付与し、かつ、殺菌や消毒効果を付与するものである。親水性モノマーとしてアニオン性モノマー、カチオン性モノマー、非イオン性モノマー、両性（ベタイン系）モノマーを例示しているが、アニオン性モノマーやカチオン性モノマーを用いた場合前述のように、殺菌や消毒作用を有する陽イオン性の化合物、洗浄作用を有する陰イオン界面活性剤の効果が発揮できない。 In the case of Patent Document 5, hydrophilicity and antifouling properties are imparted to the lens surface by a copolymer using a hydrophobic monomer and a hydrophilic monomer and further a bactericidal monomer as a third component, and a sterilizing and disinfecting effect is provided. It is given. Examples of hydrophilic monomers include anionic monomers, cationic monomers, nonionic monomers, and amphoteric (betaine) monomers. When anionic monomers and cationic monomers are used, as described above, sterilization and disinfection action The effect of a cationic compound having an anionic surfactant having a cleaning action cannot be exhibited.
また、特許文献５では殺菌効果を付与するために第三の共重合成分として陽イオン性化合物の殺菌性モノマーを用いるので、得られる高分子化合物も陽イオン性を示し、洗浄成分である陰イオン界面活性剤と共存させた場合は、殺菌効果が低下するだけでなく、水膜の形成も困難になる等、コンタクトレンズ用溶液に通常配合されるべき界面活性剤との相性について検討すべき課題がある。更に、殺菌性を有する高分子化合物の水膜が眼と長時間接触することは、眼刺激や眼障害の要因となることも考えられ、眼に対する安全性上好ましくない。 In addition, in Patent Document 5, since a bactericidal monomer of a cationic compound is used as the third copolymer component in order to impart a bactericidal effect, the resulting polymer compound also exhibits a cationic property and is an anion that is a cleaning component. When coexisting with a surfactant, not only does the bactericidal effect decrease, but it also makes it difficult to form a water film, etc. Issues that should be examined for compatibility with surfactants that should normally be incorporated into contact lens solutions There is. Furthermore, it is conceivable that a water film of a polymer compound having bactericidal properties is in contact with the eye for a long time, which may cause eye irritation and eye damage, which is not preferable in terms of safety to the eye.
更に、特定の構造式で表されるベタイン構造を有する高分子化合物を含むことを特徴とするコンタクトレンズ用溶液が開示されている（特許文献６参照）。しかしながら、特許文献６で用いられる高分子化合物は、ベタイン構造による良好な親水性を有するものの、四級アンモニウム基の強いカチオン性により、涙液中のアニオン性汚染物質を吸着する恐れがあり、耐汚染性に対し十分満足いくものではなかった。また、コンタクトレンズ基材表面への親水性の付与は、基材表面と高分子化合物中の疎水部の疎水性相互作用によりなされるが、この高分子化合物の親水性／疎水性のバランスが親水性寄りであるため、疎水性相互作用が発現され難く、親水性の持続性に対しても十分満足されるものではなかった。 Furthermore, a contact lens solution characterized in that it contains a polymer compound having a betaine structure represented by a specific structural formula (see Patent Document 6). However, although the polymer compound used in Patent Document 6 has good hydrophilicity due to the betaine structure, there is a risk of adsorbing anionic contaminants in tears due to the strong cationicity of the quaternary ammonium group. It was not satisfactory enough for pollution. In addition, imparting hydrophilicity to the surface of the contact lens substrate is performed by hydrophobic interaction between the substrate surface and the hydrophobic portion in the polymer compound. The hydrophilic / hydrophobic balance of the polymer compound is hydrophilic. Since it is close to nature, hydrophobic interaction is hardly expressed, and the hydrophilic durability is not sufficiently satisfied.
本発明の目的は、コンタクトレンズに持続性のある親水性と防汚性を付与できるコンタクトレンズ用溶液を提供することにある。更に詳細には、持続性のある親水性と防汚性を付与でき、かつ、コンタクトレンズ用溶液に通常配合されるべき陰イオン界面活性剤や陽イオン界面活性剤等の諸成分とを特定の割合で配合できるコンタクトレンズ用溶液を提供することにある。 An object of the present invention is to provide a contact lens solution that can impart persistent hydrophilicity and antifouling property to a contact lens. More specifically, specific components such as an anionic surfactant and a cationic surfactant that are capable of imparting a lasting hydrophilic property and antifouling property and that should normally be incorporated in a contact lens solution are specified. The object is to provide a solution for contact lenses that can be blended in proportions.
本発明者らは、前記の課題に鑑み、鋭意検討した結果、下記構造式で表される高分子化合物を用いることで、上記目的を達成できることを見出した。 As a result of intensive studies in view of the above problems, the present inventors have found that the above object can be achieved by using a polymer compound represented by the following structural formula.
本発明に従って、下記構造式で表される高分子化合物を含むことを特徴とするコンタクトレンズ用溶液が提供される。 According to the present invention, there is provided a contact lens solution comprising a polymer compound represented by the following structural formula.
式中、Ｒ１は水素原子又はメチル基を示し、Ｒ２は炭素数１〜２３の直鎖、分岐鎖もしくは環状のアルキル基を示し、Ｒ３〜Ｒ６はそれぞれ炭素数１〜８の直鎖もしくは分岐鎖のアルキル基を示し、ｍ及びｎは１〜４の整数であり、Ｘ、Ｙ、Ｚは正の整数である。 In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a linear, branched, or cyclic alkyl group having 1 to 23 carbon atoms, and R 3 to R 6 are each a straight chain having 1 to 8 carbon atoms. A chain or branched alkyl group is shown, m and n are integers of 1 to 4, and X, Y and Z are positive integers.
コンタクトレンズ用溶液としての洗浄、殺菌・抗菌等の基本的機能を保持し、かつレンズ表面に持続性のある親水性と防汚性を付与してコンタクトレンズの装用感を改善することができる。更に、本発明で用いる高分子化合物は、高い界面活性能を有するのでコンタクトレンズ用洗浄剤として用いた場合には、洗浄効果と汚れ付着防止効果との相乗効果が期待できる。 The contact lens solution can maintain basic functions such as cleaning, sterilization, and antibacterial, and can impart a lasting hydrophilicity and antifouling property to the lens surface to improve the wearing feeling of the contact lens. Furthermore, since the polymer compound used in the present invention has a high surface activity, a synergistic effect between the cleaning effect and the antifouling effect can be expected when used as a contact lens cleaning agent.
以下に本発明の実施形態を詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail.
本発明では、コンタクトレンズ用溶液中に（メタ）アクリロイルオキシアルキルベタイン構造と（メタ）アクリル酸（ジアルキルアミノ）アルキル構造を有する高分子化合物を用いる点に特徴がある。通常、ベタイン構造を有する親水性モノマーの単独重合体は、高い親水性を有することから、ポリビニルアルコールやポリビニルピロリドンと同様、疎水性のコンタクトレンズ表面と反発し合うため、持続的な親水性化には限界がある。本発明で用いるベタイン構造を有する高分子化合物は共重合体であり、下記構造式で示される。 The present invention is characterized in that a polymer compound having a (meth) acryloyloxyalkylbetaine structure and a (meth) acrylic acid ( dialkylamino) alkyl structure is used in the contact lens solution. Normally, a homopolymer of a hydrophilic monomer having a betaine structure has high hydrophilicity, and, like polyvinyl alcohol and polyvinylpyrrolidone, repels the surface of a hydrophobic contact lens, so that it can be made hydrophilic continuously. There are limits. The polymer compound having a betaine structure used in the present invention is a copolymer and is represented by the following structural formula.
