JP2015074841A - Fiber processing agent - Google Patents
Fiber processing agent Download PDFInfo
- Publication number
- JP2015074841A JP2015074841A JP2013210112A JP2013210112A JP2015074841A JP 2015074841 A JP2015074841 A JP 2015074841A JP 2013210112 A JP2013210112 A JP 2013210112A JP 2013210112 A JP2013210112 A JP 2013210112A JP 2015074841 A JP2015074841 A JP 2015074841A
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- Prior art keywords
- chitosan
- allergen
- fiber
- solution
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000003795 chemical substances by application Substances 0.000 title abstract description 42
- 238000012545 processing Methods 0.000 title abstract description 23
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- 229920001661 Chitosan Polymers 0.000 claims abstract description 119
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
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Images
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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
本発明は繊維にカチオン系の表面処理を施すことで繊維の表面電位を正に帯電させて負の表面電位を持つダニアレルゲン等の有害タンパク質を繊維表面に吸着除去する機能を持つ繊維処理剤に関するものである。 The present invention relates to a fiber treatment agent having a function of adsorbing and removing harmful proteins such as mite allergen having a negative surface potential by positively charging the surface potential of the fiber by subjecting the fiber to a cationic surface treatment. Is.
近年の高気密高断熱住宅の登場は、我々に快適空間を提供してくれる。しかし、この快適な住宅は換気不足になりやすくダニの増殖に適した環境になってしまうことがある。 The advent of highly airtight and highly insulated houses in recent years provides us with a comfortable space. However, this comfortable house is prone to poor ventilation and may be suitable for the growth of ticks.
アレルギー症状の発症は、生物が持つ免疫反応に由来する。杉花粉やダニの糞等のアレルゲン物質が体内に入ると、この進入タンパク質に対してＩｇＥ抗体が作られる。ＩｇＥ抗体が肥満細胞の表面に結合し、感作となる。再度、これらアレルゲン物質が体内に侵入し、ＩｇＥ抗体と結合した際には肥満細胞から種々のケミカルメディエータが放出される。これらケミカルメディエータがヒスタミンやロイコトリエンなどである。これらの体内物質が、発熱、発疹、鼻炎、咳等を発症する原因である。これらの症状が強くなると睡眠不足や集中力の低下など我々の経済活動あるいは創造活動に大きな障壁となる。 The onset of allergic symptoms stems from the immune response of the organism. When allergens such as cedar pollen and tick feces enter the body, IgE antibodies are made against this invading protein. IgE antibodies bind to the surface of mast cells and become sensitized. Again, when these allergen substances enter the body and bind to IgE antibodies, various chemical mediators are released from mast cells. These chemical mediators are histamine and leukotriene. These internal substances are the cause of developing fever, rash, rhinitis, cough and the like. When these symptoms become stronger, it becomes a major barrier to our economic or creative activities such as lack of sleep and reduced concentration.
飛散したアレルゲンを吸入することによる防止手段として、マスクなどの繊維製品による遮断がある。このマスク等の繊維製品にアレルゲン賦活化機能を付与する方法が知られている。特許文献１には、アレルゲンを賦活する方法として銀イオン、銅イオン及び亜鉛イオンなどを多孔質物質に担持して、マスクに利用している。また、特許文献２には、タンニン酸でマスクなどの繊維製品を処理することによるアレルゲンの不活化が可能であるとしている。これらは一例であるがマスクを高機能化しアレルゲンを不活化する検討は多数なされている。
As a preventive measure by inhaling scattered allergens, there is blocking by a textile product such as a mask. A method of imparting an allergen activation function to a textile product such as a mask is known. In
一方、アレルギー症状の発症は、飛散したアレルゲンを吸入することによるぜんそく等の発症の他に、皮膚からの吸収による皮膚炎などもある。ダニアレルゲンもアトピー性皮膚炎の原因と言われている。アレルゲンを皮膚から体内へ遮断する検討は少ない。特許文献３では、金属フタロシアニンのもつ酸化還元触媒機能を利用したアレルゲン分解機能を繊維に付与した製品が示されている。また、特許文献４では天然物から抽出したダニや花粉のアレルゲン不活化剤を染色工程において添加する方法とその方法で製造された繊維製品が示されている。
On the other hand, onset of allergic symptoms includes not only asthma caused by inhalation of scattered allergens but also dermatitis caused by absorption from the skin. Mite allergens are also said to cause atopic dermatitis. There are few studies to block allergens from the skin to the body. Patent Document 3 discloses a product in which an allergen decomposition function using a redox catalyst function of metal phthalocyanine is imparted to a fiber.
肌着にアレルゲン不活化剤を用いることは種々提案されている。しかし、肌着の役割として吸湿性や保湿性が同時に求められている。さらには、皮膚炎などは乾燥肌いわゆるドライスキンなどでも発症する。 Various proposals have been made to use allergen inactivating agents for underwear. However, moisture absorption and moisture retention are simultaneously required as the role of underwear. Furthermore, dermatitis or the like also develops on dry skin, so-called dry skin.
しかしながら、アレルゲン不活化剤等は一般的には高価である。また、皮膚へのダニアレルゲン等のアレルゲン物質との接触を防ぐ方法としては、直接皮膚に接触している肌着等への加工が必要になり、安全に使用できる不活化剤等も限られる。さらに、タンニン酸やフタロシアニンなどはそれ自体の色彩が強く、繊維製品の色彩が限定される課題があった。 However, allergen inactivating agents are generally expensive. In addition, as a method for preventing contact with allergen substances such as mite allergens on the skin, it is necessary to process the underwear that is in direct contact with the skin, and inactivators that can be used safely are limited. Furthermore, tannic acid and phthalocyanine have strong colors themselves, and there is a problem that the color of textile products is limited.
さらに、アレルゲン不活化剤等の薬剤は取り扱いが限定されるため、家庭で簡単にアレルゲン加工をすることは困難である。つまり、最初からアレルゲン不活化剤等で加工してある製品を購入しなくてはならず、現在使用している既存の肌着等へ加工を施すことは困難であった。 Furthermore, since the handling of drugs such as allergen inactivating agents is limited, it is difficult to easily process allergens at home. In other words, a product processed with an allergen inactivating agent or the like must be purchased from the beginning, and it has been difficult to process existing underwear currently used.
また、皮膚の炎症は、遺伝的な要因だけでなく、環境因子が発症等の引き金になる。成人アトピー性皮膚炎患者においては、非アレルギー的要因として乾燥肌（ドライスキン）があり、乾燥、摩擦などで症状が悪化することが知られている。そのため、アトピー性皮膚炎の治療においては、内服・外用治療だけでなく、日常生活においてアレルギー性および非アレルギー的な刺激を避けることがきわめて重要である。これまで、掃除の励行、空気清浄機の活用などで防ダニ、防埃などが行われてきたが、皮膚に直接接する肌着等に対する注意は払われてこなかった。 In addition, skin inflammation is triggered not only by genetic factors but also by environmental factors. In adult atopic dermatitis patients, there is dry skin as a non-allergic factor, and it is known that symptoms worsen due to dryness and friction. Therefore, in the treatment of atopic dermatitis, it is extremely important to avoid allergic and non-allergic stimuli in daily life as well as internal and external treatments. So far, mite prevention and dust prevention have been carried out through cleaning, air cleaners, etc., but attention has not been paid to underwear that comes in direct contact with the skin.
そこで、本発明の目的は、製品の色彩に影響を与えず、アレルゲン不活化剤などの高価な薬剤を使用することなく、さらに簡単に加工できるアレルゲン物質を吸着除去する機能を持つ繊維処理組成物を提供するものである。 Accordingly, an object of the present invention is to provide a fiber treatment composition having a function of adsorbing and removing an allergen substance that does not affect the color of the product and can be further easily processed without using an expensive drug such as an allergen inactivating agent. Is to provide.
本発明の発明者は、微生物などタンパク質由来粒子の表面電位について長年に渡り研究してきた。その中で、微生物やウイルス等のタンパク質由来粒子は水中では負に帯電しており、正に帯電している表面に吸着し、水中から除去できることを明らかにしてきた。また、今回アトピー性皮膚炎の原因になるダニアレルゲンについて、汗等の水中では大きく負に帯電していること明らかにした。 The inventors of the present invention have been studying the surface potential of protein-derived particles such as microorganisms for many years. Among them, it has been clarified that protein-derived particles such as microorganisms and viruses are negatively charged in water, adsorbed on a positively charged surface, and can be removed from water. The mite allergen that causes atopic dermatitis has been shown to be highly negatively charged in water such as sweat.
本発明者らは、前記課題を解決すべく鋭意開発の結果、本発明に到達した。本発明に係る繊維製品は、その表面電位を正に保つことにより、負に帯電しているダニアレルゲン等のアレルゲン粒子や有害タンパク質を静電的に繊維表面に吸着させて汗などの水中から除去することに成功した。 The inventors of the present invention have arrived at the present invention as a result of intensive development to solve the above problems. The fiber product according to the present invention removes it from water such as sweat by electrostatically adsorbing negatively charged mite allergen and allergen particles and harmful proteins on the fiber surface by keeping the surface potential positive. Succeeded in doing.
