JP2016074607A - Bactericidal agent composition - Google Patents
Bactericidal agent composition Download PDFInfo
- Publication number
- JP2016074607A JP2016074607A JP2014203981A JP2014203981A JP2016074607A JP 2016074607 A JP2016074607 A JP 2016074607A JP 2014203981 A JP2014203981 A JP 2014203981A JP 2014203981 A JP2014203981 A JP 2014203981A JP 2016074607 A JP2016074607 A JP 2016074607A
- Authority
- JP
- Japan
- Prior art keywords
- ppm
- acid
- peracetic acid
- chelating agent
- disinfectant composition
- 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.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 71
- 239000003899 bactericide agent Substances 0.000 title abstract 3
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 claims abstract description 116
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 69
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 102000016938 Catalase Human genes 0.000 claims abstract description 32
- 108010053835 Catalase Proteins 0.000 claims abstract description 32
- 230000001954 sterilising effect Effects 0.000 claims abstract description 31
- 238000004659 sterilization and disinfection Methods 0.000 claims abstract description 31
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 82
- 239000000645 desinfectant Substances 0.000 claims description 53
- 239000002738 chelating agent Substances 0.000 claims description 30
- 150000003839 salts Chemical class 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 12
- 239000002736 nonionic surfactant Substances 0.000 claims description 7
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 5
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 claims description 4
- 239000003945 anionic surfactant Substances 0.000 claims description 4
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 abstract description 22
- 239000003795 chemical substances by application Substances 0.000 abstract description 10
- 241000179039 Paenibacillus Species 0.000 abstract description 9
- 230000007797 corrosion Effects 0.000 abstract description 6
- 238000005260 corrosion Methods 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract 3
- 239000013522 chelant Substances 0.000 abstract 3
- 150000002978 peroxides Chemical class 0.000 abstract 2
- 230000001747 exhibiting effect Effects 0.000 abstract 1
- -1 alkyl diester Chemical class 0.000 description 28
- 239000012086 standard solution Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 14
- 238000004448 titration Methods 0.000 description 14
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 12
- 235000019345 sodium thiosulphate Nutrition 0.000 description 12
- 235000014113 dietary fatty acids Nutrition 0.000 description 10
- 239000000194 fatty acid Substances 0.000 description 10
- 229930195729 fatty acid Natural products 0.000 description 10
- 230000000249 desinfective effect Effects 0.000 description 7
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000012286 potassium permanganate Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 241000233866 Fungi Species 0.000 description 5
- 150000005215 alkyl ethers Chemical class 0.000 description 4
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
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- 229920000137 polyphosphoric acid Polymers 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
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- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 2
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- 150000003973 alkyl amines Chemical class 0.000 description 2
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- 230000000844 anti-bacterial effect Effects 0.000 description 2
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- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
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- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWSXRVCMGQZWBV-WDSKDSINSA-N glutathione Chemical compound OC(=O)[C@@H](N)CCC(=O)N[C@@H](CS)C(=O)NCC(O)=O RWSXRVCMGQZWBV-WDSKDSINSA-N 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
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- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- JLPULHDHAOZNQI-ZTIMHPMXSA-N 1-hexadecanoyl-2-(9Z,12Z-octadecadienoyl)-sn-glycero-3-phosphocholine Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCC\C=C/C\C=C/CCCCC JLPULHDHAOZNQI-ZTIMHPMXSA-N 0.000 description 1
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- 241000228212 Aspergillus Species 0.000 description 1
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- 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 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- 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 1
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 108010024636 Glutathione Proteins 0.000 description 1
- 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 1
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 1
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Landscapes
- Apparatus For Disinfection Or Sterilisation (AREA)
- Detergent Compositions (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
本発明は、過酢酸を含有した除菌剤組成物に関し、更に詳細には、過酢酸に抵抗性を持つ菌を制御することができ、かつ、設備腐食への影響を低減した除菌剤組成物を提供するものである。 The present invention relates to a disinfectant composition containing peracetic acid, and more specifically, a disinfectant composition capable of controlling bacteria having resistance to peracetic acid and having reduced influence on equipment corrosion. It provides things.
過酢酸は、過酢酸・過酸化水素・酢酸・水の平衡混合溶液として市販されているが、低濃度、短時間の接触で広範囲の微生物に対して高い除菌効果を示し、分解物が酢酸と水であることから安全性も高く、食品工業においては設備・機器・包装容器等の除菌目的で多量に使用されている。 Peracetic acid is commercially available as an equilibrium mixed solution of peracetic acid / hydrogen peroxide / acetic acid / water, but shows a high sterilizing effect on a wide range of microorganisms in a low concentration and in a short time contact. Since it is water and water, it is highly safe, and in the food industry, it is used in large quantities for the purpose of sterilization of equipment, equipment, and packaging containers.
過酢酸は、細菌、真菌、ウイルス等に対して優れた除菌性を示し、更に、人に対する感作性や変異原性が低く、分解生成物が酢酸と過酸化水素という比較的安全な化合物である。このため過酢酸、過酸化水素、酢酸を含む過酢酸系消毒薬は、安全性が高く、各種洗浄剤や除菌剤等に用いられ、更に、これらの洗浄剤や除菌剤の洗浄効果を補強する目的等から、ノニオン界面活性剤等の界面活性剤を配合している場合もある(例えば、特許文献1〜3を参照)。また近年、各種飲料食品関連では、この過酢酸に対して強い抵抗性を示すパエニバチルス属細菌等の抵抗性菌の問題が顕在化しており、その対策として、残留する過酸化水素の濃度を低減したり、過酸化水素濃度の高い過酢酸系殺菌剤を用いる方法(特許文献4)や、過酢酸濃度を上げる方法(特許文献5)などが提案されている。 Peracetic acid has excellent sterilizing properties against bacteria, fungi, viruses, etc., and has low sensitization and mutagenicity to humans, and its decomposition products are relatively safe compounds of acetic acid and hydrogen peroxide. It is. For this reason, peracetic acid-based disinfectants containing peracetic acid, hydrogen peroxide, and acetic acid are highly safe and are used in various cleaning agents and disinfectants. For the purpose of reinforcement, a surfactant such as a nonionic surfactant may be blended (see, for example, Patent Documents 1 to 3). In recent years, various foods and beverages have been exposed to the problem of resistant bacteria such as Paenibacillus spp. That exhibit strong resistance to peracetic acid. As a countermeasure, the concentration of residual hydrogen peroxide has been reduced. In addition, a method using a peracetic acid-based disinfectant having a high hydrogen peroxide concentration (Patent Document 4), a method for increasing the peracetic acid concentration (Patent Document 5), and the like have been proposed.
しかしながら、過酸化水素の濃度を低減することによって、酢酸の濃度が増加し、設備のパッキンに対して膨潤や劣化等の影響を及ぼす問題があり、過酸化水素濃度を高くすると、無菌水による洗浄後の容器への過酸化水素の残留量が高くなってしまい、製品への混入トラブルが起こるリスクがある。さらに、過酢酸濃度を上げる方法はコスト高となるという問題があった。 However, by reducing the concentration of hydrogen peroxide, the concentration of acetic acid increases, and there is a problem of affecting the packing of equipment, such as swelling and deterioration. There is a risk that the residual amount of hydrogen peroxide in the subsequent container becomes high, and there is a risk of mixing into the product. Furthermore, there is a problem that the method of increasing the peracetic acid concentration is expensive.
従って、本発明が解決しようとする課題は、過酢酸に対して強い抵抗性を示すパエニバチルス属細菌等の抵抗性菌に対する除菌性に優れ、ステンレスに対して低腐食性の除菌剤組成物を提供することにある。 Accordingly, the problem to be solved by the present invention is to provide a disinfectant composition excellent in disinfecting resistant bacteria such as Paenibacillus bacteria having strong resistance to peracetic acid and having low corrosiveness to stainless steel. Is to provide.
