JPH06226098A - Hydrogen peroxide decomposition catalyst and production therefor and sterilizing method for contact lens using the catalyst - Google Patents
Hydrogen peroxide decomposition catalyst and production therefor and sterilizing method for contact lens using the catalystInfo
- Publication number
- JPH06226098A JPH06226098A JP5042243A JP4224393A JPH06226098A JP H06226098 A JPH06226098 A JP H06226098A JP 5042243 A JP5042243 A JP 5042243A JP 4224393 A JP4224393 A JP 4224393A JP H06226098 A JPH06226098 A JP H06226098A
- Authority
- JP
- Japan
- Prior art keywords
- hydrogen peroxide
- catalyst
- alumina
- peroxide decomposition
- contact lens
- 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.)
- Pending
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 261
- 239000003054 catalyst Substances 0.000 title claims abstract description 96
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000001954 sterilising effect Effects 0.000 title abstract 5
- 238000004519 manufacturing process Methods 0.000 title description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 150000003751 zinc Chemical class 0.000 claims abstract description 17
- 239000007864 aqueous solution Substances 0.000 claims description 23
- 150000003839 salts Chemical class 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 230000000249 desinfective effect Effects 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 32
- 238000006386 neutralization reaction Methods 0.000 abstract description 10
- 238000000151 deposition Methods 0.000 abstract 1
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011592 zinc chloride Substances 0.000 description 11
- 235000005074 zinc chloride Nutrition 0.000 description 11
- 239000012298 atmosphere Substances 0.000 description 10
- 238000004381 surface treatment Methods 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 6
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- CALMYRPSSNRCFD-UHFFFAOYSA-J tetrachloroiridium Chemical compound Cl[Ir](Cl)(Cl)Cl CALMYRPSSNRCFD-UHFFFAOYSA-J 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000005502 peroxidation Methods 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical compound C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 2
- 206010015946 Eye irritation Diseases 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 231100000013 eye irritation Toxicity 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000008055 phosphate buffer solution Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- ZTOJFFHGPLIVKC-CLFAGFIQSA-N abts Chemical compound S/1C2=CC(S(O)(=O)=O)=CC=C2N(CC)C\1=N\N=C1/SC2=CC(S(O)(=O)=O)=CC=C2N1CC ZTOJFFHGPLIVKC-CLFAGFIQSA-N 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- DGLRDKLJZLEJCY-UHFFFAOYSA-L disodium hydrogenphosphate dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].OP([O-])([O-])=O DGLRDKLJZLEJCY-UHFFFAOYSA-L 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
- 238000010981 drying operation Methods 0.000 description 1
- MFGZXPGKKJMZIY-UHFFFAOYSA-N ethyl 5-amino-1-(4-sulfamoylphenyl)pyrazole-4-carboxylate Chemical compound NC1=C(C(=O)OCC)C=NN1C1=CC=C(S(N)(=O)=O)C=C1 MFGZXPGKKJMZIY-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 239000002504 physiological saline solution Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 231100000330 serious eye damage Toxicity 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940075562 sodium phosphate dihydrate Drugs 0.000 description 1
- 229940079864 sodium stannate Drugs 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- CRKADHVTAQCXRA-UHFFFAOYSA-K trisodium;phosphate;dihydrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]P([O-])([O-])=O CRKADHVTAQCXRA-UHFFFAOYSA-K 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 description 1
- 239000011576 zinc lactate Substances 0.000 description 1
- 235000000193 zinc lactate Nutrition 0.000 description 1
- 229940050168 zinc lactate Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- JDLYKQWJXAQNNS-UHFFFAOYSA-L zinc;dibenzoate Chemical compound [Zn+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 JDLYKQWJXAQNNS-UHFFFAOYSA-L 0.000 description 1
- XDWXRAYGALQIFG-UHFFFAOYSA-L zinc;propanoate Chemical compound [Zn+2].CCC([O-])=O.CCC([O-])=O XDWXRAYGALQIFG-UHFFFAOYSA-L 0.000 description 1
Abstract
Description
【０００１】[0001]
【技術分野】本発明は、過酸化水素にてコンタクトレン
ズの消毒を行なう一方、コンタクトレンズの表面や内部
に残留する過酸化水素を過酸化水素分解触媒を用いて中
和するようにした、コンタクトレンズの消毒システムに
関するものである。TECHNICAL FIELD The present invention disinfects a contact lens with hydrogen peroxide, while neutralizing hydrogen peroxide remaining on the surface or inside of the contact lens using a hydrogen peroxide decomposition catalyst. It relates to a lens disinfection system.
【０００２】[0002]
【背景技術】コンタクトレンズ、特に含水性のソフトコ
ンタクトレンズは、継続して使用するうちにレンズ表面
やレンズ内に細菌などが繁殖して汚染され易いところか
ら、定期的に消毒洗浄される必要がある。そして、従来
から行なわれているコンタクトレンズの消毒方法には、
大別して、煮沸消毒の如き熱を加えて消毒する加熱消毒
方法と、殺菌剤を用いる化学消毒方法があり、また化学
消毒方法では、殺菌剤として過酸化水素が広く用いられ
ている。BACKGROUND ART Contact lenses, particularly hydrous soft contact lenses, need to be regularly disinfected and washed because bacteria and the like are likely to grow and contaminate the lens surface and lens during continuous use. is there. And, in the conventional disinfection method of contact lenses,
Broadly speaking, there are a heat disinfection method such as boiling disinfection in which heat is applied to disinfect, and a chemical disinfection method using a disinfectant. In the chemical disinfection method, hydrogen peroxide is widely used as a disinfectant.
【０００３】ところで、殺菌剤として過酸化水素を使用
する場合には、過酸化水素によるコンタクトレンズの殺
菌消毒が有効に為されるようにすると共に、消毒後に
は、コンタクトレンズの表面や内部に残留する過酸化水
素を分解して無毒化（中和）する必要がある。即ち、過
酸化水素がコンタクトレンズに残留していると、僅かな
量でも、眼に重大な障害をもたらす危険性があるからで
ある。そのため、従来から、生理食塩水で濯いだり、各
種の還元剤、金属触媒、酵素触媒等を用いることによ
り、コンタクトレンズに残存する過酸化水素を完全に分
解除去するように図られているのである。By the way, when hydrogen peroxide is used as a disinfectant, the contact lens is effectively sterilized and disinfected with hydrogen peroxide, and after disinfection, it remains on the surface or inside of the contact lens. It is necessary to decompose the hydrogen peroxide to be detoxified (neutralized). That is, if hydrogen peroxide remains in the contact lens, even a small amount thereof may cause serious eye damage. Therefore, it has been conventionally attempted to completely decompose and remove the hydrogen peroxide remaining in the contact lens by rinsing with physiological saline or using various reducing agents, metal catalysts, enzyme catalysts and the like. is there.
【０００４】そして、それらの中和方法の中で、金属触
媒を用いる方法は、過酸化水素の分解力が大きいものと
して一般に用いられており、通常は、白金等の過酸化水
素分解能を有する金属を、ステンレス鋼、カーボン、ア
ルミナ、プラスチック材料等からなる担体に担持させた
形態の触媒が使用されている。また、金属触媒を用いる
場合には、過酸化水素水溶液にコンタクトレンズを浸漬
して消毒する消毒工程の後に、触媒を投入して中和を行
なう中和工程を実施するのが一般的であるが、より簡便
な方法として、過酸化水素水溶液にコンタクトレンズを
浸漬する際に、触媒を投入することにより、操作を１ス
テップとして、消毒を行ないつつ、中和を行なう方法が
検討されている。Among these neutralization methods, the method using a metal catalyst is generally used because it has a large decomposing power for hydrogen peroxide, and usually a metal such as platinum having a hydrogen peroxide decomposing ability is used. There is used a catalyst in which is carried on a carrier made of stainless steel, carbon, alumina, a plastic material or the like. Further, when a metal catalyst is used, it is common to carry out a neutralization step of adding a catalyst for neutralization after a disinfection step of immersing a contact lens in a hydrogen peroxide aqueous solution for disinfection. As a simpler method, a method of neutralizing while disinfecting is being studied by adding a catalyst when immersing a contact lens in an aqueous solution of hydrogen peroxide, and performing the operation as one step.