本願は以下の発明を要旨とする。
［１］キトサン、有機酸及び水を含有することを特徴とするアレルゲン除去用繊維処理組成物。
［２］更に、第四級アンモニウム塩を含有する前記［１］に記載のアレルゲン除去用繊維処理組成物。
［３］前記キトサンが、ＧＰＣ法による重量平均分子量が１０，０００以上２００，０００以下であり、脱アセチル化度が５０％以上である前記［１］または［２］に記載のアレルゲン除去用繊維処理組成物。
［４］キトサンを１〜３０重量部、有機酸を５〜４０重量部、水を５０〜８０重量部で含有することを特徴とする前記［１］〜［３］の何れか一項に記載のアレルゲン除去用繊維処理組成物。
［５］ ｐＨが２〜６である前記［１］〜［４］の何れか一項に記載のアレルゲン除去用繊維処理組成物。
［６］ 前記［１］〜［４］に記載のアレルゲン除去用繊維処理組成物を繊維に付着させることを特徴とするアレルゲン除去機能を繊維に付与する方法。
［７］ 繊維を水に含浸させ、これに前記［１］〜［４］に記載のアレルゲン除去用繊維処理組成物を添加した後、該繊維を乾燥することを特徴とするアレルゲン除去機能を繊維に付与する方法。
The gist of the present application is as follows.
[1] A fiber treatment composition for removing allergens, comprising chitosan, an organic acid and water.
[2] The fiber treatment composition for removing allergens according to [1], further comprising a quaternary ammonium salt.
[3] The allergen-removing fiber according to [1] or [2], wherein the chitosan has a weight average molecular weight of 10,000 or more and 200,000 or less by GPC method and a deacetylation degree of 50% or more. Treatment composition.
[4] 1 to 30 parts by weight of chitosan, 5 to 40 parts by weight of an organic acid, and 50 to 80 parts by weight of water, [1] to [3] A fiber treatment composition for removing allergens.
[5] The fiber treatment composition for removing allergens according to any one of [1] to [4], wherein the pH is 2 to 6.
[6] A method for imparting an allergen removing function to a fiber, comprising attaching the fiber treatment composition for removing allergens according to [1] to [4] to a fiber.
[7] An allergen removing function characterized by impregnating a fiber with water and adding the fiber treatment composition for removing allergens according to [1] to [4] to the fiber, followed by drying the fiber. To give to.
本発明のアレルゲン除去用繊維処理組成物は、対象繊維に当該処理組成物を付着させることにより簡便にアレルゲン除去機能を付与することができる。当該処理組成物によるアレルゲン除去機能性繊維は、アレルゲンを吸着して取り除くことができる。吸着したアレルゲンは、該繊維を洗濯等の洗浄により当該処理組成物ごと洗い落とすことができ、再び当該処理組成物にて繊維を処理することにより、繊維のアレルゲン除去機能を再生することができる。
本発明のアレルゲン除去用繊維処理組成物は、肌着、靴下、ブラウス等の一般衣料や、生地団カバー、枕カバー、生地団綿等の寝具関連繊維、包帯、ガーゼ等の医療関連繊維、あるいは、ぬいぐるみ等の玩具関連繊維等へのアレルゲン除去機能付与に好適に用いることができる。
The fiber treatment composition for allergen removal of the present invention can easily provide an allergen removal function by attaching the treatment composition to the target fiber. The allergen-removing functional fiber by the treatment composition can adsorb and remove allergen. The adsorbed allergen can be washed out together with the treatment composition by washing such as washing, and the fiber allergen removing function can be regenerated by treating the fiber again with the treatment composition.
The fiber treatment composition for removing allergens of the present invention is general clothing such as underwear, socks, blouse, bedding-related covers, pillowcases, bedding-related fibers such as fabric cots, medical-related fibers such as bandages, gauze, or It can be suitably used for imparting an allergen removing function to toy-related fibers such as stuffed animals.
本発明は、キトサン、有機酸及び水を含有することを特徴とするアレルゲン除去用繊維処理組成物に関する。以下、本発明の詳細について説明する。
本発明はキトサンをアレルゲン除去機能を付与する主成分として含有する。キトサンは、かに、えび、昆虫等の甲殻中に多量に含まれるキチン（２−アセトアミドグルコースを構成成分とする多糖類）をアルカリ中で加水分解し、脱アセチル化することにより得られる。キトサンはすでに工業化されており安価に入手できる。分子量や脱アセチル化度及び粘度等の物性値において様々な物性及び品質のキトサンを入手することができ、製造コストを抑えることが可能であり、工業上利用可能性が高い。本発明のキトサンは、特に限定されるものではなく、工業的に入手できるキトサンをそのまま用いることができる。
The present invention relates to a fiber treatment composition for removing allergens, which contains chitosan, an organic acid and water. Details of the present invention will be described below.
The present invention contains chitosan as a main component that imparts an allergen removing function. Chitosan can be obtained by hydrolyzing and deacetylating chitin (polysaccharide containing 2-acetamidoglucose as a constituent) contained in a large amount in crab, shrimp, and insect shells. Chitosan has already been industrialized and can be obtained at low cost. Chitosan having various physical properties and quality can be obtained in terms of physical properties such as molecular weight, degree of deacetylation and viscosity, and the production cost can be suppressed, and industrial applicability is high. The chitosan of the present invention is not particularly limited, and industrially available chitosan can be used as it is.
本発明に用いるキトサンは、水溶性を有する物性であれば特に限定なく用いることができる。好ましいキトサンとしては、重量平均分子量が５，０００〜５００，０００のキトサンである。特に好ましいキトサンは、重量平均分子量が１０，０００〜２００，０００のキトサンである。キトサンの重量平均分子量の測定方法は、被験キトサン試料を０．５％酢酸に溶解した分析試料を調製し、ゲル浸透クロマトグラフ（ＧＰＣ）法によりプルラン標準品を用いて測定した重量平均分子量により規定される。
所望の重量平均分子量のキトサンを得るため、原料キチン質としてカニ殻を使用する場合、塩酸を用いてカルシウムを取り除く工程の塩酸濃度と反応時間、反応温度、あるいは濃水酸化ナトリウムを用いてキチンを脱アセチル化する際の工程における水酸化ナトリウム濃度と反応時間、反応温度をコントロールすることで調整することができる。
得られたキトサンは、乾燥後、摩砕式粉砕機、凍結粉砕機、衝撃式粉砕機、エアージェット式粉砕機、遠心カッター式粉砕機等の粉砕機で粉砕し、希望の目開きのメッシュを装着した篩別機で篩分けすることで、様々な粒径のキトサンを得ることができる。
Chitosan used in the present invention can be used without particular limitation as long as it has water-soluble physical properties. Preferred chitosan is chitosan having a weight average molecular weight of 5,000 to 500,000. Particularly preferred chitosan is chitosan having a weight average molecular weight of 10,000 to 200,000. The method of measuring the weight average molecular weight of chitosan is defined by the weight average molecular weight measured by using a pullulan standard by gel permeation chromatography (GPC) method by preparing an analytical sample in which a test chitosan sample is dissolved in 0.5% acetic acid. Is done.
In order to obtain chitosan having a desired weight average molecular weight, when using crab shell as raw chitin, the concentration of hydrochloric acid and reaction time, reaction temperature, or concentration sodium hydroxide in the process of removing calcium with hydrochloric acid It can adjust by controlling the sodium hydroxide density | concentration in the process at the time of deacetylation, reaction time, and reaction temperature.
The obtained chitosan is dried and then pulverized with a pulverizer such as a grinding pulverizer, freeze pulverizer, impact pulverizer, air jet pulverizer, centrifugal cutter pulverizer, etc. By sieving with the attached sieving machine, chitosan with various particle sizes can be obtained.
本発明で使用されるキトサンは、対応するキチンから脱アセチル化処理されて調製され、少なくとも５０％以上の脱アセチル化処理されたものであれば特に問題なく使用することができる。好ましくは脱アセチル化度が７０％以上のキトサンの使用が望ましい。より好ましくは脱アセチル化度が８０％以上であり、特に好ましくは脱アセチル化度が８５％以上のものを用いることが望ましい。
なお、得られたキトサンの脱アセチル化度は、キトサンを０．５％酢酸で溶解し、トルイジンブルーを指示薬として１／４００Ｎポリビニル硫酸カリウム(和光純薬工業製)をもちいてコロイド滴定を行い、遊離のアミノ基のモル数を測定することで算出する事ができる。
The chitosan used in the present invention can be used without any particular problem as long as it is prepared by deacetylation from the corresponding chitin and is at least 50% deacetylated. It is preferable to use chitosan having a degree of deacetylation of 70% or more. More preferably, the degree of deacetylation is 80% or more, and particularly preferably, the degree of deacetylation is 85% or more.
The degree of deacetylation of the obtained chitosan was determined by dissolving the chitosan with 0.5% acetic acid and performing colloidal titration using 1 / 400N potassium polyvinyl sulfate (manufactured by Wako Pure Chemical Industries) with toluidine blue as an indicator. It can be calculated by measuring the number of moles of free amino groups.
本発明で使用されるキトサンは、粒径が５００μｍ以下の粉末状キトサンを用いる事が好ましい。粒径は篩分け法により規定される。粒径５００μｍ以下のキトサンは、脱アセチル化反応後、摩砕式粉砕機、凍結粉砕機、衝撃式粉砕機、エアージェット式粉砕機、遠心カッター式粉砕機等の粉砕機で粉砕し、目開き５００μｍのメッシュを装着した篩別機で篩分けすることで、得ることができる。 The chitosan used in the present invention is preferably powdered chitosan having a particle size of 500 μm or less. The particle size is defined by a sieving method. Chitosan with a particle size of 500 μm or less is pulverized with a pulverizer such as a grinding pulverizer, freeze pulverizer, impact pulverizer, air jet pulverizer, centrifugal cutter pulverizer, etc. after the deacetylation reaction. It can be obtained by sieving with a sieving machine equipped with a 500 μm mesh.
