JP2008202195A - Wet wiper - Google Patents
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- JP2008202195A JP2008202195A JP2007042837A JP2007042837A JP2008202195A JP 2008202195 A JP2008202195 A JP 2008202195A JP 2007042837 A JP2007042837 A JP 2007042837A JP 2007042837 A JP2007042837 A JP 2007042837A JP 2008202195 A JP2008202195 A JP 2008202195A
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本発明は、対象物の表面を拭浄し、乾燥することによって、その表面に持続性に優れた抗菌性、防黴性、消臭性等を付与し得る、対物又は対人用湿潤ワイパーに関する。 The present invention relates to an objective or interpersonal wet wiper that can impart antibacterial properties, antifungal properties, deodorizing properties, etc. with excellent durability to the surface by wiping and drying the surface of an object.
生活環境、作業環境の衛生化、快適化の観点から、抗菌性、消臭性等が付与された家庭家具、事務機器、事務用品やその他不特定多数の人が接触する可能性のある物品が安全で、衛生的且つ快適に使えるよう、抗菌性、消臭性等を付与することが望まれている。
抗菌性、消臭性を付与する方法が種々提案されてきている。例えば、特開平２−２５５８４４号公報（特許文献１）には、抗菌性金属イオンを保持しているゼオライトと塩基性金属化合物を含有してなる樹脂組成物を用いることについて開示されている。その実施例には、ポリプロピレン、ポリエチレン等の樹脂に前記の抗菌剤を配合して射出成形する例が示されている。
Home furniture, office equipment, office supplies, and other items that may come into contact with an unspecified number of people from the viewpoint of sanitizing and comforting the living environment and work environment. It is desired to provide antibacterial and deodorizing properties so that they can be used safely, hygienically and comfortably.
Various methods for imparting antibacterial and deodorant properties have been proposed. For example, JP-A-2-255844 (Patent Document 1) discloses the use of a resin composition comprising a zeolite holding an antibacterial metal ion and a basic metal compound. In the examples, an example in which the above-mentioned antibacterial agent is blended with a resin such as polypropylene or polyethylene and injection molding is shown.
特開平３−８４０６６号公報（特許文献２）には、抗菌性金属又はその酸化物を担持した無機系又は有機系複合粒子を樹脂中に含有させた樹脂組成物と、その樹脂を用いた成型品の用途について開示されている。
特開平１−３１３５３１号公報（特許文献３）には、一価の銀を含む水溶解性ガラスの粉粒状物を混合担持させた合成樹脂成形体を風呂場用カーテン、浴槽等に応用することが開示されている。
JP-A-3-84066 (Patent Document 2) discloses a resin composition in which an inorganic or organic composite particle carrying an antibacterial metal or its oxide is contained in a resin, and molding using the resin. The use of the product is disclosed.
Japanese Patent Application Laid-Open No. 1-313531 (Patent Document 3) applies a synthetic resin molded body in which powder particles of water-soluble glass containing monovalent silver are mixed and supported to a curtain for a bathroom, a bathtub, or the like. Is disclosed.
実開平１−１７８８７６号公報（特許文献４）には、抗菌性ゼオライトを配合した熱可塑性樹脂よりなるシートに熱可塑性樹脂シートを融着又は接着したシートからなる抗菌性素材で、食用ナイフの表面を構成した無菌性食用ナイフが開示されている。
これらの例は、それぞれの物品の製造時に抗菌性を有する薬剤を付与する方法を開示したものであり、従来使用している机や事務機器、事務用品、台所用品、トイレタリー用品、家庭用品、壁、床等の任意の物品に対して除菌したり、或いは抗菌性を付与したりする方法を提案するものではない。
Japanese Utility Model Laid-Open No. 1-178876 (Patent Document 4) discloses an antibacterial material made of a sheet obtained by fusing or adhering a thermoplastic resin sheet to a sheet made of a thermoplastic resin blended with antibacterial zeolite. An aseptic edible knife is disclosed.
These examples disclose a method of applying an antibacterial agent at the time of manufacture of each article, and conventionally used desks and office equipment, office supplies, kitchen supplies, toiletries, household items, walls, etc. It does not propose a method for sterilizing an arbitrary article such as a floor or imparting antibacterial properties.
一方、任意の物品の表面から除菌したり、その表面に抗菌性を付与する方法としては次のような方法が提案されている。例えば、特開昭６３−６３４１９号公報（特許文献５）には、ティシュペーパーに、殺菌消毒剤としてクロールヘキシジングリコネート、塩化ベンザルコニウム、２，４，４−トリクロロ−２−ハイドロキシジフェニールエーテル等を含む水を、使用に際して含有させてウェット状にした後、身体の清浄と消臭の目的のために使用する清浄用ドライティシュペーパーが開示されている。 On the other hand, the following methods have been proposed as a method for sterilizing the surface of an arbitrary article or imparting antibacterial properties to the surface. For example, Japanese Patent Laid-Open No. 63-63419 (Patent Document 5) describes tissue paper, chlorhexidine glycolate, benzalkonium chloride, 2,4,4-trichloro-2-hydroxydiphenyl as a disinfectant. A cleaning dry tissue paper is disclosed which is used for the purpose of cleaning the body and deodorizing after containing water such as ether in a wet state after use.
特開昭６４−２５８２１号公報（特許文献６）には、天然物で安全性の高い抗菌剤としてキトサン又は四級化キトサンの無機酸塩もしくは有機酸塩の水溶液が、紙又は不織布に含浸されてなる濡れティシュが開示されている。
特開平３−３７０１７号公報（特許文献７）には、デキストラン硫酸又はその塩を配合したウェットティシュ及びウェットティシュ用含浸液により細菌、酵母及びカビの増殖を防止する静菌作用及び対象物の表面に除菌作用を示すウェットティシュが開示されている。
特公平５−２５５０５号公報（特許文献８）には、３−（トリメトキシシリル）プロピルジデシルメチルアンモニウム塩と、３−（トリメトキシシリル）プロピルオクタデシルジメチルアンモニウム塩からなる群から選ばれる第１抗菌薬が均一に分布している繊維で形成される繊維性ウェブを、クエン酸、ソルビン酸、リンゴ酸等の天然に存在する抗菌性を示す有機酸から選ばれる第２抗菌薬を含む液体に含浸させた抗菌活性湿潤ワイパーが開示されている。
In Japanese Patent Application Laid-Open No. 64-25821 (Patent Document 6), an aqueous solution of an inorganic acid salt or organic acid salt of chitosan or quaternized chitosan as an antibacterial agent which is a natural product and high in safety is impregnated into paper or non-woven fabric. A wet tissue is disclosed.
JP-A-3-37017 (Patent Document 7) discloses a bacteriostatic action for preventing the growth of bacteria, yeasts and molds with a wet tissue containing dextran sulfate or a salt thereof and a wet tissue impregnating solution, and the surface of the object. Discloses a wet tissue exhibiting a sterilizing action.
Japanese Patent Publication No. 5-25505 (Patent Document 8) discloses a first compound selected from the group consisting of 3- (trimethoxysilyl) propyldidecylmethylammonium salt and 3- (trimethoxysilyl) propyloctadecyldimethylammonium salt. A fibrous web formed of fibers in which the antibacterial agent is uniformly distributed is converted into a liquid containing a second antibacterial agent selected from organic acids exhibiting antibacterial properties such as citric acid, sorbic acid and malic acid. An impregnated antimicrobially active wet wiper is disclosed.
特開昭６３−４０５５８号公報（特許文献９）には、メタノール、エタノール、イソプロピルアルコール等のアルコール類に、殺菌剤としてカチオン性界面活性剤やアニオン性界面活性剤を溶解した液体を噴霧容器に収容した便座用殺菌スプレーが開示されている。
これらは、任意の対象物の表面を拭浄すると同時に、基材或いは基材中の含浸液に含まれる抗菌成分によって、その対象物の表面を除菌しようとするものである。しかしながら、これらの薬剤を使用した方法では、拭浄直後の除菌効果或いは抗菌活性は得られるものの、拭浄後に持続的に抗菌効果を付与することはできないという問題がある。
In JP-A-63-40558 (Patent Document 9), a liquid obtained by dissolving a cationic surfactant or an anionic surfactant as a bactericide in an alcohol such as methanol, ethanol, isopropyl alcohol, or the like is used as a spray container. A contained toilet seat sterilization spray is disclosed.
These are intended to sterilize the surface of an object by the antibacterial component contained in the substrate or the impregnating liquid in the substrate simultaneously with wiping the surface of the object. However, although the method using these chemicals provides a sterilization effect or antibacterial activity immediately after wiping, there is a problem that it cannot provide an antibacterial effect continuously after wiping.
特開昭６３−２７５３１１号公報（特許文献１０）には、殺菌作用を有する低分子第４級アンモニウム塩とアニオン性高分子の第４級アンモニウム塩とを含水アルコールに溶解した含浸液を含浸させた清掃紙により拭浄することで、汚れを落とすと同時に極めて薄い高分子第４アンモニウム塩の皮膜を形成し、持続性のある殺菌効果を得る方法が開示されている。しかしながら、この高分子第４アンモニウム塩による皮膜は、人の手指等による接触や、水を含む拭き布、布巾等による拭取り作業により容易に脱落するため、十分な抗菌持続性を得るまでには至らなかった。 JP-A-63-275311 (Patent Document 10) impregnates an impregnation solution in which a low molecular quaternary ammonium salt having a bactericidal action and a quaternary ammonium salt of an anionic polymer are dissolved in hydrous alcohol. A method for obtaining a durable sterilizing effect by wiping with a cleaning paper to form a very thin polymer quaternary ammonium salt film while removing dirt is disclosed. However, since the film made of this polymeric quaternary ammonium salt is easily removed by contact with human fingers or the like, or by wiping work with a wiping cloth or cloth containing water, etc., until sufficient antibacterial durability is obtained. It did not come.