式中、Ｒ１は水素原子又はメチル基を示し、Ｒ２は炭素数１〜２３の直鎖、分岐鎖もしくは環状のアルキル基を示し、Ｒ３〜Ｒ６はそれぞれ炭素数１〜８の直鎖もしくは分岐鎖のアルキル基を示し、ｍ及びｎは１〜４の整数であり、Ｘ、Ｙ、Ｚ、は正の整数である。 In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a linear, branched, or cyclic alkyl group having 1 to 23 carbon atoms, and R 3 to R 6 are each a straight chain having 1 to 8 carbon atoms. A chain or branched alkyl group is shown, m and n are integers of 1 to 4, and X, Y, and Z are positive integers.
上記構造式の左側の（メタ）アクリル酸アルキル構造としては、メタクリル酸アルキルが好ましく用いられ、具体的には、メタクリル酸メチル、メタクリル酸エチル、メタクリル酸プロピル、メタクリル酸ｉ−プロピル、メタクリル酸ブチル、メタクリル酸ｉ−ブチル、メタクリル酸ｔ−ブチル、メタクリル酸ペンチル、メタクリル酸ｉ−ペンチル、メタクリル酸ｔ−ペンチル、メタクリル酸ヘキシル、メタクリル酸２−エチルヘキシル、メタクリル酸ヘプチル、メタクリル酸オクチル、メタクリル酸ノニル、メタクリル酸デシル、メタクリル酸ドデシル、メタクリル酸ラウリル、メタクリル酸トリデシル、メタクリル酸テトラデシル、メタクリル酸１−メチルブチル、メタクリル酸１−メチルヘプチル、メタクリル酸３−メチルトリデシル、メタクリル酸６−メチルトリデシル、メタクリル酸７−メチルトリデシル、メタクリル酸２，１１−ジメチルドデシル、メタクリル酸２，７−ジメチル−４，５−ジエチルオクチル、メタクリル酸シクロヘキシル、メタクリル酸ベンジル、メタクリル酸１−シクロヘキセニル等が挙げられる。 As the alkyl (meth) acrylate structure on the left side of the above structural formula, alkyl methacrylate is preferably used. Specifically, methyl methacrylate, ethyl methacrylate, propyl methacrylate, i-propyl methacrylate, butyl methacrylate , I-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate, i-pentyl methacrylate, t-pentyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate, octyl methacrylate, nonyl methacrylate , Decyl methacrylate, dodecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, 1-methylbutyl methacrylate, 1-methylheptyl methacrylate, 3-methyltridecyl methacrylate 6-methyltridecyl methacrylate, 7-methyltridecyl methacrylate, 2,11-dimethyldodecyl methacrylate, 2,7-dimethyl-4,5-diethyloctyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid 1-cyclohexenyl and the like can be mentioned.
上記構造式の中央の（メタ）アクリロイルオキシアルキルベタイン構造としては、（メタ）アクリロイルオキシアルキルカルボキシベタイン、（メタ）アクリロイルオキシアルキルスルホベタインが挙げられるが、本発明では、メタクリロイルオキシアルキルカルボキシベタインが好ましく用いられ、具体的には、Ｎ−メタクリロイルオキシメチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−メチルカルボキシベタイン、Ｎ−メタクリロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−メチルカルボキシベタイン、Ｎ−メタクリロイルオキシプロピル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−メチルカルボキシベタイン、Ｎ−メタクリロイルオキシメチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−エチルカルボキシベタイン、Ｎ−メタクリロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−エチルカルボキシベタイン、Ｎ−メタクリロイルオキシプロピル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−エチルカルボキシベタイン、Ｎ−メタクリロイルオキシメチル−Ｎ，Ｎ−ジエチルアンモニウム−α−Ｎ−メチルカルボキシベタイン、Ｎ−メタクリロイルオキシエチル−Ｎ，Ｎ−ジエチルアンモニウム−α−Ｎ−メチルカルボキシベタイン、Ｎ−メタクリロイルオキシプロピル−Ｎ，Ｎ−ジエチルアンモニウム−α−Ｎ−メチルカルボキシベタイン、Ｎ−メタクリロイルオキシメチル−Ｎ，Ｎ−ジエチルアンモニウム−α−Ｎ−エチルカルボキシベタイン、Ｎ−メタクリロイルオキシエチル−Ｎ，Ｎ−ジエチルアンモニウム−α−Ｎ−エチルカルボキシベタイン、Ｎ−メタクリロイルオキシプロピル−Ｎ，Ｎ−ジエチルアンモニウム−α−Ｎ−エチルカルボキシベタイン等が挙げられる。 Examples of the (meth) acryloyloxyalkylbetaine structure in the center of the above structural formula include (meth) acryloyloxyalkylcarboxybetaine and (meth) acryloyloxyalkylsulfobetaine. In the present invention, methacryloyloxyalkylcarboxybetaine is preferred. Specifically, N-methacryloyloxymethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N-methacryloyloxypropyl-N, N-dimethylammonium-α-N-methylcarboxybetaine, N-methacryloyloxymethyl-N, N-dimethylammonium-α-N-ethylcarboxybetaine, -Methacryloyloxyethyl-N, N-dimethylammonium-α-N-ethylcarboxybetaine, N-methacryloyloxypropyl-N, N-dimethylammonium-α-N-ethylcarboxybetaine, N-methacryloyloxymethyl-N, N -Diethylammonium-α-N-methylcarboxybetaine, N-methacryloyloxyethyl-N, N-diethylammonium-α-N-methylcarboxybetaine, N-methacryloyloxypropyl-N, N-diethylammonium-α-N- Methylcarboxybetaine, N-methacryloyloxymethyl-N, N-diethylammonium-α-N-ethylcarboxybetaine, N-methacryloyloxyethyl-N, N-diethylammonium-α-N-ethylcarboxybetaine , N- methacryloyloxypropyl -N, like N- diethylammonium-.alpha.-N- ethylcarboxamidoadenosine betaine.
上記構造式の右側の（メタ）アクリル酸（ジアルキルアミノ）アルキル構造としては、メタクリル酸（ジアルキルアミノ）アルキルが好ましく、具体的には、メタクリル酸２−（ジメチルアミノ）エチルが挙げられる。 The (meth) acrylic acid ( dialkylamino) alkyl structure on the right side of the above structural formula is preferably ( dialkylamino) alkyl methacrylate, and specifically, 2- (dimethylamino) ethyl methacrylate.
本発明で用いる高分子化合物として、具体的には、Ｎ−メタクリロイルオキシメチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−メチルカルボキシベタイン／メタクリル酸アルキル／メタクリル酸２−（ジメチルアミノ）エチルコポリマー、Ｎ−メタクリロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−メチルカルボキシベタイン／メタクリル酸アルキル／メタクリル酸２−（ジメチルアミノ）エチルコポリマー等が挙げられる。 Specifically, as the polymer compound used in the present invention, N-methacryloyloxymethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate / methacrylic acid 2- (dimethylamino) ethyl copolymer, And N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate / methacrylic acid 2- (dimethylamino) ethyl copolymer.