本発明に用いる有機酸は、水に溶解し酸性を示すカルボン酸類、スルホン酸類、リン酸類であれば特に限定されずに用いることができる。使用に適する有機酸としてはカルボン酸類が好ましく、特に指定された物ではないが、ヒトへの安全性を考慮すると食品添加物として使用されている乳酸、酢酸、クエン酸、アスコルビン酸、リン酸、グルコン酸、フマル酸、リンゴ酸、酒石酸、アジピン酸、等が望ましく、これらは１種または２種以上を混合して用いることができる。特に、乳酸、クエン酸は繊維に添加すると柔軟剤の効果を持つことから、繊維への加工剤としては最も適する。 The organic acid used in the present invention is not particularly limited as long as it is a carboxylic acid, sulfonic acid, or phosphoric acid that dissolves in water and exhibits acidity. Carboxylic acids are preferable as organic acids suitable for use, and are not particularly specified, but in consideration of safety to humans, lactic acid, acetic acid, citric acid, ascorbic acid, phosphoric acid, which are used as food additives, Gluconic acid, fumaric acid, malic acid, tartaric acid, adipic acid and the like are desirable, and these can be used alone or in combination. In particular, lactic acid and citric acid are most suitable as processing agents for fibers because they have a softening effect when added to fibers.
本発明のアレルゲン除去用繊維処理組成物はｐＨが２〜６であることが好ましい。好ましくは、ｐＨは２以上５以下である。当該処理組成物のｐＨは、前記有機酸の添加により調整することができる。本発明のアレルゲン除去用繊維処理組成物は、有機酸を添加し、ｐＨ２〜５の範囲に設定することで、十分なキトサン加工が得られ、高いアレルゲン除去機能を付与できる。また、本剤により加工処理した繊維素材が柔軟性を有する効果も奏する。 The fiber treatment composition for removing allergens of the present invention preferably has a pH of 2-6. Preferably, the pH is 2 or more and 5 or less. The pH of the treatment composition can be adjusted by adding the organic acid. The fiber treatment composition for removing allergens of the present invention can provide a sufficient allergen removing function by adding an organic acid and setting the pH within the range of 2 to 5 to obtain sufficient chitosan processing. Moreover, the fiber material processed with this agent also has an effect of having flexibility.
本発明のアレルゲン除去用繊維処理組成物は、キトサン、有機酸を水に溶解して調製される。当該処理組成物の各成分組成においてはキトサンが溶解されていればに特に制限はないが、好ましい含有量は、キトサンが１〜３０重量部、有機酸が５〜４０重量部、水が５０〜９４重量部を含む組成物である。ｐＨにおいては、有機酸含有量を調製して、当該処理組成物のｐＨが２以上６以下の範囲に設定することが好ましい。より好ましくは、キトサンが１〜２０重量部、有機酸が５〜３０重量部、水が５０〜９４重量部を含み、該処理組成物のｐＨが２以上５以下の組成物である。 The fiber treatment composition for removing allergens of the present invention is prepared by dissolving chitosan and an organic acid in water. The chitosan is not particularly limited in each component composition of the treatment composition, but preferable contents are 1 to 30 parts by weight of chitosan, 5 to 40 parts by weight of organic acid, and 50 to 50% of water. A composition comprising 94 parts by weight. In terms of pH, it is preferable to adjust the organic acid content so that the pH of the treatment composition is in the range of 2 to 6. More preferably, the treatment composition contains 1 to 20 parts by weight of chitosan, 5 to 30 parts by weight of organic acid, 50 to 94 parts by weight of water, and the treatment composition has a pH of 2 to 5.
本発明のアレルゲン除去用繊維処理組成物には、任意に第四級アンモニウム塩を添加して良い。第四級アンモニウム塩としては、塩化ベンザルコニウム酸、ポリジアルキルアミノエチルアクリレート（メタクリレート）四級塩、ポリジアリルジメチルアンモニウムクロライド、ポリエチレンイミン、ポリビニルピリジン四級塩、またこれらの共重合物、ジシアンジアミドとホルマリン、アルキレンジアミンとエピクロルヒドリンとの縮合物等、が挙げられる。ポリジアリルジメチルアンモニウムクロライドが好ましい。第四級アンモニウム塩を用いる場合、その添加量は当該処理組成物に対し１〜３０重量部が好ましい。 A quaternary ammonium salt may optionally be added to the fiber treatment composition for removing allergens of the present invention. Quaternary ammonium salts include benzalkonium chloride, polydialkylaminoethyl acrylate (methacrylate) quaternary salts, polydiallyldimethylammonium chloride, polyethyleneimine, polyvinylpyridine quaternary salts, and their copolymers, dicyandiamide, Formalin, condensates of alkylenediamine and epichlorohydrin, and the like can be mentioned. Polydiallyldimethylammonium chloride is preferred. When a quaternary ammonium salt is used, the addition amount is preferably 1 to 30 parts by weight with respect to the treatment composition.
本発明のアレルゲン除去用繊維処理組成物には、任意にアルコール類を添加して良い。用いられるアルコール類は、水に任意に混和する水溶性アルコールが好ましく、メタノール、エタノール、イソプロパノール、エチレングリコール、プロピレングリコール、グリセリン等が挙げられる。エタノール、イソプロパノール、エチレングリコールが好ましい。アルコール類を用いる場合、その添加量は当該処理組成物に対し１〜４０重量部が好ましい。 Alcohols may optionally be added to the fiber treatment composition for removing allergens of the present invention. The alcohol used is preferably a water-soluble alcohol that is arbitrarily mixed with water, and examples thereof include methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, and glycerin. Ethanol, isopropanol and ethylene glycol are preferred. When using alcohol, the addition amount is preferably 1 to 40 parts by weight with respect to the treatment composition.
本発明のアレルゲン除去用繊維処理組成物には、任意に界面活性剤を添加して良い。用いられる界面活性剤は、カチオン系界面活性剤またはノニオン系界面活性剤である。カチオン系界面活性剤としては、塩化ジステアリルジメチルアンモニウム、塩化ベンザルコニウムなどが挙げられる。
ノニオン系界面活性剤としては、ポリオキシエチレンアルキルエーテル、脂肪酸ソルビタンエステル、アルキルポリグルコシド、脂肪酸ジエタノールアミド、アルキルモノグリセリルエーテルなどが挙げられる。
界面活性剤を用いる場合、その添加量は当該処理組成物に対し１〜３０重量部が好ましい。
A surfactant may be optionally added to the fiber treatment composition for removing allergens of the present invention. The surfactant used is a cationic surfactant or a nonionic surfactant. Examples of the cationic surfactant include distearyldimethylammonium chloride and benzalkonium chloride.
Nonionic surfactants include polyoxyethylene alkyl ethers, fatty acid sorbitan esters, alkyl polyglucosides, fatty acid diethanolamides, alkyl monoglyceryl ethers, and the like.
When using surfactant, the addition amount is 1-30 weight part with respect to the said processing composition.
本発明のアレルゲン除去用繊維処理組成物には、任意に防かび剤、防腐剤、保湿剤、香料、蛍光剤等を添加しても良い。これらのさらなる添加剤は、キトサンのカチオン性官能基との相互作用がないものを選択して適用する必要がある。防かび剤、防腐剤、保湿剤、香料、蛍光剤等の添加量は、当該処理組成物に対し１０重量部以下が好ましい。 An antifungal agent, preservative, moisturizing agent, fragrance, fluorescent agent and the like may be optionally added to the fiber treatment composition for removing allergens of the present invention. These additional additives need to be selected and applied without interaction with the cationic functionality of chitosan. The amount of the fungicide, preservative, moisturizer, fragrance, fluorescent agent and the like is preferably 10 parts by weight or less with respect to the treatment composition.
本発明のアレルゲン除去用繊維処理組成物は、キトサン及び有機酸、並びに任意成分として第四級アンモニウム塩、アルコール類及び界面活性剤を水を含むものであり、これらを混合して溶液調製することで、アレルゲン除去用繊維処理剤を調製できる。各成分のそれぞれの組成は、キトサンが１〜３０重量部、有機酸が５〜４０重量部、任意成分である第四級アンモニウム塩が０〜３０重量部、アルコール類が０〜４０重量部及び界面活性剤が０〜３０重量部に対して、水を５０〜８０重量部を添加して混合し溶液とすることでアレルゲン除去用繊維処理剤が調製される。 The fiber treatment composition for removing allergens of the present invention contains chitosan and an organic acid, and quaternary ammonium salts, alcohols and surfactants as optional components, and these are mixed to prepare a solution. Thus, a fiber treatment agent for allergen removal can be prepared. The composition of each component is 1 to 30 parts by weight of chitosan, 5 to 40 parts by weight of an organic acid, 0 to 30 parts by weight of a quaternary ammonium salt as an optional component, 0 to 40 parts by weight of alcohols, and The fiber treatment agent for removing allergen is prepared by adding 50 to 80 parts by weight of water and mixing the surfactant with respect to 0 to 30 parts by weight to obtain a solution.