本発明者等は、特開平１０−９９２５０号公報（特許文献１１）において、前記問題点を解決するために、一種類以上の抗菌成分を含有する含浸液を不織布又は耐湿潤性紙に含浸させた湿潤ワイパーにおいて、該含浸液に含まれる抗菌成分のうち少なくとも一つが、抗菌性金属成分と該抗菌性金属成分以外の無機酸化物とから構成される抗菌性無機酸化物微粒子を含有させることで、水を含む拭き布によって拭っても容易に脱落せず、高い抗菌持続性を付与しうることを開示している。
しかしながら、上記湿潤ワイパーは保存環境によっては変色することがあり、粒子径がコロイド領域にあって透明性を有する抗菌性無機酸化物微粒子を用いる効果が充分得られないことがあった。また、抗菌性が得られる場合であっても消臭性が不充分で、湿潤ワイパーとしての多機能化が不充分でさらに付加価値の向上が求められていた。
In order to solve the above problems, the present inventors impregnate a nonwoven fabric or wet-resistant paper with an impregnation liquid containing one or more types of antibacterial components in JP-A-10-99250 (Patent Document 11). In the wet wiper, at least one of the antibacterial components contained in the impregnating liquid contains antibacterial inorganic oxide fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component. Further, it is disclosed that even if wiped with a wiping cloth containing water, it does not easily fall off and can impart high antimicrobial durability.
However, the wet wiper may change color depending on the storage environment, and the effect of using antibacterial inorganic oxide fine particles having a particle diameter in the colloidal region and having transparency may not be sufficiently obtained. Further, even when antibacterial properties are obtained, the deodorizing property is insufficient, the multifunctional use as a wet wiper is insufficient, and further improvement in added value has been demanded.
本発明は、対象物の表面を拭浄し、乾燥することによって、その表面に持続性に優れた抗菌性、防黴性、消臭性等を付与し得る、対物又は対人用湿潤ワイパーを提供するものであって、湿潤ワイパーの保存環境の影響を受けず耐変色性に優れると共に、抗菌性と消臭性を同時に満足する多機能型の湿潤ワイパーを提供することを発明が解決しようとする課題とするものである。 The present invention provides an objective or interpersonal wet wiper that can impart antibacterial properties, antifungal properties, deodorizing properties, etc. with excellent durability to the surface by wiping and drying the surface of an object. The invention seeks to provide a multifunctional wet wiper that is not affected by the storage environment of the wet wiper, is excellent in discoloration resistance, and simultaneously satisfies antibacterial and deodorant properties. It is to be an issue.
本発明は、含浸液を不織布又は耐湿潤性紙に含浸させた湿潤ワイパーにおいて、前記含浸液が抗菌性金属成分と該抗菌性金属成分以外の無機酸化物とからなる抗菌性無機酸化物微粒子と、キレート剤とを含有することを特徴とするものである。
前記キレート剤は、エチレンジアミン四酢酸、ヒドロキシエチルエチレンジアミン三酢酸、ジヒドロキシエチルエチレンジアミン二酢酸、１，３−プロパンジアミン四酢酸、ジエチルトリアミン五酢酸、トリエチレンテトラミン六酢酸、ニトリロ三酢酸、ヒドロキシエチルイミノ二酢酸から選ばれる１種または２種以上であることが好ましい。
The present invention relates to a wet wiper obtained by impregnating an impregnating liquid into a nonwoven fabric or wet-resistant paper, wherein the impregnating liquid comprises antibacterial inorganic oxide fine particles comprising an antibacterial metal component and an inorganic oxide other than the antibacterial metal component; And a chelating agent.
The chelating agent is ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, 1,3-propanediaminetetraacetic acid, diethyltriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid. It is preferable that it is 1 type, or 2 or more types chosen from.
前記抗菌性無機酸化物微粒子は、負の電荷を有する無機酸化物コロイド粒子に前記抗菌性金属成分が静電気的相互作用で付着または結合したものであることが好ましい。
前記抗菌性無機酸化物微粒子は、負の電荷を有する無機酸化物コロイド粒子に、前記キレート剤と錯体を形成した抗菌性金属成分が静電気的相互作用で付着または結合したものであることが好ましい。
The antibacterial inorganic oxide fine particles are preferably those in which the antibacterial metal component is attached or bonded to the inorganic oxide colloidal particles having a negative charge by electrostatic interaction.
The antibacterial inorganic oxide fine particles are preferably those in which an antibacterial metal component complexed with the chelating agent adheres or binds to inorganic oxide colloidal particles having a negative charge by electrostatic interaction.
前記抗菌性無機酸化物微粒子の平均粒子径が５〜１００ｎｍであり、該抗菌性無機酸化物微粒子中の抗菌性金属成分の含有量が金属として１．０〜１５．０重量％であり、前記含浸液に含まれる抗菌性無機酸化物微粒子の固形分濃度が０．００５〜１０．０重量％であり、該含浸液に含まれる抗菌性金属成分の含有量が金属として０．０００１〜０．０５重量％であることが好ましい。
前記抗菌性金属成分は、銀、銅、亜鉛、錫から選ばれる１種または２種以上であることが好ましい。
The average particle diameter of the antibacterial inorganic oxide fine particles is 5 to 100 nm, the content of the antibacterial metal component in the antibacterial inorganic oxide fine particles is 1.0 to 15.0% by weight as a metal, The solid content concentration of the antibacterial inorganic oxide fine particles contained in the impregnating liquid is 0.005 to 10.0% by weight, and the content of the antibacterial metal component contained in the impregnating liquid is 0.0001 to 0.00. It is preferably 05% by weight.
The antibacterial metal component is preferably one or more selected from silver, copper, zinc, and tin.
本発明の湿潤ワイパーを用いて、事務机、事務機器、事務用品、台所用品、トイレタリー用品、家庭用品、壁、床等の任意の物品の表面を拭浄し、その後乾燥することによって前記表面を除菌し、同時に対象物品の表面に優れた抗菌持続性防黴持続性、持続的消臭性等を付与することができる。
Using the wet wiper of the present invention, the surface of any article such as an office desk, office equipment, office supplies, kitchenware, toiletries, household items, walls, floors, etc. is wiped and then dried to dry the surface. The bacteria can be sterilized, and at the same time, the surface of the target article can be imparted with excellent antibacterial and antifungal sustainability, sustained deodorization property and the like.
本発明の湿潤ワイパーは含浸液を不織布又は耐湿潤性紙に含浸させた湿潤ワイパーにおいて、前記含浸液が抗菌性金属成分と該抗菌性金属成分以外の無機酸化物とからなる抗菌性無機酸化物微粒子と、キレート剤とを含有する。 The wet wiper of the present invention is a wet wiper obtained by impregnating an impregnating liquid into a nonwoven fabric or wet resistant paper, wherein the impregnating liquid comprises an antibacterial metal component and an inorganic oxide other than the antibacterial metal component. Contains fine particles and a chelating agent.
抗菌性無機酸化物微粒子
本発明の含浸液に含まれる抗菌性無機酸化物微粒子は、抗菌性金属成分と該抗菌性金属成分以外の無機酸化物とから構成される。
抗菌性無機酸化物微粒子は、好適には、抗菌性金属成分と該抗菌性金属成分以外の無機酸化物とから構成される微粒子が分散してなるコロイド溶液であって、抗菌性金属成分は、該抗菌性金属成分以外の無機酸化物との混合物又は化合物の形でコロイド粒子を形成するか、或いは抗菌性金属成分以外の無機酸化物のコロイド粒子の表面に付着または結合している。
また、前記抗菌性無機酸化物微粒子は、負の電荷を有する無機酸化物コロイド粒子に抗菌性金属成分が静電気的相互作用で付着または結合している。
Antibacterial inorganic oxide fine particles The antibacterial inorganic oxide fine particles contained in the impregnating liquid of the present invention are composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component.
The antibacterial inorganic oxide fine particle is preferably a colloidal solution in which fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component are dispersed, and the antibacterial metal component is Colloidal particles are formed in the form of a mixture or compound with an inorganic oxide other than the antibacterial metal component, or attached to or bonded to the surface of the colloidal particle of an inorganic oxide other than the antibacterial metal component.
In the antibacterial inorganic oxide fine particles, an antibacterial metal component adheres to or binds to inorganic oxide colloidal particles having a negative charge by electrostatic interaction.
無機酸化物のコロイド粒子としては単一酸化物コロイド粒子又は複合酸化物コロイド粒子、或いはこれらの混合物を適宜選択して用いることができる。単一の酸化物コロイド粒子としては、ＳｉＯ2、ＴｉＯ2、ＺｒＯ2、Ｆｅ2Ｏ3、Ｓｂ2Ｏ5、ＷＯ3等が例示され、複合酸化物コロイド粒子としては、前記各酸化物と他の無機酸化物コロイド粒子との複合化合物、例えば、ＳｉＯ2・Ａｌ2Ｏ3、ＳｉＯ2・Ｂ2Ｏ3、ＳｉＯ2・Ｐ2Ｏ5、ＴｉＯ2・ＣｅＯ2、ＴｉＯ2・ＺｒＯ2、ＳｉＯ2・ＺｒＯ2、ＳｎＯ2・Ｓｂ2Ｏ5、ＳｉＯ2・Ａｌ2Ｏ3・ＴｉＯ2、ＳｉＯ2・ＴｉＯ2・ＣｅＯ2、ＴｉＯ2・ＳｉＯ2・ＺｒＯ2、ＳｉＯ2・Ａｌ2Ｏ3・ＭｇＯ、ＳｉＯ2・Ａｌ2Ｏ3・ＣａＯ、ＳｉＯ2・ＴｉＯ2・Ｆｅ2Ｏ3等を例示することができる。通常、これらのコロイド粒子は水分散媒中で負の電荷を有している。 As the colloidal particles of inorganic oxide, single oxide colloidal particles, composite oxide colloidal particles, or a mixture thereof can be appropriately selected and used. Examples of the single oxide colloidal particles include SiO 2 , TiO 2 , ZrO 2 , Fe 2 O 3 , Sb 2 O 5 , WO 3 and the like. Compound with inorganic oxide colloidal particles of, for example, SiO 2 · Al 2 O 3 , SiO 2 · B 2 O 3 , SiO 2 · P 2 O 5 , TiO 2 · CeO 2 , TiO 2 · ZrO 2 , SiO 2 · ZrO 2 , SnO 2 · Sb 2 O 5 , SiO 2 · Al 2 O 3 · TiO 2 , SiO 2 · TiO 2 · CeO 2 , TiO 2 · SiO 2 · ZrO 2 , SiO 2 · Al 2 O 3 · Examples thereof include MgO, SiO 2 · Al 2 O 3 · CaO, and SiO 2 · TiO 2 · Fe 2 O 3 . Usually, these colloidal particles have a negative charge in the aqueous dispersion medium.