上記課題を解決するために、本発明者等は鋭意検討した結果、過酢酸、過酸化水素、酢酸、キレート剤とともに、カタラーゼ酵素を含む除菌剤組成物が、従来の過酢酸系除菌剤組成物が有していた問題を解決できることを見出し、本発明を完成するに至った。 In order to solve the above problems, the present inventors have intensively studied. As a result, a disinfectant composition containing a catalase enzyme together with peracetic acid, hydrogen peroxide, acetic acid and a chelating agent is a conventional peracetic acid disinfectant. The present inventors have found that the problems that the composition has can be solved, and have completed the present invention.
即ち本発明は、
(1)(A)過酢酸、(B)過酸化水素、(C)酢酸、(D)カタラーゼ酵素、(E)キレート剤、(F)水を含有する除菌剤組成物であって、(A)過酢酸濃度を100〜10000ppm、(D)カタラーゼ酵素を0.01〜250ppm、(E)キレート剤を1〜1000ppm、
含有し、かつ
(A)過酢酸と(B)過酸化水素の質量比(A)/(B)が1以上、(D)カタラーゼ酵素と(E)キレート剤の質量比(D)/(E)が、0.002〜10であることを特徴とする除菌剤組成液、
(2)(A)過酢酸、(B)過酸化水素、(C)酢酸、(E)キレート剤の少なくとも1つの成分を濃厚に含む濃厚組成物に、(D)カタラーゼ酵素及び(F)水を添加、希釈して、
(A)過酢酸濃度を100〜10000ppm、
(D)カタラーゼ酵素を0.01〜250ppm、
(E)キレート剤を1〜1000ppm、
含有し、かつ
(A)過酢酸と(B)過酸化水素の質量比(A)/(B)が1以上、
(D)カタラーゼ酵素と(E)キレート剤の質量比(D)/(E)が、0.002〜10、
となるように調整したものである上記(1)の除菌剤組成物、
(3)(E)成分のキレート剤が、有機ホスホン酸及び/又は有機ホスホン酸塩であることを特徴とする上記(1)または(2)の除菌剤組成物、
(4)(E)成分のキレート剤が、1−ヒドロキシエチリデン−1,1−ジホスホン酸、2−ホスホノブタン−1,2,4−トリカルボン酸又はこれらの塩より選ばれた化合物であることを特徴とする上記(1)〜(3)のいずれかの除菌剤組成物、
(5)さらに、(G)ノニオン界面活性剤及び/又は、(H)アニオン界面活性剤を10〜50000ppm含有することを特徴とする上記(1)〜(4)のいずれかの除菌剤組成物、
(6)上記(1)〜(5)のいずれかの除菌剤組成物を、使用温度が20℃〜70℃に加温して除菌処理することを特徴とする除菌方法、
を要旨とするものである。
That is, the present invention
(1) A disinfectant composition comprising (A) peracetic acid, (B) hydrogen peroxide, (C) acetic acid, (D) catalase enzyme, (E) chelating agent, (F) water, A) Peracetic acid concentration of 100-10000 ppm, (D) Catalase enzyme 0.01-250 ppm, (E) Chelating agent 1-1000 ppm,
And (A) the mass ratio (A) / (B) of peracetic acid and (B) hydrogen peroxide is 1 or more, (D) the mass ratio of catalase enzyme and (E) chelating agent (D) / (E Is a disinfectant composition liquid characterized by being 0.002-10,
(2) A concentrated composition containing at least one of (A) peracetic acid, (B) hydrogen peroxide, (C) acetic acid, (E) a chelating agent, and (D) catalase enzyme and (F) water Add, dilute,
(A) Peracetic acid concentration of 100 to 10000 ppm,
(D) 0.01-250 ppm of catalase enzyme,
(E) 1 to 1000 ppm of chelating agent,
And the mass ratio (A) / (B) of (A) peracetic acid and (B) hydrogen peroxide is 1 or more,
(D) The mass ratio (D) / (E) of catalase enzyme and (E) chelating agent is 0.002 to 10,
The disinfectant composition according to the above (1), which is adjusted to be
(3) The disinfectant composition according to (1) or (2) above, wherein the chelating agent of component (E) is an organic phosphonic acid and / or an organic phosphonate.
(4) The chelating agent of the component (E) is a compound selected from 1-hydroxyethylidene-1,1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid or a salt thereof. The disinfectant composition according to any one of (1) to (3) above,
(5) The disinfectant composition according to any one of (1) to (4) above, further comprising 10 to 50000 ppm of (G) nonionic surfactant and / or (H) anionic surfactant object,
(6) A sterilization method characterized in that the sterilizing composition according to any one of (1) to (5) above is heated to a use temperature of 20 ° C to 70 ° C and sterilized.
Is a summary.
本発明の除菌剤組成物は、細菌、真菌、ウイルス等に対して優れた除菌性を有するとともに、過酢酸に対して強い抵抗性を示すパエニバチルス属細菌等の抵抗性菌に対しても除菌効果に優れ、ステンレスに対して低腐食性である等の効果を奏する。 The disinfectant composition of the present invention has excellent disinfecting properties against bacteria, fungi, viruses and the like, and also resistant bacteria such as Paenibacillus spp. Excellent sterilization effect and low corrosion resistance to stainless steel.
本発明の除菌剤組成物は、(A)過酢酸、(B)過酸化水素、(C)酢酸、(D)カタラーゼ酵素、(E)キレート剤、(F)水を含有する除菌剤組成物であって、(A)過酢酸濃度を100〜10000ppm、(D)カタラーゼ酵素を0.01〜250ppm、(E)キレート剤を1〜1000ppm含有し、かつ、(A)過酢酸と(B)過酸化水素の質量比(A)/(B)が1以上、(D)カタラーゼ酵素と(E)キレート剤の質量比(D)/(E)が、0.002〜10である。本発明の除菌剤組成物は、(A)過酢酸、(B)過酸化水素、(C)酢酸、(E)キレート剤の少なくとも1つの成分を濃厚に含む濃厚組成物に、(D)カタラーゼ酵素及び(F)水を添加、希釈して、(A)過酢酸濃度を100〜10000ppm、(D)カタラーゼ酵素を0.01〜250ppm、(E)キレート剤を1〜1000ppm含有し、かつ(A)過酢酸と(B)過酸化水素の質量比(A)/(B)が1以上、(D)カタラーゼ酵素と(E)キレート剤の質量比(D)/(E)が、0.002〜10となるように調整したものでも良い。 The disinfectant composition of the present invention comprises (A) peracetic acid, (B) hydrogen peroxide, (C) acetic acid, (D) catalase enzyme, (E) chelating agent, (F) disinfectant containing water. A composition comprising (A) a concentration of peracetic acid of 100 to 10000 ppm, (D) a catalase enzyme of 0.01 to 250 ppm, (E) a chelating agent of 1 to 1000 ppm, and (A) peracetic acid and ( B) The mass ratio (A) / (B) of hydrogen peroxide is 1 or more, and the mass ratio (D) / (E) of (D) catalase enzyme and (E) chelating agent is 0.002-10. The disinfectant composition of the present invention comprises a concentrated composition containing at least one of (A) peracetic acid, (B) hydrogen peroxide, (C) acetic acid, and (E) a chelating agent. Add and dilute catalase enzyme and (F) water to contain (A) peracetic acid concentration of 100-10000 ppm, (D) catalase enzyme 0.01-250 ppm, (E) chelating agent 1-1000 ppm, and The mass ratio (A) / (B) of (A) peracetic acid and (B) hydrogen peroxide is 1 or more, and the mass ratio (D) / (E) of (D) catalase enzyme and (E) chelating agent is 0. It may be adjusted to be 0.002-10.
