JP2015178582A - allergen-reducing composition - Google Patents
allergen-reducing composition Download PDFInfo
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- JP2015178582A JP2015178582A JP2014057432A JP2014057432A JP2015178582A JP 2015178582 A JP2015178582 A JP 2015178582A JP 2014057432 A JP2014057432 A JP 2014057432A JP 2014057432 A JP2014057432 A JP 2014057432A JP 2015178582 A JP2015178582 A JP 2015178582A
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- Prior art keywords
- allergen
- acid
- reducing
- reducing composition
- fiber
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Landscapes
- Disinfection, Sterilisation Or Deodorisation Of Air (AREA)
Abstract
Description
本発明は、ダニや花粉等のアレルゲンのアレルゲン性を低減化させるため、あるいは不織布、繊維または繊維製品、壁紙、床材、天井材等の建築用内装材等にアレルゲン性を低減化させる機能を付与するための耐水性を有するアレルゲン低減化組成物に関する。 The present invention has a function of reducing the allergenicity of allergens of allergens such as mites and pollen, or for building interior materials such as nonwoven fabrics, fibers or textiles, wallpaper, flooring materials, ceiling materials, etc. The present invention relates to an allergen-reducing composition having water resistance for imparting.
喘息やアトピー性皮膚炎、アレルギー性鼻炎等のアレルギー性疾患は多くの人が悩まされているものであり、特に近年では増加する傾向となっている。これらのアレルギー性疾患の原因となっているのは環境中に存在する種々のアレルゲンであり、それらの中でも屋内に棲息するダニやペットの毛、花粉、カビは代表的な吸入性のアレルゲンとして、良く知られている。特に家屋内に生息する塵性ダニであるヒョウヒダニ類はアレルゲンの発生源として大きな問題となっている。ヒョウヒダニ類は畳、絨毯、寝具、カーテン等の家屋内の繊維製品、あるいは屋外においても電車や自動車等の移動車両の座席シート生地等が生育の温床となる。 Allergic diseases such as asthma, atopic dermatitis, and allergic rhinitis are plagued by many people, and in recent years, the tendency has been increasing. The causes of these allergic diseases are various allergens present in the environment. Among them, mites, pet hair, pollen, and mold that inhabit indoors are typical inhalable allergens. Well known. In particular, leopard mites, which are dust mites that live in the house, are a major problem as a source of allergens. Leopard mites are a hotbed for growing textile products in the house such as tatami mats, carpets, bedding, curtains, etc., or seat sheet fabrics of moving vehicles such as trains and cars outdoors.
ヒョウヒダニ類の中でも、コナヒョウヒダニ(Dermatophagoides farinae)とヤケヒョウヒダニ(Dermatophagoides pteronyssinus)は代表的な種であり、これらのダニの死骸や糞が強いアレルゲン物質となる。また春先に飛散するスギ(Cryptomeria japonica)の花粉を初め、多種の植物の花粉もアレルゲンとなるものであり、特にアレルギー性鼻炎を発症させる原因となっている。飛散する花粉は春先のスギ花粉だけでなく、ヒノキ、ヨモギ、ブタクサ、カモガヤ等、多くの種類があり一年を通じて何らかの花粉が飛散している状態であり、いつの時期でも花粉によるアレルギーを引き起こす危険性があると考えられる。 Among the leopard mites, Dermatophagoides farinae and Dermatophagoides pteronysinsinus are typical species, and the dead bodies and feces of these mites are strong allergen substances. In addition, pollen of various plants including cedar ( Cryptomeria japonica ) pollen scattered in early spring is also an allergen, and causes allergic rhinitis in particular. The pollen that scatters is not only cedar pollen in the early spring, but also many kinds of cypress, mugwort, ragweed, camo, etc. There is a state that some kind of pollen is scattered throughout the year, and there is a risk of causing pollen allergies at any time It is thought that there is.
このようなダニや花粉等のアレルゲンを除去するためには、エアコンや空気清浄機を用いて空気をフィルターに通じる方法があるが、除去できるのは空気中に舞うアレルゲンのみであり、フィルターにアレルゲン物質を集める結果となり、フィルターを交換する際にはアレルゲンが再飛散する危険性がある。また、マスクはスギ等の花粉を吸入するのを防ぐために用いられているが、マスクに付着した花粉はアレルゲン性が消失するわけではないので、再飛散することによって吸収してしまう危険性がある。電気掃除機はアレルゲン除去の方法として有効であるが、吸引したゴミに含まれる多量のアレルゲンは集塵袋に貯蔵されるだけであり、集塵袋の廃棄時にアレルゲンが再飛散する危険性が考えられる。 In order to remove such allergens such as mites and pollen, there is a method of passing air to the filter using an air conditioner or an air purifier, but only allergens flying in the air can be removed, and allergens in the filter can be removed. As a result of collecting the material, there is a risk of allergen re-entrainment when changing the filter. Also, the mask is used to prevent inhalation of cedar pollen, but the pollen attached to the mask does not lose allergenicity, so there is a risk that it will be absorbed by re-scattering. . A vacuum cleaner is an effective method for removing allergens, but a large amount of allergens contained in the sucked garbage is only stored in the dust bag, and there is a risk that the allergen will re-scatter when the dust bag is discarded. It is done.