コンタクトレンズ用溶液は通常水溶液であるため、添加する高分子化合物の水に対する溶解性を考慮して上記化合物中より構成成分を選択する。選択されたメタクリル酸アルキルは単独、又は２種類以上を組合せて用いることができ、Ｎ−メタクリロイルオキシアルキル−Ｎ，Ｎ−ジアルキルアンモニウム−α−Ｎ−アルキルカルボキシベタイン、及びメタクリル酸（ジアルキルアミノ）アルキルとの共重合比（Ｘ／Ｙ／Ｚ）も決定される。 Since the contact lens solution is usually an aqueous solution, the constituent components are selected from the above compounds in consideration of the solubility of the polymer compound to be added in water. The selected alkyl methacrylates can be used alone or in combination of two or more, N-methacryloyloxyalkyl-N, N-dialkylammonium-α-N-alkylcarboxybetaines, and ( dialkylamino) alkyl methacrylates The copolymerization ratio with (X / Y / Z) is also determined.
これらの高分子化合物の分子量は、２０００〜１００００００の平均分子量のものを用いることができるが、平均分子量は、５０００〜５０００００が好ましく、より好ましくは１００００〜３０００００である。この範囲内であることにより高い親水性と防汚性を兼ね備えることが可能である。 The molecular weight of these polymer compounds can be those having an average molecular weight of 2,000 to 1,000,000, but the average molecular weight is preferably 5,000 to 500,000, more preferably 10,000 to 300,000. By being in this range, it is possible to have both high hydrophilicity and antifouling properties.
本発明で用いる高分子化合物は、上記化合物より適宜選択された、（メタ）アクリル酸アルキル、Ｎ−メタクリロイルオキシアルキル−Ｎ，Ｎ−ジアルキルアンモニウム−α−Ｎ−アルキルカルボキシベタイン、（メタ）アクリル酸（ジアルキルアミノ）アルキル及び重合開始剤を水／アルコール溶液に溶解し、窒素置換した後、攪拌しながら加温させ前記３成分を共重合させることにより得ることができる。また、商業的に容易に入手可能なＲＡＭレジンシリーズ（大阪有機化学工業株式会社）も高分子化合物として用いることができる。 The polymer compound used in the present invention is an alkyl (meth) acrylate, N-methacryloyloxyalkyl-N, N-dialkylammonium-α-N-alkylcarboxybetaine, (meth) acrylic acid , which is appropriately selected from the above compounds. It can be obtained by dissolving ( dialkylamino) alkyl and a polymerization initiator in a water / alcohol solution and replacing with nitrogen, followed by heating with stirring and copolymerization of the three components. Also, a commercially available RAM resin series (Osaka Organic Chemical Co., Ltd.) can be used as the polymer compound.
本発明に用いる、高分子化合物は、親水性部位と疎水性部位からなる共重合体であるが、ポリオキシエチレンポリオキシプロピレンブロックポリマーと異なり、従来のポリオキシプロピレンよりも高い疎水性を示す疎水性部位を有するため、コンタクトレンズ表面と良好な相互作用を発揮し、一方のベタイン構造を有する親水性部位が、ポリオキシエチレンよりも高い水濡れ性を発揮するため、持続性のある親水性をコンタクトレンズ表面に付与することができる。 The polymer compound used in the present invention is a copolymer comprising a hydrophilic part and a hydrophobic part, but unlike a polyoxyethylene polyoxypropylene block polymer, a hydrophobic compound having higher hydrophobicity than conventional polyoxypropylene. Because it has a hydrophilic part, it exhibits good interaction with the contact lens surface, and the hydrophilic part with one betaine structure exhibits higher water wettability than polyoxyethylene. It can be applied to the contact lens surface.
本発明の一つの特徴として、用いる高分子化合物の構成成分中に、温度応答性を示す基を側鎖に有する化合物が含まれることが挙げられ、具体的には、メタクリル酸２−（ジメチルアミノ）エチルが挙げられる。ポリメタクリル酸２−（ジメチルアミノ）エチルは、温度応答性高分子として知られており（非特許文献１）、下限臨界溶解温度（ＬＣＳＴ）の３５℃前後で親水性／疎水性が反転する。即ち、コンタクトレンズを装用した場合に、その効果が好適に発揮されることとなる。体温による温度応答現象により、メタクリル酸２−（ジメチルアミノ）エチルは疎水化し、疎水性相互作用が増強するため、ベタイン構造を有する高分子化合物のコンタクトレンズ表面への保持性は更に向上され、より持続性の高い親水性が得られる。４級アンモニウム塩の場合、装用時においても親水性／疎水性の反転現象は起きないために疎水性の向上は見られず、ベタイン構造を有する高分子化合物のコンタクトレンズ表面への保持性向上は得られない。また、メタクリル酸２−（ジメチルアミノ）エチルはカチオン性を有するものの、４級アンモニウム塩と比較し低度であるため、アニオン性汚染物質の吸着量は低減することから、持続性の高い耐汚染性も発揮される。 One feature of the present invention is that a component having a temperature-responsive group in the side chain is included in the constituent components of the polymer compound used. Specifically, 2- (dimethylamino methacrylate) ) Ethyl. Poly (2- (dimethylamino) ethyl methacrylate) is known as a temperature-responsive polymer (Non-Patent Document 1), and the hydrophilicity / hydrophobicity is reversed around 35 ° C. of the lower critical solution temperature (LCST). That is, when a contact lens is worn, the effect is suitably exhibited. Due to the temperature response phenomenon due to body temperature, 2- (dimethylamino) ethyl methacrylate is hydrophobized and the hydrophobic interaction is enhanced, so that the retention property of the polymer compound having a betaine structure on the contact lens surface is further improved. Long lasting hydrophilicity is obtained. In the case of a quaternary ammonium salt, the hydrophilicity / hydrophobicity reversal phenomenon does not occur even when worn, and thus the hydrophobicity is not improved, and the retention property of the polymer compound having a betaine structure on the contact lens surface is improved. I can't get it. In addition, although 2- (dimethylamino) ethyl methacrylate has a cationic property, it is low in comparison with a quaternary ammonium salt, so that the amount of adsorbed anionic contaminants is reduced. Sex is also demonstrated.
その上、高分子化合物自体が両イオン性を示すので他のイオン性化合物との共存も可能である。特に、本発明で用いるベタイン構造を有する高分子化合物は、イオン性を示す界面活性剤等との相性を、通常のコンタクトレンズ溶液に適するｐＨ領域（ｐＨ６．５〜７．５）内で制御することができる。すなわち、洗浄効果を発揮させるために陰イオン界面活性剤を共存させた場合でも、相互作用によるイオンコンプレックスを形成しないため白濁することもなく、洗浄効果とレンズ表面の水濡れ性や防汚性を付与できる。また、殺菌や消毒効果を発揮させるために陽イオン性の化合物、例えば陽イオン界面活性剤を共存させた場合でも、殺菌・消毒効果を低下させることはない。本発明で用いる高分子化合物の配合量は、通常０．００１〜２０（Ｗ／Ｖ）％程度を添加すれば良いが、好ましくは、０．１〜１０（Ｗ／Ｖ）％、より好ましくは０．１〜５（Ｗ／Ｖ）％、特に好ましくは０．３〜３（Ｗ／Ｖ）％である。配合量が少な過ぎると、親水性及び防汚性の付与効果が不十分となり、多過ぎると他の成分との相互作用によって洗浄効果、殺菌や消毒効果、及びコンタクトレンズへの悪影響が生じる場合がある。 In addition, since the polymer compound itself exhibits amphoteric nature, it can coexist with other ionic compounds. In particular, the polymer compound having a betaine structure used in the present invention controls the compatibility with an ionic surfactant or the like within a pH range (pH 6.5 to 7.5) suitable for ordinary contact lens solutions. be able to. In other words, even when an anionic surfactant is coexisted in order to exert a cleaning effect, it does not form an ion complex due to interaction, so it does not become cloudy, and the cleaning effect and water wettability and antifouling property of the lens surface are achieved. Can be granted. Further, even when a cationic compound such as a cationic surfactant is used in order to exert a sterilizing or disinfecting effect, the disinfecting / disinfecting effect is not lowered. The compounding amount of the polymer compound used in the present invention may be usually about 0.001 to 20 (W / V)%, preferably 0.1 to 10 (W / V)%, more preferably It is 0.1 to 5 (W / V)%, particularly preferably 0.3 to 3 (W / V)%. If the blending amount is too small, the effect of imparting hydrophilicity and antifouling properties will be insufficient, and if it is too large, the interaction with other components may cause cleaning effects, sterilization and disinfection effects, and adverse effects on contact lenses. is there.