本発明で使用されるカタラーゼ酵素としては、微生物を起源とするものが使用できるが、好ましくはアスペルギルス属またはマイクロコッカス属を起源とするカタラーゼが挙げられ、より好ましくはアスペルギルス・ニガーを起源とするカタラーゼが挙げられる。カタラーゼ酵素の形態は水溶液でも粉末状でもよく、水溶液中または粉末化時の安定性向上の目的で使用される安定化成分としては、メタノール、エタノール、グリセリン、ソルビトール、マルチトール、マンニトール、シクロデキストリン、デキストリン、システイン、アセチルシステイン、グルタチオン、トコフェロール、アスコルビン酸、チオグリコール酸又はその塩類、クエン酸ナトリウムが挙げられる。好ましい安定化成分としてはエタノール、デキストリンが挙げられ、より好ましい安定化成分はデキストリンが挙げられる。塩酸、硝酸、硫酸、スルホン酸類等の強酸由来の塩類は、使用環境において設備の腐食に影響を及ぼすため強酸由来の塩類の少ないことが好ましい。 As the catalase enzyme used in the present invention, those originating from microorganisms can be used, preferably catalase originating from the genus Aspergillus or Micrococcus, more preferably a catalase originating from Aspergillus niger Is mentioned. Catalase enzyme may be in the form of an aqueous solution or powder, and the stabilizing components used for the purpose of improving the stability in aqueous solution or when powdered include methanol, ethanol, glycerin, sorbitol, maltitol, mannitol, cyclodextrin, Examples include dextrin, cysteine, acetylcysteine, glutathione, tocopherol, ascorbic acid, thioglycolic acid or salts thereof, and sodium citrate. Preferable stabilizing components include ethanol and dextrin, and more preferable stabilizing components include dextrin. Salts derived from strong acids such as hydrochloric acid, nitric acid, sulfuric acid, sulfonic acids and the like preferably have less salts derived from strong acids in order to affect the corrosion of the equipment in the environment of use.
本発明の除菌剤組成物において、(A)成分の過酢酸濃度は100〜10000ppmであるが、500〜5000ppmであることが好ましく、1000〜3000ppmであることがより好ましい。(A)成分の過酢酸濃度が100ppm未満であると、過酢酸抵抗性菌に対する除菌性が低下する場合があり、10000ppmを超えると、設備の腐食に影響をあたえることがあり、またコスト的に好ましくない。 In the disinfectant composition of the present invention, the concentration of peracetic acid in the component (A) is 100 to 10,000 ppm, preferably 500 to 5000 ppm, and more preferably 1000 to 3000 ppm. If the peracetic acid concentration of component (A) is less than 100 ppm, sterilization against peracetic acid-resistant bacteria may be reduced, and if it exceeds 10000 ppm, it may affect the corrosion of the equipment and is costly. It is not preferable.
(B)成分の過酸化水素濃度は2000ppm未満であることが好ましいが、200ppm未満であることがより好ましく、20ppm未満であることがさらに好ましい。過酸化水素の下限は0.1ppmが好ましく、本発明の除菌剤組成物中における過酸化水素濃度は、0.1〜10ppmであることが最も好ましい。2000ppmを超えると、過酢酸抵抗性菌に対する除菌性が低下する場合がある。 The hydrogen peroxide concentration of the component (B) is preferably less than 2000 ppm, more preferably less than 200 ppm, and even more preferably less than 20 ppm. The lower limit of hydrogen peroxide is preferably 0.1 ppm, and the hydrogen peroxide concentration in the disinfectant composition of the present invention is most preferably 0.1 to 10 ppm. If it exceeds 2000 ppm, sterilization against peracetic acid-resistant bacteria may be reduced.
(C)成分の酢酸濃度は、100〜20000ppmであることが好ましいが、500〜10000ppmであることがより好ましく、1000〜6000ppmであることがさらに好ましい。(C)成分の酢酸濃度が100ppm未満であると、無機物の汚れを除去する効果が低下する場合があり、20000ppmを超えると酢酸の臭いが激しくなるため取扱いが困難になることや設備のパッキンへの膨潤や劣化を起こす場合があるために好ましくない。 The acetic acid concentration of the component (C) is preferably 100 to 20000 ppm, more preferably 500 to 10000 ppm, and further preferably 1000 to 6000 ppm. When the concentration of acetic acid in component (C) is less than 100 ppm, the effect of removing inorganic stains may be reduced, and if it exceeds 20000 ppm, the odor of acetic acid becomes intense and handling becomes difficult and packing of equipment This is not preferable because it may cause swelling and deterioration of the material.
(D)成分のカタラーゼは、0.01〜250ppm配合されるが、0.05〜20ppm配合することが好ましく、0.1〜10ppm配合することがより好ましく、0.5〜5ppm配合することが更に好ましい。(D)成分の配合量が0.01ppm未満であると、過酸化水素の分解スピードが低下するため、パエニバチルス属細菌への除菌性が低下する場合があり、250ppmを超えると、リユース使用時にカタラーゼの分解物が過酢酸の安定性に影響を与えること、カタラーゼ酵素に起因する凝集物が発生することから好ましくない。 The component (D), catalase, is blended in an amount of 0.01 to 250 ppm, preferably 0.05 to 20 ppm, more preferably 0.1 to 10 ppm, and more preferably 0.5 to 5 ppm. Further preferred. When the blending amount of the component (D) is less than 0.01 ppm, the decomposition speed of hydrogen peroxide decreases, so that the disinfection to Paenibacillus genus bacteria may decrease, and if it exceeds 250 ppm, It is not preferable because the degradation product of catalase affects the stability of peracetic acid and aggregates resulting from the catalase enzyme are generated.
(E)成分のキレート剤としては、ポリリン酸、有機ホスホン酸、フィチン酸、エチレンジアミン四酢酸、ジエチレントリアミン五酢酸、ロダンカリ、ポリアミノカルボン酸等や、これらの塩が挙げられる。ポリリン酸としては、例えば、ピコリン酸、ジピコリン酸、ピロリン酸、トリポリリン酸、テトラポリリン酸、ヘキサポリリン酸等のポリリン酸等が挙げられ、有機ホスホン酸としては、例えば、1−ヒドロキシエチリデン−1,1−ジホスホン酸、2−ホスホノブタン−1,2,4−トリカルボン酸、アミノトリメチレンホスホン酸や、エチレンジアミンテトラ(メチレンホスホン酸)、ジエチレントリアミンペンタ(メチレンホスホン酸)等のポリエチレンポリアミン系ホスホン酸等が挙げられる。キレート剤としては、有機ホスホン酸やその塩が好ましく、なかでも1−ヒドロキシエチリデン−1,1−ジホスホン酸、2−ホスホノブタン−1,2,4−トリカルボン酸が好ましい。(E)成分のキレート剤は、1〜1000ppm配合されるが、5〜500ppm配合することが好ましく、10〜100ppm配合することがより好ましく、15〜50ppm配合することが更に好ましい。(E)キレート剤の配合量が1ppmより少ないと、過酢酸の安定性が低下する場合があり、1000ppmを超えて配合した場合、カタラーゼ酵素が失活してしまい好ましくない。 Examples of the chelating agent for component (E) include polyphosphoric acid, organic phosphonic acid, phytic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, rodankari, polyaminocarboxylic acid, and salts thereof. Examples of polyphosphoric acid include picolinic acid, dipicolinic acid, pyrophosphoric acid, tripolyphosphoric acid, tetrapolyphosphoric acid, and polyphosphoric acid such as hexapolyphosphoric acid. Examples of organic phosphonic acid include 1-hydroxyethylidene-1, Examples include 1-diphosphonic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, aminotrimethylenephosphonic acid, and polyethylenepolyamine-based phosphonic acids such as ethylenediaminetetra (methylenephosphonic acid) and diethylenetriaminepenta (methylenephosphonic acid). It is done. As a chelating agent, organic phosphonic acid and its salt are preferable, and 1-hydroxyethylidene-1,1-diphosphonic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid are particularly preferable. (E) Although the chelating agent of a component is mix | blended 1-1000 ppm, it is preferable to mix | blend 5-500 ppm, It is more preferable to mix | blend 10-100 ppm, It is still more preferable to mix | blend 15-50 ppm. (E) When the compounding amount of the chelating agent is less than 1 ppm, the stability of peracetic acid may be lowered, and when it exceeds 1000 ppm, the catalase enzyme is deactivated, which is not preferable.