上記複合無機酸化物コロイド粒子を含むコロイド溶液として、特に、特開平５−１３２３０９号公報に記載された複合酸化物コロイド溶液を用いることが望ましい。即ち、この複合酸化物コロイド溶液中のコロイド粒子は、多孔質で比表面積が大きく、コロイド粒子自体の負の電荷が高いので、当該コロイド粒子表面に後述する正電荷を有する抗菌性金属成分を導入するのが容易であり、また、コロイド粒子表面と抗菌性金属成分および後述するキレート剤との静電的相互作用による付着力が強くなるからである。 As the colloidal solution containing the composite inorganic oxide colloidal particles, it is particularly desirable to use the composite oxide colloidal solution described in JP-A-5-132309. That is, the colloidal particles in this complex oxide colloidal solution are porous, have a large specific surface area, and the colloidal particles themselves have a high negative charge. Therefore, an antibacterial metal component having a positive charge described later is introduced on the surface of the colloidal particles. This is because the adhesion force due to electrostatic interaction between the colloidal particle surface, the antibacterial metal component, and a chelating agent described later is increased.
本発明に用いる抗菌性無機酸化物微粒子の平均粒子径は５〜１００ｎｍ、さらには１０〜７０ｎｍの範囲にあることが好ましい。
抗菌性無機酸化物微粒子の平均粒子径が５ｎｍ未満の場合は、得ることが困難で、得られたとしても安定性が不充分で凝集しやすく、本発明の用途に不向きである。抗菌性無機酸化物微粒子の平均粒子径が１００ｎｍを越えると、物品の表面に抗菌性を付与することは可能であるが、水を含む拭き布等で何回も拭うと表面より微粒子が剥離し易くなり、このため抗菌性および抗菌性の持続性が不充分となることがある。
The average particle diameter of the antibacterial inorganic oxide fine particles used in the present invention is preferably in the range of 5 to 100 nm, more preferably 10 to 70 nm.
When the average particle diameter of the antibacterial inorganic oxide fine particles is less than 5 nm, it is difficult to obtain, and even if obtained, the stability is insufficient and the agglomeration tends to aggregate, which is unsuitable for the use of the present invention. If the average particle diameter of the antibacterial inorganic oxide fine particles exceeds 100 nm, it is possible to impart antibacterial properties to the surface of the article. However, if the wipe is wiped with a wiping cloth containing water many times, the fine particles will peel off from the surface. This may result in insufficient antibacterial and antibacterial persistence.
本発明に使用する抗菌性無機酸化物微粒子のコロイド溶液は、前記特開平５−１３２３０９号公報に記載された複合酸化物コロイド溶液の製造方法に準じて、アルカリ金属、アンモニウム、又は有機塩基の珪酸塩と、アルカリ可溶の無機化合物と、抗菌性金属成分の水溶液とを、ｐＨ１０以上のアルカリ水溶液中に同時に添加し、抗菌性金属成分を含有する無機酸化物コロイド粒子を生成させることができる。 The colloidal solution of the antibacterial inorganic oxide fine particles used in the present invention is an alkali metal, ammonium, or organic base silicic acid according to the method for producing a composite oxide colloidal solution described in Japanese Patent Laid-Open No. 5-132309. A salt, an alkali-soluble inorganic compound, and an aqueous solution of an antibacterial metal component can be simultaneously added to an alkaline aqueous solution having a pH of 10 or more to produce inorganic oxide colloidal particles containing the antibacterial metal component.
或いはまた、特開昭６３−２７０６２０号公報に記載された製造方法に準じて、含水チタン酸のゲル又はゾルに過酸化水素水を加えて得られるチタン酸水溶液と抗菌性金属成分の水溶液とを、ケイ素化合物及び／又はジルコニウム化合物の存在下で加熱処理して無機酸化物コロイド粒子を生成させても良い。 Alternatively, an aqueous titanic acid solution obtained by adding hydrogen peroxide to a gel or sol of hydrous titanic acid and an aqueous solution of an antibacterial metal component according to the production method described in JP-A-63-270620 The inorganic oxide colloidal particles may be produced by heat treatment in the presence of a silicon compound and / or a zirconium compound.
更に、特開平６−８０５２７号公報に記載された抗菌性無機酸化物コロイド溶液からなる抗菌剤の製造方法において、負の電荷を有する無機酸化物コロイド粒子が分散したコロイド溶液に抗菌性金属成分の水溶液を添加した後、コロイド溶液を６０℃以上、好ましくは１００〜２００℃で加熱する方法によっても良い。前記製造方法において用いられる抗菌性金属成分の水溶液としては、例えば、酸化亜鉛、酸化銀、酸化銅、酸化錫等から選ばれた金属成分をアンモニア水に溶解して得られる亜鉛、銀、銅、錫等のアンミン錯塩水溶液を用いるのが好適である。 Furthermore, in the method for producing an antibacterial agent comprising an antibacterial inorganic oxide colloid solution described in JP-A-6-80527, an antibacterial metal component is dispersed in a colloid solution in which inorganic oxide colloid particles having a negative charge are dispersed. After adding the aqueous solution, the colloidal solution may be heated at 60 ° C. or higher, preferably 100 to 200 ° C. As an aqueous solution of the antibacterial metal component used in the manufacturing method, for example, zinc, silver, copper obtained by dissolving a metal component selected from zinc oxide, silver oxide, copper oxide, tin oxide and the like in aqueous ammonia, It is preferable to use an aqueous solution of an ammine complex salt such as tin.
抗菌性金属成分
抗菌性金属成分としては、通常知られている抗菌性金属成分を用いることができ、例えば、銀、銅、亜鉛、錫から選ばれる１種または２種以上の抗菌性金属成分が抗菌作用、変色及び人体に対する安全性の観点から好ましい。
抗菌性無機酸化物微粒子中の抗菌性金属成分の含有量は、金属として１．０〜１５．０重量％、さらには１．５〜１０重量％の範囲にあることが好ましい。
抗菌性無機酸化物微粒子中の抗菌性金属成分の含有量が金属として１．０重量％未満の場合は、湿潤ワイパーの基材にもよるが、例えば０．１重量％でも初期は充分な抗菌活性を発現するが、長期にわたって抗菌活性を維持できない場合がある。抗菌性金属成分の含有量が金属として１５重量％を越えてもさらに抗菌活性が向上することもなく、経済性が低下する問題がある。
Antibacterial metal component As the antibacterial metal component, a commonly known antibacterial metal component can be used. For example, one or more antibacterial metal components selected from silver, copper, zinc, and tin are used. From the viewpoint of antibacterial action, discoloration and safety to the human body.
The content of the antibacterial metal component in the antibacterial inorganic oxide fine particles is preferably 1.0 to 15.0% by weight, more preferably 1.5 to 10% by weight as a metal.
When the content of the antibacterial metal component in the antibacterial inorganic oxide fine particles is less than 1.0% by weight as a metal, depending on the substrate of the wet wiper, for example, even at 0.1% by weight, sufficient initial antibacterial properties Although it exhibits activity, it may not be able to maintain antibacterial activity over a long period of time. Even if the content of the antibacterial metal component exceeds 15% by weight as a metal, there is a problem that the antibacterial activity is not further improved and the economic efficiency is lowered.
キレート剤
本発明の含浸液は前記抗菌性無機酸化物微粒子に加えてキレート剤を含む。
キレート剤は正の電荷を有する抗菌性金属成分と安定な錯体を形成し、この錯体が高い負電荷を有する無機酸化物コロイド粒子表面に静電気的相互作用により安定して付着または結合する結果、抗菌性金属成分が無機酸化物コロイド粒子から容易に脱離して散逸することがなくなる。また、これに加えて、従来変色することのあった抗菌性金属成分が変色することがなくなり、長期にわたって抗菌性能、消臭性能等を維持することができるものである。
Chelating Agent The impregnating liquid of the present invention contains a chelating agent in addition to the antibacterial inorganic oxide fine particles.
The chelating agent forms a stable complex with the antibacterial metal component having a positive charge, and this complex stably adheres or binds to the surface of the inorganic oxide colloidal particle having a high negative charge by electrostatic interaction. The conductive metal component is not easily detached from the inorganic oxide colloidal particles and dissipated. In addition, the antibacterial metal component that has been discolored in the past does not discolor, and the antibacterial performance, deodorization performance, etc. can be maintained over a long period of time.
キレート剤は、エチレンジアミン四酢酸、ヒドロキシエチルエチレンジアミン三酢酸、ジヒドロキシエチルエチレンジアミン二酢酸、１，３−プロパンジアミン四酢酸、ジエチルトリアミン五酢酸、トリエチレンテトラミン六酢酸、ニトリロ三酢酸、ヒドロキシエチルイミノ二酢酸から選ばれる１種または２種以上であることが好ましい。
なお、キレート剤としてエチレンジアミン四酢酸ナトリウム等の塩を用いると無機酸化物コロイド粒子への付着が不充分なためか、抗菌性能、消臭性能等を長期に亘って維持することが困難である。
Chelating agents are ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, 1,3-propanediaminetetraacetic acid, diethyltriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid. It is preferable that it is 1 type, or 2 or more types selected.
When a salt such as sodium ethylenediaminetetraacetate is used as the chelating agent, it is difficult to maintain antibacterial performance, deodorization performance, etc. for a long period of time because of insufficient adhesion to the inorganic oxide colloidal particles.