次に本発明のアレルゲン除去用繊維処理剤を用いて、繊維にアレルゲン除去機能を付与する方法を説明する。
本発明のアレルゲン除去用繊維処理剤は、キトサン濃度として０．１〜０．００１重量％となる様に水で希釈し、アレルゲン除去機能を付与したい繊維を浸漬して十分に処理剤液を繊維に含ませた後、乾燥することにより簡便に加工処理をすることが可能である。キトサン濃度として、０．１重量％より高濃度溶液で処理する場合、キトサンの吸着処理に偏りが生じる等の影響で、十分なアレルゲン除去機能が付与されない場合がある。また、０．００１重量％より低濃度溶液を用いた場合、キトサン吸着量が不十分で、アレルゲン除去機能が低い場合がある。
具体的には、直径約４０ｃｍの洗面器であれば、水３Ｌに対して本発明のアレルゲン除去用繊維処理剤（キトサン３．３％含有）を３ｇ加え良く撹拌した後、Ｔシャツ３枚分（約４００ｇ）に相当する衣類を入れ、良く揉みこみながら液を染み込ませ、手搾りあるいは洗濯機の脱水機能を用いて脱水して通常通り洗濯物として干せば、アレルゲン除去機能を付与することができる。
さらには、全自動洗濯機の場合、柔軟剤投入口に本発明のアレルゲン除去用繊維処理剤（キトサン１０重量％含有溶液）を１０ｇ入れ、濯ぎの水量が３０〜１０Ｌとなる様に投入衣類重量の調整あるいは洗濯機の濯ぎ水量設定を行い、当該処理対象の衣類等を通常の自動洗濯を行えば、濯ぎ水に希釈されながら投入され、そのまま濯ぎ工程中に衣類にアレルゲン除去用繊維処理剤が染み込みそのまま脱水されるため、脱水後、通常通り洗濯物として干すことにより衣類等にアレルゲン除去機能を付与することができる。
また、当該アレルゲン除去用繊維処理剤を、水を主成分とする溶媒でキトサン濃度として０．１〜０．００１重量％の希釈液を調製し、繊維素材に対し、この希釈液をスプレーによる噴霧添加することで、簡便に繊維素材にアレルゲン除去機能を付与できる。スプレーによる噴霧添加方法は、特に乾燥工程を実施する必要がなく自然乾燥により、アレルゲン除去機能を付与した繊維素材を調製できる。
Next, a method for imparting an allergen removing function to a fiber using the allergen removing fiber treatment agent of the present invention will be described.
The fiber treatment agent for removing allergens of the present invention is diluted with water so that the chitosan concentration is 0.1 to 0.001% by weight, and the treatment agent solution is sufficiently dispersed by immersing the fibers to be provided with an allergen removal function. It is possible to process simply by drying after it is contained. When the chitosan concentration is treated with a solution having a concentration higher than 0.1% by weight, a sufficient allergen removal function may not be provided due to the influence of bias in the chitosan adsorption treatment. In addition, when a solution having a concentration lower than 0.001% by weight is used, the amount of chitosan adsorption may be insufficient and the allergen removal function may be low.
Specifically, in the case of a basin having a diameter of about 40 cm, 3 g of the fiber treatment agent for allergen removal (containing 3.3% of chitosan) of the present invention is added to 3 L of water, and the mixture is thoroughly stirred, and then 3 T-shirts. (Approx. 400g) put clothes, soak in the liquid while squeezing well, dehydrated by hand squeezing or using the dehydration function of the washing machine, and dried as laundry as usual to give allergen removal function it can.
Furthermore, in the case of a fully automatic washing machine, 10 g of the fiber treatment agent for removing allergens of the present invention (solution containing 10% by weight of chitosan) is added to the softener inlet, and the weight of the input clothing is adjusted so that the amount of water for rinsing is 30 to 10 L. If the garment or the like to be processed is subjected to normal automatic washing, it is introduced while being diluted in the rinsing water, and the fiber treatment agent for removing allergens is applied to the garment as it is during the rinsing process. Since it soaks and is dehydrated as it is, the allergen-removing function can be imparted to clothing and the like by drying as usual after dehydration.
In addition, the fiber treatment agent for removing allergen is prepared as a chitosan concentration 0.1 to 0.001% by weight in a solvent mainly composed of water, and this diluted solution is sprayed on the fiber material by spraying. By adding, the allergen removal function can be easily imparted to the fiber material. The spray addition method by spraying does not require any particular drying step, and a fiber material having an allergen removing function can be prepared by natural drying.
アレルゲン除去機能付与繊維として適用できる繊維材料は特に限定されるものではなく、衣服等に用いられる繊維生地、フィルター等に用いられる繊維織布等に用いることができる。繊維素材としては、綿、絹、麻、ウール、セルロース等の天然素材、ポリエステル、ナイロン、ポリエチレンテレフタレート、ポリエチレン、ポリプロピレン等の合成繊維に対し、アレルゲン除去機能を付与した繊維素材とすることができる。すなわち、本発明のアレルゲン除去用繊維処理剤は、肌着、靴下、ブラウス等の一般衣料や、生地団カバー、枕カバー、生地団綿等の寝具関連繊維、包帯、ガーゼ等の医療関連繊維、あるいは、ぬいぐるみ等の玩具関連繊維、または、エアコンや空気清浄器のフィルター等へのアレルゲン除去機能付与に好適に用いることができる。 The fiber material that can be used as the allergen-removing function-imparting fiber is not particularly limited, and can be used for fiber fabrics used for clothes, fiber woven fabrics used for filters, and the like. As a fiber material, it can be set as the fiber material which provided the allergen removal function with respect to synthetic materials, such as natural materials, such as cotton, silk, hemp, wool, and cellulose, polyester, nylon, polyethylene terephthalate, polyethylene, and polypropylene. That is, the fiber treatment agent for removing allergens of the present invention includes general clothing such as underwear, socks, blouse, bedding-related fibers such as fabric cover, pillow cover, and fabric cotton, medical-related fibers such as bandages and gauze, or It can be suitably used for imparting an allergen removing function to toy-related fibers such as stuffed animals or filters of air conditioners and air purifiers.
以下、本発明を実施例に基づき具体的に説明する。
［製造例１］重量平均分子量約３０，０００のキトサンの調製
３ｍｍ角のチップ状に粗粉砕したベニズワイガニの乾燥カニ殻１ｋｇに対して８％（ｗ／ｗ）濃度の水酸化ナトリウム水溶液１０ｋｇを加え、撹拌しながら８０℃で２時間加熱し脱タンパクを行った。反応終了後、水を用いて洗液がのｐＨが８以下になるまで洗浄した。その後、水分が１０％以下になるまで８０℃で乾燥した。乾燥後、１０％（ｗ／ｗ）塩酸６ｋｇを投入し、７０℃で３時間撹拌しながら加熱し脱カルシウム処理を行った。反応終了後、水を用いて洗液がのｐＨが６以上になるまで洗浄した後、水分が１０％以下になるまで８０℃で乾燥することで乾燥キチンを得た。
得られた乾燥キチン５００ｇに対して、５０％（ｗ／ｗ）水酸化ナトリウム溶液２ｋｇを加え均一に混合した後、１１０℃で３時間反応させることにより脱アセチル化を行った。反応終了後、水を用いて洗液のｐＨが８以下になるまで洗浄した後、水分が１０％以下になるまで８０℃で乾燥することで、重量平均分子量約３０，０００のキトサンを得た。
得られたキトサンについて下記分析条件にて、重量平均分子量、粘度、脱アセチル化度を求めたところ、重量平均分子量３１，０００、粘度６ｍＰａ・ｓ、脱アセチル化度９５％であった。
Hereinafter, the present invention will be specifically described based on examples.
[Production Example 1] Preparation of chitosan having a weight average molecular weight of about 30,000 10 kg of 8% (w / w) sodium hydroxide aqueous solution was added to 1 kg of dried crab shells roughly ground into 3 mm square chips. The protein was deproteinized by heating at 80 ° C. for 2 hours with stirring. After completion of the reaction, washing was performed with water until the pH of the washing liquid became 8 or less. Then, it dried at 80 degreeC until the water | moisture content became 10% or less. After drying, 6 kg of 10% (w / w) hydrochloric acid was added, and the mixture was heated with stirring at 70 ° C. for 3 hours for decalcification treatment. After completion of the reaction, the mixture was washed with water until the pH of the washing liquid became 6 or higher, and then dried at 80 ° C. until the water content became 10% or lower to obtain dry chitin.
To 500 g of the obtained dried chitin, 2 kg of 50% (w / w) sodium hydroxide solution was added and mixed uniformly, and then reacted at 110 ° C. for 3 hours for deacetylation. After completion of the reaction, washing was performed with water until the pH of the washing solution became 8 or less, and then dried at 80 ° C. until the water content became 10% or less, thereby obtaining chitosan having a weight average molecular weight of about 30,000. .
When the weight average molecular weight, viscosity, and degree of deacetylation were determined for the obtained chitosan under the following analysis conditions, the weight average molecular weight was 31,000, the viscosity was 6 mPa · s, and the degree of deacetylation was 95%.