また、(F)成分の水としては、特に限定はなく、イオン交換水、軟水、純水、水道水などが挙げられ、除菌剤組成物の安定性の観点から、イオン交換水又は純水が好ましい。 Further, the water of component (F) is not particularly limited, and examples thereof include ion exchange water, soft water, pure water, tap water, and the like. From the viewpoint of the stability of the disinfectant composition, ion exchange water or pure water. Is preferred.
本発明除菌剤組成物における(A)成分と(B)成分の濃度比率は、過酢酸抵抗性菌への除菌性、除菌剤組成物の安定性の観点から(A)/(B)が1以上であるが、好ましくは(A)/(B)が2以上であり、さらに好ましくは(A)/(B)=26以上であり、最も好ましくは(A)/(B)=100以上である。(A)/(B)が1未満であると、過酢酸抵抗性菌への除菌性が低下する場合がある。また(D)成分と(E)成分の濃度比率は、過酢酸抵抗性菌への除菌性、凝集物の抑制性の観点から(D)/(E)=0.002〜10(質量比)であるが、好ましくは(D)/(E)=0.005〜5であり、さらに好ましくは(D)/(E)=0.01〜3である。(D)/(E)が0.002未満であると、過酢酸抵抗性菌への除菌性が低下する場合があり、(D)/(E)が10を超えると、凝集物の抑制性が低下する場合がある。 The concentration ratio of the component (A) to the component (B) in the disinfectant composition of the present invention is (A) / (B) from the viewpoint of disinfecting to peracetic acid-resistant bacteria and stability of the disinfectant composition. ) Is 1 or more, preferably (A) / (B) is 2 or more, more preferably (A) / (B) = 26 or more, and most preferably (A) / (B) =. 100 or more. If (A) / (B) is less than 1, disinfection to peracetic acid-resistant bacteria may be reduced. The concentration ratio of the component (D) and the component (E) is (D) / (E) = 0.002 to 10 (mass ratio) from the viewpoint of disinfecting peracetic acid-resistant bacteria and suppressing the aggregates. ), Preferably (D) / (E) = 0.005-5, and more preferably (D) / (E) = 0.3-1. When (D) / (E) is less than 0.002, sterilization to peracetic acid-resistant bacteria may be reduced. When (D) / (E) exceeds 10, suppression of aggregates may occur. May decrease.
更に、本発明の除菌剤組成物には、上記(A)成分、(B)成分、(C)成分、(D)成分、(E)成分、(F)成分の他に、(G)成分としてノニオン界面活性剤が配合されていてもよい。(G)成分のノニオン界面活性剤としては、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンジアルキルエーテル、ポリオキシアルキレンアルキルエステル、ポリオキシアルキレンアルキルジエステル、ポリオキシアルキレンアルキルアリールエーテル、グリセリン脂肪酸エステル又はそのエチレンオキサイド付加物、ポリグリセリン脂肪酸エステル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル、ポリオキシエチレンソルビット脂肪酸エステル、ポリオキシエチレングリセリン脂肪酸エステル、ポリオキシエチレンヒマシ油、ポリオキシエチレン硬化ヒマシ油、ポリオキシエチレンアルキルアミン、高級脂肪酸アルカノールアミド、アルキルグリコシド、アルキルアミンオキサイド、N−オクチルピロリドン等が挙げられる。これらの中でも、泡立ちが少ない点から、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アルケニルエーテル、ポリオキシエチレンポリオキシプロピレンアルキルエーテル、エチレンオキシドとプロピレンオキシドのランダム或いはブロック付加体等のポリアルキレンオキサイド付加物が好ましく、下記の一般式(I)で表されるポリオキシアルキレンアルキルエーテル型ノニオン界面活性剤、或いはポリオキシアルキレンアルケニルエーテル型ノニオン界面活性剤がより好ましい。 Furthermore, in the disinfectant composition of the present invention, in addition to the component (A), component (B), component (C), component (D), component (E), component (F), (G) A nonionic surfactant may be blended as a component. As the nonionic surfactant of component (G), polyoxyalkylene alkyl ether, polyoxyalkylene dialkyl ether, polyoxyalkylene alkyl ester, polyoxyalkylene alkyl diester, polyoxyalkylene alkyl aryl ether, glycerin fatty acid ester or ethylene oxide thereof Additives, polyglycerin fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbit fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkyl Amines, higher fatty acid alkanolamides, alkylglycosides, alkylamine oxides, N-octides Rupiroridon, and the like. Among these, polyoxyethylene alkyl ethers, polyoxyethylene alkenyl ethers, polyoxyethylene polyoxypropylene alkyl ethers, and polyalkylene oxide adducts such as random or block adducts of ethylene oxide and propylene oxide are preferred from the viewpoint of less foaming. A polyoxyalkylene alkyl ether type nonionic surfactant represented by the following general formula (I) or a polyoxyalkylene alkenyl ether type nonionic surfactant is more preferable.
(化1)
R−(OA)n −OH (I)
(式中、Rは炭素数8〜18の脂肪族炭化水素基を表し、nは3〜50の数を表わし、Aは炭素数2〜4のアルキレン基を表す。)
(Chemical formula 1)
R- (OA) n-OH (I)
(In the formula, R represents an aliphatic hydrocarbon group having 8 to 18 carbon atoms, n represents a number of 3 to 50, and A represents an alkylene group of 2 to 4 carbon atoms.)
更に、(H)成分としてアニオン界面活性剤が配合されていてもよい。(H)成分のアニオン界面活性剤としては、高級アルコール硫酸エステル塩、硫化オレフィン塩、高級アルキルスルホン酸又はその塩、α−オレフィンスルホン酸又はその塩、硫酸化脂肪酸又はその塩、スルホン化脂肪酸又はその塩、アルキルリン酸エステル塩、α−スルホ脂肪酸メチルエステル塩、ポリオキシアルキレンアルキルエーテル硫酸エステル塩、ポリオキシアルキレンアルキルフェニルエーテル硫酸エステル塩、脂肪酸アルカノールアミド又はそのアルキレンオキサイド付加物の硫酸エステル塩、スルホコハク酸エステル、アルキルベンゼンスルホン酸又はその塩、アルキルナフタレンスルホン酸又はその塩、アルキルベンゾイミダゾールスルホン酸又はその塩、N−アシル−N−メチルタウリン又はその塩、アシルオキシエタンスルホン酸又はその塩、アルコキシエタンスルホン酸又はその塩、N−アシル−N−カルボキシエチルタウリン又はその塩、及びアルキル又はアルケニルアミノカルボキシメチル硫酸又はその塩、アルキルエーテルカルボン酸塩等を挙げることができる。 Furthermore, an anionic surfactant may be blended as the component (H). As the anionic surfactant of component (H), higher alcohol sulfate ester salt, sulfurized olefin salt, higher alkyl sulfonic acid or salt thereof, α-olefin sulfonic acid or salt thereof, sulfated fatty acid or salt thereof, sulfonated fatty acid or A salt thereof, an alkyl phosphate ester salt, an α-sulfo fatty acid methyl ester salt, a polyoxyalkylene alkyl ether sulfate ester salt, a polyoxyalkylene alkyl phenyl ether sulfate ester salt, a fatty acid alkanolamide or a sulfate ester salt of an alkylene oxide adduct thereof, Sulfosuccinic acid ester, alkylbenzene sulfonic acid or its salt, alkyl naphthalene sulfonic acid or its salt, alkyl benzimidazole sulfonic acid or its salt, N-acyl-N-methyl taurine or its salt, acyloxyethane Examples thereof include sulfonic acid or a salt thereof, alkoxyethanesulfonic acid or a salt thereof, N-acyl-N-carboxyethyl taurine or a salt thereof, and alkyl or alkenylaminocarboxymethyl sulfate or a salt thereof, and an alkyl ether carboxylate. .