前記キレート剤は、含浸液中の抗菌性金属成分のモル数を（Ｍab）とし、含浸液中のキレート剤のモル数を（Ｍch）としたときのモル比（Ｍab）／（Ｍch）が０．１〜３００、さらには１〜２５０の範囲にあることが好ましい。
モル比（Ｍab）／（Ｍch）が０．１未満の場合は、抗菌性金属成分の量によっても異なるが、キレート剤の量が多くなり、無機酸化物コロイド粒子表面の電荷が減少し、抗菌性無機酸化物コロイド粒子の安定性が低下し凝集することがある。他方、モル比（Ｍab）／（Ｍch）が３００を超えると、キレート剤の量が少なく、安定化効果、変色抑制効果が得られないことがある。
The chelating agent has a molar ratio (M ab ) / (M a) where the number of moles of the antibacterial metal component in the impregnation liquid is (M ab ) and the number of moles of the chelating agent in the impregnation liquid is (M ch ). ch ) is preferably in the range of 0.1 to 300, more preferably 1 to 250.
When the molar ratio (M ab ) / (M ch ) is less than 0.1, the amount of chelating agent increases and the charge on the surface of the inorganic oxide colloidal particles decreases, although it depends on the amount of the antibacterial metal component. The stability of the antibacterial inorganic oxide colloidal particles may decrease and agglomerate. On the other hand, when the molar ratio (M ab ) / (M ch ) exceeds 300, the amount of the chelating agent is small, and the stabilizing effect and the discoloration suppressing effect may not be obtained.
前記キレート剤は、種々の方法により含浸液に混合することができる。例えば、負の電荷を有する無機酸化物コロイド粒子が分散したコロイド溶液に、（１）抗菌性金属成分の金属塩水溶液を添加した後、キレート剤の水溶液を添加する方法、（２）キレート剤の水溶液を添加した後、抗菌性金属成分の金属塩水溶液を添加する方法、（３）抗菌性金属成分の金属塩水溶液とキレート剤の水溶液とを混合して抗菌性金属成分の錯体を形成させた水溶液を添加する方法、等を挙げることができる。但し、必ずしも、これらの方法に限定されるものではない。 The chelating agent can be mixed into the impregnating solution by various methods. For example, (1) a method of adding an aqueous solution of a metal salt of an antibacterial metal component to a colloidal solution in which inorganic oxide colloidal particles having a negative charge are dispersed, and then adding an aqueous solution of a chelating agent. Method of adding metal salt aqueous solution of antibacterial metal component after adding aqueous solution, (3) Metal salt aqueous solution of antibacterial metal component and aqueous solution of chelating agent were mixed to form a complex of antibacterial metal component Examples include a method of adding an aqueous solution. However, it is not necessarily limited to these methods.
含浸液
本発明の含浸液は前記した抗菌性無機酸化物微粒子を含有し、該抗菌性無機酸化物微粒子の含有量が固形分として０．００５〜１０．０重量％、さらには０．０１〜８．０重量％の範囲にあり、該含浸液に含まれる抗菌性金属成分の含有量が金属として０．０００１〜０．０５重量％、さらには０．０００３〜０．０４重量％の範囲にあることが好ましい。
含浸液中の抗菌性無機酸化物微粒子の含有量が固形分として０．００５重量％未満の場合は抗菌性の持続性が不充分となることがある。他方、含浸液中の抗菌性無機酸化物微粒子の含有量が固形分として１０．０重量％を越えてもさらに抗菌活性、抗菌性能の持続性がさらに向上することもなく、経済性が低下する問題がある。
Impregnating liquid The impregnating liquid of the present invention contains the antibacterial inorganic oxide fine particles described above, and the content of the antibacterial inorganic oxide fine particles is 0.005 to 10.0% by weight as a solid content, and further 0.01 to The content of the antibacterial metal component contained in the impregnating liquid is in the range of 0.0001 to 0.05% by weight, further 0.0003 to 0.04% by weight as a metal. Preferably there is.
When the content of the antibacterial inorganic oxide fine particles in the impregnating liquid is less than 0.005% by weight as a solid content, the antibacterial durability may be insufficient. On the other hand, even if the content of the antibacterial inorganic oxide fine particles in the impregnating liquid exceeds 10.0% by weight as the solid content, the antibacterial activity and the durability of the antibacterial performance are not further improved, and the economic efficiency is lowered. There's a problem.
また、含浸液に含まれる抗菌性金属成分の含有量が金属として０．０００１重量％未満の場合は、抗菌性の持続性が不充分となることがある。他方、含浸液に含まれる抗菌性金属成分の含有量が金属として０．０５重量％を越えてもさらに抗菌活性、抗菌性能の持続性がさらに向上することもなく、経済性が低下する問題がある。
なお、本発明の含浸液は、前記抗菌性無機酸化物微粒子に加えて他の抗菌成分を含有することもある。
Moreover, when the content of the antibacterial metal component contained in the impregnating liquid is less than 0.0001% by weight as a metal, the antibacterial durability may be insufficient. On the other hand, even if the content of the antibacterial metal component contained in the impregnating liquid exceeds 0.05% by weight as a metal, the antibacterial activity and the durability of the antibacterial performance are not further improved, and there is a problem that the economic efficiency is lowered. is there.
The impregnating liquid of the present invention may contain other antibacterial components in addition to the antibacterial inorganic oxide fine particles.
分散媒・添加剤
前記含浸液に用いる分散媒には主として水を用いるが、必要に応じてエタノール、イソプロパノール等のアルコール類、パラオキシ安息香酸メチル、パラオキシ安息香酸エチル、パラオキシ安息香酸プロピル、パラオキシ安息香酸ブチル等のパラオキシ安息香酸エステル類、塩化ベンザルコニウム等の第４級アンモニウム塩、クエン酸、ソルビン酸、リンゴ酸等の有機酸、或いはその他の抗菌剤、殺菌剤、防腐剤等を１種類或いは複数種類併用して含浸液に配合して使用しても良い。
Dispersion medium / additives Water is mainly used as the dispersion medium used in the impregnation liquid, but alcohols such as ethanol and isopropanol, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, and paraoxybenzoic acid as necessary. 1 type of paraoxybenzoates such as butyl, quaternary ammonium salts such as benzalkonium chloride, organic acids such as citric acid, sorbic acid, malic acid, or other antibacterial agents, bactericides, preservatives, etc. A plurality of types may be used in combination in the impregnation liquid.
また、パラオキシ安息香酸エステル類或いはその他の抗菌剤、殺菌剤、防腐剤等を含浸液中に併用して使用する場合に、それらを含浸液中に効率よく溶解させる目的で、プロピレングリコール、ブチレングリコール等のグリコール類を添加しても良い。更に、湿潤ワイパーを使用して拭浄する際の清浄効果を高める目的で、カルボン酸塩、硫酸エステル塩、スルホン酸塩等のアニオン界面活性剤、第２級アミン塩、第３級アミン塩、第４級アンモニウム塩等のカチオン界面活性剤、アミノ酸型両性界面活性剤、ベタイン型両性界面活性剤、硫酸エステル塩型両性界面活性剤、スルホン酸型両性界面活性剤等の両性界面活性剤、ポリエチレングリコール型非イオン界面活性剤、多価アルコール型非イオン界面活性剤等の非イオン界面活性剤等の界面活性剤を使用することもできる。 In addition, when using paraoxybenzoates or other antibacterial agents, bactericides, preservatives, etc. in the impregnating liquid, in order to efficiently dissolve them in the impregnating liquid, propylene glycol, butylene glycol Glycols such as may be added. Furthermore, for the purpose of enhancing the cleaning effect when wiping with a wet wiper, anionic surfactants such as carboxylates, sulfate esters, sulfonates, secondary amine salts, tertiary amine salts, Cationic surfactants such as quaternary ammonium salts, amino acid type amphoteric surfactants, betaine type amphoteric surfactants, sulfate ester type amphoteric surfactants, amphoteric surfactants such as sulfonic acid type amphoteric surfactants, polyethylene Surfactants such as nonionic surfactants such as glycol type nonionic surfactants and polyhydric alcohol type nonionic surfactants can also be used.
湿潤ワイパー
本発明の湿潤ワイパーは不織布又は耐湿潤性を有する基材に前記含浸液が含浸されている。本発明の湿潤ワイパーに使用する不織布又は耐湿潤性を有する基材としては公知の不織布、湿潤性が付与された繊維シート或いは不織布と前記のシートを積層して複合化したシートを使用することができるが、含浸液を十分に保持できることが望ましいため、繊維の全部又は一部にレーヨン繊維、パルプ繊維、コットン繊維等の親水性繊維が含まれているのが好ましい。
本発明に使用する不織布の一例としては、レーヨン不織布、コットン不織布、パルプ不織布等の不織布、或いはレーヨン繊維、コットン繊維、パルプ繊維等の親水性繊維のうちの１種類又は複数種類と、ポリエステル繊維、ポリプロピレン繊維、ナイロン繊維、アラミド繊維等の合成繊維の１種類又は複数種類とが複合されてなる不織布等が好適に使用できる。
Wet wiper In the wet wiper of the present invention, a nonwoven fabric or a substrate having wet resistance is impregnated with the impregnation liquid. The nonwoven fabric used for the wet wiper of the present invention or the substrate having wet resistance may be a known nonwoven fabric, a fiber sheet imparted with wettability, or a sheet obtained by laminating the above sheet and a composite sheet. However, since it is desirable that the impregnation liquid can be sufficiently retained, it is preferable that hydrophilic fibers such as rayon fiber, pulp fiber, and cotton fiber are contained in all or part of the fiber.
As an example of the nonwoven fabric used in the present invention, rayon nonwoven fabric, cotton nonwoven fabric, nonwoven fabric such as pulp nonwoven fabric, or one or more kinds of hydrophilic fibers such as rayon fiber, cotton fiber, pulp fiber, and polyester fiber, Nonwoven fabrics formed by combining one or more synthetic fibers such as polypropylene fibers, nylon fibers, and aramid fibers can be suitably used.