本発明のコンタクトレンズ用溶液では、その用途に合わせて、陰イオン界面活性剤、陽イオン界面活性剤、非イオン界面活性剤、両性界面活性剤の中から選択した各種低分子量の界面活性剤、殺菌消毒剤、抗菌防腐剤、緩衝剤、酵素、浸透圧調整剤、粘稠化剤、その他成分を本発明の効果を損なわない範囲において、各々１種単独、又は２種以上を適宜組合せて用いることができ、特にイオン性界面活性剤、殺菌消毒剤を含有することが好ましい。例えば、洗浄液や保存液として用いる場合には、陰イオン界面活性剤単独、あるいは、陰イオン界面活性剤と非イオン界面活性剤を組合せることが好ましい。また、擦り洗い等の物理的作用による洗浄効果を期待する洗浄消毒液の場合には、殺菌や消毒効果を阻害しない非イオン界面活性剤が好ましく用いられる。これらの界面活性剤の配合量は、本発明で用いる両性高分子化合物の親水性及び防汚性の付与効果を阻害せず、コンタクトレンズの形状安定性等に悪影響を与えることなく、且つ眼に対する刺激のない濃度であれば特に制限はないが、好ましくは０．０５〜２０（Ｗ／Ｖ）％、より好ましくは０．１〜５（Ｗ／Ｖ）％の範囲である。 In the contact lens solution of the present invention, various low molecular weight surfactants selected from anionic surfactants, cationic surfactants, nonionic surfactants, and amphoteric surfactants according to the application, A disinfectant, an antibacterial preservative, a buffer, an enzyme, an osmotic pressure adjusting agent, a thickening agent, and other components are used singly or in combination of two or more as long as the effects of the present invention are not impaired. In particular, it is preferable to contain an ionic surfactant and a bactericidal disinfectant. For example, when used as a cleaning solution or a preservation solution, it is preferable to use an anionic surfactant alone or a combination of an anionic surfactant and a nonionic surfactant. In the case of a cleaning / disinfecting solution that expects a cleaning effect due to a physical action such as scrubbing, a nonionic surfactant that does not inhibit the sterilization or disinfection effect is preferably used. The compounding amount of these surfactants does not hinder the hydrophilicity and antifouling imparting effect of the amphoteric polymer compound used in the present invention, does not adversely affect the shape stability of the contact lens, etc. The concentration is not particularly limited as long as it does not cause irritation, but is preferably in the range of 0.05 to 20 (W / V)%, more preferably 0.1 to 5 (W / V)%.
陰イオン界面活性剤としては、ラウリル硫酸ナトリウム、ラウリル硫酸トリエタノールアミン等のアルキル硫酸塩、ドデシルベンゼンスルホン酸ナトリウム、ドデシルベンゼンスルホン酸トリエタノールアミン等のアルキルベンゼンスルホン酸塩、ポリオキシエチレンラウリルエーテル硫酸ナトリウム、ポリオキシエチレンラウリルエーテル硫酸トリエタノールアミン等のポリオキシエチレンアルキルエーテル硫酸塩、α−オレフィンスルホン酸ナトリウム等のα−オレフィンスルホン酸ナトリウム、ラウリルリン酸ナトリウム、ラウリルリン酸トリエタノールアミン等のアルキルリン酸塩、ポリオキシエチレンラウリルエーテルリン酸ナトリウム、ポリオキシエチレンラウリルエーテルリン酸トリエタノールアミン等のポリオキシエチレンアルキルエーテルリン酸塩等が挙げられる。 Anionic surfactants include alkyl sulfonates such as sodium lauryl sulfate and triethanolamine lauryl sulfate, alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate and triethanolamine dodecylbenzene, sodium polyoxyethylene lauryl ether sulfate Polyoxyethylene alkyl ether sulfates such as polyoxyethylene lauryl ether sulfate triethanolamine, sodium α-olefin sulfonates such as sodium α-olefin sulfonate, sodium lauryl phosphate, alkyl phosphorus such as triethanolamine lauryl phosphate Acid salts, polyoxyethylene lauryl ether sodium phosphate, polyoxyethylene lauryl ether triethanolamine, etc. Examples include alkyl ether phosphate.
非イオン界面活性剤としては、ポリオキシエチレンラウリルエーテル等のポリオキシエチレンアルキルエーテル、ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンポリオキシプロピレンセチルエーテル等のポリオキシエチレンポリオキシプロピレンアルキルエーテル、ポリオキシエチレンポリオキシプロピレンブロックポリマー、ヤシ油脂肪酸ジエタノールアミド、ラウリン酸ジエタノールアミド等のアルキロールアマイド、ポリオキシエチレン硬化ヒマシ油６０等のポリオキシエチレンオキシステアリン酸トリグリセライド、ポリソルベート８０等のモノオレイン酸ポリオキシエチレンソルビタン、アルキルポリグルコシド等が挙げられる。 Nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether, and polyoxyethylene polyethers such as polyoxyethylene polyoxypropylene cetyl ether. Oxypropylene alkyl ether, polyoxyethylene polyoxypropylene block polymer, coconut oil fatty acid diethanolamide, alkylamides such as diethanolamide lauric acid, polyoxyethylene oxystearic acid triglyceride such as polyoxyethylene hydrogenated castor oil 60, polysorbate 80, etc. And polyoxyethylene sorbitan monooleate, alkyl polyglucoside and the like.
両性界面活性剤としては、アルキルジメチルアミノ酢酸ベタイン等のアルキルベタイン型、ヤシ油脂肪酸アミドプロピルベタイン等のアルキルアミドベタイン型、塩酸アルキルジアミノエチルグリシン等のグリシン型、Ｎ−［３−アルキル（１２，１４）オキシ−２−ヒドロキシプロピル］−Ｌ−アルギニン塩酸塩液等が挙げられる。 Examples of amphoteric surfactants include alkylbetaine types such as alkyldimethylaminoacetic acid betaine, alkylamide betaine types such as coconut oil fatty acid amidepropylbetaine, glycine types such as alkyldiaminoethylglycine hydrochloride, N- [3-alkyl (12, 14) Oxy-2-hydroxypropyl] -L-arginine hydrochloride solution and the like.