アレルゲン物質のアレルギー性を低減あるいは除去するための薬剤に関しては、タンニン酸が古くから知られており、タンニン酸等のポリフェノール類化合物を応用する方法が提案されてきた。例えば、タンニン酸をアレルゲンの不活性化剤として使用する方法(特許文献1)、茶抽出物、ハイドロキシアパタイト、エピカテキン、エピガロカテキン、エピカテキンガレート、エピガロカテキンガレート、没食子酸および没食子酸と炭素数1から4までのアルコールとのエステルをアレルゲンの不活性化剤として使用する方法(特許文献2)が開示されている。タンニン酸は褐色に呈色しており、さらに経時的に着色が進行することで用途が制限される短所があったが、安全性の高い天然物であること、優れたアレルゲン低減化効果を有していることから、着色が問題とならない用途では優秀な剤であった。しかしタンニン酸は水溶性であるため、耐水性を要求される用途では依然として使用に適していないという問題があった。 With regard to drugs for reducing or eliminating allergenicity of allergen substances, tannic acid has been known for a long time, and a method of applying a polyphenol compound such as tannic acid has been proposed. For example, a method of using tannic acid as an allergen inactivating agent (Patent Document 1), tea extract, hydroxyapatite, epicatechin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, gallic acid and gallic acid A method of using an ester with an alcohol having 1 to 4 carbon atoms as an allergen inactivating agent (Patent Document 2) is disclosed. Tannic acid has a brown color and has the disadvantage that its use is limited by the progress of coloring over time, but it is a highly safe natural product and has an excellent allergen-reducing effect. Therefore, it was an excellent agent in applications where coloring is not a problem. However, since tannic acid is water-soluble, there is a problem that it is still unsuitable for use in applications requiring water resistance.
またタンニン酸等のポリフェノール化合物以外のアレルゲン低減化剤として、非水溶性亜鉛化合物あるいは非水溶性亜鉛・金属酸化物の複合粒子を用いたアレルゲン不活化剤が提案され(特許文献3)、さらに二酸化ケイ素、酸化亜鉛、酸化アルミニウムを用いたアレルゲン不活化剤が提案されているが(特許文献4)、耐水性やアレルゲン不活化性能は満足できるものではなかった。またこれらのアレルゲン低減化剤は水溶性ではないが、不織布、繊維、繊維製品、プラスチック製品、木質材料にバインダーとしてアクリルエマルジョン等の樹脂エマルジョンを用いて加工した場合、バインダー量が十分な場合はアレルゲン低減化剤を覆ってしまい、流脱を防ぐもののアレルゲン低減化性能そのものが発揮されず、バインダー量が少ないと流脱を防ぐことができずに効力を維持できないことが多かった。さらに無機塩、無機酸化物は有機溶剤に不溶であるため、油性の液剤に対して相溶性が低いため分散剤として添加するより方法がなく、分散液において安定した分散性が得られにくく容易に分離しやすいという問題があった。 Further, as an allergen reducing agent other than a polyphenol compound such as tannic acid, an allergen inactivating agent using a water-insoluble zinc compound or a water-insoluble zinc / metal oxide composite particle has been proposed (Patent Document 3). Although an allergen inactivating agent using silicon, zinc oxide, and aluminum oxide has been proposed (Patent Document 4), water resistance and allergen inactivating performance have not been satisfactory. These allergen reducing agents are not water-soluble, but when processed with a resin emulsion such as an acrylic emulsion as a binder to nonwoven fabrics, fibers, textile products, plastic products, and wood materials, allergens are used when the amount of binder is sufficient. Although the reducing agent is covered to prevent the outflow, the allergen reducing performance itself is not exhibited, and when the amount of the binder is small, the outflow cannot be prevented and the effect cannot often be maintained. Furthermore, since inorganic salts and inorganic oxides are insoluble in organic solvents, they are less compatible with oily liquids, so there is no way to add them as dispersants, and it is difficult to obtain stable dispersibility in dispersions. There was a problem that it was easy to separate.
ダニやスギ花粉等のアレルゲンのアレルゲン性を低減化させること、また不織布、繊維または繊維製品、建築用内装材にアレルゲン性を低減化させる機能を付与し、有機溶剤に相溶性が高く、容易に流脱することのないアレルゲン低減化組成物、およびこれらのアレルゲン低減化組成物を加工した不織布、繊維または繊維製品、建築用内装材を提供することが、本発明の課題である。 Reducing allergenicity of allergens such as mites and cedar pollen, and adding non-allergenic properties to non-woven fabrics, fibers or textiles, and building interior materials, and is highly compatible with organic solvents and easily It is an object of the present invention to provide an allergen-reducing composition that does not run off, and a nonwoven fabric, a fiber or a fiber product, and an architectural interior material obtained by processing these allergen-reducing compositions.
本発明者は、このような課題を解決するため鋭意研究を行った結果、1価または2価のカルボン酸の金属塩にダニやスギ花粉のアレルゲンを低減化し、耐水性のあるアレルゲン低減化加工が可能であることを見出し、本発明を完成させた。 As a result of diligent research to solve such problems, the present inventor reduced allergens of mites and cedar pollen to monovalent or divalent carboxylic acid metal salts, and has water-resistant allergen-reducing processing. The present invention has been completed.