湿潤ワイパーに使用する不織布又は耐湿潤性を有する基材の目付は、用途に応じて適宜選択できるが、ＪＩＳ Ｌ １９０６により測定した目付が、１５〜１００ｇ／ｍ2の範囲、好ましくは２０〜８０ｇ／ｍ2の範囲である。この目付が１５ｇ／ｍ2未満では、湿潤ワイパーを使用する際に薄すぎて使用感が悪く、破れ易くなる。逆に、目付が１００ｇ／ｍ2が超えて大きくなると、湿潤ワイパーの剛度が高くなり、使用し難くなる。 The basis weight of the nonwoven fabric used for the wet wiper or the substrate having wet resistance can be appropriately selected according to the use, but the basis weight measured according to JIS L 1906 is in the range of 15 to 100 g / m 2 , preferably 20 to 80 g. / M 2 range. When the basis weight is less than 15 g / m 2 , the wet wiper is too thin to be unusable and easily broken. On the other hand, when the basis weight increases beyond 100 g / m 2 , the stiffness of the wet wiper increases, making it difficult to use.
湿潤ワイパーに使用する不織布又は耐湿潤性を有する基材は、柔軟性を向上させる目的でクレープ加工等を施しても良いし、表面強度を増し、紙粉等の脱落繊維を減じる目的で、例えばポリアクリル酸エステル、ポリメタクリル酸エステル、エチレン−酢酸ビニル共重合物、スチレンブタジエン共重合物、ニトリル−ブタジエン共重合物、ポリエステル樹脂、ポリウレタン樹脂等の水系エマルジョン或いはラテックス等の公知の合成高分子の水系エマルジョンやラテックスを、含浸法、スプレー法、グラビア塗工法等を用いて塗布してあっても良い。 The nonwoven fabric used for the wet wiper or the substrate having wet resistance may be subjected to creping for the purpose of improving flexibility, and for the purpose of increasing the surface strength and reducing the falling fibers such as paper dust. Polyacrylic acid ester, polymethacrylic acid ester, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, nitrile-butadiene copolymer, polyester resin, polyurethane resin, and other known synthetic polymers such as latex or latex An aqueous emulsion or latex may be applied using an impregnation method, a spray method, a gravure coating method, or the like.
本発明の湿潤ワイパーは、前記のようにして調製された抗菌性無機酸化物微粒子を含む含浸液を不織布又は耐湿潤性を有する基材に含浸することで製造することができる。含浸液の量は、含浸する不織布又は耐湿潤性を有する基材の種類、使用目的等に応じて任意に調製することができるが、含浸する不織布又は耐湿潤性を付与された基材のＪＩＳ Ｌ １９０６で測定した絶乾目付に対して５０〜４００重量％の範囲、好ましくは１００重量％〜３００重量％の範囲である。 The wet wiper of the present invention can be produced by impregnating a non-woven fabric or a substrate having wet resistance with an impregnation liquid containing antibacterial inorganic oxide fine particles prepared as described above. The amount of the impregnating liquid can be arbitrarily adjusted according to the kind of nonwoven fabric to be impregnated or a substrate having wet resistance, the purpose of use, etc. It is in the range of 50 to 400% by weight, preferably in the range of 100% to 300% by weight, based on the absolute dryness measured by L1906.
前記含浸液の量が、５０重量％未満では、湿潤ワイパーの含む水分が少な過ぎ、対象となる物品の表面を清拭する際に、ばらつきが生じ、十分均一に清浄し難くなり、同時に湿潤ワイパーに含まれる抗菌性無機酸化物微粒子の絶対量が少ないため、対象物の表面に転移する含浸液の量も少なくなるため、拭浄した物品の表面に転着する抗菌性無機酸化物微粒子の量が少なくなり、拭浄した物品の表面に十分な抗菌性と抗菌持続性を付与できないので適さない。
逆に、含浸量が４００重量％を超えて多くなると、湿潤ワイパーの含む液量が多過ぎ、対象となる物品を拭浄する際に水浸しになってしまい、十分に拭浄できなくなると共に、拭浄した物品の表面に転移する含浸液量も多過ぎるため、乾燥に時間がかかりすぎるので適さない。もし、未乾燥の状態で拭浄した物品をそのまま使用に供したり、拭浄した物品の表面を乾燥したワイパーで拭って使用に供すると、物品の表面にある抗菌性無機酸化物微粒子が除去されたり、脱落してしまい、対象となる物品表面に十分な抗菌性と抗菌持続性を付与できない。
When the amount of the impregnating liquid is less than 50% by weight, the wet wiper contains too little moisture, and when the surface of the target article is wiped, variation occurs and it becomes difficult to clean the surface sufficiently. At the same time, the wet wiper Since the absolute amount of the antibacterial inorganic oxide fine particles contained in the liquid is small, the amount of the impregnating liquid transferred to the surface of the object is also small, so the amount of the antibacterial inorganic oxide fine particles transferred to the surface of the wiped article This is not suitable because the surface of the cleaned article cannot be given sufficient antibacterial and antibacterial durability.
On the other hand, if the impregnation amount exceeds 400% by weight, the wet wiper contains too much liquid, and when the target article is wiped, it becomes immersed in water and cannot be wiped sufficiently. Since the amount of the impregnating liquid transferred to the surface of the cleaned article is too large, it takes too much time for drying, which is not suitable. If the article wiped in an undried state is used as it is, or if the surface of the wiped article is wiped with a dry wiper, the antibacterial inorganic oxide fine particles on the surface of the article are removed. Or fall off and cannot give sufficient antibacterial and antibacterial durability to the surface of the target article.
本発明の湿潤ワイパーは、これで対象物品の表面を拭浄し、次いで乾燥することにより対象物品の表面に持続性の高い抗菌性、防黴性、消臭性等を付与できるものである。対象物品を清拭することによりその表面に付与できる抗菌持続性の程度は、対象物品の表面状態と吸液性、対象物品の表面への抗菌性無機酸化物微粒子の転着のし易さ、拭浄後の乾燥の仕方等により変化するため、一概に論ずることはできないが、例えばステンレス板、プラスチック板等の平滑な面を本発明の湿潤ワイパーで１〜２回清拭し、室温にて乾燥すれば、その面を水を含むワイパーで１回拭った後も、好ましくは３回拭った後も、更に好ましくは５回拭った後も、その表面は抗菌性を有するものである。
The wet wiper of the present invention can impart highly durable antibacterial properties, antifungal properties, deodorizing properties and the like to the surface of the target article by wiping the surface of the target article and then drying. The degree of antibacterial durability that can be imparted to the surface of the target article by wiping the target article is the surface state and liquid absorbency of the target article, the ease of transfer of the antibacterial inorganic oxide fine particles to the surface of the target article, Since it changes depending on the drying method after wiping, etc., it cannot be discussed in general, but for example, a smooth surface such as a stainless steel plate or plastic plate is wiped once or twice with the wet wiper of the present invention, and at room temperature. When dried, the surface of the surface has antibacterial properties even after wiping once with a wiper containing water, preferably after wiping three times, and more preferably after wiping five times.
以下に実施例を示し、本発明を更に具体的に説明するが、実施例中の各々の特性値は次の方法によって求めた。
（１）付着抗菌性金属成分の量
プラズマ発光分光分析装置（セイコー社製）により、金属原子を定量して求めた。
（２）コロイド粒子の平均粒子径
レーザー散乱粒子径測定装置（ナイコンプ社製）を使用して測定した。
The present invention will be described more specifically with reference to the following examples. The characteristic values in the examples were determined by the following methods.
(1) Amount of attached antibacterial metal component The amount of metal atoms was determined by a plasma emission spectrometer (Seiko Co., Ltd.).
(2) Average particle diameter of colloidal particles Measurement was performed using a laser scattering particle diameter measuring apparatus (manufactured by Nikonp).
（３）抗菌性の評価
［試験片の作製］
２０ｍｍ×２０ｍｍの大きさに切った湿潤ワイパーを試験片とした。試験片は、一度の評価に５枚使用した。
(3) Antibacterial evaluation [preparation of test piece]
A wet wiper cut to a size of 20 mm × 20 mm was used as a test piece. Five test pieces were used for one evaluation.
［抗菌性評価］
まず、ブドウ状球菌および大腸菌の供試菌株を普通ブイヨン培地において３７℃で２４時間培養し、その培養液を高圧蒸気で殺菌済みのリン酸緩衝液からなる保存液に添加し、菌濃度が１０４個／ｍｌとなるように希釈してブドウ状球菌および大腸菌の試験菌液を調製した。この液の７５ｍｌを三角フラスコに入れ、次いで、試験片を絶乾換算で０．７５ｇ入れた。その後、この三角フラスコを振とう器にかけ、３４０ｒｐｍ、２８℃、６０分の条件で振とうして菌液中の菌と試験片を十分に接触させた。
次に、菌液の１０倍から１００，０００倍までの１０倍希釈列を作り、それぞれの濃度の菌液１ｍｌと普通寒天培地１５ｍｌを用いて混釈法でプレートを作った。その後３７℃の培養器で４８時間培養した後、コロニーを数え、接触前の菌数に対する減菌率を式（１）で計算し、抗菌性を評価した。
減菌率（％）＝１００×（初期生菌数−４８時間後の生菌数）／初期生菌数・・・（１）
[Antimicrobial evaluation]
First, staphylococci and Escherichia coli test strains are cultured in a normal broth medium at 37 ° C. for 24 hours, and the culture solution is added to a preservation solution composed of a phosphate buffer sterilized with high-pressure steam, so that the bacterial concentration is 104. A test bacterial solution of staphylococci and Escherichia coli was prepared by diluting to the number of cells / ml. 75 ml of this liquid was put into an Erlenmeyer flask, and then 0.75 g of a test piece was put in absolute dry conversion. Then, this Erlenmeyer flask was put on a shaker and shaken under the conditions of 340 rpm, 28 ° C., 60 minutes to sufficiently bring the bacteria in the bacterial solution into contact with the test piece.
Next, a 10-fold dilution series from 10 times to 100,000 times the bacterial solution was prepared, and plates were prepared by the pour method using 1 ml of the bacterial solution of each concentration and 15 ml of a normal agar medium. Thereafter, after culturing in a 37 ° C. incubator for 48 hours, colonies were counted, and the sterilization rate relative to the number of bacteria before contact was calculated by formula (1) to evaluate antibacterial properties.