本発明で用いるベタイン構造を有する高分子化合物は両イオン性を示すため、一般的に殺菌や消毒剤として用いられる陽イオン性化合物の効果を低下させることなく用いることができることに特徴がある。これらの配合量は、目的とする効果と眼に対する安全性、コンタクトレンズに対する影響を考慮して決定するが、０．００００１〜１０（Ｗ／Ｖ）％が好ましく、より好ましくは０．００００５〜６．５（Ｗ／Ｖ）％である。 Since the polymer compound having a betaine structure used in the present invention exhibits amphoteric properties, it is characterized in that it can be used without reducing the effect of a cationic compound generally used as a bactericidal or disinfectant. These compounding amounts are determined in consideration of the intended effect, safety for eyes, and influence on contact lenses, but are preferably 0.00001 to 10 (W / V)%, more preferably 0.00005 to 6 .5 (W / V)%.
具体的には、塩酸ポリヘキサメチレンビグアニド、塩化ポリドロニウム、過酸化水素、ポビドンヨード、アルキルポリアミノエチルグリシン等、抗菌・防腐剤として、グルコン酸クロルヘキシジン、塩化ベンザルコニウム、塩化セチルピリジニウム、５，５−ジメチルヒダントイン、メチロール化ヒダントイン、ハロゲン化ヒダントイン、ソルビン酸（及びその塩）、パラオキシ安息香酸メチル、パラオキシ安息香酸エチル、パラオキシ安息香酸プロピル、パラオキシ安息香酸ブチル等が挙げられる。上記化合物のうち、５，５−ジメチルヒダントインは陰イオン界面活性剤の共存下で洗浄効果と抗菌防腐効果を両立させた洗浄保存剤に好ましく用いられる。また、塩酸ポリヘキサメチレンビグアニドは非イオン界面活性剤の共存下での殺菌消毒剤に好ましく用いられる。 Specifically, polyhexamethylene biguanide hydrochloride, polydronium chloride, hydrogen peroxide, povidone iodine, alkylpolyaminoethylglycine, etc., antibacterial and antiseptic agents, chlorhexidine gluconate, benzalkonium chloride, cetylpyridinium chloride, 5,5-dimethyl Hydantoin, methylolated hydantoin, halogenated hydantoin, sorbic acid (and salts thereof), methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate and the like can be mentioned. Among the above compounds, 5,5-dimethylhydantoin is preferably used as a cleaning preservative that achieves both a cleaning effect and an antibacterial and antiseptic effect in the presence of an anionic surfactant. Polyhexamethylene biguanide hydrochloride is preferably used as a disinfectant in the presence of a nonionic surfactant.
また、本発明のコンタクトレンズ用溶液は、使用目的に応じて眼に対する刺激やコンタクトレンズに対する影響を考慮して、ｐＨ５〜９の範囲内で調製されるのが好ましく、より好ましくはｐＨ５．５〜８．５程度の範囲での調整である。特に、イオン性の界面活性剤等の共存下では、本発明で用いる両性高分子化合物の特徴である親水性や防汚性付与の効果を低下しないｐＨにて調整すると好ましい。例えば、洗浄効果付与を目的として陰イオン界面活性剤を配合する場合には、ｐＨ６．５〜８．５の範囲内で調整するとより一層効果が発揮でき、殺菌や消毒効果付与を目的として陽イオン性化合物を配合する場合には、ｐＨ５．５〜７．５程度に調整するとより一層効果が発揮できる。 In addition, the contact lens solution of the present invention is preferably prepared within the range of pH 5 to 9, more preferably pH 5.5, in consideration of irritation to the eye and influence on the contact lens depending on the purpose of use. Adjustment is in the range of about 8.5. In particular, in the coexistence of an ionic surfactant or the like, it is preferable to adjust at a pH that does not lower the hydrophilicity and antifouling imparting effects characteristic of the amphoteric polymer compound used in the present invention. For example, when an anionic surfactant is blended for the purpose of imparting a cleaning effect, the effect can be further improved by adjusting the pH within the range of 6.5 to 8.5, and a cation for the purpose of providing a sterilizing and disinfecting effect. In the case of blending a functional compound, the effect can be further enhanced by adjusting the pH to about 5.5 to 7.5.
緩衝剤としては、ホウ酸、ホウ砂、トリスヒドロキシメチルアミノメタン、リン酸水素ナトリウム、リン酸ナトリウム、クエン酸、クエン酸ナトリウム等、従来から用いられているものの中から適宜選択して用いる。具体的には、トリスヒドロキシメチルアミノメタンと塩酸あるいはクエン酸とを組み合わせた緩衝剤や、ホウ酸及び／又はホウ砂を組み合わせた緩衝剤等が挙げられる。配合量は、好ましくは０．１〜１０（Ｗ／Ｖ）％の範囲である。０．１（Ｗ／Ｖ）％未満では十分なｐＨ安定性が得られ難く、また、１０（Ｗ／Ｖ）％を超えてもｐＨの顕著な安定性が認められないばかりか、低温下で保存する場合に緩衝剤が析出する可能性がある。 The buffering agent is appropriately selected from those conventionally used, such as boric acid, borax, trishydroxymethylaminomethane, sodium hydrogen phosphate, sodium phosphate, citric acid, sodium citrate and the like. Specifically, a buffering agent combining trishydroxymethylaminomethane and hydrochloric acid or citric acid, a buffering agent combining boric acid and / or borax, and the like can be mentioned. The blending amount is preferably in the range of 0.1 to 10 (W / V)%. If it is less than 0.1 (W / V)%, it is difficult to obtain sufficient pH stability, and if it exceeds 10 (W / V)%, no remarkable pH stability is observed. When stored, the buffer may precipitate.
酵素としては、タンパク分解酵素、脂質分解酵素、糖質分解酵素等の中から適宜選択して用いる。具体的には、トリプシン、キモトリプシン、パンクレアチン、パパイン、コラゲナーゼ、プロメライン、アミノペプチダーゼ、アスペルギロ・ペプチダーゼ、プロナーゼＥ、ディスパーゼ、ズブチリシンＡ、ズブチリシンＢ、リパーゼ、グルコシダーゼ、ムタナーゼ、α−アミラーゼ、デキストラナーゼ等が挙げられる。特に、タンパク分解酵素は、コンタクトレンズ装用時にレンズ表面に付着するタンパク質汚れを除去するために、好ましく配合される。これら酵素の配合量は、洗浄効果に応じた有効量に基づいて適宜決定されるものであるが、好ましくは０．０１〜１０（Ｗ／Ｖ）％、より好ましくは０．０５〜５（Ｗ／Ｖ）％の範囲である。 As the enzyme, an appropriate enzyme selected from a proteolytic enzyme, a lipolytic enzyme, a carbohydrase and the like is used. Specifically, trypsin, chymotrypsin, pancreatin, papain, collagenase, promeline, aminopeptidase, aspergillopeptidase, pronase E, dispase, subtilisin A, subtilisin B, lipase, glucosidase, mutanase, α-amylase, dextranase Etc. In particular, a proteolytic enzyme is preferably blended in order to remove protein stains attached to the lens surface when a contact lens is worn. The compounding amount of these enzymes is appropriately determined based on the effective amount corresponding to the cleaning effect, but is preferably 0.01 to 10 (W / V)%, more preferably 0.05 to 5 (W / V)%.