【０００５】しかしながら、市販されている金属触媒
（例えばCIBA Vision Corp. 製のフェニレンオキシドポ
リマーからなる担体に白金黒を担持させた触媒、商品名
『AODISK Catalyst 』等）では、消毒工程の最初から触
媒を投入すると、コンタクトレンズの消毒が不十分とな
る問題点を有している。何故なら、かかる触媒は、過酸
化水素分解能との関係で、過酸化水素の残留を防止する
ために大量の触媒を投入する必要があることから、消毒
工程の最初から投入すると、初期の過酸化水素分解速度
が大きくなって、消毒に必要な過酸化水素を短時間のう
ちに分解してしまうこととなるからである。而して、初
期の過酸化水素分解速度を落とすために、触媒の使用量
を減らすと、中和工程が終了した段階でも過酸化水素が
残留してしまい、眼刺激等を惹起する恐れが生じるので
ある。However, in commercially available metal catalysts (for example, a catalyst made of CIBA Vision Corp. in which platinum black is supported on a carrier made of phenylene oxide polymer, trade name "AODISK Catalyst", etc.), the catalyst is used from the beginning of the disinfection process. However, there is a problem that the disinfection of the contact lens becomes insufficient. Because such a catalyst needs to be charged with a large amount of catalyst in order to prevent hydrogen peroxide from remaining in relation to hydrogen peroxide decomposing ability, if the catalyst is added from the beginning of the disinfection process, the initial peroxide This is because the rate of hydrogen decomposition increases and hydrogen peroxide required for disinfection is decomposed in a short time. Therefore, if the amount of the catalyst used is reduced in order to reduce the initial hydrogen peroxide decomposition rate, hydrogen peroxide will remain even at the stage where the neutralization step is completed, which may cause eye irritation and the like. Of.
【０００６】このため、従来では、消毒工程と中和工程
とを区別して、一定時間過酸化水素消毒した後、中和す
るための触媒を消毒システムの系に接触させており、通
常、使用者は、過酸化水素水溶液中にコンタクトレンズ
を浸漬、接触させる操作と、一定時間後に消毒システム
を中和すべく触媒を投入する操作とを行なわなければな
らず、煩雑な作業を強いられていたのである。For this reason, conventionally, the disinfection process and the neutralization process are distinguished from each other, and after a certain period of hydrogen peroxide disinfection, a catalyst for neutralization is brought into contact with the system of the disinfection system. Requires the operation of immersing and contacting the contact lens in an aqueous hydrogen peroxide solution and the operation of adding a catalyst to neutralize the disinfection system after a certain period of time, which complicates the work. is there.
【０００７】さらに、従来では、アルミナ等の担体に金
属触媒を担持させるには、担持させる金属の塩の水溶液
をアルミナに含浸せしめ、焼成した後、還元することが
一般的であるが、このような操作だけの場合には、アル
ミナ上に金属が不均一に吸着したり、吸着力が弱くて、
過酸化水素の分解中に金属の遊離等を引き起こしたりす
る問題があった。また、市販の白金黒触媒を手で触れた
りすると、白金黒が手に付いたり、過酸化水素水を分解
中に白金黒の粉が溶液中に分散したりすることがあっ
た。Further, conventionally, in order to support a metal catalyst on a carrier such as alumina, it is general to impregnate alumina with an aqueous solution of a metal salt to be supported, calcining it, and then reducing it. In the case of only simple operation, the metal may be non-uniformly adsorbed on the alumina, or the adsorption force is weak,
There has been a problem that metal is released during the decomposition of hydrogen peroxide. In addition, when a commercially available platinum black catalyst was touched with hands, platinum black was sometimes attached to the hands, and platinum black powder was sometimes dispersed in the solution during the decomposition of hydrogen peroxide solution.
【０００８】[0008]
【解決課題】ここにおいて、本発明は、このような事情
を背景として為されたものであって、その解決課題とす
るところは、過酸化水素分解能を有する金属を担体上に
均一且つ強固に担持せしめて、安定した過酸化水素分解
力を発揮する過酸化水素分解触媒を提供することにあ
る。また、かかる触媒を用いることにより、過酸化水素
を用いたコンタクトレンズの消毒システムにおいて、１
ステップの簡便な操作によって、有効な消毒と過酸化水
素の中和とを行ない得るようにすることにある。The present invention has been made in view of such circumstances, and the problem to be solved by the present invention is to uniformly and firmly support a metal having a hydrogen peroxide decomposing ability on a carrier. At the very least, it is to provide a hydrogen peroxide decomposition catalyst that exhibits a stable hydrogen peroxide decomposition power. In addition, by using such a catalyst, in a contact lens disinfection system using hydrogen peroxide,
It is to enable effective disinfection and neutralization of hydrogen peroxide by a simple operation of steps.
【０００９】[0009]
【解決手段】そして、かかる課題を解決するために、本
発明の要旨とするところは、過酸化水素分解能を有する
金属を、亜鉛の塩にて表面処理されたγ−アルミナに担
持せしめたことを特徴とする過酸化水素分解触媒にあ
る。In order to solve such a problem, the gist of the present invention is that a metal having a hydrogen peroxide decomposing property is supported on γ-alumina surface-treated with a salt of zinc. It is a characteristic hydrogen peroxide decomposition catalyst.
【００１０】また、本発明は、（１）亜鉛の塩の水溶液
にγ−アルミナを浸漬することにより、該γ−アルミナ
に亜鉛の塩を含浸せしめて、これを焼成する工程と、
（２）かかる焼成されたγ−アルミナを、所定の過酸化
水素分解能を有する金属の塩の水溶液または水分散液に
浸漬することにより、該γ−アルミナに該金属の塩を含
浸せしめて、これを焼成し、更に水素ガスで還元するこ
とによって、前記過酸化水素分解能を有する金属をγ−
アルミナに担持せしめる工程とを、含むことを特徴とす
る過酸化水素分解触媒の製造方法をも、その要旨とする
ものである。The present invention also includes (1) a step of immersing γ-alumina in an aqueous solution of a zinc salt to impregnate the γ-alumina with the zinc salt and firing the same.
(2) The calcined γ-alumina is immersed in an aqueous solution or aqueous dispersion of a metal salt having a predetermined hydrogen peroxide decomposing ability to impregnate the γ-alumina with the metal salt. Is calcined and further reduced with hydrogen gas to give a metal having a hydrogen peroxide decomposing ability to γ-
A method for producing a hydrogen peroxide decomposition catalyst, which comprises a step of supporting the catalyst on alumina, is also the subject of the present invention.
【００１１】さらに、本発明は、コンタクトレンズを過
酸化水素水溶液に浸漬する一方、前記の過酸化水素分解
触媒を投入することにより、初期の過酸化水素の分解速
度を抑える一方、所定時間後には過酸化水素の殆どを分
解するようにして、過酸化水素による消毒を有効に行な
いつつ、過酸化水素の中和を行なうことを特徴とするコ
ンタクトレンズの消毒方法をも、その要旨とするもので
ある。Further, according to the present invention, while the contact lens is dipped in an aqueous solution of hydrogen peroxide, the initial decomposition rate of hydrogen peroxide is suppressed by introducing the above-mentioned hydrogen peroxide decomposition catalyst. A disinfecting method for contact lenses, which is characterized in that most of hydrogen peroxide is decomposed so that disinfection with hydrogen peroxide is effectively performed while neutralizing the hydrogen peroxide, is also the gist thereof. is there.