すなわち本発明は、(1)希土類金属、亜鉛、銅、ジルコニウムから選択される金属と、炭素数6〜12の、1価または2価のカルボン酸の塩を含有するアレルゲン低減化組成物であり、(2)金属が、亜鉛、銅またはジルコニウムであるアレルゲン低減化組成物であり、(3)カルボン酸が、炭素数8〜12の、1価の飽和カルボン酸であるアレルゲン低減化組成物であり、(4)金属が、亜鉛またはジルコニウムであるアレルゲン低減化組成物であり、(5)これらのアレルゲン低減化組成物を加工した不織布、繊維または繊維製品、建築用内装材である。 That is, the present invention is an allergen-reducing composition comprising (1) a metal selected from rare earth metals, zinc, copper, and zirconium and a salt of a monovalent or divalent carboxylic acid having 6 to 12 carbon atoms. (2) An allergen-reducing composition in which the metal is zinc, copper or zirconium, and (3) an allergen-reducing composition in which the carboxylic acid is a monovalent saturated carboxylic acid having 8 to 12 carbon atoms. And (4) an allergen-reducing composition in which the metal is zinc or zirconium, and (5) a non-woven fabric, a fiber or a fiber product, or an interior material for construction, obtained by processing these allergen-reducing compositions.
本発明のアレルゲン低減化組成物を用いて、不織布、繊維または繊維製品、建築用内装材に加工することにより、ダニやスギ花粉等のアレルゲンのアレルゲン性を低減化させる機能、さらにその機能に耐水性を持たせ、アレルゲン性を低減化させる機能を持った、フィルター材、マスク等の不織布、繊維または繊維製品、床材、天井材、壁紙等の建築用内装材を提供することができる。 Using the allergen-reducing composition of the present invention, the function of reducing the allergenicity of allergens such as mites and cedar pollen by processing into non-woven fabrics, fibers or textiles, and building interior materials, and water resistance It is possible to provide interior materials for buildings such as filter materials, non-woven fabrics such as masks, fibers or textiles, flooring materials, ceiling materials, wallpaper, etc., which have functions to reduce allergenicity.
本発明の1価または2価のカルボン酸の金属塩において、金属は希土類金属、亜鉛、ジルコニウムおよび銅の中から一種類以上を選択することができる。希土類金属としては、スカンジウム、イットリウム、ランタン、セリウム、プラセオジム、ネオジム、サマリウム、ユーロピウム、ガドリニウム、テルビウム、ジスウロシウム、ホルミウム、エルビウム、ツリウム、イッテルビウム、ルテチウムを挙げることができる。ただし、原子番号61番のプロメチウムは安定同位体が存在しないため適さない。これらの希土類金属の中では、着色が少なく比較的安価であるイットリウム、ランタン、セリウム、ガドリニウムが好ましく、さらにランタン、セリウムがより好ましい。希土類金属塩は通常、3価の塩であるが、3価の塩に限らず、例えばセリウムでは4価の塩、ユーロピウムであれば2価の塩等を使用することも可能である。 In the metal salt of monovalent or divalent carboxylic acid of the present invention, one or more kinds of metals can be selected from rare earth metals, zinc, zirconium and copper. Examples of rare earth metals include scandium, yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysurosium, holmium, erbium, thulium, ytterbium, and lutetium. However, promethium with atomic number 61 is not suitable because there is no stable isotope. Among these rare earth metals, yttrium, lanthanum, cerium, and gadolinium that are less colored and relatively inexpensive are preferable, and lanthanum and cerium are more preferable. The rare earth metal salt is usually a trivalent salt, but is not limited to a trivalent salt. For example, a tetravalent salt can be used for cerium, and a divalent salt can be used for europium.
亜鉛、ジルコニウムおよび銅の塩は、希土類の塩と比較すると安価であるため、希土類金属の塩よりも好適に使用することができる。さらに亜鉛およびジルコニウムは、銅と比較すると無色であるため、より好適に使用することが可能である。 Since zinc, zirconium and copper salts are less expensive than rare earth salts, they can be used more favorably than rare earth metal salts. Furthermore, since zinc and zirconium are colorless compared to copper, they can be used more suitably.
1価または2価のカルボン酸に関しては、炭素数6〜12であるカルボン酸を用いることができ、このようなカルボン酸の例としてはヘキサン酸、ヘプタン酸、オクタン酸、ノナン酸、デカン酸、ドデカン酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等を挙げることができる。このような1価または2価のカルボン酸には、不飽和結合や他の官能基が含まれていても差し支えなく、また分岐した脂肪鎖や環状構造、芳香族環を有していても差し支えない。ただし他の官能基を有するカルボン酸は、非水溶性であることが好ましい。このような酸として例えば、2−エチルヘキサン酸(オクチル酸)、ネオデカン酸(バーサチック酸)、安息香酸、フタル酸、イソフタル酸、テレフタル酸等が挙げられる。これらの中でもオクタン酸、2−エチルヘキサン酸、ネオデカン酸が好ましい。これらの1価または2価のカルボン酸は、一般に試薬や工業用原料として市販されているものを使用することができる。 As for the monovalent or divalent carboxylic acid, a carboxylic acid having 6 to 12 carbon atoms can be used. Examples of such carboxylic acid include hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, Examples include dodecanoic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid. Such a monovalent or divalent carboxylic acid may contain an unsaturated bond or other functional group, and may have a branched fatty chain, a cyclic structure, or an aromatic ring. Absent. However, the carboxylic acid having another functional group is preferably water-insoluble. Examples of such acids include 2-ethylhexanoic acid (octylic acid), neodecanoic acid (versaic acid), benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like. Of these, octanoic acid, 2-ethylhexanoic acid, and neodecanoic acid are preferred. As these monovalent or divalent carboxylic acids, those commercially available as reagents or industrial raw materials can be used.