また、タンパク分解酵素を配合する場合、界面活性剤、特に陰イオン界面活性剤の共存下での安定性を向上させるために、グリセリン、ソルビトール、エチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−ブチレングリコール等の水溶性多価アルコール、トリメチルグリシンを添加することもできる。水溶性多価アルコールとしては、その種類に特に制限はなく、グリセリン、ソルビトール、エチレングリコール、プロピレングリコール、ジプロピレングリコール、１，３−ブチレングリコール等が挙げられる。その配合量は、洗浄効果、殺菌・消毒効果及びコンタクトレンズの形状安定性に影響のない濃度であれば特に制限はないが、タンパク分解酵素の安定性、並びに、性状及び触感を考慮すると、好ましくは３〜６５（Ｗ／Ｖ）％、より好ましくは１０〜３５（Ｗ／Ｖ）％の範囲である。３％未満ではタンパク分解酵素の安定性が十分ではなく、また６５％を超えても安定性の顕著な向上は認められない。 When a proteolytic enzyme is added, glycerin, sorbitol, ethylene glycol, propylene glycol, dipropylene glycol, 1, 3 are used to improve the stability in the presence of a surfactant, particularly an anionic surfactant. -Water-soluble polyhydric alcohols such as butylene glycol, and trimethylglycine can also be added. There is no restriction | limiting in particular as a water-soluble polyhydric alcohol, Glycerin, sorbitol, ethylene glycol, propylene glycol, dipropylene glycol, 1, 3- butylene glycol etc. are mentioned. The blending amount is not particularly limited as long as it is a concentration that does not affect the cleaning effect, the sterilizing / disinfecting effect, and the shape stability of the contact lens. Is in the range of 3 to 65 (W / V)%, more preferably 10 to 35 (W / V)%. If it is less than 3%, the stability of the proteolytic enzyme is not sufficient, and if it exceeds 65%, no significant improvement in stability is observed.
浸透圧調整剤は、眼科的に従来から公知の無機塩、例えば塩化ナトリウム、塩化カリウム、硫酸ナトリウム、リン酸ナトリウム等のイオン性浸透圧調整剤の他に、グリセリン、プロピレングリコール等の水溶性多価アルコール、グリシン、アラニン等のアミノ酸、キシリトール、マンニトール等の糖アルコール、グルコース、フルクトース等の単糖類をはじめトレハロース等の二糖類、それ以上の多糖類（環状多糖類であるサイクロデキストリン等も含む）等の非イオン性、あるいはトリメチルグリシン等の両性の浸透圧調整剤の中から適宜選択して使用することができる。また、その配合量は、目的とする浸透圧に調整するのに必要な量であり、コンタクトレンズの形状安定性等に悪影響を与えることなく、且つ眼に対する刺激のない濃度であれば特に制限はないが、含水性コンタクトレンズに用いる場合は、１５０〜５００ｍｍｏｌ／Ｌが好ましく、より好ましくは２００〜４５０ｍｍｏｌ／Ｌの浸透圧となるように調整するのに必要な量を使用する。 The osmotic pressure adjusting agent is an ophthalmologically known inorganic salt, for example, an ionic osmotic pressure adjusting agent such as sodium chloride, potassium chloride, sodium sulfate, sodium phosphate and the like, as well as a water-soluble glycerin and propylene glycol. Amino acids such as monohydric alcohol, glycine and alanine, sugar alcohols such as xylitol and mannitol, monosaccharides such as glucose and fructose, disaccharides such as trehalose, and higher polysaccharides (including cyclodextrins which are cyclic polysaccharides) It can be used by appropriately selecting from nonionic such as non-ionic or amphoteric osmotic pressure regulator such as trimethylglycine. Further, the blending amount is an amount necessary to adjust to the target osmotic pressure, and there is no particular limitation as long as it is a concentration that does not adversely affect the shape stability of the contact lens and does not irritate the eyes. However, when it is used for a hydrous contact lens, 150 to 500 mmol / L is preferable, and an amount necessary for adjusting to an osmotic pressure of 200 to 450 mmol / L is more preferable.
粘稠化剤としては、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、ヒドロキシプロピルエチルセルロース、ヒドロキシエチルセルロース、メチルセルロース、カルボキシメチルセルロース、ポリエチレングリコール、ポリビニルアルコール、ポリビニルピロリドン、カルボキシビニルポリマー、無水マレイン酸とメチルビニルエーテルの共重合体、デキストラン、プルラン、ヒアルロン酸ナトリウム、アルギン酸ナトリウム、コンドロイチン硫酸ナトリウム、ポリ（メタ）アクリロイルオキシエチルホスホリルコリン等が挙げられ、これらの中から単独あるいは適宜組合せて使用することができる。その配合量は、通常０．０１〜１０（Ｗ／Ｖ）％の範囲である。 As the thickening agent, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxypropylethylcellulose, hydroxyethylcellulose, methylcellulose, carboxymethylcellulose, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, copolymer of maleic anhydride and methyl vinyl ether Dextran, pullulan, sodium hyaluronate, sodium alginate, sodium chondroitin sulfate, poly (meth) acryloyloxyethyl phosphorylcholine, and the like, and these can be used alone or in appropriate combination. The blending amount is usually in the range of 0.01 to 10 (W / V)%.
上記成分の他にも、本発明の目的を損なわない限り、保存剤、キレート剤、溶解補助剤等の各種添加剤を更に配合することができる。 In addition to the above components, various additives such as preservatives, chelating agents, and solubilizing agents can be further blended so long as the object of the present invention is not impaired.
本発明のコンタクトレンズ用溶液の対象となるコンタクトレンズの種類は、含水（低含水、高含水）、非含水、イオン性等の素材・材質的な制限は特になく、全てのコンタクトレンズに適用することができる。また、本発明におけるコンタクトレンズ用溶液とは、コンタクトレンズの洗浄液、保存液、洗浄・保存液、消毒液、すすぎ液、溶解水、マルチパーパスソリューション、コンデショニングソリューション、リンスソリューション、コンタクトレンズ装着液等が挙げられる。 There are no particular restrictions on materials and materials such as water content (low water content, high water content), non-water content, ionicity, etc., as the types of contact lenses that are the target of the contact lens solution of the present invention, and it applies to all contact lenses. be able to. The contact lens solution in the present invention is a contact lens cleaning solution, preserving solution, cleaning / preserving solution, disinfecting solution, rinsing solution, dissolving water, multi-purpose solution, conditioning solution, rinsing solution, contact lens mounting solution, etc. Is mentioned.
更に本発明は、目的に応じて用時調製用の顆粒、粉末、タブレット、ゲル等の剤形として用いることができる。 Furthermore, this invention can be used as dosage forms, such as a granule for preparation at the time of use, a powder, a tablet, a gel, according to the objective.
以下実施例によって本発明を具体的に説明するが、これらは本発明を限定するものではない。なお、実施例における単位は、特に断らない限りＷ／Ｖ％である。 EXAMPLES Hereinafter, the present invention will be specifically described by way of examples, but these examples do not limit the present invention. The unit in the examples is W / V% unless otherwise specified.
（実施例１〜６及び比較例１〜４）
表１に記載した各配合成分を精製水１００ｍｌ中に混合し溶解して、実施例及び比較例のコンタクトレンズ用溶液を調製して親水性付与の効果と防汚性付与の効果及びその持続性を次の方法により評価した。
(Examples 1-6 and Comparative Examples 1-4)
Each compounding ingredient listed in Table 1 is mixed and dissolved in 100 ml of purified water to prepare solutions for contact lenses of Examples and Comparative Examples to provide hydrophilicity and antifouling properties and sustainability. Was evaluated by the following method.