【００１２】[0012]
【作用・効果】要するに、本発明に従う過酸化水素分解
触媒にあっては、亜鉛の塩にて表面処理されたγ−アル
ミナに過酸化水素分解能を有する金属を担持せしめたこ
とによって、該金属がアルミナ上に均一に且つ強固に吸
着され、該金属の剥がれ等が良好に防止され得るように
なっている。それ故、安定した過酸化水素分解力を有
し、優れた過酸化水素分解効率を発揮するのであり、少
量で過酸化水素を効率的に分解して、過酸化水素の残留
を防止することができる。また、このようにして触媒の
使用量を少なくすることにより、過酸化水素の初期の分
解速度を効果的に遅くすることができるため、コンタク
トレンズの消毒工程から触媒を投入しておいても、過酸
化水素によるコンタクトレンズの消毒を充分に行なうこ
とができるのである。ACTIONS AND EFFECTS In summary, in the hydrogen peroxide decomposition catalyst according to the present invention, γ-alumina surface-treated with a zinc salt is loaded with a metal capable of decomposing hydrogen peroxide. It is uniformly and strongly adsorbed on alumina, and peeling of the metal can be favorably prevented. Therefore, it has a stable hydrogen peroxide decomposing power and exerts an excellent hydrogen peroxide decomposition efficiency. Therefore, it is possible to efficiently decompose hydrogen peroxide with a small amount and prevent hydrogen peroxide from remaining. it can. Further, by reducing the amount of the catalyst used in this way, the initial decomposition rate of hydrogen peroxide can be effectively slowed down, so even if the catalyst is added from the contact lens disinfection step, The contact lens can be sufficiently disinfected with hydrogen peroxide.
【００１３】また、本発明の過酸化水素分解触媒の製造
方法によれば、かかる触媒を簡便且つ効率的に製造する
ことができる。Further, according to the method for producing a hydrogen peroxide decomposition catalyst of the present invention, such a catalyst can be produced simply and efficiently.
【００１４】そして、かかる触媒を用いることによっ
て、本発明のコンタクトレンズ消毒方法では、過酸化水
素によるコンタクトレンズの消毒と、過酸化水素の中和
を１ステップで簡便に実施することができ、所定時間経
過後には、清浄化され且つ無毒化されたコンタクトレン
ズを有利に得ることができるのである。By using such a catalyst, in the contact lens disinfecting method of the present invention, disinfection of the contact lens with hydrogen peroxide and neutralization of hydrogen peroxide can be easily carried out in one step. After a lapse of time, a cleaned and detoxified contact lens can be advantageously obtained.
【００１５】[0015]
【具体的構成】ところで、本発明では、過酸化水素分解
触媒の担体としてγ−アルミナが使用されるが、特に、
触媒の耐久性を高めるうえで、１００m2／ｇ〜３５０m2
／ｇの比表面積を有するγ−アルミナが好ましく使用さ
れる。より好ましくは、１３０〜３００m2／ｇの比表面
積を有するγ−アルミナが使用される。そして、かかる
γ−アルミナは、ｐＨスウィング法、加水分解法（アル
コキシド法）、Ｙｏｌｄａｓ法、物理的制御法等の一般
的な製造手法によって製造され得るが、上記範囲の比表
面積のγ−アルミナが得られ易い、加水分解法が好適に
採用されることとなる。SPECIFIC STRUCTURE By the way, in the present invention, γ-alumina is used as a carrier of a hydrogen peroxide decomposition catalyst.
100m 2 / g ~ 350m 2 to improve the durability of the catalyst
Γ-alumina having a specific surface area of / g is preferably used. More preferably, γ-alumina having a specific surface area of 130 to 300 m 2 / g is used. And such γ-alumina can be produced by a general production method such as a pH swing method, a hydrolysis method (alkoxide method), a Yoldas method, a physical control method, etc. The hydrolysis method, which is easy to obtain, is preferably adopted.
【００１６】また、かかるγ−アルミナは、粒状、ペレ
ット状、ディスク状等に圧縮成形して、使用されること
となり、４〜６mmφの粒状のものが好ましく使用される
こととなる。なお、原因は不明であるが、有機系結合剤
を使用したものは、有機結合剤を使用しないものに比較
して、その触媒活性が数十％程度に減少することから、
良好な触媒活性を得るうえで、純粋なアルミナ（Ａｌ2
Ｏ3 ）のみを使用し、圧縮成形することが望ましい。Further, such γ-alumina is used by being compression-molded into a granular shape, a pellet shape, a disk shape or the like, and a granular shape of 4 to 6 mmφ is preferably used. In addition, although the cause is unknown, since the catalyst activity of the one using the organic binder is reduced to about several tens% as compared with the one not using the organic binder,
In order to obtain good catalytic activity, pure alumina (Al 2
It is desirable to use only O 3 ) for compression molding.
【００１７】そして、本発明では、そのようなγ−アル
ミナに対して、亜鉛の塩を用いた表面処理を施すことと
なり、この表面処理は、亜鉛の塩の水溶液にγ−アルミ
ナを浸漬することにより、該γ−アルミナに亜鉛の塩を
含浸せしめて、これを焼成することによって有利に実施
され得る。In the present invention, such γ-alumina is subjected to surface treatment using a zinc salt, and this surface treatment is performed by immersing γ-alumina in an aqueous solution of zinc salt. According to the above, it can be advantageously carried out by impregnating the γ-alumina with a zinc salt and calcining the salt.
【００１８】なお、亜鉛の塩としては、塩化亜鉛、酢酸
亜鉛、硝酸亜鉛、臭化亜鉛、ヨウ化亜鉛、ギ酸亜鉛、プ
ロピオン酸亜鉛、乳酸亜鉛、安息香酸亜鉛、サリチル酸
亜鉛、炭酸亜鉛、リン酸亜鉛、硫酸亜鉛等が用いられ得
る。中でも、塩化亜鉛、酢酸亜鉛、硝酸亜鉛が好ましく
用いられる。また、亜鉛の塩の担持量は、０．１〜１０
ｗｔ％程度に調整することが好ましく、コストの面から
０．１〜２ｗｔ％程度がより好ましい。Examples of the zinc salt include zinc chloride, zinc acetate, zinc nitrate, zinc bromide, zinc iodide, zinc formate, zinc propionate, zinc lactate, zinc benzoate, zinc salicylate, zinc carbonate and phosphoric acid. Zinc, zinc sulfate, etc. may be used. Among them, zinc chloride, zinc acetate and zinc nitrate are preferably used. The amount of zinc salt supported is 0.1 to 10
It is preferable to adjust to about wt%, and from the viewpoint of cost, about 0.1 to 2 wt% is more preferable.
【００１９】より具体的に、塩化亜鉛（ＺｎＣｌ2 ）に
てγ−アルミナの表面処理を行なうには、先ず、γ−ア
ルミナの表面を清浄化するために、該γ−アルミナを熱
水中で煮沸（例えば８０℃、３０分）し、乾燥して（例
えば１１０℃）、前処理が実施される。そして、該γ−
アルミナを０．５％ＺｎＣｌ2 水溶液に浸漬し、ＺｎＣ
ｌ2 を含浸させることとなり、これを乾燥した後、焼成
するのである。More specifically, in order to perform the surface treatment of γ-alumina with zinc chloride (ZnCl 2 ), first, in order to clean the surface of γ-alumina, the γ-alumina is heated in hot water. It is boiled (for example, 80 ° C., 30 minutes), dried (for example, 110 ° C.), and pretreated. And the γ-
Alumina was dipped in a 0.5% ZnCl 2 aqueous solution to obtain ZnC.