1価のカルボン酸の金属塩の具体的な例としては、オクチル酸亜鉛、オクチル酸銅、オクチル酸ジルコニウム等が挙げられ、工業用原料として市販されている。このような工業用原料として市販されているオクチル酸塩は直鎖のオクチル酸(オクタン酸)ではなく、分岐した2−エチルヘキサン酸が使用されている。 Specific examples of the metal salt of monovalent carboxylic acid include zinc octylate, copper octylate, zirconium octylate and the like, which are commercially available as industrial raw materials. The octylate marketed as such an industrial raw material uses branched 2-ethylhexanoic acid instead of linear octylic acid (octanoic acid).
またこのような市販されている工業用原料ではなく、1価または2価のカルボン酸と、無機金属塩あるいは金属酸化物を原料として反応、合成したものも使用することができる。カルボン酸金属塩を合成する場合には、カルボン酸を水に可溶なアルカリ金属塩(通常はナトリウム塩)として水溶液化し、これに金属の水可溶性塩、例えば金属の塩化物を反応させる方法(複分解法)があり、またカルボン酸と、金属、金属酸化物、金属水酸化物を直接に反応させる方法(直接法)があるが、いずれの方法を使用しても差し支えない。 Further, instead of such commercially available industrial raw materials, those obtained by reacting and synthesizing monovalent or divalent carboxylic acids with inorganic metal salts or metal oxides as raw materials can also be used. When synthesizing a carboxylic acid metal salt, a method in which the carboxylic acid is converted into an aqueous solution as an alkali metal salt (usually a sodium salt) soluble in water and then reacted with a metal water-soluble salt such as a metal chloride ( There is a metathesis method), and there is a method of directly reacting a carboxylic acid with a metal, a metal oxide, or a metal hydroxide (direct method), but any method may be used.
本発明のアレルゲン低減化組成物は、カルボン酸の炭素数が6以上であるため、カルボン酸に極性の官能基が多く含まれない限り非水溶性となる。カルボン酸金属塩を加工するための製剤を行うには、単独のカルボン酸金属塩を用いて製剤を行っても良いが、二種類以上のカルボン酸金属塩を使用しても差し支えない。二種類以上のカルボン酸金属塩を使用する場合、金属は同じでカルボン酸が異なるもの、またカルボン酸が同じで金属が異なるもののいずれでも差支えない。 Since the carboxylic acid has 6 or more carbon atoms, the allergen-reducing composition of the present invention is insoluble in water unless the carboxylic acid contains a large number of polar functional groups. In order to prepare a preparation for processing a carboxylic acid metal salt, the preparation may be performed using a single carboxylic acid metal salt, but two or more kinds of carboxylic acid metal salts may be used. When two or more kinds of carboxylic acid metal salts are used, either the same metal and different carboxylic acids, or the same carboxylic acid and different metals can be used.
本発明のアレルゲン低減化組成物が対象とするアレルゲンには、ヤケヒョウヒダニ(Dermatophagoides pteronyssinus)の糞由来のアレルゲン(Der p1)および虫体由来のアレルゲン(Der p2)、コナヒョウヒダニ(Dermatophagoides farinae)の糞由来のアレルゲン(Der f1)および虫体由来のアレルゲン(Der f2)が挙げられる。また植物を由来とするアレルゲンとして、スギ(Cryptomeria japonica)の花粉由来のアレルゲン(Cry j1)を筆頭に、ヒノキ、ブタクサ、ヨモギ、カモガヤ、ハルガヤ等のアレルゲンが挙げられる。その他にも、イヌの毛やフケ由来のアレルゲン(Can f1、Can f2)、ネコの毛やフケ由来のアレルゲン(Fel d1)、ゴキブリ由来のアレルゲン(Bra g1、Bra g2)、カビ由来のアレルゲン(Alt a1)、天然ゴムラテックス由来のアレルゲン等が挙げられる。これらの中でも、ダニ由来のアレルゲンおよびスギ花粉由来のアレルゲンは、特に低減化が必要なアレルゲンとして重要視されている。本発明組成物、および本発明組成物を加工した不織布、繊維または繊維製品、建築用内装材の使用により、上記に挙げた種々のアレルゲンを低減化することができ、多種のアレルゲンを実質的になくすことができる。 The allergens targeted by the allergen-reducing composition of the present invention include the allergen (Der p1) derived from the feces of Dermatophagoides pteronyssinus , the allergen derived from the worm body (Der p2), and the Dermatophagoid mite ( Dermatophagoid mite ). Examples include allergen (Der f1) and worm-derived allergen (Der f2). Moreover, as an allergen derived from a plant, allergens such as cypress, ragweed, mugwort, camogaya, and hurghaya are mentioned, starting with the allergen (Cry j1) derived from pollen of cedar ( Cryptomeria japonica ). In addition, allergens derived from dog hair and dandruff (Can f1, Can f2), feline hair and dandruff allergens (Fel d1), cockroach-derived allergens (Brag 1, Bra g 2), fungi allergens ( Alt a1), natural rubber latex-derived allergen and the like. Among these, allergens derived from ticks and allergens derived from cedar pollen are regarded as important as allergens that particularly require reduction. The use of the composition of the present invention, and the nonwoven fabric, fiber or fiber product processed from the composition of the present invention, and the interior material for buildings can reduce the various allergens listed above and substantially reduce the various allergens. Can be eliminated.