Bacteria reduction rate (%) = 100 × (initial viable cell count−viable cell count after 48 hours) / initial viable cell count (1)
（４）抗菌持続性の評価
［サンプル板の作製］
ステンレス板（ＳＵＳ３１６）および軟質ＰＶＣシートからなる大きさが１００ｍｍ×１００ｍｍの２種類の試験板を用意した。次に、紙製キッチンタオル（商品名：ネピアキッチンタオル、新王子製紙社製）に７５％エタノールを含浸させ、このタオルで各試験板の表面を拭い、殺菌、清浄し、乾燥した後、更にイオン交換水を含ませた紙製キッチンタオルで清拭し、室内に７２時間放置し乾燥した。その後、実施例と比較例で得られた湿潤ワイパーを用いて各試験板を４回往復清拭し、室温で１時間乾燥したものを抗菌持続性試験（拭い取り回数０回）のサンプル板とする。
各サンプル板表面を、イオン交換水を含浸した紙製キッチンタオルを用いて、１回拭い、これを抗菌持続性試験の拭い取り回数１回のサンプル板とし、次いで順次同様にして１回目の拭い取りの後に１時間の乾燥時間を設け２回拭い、拭い取り回数２回のサンプル板とし、同様にして拭い取り回数７回までのサンプル板を用意した。それぞれ拭い取りの間に１時間の乾燥時間を設けた。
(4) Evaluation of antibacterial durability [Preparation of sample plate]
Two types of test plates having a size of 100 mm × 100 mm made of a stainless steel plate (SUS316) and a soft PVC sheet were prepared. Next, a paper kitchen towel (trade name: Napier Kitchen Towel, manufactured by Shin-Oji Paper Co., Ltd.) is impregnated with 75% ethanol, the surface of each test plate is wiped with this towel, sterilized, cleaned, dried, and further It was wiped with a paper kitchen towel soaked with ion-exchanged water, left in the room for 72 hours and dried. Then, each test plate was wiped back and forth four times using the wet wipers obtained in the examples and comparative examples, and dried for 1 hour at room temperature to obtain a sample plate for an antibacterial sustainability test (number of wipes 0 times) To do.
The surface of each sample plate is wiped once with a paper kitchen towel impregnated with ion-exchanged water, and this is used as a sample plate with one wiping of the antibacterial sustainability test. After the removal, a drying time of 1 hour was provided and wiped twice to obtain a sample plate with two wiping times. Similarly, sample plates with a maximum of seven wiping times were prepared. There was a drying time of 1 hour between each wipe.
［抗菌持続性評価］
上記抗菌性の評価と同様の方法でサンプル板表面へ滴下前の菌数に対する減菌率を計算で求め、抗菌持続性を評価した。この時、菌液の菌数が滴下前の菌液の菌数より多い場合は、＋の記号で示した。抗菌性と抗菌持続性は、減菌率の高いものほど強いといえるが、減菌率が６５％以上あれば抗菌性又は抗菌持続性があるといえる。更に、減菌率が８０％以上の値を示せば非常に高い抗菌性又は抗菌持続性を有していることになり望ましい。
[Antimicrobial durability evaluation]
The antibacterial sustainability was evaluated by calculating the sterilization rate relative to the number of bacteria before dropping onto the sample plate surface by the same method as the above antibacterial evaluation. At this time, when the number of bacteria in the bacterial solution is larger than the number of bacteria in the bacterial solution before dropping, it is indicated by a + sign. The higher the sterilization rate, the stronger the antibacterial property and the antibacterial persistence. However, if the sterilization rate is 65% or more, it can be said that the antibacterial property or the antibacterial durability is present. Furthermore, if the sterilization rate shows a value of 80% or more, it is desirable because it has a very high antibacterial property or antibacterial durability.
（５）耐候性
２０ｍｍ×２０ｍｍの大きさに切った湿潤ワイパーを試験片とした。試験片は、８０℃で２４時間、乾燥機内で乾燥させた後、ウェザーメーター（ガス試験機器（株）製）を用いて１００時間の耐候試験を行い、変色度合いを観察した。
○ ・・・変色が見られないもの
△ ・・・変色が僅かに見られるもの
× ・・・変色が見られるもの
(5) Weather resistance A wet wiper cut to a size of 20 mm × 20 mm was used as a test piece. The test piece was dried in a dryer at 80 ° C. for 24 hours, and then subjected to a weather resistance test for 100 hours using a weather meter (manufactured by Gas Test Equipment Co., Ltd.) to observe the degree of discoloration.
○ ・ ・ ・ No discoloration △ ・ ・ ・ Slight discoloration × ・ ・ ・ Those discoloration
（６）消臭性の評価
５Lテトラパックに、湿潤ワイパー用含浸液を１２０℃、１２時間乾燥して得た粉末試料１ｇと、初期濃度１００ｐｐｍのアンモニア試験臭３Ｌおよび初期濃度４ｐｐｍの硫化水素試験臭３Ｌを封入して２時間放置した後、検知管にて試験臭濃度を測定し、式（２）により臭気成分の減少率（消臭率）を求めた。
消臭率（％）＝１００×（初期臭気成分濃度−２時間後の臭気成分濃度）／初期臭気成分濃度・・・（２）
(6) Evaluation of deodorizing property 1 g of a powder sample obtained by drying an impregnating liquid for wet wiper at 120 ° C. for 12 hours in a 5 L tetrapack, an ammonia test odor of 3 L with an initial concentration of 100 ppm, and a hydrogen sulfide test with an initial concentration of 4 ppm After 3 L of odor was sealed and allowed to stand for 2 hours, the test odor concentration was measured with a detector tube, and the reduction rate (deodorization rate) of the odor component was determined by the formula (2).
Deodorization rate (%) = 100 × (initial odor component concentration−odor component concentration after 2 hours) / initial odor component concentration (2)
ＳｉＯ2濃度２０重量％のコロイド溶液２０ｇと純水３８０ｇの混合物を８０℃に加温した。この反応母液のｐＨは１０．７であり、同母液にＳｉＯ2として１．５重量％の珪酸ソーダ水溶液１５００ｇとＡｌ2Ｏ3として０．５重量％のアルミン酸ソーダ水溶液１５００ｇとを同時に添加して、ｐＨ１２．３のシリカ・アルミナ複合酸化物コロイド溶液とした後、限外濾過膜で濃縮して固形分濃度２２．２重量％のコロイド溶液を調製した。
このコロイド溶液（シリカ・アルミナ複合酸化物粒子、平均粒子径３０ｎｍ）２２ｇを水で希釈して固形分としての濃度１．０重量％のコロイド溶液（１）とした。
A mixture of 20 g of a colloidal solution having a SiO 2 concentration of 20% by weight and 380 g of pure water was heated to 80 ° C. The pH of this reaction mother liquor was 10.7, and 1500 g of a 1.5 wt% sodium silicate aqueous solution as SiO 2 and 1500 g of a 0.5 wt% sodium aluminate aqueous solution as Al 2 O 3 were simultaneously added to the mother liquor. After preparing a silica-alumina composite oxide colloidal solution having a pH of 12.3, the colloidal solution having a solid concentration of 22.2% by weight was prepared by concentrating with an ultrafiltration membrane.
22 g of this colloidal solution (silica / alumina composite oxide particles, average particle size 30 nm) was diluted with water to obtain a colloidal solution (1) having a solid content of 1.0% by weight.
一方、金属銀として固形分（シリカ・アルミナ複合酸化物粒子）に対し５重量％になるように硝酸銀（関東化学社製、試薬特級）０．３９ｇを１０ｇの水で溶解した。ついで５００ｇのコロイド溶液（１）を８０℃に加温し、このコロイド溶液に攪拌しながら添加し、８０℃、1時間攪拌熟成を行い抗菌性無機酸化物微粒子（１）分散液とした。分散液中の硝酸根を除去するため５０℃に冷却後、固形分の１００倍の温水（５０℃）で限外濾過膜を用い洗浄した。抗菌性無機酸化物微粒子（１）分散液の固形分濃度は１重量％であった。 On the other hand, 0.39 g of silver nitrate (manufactured by Kanto Chemical Co., Ltd., reagent grade) was dissolved in 10 g of water so as to be 5 wt% as solid silver (silica / alumina composite oxide particles). Next, 500 g of the colloidal solution (1) was heated to 80 ° C., added to the colloidal solution while stirring, and stirred and aged at 80 ° C. for 1 hour to obtain antibacterial inorganic oxide fine particle (1) dispersion. In order to remove nitrate radicals in the dispersion, the solution was cooled to 50 ° C. and then washed with hot water (50 ° C.) 100 times the solid content using an ultrafiltration membrane. The solid content concentration of the antibacterial inorganic oxide fine particles (1) dispersion was 1% by weight.
ついで、別途、キレート剤としてエチレンジアミン四酢酸０．００４５ｇを水１０ｇに溶解して調製した水溶液を添加して充分に攪拌し、キレート剤を添加した抗菌性無機酸化物微粒子（１）分散液を調製した。
ついで、キレート剤を添加した抗菌性無機酸化物微粒子（１）分散液１重量％、水９９重量％となるように混合して湿潤ワイパー用含浸液（１）を調製した。
Subsequently, an aqueous solution prepared by dissolving 0.0045 g of ethylenediaminetetraacetic acid in 10 g of water as a chelating agent was added and stirred sufficiently to prepare a dispersion of antibacterial inorganic oxide fine particles (1) to which the chelating agent was added. did.
Next, an antibacterial inorganic oxide fine particle (1) to which a chelating agent was added (1) was mixed so that the dispersion was 1 wt% and water was 99 wt% to prepare a wet wiper impregnation liquid (1).