This is impregnated with l 2 , which is dried and then calcined.
【００２０】なお、亜鉛の塩を含浸せしめた後の乾燥工
程は、通常、８０〜１２０℃程度の温度雰囲気で８〜４
８時間行なわれ、好ましくは９０〜１１０℃で１６〜３
６時間、より好ましくは１００℃で２４時間程度とされ
る。また、その後の焼成工程は、通常、３００〜５００
℃程度の温度雰囲気で行なわれ、好ましくは３５０〜４
５０℃、より好ましくは４００℃程度とされる。The drying step after impregnation with the zinc salt is usually carried out in the temperature atmosphere of about 80 to 120 ° C. for 8 to 4 times.
It is carried out for 8 hours, preferably 16 to 3 at 90 to 110 ° C.
It is set to 6 hours, more preferably at 100 ° C. for about 24 hours. The subsequent firing step is usually 300 to 500.
It is carried out in a temperature atmosphere of about ℃, preferably 350-4
The temperature is 50 ° C., and more preferably about 400 ° C.
【００２１】そして、上述の如くして表面処理が施され
たγ−アルミナに対して、過酸化水素分解能を有する金
属（以下、触媒金属という）を担持せしめることによ
り、目的とする過酸化水素分解触媒が得られるのであ
る。この担持操作は、亜鉛の塩にて表面処理されたγ−
アルミナを、所定の触媒金属の塩の水溶液または水分散
液に浸漬することにより、該γ−アルミナに該金属の塩
を含浸せしめて、これを焼成し、更に水素ガスで還元す
ることによって、有利に実施することができる。Then, the target hydrogen peroxide decomposition is carried out by loading a metal having hydrogen peroxide decomposing ability (hereinafter referred to as a catalyst metal) on the γ-alumina surface-treated as described above. The catalyst is obtained. This loading operation was carried out by γ-surface-treated with a zinc salt.
Alumina is immersed in an aqueous solution or water dispersion of a salt of a predetermined catalyst metal to impregnate the γ-alumina with the salt of the metal, calcined, and further reduced with hydrogen gas, which is advantageous. Can be carried out.
【００２２】なお、触媒金属としては、公知のものを何
れも用いることができ、例えばＩｒ、Ｐｔ、Ｒｕ、Ｐ
ｄ、Ｒｈ、Ｒｅ、Ａｕ、Ａｇ、Ｃｕ、Ｃｒ、Ｏｓ、Ｃ
ｏ、Ｆｅ、Ｍｏ、Ｗ、Ｍｎ、Ｃｅ、Ｔｈ等を挙げること
ができる。それらの中でも、Ｉｒ、Ｐｔ、Ｒｕ等が好ま
しく、特に触媒活性度の高いＩｒが好ましい。また、γ
−アルミナに担持させる触媒金属の担持量は、０．１〜
１０ｗｔ％程度が好ましいが、Ｉｒ等は比較的低濃度で
あっても過酸化水素分解効果があることから、約０．１
〜２ｗｔ％程度に調整することがコストの面から好まし
い。Any known catalyst metal can be used as the catalyst metal, for example Ir, Pt, Ru, P.
d, Rh, Re, Au, Ag, Cu, Cr, Os, C
o, Fe, Mo, W, Mn, Ce, Th, etc. can be mentioned. Among them, Ir, Pt, Ru and the like are preferable, and Ir having a high catalytic activity is particularly preferable. Also, γ
-The amount of the catalytic metal supported on the alumina is 0.1 to
About 10 wt% is preferable, but Ir or the like has an effect of decomposing hydrogen peroxide even at a relatively low concentration.
It is preferable to adjust it to about 2 wt% from the viewpoint of cost.
【００２３】より具体的に、触媒金属としてＩｒを担持
させるには、先ず、亜鉛の塩にて表面処理されたγ−ア
ルミナを０．１〜１％程度の濃度の塩化イリジウム（Ｉ
ｒＣｌ3 ）水溶液に浸漬し、ＩｒＣｌ3 を含浸させるこ
ととなり、これを乾燥した後、焼成するのである。そし
て、通常、水による洗浄操作及び乾燥操作（１１０℃程
度）が後処理として行なわれる。また、必要に応じて、
かかるＩｒＣｌ3 の含浸−乾燥−焼成−洗浄−乾燥の一
連の工程を複数回繰り返すことによって、ＩｒＣｌ3 の
担持量を調節することができる。More specifically, in order to support Ir as a catalyst metal, first, γ-alumina surface-treated with a zinc salt is added to iridium chloride (I) having a concentration of about 0.1 to 1%.
It is soaked in an aqueous solution of rCl 3 ) and impregnated with IrCl 3 , which is dried and then calcined. Then, a washing operation with water and a drying operation (about 110 ° C.) are usually performed as a post-treatment. Also, if necessary,
The amount of IrCl 3 carried can be adjusted by repeating the series of steps of impregnation of IrCl 3 -drying-calcination-washing-drying a plurality of times.
【００２４】なお、触媒金属の塩を含浸せしめた後の乾
燥工程は、通常、５０〜２００℃程度の温度雰囲気で
０．５〜６時間行なわれ、好ましくは８０〜１５０℃で
０．５〜４時間、より好ましくは１１０℃で１〜２時間
程度とされる。また、その後の焼成工程は、通常、２０
０〜６００℃程度の温度雰囲気で０．５〜５時間行なわ
れ、好ましくは３００〜５００℃で０．５〜２時間、よ
り好ましくは４００℃で１時間程度とされる。The drying step after impregnation with the salt of the catalytic metal is usually carried out in an atmosphere of a temperature of about 50 to 200 ° C. for 0.5 to 6 hours, preferably at 80 to 150 ° C. for 0.5 to It is set to 4 hours, more preferably at 110 ° C. for about 1 to 2 hours. In addition, the subsequent firing step is usually 20
It is carried out in a temperature atmosphere of about 0 to 600 ° C. for 0.5 to 5 hours, preferably at 300 to 500 ° C. for 0.5 to 2 hours, and more preferably at 400 ° C. for about 1 hour.
【００２５】次いで、γ−アルミナに担持せしめたＩｒ
Ｃｌ3 を還元せしめるべく、水素ガス雰囲気下若しくは
水素ガス／不活性ガスの混合雰囲気下において、加熱操
作が行なわれることとなる。そして、雰囲気ガス中の水
素ガスの割合は、通常、５〜１００％程度とされ、好ま
しくは５〜５０％、より好ましくは２０％程度とされ
る。また、加熱操作は、通常、２００〜６００℃の温度
雰囲気で１〜６時間行なわれ、好ましくは３００〜５０
０℃で２〜４時間、より好ましくは４００℃で３時間程
度とされる。Then, Ir supported on γ-alumina was used.
In order to reduce Cl 3 , the heating operation is carried out in a hydrogen gas atmosphere or a mixed atmosphere of hydrogen gas / inert gas. The proportion of hydrogen gas in the atmosphere gas is usually about 5 to 100%, preferably 5 to 50%, more preferably about 20%. The heating operation is usually performed in a temperature atmosphere of 200 to 600 ° C. for 1 to 6 hours, preferably 300 to 50.
The temperature is 0 ° C. for 2 to 4 hours, more preferably 400 ° C. for about 3 hours.
【００２６】そして、かかる還元操作の後、水で洗浄
し、乾燥（１１０℃程度）することによって、目的とす
る過酸化水素分解触媒を得ることができるのである。After the reduction operation, the target hydrogen peroxide decomposition catalyst can be obtained by washing with water and drying (about 110 ° C.).