［製造例２］重量平均分子量約１００，０００のキトサンの調製
３ｍｍ角のチップ状に粗粉砕したベニズワイガニの乾燥カニ殻１ｋｇに対して６％（ｗ／ｗ）濃度の塩酸を１０ｋｇを加え、撹拌しながら７０℃で１時間加熱し脱カルシウム処理を行った。反応終了後、水を用いて洗液がのｐＨが６以上になるまで洗浄した。その後、水分が１０％以下になるまで８０℃で乾燥した。乾燥後、８％（ｗ／ｗ）水酸化ナトリウム水溶液を１０ｋｇを投入し８０℃で３時間撹拌・加熱し、脱タンパク処理を行った。反応終了後は、水を用いて洗液がのｐＨが８以下になるまで洗浄した後、水分が１０％以下になるまで８０℃で乾燥することで乾燥キチンを得た。
得られた乾燥キチン５００ｇに対して、５０％（ｗ／ｗ）水酸化ナトリウム溶液２ｋｇを加え均一に混合した後、１１０℃で３時間反応させることにより脱アセチル化を行った。反応終了後、水を用いて洗液のｐＨが８以下になるまで洗浄した後、水分が１０％以下になるまで８０℃で乾燥することで、重量平均分子量約１００，０００のキトサンを得た。
得られたキトサンについて下記分析条件にて、重量平均分子量、粘度、脱アセチル化度を求めたところ、重量平均分子量９８，０００、粘度９ｍＰａ・ｓ、脱アセチル化度８７％であった。
[Production Example 2] Preparation of chitosan having a weight average molecular weight of about 100,000 10 kg of 6% (w / w) hydrochloric acid was added to 1 kg of dried crab shells roughly ground into 3 mm square chips and stirred. While being heated at 70 ° C. for 1 hour, decalcification treatment was performed. After completion of the reaction, washing was performed with water until the pH of the washing liquid became 6 or more. Then, it dried at 80 degreeC until the water | moisture content became 10% or less. After drying, 10 kg of an 8% (w / w) aqueous sodium hydroxide solution was added, and the mixture was stirred and heated at 80 ° C. for 3 hours for deproteinization treatment. After the completion of the reaction, washing was performed using water until the pH of the washing solution was 8 or less, and then dried at 80 ° C. until the moisture content was 10% or less to obtain dry chitin.
To 500 g of the obtained dried chitin, 2 kg of 50% (w / w) sodium hydroxide solution was added and mixed uniformly, and then reacted at 110 ° C. for 3 hours for deacetylation. After completion of the reaction, washing was performed using water until the pH of the washing solution was 8 or less, and then drying at 80 ° C. until the moisture content was 10% or less, thereby obtaining chitosan having a weight average molecular weight of about 100,000. .
When the weight average molecular weight, viscosity, and degree of deacetylation of the obtained chitosan were determined under the following analysis conditions, the weight average molecular weight was 98,000, the viscosity was 9 mPa · s, and the degree of deacetylation was 87%.
上述の製造例で得られたキトサンの回転粘度、脱アセチル化度、平均重量分子量を測定した。回転粘度は、キトサンを０．５％酢酸水溶液に０．５％（ｗ／ｗ）になる様に溶解し、液温２０℃にて、Ｂ型回転粘度計で粘度を測定した。キトサンの脱アセチル化度はトルイジンブルーを指示薬として、１／４００Ｎポリビニル硫酸カリウム液を用いるコロイド滴定で求めた。キトサンの分子量は、昭和電工社製のプルラン標準（Ｓｈｏｄｅｘ ＳＴＡＮＤＡＲＤ Ｐ８２）を標準試料に用い、下記表の条件にてＧＰＣ法で測定した。 The rotational viscosity, the degree of deacetylation, and the average weight molecular weight of the chitosan obtained in the above production example were measured. For rotational viscosity, chitosan was dissolved in 0.5% acetic acid aqueous solution so as to be 0.5% (w / w), and the viscosity was measured with a B-type rotational viscometer at a liquid temperature of 20 ° C. The degree of deacetylation of chitosan was determined by colloid titration using toluidine blue as an indicator and a 1 / 400N potassium potassium sulfate solution. The molecular weight of chitosan was measured by the GPC method under the conditions shown in the table below using a pullulan standard (Shodex STANDARD P82) manufactured by Showa Denko KK as a standard sample.
［ＧＰＣ測定条件］
カラム：ＴＳＫ−ｇｅｌ ＧＭＰＷＸＬ（７．８ｍｍ×３０ｃｍ）
ＴＳＫ−ｇｅｌ Ｇ２５００ＰＷＸＬ（７．８ｍｍ×３０ｃｍ）
ガードカラム：ＴＳＫ−ｇｕａｒｄｃｏｌｕｍｎ ＰＷＸＬ（６．０ｍｍ×４．０ｃｍ）
移動相：０．２Ｍ 酢酸−酢酸ナトリウム緩衝液（ｐＨ４．０）
流速：１．０ｍＬ／ｍｉｎ．
温度：４０℃
検出器：ＲＩ
[GPC measurement conditions]
Column: TSK-gel GMPWXL (7.8 mm × 30 cm)
TSK-gel G2500PWXL (7.8mm x 30cm)
Guard column: TSK-guardcolumn PWXL (6.0 mm × 4.0 cm)
Mobile phase: 0.2 M acetic acid-sodium acetate buffer (pH 4.0)
Flow rate: 1.0 mL / min.
Temperature: 40 ° C
Detector: RI
［実施例１］
製造例１によるキトサン（重量平均分子量３１，０００、粘度６ｍＰａ・ｓ、脱アセチル化度９５%）３０ｇに水２３１ｍＬを加え、撹拌しながらクエン酸３９ｇを徐々加え溶解し、ｐＨ２．５のアレルゲン除去用繊維処理剤を得た。
[Example 1]
Add 231 mL of water to 30 g of chitosan according to Production Example 1 (weight average molecular weight 31,000,
［実施例２］
製造例２によるキトサン（重量平均分子量９８，０００、粘度９ｍＰａ・ｓ、脱アセチル化度８７％）３ｇに水９３．７ｍＬを加え、撹拌しながら５０％（ｗ／ｗ）乳酸３．３ｇを徐々加え溶解し、ｐＨ６のアレルゲン除去用繊維処理剤を得た。
[Example 2]
93.7 mL of water is added to 3 g of chitosan according to Production Example 2 (weight average molecular weight 98,000,
［試験例１］ダニアレルゲンのゼータ電位測定
実験にはダニ抗原は、精製ダニ抗原rDerfII（アサヒフードアンドヘルスケア(株)製）を用いた。ダニ抗原濃度は、１００μｇ／ｍＬになるよう蒸留水で希釈した。ダニ抗原のゼータ電位の測定は、顕微鏡電気泳動装置（ZEECOM、マイクロテックニチオン製）で行った。精製ダニ抗原rDerf2は、レーザー光を用いることで微少な粒子として確認できることがわかった。そのため、顕微鏡電気泳動法でゼータ電位を測定することができた。
結果を図２に示す。図から明らかなようにダニアレルゲンは、（ａ）水道水（実験に使用した水は、浄水器（東レ製：トレビーノカセッティー203X）で処理し、オートクレーブ滅菌をおこなった桐生市水道水で作製した）、（ｂ）酸性汗液（JIS L0848）、（ｃ）アルカリ性汗液（JIS L0848）ともに負に帯電していることがわかった。汗液などのイオン強度の大きい溶液の中ではダニアレルゲンのゼータ電位が小さくなると予想したが、結果から負の帯電を維持していることがわかった。特に、アルカリ性汗液中では大きく負に帯電していた。これは、通常のタンパク質の変化と同じ傾向である。
[Test Example 1] Zeta potential measurement of mite allergen Purified mite antigen rDerfII (manufactured by Asahi Food and Healthcare Co., Ltd.) was used for experiments. The mite antigen concentration was diluted with distilled water to 100 μg / mL. The measurement of the zeta potential of mite antigen was performed with a microscope electrophoresis apparatus (ZEECOM, manufactured by Microtech Nichion). It was found that the purified mite antigen rDerf2 can be confirmed as fine particles by using laser light. Therefore, the zeta potential could be measured by microscopic electrophoresis.
The results are shown in FIG. As is clear from the figure, mite allergens were prepared with Kira City tap water (a) tap water (the water used in the experiment was treated with a water purifier (Toray Industries: Trebino Cassetti 203X) and autoclaved. ), (B) Acidic sweat (JIS L0848) and (c) Alkaline sweat (JIS L0848) were both negatively charged. We predicted that the zeta potential of mite allergen would be smaller in solutions with high ionic strength, such as sweat, but the results showed that the negative charge was maintained. In particular, the alkaline sweat solution was largely negatively charged. This is the same trend as normal protein changes.
［試験例２］加工綿布のゼータ電位測定
試験に用いる綿布は堅ろう度用綿布（JIS L0803）を使用した。アレルゲン除去用繊維処理剤として実施例１のキトサン溶液を水道水で希釈しキトサン０．１重量％溶液とした。綿布の加工方法は、試験綿布１．５ｇに対して、実施例２のキトサン０．１重量％液３０ｍＬを加えて、水温を５０℃に保ちながら、時々攪拌した。１０分後、綿布を取り出し、絞った後、５５℃で十分に乾燥させて加工綿布を作製した。
未加工綿布（JIS堅ろう度白布）と本発明品で加工した綿布のゼータ電位を測定した。
各試験布をミキサー（ワンダーブレンダー 大阪ケミカル製）にして粉砕した。粉砕試料を水中に分散し、ゼータ電位を測定した。実験に使用した水は、浄水器（東レ製：トレビーノカセッティー203X）で処理し、オートクレーブ滅菌をおこなった桐生市水道水で作製した。尚、これらの作製した水に微粒子などの夾雑物がないことをゼータ電位測定装置のレーザー光下で確認した。
結果を図３に示す。未加工綿布はゼータ電位−１０ｍＶにピークが確認でき、表面電位は負に帯電していることがわかった（図３（ａ））。一方、キトサン加工綿布（本発明品による加工処理品）は、ゼータ電位＋１５ｍＶと大きく正に帯電することがわかった（図３（ｂ））。これらのゼータ電位測定の結果から、本発明品により綿布を大きく正に帯電させることが可能で、負に帯電しているダニアレルゲンの吸着除去が期待できることが予想された。
[Test Example 2] Measurement of zeta potential of processed cotton cloth The cotton cloth used for the test was a cotton cloth (JIS L0803) for hardness. As a fiber treatment agent for removing allergens, the chitosan solution of Example 1 was diluted with tap water to obtain a 0.1 wt% chitosan solution. The cotton cloth was processed by adding 30 ml of the 0.1% by weight chitosan solution of Example 2 to 1.5 g of the test cotton cloth and stirring occasionally while keeping the water temperature at 50 ° C. After 10 minutes, the cotton cloth was taken out and squeezed, and then sufficiently dried at 55 ° C. to prepare a processed cotton cloth.