１．親水性付与効果及び持続性の評価
コンタクトレンズ材料（ＲＧＰＣＬ材料：シード社製Ａ−１、ＳＣＬ材料：シード社製ＳＸ）から切削・研磨により試験用ディスクを作製した。Ａ−１ディスクは５ｍｍ厚、ＳＸディスクは１ｍｍ厚とし、ＳＸディスクはダルベッコリン酸緩衝生理食塩水にて膨潤・含水させた後、試験に用いた。試験用ディスクの浸漬処理前の接触角を測定（初期値）した後、実施例１〜４及び比較例１〜２のコンタクトレンズ用溶液にはＡ−１ディスク、実施例５〜６及び比較例３〜４のコンタクトレンズ用溶液にはＳＸディスクを６時間浸漬処理した。６時間後、Ａ−１ディスクは３７℃に保った純水で、ＳＸディスクは３７℃に保ったダルベッコリン酸緩衝生理食塩水で３０秒間すすいだ後、各コンタクトレンズ用溶液による浸漬処理後の試験用ディスクの接触角を測定した。試験用ディスクの各コンタクトレンズ用溶液による浸漬処理前後の接触角の差（接触角変化量）により親水性付与効果を評価した。接触角は、協和界面科学株式会社製、接触角計ＣＡ−Ｄ型を用いた気泡法により測定し、下記の計算式に従い、接触角変化量を算出した。
1. Evaluation of hydrophilicity and sustainability Test disks were prepared from contact lens materials (RGPCL material: A-1 manufactured by Seed, SCL material: SX manufactured by Seed) by cutting and polishing. The A-1 disk was 5 mm thick, the SX disk was 1 mm thick, and the SX disk was swollen and hydrated with Dulbecco's phosphate buffered saline and used for the test. After measuring the contact angle of the test disk before the immersion treatment (initial value), the contact lens solutions of Examples 1 to 4 and Comparative Examples 1 to 2 are A-1 disks, Examples 5 to 6 and Comparative Examples. The SX disk was immersed in 3-4 contact lens solutions for 6 hours. After 6 hours, the A-1 disc was rinsed with pure water kept at 37 ° C., and the SX disc was rinsed with Dulbecco's phosphate buffered saline kept at 37 ° C. for 30 seconds, and after immersion treatment with each contact lens solution. The contact angle of the test disk was measured. The hydrophilicity imparting effect was evaluated by the difference in contact angle before and after the immersion treatment with each contact lens solution of the test disk (contact angle change amount). The contact angle was measured by a bubble method using a contact angle meter CA-D type manufactured by Kyowa Interface Science Co., Ltd., and the contact angle change amount was calculated according to the following calculation formula.
接触角変化量（°）＝（浸漬処理前の接触角）−（浸漬処理後の接触角）
算出した接触角変化量（°）から、以下に示すように５段階で親水性付与効果を評価した。その結果を表１に示す。
Contact angle variation (°) = (Contact angle before immersion treatment) − (Contact angle after immersion treatment)
From the calculated contact angle change (°), the hydrophilicity imparting effect was evaluated in five stages as shown below. The results are shown in Table 1.
◎；２５°以上
○；１５°以上〜２５°未満
△；１０°以上〜１５°未満
▲；５°以上〜１０°未満
×；５°未満
◎; 25 ° or more ○; 15 ° or more to less than 25 ° △; 10 ° or more to less than 15 ° ▲; 5 ° or more to less than 10 ° ×: less than 5 °
次いで、Ａ−１ディスクは３７℃に保った純水で、ＳＸディスクは３７℃に保ったダルベッコリン酸緩衝生理食塩水で３０秒間すすぎ洗いを繰り返し、各回すすぎ後の接触角を測定した。前回サイクル後との接触角の差（接触角変化量）により親水性付与の持続性を評価した。接触角は、協和界面科学株式会社製、接触角計ＣＡ−Ｄ型を用いた気泡法により測定し、下記の計算式に従い、接触角変化量を算出した。 Next, the A-1 disk was rinsed with pure water kept at 37 ° C., and the SX disk was rinsed with Dulbecco's phosphate buffered saline kept at 37 ° C. for 30 seconds, and the contact angle after each rinse was measured. The sustainability of imparting hydrophilicity was evaluated by the difference in contact angle after the previous cycle (contact angle change amount). The contact angle was measured by a bubble method using a contact angle meter CA-D type manufactured by Kyowa Interface Science Co., Ltd., and the contact angle change amount was calculated according to the following calculation formula.
接触角変化量（°）＝（前回サイクル後の接触角）−（今回サイクル後の接触角）
算出した接触角変化量（°）から、以下に示すように５段階で親水性付与効果を評価した。その結果を表１に示す。
Contact angle change (°) = (Contact angle after previous cycle)-(Contact angle after current cycle)
From the calculated contact angle change (°), the hydrophilicity imparting effect was evaluated in five stages as shown below. The results are shown in Table 1.
◎；５°未満
○；５°以上〜１０°未満
△；１０°以上〜１５°未満
▲；１５°以上〜２５°未満
×；２５°以上
◎; Less than 5 ° ○; 5 ° or more and less than 10 ° △; 10 ° or more and less than 15 ° ▲; 15 ° or more and less than 25 ° ×: 25 ° or more
２．防汚性付与効果及び持続性の評価
人工汚れ液に浸漬して汚れを付着させる操作と、コンタクトレンズ用溶液によるケア（洗浄・保存）操作を繰返し行ない、実際のコンタクトレンズ使用を模倣したサイクル処理によって付着していく汚れの増加量を、ヘーズ値（濁度）により測定することで、コンタクトレンズ用溶液の防汚性付与効果を評価した。公知の涙液成分（タンパク質、脂質及び無機塩）を含有し、３７℃に保った人工汚れ液に、試験用レンズ（ＲＧＰＣＬ：シード社製Ａ−１、ＳＣＬ：シード社製ＳＸブルー）を６時間浸漬する。６時間後のＲＧＰＣＬは、レンズを人工汚れ液から取出して、実施例１〜４及び比較例１〜２のコンタクトレンズ用溶液に６時間浸漬する。６時間後は、水道水ですすいだ後、再び３７℃の人工汚れ液に浸漬する。ＳＣＬは、レンズを人工汚れ液から取出した時点で実施例５〜６及び比較例３〜４のコンタクトレンズ用溶液で擦り洗いとすすぎを行なった後、４時間浸漬した。４時間後、コンタクトレンズ用溶液から取出して、そのまま３７℃の人工汚れ液に浸漬した。上記の手順を１サイクルとして、その都度ヘーズ値（濁度）を測定して防汚性付与効果を評価した。ヘーズ値の測定には、スガ試験機株式会社製、全自動ヘーズコンピューター ＨＧＭ−２ＤＰを使用した。測定したレンズのヘーズ値から、以下に示すように５段階で防汚性付与効果を評価した。
2. Antifouling effect and evaluation of durability Cycle treatment that imitates actual contact lens use by repeating the operation of attaching dirt by immersing it in artificial dirt liquid and the care (cleaning / preservation) operation with the solution for contact lenses By measuring the increase in the amount of dirt adhered by the haze value (turbidity), the antifouling effect of the contact lens solution was evaluated. A test lens (RGPCL: Seed A-1, SCL: Seed SX Blue) is added to an artificial soil solution containing known tear components (proteins, lipids and inorganic salts) and maintained at 37 ° C. Immerse for hours. After 6 hours, RGPCL removes the lens from the artificial soil solution and immerses it in the contact lens solutions of Examples 1-4 and Comparative Examples 1-2 for 6 hours. After 6 hours, after rinsing with tap water, it is again immersed in an artificial soil solution at 37 ° C. The SCL was immersed for 4 hours after scrubbing and rinsing with the contact lens solutions of Examples 5-6 and Comparative Examples 3-4 when the lens was removed from the artificial soil solution. After 4 hours, the contact lens solution was taken out and immersed in an artificial soil solution at 37 ° C. as it was. Taking the above procedure as one cycle, the haze value (turbidity) was measured each time to evaluate the antifouling effect. For the measurement of the haze value, a fully automatic haze computer HGM-2DP manufactured by Suga Test Instruments Co., Ltd. was used. From the measured haze value of the lens, the antifouling property imparting effect was evaluated in five stages as shown below.
