JP5813515B2 - 過酸化物からなる高吸収性材料 - Google Patents
過酸化物からなる高吸収性材料 Download PDFInfo
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- JP5813515B2 JP5813515B2 JP2011550328A JP2011550328A JP5813515B2 JP 5813515 B2 JP5813515 B2 JP 5813515B2 JP 2011550328 A JP2011550328 A JP 2011550328A JP 2011550328 A JP2011550328 A JP 2011550328A JP 5813515 B2 JP5813515 B2 JP 5813515B2
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- Prior art keywords
- superabsorbent polymer
- antibacterial
- hydrogen peroxide
- polymer
- grams
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- 239000000463 material Substances 0.000 title description 56
- 150000002978 peroxides Chemical class 0.000 title description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 327
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- 230000000844 anti-bacterial effect Effects 0.000 claims description 125
- 150000003839 salts Chemical class 0.000 claims description 72
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- 238000001035 drying Methods 0.000 claims description 61
- 229910052751 metal Inorganic materials 0.000 claims description 60
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- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 27
- 159000000000 sodium salts Chemical group 0.000 claims description 26
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 24
- 239000004246 zinc acetate Substances 0.000 claims description 24
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 19
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- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 3
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
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- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 241000233866 Fungi Species 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000011609 ammonium molybdate Substances 0.000 description 3
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 3
- 235000018660 ammonium molybdate Nutrition 0.000 description 3
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- SCKXCAADGDQQCS-UHFFFAOYSA-N Performic acid Chemical group OOC=O SCKXCAADGDQQCS-UHFFFAOYSA-N 0.000 description 2
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- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 2
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- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 description 2
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- DLINORNFHVEIFE-UHFFFAOYSA-N hydrogen peroxide;zinc Chemical compound [Zn].OO DLINORNFHVEIFE-UHFFFAOYSA-N 0.000 description 2
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- FHVDTGUDJYJELY-UHFFFAOYSA-N 6-{[2-carboxy-4,5-dihydroxy-6-(phosphanyloxy)oxan-3-yl]oxy}-4,5-dihydroxy-3-phosphanyloxane-2-carboxylic acid Chemical compound O1C(C(O)=O)C(P)C(O)C(O)C1OC1C(C(O)=O)OC(OP)C(O)C1O FHVDTGUDJYJELY-UHFFFAOYSA-N 0.000 description 1
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- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
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- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