【００２７】このような触媒は、亜鉛の塩にて表面処理
されたγ−アルミナに、触媒金属が担持されていること
により、該触媒金属がγ−アルミナに均一に且つ強固に
担持せしめられて、剥がれ難くなっており、安定した過
酸化水素分解力を示すと共に、過酸化水素の分解効率が
高い。それ故に、少量で過酸化水素を効率的に分解する
ことができ、過酸化水素の残留を防止できる。また、そ
のように少量の触媒を使用することにより、コンタクト
レンズの消毒工程から触媒を投入しておいても、過酸化
水素の初期の分解速度を効果的に遅くすることができる
ため、過酸化水素による消毒を充分に行なうことができ
るのである。In such a catalyst, the catalytic metal is supported on the γ-alumina surface-treated with zinc salt, so that the catalytic metal is uniformly and firmly supported on the γ-alumina. Since it is difficult to peel off, it exhibits a stable hydrogen peroxide decomposing power and has a high hydrogen peroxide decomposition efficiency. Therefore, hydrogen peroxide can be efficiently decomposed with a small amount, and hydrogen peroxide can be prevented from remaining. In addition, by using such a small amount of catalyst, the initial decomposition rate of hydrogen peroxide can be effectively slowed down even if the catalyst is added during the contact lens disinfection process. Sufficient disinfection with hydrogen can be performed.
【００２８】従って、かかる触媒を用いることによっ
て、本発明に従うコンタクトレンズの消毒方法では、コ
ンタクトレンズを過酸化水素水溶液に浸漬する一方、上
述した如き過酸化水素分解触媒を投入して、実質的に一
回の操作で簡便にコンタクトレンズの消毒と過酸化水素
の中和を行なうことができる。そして、所定時間経過後
には、清浄化され且つ無毒化されたコンタクトレンズを
有利に得ることができるのである。Therefore, in the method for disinfecting a contact lens according to the present invention, by using such a catalyst, the contact lens is immersed in an aqueous solution of hydrogen peroxide, and the hydrogen peroxide decomposition catalyst as described above is added to the contact lens to substantially It is possible to easily disinfect contact lenses and neutralize hydrogen peroxide with a single operation. Then, after a lapse of a predetermined time, a clean and detoxified contact lens can be advantageously obtained.
【００２９】なお、触媒の量が少なすぎると、所定時間
（例えば４〜６時間）経過後にも過酸化水素が残留する
ようになる一方、触媒の量が多いと、初期の過酸化水素
分解速度が速まって、消毒効果が低減することとなるた
め、有効な消毒を行ない且つ過酸化水素の残留を防止す
るためには、消毒に使用する過酸化水素水溶液の量と使
用する触媒の量とを、触媒の活性度等に応じて、互いに
適した範囲に調整することとなる。例えば、塩化亜鉛で
表面処理したγ−アルミナにＩｒを担持させてなる粒
径：４．５mmの触媒（一粒当たりの表面積：約０．６３
６cm2 ）を、３％過酸化水素水溶液の１０mlに対して投
入する場合であれば、３％過酸化水素水溶液の１mlに対
して触媒の表面積が合計で０．３〜１cm2 になるよう
に、５〜１５粒の触媒を使用することが好ましい。ま
た、触媒は、過酸化水素水溶液中においてなるべく分散
して配置せしめられるようにすることが望ましい。If the amount of the catalyst is too small, hydrogen peroxide will remain after a predetermined time (for example, 4 to 6 hours), while if the amount of the catalyst is large, the initial hydrogen peroxide decomposition rate will be high. Therefore, in order to perform effective disinfection and prevent residual hydrogen peroxide, the amount of hydrogen peroxide solution used for disinfection and the amount of catalyst used must be Are adjusted to ranges suitable for each other, depending on the activity of the catalyst and the like. For example, a catalyst having a particle diameter of 4.5 mm formed by supporting Ir on γ-alumina surface-treated with zinc chloride (surface area per grain: about 0.63
6 cm 2 ) to 10 ml of 3% hydrogen peroxide solution, the total surface area of the catalyst should be 0.3-1 cm 2 for 1 ml of 3% hydrogen peroxide solution. It is preferable to use 5 to 15 particles of catalyst. Further, it is desirable that the catalyst is arranged in the hydrogen peroxide aqueous solution as dispersed as possible.
【００３０】[0030]
【実施例】以下に、本発明の幾つかの実施例を示し、本
発明を更に具体的に明らかにすることとするが、本発明
が、そのような実施例の記載によって、何等の制約をも
受けるものでないことは、言うまでもないところであ
る。また、本発明には、以下の実施例の他にも、更には
上記の具体的記述以外にも、本発明の趣旨を逸脱しない
限りにおいて、当業者の知識に基づいて種々なる変更、
修正、改良等を加え得るものであることが、理解される
べきである。EXAMPLES Some examples of the present invention will be shown below to clarify the present invention in more detail. However, the present invention is not limited by the description of such examples. Needless to say, it is not something to receive. Further, in addition to the following specific examples, in addition to the following embodiments, the present invention includes various modifications based on the knowledge of those skilled in the art without departing from the spirit of the present invention.
It should be understood that modifications, improvements, etc. may be made.
【００３１】実施例 １触媒の調製 （１） 先ず、市販のγ−アルミナ（住友化学工業
（株）製、商品番号ＫＨＡ−４６、比表面積：１５０〜
１５５m2／ｇ）を整粒して、粒径：４〜５mmのもののみ
を選別する。そして、そのγ−アルミナの１０ｇを量
り、１００mlの精製水中に入れて、８０℃で３０分間煮
沸した後、取り出して、１１０℃で２時間乾燥する。 （２） 次いで、表面処理を行なうべく、０．５ｗ／ｖ
％塩化亜鉛水分散液の２０mlに該γ−アルミナを浸漬し
て、完全に含浸させた後、１１０℃で１時間乾燥して、
更に４００℃で２時間焼成を行ない、塩化亜鉛をγ−ア
ルミナに担持させる。また、焼成後は、精製水で洗浄し
て、１１０℃で２時間乾燥する。 （３） そして、かかる表面処理が為されたγ−アルミ
ナを、０．５ｗ／ｖ％塩化イリジウム（IV）水溶液の２
７mlに浸漬して、完全に含浸させた後、１１０℃で１時
間乾燥して、更に４００℃で１時間焼成を行ない、塩化
イリジウムをγ−アルミナに担持させる。また、焼成後
は、精製水で洗浄して、１１０℃で２時間乾燥する。 （４） さらに、該γ−アルミナを２０％水素−アルゴ
ン雰囲気下において４００℃で３時間還元することによ
り、イリジウム金属をγ−アルミナに担持させる。そし
て、精製水で洗浄して、１１０℃で２時間乾燥して、約
１０ｇの過酸化水素分解触媒を得る。Example 1 Preparation of catalyst (1) First, commercially available γ-alumina (manufactured by Sumitomo Chemical Co., Ltd., product number KHA-46, specific surface area: 150-)
155 m 2 / g) is sized, and only those having a particle size of 4 to 5 mm are selected. Then, 10 g of the γ-alumina is weighed, put in 100 ml of purified water, boiled at 80 ° C. for 30 minutes, taken out, and dried at 110 ° C. for 2 hours. (2) Next, 0.5 w / v for surface treatment
% Γ-alumina was immersed in 20 ml of an aqueous zinc chloride dispersion to completely impregnate it, and then dried at 110 ° C. for 1 hour.
Further, firing is performed at 400 ° C. for 2 hours to support zinc chloride on γ-alumina. After baking, the product is washed with purified water and dried at 110 ° C for 2 hours. (3) Then, the surface-treated γ-alumina was added to an aqueous solution of 0.5 w / v% iridium (IV) chloride to prepare 2
After immersing in 7 ml to completely impregnate it, it is dried at 110 ° C. for 1 hour and further calcined at 400 ° C. for 1 hour to support iridium chloride on γ-alumina. After baking, the product is washed with purified water and dried at 110 ° C for 2 hours. (4) Further, the γ-alumina is reduced in an atmosphere of 20% hydrogen-argon at 400 ° C. for 3 hours so that the iridium metal is supported on the γ-alumina. Then, it is washed with purified water and dried at 110 ° C. for 2 hours to obtain about 10 g of hydrogen peroxide decomposition catalyst.