本発明のアレルゲン低減化組成物を適用する用途としては、例えば不織布、繊維または繊維製品への加工が考えられ、その使用方法としては、不織布、繊維または繊維製品に浸漬、塗布、スプレー等の方法によって加工することができる。繊維または繊維製品としては、衣料品、カーペット、ソファー、壁紙、カーテン等のインテリア類、布団側地、布団カバー、布団中綿、シーツ、枕カバー、マット等の寝具類、カーシート、カーマット等の自動車部品類、ぬいぐるみ等が挙げられ、不織布としては掃除用ウェットワイパー、マスク、フィルター材料、電気掃除機の集塵袋等があげられる。また建築用内装材としては、塩ビ等の樹脂を用いた壁紙、天井材、合板等の木質材料、床材等が挙げられ、これらの内装材料に表面加工を行うための表面処理剤、コーティング剤、塗料等も含まれる。 As an application to which the allergen-reducing composition of the present invention is applied, for example, processing into a non-woven fabric, fiber or textile product is conceivable. Can be processed. Textiles or textile products include clothing, carpets, sofas, wallpaper, curtains, and other interior items, futon linings, futon covers, futon batting, sheets, pillow covers, mats and other bedding, car seats, car mats, and other automobiles. Examples include non-woven fabrics, stuffed animals, etc. Nonwoven fabrics include wet wipers for cleaning, masks, filter materials, and dust collection bags for vacuum cleaners. In addition, examples of the interior material for building include wallpaper using resin such as PVC, wood materials such as ceiling materials and plywood, floor materials, etc., and surface treatment agents and coating agents for surface treatment of these interior materials. Also included are paints and the like.
本発明のアレルゲン低減化組成物を加工することができる不織布や繊維には種々のものがあるが、たとえばナイロン、綿、ポリエステル、羊毛等が挙げられ、これらの繊維を二種類以上使用した複合繊維であっても差し支えない。またポリエチレンやポリプロピレンを用いた不織布にも使用することが可能である。本発明のアレルゲン低減化組成物の不織布、繊維または繊維製品への加工方法は特に限定されるものではないが、浸漬処理、スプレー処理、吸尽加工等を行うことが可能である。 There are various non-woven fabrics and fibers that can be used to process the allergen-reducing composition of the present invention. Examples include nylon, cotton, polyester, wool, and the like, and composite fibers using two or more of these fibers. It doesn't matter. It can also be used for non-woven fabrics using polyethylene or polypropylene. The method for processing the allergen-reducing composition of the present invention into a non-woven fabric, fiber, or fiber product is not particularly limited, and immersion treatment, spray treatment, exhaustion processing, and the like can be performed.
以上に挙げた種々の用途に本発明のアレルゲン低減化組成物の加工を行う場合、処理を行うことが容易にできるように、アレルゲン低減化組成物を加工に適した製剤とすることができる。このような製剤としては、極性溶剤に溶解した水溶性剤、非水溶性剤に溶解性を高くした油剤または乳剤、また適当な担体に保持させた粉剤、粒剤等が挙げられる。 When processing the allergen-reducing composition of the present invention for the various uses mentioned above, the allergen-reducing composition can be made into a preparation suitable for processing so that the processing can be easily performed. Examples of such preparations include water-soluble agents dissolved in polar solvents, oils or emulsions made highly soluble in water-insoluble agents, and powders and granules held on appropriate carriers.
本発明のアレルゲン低減化組成物は非水溶性であり、不織布、繊維または繊維製品、建築用内装材に耐水性のある加工を行うことが可能であるが、耐水性をさらに増強させるために樹脂を含有するバインダーを併用することも可能である。このようなバインダーとして特に制限はないが、例えばアクリル系バインダー、ウレタン系バインダー等が挙げられる。 The allergen-reducing composition of the present invention is water-insoluble, and can be processed with water resistance to nonwoven fabrics, fibers or textiles, and building interior materials. In order to further enhance water resistance, a resin is used. It is also possible to use a binder containing. Although there is no restriction | limiting in particular as such a binder, For example, an acrylic binder, a urethane type binder, etc. are mentioned.
アクリル系バインダーはアクリル樹脂を含有するバインダーであり、アクリル樹脂は(メタ)アクリル酸、(メタ)アクリル酸エステル、(メタ)アクリルアミド誘導体等の一種以上のモノマーを原材料として、ラジカル重合法によって得られるポリマーである。 The acrylic binder is a binder containing an acrylic resin, and the acrylic resin is obtained by radical polymerization using one or more monomers such as (meth) acrylic acid, (meth) acrylic acid ester, and (meth) acrylamide derivatives as raw materials. It is a polymer.