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- 230000001629 suppression Effects 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 235000019818 tetrasodium diphosphate Nutrition 0.000 description 1
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 description 1
- MSLRPWGRFCKNIZ-UHFFFAOYSA-J tetrasodium;hydrogen peroxide;dicarbonate Chemical compound [Na+].[Na+].[Na+].[Na+].OO.OO.OO.[O-]C([O-])=O.[O-]C([O-])=O MSLRPWGRFCKNIZ-UHFFFAOYSA-J 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- WRTMQOHKMFDUKX-UHFFFAOYSA-N triiodide Chemical compound I[I-]I WRTMQOHKMFDUKX-UHFFFAOYSA-N 0.000 description 1
- 229940006158 triiodide ion Drugs 0.000 description 1
- 239000012588 trypsin Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 239000011240 wet gel Substances 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- A—HUMAN NECESSITIES
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Description
金属過酸化物または金属塩及び過酸化水素(「HP」)の複合体は、織物のための抗菌処理として言及されている。これらの組成物は、酢酸亜鉛のような金属塩類の反応によって形成されることがある(米国特許5,656,037、5,152,996、4,199,32及び 4,174,418)。
(産業上の利用可能性)
高吸収性高分子(SAP)の産業は、頻繁に、それらの吸収及び保持能力の性質に加えて、それらの製品に他の性質を付加する必要性に直面している。例えば、吸収性用品が適所に体液を注入される際は、特に尿において、強力で不快な匂いを放つ。例えば、皮膚上及び消化管内に存在する細菌ウレアーゼによる尿素の加水分解に起因するアンモニア臭が挙げられる。いくつかのSAP製品からのこれらの匂いを除去することを狙いとして、特定の防臭剤が教示されている。したがって、WO 98/20915及びEP739635は、それぞれ、ゼオライト及びホウ砂を含む混合物を記載している。米国特許4,842,593は、非浸出方法で取り込まれない、パッド剤及び非中毒性、非刺激性及び不揮発性の抗菌剤を有するSAPを含むおむつについて記載している。
この出願の発明に関連する先行技術文献情報としては、以下のものがある(国際出願日以降国際段階で引用された文献及び他国に国内移行した際に引用された文献を含む)。
【先行技術文献】
【特許文献】
【特許文献02】 米国特許第4654039号明細書
【特許文献03】 米国特許第4199322号明細書
【特許文献04】 米国特許第4172841号明細書
【特許文献05】 米国特許出願公開第2008/0081848号明細書
【特許文献06】 米国特許出願公開第2007/0129515号明細書
【特許文献07】 米国特許出願公開第2007/0110779号明細書
【特許文献08】 米国特許出願公開第2007/0020452号明細書
【特許文献09】 米国特許出願公開第2006/0089611号明細書
【特許文献10】 米国特許出願公開第2007/0077428号明細書
【特許文献11】 米国特許出願公開第2004/0185735号明細書
【特許文献12】 米国特許第6399092号明細書
【特許文献13】 米国特許出願公開第2005/0113277号明細書
【特許文献14】 米国特許第5442014号明細書
【特許文献15】 米国特許出願公開第2005/0124724号明細書
【特許文献16】 米国特許第5293885号明細書
【特許文献17】 米国特許第6043209号明細書
【特許文献18】 米国特許第2976576号明細書
【特許文献19】 米国特許第2988539号明細書
【特許文献20】 米国特許第3220960号明細書
【特許文献21】 米国特許第3393168号明細書
【特許文献22】 米国特許第3514419号明細書
【特許文献23】 米国特許第3557067号明細書
【特許文献24】 米国特許第3783872号明細書
【特許文献25】 米国特許第3900378号明細書
【特許文献26】 米国特許第3993616号明細書
【特許文献27】 米国特許第3966679号明細書
【特許文献28】 米国特許第4069177号明細書
【特許文献29】 米国特許第4076663号明細書
【特許文献30】 米国特許第4115332号明細書
【特許文献31】 米国特許第4117222号明細書
【特許文献32】 米国特許第4167464号明細書
【特許文献33】 米国特許第4174418号明細書
【特許文献34】 米国特許第4192727号明細書
【特許文献35】 米国特許第4192827号明細書
【特許文献36】 米国特許第4235237号明細書
【特許文献37】 米国特許第4401793号明細書
【特許文献38】 米国特許第4449977号明細書
【特許文献39】 米国特許第4529739号明細書
【特許文献40】 米国特許第4842593号明細書
【特許文献41】 米国特許第4985023号明細書
【特許文献42】 米国特許第4990338号明細書
【特許文献43】 米国特許第5035892号明細書
【特許文献44】 米国特許第5045322号明細書
【特許文献45】 米国特許第5061487号明細書
【特許文献46】 米国特許第5079004号明細書
【特許文献47】 米国特許第5152996号明細書
【特許文献48】 米国特許第5599335号明細書
【特許文献49】 米国特許第5656037号明細書
【特許文献50】 米国特許第5669894号明細書
【特許文献51】 米国特許第7429632号明細書
【特許文献52】 米国特許第4154898号明細書
【特許文献53】 欧州特許出願公開第0739635号明細書
【特許文献54】 国際公開第98/20915号
【非特許文献】
【非特許文献02】 KUNIO NAKAGAWA and KYAJI MINAMI,"Reduction of Organic Compounds with Thiourea Dioxide.I.Reduction of Ketones to Secondary Alcohols"Tetrahedron Letters No.5,343−346(1972).