この湿潤ワイパー用含浸液（１）１００ｇを用い、レーヨン製不織布（旭化成工業株式会社製）５０ｇに含浸し、湿潤ワイパー（１）を調製した。含浸液の含浸量は不織布当り２００重量％となるように調整した。
湿潤ワイパー用含浸液(１)は３ヶ月以上たっても変色、凝集等による透明性の低下がなく安定であった。湿潤ワイパー用含浸液(１)の調製条件と、得られた湿潤ワイパー(１)の評価結果を表１に示す。
Using 100 g of this wet wiper impregnation liquid (1), 50 g of rayon nonwoven fabric (Asahi Kasei Kogyo Co., Ltd.) was impregnated to prepare wet wiper (1). The impregnation amount of the impregnation liquid was adjusted to 200% by weight per nonwoven fabric.
The impregnating liquid for wet wiper (1) was stable with no decrease in transparency due to discoloration, aggregation, etc. even after 3 months. Table 1 shows the preparation conditions of the wet wiper impregnation liquid (1) and the evaluation results of the obtained wet wiper (1).
実施例１において、金属銀として固形分（シリカ・アルミナ複合酸化物粒子）に対し２重量％になるように硝酸銀０．１６ｇ、キレート剤としてエチレンジアミン四酢酸０．００１８ｇを用いた以外は同様にして、湿潤ワイパー用含浸液(２)、ついで、湿潤ワイパー(２)を調製した。実施例１と同様の評価を行い、結果を表１に示す。 In Example 1, the same procedure was performed except that 0.16 g of silver nitrate was used as the metal silver to a solid content (silica / alumina composite oxide particles) of 2% by weight and 0.0018 g of ethylenediaminetetraacetic acid was used as the chelating agent. An impregnating solution for wet wiper (2) and then a wet wiper (2) were prepared. Evaluation similar to Example 1 was performed and the results are shown in Table 1.
実施例１において、金属銀として固形分（シリカ・アルミナ複合酸化物粒子）に対し８重量％になるように硝酸銀０．６３ｇ、キレート剤としてエチレンジアミン四酢酸０．００７２ｇを用い、キレート剤を添加した抗菌性無機酸化物微粒子（３）分散液１．１重量％、水９８．９重量％となるように混合した以外は同様にして、湿潤ワイパー用含浸液（３）、ついで、湿潤ワイパー(３)を調製した。実施例１と同様の評価を行い、結果を表１に示す。 In Example 1, 0.63 g of silver nitrate and 0.0072 g of ethylenediaminetetraacetic acid were added as a chelating agent so that the solid content (silica / alumina composite oxide particles) was 8 wt% as metallic silver, and a chelating agent was added. Antibacterial inorganic oxide fine particles (3) Dispersion liquid 1.1 wt%, water 98.9 wt% was mixed in the same manner except that the wet wiper impregnating liquid (3), then wet wiper (3 ) Was prepared. Evaluation similar to Example 1 was performed and the results are shown in Table 1.
硫酸チタンを水に溶解し、ＴｉＯ2として１．０％を含む水溶液を準備した。この溶液に、攪拌しながら１５％濃度のアンモニア水を徐々に添加し、白色スラリー液を得、このスラリー液をガラスフィルター（細孔Ｇ２）でろ過し、ケーキを水で十分洗浄し、含水チタン酸のケーキを得た。このケーキ３１．４ｇに、水と３３％濃度の過酸化水素２１９．８ｇを加えた後、８０℃で１４時間加熱し、ＴｉＯ2として１．０％濃度、ｐＨ８．２、黄褐色透明のチタン酸溶液３１３６ｇを得た。 An aqueous solution containing 1.0% as TiO 2 was prepared by dissolving titanium sulfate in water. To this solution, 15% ammonia water was gradually added with stirring to obtain a white slurry liquid, which was filtered through a glass filter (pore G2), the cake was thoroughly washed with water, and water-containing titanium An acid cake was obtained. Water and 219.8 g of 33% hydrogen peroxide were added to 31.4 g of this cake, and then heated at 80 ° C. for 14 hours to obtain 1.0% TiO 2 , pH 8.2, yellowish brown transparent titanium as TiO 2. 3136 g of acid solution was obtained.
次いで、１５％濃度のアンモニア水溶液２１．３ｇを水６１８．１ｇで希釈したアンモニア水溶液中で酸化銀２．１０ｇを溶解して、アンミン錯塩水溶液とし、この水溶液を前記チタン酸溶液に添加攪拌した。次に濃度２０重量％のシリカゾル３８．７ｇを加え後、１５０℃で３６時間加熱し、固形分（酸化チタン・シリカ複合酸化物粒子）濃度１．０重量％の透明な抗菌性無機酸化物微粒子（４）分散液とした。酸化チタン・シリカ複合酸化物粒子の平均粒子径は２５ｎｍであった。この溶液は初期は黄褐色であったが、３６時間後淡乳白色の透明性のコロイド溶液となった。 Next, 2.10 g of silver oxide was dissolved in an aqueous ammonia solution obtained by diluting 21.3 g of a 15% aqueous ammonia solution with 618.1 g of water to form an ammine complex salt aqueous solution, and this aqueous solution was added to the titanic acid solution and stirred. Next, 38.7 g of silica sol having a concentration of 20% by weight was added, followed by heating at 150 ° C. for 36 hours, and transparent antibacterial inorganic oxide fine particles having a solid content (titanium oxide / silica composite oxide particle) concentration of 1.0% by weight. (4) A dispersion was obtained. The average particle size of the titanium oxide / silica composite oxide particles was 25 nm. This solution was initially yellowish brown, but after 36 hours became a pale milky white transparent colloidal solution.
ついで、別途、キレート剤としてエチレンジアミン四酢酸０．００４５ｇを水１０ｇに溶解して調製した水溶液を添加して充分に攪拌し、キレート剤を添加した抗菌性無機酸化物微粒子（４）分散液を調製した。
ついで、キレート剤を添加した抗菌性無機酸化物微粒子（４）分散液１重量％、水９９重量％となるように混合して湿潤ワイパー用含浸液（４）を調製した。得られた湿潤ワイパー用含浸液(４)は３ヶ月以上たっても変色、凝集等による透明性の低下がなく安定であった。
Then, separately, an aqueous solution prepared by dissolving 0.0045 g of ethylenediaminetetraacetic acid in 10 g of water as a chelating agent was added and sufficiently stirred to prepare an antibacterial inorganic oxide fine particle (4) dispersion containing the chelating agent. did.
Subsequently, the impregnating liquid (4) for wet wiper was prepared by mixing the antibacterial inorganic oxide fine particles (4) to which the chelating agent had been added to 1% by weight of the dispersion and 99% by weight of water. The obtained wet wiper impregnating liquid (4) was stable without deterioration of transparency due to discoloration, aggregation, etc. even after 3 months or more.
この湿潤ワイパー用含浸液（４）１００ｇを用い、レーヨン不織布（旭化成工業株式会社製）５０ｇに含浸し、湿潤ワイパー（４）を作製した。含浸液の含浸量は不織布当り２００％となるように調整した。湿潤ワイパー(４)について実施例１と同様の評価を行い、結果を表１に示す。 Using 100 g of this wet wiper impregnation liquid (4), 50 g of rayon nonwoven fabric (Asahi Kasei Kogyo Co., Ltd.) was impregnated to prepare wet wiper (4). The impregnation amount of the impregnation liquid was adjusted to 200% per nonwoven fabric. The wet wiper (4) was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
実施例４において、金属銀として固形分（酸化チタン・シリカ複合酸化物粒子）に対し２重量％になるように酸化銀０．８４ｇおよびエチレンジアミン四酢酸０．０１５ｇを用い、キレート剤を添加した抗菌性無機酸化物微粒子（５）分散液１．１％と水９８．９％とした以外は同様にして、湿潤ワイパー用含浸液(５)、および湿潤ワイパー(５)を調製した。湿潤ワイパー(５)について実施例１と同様の評価を行い、結果を表１に示す。 In Example 4, an antibacterial solution in which 0.84 g of silver oxide and 0.015 g of ethylenediaminetetraacetic acid were added as metal silver to a solid content (titanium oxide / silica composite oxide particles) of 2% by weight and a chelating agent was added. A wet wiper impregnating solution (5) and a wet wiper (5) were prepared in the same manner except that the fine inorganic oxide fine particle (5) dispersion was 1.1% and the water was 98.9%. The wet wiper (5) was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
実施例４において、金属銀として固形分（酸化チタン・シリカ複合酸化物粒子）に対し２重量％になるように酸化銀３．３６ｇ、キレート剤としてエチレンジアミン四酢酸０．０６１ｇを用い、キレート剤を添加した抗菌性無機酸化物微粒子（６）分散液１．１重量％、水９８．９重量％となるように混合した以外は同様にして、湿潤ワイパー用含浸液(６)、および湿潤ワイパー(６)を調製した。湿潤ワイパー(６)について実施例１と同様の評価を行い、結果を表１に示す。 In Example 4, 3.36 g of silver oxide was used so that the solid content (titanium oxide / silica composite oxide particles) was 2% by weight as metallic silver, and 0.061 g of ethylenediaminetetraacetic acid was used as the chelating agent. The impregnating liquid for wet wiper (6), and the wet wiper (6), except that the added antibacterial inorganic oxide fine particle (6) dispersion was 1.1 wt% and water was 98.9 wt%. 6) was prepared. The wet wiper (6) was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
実施例１において、金属銀として固形分（シリカ・アルミナ複合酸化物粒子）に対し８重量％になるように硝酸銀０．３９ｇ、キレート剤としてヒドロキシエチルエチレンジアミン三酢酸０．００６７ｇを用い、キレート剤を添加した抗菌性無機酸化物微粒子（７）分散液１．１重量％、水９８．９重量％となるように混合した以外は同様にして、湿潤ワイパー用含浸液（７）、ついで、湿潤ワイパー(７)を調製した。実施例１と同様の評価を行い、結果を表１に示す。 In Example 1, 0.39 g of silver nitrate was used as metallic silver so that the solid content (silica / alumina composite oxide particles) was 8% by weight, and 0.0067 g of hydroxyethylethylenediaminetriacetic acid was used as the chelating agent. The antibacterial inorganic oxide fine particles (7) added were similarly mixed except that the dispersion was 1.1% by weight and the water was 98.9% by weight. (7) was prepared. Evaluation similar to Example 1 was performed and the results are shown in Table 1.