ポリウレタン系バインダーはウレタン樹脂を含有するバインダーであり、ウレタン樹脂は高分子ジオール成分とイソシアネート基を有する有機イソシアネート化合物からなり、ジオール成分の種類によって、ポリエーテル系、ポリエステル系,ポリカーボネート系およびこれらの混合系等、種々のものがある。ポリウレタンバインダーはこれらのポリエーテル系、ポリエステル系,ポリカーボネート系等のいずれを使用しても差し支えなく、また二種類以上を混合して使用することも可能である。また溶剤系のポリウレタン樹脂とポリウレタン樹脂エマルジョンのいずれもバインダーとして使用可能である。ポリウレタン樹脂のエマルジョンには自己乳化型または強制乳化型があるがいずれの型のものをバインダーとして使用しても差し支えなく、各々の型のものを混合して使用しても差し支えない。 A polyurethane binder is a binder containing a urethane resin, and the urethane resin is composed of a polymer diol component and an organic isocyanate compound having an isocyanate group. Depending on the type of the diol component, a polyether, polyester, polycarbonate or a mixture thereof There are various types of systems. As the polyurethane binder, any of these polyether-based, polyester-based, and polycarbonate-based materials may be used, and two or more types may be mixed and used. Also, both solvent-based polyurethane resins and polyurethane resin emulsions can be used as binders. The polyurethane resin emulsion includes a self-emulsifying type and a forced emulsifying type, but any type may be used as a binder, and each type may be mixed and used.
製剤を行なう上で必ずしも配合されるべきものではないが、安定性の向上等の目的のために界面活性剤を添加することが可能である。界面活性剤は特に限定されず、非イオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤を挙げることができる。非イオン性界面活性剤の種類は特に限定されるものではないが、例えばポリオキシエチレンアルキルフェニルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルケニルエーテル、ソルビタン脂肪酸エステル、ポリオキシエチレンソルビタン脂肪酸エステル等が挙げられる。アニオン性界面活性剤にはアルキルベンゼンスルホネート、ポリオキシエチレンアルキルフェニルエーテルサルフェート、ジアルキルスルホサクシネート等が挙げられる。カチオン性界面活性剤では脂肪族アミン塩およびその4級アンモニウム塩等が挙げられ、両イオン性界面活性剤ではベタイン型界面活性剤、アミノカルボン酸塩等が挙げられる。また、これらの非イオン性界面活性剤、アニオン性界面活性剤、カチオン性界面活性剤および両イオン性界面活性剤は一種を単独に用いても二種以上を併用してもよい。 Although not necessarily blended in preparation, a surfactant can be added for the purpose of improving stability. The surfactant is not particularly limited, and examples thereof include a nonionic surfactant, an anionic surfactant, a cationic surfactant, and an amphoteric surfactant. The type of nonionic surfactant is not particularly limited. For example, polyoxyethylene alkyl phenyl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkenyl ether, sorbitan fatty acid ester, Examples thereof include oxyethylene sorbitan fatty acid esters. Examples of the anionic surfactant include alkyl benzene sulfonate, polyoxyethylene alkyl phenyl ether sulfate, and dialkyl sulfosuccinate. Cationic surfactants include aliphatic amine salts and quaternary ammonium salts thereof, and amphoteric surfactants include betaine surfactants and aminocarboxylates. These nonionic surfactants, anionic surfactants, cationic surfactants and amphoteric surfactants may be used alone or in combination of two or more.
本発明のアレルゲン低減化組成物には、物性を損なわない範囲で、公知となっているアレルゲン低減化成分をさらに添加することも可能である。アレルゲン低減化成分としては、ジヒドロキシ安息香酸や2,4,6−トリヒドロキシ安息香酸等のヒドロキシ安息香酸系化合物またはその塩、パラヒドロキシポリスチレンやポリスチレンスルホン酸塩等のポリスチレン系化合物、柿渋等の天然抽出物、カルシウム塩やストロンチウム塩や、希土類塩等の無機塩系化合物が挙げられる。 To the allergen-reducing composition of the present invention, a known allergen-reducing component can be further added as long as the physical properties are not impaired. Examples of allergen-reducing components include hydroxybenzoic acid compounds such as dihydroxybenzoic acid and 2,4,6-trihydroxybenzoic acid or salts thereof, polystyrene compounds such as parahydroxypolystyrene and polystyrenesulfonate, Examples include extracts, calcium salts, strontium salts, and inorganic salt compounds such as rare earth salts.