a.過酸化水素を有する処理液によって高吸収性高分子を膨潤させる工程と、
b.当該高分子を乾燥させる工程と、
を有するものであり、これにより、過酸化水素は、高吸収性高分子の内部または表面で隔離されるものである方法、を提供することは本発明の実施形態である。
a.過酸化水素を有する処理液によって高吸収性高分子を膨潤させること工程と、
b.当該高分子を乾燥させる工程と、
を有し、これにより、非浸出性の抗菌活性を有する高吸収性高分子が生じるものである方法、を提供することは、本発明の実施形態である。
「病原菌」または「微生物」とは、バクテリア、ウイルス、原生動物、酵母菌、菌類、カビまたはこれらの任意により形成される胞子のような任意の有機体または有機体の組み合わせを意味する。
粒子に関連するものである。
実施例1:アクリル酸SAPの酢酸亜鉛及び過酸化水素による処理(サンプルZNP−1):
20グラムのSAP粉末(BASF社により製造されたLuquasorb又はHySorb素材と同様の、架橋親水性ナトリウム塩の形をとった、部分的に中和されたアクリル酸ベース高分子)を、4グラムの酢酸亜鉛二水和物(アルドリッチ・ケミカル社(Aldrich Chemical)カタログ番号383058)及び9.3グラムの過酸化水素(35%、アルドリッチ・ケミカル社カタログ番号349887)を、187.5mLの脱イオン水に溶解させて調製した溶液に、加えた。この混合物を、前記液体が吸収されるまで、数分間撹拌した。この湿潤したゲルを、プラスチック皿の上に塗布し、電機ファンの前に置いて室温で3日間乾燥させた。この乾燥させた素材を収集し、最初のSAP粉末と同じくらいの均一性になるまで、乳鉢と乳棒を用いて軽く磨り潰した。
より低い酢酸亜鉛と過酸化水素の濃度を用いた点を除いて、実施例1に記載の手順とほとんど同じ手順を用いた。処理溶液は、1.5グラムの酢酸亜鉛、3.5グラムの過酸化水素、及び195mLの水を用いて調製した。
過酸化水素を省略した点を除いて、実施例2に記載の手順に従った。
酢酸亜鉛を省略した点を除いて、実施例2に記載の手順に従った。
6グラムの過酸化水素及び94グラムの脱イオン水を用いた点を除いて、実施例4に記載の手順に従った。
6グラムの過酸化水素及び94グラムの脱イオン水を用い、サンプルを80℃に設定したオーブン内で3時間乾燥させた点を除いて、実施例4に記載の手順に従った。
この熱処理した粉末における、吸収性及び抗菌効果の結果(下記を参照)は、室温で乾燥させた粉末における結果と、差異は無かった。このことは、この組成物の良い温度安定性を示している。
実施例2及び4において調製された素材のサンプルを、60℃、72時間に設定したオーブン内に置いた覆いの無いビーカーに入れ、前記抗菌SAP粉末の熱安定性を検査した。前記熱処理した粉末における、吸収性及び抗菌効果の結果(下記を参照)は、製造されたままの粉末における結果と、差異は無かった。このことでは、この組成物の良い温度安定性を示している。
10グラムのカルボキシルメチルセルロース(carboxymethylcellulose:CMC)粉末を、5グラムの35%HPと45mLの蒸留水を混合して調製した、50mLの溶液によって処理した。この混合物を、数分間、一様な均一性が得られるまで、撹拌、混練した。得られた抗菌CMC組成物を、次いで、72時間空気乾燥し、乳鉢と乳棒によって軽く磨り潰した。
実施例1から8までの各粉末を、10mLのリン酸緩衝食塩水(phosphate buffered saline:PBS、pH=7.4)に対して0.2グラムの粉末の比率で、PBSと一緒にプラスチックの遠沈管に入れた。この遠沈管を振盪し、1時間静置した。この遠沈管を再度振盪し、次いで10分間、約2000rpmで遠心分離した。各遠沈管における上清液に対する膨潤SAPゲルの比率を、前記抗菌SAP粉末の吸収容量を計算するために用いた。未処理のSAP粉末はその重量の約45倍のPBSを吸収した。上記の各実施例における素材は、実施例1の素材においてその重量の30倍のPBSしか吸収しなかったケースを除いて、その重量の少なくとも35倍のPBSを吸収した。
実施例9に記載の吸収性の研究において調製した、各遠沈管から分離したPBS溶液を、新しくS.aureus菌の菌叢を播種した寒天プレート上に入れ、一晩培養したところ、前記溶液を入れた領域において、細菌増殖の抑制が見られないことがわかった。このことは、抗菌成分(HP又は亜鉛など)の、溶液中への著しい浸出が無いことを示している。従って、下に記述した抗菌効果は、前記SAP粉末へのPBSの吸収により形成された固形ゲルとの接触によるものであるはずである。言い換えると、その作用機序は、単にHPが乾燥SAPのマトリックス内に捕捉されている結果や、又は隔離されたHPの抗菌性組成物からの放出によるものではないようである。