The zeta potential of unprocessed cotton cloth (JIS white fastness cloth) and cotton cloth processed with the product of the present invention was measured.
Each test cloth was pulverized with a mixer (Wonder Blender, Osaka Chemical). The ground sample was dispersed in water and the zeta potential was measured. The water used in the experiment was prepared with Kiryu City tap water that had been treated with a water purifier (Toray Industries: Trebino Cassetti 203X) and autoclaved. In addition, it was confirmed under laser light from a zeta potential measuring device that these produced waters were free from foreign substances such as fine particles.
The results are shown in FIG. The unprocessed cotton fabric was confirmed to have a peak at a zeta potential of −10 mV, and the surface potential was found to be negatively charged (FIG. 3A). On the other hand, it was found that chitosan-processed cotton cloth (processed product according to the present invention) was positively charged with a zeta potential of +15 mV (FIG. 3B). From the results of these zeta potential measurements, it was predicted that the cotton cloth can be largely positively charged with the product of the present invention, and adsorption and removal of negatively charged mite allergen can be expected.
［試験例３］キトサン加工濃度比較試験
キトサン加工による綿布のカチオン化度を測定した。試験に用いる綿布は堅ろう度用綿布（JIS
L0803）を使用した。また、家庭で洗濯処理後にキトサン加工を行うことを想定し、堅ろう度洗濯試験（JIS L0844）を参考に洗濯処理を行った綿布も用意した。
アレルゲン除去用繊維処理剤として実施例１のキトサン溶液を水道水で希釈しキトサン濃度で０．１％（ｗ／ｗ）溶液、０．０１％（ｗ／ｗ）溶液、０．００１％（ｗ／ｗ）溶液を調製した。ブランク液として、水道水を用いた。
綿布の加工方法は、試験綿布１．５ｇに対して、実施例２のアレルゲン除去用繊維処理剤を希釈して調製したキトサン希釈液（０．１％（ｗ／ｗ）溶液、０．０１％（ｗ／ｗ）溶液、０．００１％（ｗ／ｗ）溶液）を３０ｍＬを加えて、水温を５０℃に保ちながら、時々攪拌した。１０分後、綿布を取り出し、絞った後、５５℃で十分に乾燥させて加工綿布を作製した。また、家庭で洗濯処理後にキトサン加工を行うことを想定し、堅ろう度洗濯試験（JIS L0844）を参考に洗濯処理を行った綿布も用意し、同様の操作によりキトサン加工処理綿布を調製した。
実施例２に係るキトサン溶液で処理した綿布の表面加工処理度を、綿布の染色による方法で比較した。染色には、アニオン性の染料であるＤｉｒｅｃｔ Ｂｌｕｅ８６(以下、ＤＢ８６ 東京化成工業製)を使用した。染色液は、ＤＢ８６濃度０．１ｍｇ／Ｌに調整した溶液を用いた。染色は０．５ｇの綿布に対して、染色液５ｍＬを加えて１０分程室温で保持した後、水道水でよく洗浄した。乾燥後、それぞれの綿布について分光測色器を用いてＫ／Ｓ値を測定して、染色の程度から加工綿布のキトサン処理によるカチオン化度を測定した。これは、ＤＢ８６ががアニオン性の染料であり、表面が大きく正に帯電している綿布には濃く染まる性質を利用したキトサン処理によるカチオン化度の評価方法である。Ｋ／Ｓ値は反射率とは異なり、色剤層の性質を数値化したもので、色を濃度で見る数値と解釈できる。反射率は値が高いほど色濃度は低くなり、値が低いほど色濃度は高くなるが、Ｋ／Ｓ値は値が高いほど色濃度は高くなり、値が低いほど色濃度は低くなる。つまり、Ｋ／Ｓ値の数値が高ければ染色濃度が高くなる。また、このことは繊維表面のカチオン化度と高い相関があることは知られている。すなわち、キトサン処理に基づくカチオン化度が大きい綿布は染色度が高く濃色になるため、Ｋ／Ｓ値が高く表れる。なお、Ｋ／Ｓ値は、Ｋｕｂｅｌｋａ−Ｍｕｎｋ式：Ｋ／Ｓ＝（１−Ｒ）２／２Ｓ （Ｋ：光の吸収係数、Ｓ：光の散乱係数、Ｒ：表面反射率）で定義される表面色濃度の指数である。
実施例２のキトサン溶液による各種キトサン濃度溶液処理綿布のカチオン化度を、ＤＢ８６で染色した綿布のＫ／Ｓ値による評価結果を図４に示す。Ｋ／Ｓ値が大きいほど濃色に染色されており、綿布のカチオン化度が高い。図４からキトサン濃度０．１％溶液で処理した綿布が最も濃色であり、キトサン加工程度が大きい結果となった。洗濯後とは洗濯処理した綿布に、各キトサン濃度の溶液によりキトサン加工したものである。洗濯処理は、界面活性剤がアニオンのため、洗濯処理後綿布表面は負に大きく帯電する。家庭での洗濯の場合、一般的には繊維表面の負帯電を中和するため柔軟剤が用いられている。キトサンは柔軟剤と同様のカチオン性の分子なので、洗濯処理を行うことで吸着力が高くなると予想される。結果は、キトサン濃度０．０１％溶液による加工綿布は、洗濯処理後でＫ／Ｓ値が高くなっており、染色ムラもなかった。キトサン濃度０．００１％溶液による処理やブランク液処理ではわずかに染色される程度であった。以上の結果から、綿布を有効にカチオン化できるキトサン濃度は、キトサン濃度が０．０１〜０．１％（ｗ／ｗ）溶液が適当であることが判明した。
[Test Example 3] Chitosan processing concentration comparison test The degree of cationization of cotton fabric by chitosan processing was measured. The cotton cloth used for the test is a cotton cloth for hardness (JIS
L0803) was used. In addition, assuming that the chitosan processing is performed after the laundry treatment at home, a cotton fabric subjected to the laundry treatment with reference to the fastness wash test (JIS L0844) was also prepared.
The chitosan solution of Example 1 was diluted with tap water as a fiber treatment agent for allergen removal, and the chitosan concentration was 0.1% (w / w) solution, 0.01% (w / w) solution, 0.001% (w / W) A solution was prepared. Tap water was used as the blank solution.
The processing method of the cotton fabric was a chitosan diluted solution (0.1% (w / w) solution, 0.01%) prepared by diluting the fiber treatment agent for allergen removal of Example 2 with respect to 1.5 g of the test cotton fabric. 30 mL of (w / w) solution, 0.001% (w / w) solution) was added, and the mixture was sometimes stirred while keeping the water temperature at 50 ° C. After 10 minutes, the cotton cloth was taken out and squeezed, and then sufficiently dried at 55 ° C. to prepare a processed cotton cloth. In addition, assuming that the chitosan processing is performed after the laundry processing at home, a cotton fabric subjected to the laundry processing with reference to the fastness wash test (JIS L0844) was also prepared, and a chitosan processed cotton fabric was prepared by the same operation.
The degree of surface processing of the cotton fabric treated with the chitosan solution according to Example 2 was compared by a method by dyeing the cotton fabric. For the dyeing, Direct Blue 86 (hereinafter referred to as DB86 manufactured by Tokyo Chemical Industry Co., Ltd.), which is an anionic dye, was used. As the staining solution, a solution adjusted to a DB86 concentration of 0.1 mg / L was used. For dyeing, 5 mL of a dyeing solution was added to 0.5 g of cotton cloth and kept at room temperature for about 10 minutes, and then washed well with tap water. After drying, the K / S value of each cotton cloth was measured using a spectrocolorimeter, and the degree of cationization by chitosan treatment of the processed cotton cloth was measured from the degree of dyeing. This is a method for evaluating the degree of cationization by chitosan treatment utilizing the property that DB86 is an anionic dye and the surface is heavily dyed on a cotton fabric that is positively charged. Unlike the reflectance, the K / S value is a numerical value of the properties of the colorant layer, and can be interpreted as a numerical value for viewing the color in terms of density. The higher the reflectance, the lower the color density, and the lower the value, the higher the color density. However, the higher the K / S value, the higher the color density, and the lower the value, the lower the color density. In other words, the higher the K / S value, the higher the staining density. It is also known that this has a high correlation with the degree of cationization on the fiber surface. That is, a cotton fabric having a high degree of cationization based on the chitosan treatment has a high dyeing degree and a dark color, and thus a high K / S value appears. The K / S value is defined by the Kubelka-Munk equation: K / S = (1-R) 2 / 2S (K: light absorption coefficient, S: light scattering coefficient, R: surface reflectance). It is an index of surface color density.