【００３２】過酸化水素水溶液の調製 一方、過酸化水素：３．０４ｗ／ｖ％、塩化ナトリウ
ム：０．８５ｗ／ｖ％及びスズ酸ナトリウム：０．００
８ｗ／ｖ％を含有する過酸化水素水溶液を調製し、０．
００８４ mol／ｌのリン酸緩衝液によりｐＨ６．７５に
調整した。 Preparation of Hydrogen Peroxide Aqueous Solution On the other hand, hydrogen peroxide: 3.04 w / v%, sodium chloride: 0.85 w / v% and sodium stannate: 0.00
An aqueous hydrogen peroxide solution containing 8 w / v% was prepared and
The pH was adjusted to 6.75 with a phosphate buffer of 0084 mol / l.
【００３３】過酸化水素の分解試験 そして、約１０ml容のバイアル瓶に前記過酸化水素水溶
液を４ml入れる一方、前記過酸化水素分解触媒を３粒投
入して（平均表面積：０．６３６cm2 ×３粒＝約１．９
cm2 ）、過酸化水素の分解を行ない、該試験液の一定時
間経過ごとの残留過酸化水素濃度をＡＢＴＳ法（下記参
照）に従って測定し、過酸化水素分解挙動を調べた。な
お、当該試験における「触媒の表面積／３％Ｈ2 Ｏ
2 （ml）」の値は、０．４８cm2 ／mlであった。そし
て、その結果を、下記表１に示した。 Decomposition Test of Hydrogen Peroxide Then, while putting 4 ml of the hydrogen peroxide solution into a vial of about 10 ml volume, 3 particles of the hydrogen peroxide decomposition catalyst were placed (average surface area: 0.636 cm 2 × 3). Grain = about 1.9
cm 2 ), hydrogen peroxide was decomposed, and the residual hydrogen peroxide concentration of the test solution after a certain period of time was measured according to the ABTS method (see below) to investigate the hydrogen peroxide decomposition behavior. In the test, "surface area of catalyst / 3% H 2 O
2 (ml) "was 0.48 cm 2 / ml. The results are shown in Table 1 below.
【００３４】ＡＢＴＳ法 先ず、リン酸−ナトリウム二水和物（試薬特級）：１
０．９２ｇ及びリン酸二ナトリウム十二水和物（試薬特
級）：４６．００ｇを精製水に溶かし、ｐＨ７．０±
０．１に調整した後、全量を１リットルとして、リン酸
緩衝液を得る。次いで、２，２’−アジノビス（３−エ
チルベンゾチアゾリン−６−スルホン酸）２ＮＨ4 塩
（ＡＢＴＳ試薬特級）：０．１１３ｇ及びペルオキシダ
ーゼ（シグマＴｙｐｅ１）：１００units を前記リン酸
緩衝液に溶かして、１００mlとし、ＡＢＴＳ試薬を調製
する（用時調製）。 ABTS Method First, sodium phosphate dihydrate (special grade reagent): 1
0.92 g and disodium phosphate dodecahydrate (reagent special grade): 46.00 g were dissolved in purified water to obtain pH 7.0 ±.
After adjusting to 0.1, the total amount is adjusted to 1 liter to obtain a phosphate buffer solution. Then, 2,2′-azinobis (3-ethylbenzothiazoline-6-sulfonic acid) 2NH 4 salt (ABTS reagent special grade): 0.113 g and peroxidase (Sigma Type 1): 100 units were dissolved in the phosphate buffer solution, Prepare 100 ml of ABTS reagent (prepared before use).
【００３５】そして、試験液（過酸化水素水溶液）を７
０ｐｐｍ以下に希釈して、その０．１mlを採取し、前記
ＡＢＴＳ試薬４．９mlに加えて、攪拌した後、４２０ｎ
ｍでの吸光度を測定し（空試験を対照とする）、同時に
検量線を作成して、濃度を算出する。Then, the test liquid (hydrogen peroxide aqueous solution) is added to 7
After diluting to 0 ppm or less, 0.1 ml of the sample was taken, added to 4.9 ml of the ABTS reagent and stirred, and then 420 n
The absorbance at m is measured (a blank test is used as a control), and at the same time, a calibration curve is prepared to calculate the concentration.
【００３６】実施例 ２ アルミニウムイソプロポキシドを出発原料とした加水分
解法により調製したγ−アルミナ（比表面積：２１０m2
／ｇ）を、球状成形機を用いたプレス成形により成形し
て、粒径：４〜５mmのものを選別した。そして、触媒金
属の担持工程で用いる塩化イリジウム（IV）を塩化イリ
ジウム（III ）に変更し、また還元工程における２０％
水素−アルゴン雰囲気を２０％水素−ヘリウム雰囲気と
した他は、実施例１と同様にして、一連の工程を実施
し、過酸化水素分解触媒を調製した。Example 2 γ-alumina prepared by a hydrolysis method using aluminum isopropoxide as a starting material (specific surface area: 210 m 2
/ G) was molded by press molding using a spherical molding machine, and particles having a particle size of 4 to 5 mm were selected. Then, iridium (IV) chloride used in the step of supporting the catalytic metal is changed to iridium (III) chloride, and 20% in the reduction step is used.
A hydrogen peroxide decomposition catalyst was prepared by carrying out a series of steps in the same manner as in Example 1 except that the hydrogen-argon atmosphere was changed to a 20% hydrogen-helium atmosphere.
【００３７】そして、約１０ml容のバイアル瓶に実施例
１で調製した過酸化水素水溶液を３ml入れる一方、前記
過酸化水素分解触媒を３粒投入して、過酸化水素の分解
を行ない、該試験液の一定時間経過ごとの残留過酸化水
素濃度をＡＢＴＳ法に従って測定し、過酸化水素分解挙
動を調べた。なお、当該試験における「触媒の表面積／
３％Ｈ2 Ｏ2 （ml）」の値は、０．６４cm2 ／mlであっ
た。そして、その結果を、下記表１に示した。Then, while putting 3 ml of the hydrogen peroxide solution prepared in Example 1 into a vial having a capacity of about 10 ml, 3 particles of the hydrogen peroxide decomposition catalyst were added to decompose hydrogen peroxide, and the test was conducted. The residual hydrogen peroxide concentration of the liquid was measured according to the ABTS method after every certain period of time, and the hydrogen peroxide decomposition behavior was investigated. In the test, "surface area of catalyst /
The value of "3% H 2 O 2 (ml)" was 0.64 cm 2 / ml. The results are shown in Table 1 below.
【００３８】実施例 ３ γ−アルミナとして、比表面積が１１０m2／ｇのものを
使用した他は、実施例２と同様にして過酸化水素分解触
媒を調製した。そして、該触媒を用いた過酸化水素分解
挙動を実施例２と同様にして調べ、その結果を下記表１
に示した。Example 3 A hydrogen peroxide decomposition catalyst was prepared in the same manner as in Example 2 except that γ-alumina having a specific surface area of 110 m 2 / g was used. Then, the hydrogen peroxide decomposition behavior using the catalyst was examined in the same manner as in Example 2, and the results are shown in Table 1 below.
It was shown to.
【００３９】実施例 ４ γ−アルミナとして、比表面積が３４０m2／ｇのものを
使用した他は、実施例２と同様にして過酸化水素分解触
媒を調製した。そして、該触媒を用いた過酸化水素分解
挙動を実施例２と同様にして調べ、その結果を下記表１
に示した。Example 4 A hydrogen peroxide decomposition catalyst was prepared in the same manner as in Example 2 except that γ-alumina having a specific surface area of 340 m 2 / g was used. Then, the hydrogen peroxide decomposition behavior using the catalyst was examined in the same manner as in Example 2, and the results are shown in Table 1 below.