本発明の除菌剤組成物は、除菌剤組成物の濃厚組成物をそのまま或いは水で希釈して使用することができる。輸送するときは、除菌剤組成物の濃厚組成物のほうが輸送コストを抑えられるため、輸送時には(A)成分の濃度は1〜15重量%が好ましく、3〜14重量%がより好ましく、5〜13重量%が更に好ましい。(E)成分の濃度は0.01〜1.5重量%が好ましく、0.03〜1.0重量%がより好ましく、0.05〜0.8重量%が更に好ましい。本発明において、除菌剤組成物の調整や希釈に用いる水としては、特に限定はなく、イオン交換水(イオン交換樹脂によりイオンを除去した水)、軟水、純水(RO水つまり逆浸透膜を通した水、蒸留水つまり蒸留器で蒸留した水)、水道水などが挙げられ、除菌性の点から純水、特にRO水が好ましい。 The disinfectant composition of the present invention can be used as it is or after diluting the concentrated composition of the disinfectant composition with water. When transporting, since the concentrated composition of the disinfectant composition can reduce the transportation cost, the concentration of the component (A) is preferably 1 to 15% by weight, more preferably 3 to 14% by weight during transportation. More preferred is ˜13% by weight. The concentration of the component (E) is preferably 0.01 to 1.5% by weight, more preferably 0.03 to 1.0% by weight, and still more preferably 0.05 to 0.8% by weight. In the present invention, the water used for the preparation and dilution of the disinfectant composition is not particularly limited. Ion exchange water (water from which ions have been removed by an ion exchange resin), soft water, pure water (RO water, that is, reverse osmosis membrane) Water, distilled water, i.e. water distilled with a still), tap water and the like. Pure water, particularly RO water is preferred from the viewpoint of sterilization.
本発明の除菌剤組成物は、(B)過酸化水素、(C)酢酸、(E)キレート剤、(F)水、を混合して平衡状態となるまで放置して(A)過酢酸、(B)過酸化水素、(C)酢酸、(E)キレート剤、(F)水を含む混合平衡溶液を得、更に必要に応じて、(G)成分、(H)成分を配合して調製することができる。本発明の除菌剤組成物は、予め全ての成分が混合された状態で調製してもよいが、使用する直前に調製する方が、高い除菌効果を得る上で好適である。使用に際して調製する方法としては、平衡状態に達した(A)成分、(B)成分、(C)成分、(E)キレート剤、(F)水及び所望によりその他成分の所定量を、それぞれ個別に水に溶解して調整する方法を用いることができるが、簡便性の点から(A)成分、(B)成分及び(C)成分、(E)成分、(F)成分及び所望によりその他成分を含有する第1剤と、(D)成分を含有する第2剤とからなり、第1剤、第2剤を使用直前に混合することによって、除菌操作に供することが好ましい。 The disinfectant composition of the present invention is prepared by mixing (B) hydrogen peroxide, (C) acetic acid, (E) chelating agent, and (F) water and leaving it in an equilibrium state (A) peracetic acid. , (B) Hydrogen peroxide, (C) Acetic acid, (E) Chelating agent, (F) A mixed equilibrium solution containing water is obtained, and (G) component and (H) component are further blended as necessary. Can be prepared. The disinfectant composition of the present invention may be prepared in a state where all the components are mixed in advance, but it is preferable to prepare it immediately before use in order to obtain a high disinfecting effect. As a method of preparation at the time of use, (A) component, (B) component, (C) component, (E) chelating agent, (F) water that has reached an equilibrium state, and predetermined amounts of other components, if necessary, are individually added. Can be prepared by dissolving in water, but from the viewpoint of simplicity, component (A), component (B) and component (C), component (E), component (F) and other components as desired It is preferable to use for the sterilization operation by mixing the first agent and the second agent immediately before use.
本発明の除菌剤組成物は、強力な除菌性を有するため、パエニバチルス属細菌を含む菌類・微生物の汚染・混入が問題となる幅広い分野(食品分野、醸造分野、医療分野、農業分野など)での除菌に有用である。例えば、乳製品・乳加工品、ビール・ワイン・清酒、味噌・醤油などの食品加工工場での容器や製造ラインの除菌、内視鏡等の医療器具の消毒や滅菌、透析ラインの洗浄、野菜及び果物の処理水の病原菌微生物の制御、植物の病気又は損傷及び苗木の腐敗の原因となる種子に取り付いた微生物の制御、食鳥肉の処理場での食鳥肉の表面の病原菌の減少、特に、無菌充填法によるPETボトル入り清涼飲料の製造での容器包材(PETボトル及びキャップ)の除菌、またはそのラインの強化除菌に好適に用いることができる。 Since the disinfectant composition of the present invention has a strong disinfecting property, it can be used in a wide range of fields in which contamination / contamination of fungi and microorganisms including Paenibacillus bacteria (food field, brewing field, medical field, agricultural field, etc.) ) Is useful for sterilization. For example, sterilization of containers and production lines in food processing factories such as dairy products, dairy products, beer, wine, sake, miso and soy sauce, disinfection and sterilization of medical equipment such as endoscopes, dialysis line cleaning, Control of pathogenic microorganisms in treated water of vegetables and fruits, control of microorganisms attached to seeds that cause plant disease or damage and seedling decay, reduction of pathogenic bacteria on the surface of poultry meat at poultry processing plants In particular, it can be suitably used for the sterilization of container packaging materials (PET bottles and caps) in the production of soft drinks containing PET bottles by the aseptic filling method, or the enhanced sterilization of the line.
本発明の除菌剤組成物による除菌処理を行う際の温度は、20℃〜70℃であるが、除菌性を高めるために、40℃〜65℃であることがより好ましく、50℃〜59℃であることが更に好ましい。除菌剤組成物の温度が20℃未満であると、過酢酸に対して強い抵抗性を示すパエニバチルス属細菌等の抵抗性菌に対する除菌性が悪くなる場合があり、70℃を超えると、製造設備の材質であるステンレスの腐食性、カタラーゼ酵素が失活してしまう場合がある。 The temperature at the time of performing the sterilization treatment with the sterilizing agent composition of the present invention is 20 ° C. to 70 ° C., but more preferably 40 ° C. to 65 ° C. in order to increase the sterilization property, More preferably, it is -59 degreeC. If the temperature of the disinfectant composition is less than 20 ° C, the disinfecting property against resistant bacteria such as Paenibacillus bacteria showing strong resistance to peracetic acid may deteriorate, and if it exceeds 70 ° C, Corrosiveness of stainless steel, which is a material of manufacturing equipment, and catalase enzyme may be deactivated.