FIG. 4 shows the results of evaluation of the cationization degree of various chitosan-concentrated solution-treated cotton cloths with the chitosan solution of Example 2 according to the K / S value of the cotton cloth dyed with DB86. The larger the K / S value, the deeper the color, and the higher the degree of cationization of the cotton cloth. From FIG. 4, the cotton fabric treated with the 0.1% chitosan concentration solution was the darkest color, and the chitosan processing degree was large. After washing is a cotton cloth that has been subjected to a washing process and is processed with a chitosan-concentrated solution. In the washing process, since the surfactant is an anion, the surface of the cotton cloth after the washing process is greatly negatively charged. In the case of washing at home, a softener is generally used to neutralize the negative charge on the fiber surface. Since chitosan is a cationic molecule similar to a softener, it is expected that the adsorption power will be increased by washing treatment. As a result, the processed cotton fabric with a 0.01% chitosan concentration solution had a high K / S value after washing, and there was no uneven dyeing. In the treatment with the chitosan concentration 0.001% solution and the blank solution treatment, it was only slightly stained. From the above results, it has been found that a chitosan concentration capable of effectively cationizing a cotton cloth is suitably a solution having a chitosan concentration of 0.01 to 0.1% (w / w).
［試験例４］アレルゲン除去用繊維処理剤のキトサン分子量の検討
実施例１（キトサン分子量約３万）及び実施例２（キトサン分子量約１０万）のアレルゲン除去用繊維処理剤を用いて綿布をキトサン溶液処理した場合の、処理綿布のカチオン化度を染色によるＫ／Ｓ値を用いて評価した。
アレルゲン除去用繊維処理剤として、実施例１（キトサン分子量約３万）及び実施例２（キトサン分子量約１０万）を、それぞれキトサン濃度で０．０１％（ｗ／ｗ）に水道水にて希釈して処理液を調製した。ブランク液として、水道水を用いた。試験に用いる綿布は堅ろう度用綿布（JIS L0803）を使用した。
綿布の加工方法は、アレルゲン除去用繊維処理剤として実施例１及び２を用い、それぞれキトサン濃度で０．０１％（ｗ／ｗ）の溶液を用いた以外は、試験例３と同様の操作で、綿布のキトサン加工処理を行った。また、洗濯によるキトサン処理による堅ろう性を確認するため、キトサン加工処理済み綿布を、洗濯洗剤を用いた通常の洗濯処理を行った洗濯処理後綿布も調製して試験試料とした。
得られた加工綿布を、試験例３と同様の操作にて染色処理し、それぞれの綿布について分光測色器を用いてＫ／Ｓ値を測定することにより、加工綿布のキトサン処理によるカチオン化度を測定した。
結果を図５に示す。実施例１（キトサン分子量約３万）及び実施例２（キトサン分子量約１０万）により処理した綿布はともに同程度の綿布のカチオン化度であり、分子量によるキトサン処理効果に違いはなかった。また、キトサン処理した綿布を洗濯した場合も、実施例１（キトサン分子量約３万）及び実施例２（キトサン分子量約１０万）で処理した綿布は、洗濯前よりカチオン化度の低下は認められたものの、ともに同程度の綿布のカチオン化度であり、分子量によるキトサン処理効果に違いはなかった。
高分子量キトサンは分子量が大きいため水への溶解度が低くなることに起因し、低分子量キトサンに比べて洗濯耐性が高いと考えていた。しかし、結果は高分子キトサン、低分子キトサンともに洗濯によって同程度にカチオン化度が低下した。これは、洗濯において界面活性剤の存在により、高分子量キトサンも溶解するためであると考えている。そのため、肌着等の衣類表面へ加工したキトサンの効果は洗濯により失われることが推察される。このため、本発明のアレルゲン除去用繊維処理剤を肌着等の衣類に用いる場合は、洗濯毎に当該処理剤でキトサン処理してアレルゲン除去機能を付与する使用方法が好ましい。
[Test Example 4] Examination of chitosan molecular weight of fiber treatment agent for removing allergen Chitosan was treated with the fiber treatment agent for removing allergen of Example 1 (chitosan molecular weight of about 30,000) and Example 2 (chitosan molecular weight of about 100,000). When the solution was treated, the degree of cationization of the treated cotton fabric was evaluated using the K / S value by dyeing.
As fiber treatment agents for allergen removal, Example 1 (chitosan molecular weight of about 30,000) and Example 2 (chitosan molecular weight of about 100,000) were each diluted with tap water to a chitosan concentration of 0.01% (w / w). Thus, a treatment liquid was prepared. Tap water was used as the blank solution. As the cotton cloth used for the test, a cotton cloth (JIS L0803) was used.
The processing method for cotton fabric was the same as in Test Example 3 except that Examples 1 and 2 were used as fiber treatment agents for removing allergens, and each used a 0.01% (w / w) solution in chitosan concentration. The chitosan processing of the cotton cloth was performed. Moreover, in order to confirm the fastness by the chitosan treatment by washing, a cotton cloth after the washing treatment in which a normal washing treatment using a laundry detergent was prepared from a cotton cloth treated with a chitosan was prepared as a test sample.
The obtained processed cotton fabric was dyed by the same operation as in Test Example 3, and the K / S value of each cotton fabric was measured using a spectrocolorimeter. Was measured.
The results are shown in FIG. Both the cotton fabrics treated in Example 1 (chitosan molecular weight of about 30,000) and Example 2 (chitosan molecular weight of about 100,000) had the same degree of cationization of the cotton fabric, and there was no difference in the chitosan treatment effect depending on the molecular weight. In addition, when the cotton fabric treated with chitosan was washed, the cotton fabric treated with Example 1 (chitosan molecular weight of about 30,000) and Example 2 (chitosan molecular weight of about 100,000) was found to have a lower degree of cationization than before washing. However, both had the same degree of cationization of cotton fabric, and there was no difference in the chitosan treatment effect depending on the molecular weight.
High molecular weight chitosan was considered to have higher wash resistance than low molecular weight chitosan due to its high molecular weight and low water solubility. However, the results showed that the degree of cationization was reduced to the same extent by washing both high-molecular chitosan and low-molecular chitosan. This is considered to be because high molecular weight chitosan is dissolved due to the presence of the surfactant in washing. Therefore, it is presumed that the effect of chitosan processed on the surface of clothes such as underwear is lost by washing. For this reason, when using the fiber treatment agent for allergen removal of this invention for clothes, such as an underwear, the usage method which provides a allergen removal function by carrying out chitosan treatment with the said treatment agent for every washing | cleaning is preferable.
［試験例４］キトサン加工綿におけるダニアレルゲン除去効果
実施例２のアレルゲン除去用繊維処理剤を、水道水によりキトサン濃度で０．１％（ｗ／ｗ）及び０．０１％（ｗ／ｗ）の溶液を調製し、綿布加工処理溶液とした。ブランク液として、水道水を用いた。
試験に用いる綿布は堅ろう度用綿布（JIS
L0803）を使用した。また、家庭で洗濯処理後にキトサン加工を行うことを想定し、堅ろう度洗濯試験（JIS L0844）を参考に洗濯処理を行った洗濯後綿布も試験綿布とした。
試験綿布の加工方法は、各試験綿布１．５ｇに対して、実施例２のアレルゲン除去用繊維処理剤を希釈して調製したキトサン希釈液（０．１％（ｗ／ｗ）溶液及び０．０１％（ｗ／ｗ）溶液）を３０ｍＬを加えて、水温を５０℃に保ちながら、時々攪拌した。１０分後、綿布を取り出し、絞った後、５５℃で十分に乾燥させて加工綿布をそれぞれ作製した。
ダニアレルゲン除去効果試験は、加工綿布を後述するダニアレルゲン溶液で処理し、加工綿布のキトサン処理により正に帯電させた繊維表面にダニアレルゲンを静電的に付着させ、ダニアレルゲン溶液中に残存するダニアレルゲンの濃度を測定することで評価した。
ダニアレルゲン溶液は、精製ダニ抗原rDerfII（アサヒフードアンドヘルスケア(株)製）を用い、ダニ抗原濃度が１００μｇ／ｍＬになるよう蒸留水で希釈し、ダニアレルゲン溶液とした。
各加工綿布０．５ｇを約１０ｍｍ×１０ｍｍに切断して、それぞれ５０ｍＬのサンプルチューブに入れ、各溶液（水道水、酸性汗液、アルカリ性汗液）５ｍＬと上記ダニアレルゲン溶液を５μＬを加えた。よく撹拌してから、３７℃、２００ｒｐｍで２時間浸透させた。その後、０．４５ｍｍのフィルターで濾過し、その濾過液を評価試料（サンプル）とした。
繊維表面のカチオン化層によって除去されたダニアレルゲン濃度を評価する方法として、酵素標識した抗体との抗原抗体反応を利用して定量的に検出する酵素免疫測定法で行った。今回行った方法は、ダニアレルゲン汚染測定の国際的スタンダードであり、以下に述べる測定原理から、一般にサンドイッチ法（非競合法）と呼ばれる方法である。
マイクロプレートのウェルの固相に、あらかじめ目的物質であるダニ抗原（コナヒョウヒダニ）に対する抗体を結合させておく。これにサンプルを添加すると、サンプル中の目的物質が抗原抗体反応により固相に結合する。夾雑物を洗い流した後、酵素標識した第二の抗体を添加すると再度抗原抗体反応が起こり、「固相化抗体/目的物質/酵素標識抗体」のサンドイッチ構造が構築される。ここで遊離の酵素標識抗体を洗い流し、発色基質を添加すると、サンドイッチ構造の量（すなわちサンプル中の目的物質量）に比例して発色反応が起こる。生成した発色物質の吸光度を吸光度計で読み取り、濃度既知の標準品を用いて作製した標準曲線からサンプル中の目的物質量を定量する。
ダニアレルゲンの測定は、ダニアレルゲン測定試薬TAC(R) DerfII ELISA KIT（和光純薬工業製）を用いて常法により行った。検量線は、ダニ抗原濃度５０、２５、１２．５、６．２５、３．１３、１．５６、０．７８ｎｇ／ｍＬ溶液の測定値から作成した。以下に測定操作の概要を示す。
[Test Example 4] Mite allergen removal effect in chitosan-processed cotton The fiber treatment agent for removing allergens of Example 2 was 0.1% (w / w) and 0.01% (w / w) at a chitosan concentration with tap water. Was prepared as a cotton fabric processing solution. Tap water was used as the blank solution.