本発明のアレルゲン低減化組成物は、屋内塵性ダニのアレルゲン除去を目的に使用する場合、殺ダニ剤と同時に加工することにより、そのアレルゲン低減化効果をさらに持続させることも可能である。使用する殺ダニ剤は、屋内塵性ダニに対して致死効果や忌避効果のあるものであれば特に限定はなく、例えば、ベンジルアルコール、ベンジルベンゾエート、サリチル酸フェニル、シンナムアルデヒド、ヒソップ油、ニンジン種子油等を用いることができ、また天然ピレトリン、フェノトリン、ペルメトリン等のピレスロイド系化合物、フェニトロチオン、マラチオン、フェンチオン、ダイアジノン等の有機リン系化合物、ジコホル、クロルベンジレート、ヘキシチアゾクス、テブフェンピラド、ピリダベン、アミドフルメト等を用いることができる。 When the allergen-reducing composition of the present invention is used for the purpose of removing allergens from indoor dust mites, the allergen-reducing effect can be further maintained by processing simultaneously with the acaricide. The acaricide used is not particularly limited as long as it has a lethal and repellent effect on indoor dust mites. For example, benzyl alcohol, benzyl benzoate, phenyl salicylate, cinnamaldehyde, hyssop oil, carrot seed oil In addition, pyrethroid compounds such as natural pyrethrin, phenothrin, and permethrin, organophosphorus compounds such as fenitrothion, malathion, fenthion, and diazinon, dicofol, chlorbenzilate, hexityazox, tebufenpyrad, pyridaben, and amidoflumet are used. be able to.
本発明のアレルゲン低減化組成物は、カビあるいは菌の増殖が懸念される場合がある。そのために防カビ剤または抗菌剤を同時に併用することが可能である。防カビ剤または抗菌剤の種類は、防カビまたは抗菌効果を有するものであれば特に限定されないが、例えば、5−クロロ−N−メチルイソチアゾロン、メチレンビスチオシアネート、2−ブロモ−2−ニトロプロパン−1,3−ジオール、グルタルアルデヒド、ヨードプロピニルブチルカーバメート、ピリジンチオール−N−オキシドの亜鉛塩、1,2−ベンゾイソチアゾロン、1,2−ジブロモ−2,4−ジシアノブタン、グルコン酸クロルヘキシジン、2−イソプロピル−5−メチルフェノール、3−メチル−4−イソプロピルフェノール、オルトフェニルフェノール、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、パラクロロメタキシレノール、パラクロロメタクレゾール、ポリリジン、塩化ベンザルコニウム、塩化ジデシルジメチルアンモニウム、N−n−ブチルベンゾイソチアゾロン、N−オクチルイソチアゾロン、2−(4−チアゾリル)ベンズイミダゾール、2−ベンズイミダゾリルカルバミン酸メチル、テトラクロロイソフタロニトリル、ジヨードメチルパラトリルスルホン、パラクロロフェニル−3−ヨードプロパギルホルマール、2,3,5,6−テトラクロロ−4−(メチルスルホニル)ピリジン、脂肪酸グリセリンエステル、ヒノキチオール等を用いることができる。 In the allergen-reducing composition of the present invention, there is a possibility that mold or fungus grows. Therefore, it is possible to use a fungicide or an antibacterial agent at the same time. The type of the fungicide or antibacterial agent is not particularly limited as long as it has a fungicide or antibacterial effect. For example, 5-chloro-N-methylisothiazolone, methylenebisthiocyanate, 2-bromo-2-nitropropane- 1,3-diol, glutaraldehyde, iodopropynyl butyl carbamate, zinc salt of pyridinethiol-N-oxide, 1,2-benzisothiazolone, 1,2-dibromo-2,4-dicyanobutane, chlorhexidine gluconate, 2- Isopropyl-5-methylphenol, 3-methyl-4-isopropylphenol, orthophenylphenol, methyl paraoxybenzoate, ethyl paraoxybenzoate, propyl paraoxybenzoate, butyl paraoxybenzoate, parachlorometaxylenol, parachlorometac Sol, polylysine, benzalkonium chloride, didecyldimethylammonium chloride, Nn-butylbenzisothiazolone, N-octylisothiazolone, 2- (4-thiazolyl) benzimidazole, methyl 2-benzimidazolylcarbamate, tetrachloroisophthalo Nitrile, diiodomethyl paratolyl sulfone, parachlorophenyl-3-iodopropargyl formal, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, fatty acid glycerin ester, hinokitiol and the like can be used.
本発明のアレルゲン低減化組成物の製剤化に際しては、前述の界面活性剤、防ダニ剤、抗菌剤の他に、必要に応じてキレート剤、防錆剤、香料、スケール防止剤、消泡剤、帯電防止剤、増粘剤、柔軟加工剤等を添加することも可能である。 In formulating the allergen-reducing composition of the present invention, in addition to the aforementioned surfactant, anti-mite agent and antibacterial agent, if necessary, chelating agent, anti-rust agent, perfume, scale inhibitor, antifoaming agent It is also possible to add antistatic agents, thickeners, softening agents and the like.
本発明のアレルゲン低減化組成物の使用形態としては主に加工剤用途が挙げられるが、繊維または繊維製品、建築用内装材以外にも、環境中で人が接触する可能性のある組成物、たとえば柔軟剤、消臭剤、防カビ剤、除菌剤、殺虫剤、塗料、接着剤等に添加することによって環境中のアレルゲンを低減化させることも可能であり、環境中で人が接触する可能性のある材料、たとえば木材、コンクリート、金属、石、ガラス等の建材等、ゴム、紙、樹脂、プラスチックのよる成型品等に加工することによって環境中のアレルゲンを低減化させることも可能である。 The use form of the allergen-reducing composition of the present invention mainly includes the use of a processing agent, but in addition to fibers or textiles, building interior materials, a composition that may come into contact with people in the environment, For example, it is possible to reduce allergens in the environment by adding them to softeners, deodorants, fungicides, disinfectants, insecticides, paints, adhesives, etc. It is also possible to reduce allergens in the environment by processing into possible materials, such as building materials such as wood, concrete, metal, stone, glass, etc., molded products made of rubber, paper, resin, plastic, etc. is there.