除菌処理は、除菌液を対象物に噴霧したり、除菌液に対象物を浸漬したりする方法を採用することができるが、噴霧時間や浸漬時間は、微生物の種類や量、有機汚れあるいは無機汚れの種類や量、除菌液の濃度等によって適宜選択することができる。 For the sterilization treatment, a method of spraying a sterilization solution onto the target object or immersing the target object in the sterilization solution can be adopted. It can be appropriately selected depending on the type and amount of dirt or inorganic dirt, the concentration of the sterilizing solution, and the like.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例1〜69、比較例1〜6
表1〜7に示す配合の除菌剤組成物を調製した。各除菌剤組成物中の過酸化水素濃度、過酢酸濃度、酢酸濃度は以下の方法で測定した。また各除菌剤組成物について、除菌性試験、腐食性試験を行った。結果を表1〜8に併せて示す。
実施例1〜10、実施例21〜69、比較例5〜6に関しては、(A)成分、(B)成分及び(C)成分、(E)成分、(F)成分及び所望によりその他成分を含有する第1剤と、(D)成分を含有する第2剤を使用直前に混合してから5分後に除菌操作に供したものであり、実施例11〜20、比較例1〜4に関しては、第1剤と、第2剤を使用直前に混合してから60分後に除菌操作に供したものである。また、実施例64の除菌剤組成物は、(A)過酢酸を10%、(B)過酸化水素を20%、(C)酢酸を15%、(E)1−ヒドロキシエチリデン−1,1−ジホスホン酸を0.25%、を含有する濃厚組成物を純水で2%に希釈し、その後、(D)カタラーゼ酵素を10ppm、を除菌剤組成物中に添加し、5分後の状態であり、表9に示す異なる試験温度で除菌性試験を行った。結果を表9に示す。なお、表1〜9において各成分の配合割合は“ppm”である。また、表1〜表9中の(A)/(B)の値は、割りきれない場合は小数点一桁を四捨五入した値で示した。
Examples 1 to 69, Comparative Examples 1 to 6
Disinfectant compositions having the formulations shown in Tables 1 to 7 were prepared. The hydrogen peroxide concentration, peracetic acid concentration, and acetic acid concentration in each disinfectant composition were measured by the following methods. Moreover, about each disinfectant composition, the disinfection test and the corrosivity test were done. A result is combined with Tables 1-8 and shown.
For Examples 1-10, Examples 21-69, and Comparative Examples 5-6, (A) component, (B) component and (C) component, (E) component, (F) component and other components as desired. The first agent contained and the second agent containing the component (D) were mixed immediately before use and subjected to sterilization operation 5 minutes later. Examples 11 to 20 and Comparative Examples 1 to 4 Is used for the sterilization operation 60 minutes after mixing the first agent and the second agent immediately before use. Further, the disinfectant composition of Example 64 is (A) 10% peracetic acid, (B) 20% hydrogen peroxide, (C) 15% acetic acid, (E) 1-hydroxyethylidene-1, A concentrated composition containing 0.25% of 1-diphosphonic acid was diluted to 2% with pure water, and then (D) 10 ppm of catalase enzyme was added to the disinfectant composition, and after 5 minutes. The sterilization test was conducted at different test temperatures shown in Table 9. The results are shown in Table 9. In Tables 1 to 9, the blending ratio of each component is “ppm”. In addition, the values of (A) / (B) in Tables 1 to 9 are shown by rounding off one decimal place when it is not divisible.
(1)過酸化水素濃度測定法 (1) Hydrogen peroxide concentration measurement method
高濃度(50.0ppm超)の過酸化水素を測定する場合
100mLのコニカルビーカーに、調製した除菌剤組成物(原液)をマイクロピペッターで1mL採取し、10%硫酸溶液10mLを加えた後、0.1N過マンガン酸カリウム標準液により、薄桃色を呈するまで滴定し、滴定に要した過マンガン酸カリウム標準液量:A(mL)、0.1N過マンガン酸カリウム標準液のファクター:F1より、下記(1)式により過酸化水素濃度を求めた。
(数1)
過酸化水素濃度(w/v%)=A×0.17×F1 (1)
When measuring high-concentration (over 50.0 ppm) hydrogen peroxide In a 100 mL conical beaker, 1 mL of the prepared disinfectant composition (stock solution) was collected with a micropipette, and 10 mL of 10% sulfuric acid solution was added. Titrate with 0.1N potassium permanganate standard solution until it shows light pink color. Amount of potassium permanganate standard solution required for titration: A (mL), Factor of 0.1N potassium permanganate standard solution: F1 The hydrogen peroxide concentration was determined by the following formula (1).
(Equation 1)
Hydrogen peroxide concentration (w / v%) = A × 0.17 × F1 (1)
低濃度(0.1〜50.0ppm)の過酸化水素を測定する場合
300mLのコニカルビーカーに、調製した除菌剤組成物(原液)をホールピペットで100mL採取し、10%硫酸溶液10mLを加えた後、0.05N過マンガン酸カリウム標準液により、薄桃色を呈するまで滴定し、滴定に要した過マンガン酸カリウム標準液量:B(mL)、0.05N過マンガン酸カリウム標準液のファクター:F2より、下記(2)式により過酸化水素濃度を求めた。
(数2)
過酸化水素濃度(w/v%)=B×0.01×0.085×F2 (2)
When measuring low concentration (0.1 to 50.0 ppm) hydrogen peroxide 100 mL of prepared disinfectant composition (stock solution) with a whole pipette in a 300 mL conical beaker and adding 10 mL of 10% sulfuric acid solution After that, the solution was titrated with a 0.05N potassium permanganate standard solution until a light pink color was obtained, and the amount of the potassium permanganate standard solution required for the titration: B (mL), the factor of the 0.05N potassium permanganate standard solution : From F2, the hydrogen peroxide concentration was determined by the following formula (2).
(Equation 2)
Hydrogen peroxide concentration (w / v%) = B × 0.01 × 0.085 × F2 (2)
(2)過酢酸濃度測定法 (2) Peracetic acid concentration measurement method
組成物中に高濃度(50.0ppm超)の過酸化水素が含有している場合
上記高濃度過酸化水素を測定する方法に基づいて過酸化水素濃度を滴定した後の溶液に、10%ヨウ化カリウム溶液1mLを添加後、0.01Nチオ硫酸ナトリウム標準液で淡黄色になるまで滴定し、1%デンプン溶液を1mL加え、暗青色が消えるまで滴定し、滴定に要した0.01Nチオ硫酸ナトリウム標準液量:C(mL)を求めた。ブランクとして、精製水1mLを採取し上記と同様の滴定を行い、0.01Nチオ硫酸ナトリウム標準液の滴定量:C0(mL)を求めた。試料の滴定に要したチオ硫酸ナトリウム標準液量:C(mL)、ブランクの滴定に要したチオ硫酸ナトリウム標準液量:C0(mL)、及び、0.01Nチオ硫酸ナトリウム標準液のファクター:F3より、下記(3)式により過酢酸濃度を求めた。
(数3)
過酢酸濃度(w/v%)=(C−C0)×0.038×F3 (3)
When the composition contains high concentration (over 50.0 ppm) of hydrogen peroxide 10% iodine is added to the solution after titration of the hydrogen peroxide concentration based on the above method for measuring high concentration hydrogen peroxide. After adding 1 mL of potassium halide solution, titrate with 0.01N sodium thiosulfate standard solution until pale yellow, add 1 mL of 1% starch solution, titrate until dark blue color disappears, and 0.01N thiosulfate required for titration Sodium standard solution amount: C (mL) was determined. As a blank, 1 mL of purified water was collected and titrated in the same manner as described above to obtain a titration amount of 0.01 N sodium thiosulfate standard solution: C 0 (mL). Standard amount of sodium thiosulfate required for sample titration: C (mL), Standard amount of sodium thiosulfate required for blank titration: C 0 (mL), and factors of 0.01 N sodium thiosulfate standard solution: From F3, the peracetic acid concentration was determined by the following formula (3).