It was shown to.
【００４０】実施例 ５ 触媒金属の担持工程で用いる０．５ｗ／ｖ％塩化イリジ
ウム（IV) 水溶液：２７mlの代わりに、０．７３ｗ／ｖ
％塩化白金（IV) 酸カリウム水溶液：２７mlを用いた他
は、実施例１と同様にして過酸化水素分解触媒を調製し
た。そして、該触媒を用いた過酸化水素分解挙動を実施
例１と同様にして調べ、その結果を下記表１に示した。Example 5 0.5 w / v% iridium (IV) chloride aqueous solution used in the catalyst metal supporting step: 0.73 w / v instead of 27 ml
% Hydrogen chloride aqueous solution of platinum (IV): A hydrogen peroxide decomposition catalyst was prepared in the same manner as in Example 1 except that 27 ml was used. Then, the hydrogen peroxide decomposition behavior using the catalyst was examined in the same manner as in Example 1, and the results are shown in Table 1 below.
【００４１】実施例 ６ 触媒金属の担持工程で用いる０．５ｗ／ｖ％塩化イリジ
ウム（IV) 水溶液：２７mlの代わりに、０．３５ｗ／ｖ
％塩化ルテニウム（III)・ｎＨ2 Ｏ（ｎ＝１〜３）水溶
液：２７mlを用いた他は、実施例１と同様にして過酸化
水素分解触媒を調製した。そして、該触媒を用いた過酸
化水素分解挙動を実施例１と同様にして調べ、その結果
を下記表１に示した。Example 6 0.5 w / v% iridium (IV) chloride aqueous solution used in the catalyst metal loading step: 0.35 w / v instead of 27 ml
% Ruthenium (III) chloride.nH 2 O (n = 1 to 3) aqueous solution: A hydrogen peroxide decomposition catalyst was prepared in the same manner as in Example 1 except that 27 ml was used. Then, the hydrogen peroxide decomposition behavior using the catalyst was examined in the same manner as in Example 1, and the results are shown in Table 1 below.
【００４２】実施例 ７ 表面処理工程で用いる０．５ｗ／ｖ％塩化亜鉛水分散液
の代わりに、０．８１ｗ／ｖ％酢酸亜鉛水溶液を用いた
他は、実施例１と同様にして過酸化水素分解触媒を調製
した。そして、該触媒を用いた過酸化水素分解挙動を実
施例１と同様にして調べ、その結果を下記表１に示し
た。Example 7 Peroxidation was carried out in the same manner as in Example 1 except that a 0.81 w / v% zinc acetate aqueous solution was used instead of the 0.5 w / v% zinc chloride aqueous dispersion used in the surface treatment step. A hydrogen decomposition catalyst was prepared. Then, the hydrogen peroxide decomposition behavior using the catalyst was examined in the same manner as in Example 1, and the results are shown in Table 1 below.
【００４３】実施例 ８ 表面処理工程で用いる０．５ｗ／ｖ％塩化亜鉛水分散液
の代わりに、１．０９ｗ／ｖ％硝酸亜鉛水溶液を用いた
他は、実施例１と同様にして過酸化水素分解触媒を調製
した。そして、該触媒を用いた過酸化水素分解挙動を実
施例１と同様にして調べ、その結果を下記表１に示し
た。Example 8 Peroxidation was carried out in the same manner as in Example 1 except that an aqueous 1.09 w / v% zinc nitrate solution was used in place of the 0.5 w / v% zinc chloride aqueous dispersion used in the surface treatment step. A hydrogen decomposition catalyst was prepared. Then, the hydrogen peroxide decomposition behavior using the catalyst was examined in the same manner as in Example 1, and the results are shown in Table 1 below.
【００４４】比較例 １ 高分子担体（フェニレンオキシドポリマー）に白金黒を
担持させてなる市販の触媒（CIBA Vision Corp. 製、商
品名『ＡＯＤＩＳＣ』、表面積：１３．５cm2）の１個
を、実施例１で調製した３％過酸化水素水溶液の１０ml
に投入して、商品名『ＡＯＳＥＰＴシステム』として公
知の過酸化水素分解システムを実施し、実施例１と同様
にして過酸化水素分解挙動を調べ、その結果を下記表１
に示した。なお、本システムにおける「触媒の表面積／
３％Ｈ2 Ｏ2 （ml）」は、１．３５cm2 ／mlであった。Comparative Example 1 One of commercially available catalysts (made by CIBA Vision Corp., trade name "AODISC", surface area: 13.5 cm 2 ) in which platinum black is supported on a polymer carrier (phenylene oxide polymer), 10 ml of 3% aqueous hydrogen peroxide solution prepared in Example 1
Then, a hydrogen peroxide decomposition system known under the trade name “AOSEPT system” was implemented, and the hydrogen peroxide decomposition behavior was examined in the same manner as in Example 1. The results are shown in Table 1 below.
It was shown to. In addition, in this system, "the surface area of the catalyst /
3% H 2 O 2 (ml) "was 1.35 cm 2 / ml.
【００４５】比較例 ２ 「触媒の表面積／３％Ｈ2 Ｏ2 （ml）」の値を０．４８
cm2 ／mlとした他は、比較例１と同様にして、過酸化水
素分解挙動を調べ、その結果を下記表１に示した。Comparative Example 2 The value of "catalyst surface area / 3% H 2 O 2 (ml)" was 0.48.
Except for cm 2 / ml, hydrogen peroxide decomposition behavior was examined in the same manner as in Comparative Example 1, and the results are shown in Table 1 below.
【００４６】比較例 ３ 塩化亜鉛を用いたγ−アルミナの表面処理工程を除いた
他は、実施例１と同様にして過酸化水素分解触媒を調製
した。そして、該触媒を用いた過酸化水素分解挙動を実
施例１と同様にして調べ、その結果を下記表１に示し
た。Comparative Example 3 A hydrogen peroxide decomposition catalyst was prepared in the same manner as in Example 1 except that the surface treatment step of γ-alumina using zinc chloride was omitted. Then, the hydrogen peroxide decomposition behavior using the catalyst was examined in the same manner as in Example 1, and the results are shown in Table 1 below.
【００４７】比較例 ４ 塩化亜鉛を用いたγ−アルミナの表面処理工程を除いた
他は、実施例５と同様にして過酸化水素分解触媒を調製
した。そして、該触媒を用いた過酸化水素分解挙動を実
施例１と同様にして調べ、その結果を下記表１に示し
た。Comparative Example 4 A hydrogen peroxide decomposition catalyst was prepared in the same manner as in Example 5 except that the surface treatment step of γ-alumina using zinc chloride was omitted. Then, the hydrogen peroxide decomposition behavior using the catalyst was examined in the same manner as in Example 1, and the results are shown in Table 1 below.
【００４８】比較例 ５ 塩化亜鉛を用いたγ−アルミナの表面処理工程を除いた
他は、実施例６と同様にして過酸化水素分解触媒を調製
した。そして、該触媒を用いた過酸化水素分解挙動を実
施例１と同様にして調べ、その結果を下記表１に示し
た。Comparative Example 5 A hydrogen peroxide decomposition catalyst was prepared in the same manner as in Example 6 except that the surface treatment step of γ-alumina using zinc chloride was omitted. Then, the hydrogen peroxide decomposition behavior using the catalyst was examined in the same manner as in Example 1, and the results are shown in Table 1 below.