実施例１において、キレート剤としてエチレンジアミン四酢酸水溶液を添加しなかった以外は実施例１と同様にして湿潤ワイパー用含浸液(Ｒ１)を得た。得られた湿潤ワイパー用含浸液（Ｒ１）は約１．５月後に白濁が認められた。
ついで、湿潤ワイパー(Ｒ１)を調製し、実施例１と同様の評価を行った。結果を表１に示す。
In Example 1, an impregnating solution for wet wiper (R1) was obtained in the same manner as in Example 1 except that the ethylenediaminetetraacetic acid aqueous solution was not added as a chelating agent. The obtained wet wiper impregnating solution (R1) was found cloudy after about 1.5 months.
Next, a wet wiper (R1) was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
実施例４において、キレート剤としてエチレンジアミン四酢酸水溶液を添加しなかった以外は実施例４と同様にして湿潤ワイパー用含浸液(Ｒ２)を得た。得られた湿潤ワイパー用含浸液（Ｒ２）は約１．５ヶ月後に白濁が認められた。
ついで、湿潤ワイパー（Ｒ２）を調製し、実施例１と同様の評価を行い、結果を表１に示す。
In Example 4, an impregnating liquid for wet wiper (R2) was obtained in the same manner as in Example 4 except that no ethylenediaminetetraacetic acid aqueous solution was added as a chelating agent. The obtained wet wiper impregnation liquid (R2) was found to be cloudy after about 1.5 months.
Next, a wet wiper (R2) was prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.
実施例１において、金属銀として固形分（シリカ・アルミナ複合酸化物粒子）に対し２０重量％になるように硝酸銀１．５７ｇを用いた以外は同様にして抗菌性無機酸化物微粒子（Ｒ３）分散液を調製した。ついで、抗菌性無機酸化物微粒子（Ｒ３）分散液１．２重量％と水９８．８重量％となるように混合して湿潤ワイパー用含浸液(Ｒ３)を得た。
この湿潤ワイパー用含浸液（Ｒ３）１００ｇを用い、木材パルプとポリプロピレン繊維とからなる複合不織布（旭化成工業株式会社製）５０ｇに含浸し、湿潤ワイパー（Ｒ３）を作製した。含浸液の含浸量は複合不織布重量当り２００重量％となるように調製した。
湿潤ワイパー(Ｒ３)について実施例１と同様の評価を行い、結果を表１に示す。複合不織布が太陽光にあたると短時間で黒く変色した。
In Example 1, antibacterial inorganic oxide fine particles (R3) were dispersed in the same manner except that 1.57 g of silver nitrate was used as the metal silver to a solid content (silica / alumina composite oxide particles) of 20% by weight. A liquid was prepared. Subsequently, 1.2 wt% of the antibacterial inorganic oxide fine particle (R3) dispersion and 98.8 wt% of water were mixed to obtain an impregnating solution for wet wiper (R3).
Using 100 g of this wet wiper impregnating solution (R3), 50 g of a composite nonwoven fabric (manufactured by Asahi Kasei Kogyo Co., Ltd.) made of wood pulp and polypropylene fibers was impregnated to prepare a wet wiper (R3). The impregnation amount of the impregnation liquid was adjusted to 200% by weight with respect to the weight of the composite nonwoven fabric.
The wet wiper (R3) was evaluated in the same manner as in Example 1, and the results are shown in Table 1. The composite nonwoven fabric turned black in a short time when exposed to sunlight.
実施例１において、金属銀として固形分（シリカ・アルミナ複合酸化物粒子）に対し０．５重量％になるように硝酸銀０．２ｇを用いた以外は同様にして抗菌性無機酸化物微粒子（Ｒ４）分散液を調製した。ついで、抗菌性無機酸化物微粒子（Ｒ４）分散液５．２重量％と水９４．８重量％となるように混合して湿潤ワイパー用含浸液(Ｒ４)を得た。
この湿潤ワイパー用含浸液（Ｒ４）１００ｇを用い、木材パルプとポリプロピレン繊維とからなる複合不織布（旭化成工業株式会社製）５０ｇに含浸し、湿潤ワイパー（Ｒ４）を作製した。含浸液の含浸量は複合不織布重量当り２００％となるように調製した。
湿潤ワイパー(Ｒ４)について実施例１と同様の評価を行い、結果を表１に示す。
In Example 1, antibacterial inorganic oxide fine particles (R4) were used in the same manner except that 0.2 g of silver nitrate was used as metal silver so that the solid content (silica / alumina composite oxide particles) was 0.5% by weight. ) A dispersion was prepared. Subsequently, the impregnating liquid for wet wiper (R4) was obtained by mixing 5.2% by weight of the antibacterial inorganic oxide fine particle (R4) dispersion and 94.8% by weight of water.
Using 100 g of this wet wiper impregnation liquid (R4), 50 g of a composite nonwoven fabric (manufactured by Asahi Kasei Kogyo Co., Ltd.) made of wood pulp and polypropylene fibers was impregnated to prepare a wet wiper (R4). The impregnation amount of the impregnation liquid was prepared to be 200% per weight of the composite nonwoven fabric.
The wet wiper (R4) was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
エタノール７５％とイオン交換水２５％を混合して湿潤ワイパー用含浸液（Ｒ５）を調製した。
この湿潤ワイパー用含浸液（Ｒ５）１００ｇを用い、木材パルプとポリプロピレン繊維とからなる複合不織布（旭化成工業株式会社製）５０ｇに含浸し、湿潤ワイパー（Ｒ５）を作製した。含浸液の含浸量は複合不織布重量当り２００％となるように調製した。
湿潤ワイパー(Ｒ５)について実施例１と同様の評価を行い、結果を表１に示す。
A wet wiper impregnating solution (R5) was prepared by mixing 75% ethanol and 25% ion-exchanged water.
Using 100 g of this wet wiper impregnation liquid (R5), 50 g of a composite nonwoven fabric (manufactured by Asahi Kasei Kogyo Co., Ltd.) made of wood pulp and polypropylene fibers was impregnated to prepare a wet wiper (R5). The impregnation amount of the impregnation liquid was prepared to be 200% per weight of the composite nonwoven fabric.
The wet wiper (R5) was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
エタノール５．０％、プロピレングリコール５．０％、パラオキシ安息香酸メチル０．２％、パラオキシ安息香酸エチル０．１％、及びイオン交換水８９．７％を混合して湿潤ワイパー用含浸液（Ｒ６）を調製した。
この湿潤ワイパー用含浸液（Ｒ６）１００ｇを用い、木材パルプとポリプロピレン繊維とからなる複合不織布（旭化成工業株式会社製）５０ｇに含浸し、湿潤ワイパー（Ｒ６）を作製した。含浸液の含浸量は複合不織布重量当り２００％となるように調製した。
湿潤ワイパー用含浸液(Ｒ６)について実施例１と同様の評価を行い、結果を表１に示す。
An impregnating solution for wet wiper (R6) by mixing ethanol 5.0%, propylene glycol 5.0%, methyl paraoxybenzoate 0.2%, ethyl paraoxybenzoate 0.1%, and ion-exchanged water 89.7%. ) Was prepared.
Using 100 g of this wet wiper impregnation liquid (R6), 50 g of a composite nonwoven fabric (manufactured by Asahi Kasei Kogyo Co., Ltd.) made of wood pulp and polypropylene fibers was impregnated to prepare a wet wiper (R6). The impregnation amount of the impregnation liquid was prepared to be 200% per weight of the composite nonwoven fabric.
The wet wiper impregnating solution (R6) was evaluated in the same manner as in Example 1, and the results are shown in Table 1.
Claims (6)
In a wet wiper obtained by impregnating a non-woven fabric or wet-resistant paper with an impregnating liquid, the impregnating liquid comprises antibacterial inorganic oxide fine particles composed of an antibacterial metal component and an inorganic oxide other than the antibacterial metal component, and a chelating agent. A wet wiper characterized by containing.
The chelating agent is ethylenediaminetetraacetic acid, hydroxyethylethylenediaminetriacetic acid, dihydroxyethylethylenediaminediacetic acid, 1,3-propanediaminetetraacetic acid, diethyltriaminepentaacetic acid, triethylenetetraminehexaacetic acid, nitrilotriacetic acid, hydroxyethyliminodiacetic acid. The wet wiper according to claim 1, which is one or more selected.
The wet wiper according to claim 1 or 2, wherein the antibacterial inorganic oxide fine particles are obtained by attaching or binding the antibacterial metal component to the inorganic oxide colloidal particles having a negative charge by electrostatic interaction.
The antibacterial inorganic oxide fine particles are obtained by attaching or binding an antibacterial metal component complexed with the chelating agent to an inorganic oxide colloidal particle having a negative charge by electrostatic interaction. 2. The wet wiper according to 2.
The average particle diameter of the antibacterial inorganic oxide fine particles is 5 to 100 nm, the content of the antibacterial metal component in the antibacterial inorganic oxide fine particles is 1.0 to 15.0% by weight as a metal, The solid content concentration of the antibacterial inorganic oxide fine particles contained in the impregnating liquid is 0.005 to 10.0% by weight, and the content of the antibacterial metal component contained in the impregnating liquid is 0.0001 to 0.00. The wet wiper according to any one of claims 1 to 4, which is 05% by weight.
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| JP2018119254A (en) * | 2017-01-20 | 2018-08-02 | 榮一 中川 | Clarification material of bacteria in soil |
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| JP2008094738A (en) * | 2006-10-10 | 2008-04-24 | Catalysts & Chem Ind Co Ltd | Antimicrobial agent |
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| JP2011246859A (en) * | 2010-05-28 | 2011-12-08 | Suminoe Textile Co Ltd | Fiber fabric with antimicrobial, antiviral and anti-allergy functions |
| JP2018119254A (en) * | 2017-01-20 | 2018-08-02 | 榮一 中川 | Clarification material of bacteria in soil |
| JP7003366B2 (en) | 2017-01-20 | 2022-01-20 | 榮一 中川 | Soil bacteria purifier |
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