(Equation 3)
Peracetic acid concentration (w / v%) = (C−C 0 ) × 0.038 × F3 (3)
組成物中に低濃度(0.1〜50.0ppm)の過酸化水素が含有している場合
上記低濃度過酸化水素を測定する方法に基づいて過酸化水素濃度を滴定した後の溶液に、10%ヨウ化カリウム溶液1mLを添加後、1Nチオ硫酸ナトリウム標準液で淡黄色になるまで滴定し、1%デンプン溶液を1mL加え、暗青色が消えるまで滴定し、滴定に要した1Nチオ硫酸ナトリウム標準液量:D(mL)を求めた。ブランクとして、精製水100mLを採取し上記と同様の滴定を行い、1Nチオ硫酸ナトリウム標準液の滴定量:D0(mL)を求めた。試料の滴定に要したチオ硫酸ナトリウム標準液量:D(mL)、ブランクの滴定に要したチオ硫酸ナトリウム標準液量:D0(mL)、及び、1Nチオ硫酸ナトリウム標準液のファクター:F4より、下記(4)式により過酢酸濃度を求めた。
(数4)
過酢酸濃度(w/v%)=(D−D0)×0.01×3.8×F4 (4)
When a low concentration (0.1 to 50.0 ppm) of hydrogen peroxide is contained in the composition, the solution after titrating the hydrogen peroxide concentration based on the method for measuring the low concentration hydrogen peroxide, After adding 1 mL of 10% potassium iodide solution, titrate with 1N sodium thiosulfate standard solution until pale yellow, add 1 mL of 1% starch solution, titrate until dark blue color disappears, 1N sodium thiosulfate required for titration Standard solution volume: D (mL) was determined. As a blank, 100 mL of purified water was collected and titrated in the same manner as described above to obtain a titration amount of 1N sodium thiosulfate standard solution: D 0 (mL). Sodium thiosulfate standard solution volume required for sample titration: D (mL), sodium thiosulfate standard solution volume required for blank titration: D 0 (mL), and factor of 1N sodium thiosulfate standard solution: F4 The peracetic acid concentration was determined by the following formula (4).
(Equation 4)
Peracetic acid concentration (w / v%) = (D−D 0 ) × 0.01 × 3.8 × F4 (4)
(3)酢酸濃度測定法
200mLコニカルビーカーに除菌剤組成物:W(g)を精秤し、純水100mLを加えた後、自動滴定装置(京都電子製、AT−610−PT)を用いて、0.5N水酸化ナトリウム標準液で中和滴定をおこなった。pH6.8付近(t1)の変曲点(中和点)を与える滴定所要量から酢酸濃度を算出した。pH6.8付近(t1)の変曲点を与える滴定所要量:T1(mL)、0.5N水酸化ナトリウム標準液のファクター:F5、及び、除菌剤組成物の質量:Wより、下記(5)式により酢酸濃度を求めた。
(数5)
酢酸濃度(w/v%)=3×T1×F5/W (5)
(3) Method for measuring acetic acid concentration Disinfectant composition: W (g) was precisely weighed in a 200 mL conical beaker, 100 mL of pure water was added, and then an automatic titrator (AT-610-PT, manufactured by Kyoto Electronics Co., Ltd.) was used. Then, neutralization titration was performed with 0.5N sodium hydroxide standard solution. The acetic acid concentration was calculated from the required titration amount giving an inflection point (neutralization point) around pH 6.8 (t1). From the required amount of titration giving an inflection point around pH 6.8 (t1): T1 (mL), 0.5N sodium hydroxide standard solution factor: F5, and the mass of the disinfectant composition: W 5) Acetic acid concentration was determined by the equation.
(Equation 5)
Acetic acid concentration (w / v%) = 3 × T1 × F5 / W (5)
※1:除菌性(芽胞菌、過酢酸に抵抗性を持つ芽胞菌)
(a)試験用芽胞菌
芽胞菌として、バチルス・サブチリス(Bacillus subtilis)(NBRC3134)を用いた。
過酢酸に抵抗性を持つ芽胞菌として、分析・試験受託の総合サービスサイトであるアナライズ・ジェイ・ネットのGermspediaより入手した菌株、Paenibacillus favisporus(注文番号:E123)、飲料工場で採取し、分離同定したパエニバチルス属細菌であるパエニバチルス・チベンシス(Paenibacillus chibensis)を用いた。
(b)芽胞懸濁液の作製
供試菌株をSCD寒天培地(日水製薬品)に塗抹し、37℃で培養し、培養後、顕微鏡観察にて芽胞が十分に形成されていることを確認した。平板培地上に滅菌済み純水を10mL入れ、コロニーを掻き取り懸濁液を収集した。10000rpmで、4℃、15分間の条件で遠心洗浄を3回実施し、遠心後、滅菌済み純水を適量加え、2.0〜9.0×108CFU/ml程度になるように菌数を調製し、ウォーターバスにて80℃、15分間の加熱処理をして芽胞懸濁液とした。
(c)滅菌中和液の調整
大豆レシチンを10g、Tween80を30g、L−ヒスチジンを1g、チオ硫酸ナトリウムを20g、1Lの蒸留水に加温溶解し、攪拌しながら冷却をおこなった。その後、スクリューキャップ付き試験管に各9mL分注し、高圧殺菌(121℃、20分間)をおこない、滅菌中和溶液とした
(d)除菌性試験
滅菌済み100mL三角フラスコに、供試除菌剤組成物100mLを入れた。各供試除菌剤組成物を入れた三角フラスコを所定温度に設定したウォーターバス中のマグネチックスターラー上に置き、三角フラスコの攪拌子を回転させながら薬剤の温度を上昇させた。三角フラスコ内の各供試除菌剤組成物が59℃になったことを確認後、供試菌懸濁液1mLを添加した。1分(薬剤接触時間)ごとに、1mLを滅菌中和溶液入り試験管に採取し、よく攪拌した。混合液をSCD寒天培地にて混和固化し、37℃で2日間培養した。培養後、平板にコロニーの形成が見られなくなるまでの時間より、以下の基準で除菌性(芽胞菌、過酢酸に抵抗性を持つ芽胞菌)を評価し、△、○、◎の評価のものを実用性のあるものとして判定した。
評価基準
◎:接触後2分以内にコロニーの形成がみられなくなる。
○:接触後2分超、5分以内にコロニーの形成がみられなくなる。
△:接触後5分超、8分以内にコロニーの形成がみられなくなる。
×:接触後8分を超えてもコロニーの形成がみられる。
* 1: Bactericidal (spore bacteria, spore bacteria resistant to peracetic acid)
(A) Spore Bacteria for Test Bacillus subtilis (NBRC3134) was used as a spore bacterium.
As a spore bacteria resistant to peracetic acid, a strain obtained from Germspedia of Analyze Jay Net, a comprehensive service site for analysis and testing, Paenibacillus fabisporus (order number: E123), collected at a beverage factory, isolated and identified Paenibacillus chibensis, a Paenibacillus bacterium, was used.
(B) Preparation of spore suspension The test strain was smeared on an SCD agar medium (Nissui Chemicals), cultured at 37 ° C, and after culturing, the spore was confirmed to be sufficiently formed by microscopic observation. did. 10 mL of sterilized pure water was put on the plate medium, and the colonies were scraped to collect the suspension. Centrifugal washing was performed 3 times at 10,000 rpm at 4 ° C. for 15 minutes. After centrifugation, an appropriate amount of sterilized pure water was added, and the number of bacteria was adjusted to about 2.0 to 9.0 × 10 8 CFU / ml. Was heated in a water bath at 80 ° C. for 15 minutes to obtain a spore suspension.