各サンプルについて三重に評価を行った。試験する粉末(0.25g)を、50mlの円錐状ポリプロピレン遠沈管内に量り入れ、11.5mLのPBS(リン酸緩衝食塩水、1倍、フィッシャー・サイエンティフィック社(Fischer Scientific)#BP−399−1)を、ピペットを用いて各遠沈管に加えた。未処理SAPコントロールの試験サンプルも、同様に三重に調製した。Escherichia coli(ATCC#15597)又はStaphylococcus aureus(ATCC#6538)の10−1接種菌液は、グリセロールストックをトリプシン大豆ブロス(tryptic soy broth:TSB、ベクトン・ディッキンソン社(Becton Dickinson)Bacto(商標)、REF211825)中で一晩培養し、10−2倍希釈することで調製した。試験を行う粉末を含んでいる各遠沈管に、1mLの接種菌液を加えた。遠沈管を10秒間ボルテックス(vortex)して、次いで縦型回転機に乗せて、室温で24時間25rpmで回転させた。次いで遠沈管を回転機から取り外し、ピペットを用いて10mLのLetheenブロスを各遠沈管に加えた。遠沈管を30秒間最大速度でボルテックスした。溶液を希釈し、標準的な混釈平板法(pour plate method)を用いて、適切な寒天に蒔いた。プレートを37℃で一晩培養し、次いで細菌コロニーを計数した。その結果を以下に要約し、未処理SAP粉末を含む遠沈管で見られた増殖と比較した生存微生物の「log減少」で表した。
実施例11の素材及び手順を用いた。抗菌SAP素材を密閉容器の中で、室温で8か月間保存し、次いで抗菌活性を試験した。以下の結果が得られ、この結果は保存の間も素材が安定であることを示している:
上述の実施例に記載の抗菌SAP粉末について滴定を行い、その中に含まれて抗菌活性に利用されているHPの量を決定した。全てのSAP粉末は、滴定の前に1年より長い期間保存されていたものであった。
以下の結果が得られた。
Claims (10)
- 高吸収性高分子および隔離された過酸化水素から基本的になる抗菌性高吸収性高分子であって、前記高吸収性高分子は、アクリル酸系高分子の架橋された完全にまたは部分的に中和された塩であり、前記抗菌性高吸収性高分子は前記アクリル酸系高吸収性高分子のグラムあたり0.005〜0.2グラムの過酸化水素を有し、前記隔離された過酸化水素はヨウ素滴定による測定で少なくとも24時間にわたって持続放出が可能であり、11ミリリットルの水性液体中における1,000,000の生菌への0.2グラムの前記抗菌性高吸収性高分子の添加が、前記水性液体中における生菌を3−log減少させ、および前記抗菌性高吸収性高分子は乾燥状態の粒子の形態である、抗菌性高吸収性高分子。
- 高吸収性高分子、隔離された過酸化水素、および高吸収性高分子のグラムあたり少なくとも0.02グラムの金属塩から基本的になる抗菌性高吸収性高分子であって、前記高吸収性高分子は、アクリル酸系高分子の架橋された完全にまたは部分的に中和された塩であり、前記抗菌性高吸収性高分子は前記アクリル酸系高吸収性高分子のグラムあたり0.005〜0.2グラムの過酸化水素を有し、前記隔離された過酸化水素はヨウ素滴定による測定で少なくとも24時間にわたって持続放出が可能であり、前記金属塩は酢酸亜鉛、酢酸マグネシウム、及び酢酸ジルコニウムの群から選択される酢酸塩であり、11ミリリットルの水性液体中における1,000,000の生菌への0.2グラムの前記抗菌性高吸収性高分子の添加が、前記水性液体中における生菌を3−log減少させ、および前記抗菌性高吸収性高分子は乾燥状態の粒子の形態である、抗菌性高吸収性高分子。
- 請求項1〜2のいずれか記載の抗菌性高吸収性高分子において、前記アクリル酸系高吸収性高分子は、部分的に中和されたアクリル酸高分子の架橋された親水性ナトリウム塩形態である、抗菌性高吸収性高分子。
- 請求項1〜3のいずれか記載の抗菌性高吸収性高分子を有する、包帯、創傷ドレッシング、タンポン、生理用ナプキン、おむつ、雑巾、失禁装置または衣服、食品包装、または医療装置。
- 請求項1記載の抗菌性高吸収性高分子を製造する方法であって、
(a)アクリル酸系高吸収性高分子のグラムあたり0.005〜0.2グラムの過酸化水素を有する水性処理液によって前記アクリル酸系高吸収性高分子の架橋された完全にまたは部分的に中和された塩を膨潤させる工程と、
(b)前記処理したアクリル酸系高吸収性高分子を乾燥させる工程と
を有し、前記抗菌性高吸収性高分子は乾燥状態の粒子の形態であり、これにより非浸出性抗菌活性を有する前記抗菌性高吸収性高分子が生成され、過酸化水素が前記抗菌性高吸収性高分子の内部または表面で隔離され、前記過酸化水素はヨウ素滴定による測定で少なくとも24時間にわたって持続放出が可能であり、且つ11ミリリットルの水性液体中における1,000,000の生菌への0.2グラムの前記抗菌性高吸収性高分子の添加が、前記水性液体中における生菌を3−log減少させるものである、方法。 - 請求項2記載の抗菌性高吸収性高分子を製造する方法であって、
(a)アクリル酸系高吸収性高分子のグラムあたり0.005〜0.2グラムの過酸化水素と、さらに、アクリル酸系高吸収性高分子のグラムあたり少なくとも0.02グラムの金属塩で前記アクリル酸系高吸収性高分子を処理するのに適した量の金属塩とを有する水性処理液によって前記アクリル酸系高吸収性高分子の架橋された完全にまたは部分的に中和された塩を膨潤させる工程であって、前記金属塩は酢酸亜鉛、酢酸マグネシウム、及び酢酸ジルコニウムからなる群から選択される酢酸塩である、前記膨潤させる工程と、