The cotton cloth used for the test is a cotton cloth for hardness (JIS
L0803) was used. In addition, assuming that the chitosan processing is performed after the laundry treatment at home, the cotton fabric after the laundry subjected to the laundry treatment with reference to the fastness wash test (JIS L0844) was also used as the test cotton fabric.
The processing method of the test cotton fabric was a chitosan diluted solution (0.1% (w / w) solution and 0. 0%) prepared by diluting the fiber treatment agent for allergen removal of Example 2 with respect to 1.5 g of each test cotton fabric. (01% (w / w) solution) was added in an amount of 30 mL, and the mixture was stirred occasionally while maintaining the water temperature at 50 ° C. After 10 minutes, the cotton cloth was taken out and squeezed, and then sufficiently dried at 55 ° C. to prepare each processed cotton cloth.
In the mite allergen removal effect test, the processed cotton cloth is treated with a mite allergen solution described later, and the mite allergen is electrostatically attached to the fiber surface that is positively charged by the chitosan treatment of the processed cotton cloth, and remains in the mite allergen solution. Evaluation was made by measuring the concentration of mite allergen.
The mite allergen solution was purified mite antigen rDerfII (manufactured by Asahi Food and Healthcare Co., Ltd.) and diluted with distilled water to a mite antigen concentration of 100 μg / mL to obtain a mite allergen solution.
0.5 g of each processed cotton cloth was cut into about 10 mm × 10 mm, put in a 50 mL sample tube, and 5 mL of each solution (tap water, acidic sweat solution, alkaline sweat solution) and the above mite allergen solution were added. After stirring well, the solution was infiltrated at 37 ° C. and 200 rpm for 2 hours. Then, it filtered with the 0.45 mm filter and used the filtrate as the evaluation sample (sample).
As a method for evaluating the mite allergen concentration removed by the cationized layer on the fiber surface, an enzyme immunoassay method that quantitatively detects antigen-antibody reaction with an enzyme-labeled antibody was used. The method performed this time is an international standard for measuring mite allergen contamination. From the measurement principle described below, the method is generally called the sandwich method (non-competitive method).
An antibody against a target substance, mite antigen (Coleander mite), is previously bound to the solid phase of the well of the microplate. When a sample is added thereto, the target substance in the sample is bound to the solid phase by an antigen-antibody reaction. After the impurities are washed away, when the second antibody labeled with an enzyme is added, an antigen-antibody reaction occurs again, and a sandwich structure of “immobilized antibody / target substance / enzyme labeled antibody” is constructed. When the free enzyme-labeled antibody is washed away and a chromogenic substrate is added, a chromogenic reaction occurs in proportion to the amount of the sandwich structure (that is, the amount of the target substance in the sample). The absorbance of the generated color substance is read with an absorptiometer, and the amount of the target substance in the sample is quantified from a standard curve prepared using a standard product with a known concentration.
Mite allergen was measured by a conventional method using a mite allergen measuring reagent TAC (R) DerfII ELISA KIT (manufactured by Wako Pure Chemical Industries, Ltd.). A calibration curve was prepared from measured values of mite antigen concentrations of 50, 25, 12.5, 6.25, 3.13, 1.56, and 0.78 ng / mL. The outline of the measurement operation is shown below.
各処理綿布のダニアレルゲンの除去の結果を図６に示す。洗濯処理後０．０１％のキトサン溶液で加工した綿布が、中性液でダニアレルゲンが検出されず（ＮＤ；未検出）、最もダニアレルゲン除去効果が高いことが明らかとなった。洗濯処理後０．１％キトサン加工綿布では、アルカリ性汗液、酸性汗液で除去できたが、中性（水道水）では除去できなかった。これは、キトサンが均等に綿布繊維表面に吸着加工されず、繊維表面のカチオン電荷分布が均一でないことに起因し、ダニアレルゲンを吸着できる部分に偏りが生じたためと考えられる。各汗液ではイオン強度が高いため、繊維表面の電位分布の偏りが打ち消され、打ち消される方向に働いたため、ある程度のダニアレルゲン吸着が得られたものと推察している。洗濯処理した綿布（洗濯後綿布）は、酸性汗液でのダニアレルゲン除去効果が高まった。以上の結果から、本発明のアレルゲン除去用繊維処理剤は、キトサン濃度として０．０１〜０．１％（ｗ／ｗ）で繊維素材を処理することにより、ダニアレルゲンを吸着除去する機能を付与できることが明らかとなった。本発明のアレルゲン除去用繊維処理剤は、洗濯した繊維素材に対してより一層のアレルゲン除去機能を発揮することから、洗濯して繰り返し使用する肌着等の衣類への適用が好ましいと考えられる。 The result of removing mite allergen from each treated cotton fabric is shown in FIG. It was revealed that the cotton fabric processed with the 0.01% chitosan solution after the washing treatment did not detect mite allergen in the neutral solution (ND; not detected), and had the highest mite allergen removal effect. The 0.1% chitosan-treated cotton cloth after washing treatment could be removed with alkaline sweat solution and acidic sweat solution, but not with neutral (tap water). This is presumably because chitosan was not evenly adsorbed on the surface of the cotton fabric, and the cationic charge distribution on the surface of the fiber was not uniform, resulting in a bias in the part capable of adsorbing mite allergen. Since each ionic fluid has high ionic strength, the bias of the potential distribution on the fiber surface is canceled out, and it works in the direction of cancellation, so it is presumed that some mite allergen adsorption was obtained. Washed cotton cloth (cotton cloth after washing) increased the mite allergen removal effect with acidic sweat. From the above results, the fiber treatment agent for removing allergens of the present invention has a function of adsorbing and removing mite allergens by treating fiber materials with a chitosan concentration of 0.01 to 0.1% (w / w). It became clear that we could do it. Since the fiber treatment agent for removing allergens of the present invention exhibits a further allergen removing function for the washed fiber material, it is considered preferable to apply it to clothing such as underwear that is washed and used repeatedly.
１ 綿繊維
２ キトサン層
３ 水道水（中性）中のダニアレルゲンのゼータ電位
４ 酸性汗液中のダニアレルゲンのゼータ電位
５ アルカリ汗液中のダニアレルゲンのゼータ電位
６ 綿布のゼータ電位
７ キトサン加工（本発明品）済みの綿布のゼータ電位
８ 高分子キトサン加工の洗濯処理前のＤＢ８６の染色におけるＫ/Ｓ値
９ 高分子キトサン加工の洗濯処理後のＤＢ８６の染色におけるＫ/Ｓ値
１０ 未処理綿布（ブランク）のＤＢ８６の染色におけるＫ/Ｓ値
１１ 低分子キトサン加工の洗濯処理前のＤＢ８６の染色におけるＫ/Ｓ値
１２ 低分子キトサン加工の洗濯処理後のＤＢ８６の染色におけるＫ/Ｓ値
１３ 未処理綿布（ブランク）のＤＢ８６の染色におけるＫ/Ｓ値
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| JPH08199478A (en) * | 1995-01-20 | 1996-08-06 | Daiyu Shoji:Kk | Deodorizing fiber and fabric |
| JP2006052374A (en) * | 2003-10-22 | 2006-02-23 | Kao Corp | Allergen depressant |
| JP2006265116A (en) * | 2005-03-22 | 2006-10-05 | Univ Kansai | Antimicrobial composition containing chitosan |
| JP2012026054A (en) * | 2010-07-23 | 2012-02-09 | Art:Kk | Textile product adsorbing and removing allergen substance |
| WO2014038620A1 (en) * | 2012-09-10 | 2014-03-13 | ロート製薬株式会社 | Allergen-reducing agent |
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|---|---|---|---|---|
| JPH08199478A (en) * | 1995-01-20 | 1996-08-06 | Daiyu Shoji:Kk | Deodorizing fiber and fabric |
| JP2006052374A (en) * | 2003-10-22 | 2006-02-23 | Kao Corp | Allergen depressant |
| JP2006265116A (en) * | 2005-03-22 | 2006-10-05 | Univ Kansai | Antimicrobial composition containing chitosan |
| JP2012026054A (en) * | 2010-07-23 | 2012-02-09 | Art:Kk | Textile product adsorbing and removing allergen substance |
| WO2014038620A1 (en) * | 2012-09-10 | 2014-03-13 | ロート製薬株式会社 | Allergen-reducing agent |
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