(C) Preparation of Sterilization Neutralization Solution 10 g of soybean lecithin, 30 g of Tween 80, 1 g of L-histidine, 20 g of sodium thiosulfate, and 1 L of distilled water were dissolved by heating and cooled with stirring. Thereafter, 9 mL each was dispensed into a test tube with a screw cap and subjected to high-pressure sterilization (121 ° C., 20 minutes) to obtain a sterilized neutralizing solution. (D) Bactericidal test 100 mL of the agent composition was added. The Erlenmeyer flask containing each test disinfectant composition was placed on a magnetic stirrer in a water bath set to a predetermined temperature, and the temperature of the drug was raised while rotating the stirring bar of the Erlenmeyer flask. After confirming that each test disinfectant composition in the Erlenmeyer flask reached 59 ° C., 1 mL of the test bacteria suspension was added. Every 1 minute (drug contact time), 1 mL was taken into a test tube containing a sterilized neutralizing solution and stirred well. The mixed solution was mixed and solidified on an SCD agar medium and cultured at 37 ° C. for 2 days. After culturing, from the time until colony formation is not observed on the plate, sterilization (spore fungus, spore fungus resistant to peracetic acid) is evaluated according to the following criteria, and evaluation of Δ, ○, ◎ The thing was determined to be practical.
Evaluation criteria A: No colony formation is observed within 2 minutes after contact.
○: More than 2 minutes after contact, colony formation is not observed within 5 minutes.
Δ: More than 5 minutes after contact, no colony formation within 8 minutes.
X: Even if it exceeds 8 minutes after a contact, formation of a colony is seen.
※2:ステンレス腐食性試験
除菌剤組成物50mlを100ml容積のキャップつきポリ瓶に入れ、SUS304製のパネル(縦×横×厚み=75mm×25mm×1mm)を面積の半分まで除菌剤組成物中に浸るように入れ、キャップをする。キャップをしたポリ瓶を59℃に昇温した後、7日間静置する。7日後パネルを取り出し、流水で洗浄後、105℃で2時間乾燥させ、乾燥後の外観を、除菌剤組成物に浸漬する前の状態と比較評価し、腐食性を判定し、△、○の評価のものを実用性のあるものとして判定した。
評価基準
○:浸漬前と変化なし
△:浸漬前とほぼ変化なし
×:腐食した
* 2: Stainless Corrosion Test 50ml of disinfectant composition is put into a 100ml plastic bottle with cap and SUS304 panel (length x width x thickness = 75mm x 25mm x 1mm) is disinfected to half the area. Put it in the object and cap it. After raising the temperature of the capped plastic bottle to 59 ° C., it is allowed to stand for 7 days. After 7 days, the panel was taken out, washed with running water, dried at 105 ° C. for 2 hours, the appearance after drying was compared with the state before being immersed in the disinfectant composition, the corrosivity was judged, and Δ, ○ Were evaluated as practical.
Evaluation criteria ○: No change from before immersion △: Almost unchanged from before immersion ×: Corroded
※3:ゴムパッキン適合性
除菌剤組成物50mLを100mLキャップ付きガラス瓶に入れ、このガラス瓶にEPDMゴムパネル(入間川ゴム株式会社製:縦×横×厚み=50mm×25mm×2mm(体積2500立方ミリメートル))を全体が浸るように入れ、キャップをする。65℃に昇温した後、同温度に保持して24時間静置後、EPDMゴムパネルを取り出し、流水で洗浄した。105℃で3時間乾燥した後体積を測定し、下記(4)式より膨張率を求めた。
膨張率=(浸漬後体積‐浸漬前体積)/浸漬前体積 (4)
膨張率より、以下の基準でゴムパッキン適合性を評価し、△、○、◎の評価のものを実用性のあるものとして判定した。
評価基準:
◎:膨張率が0.03未満。
○:膨張率が0.03以上、0.05未満。
△:膨張率が0.05以上、0.1未満。
×:膨張率が0.1以上。
* 3: Rubber packing compatibility 50mL of disinfectant composition is put into a glass bottle with a 100mL cap, and EPDM rubber panel (manufactured by Irumagawa Rubber Co., Ltd .: vertical x horizontal x thickness = 50mm x 25mm x 2mm (volume 2500 cubic millimeters)) ) So that it is fully immersed, and cap it. After raising the temperature to 65 ° C., the same temperature was maintained, and the mixture was allowed to stand for 24 hours, and then the EPDM rubber panel was taken out and washed with running water. After drying at 105 ° C. for 3 hours, the volume was measured, and the expansion coefficient was determined from the following formula (4).
Expansion rate = (volume after immersion−volume before immersion) / volume before immersion (4)
From the expansion coefficient, rubber packing compatibility was evaluated according to the following criteria, and those evaluated as Δ, ○, and ◎ were determined to be practical.
Evaluation criteria:
A: The expansion coefficient is less than 0.03.
○: Expansion coefficient is 0.03 or more and less than 0.05.
(Triangle | delta): An expansion coefficient is 0.05 or more and less than 0.1.
X: Expansion coefficient is 0.1 or more.
Claims (6)
(A)過酢酸濃度を100〜10000ppm、
(D)カタラーゼ酵素を0.01〜250ppm、
(E)キレート剤を1〜1000ppm、
含有し、かつ
(A)過酢酸と(B)過酸化水素の質量比(A)/(B)が1以上、
(D)カタラーゼ酵素と(E)キレート剤の質量比(D)/(E)が、0.002〜10、
であることを特徴とする除菌剤組成物。 A disinfectant composition containing (A) peracetic acid, (B) hydrogen peroxide, (C) acetic acid, (D) catalase enzyme, (E) chelating agent, and (F) water,
(A) Peracetic acid concentration of 100 to 10000 ppm,
(D) 0.01-250 ppm of catalase enzyme,
(E) 1 to 1000 ppm of chelating agent,
And the mass ratio (A) / (B) of (A) peracetic acid and (B) hydrogen peroxide is 1 or more,
(D) The mass ratio (D) / (E) of catalase enzyme and (E) chelating agent is 0.002 to 10,
A disinfectant composition characterized by the above.
(A)過酢酸濃度を100〜10000ppm、
(D)カタラーゼ酵素を0.01〜250ppm、
(E)キレート剤を1〜1000ppm、
含有し、かつ
(A)過酢酸と(B)過酸化水素の質量比(A)/(B)が1以上、
(D)カタラーゼ酵素と(E)キレート剤の質量比(D)/(E)が、0.002〜10、
となるように調整したものである請求項1記載の除菌剤組成物。 (D) catalase enzyme and (F) water are added to a concentrated composition containing at least one of (A) peracetic acid, (B) hydrogen peroxide, (C) acetic acid, and (E) chelating agent. Dilute
(A) Peracetic acid concentration of 100 to 10000 ppm,
(D) 0.01-250 ppm of catalase enzyme,
(E) 1 to 1000 ppm of chelating agent,
And the mass ratio (A) / (B) of (A) peracetic acid and (B) hydrogen peroxide is 1 or more,
(D) The mass ratio (D) / (E) of catalase enzyme and (E) chelating agent is 0.002 to 10,
The disinfectant composition according to claim 1, wherein the disinfectant composition is adjusted to be.
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US12029218B2 (en) | 2018-09-27 | 2024-07-09 | Medivators Inc. | Peracetic acid stabilized compositions with stable lining |
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JP2013213017A (en) * | 2012-04-04 | 2013-10-17 | Hodogaya Chem Co Ltd | Peracetic acid-including microbicidal composition |
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