【００４９】[0049]
【表１】 [Table 1]
【００５０】かかる表１の結果より明らかなように、本
発明に従って実施された実施例１〜８では、初期の過酸
化水素分解速度が低く抑えられ、試験開始から１０〜３
０分経過後においては、残留過酸化水素濃度が高く保た
れている。一方、２４０分経過後においては、過酸化水
素が殆ど分解されていることが判る。従って、有効な消
毒効果が得られると共に、所定時間経過後には過酸化水
素の残留のない安全なコンタクトレンズを得ることがで
きるのである。As is clear from the results of Table 1, in Examples 1 to 8 carried out according to the present invention, the initial hydrogen peroxide decomposition rate was suppressed to a low level, and 10 to 3 from the start of the test.
After 0 minutes, the residual hydrogen peroxide concentration is kept high. On the other hand, it can be seen that hydrogen peroxide is almost decomposed after 240 minutes. Therefore, it is possible to obtain an effective disinfecting effect and to obtain a safe contact lens in which hydrogen peroxide does not remain after a lapse of a predetermined time.
【００５１】これに対して、実施例１と比較例３、実施
例５と比較例４、及び実施例６と比較例５を、それぞれ
比較することにより、亜鉛の塩にて表面処理をしていな
いγアルミナに触媒金属を直接に担持させた場合には、
初期の過酸化水素分解速度が速くなっていることが判
る。On the other hand, by comparing Example 1 with Comparative Example 3, Example 5 with Comparative Example 4, and Example 6 with Comparative Example 5, the surface treatment was performed with a zinc salt. When a catalytic metal is directly supported on non-γ-alumina,
It can be seen that the initial hydrogen peroxide decomposition rate is faster.
【００５２】また、比較例１及び比較例２の結果より、
従来の消毒・中和システムでは、過酸化水素の残留を防
止する量で触媒を使用すると、初期の過酸化水素分解速
度が速くなって、充分な消毒効果が得られなくなる一
方、初期の過酸化水素分解速度を遅くするために、触媒
量を減らすと、残留過酸化水素濃度が高くなって、眼刺
激等を惹起する恐れがあることが判る。From the results of Comparative Example 1 and Comparative Example 2,
In the conventional disinfection / neutralization system, if a catalyst is used in an amount that prevents the residual hydrogen peroxide, the initial hydrogen peroxide decomposition rate will increase and a sufficient disinfection effect will not be obtained, while the initial peroxidation It can be seen that when the amount of catalyst is reduced in order to slow the rate of hydrogen decomposition, the concentration of residual hydrogen peroxide increases, which may cause eye irritation and the like.
Claims (4)
の塩にて表面処理されたγ−アルミナに担持せしめたこ
とを特徴とする過酸化水素分解触媒。1. A hydrogen peroxide decomposition catalyst characterized in that a metal having a hydrogen peroxide decomposing property is supported on γ-alumina surface-treated with a zinc salt.
５０m2／ｇの比表面積を有するものであることを特徴と
する請求項１記載の過酸化水素分解触媒。2. The γ-alumina is 100 m 2 / g to 3
The hydrogen peroxide decomposition catalyst according to claim 1, which has a specific surface area of 50 m 2 / g.
を浸漬することにより、該γ−アルミナに亜鉛の塩を含
浸せしめて、これを焼成する工程と、（２）かかる焼成
されたγ−アルミナを、所定の過酸化水素分解能を有す
る金属の塩の水溶液または水分散液に浸漬することによ
り、該γ−アルミナに該金属の塩を含浸せしめて、これ
を焼成し、更に水素ガスで還元することによって、前記
過酸化水素分解能を有する金属をγ−アルミナに担持せ
しめる工程とを、含むことを特徴とする過酸化水素分解
触媒の製造方法。3. A step of (1) immersing γ-alumina in an aqueous solution of a zinc salt to impregnate the γ-alumina with the zinc salt and calcining the same, and (2) the calcining. The γ-alumina is immersed in an aqueous solution or an aqueous dispersion of a metal salt having a predetermined hydrogen peroxide decomposing ability, so that the γ-alumina is impregnated with the metal salt, followed by firing, and further hydrogen gas. And a step of supporting the metal having a hydrogen peroxide decomposing ability on γ-alumina by reducing with.
浸漬する一方、前記請求項１に記載の過酸化水素分解触
媒を投入することにより、初期の過酸化水素の分解速度
を抑える一方、所定時間後には過酸化水素の殆どを分解
するようにして、過酸化水素による消毒を有効に行ない
つつ、過酸化水素の中和を行なうことを特徴とするコン
タクトレンズの消毒方法。4. The contact lens is dipped in an aqueous solution of hydrogen peroxide while the hydrogen peroxide decomposition catalyst according to claim 1 is added to suppress the initial decomposition rate of hydrogen peroxide, and after a predetermined time. Is a method for disinfecting contact lenses, characterized in that most of hydrogen peroxide is decomposed to effectively disinfect with hydrogen peroxide while neutralizing hydrogen peroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5042243A JPH06226098A (en) | 1993-02-05 | 1993-02-05 | Hydrogen peroxide decomposition catalyst and production therefor and sterilizing method for contact lens using the catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5042243A JPH06226098A (en) | 1993-02-05 | 1993-02-05 | Hydrogen peroxide decomposition catalyst and production therefor and sterilizing method for contact lens using the catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06226098A true JPH06226098A (en) | 1994-08-16 |
Family
ID=12630594
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5042243A Pending JPH06226098A (en) | 1993-02-05 | 1993-02-05 | Hydrogen peroxide decomposition catalyst and production therefor and sterilizing method for contact lens using the catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06226098A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999052567A1 (en) * | 1998-04-14 | 1999-10-21 | Novartis Ag | Catalytic chamber |
| JP2001070937A (en) * | 1999-09-06 | 2001-03-21 | Kurita Water Ind Ltd | Membrane for treating water containing oxidizing agent and treating method |
| KR100343972B1 (en) * | 1999-11-25 | 2002-07-24 | 주식회사 유니테크 | Treatment process and the device of waste watrer including hydrogen peroxide |
| JP2005538508A (en) * | 2002-09-04 | 2005-12-15 | ユーティーシー フューエル セルズ，エルエルシー | Membrane electrode assembly using peroxide decomposition catalyst |
| JP2013511337A (en) * | 2009-11-17 | 2013-04-04 | ノバルティス アーゲー | Hydrogen peroxide solution and kit for disinfection of contact lenses |
| US9118081B2 (en) | 2002-09-04 | 2015-08-25 | Audi Ag | Membrane electrode assemblies with hydrogen peroxide decomposition catalyst |
-
1993
- 1993-02-05 JP JP5042243A patent/JPH06226098A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999052567A1 (en) * | 1998-04-14 | 1999-10-21 | Novartis Ag | Catalytic chamber |
| JP2001070937A (en) * | 1999-09-06 | 2001-03-21 | Kurita Water Ind Ltd | Membrane for treating water containing oxidizing agent and treating method |
| KR100343972B1 (en) * | 1999-11-25 | 2002-07-24 | 주식회사 유니테크 | Treatment process and the device of waste watrer including hydrogen peroxide |
| JP2005538508A (en) * | 2002-09-04 | 2005-12-15 | ユーティーシー フューエル セルズ，エルエルシー | Membrane electrode assembly using peroxide decomposition catalyst |
| US9118081B2 (en) | 2002-09-04 | 2015-08-25 | Audi Ag | Membrane electrode assemblies with hydrogen peroxide decomposition catalyst |
| US9455450B2 (en) | 2002-09-04 | 2016-09-27 | Audi Ag | Membrane electrode assemblies with hydrogen peroxide decomposition catalyst |
| JP2013511337A (en) * | 2009-11-17 | 2013-04-04 | ノバルティス アーゲー | Hydrogen peroxide solution and kit for disinfection of contact lenses |
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