◎；１０以下
○；１０超過〜２０未満
△；２０以上〜３０未満
▲；３０以上〜４０未満
×；４０以上
◎; 10 or less ○; 10 or more to less than 20 △; 20 or more to less than 30 ▲; 30 or more to less than 40 ×; 40 or more
＊ベタイン含有高分子１：Ｎ−メタクリロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−メチルカルボキシベタイン／メタクリル酸アルキル／メタクリル酸２−（ジメチルアミノ）エチルコポリマー（平均分子量５００００〜１０００００、メタクリル酸アルキルはメタクリル酸ｎ−ブチル：メタクリル酸２−エチルヘキシル＝５：２）
＊ベタイン含有高分子２：Ｎ−メタクリロイルオキシメチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−メチルカルボキシベタイン／メタクリル酸アルキル／メタクリル酸２−（ジメチルアミノ）エチルコポリマー（平均分子量５００００〜１０００００、メタクリル酸アルキルはメタクリル酸トリデシル：メタクリル酸シクロヘキシル＝１：２）
＊ベタイン含有高分子３：Ｎ−メタクリロイルオキシエチル−Ｎ，Ｎ−ジメチルアンモニウム−α−Ｎ−メチルカルボキシベタイン／メタクリル酸アルキル／メタクリロイルオキシエチルジメチルアミノエチルクロライドコポリマー（平均分子量５００００〜１０００００、メタクリル酸アルキルはメタクリル酸ｎ−ブチル：メタクリル酸２−エチルヘキシル＝５：２）
＊界面活性剤の配合量は、純分換算後の配合量である。
＊界面活性剤１：α−オレフィンスルホン酸ナトリウム（（株）ライオン：リポランＰＪ−４００）
＊界面活性剤２：ポリオキシエチレンポリオキシプロピレンブロックポリマー（ＢＡＳＦジャパン（株）：ルトロールＦ−１２７）
＊ＣＨＧ：グルコン酸クロルヘキシジン
＊ＰＨＭＢ：塩酸ポリヘキサメチレンビグアニド
＊酵素：蛋白分解酵素（ノボザイムズ（株）：ＣＬ−Ｐｒｏ２．５ＭＧ）
* Betaine-containing polymer 1: N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate / methacrylic acid 2- (dimethylamino) ethyl copolymer (average molecular weight 50,000 to 100,000, methacryl The alkyl acid is n-butyl methacrylate: 2-ethylhexyl methacrylate = 5: 2)
* Betaine-containing polymer 2: N-methacryloyloxymethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate / methacrylic acid 2- (dimethylamino) ethyl copolymer (average molecular weight 50,000 to 100,000, methacrylic) The alkyl acid is tridecyl methacrylate: cyclohexyl methacrylate = 1: 2.
* Betaine-containing polymer 3: N-methacryloyloxyethyl-N, N-dimethylammonium-α-N-methylcarboxybetaine / alkyl methacrylate / methacryloyloxyethyldimethylaminoethyl chloride copolymer (average molecular weight 50,000 to 100,000, alkyl methacrylate) N-butyl methacrylate: 2-ethylhexyl methacrylate = 5: 2)
* The compounding amount of the surfactant is the compounding amount after conversion to the pure component.
* Surfactant 1: Sodium α-olefin sulfonate (Lion: Lipolane PJ-400)
* Surfactant 2: Polyoxyethylene polyoxypropylene block polymer (BASF Japan K.K .: Lutrol F-127)
* CHG: Chlorhexidine gluconate * PHMB: Polyhexamethylene biguanide hydrochloride * Enzyme: Proteolytic enzyme (Novozymes Co., Ltd .: CL-Pro2.5MG)
表中から実施例１〜６では親水性及び防汚性付与効果並びに持続性が確認できた。しかしながら、コンタクトレンズ用溶液中に添加されたベタイン構造を有する高分子化合物の構成成分に、四級アンモニウム塩が含まれる場合、使用初期には親水性、防汚性付与効果は認められたものの、体温付近である３７℃における長時間の使用により耐久性が低下することが比較例１及び３により確認された。また、コンタクトレンズ溶液中にベタイン構造を有する高分子化合物が添加されない場合、親水性付与効果は認められず、防汚性も低いことが比較例２及び４により確認できる。 In Examples 1 to 6 from the table, hydrophilicity and antifouling imparting effects and sustainability could be confirmed. However, when the quaternary ammonium salt is included in the component of the polymer compound having a betaine structure added to the contact lens solution, hydrophilicity and antifouling imparting effects were recognized at the initial stage of use, It was confirmed by Comparative Examples 1 and 3 that durability was lowered by long-term use at 37 ° C., which is around the body temperature. Moreover, when the high molecular compound which has a betaine structure is not added in a contact lens solution, it can confirm by Comparative Examples 2 and 4 that a hydrophilicity provision effect is not recognized but antifouling property is also low.
以上の評価結果から、本発明のコンタクトレンズ用溶液では、処理を施す度に親水性と防汚性が付与され、また、体温付近の３７℃においてレンズ表面に良好な保持性を示すため、レンズ表面の水濡れ低下や汚れの付着による異物感、くもり等を原因とするコンタクトレンズ装用中の装用感の低下による不快な症状を解消することが可能である。 From the above evaluation results, in the contact lens solution of the present invention, hydrophilicity and antifouling properties are imparted each time treatment is performed, and the lens surface exhibits good retention at 37 ° C. near body temperature. It is possible to eliminate an unpleasant symptom due to a decrease in wearing feeling during contact lens wearing due to a decrease in surface wetness, a foreign body feeling due to adhesion of dirt, cloudiness, and the like.
Claims (7)
（式中、Ｒ１は水素原子又はメチル基を示し、Ｒ２は炭素数１〜２３の直鎖、分岐鎖もしくは環状のアルキル基を示し、Ｒ３〜Ｒ６はそれぞれ炭素数１〜８の直鎖もしくは分岐鎖のアルキル基を示し、ｍ及びｎは１〜４の整数であり、Ｘ、Ｙ、Ｚは正の整数である。） A contact lens solution comprising a polymer compound represented by the following structural formula.
(In the formula, R 1 represents a hydrogen atom or a methyl group, R 2 represents a linear, branched or cyclic alkyl group having 1 to 23 carbon atoms, and R 3 to R 6 each have 1 to 8 carbon atoms. A linear or branched alkyl group is shown, m and n are integers of 1-4, and X, Y, and Z are positive integers.)
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