(b)前記処理したアクリル酸系高吸収性高分子を乾燥させる工程と
を有し、前記抗菌性高吸収性高分子は乾燥状態の粒子の形態であり、これにより非浸出性抗菌活性を有する前記抗菌性高吸収性高分子が生成され、過酸化水素が前記抗菌性高吸収性高分子の内部または表面で隔離され、前記過酸化水素はヨウ素滴定による測定で少なくとも24時間にわたって持続放出が可能であり、且つ11ミリリットルの水性液体中における1,000,000の生菌への0.2グラムの前記抗菌性高吸収性高分子の添加が、前記水性液体中における生菌を3−log減少させるものである、方法。 - 請求項5および6のいずれか1つに記載の方法において、前記アクリル酸系高吸収性高分子は、部分的に中和されたアクリル酸高分子の架橋された親水性ナトリウム塩形態である、方法。
- 感染した液体中の生菌を3−log減少させるために前記液体を消毒する方法であって、請求項1〜2のいずれか記載の抗菌性高吸収性高分子と前記液体とを接触させる工程を有し、前記抗菌性高吸収性高分子は前記感染した液体のリッターあたり18グラムで存在するものである、方法。
- 請求項4記載のおむつまたは失禁用衣服を使用することによりおむつかぶれを制御する方法。
- 請求項5または6記載の方法において、前記水性処理液は、前記高吸収性高分子の少なくとも5倍の重量である、方法。
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2010
- 2010-02-18 WO PCT/US2010/024635 patent/WO2010096595A2/en active Application Filing
- 2010-02-18 BR BRPI1006008-1A patent/BRPI1006008B1/pt not_active IP Right Cessation
- 2010-02-18 JP JP2011550328A patent/JP5813515B2/ja not_active Expired - Fee Related
- 2010-02-18 AU AU2010215966A patent/AU2010215966A1/en not_active Abandoned
- 2010-02-18 CA CA2751852A patent/CA2751852C/en active Active
- 2010-02-18 EP EP10744319.4A patent/EP2398508B1/en not_active Not-in-force
- 2010-02-18 CN CN201080017268.6A patent/CN102405063B/zh not_active Expired - Fee Related
- 2010-06-09 US US12/796,708 patent/US20100247615A1/en not_active Abandoned
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2014
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Also Published As
Publication number | Publication date |
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US20100247615A1 (en) | 2010-09-30 |
BRPI1006008B1 (pt) | 2018-07-31 |
AU2010215966A1 (en) | 2011-08-18 |
CN102405063A (zh) | 2012-04-04 |
US20150071870A1 (en) | 2015-03-12 |
BRPI1006008A2 (pt) | 2015-09-01 |
CN102405063B (zh) | 2015-12-09 |
WO2010096595A4 (en) | 2011-03-03 |
JP2012518062A (ja) | 2012-08-09 |
WO2010096595A3 (en) | 2011-01-06 |
EP2398508A4 (en) | 2014-03-19 |
WO2010096595A2 (en) | 2010-08-26 |
US9873751B2 (en) | 2018-01-23 |
EP2398508B1 (en) | 2016-05-11 |
CA2751852C (en) | 2017-02-28 |
CA2751852A1 (en) | 2010-08-26 |
EP2398508A2 (en) | 2011-12-28 |
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