本発明を実施例、試験例により更に詳しく説明するが、本発明がこれらによって限定されるものではない。なお、下記に示す%はすべて重量%である。 The present invention will be described in more detail with reference to examples and test examples, but the present invention is not limited thereto. In addition, all% shown below are weight%.
[実施例1]
2−エチルヘキサン酸亜鉛としてオクトライフZNS(住化エンビロサイエンス株式会社製)を用い、エタノールに溶解して2%のエタノール溶液とした。
[Example 1]
Octlife ZNS (manufactured by Sumika Enviro Science Co., Ltd.) was used as zinc 2-ethylhexanoate and dissolved in ethanol to give a 2% ethanol solution.
[実施例2]
オクトライフZNS(住化エンビロサイエンス株式会社製)10%、溶剤としてエチルヘキシルジグリコールを80%、乳化剤としてサニマールSF−T(日本乳化剤株式会社製)5%およびニューカルゲンCP−120(竹本油脂株式会社製)5%を添加し、10%乳剤とした。
[Example 2]
Octlife ZNS (manufactured by Sumika Enviro Science Co., Ltd.) 10%, ethylhexyl diglycol 80% as a solvent, Sanimar SF-T (manufactured by Nippon Emulsifier Co., Ltd.) 5% and New Calgen CP-120 (Takemoto Yushi Co., Ltd.) 5%) was added to make a 10% emulsion.
[実施例3]
オクチル酸(田岡化学株式会社製の2−エチルヘキサン酸)7gをイオン交換水約30gに混合し、撹拌しながら10%水酸化ナトリウム水溶液を20g添加した。さらに硫酸銅五水和物(和光純薬工業株式会社製)を12.5g添加し、撹拌しながら100〜135℃に加熱した。生成した青色沈殿をろ別し、水洗後に乾燥させて2−エチルヘキサン酸銅を得た。この2−エチルヘキサン酸銅をエタノールに溶解し、2%の溶液とした。
[Example 3]
7 g of octylic acid (2-ethylhexanoic acid manufactured by Taoka Chemical Co., Ltd.) was mixed with about 30 g of ion-exchanged water, and 20 g of 10% aqueous sodium hydroxide solution was added with stirring. Further, 12.5 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated to 100 to 135 ° C. while stirring. The produced blue precipitate was filtered off, washed with water and dried to obtain copper 2-ethylhexanoate. This copper 2-ethylhexanoate was dissolved in ethanol to make a 2% solution.
[実施例4]
実施例3で得られた2-エチルヘキサン酸銅を10%、溶剤としてエチルヘキシルジグリコールを77%、乳化剤としてニューカルゲンD−220K(竹本油脂株式会社製)8%およびニューカルゲンCP−120(竹本油脂株式会社製)5%を添加し、10%乳剤とした。
[Example 4]
10% of the copper 2-ethylhexanoate obtained in Example 3, 77% of ethylhexyl diglycol as a solvent, 8% of Newkalgen D-220K (manufactured by Takemoto Yushi Co., Ltd.) as an emulsifier and Newkalgen CP-120 (Takemoto) 5%) was added to make a 10% emulsion.
[実施例5]
2−エチルヘキサン酸ジルコニウムとしてオクトライフZr12%(住化エンビロサイエンス株式会社製)83%、乳化剤としてニューカルゲン1105H(竹本油脂株式会社製)3.5%およびニューカルゲン1105L(竹本油脂株式会社製)3.5%を添加し、10%乳剤とした。
[Example 5]
Octyl Life Zr 12% (made by Sumika Enviro Science Co., Ltd.) 83% as zirconium 2-ethylhexanoate, New Calgen 1105H (made by Takemoto Yushi Co., Ltd.) 3.5% and New Calgen 1105L (made by Takemoto Yushi Co., Ltd.) as emulsifiers ) 3.5% was added to make a 10% emulsion.
[実施例6]
2−エチルヘキサン酸(田岡化学株式会社製オクチル酸)7gをイオン交換水約30gに混合し、撹拌しながら10%水酸化ナトリウム水溶液を20g添加した。さらに硫酸第二セリウム(和光純薬工業株式会社製)を5.1g添加し、撹拌しながら100℃に加熱した。生成した淡黄色油状液体を分離し、2−エチルヘキサン酸セリウムを得た。この2−エチルヘキサン酸セリウムをエタノールに溶解し、2%の溶液とした。
[Example 6]
7 g of 2-ethylhexanoic acid (octyl acid manufactured by Taoka Chemical Co., Ltd.) was mixed with about 30 g of ion-exchanged water, and 20 g of 10% sodium hydroxide aqueous solution was added while stirring. Further, 5.1 g of ceric sulfate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated to 100 ° C. with stirring. The produced pale yellow oily liquid was separated to obtain cerium 2-ethylhexanoate. This cerium 2-ethylhexanoate was dissolved in ethanol to give a 2% solution.
[実施例7]
ネオデカン酸(シェル株式会社製バーサチック酸)340gに撹拌しながら亜鉛華(東栄化工株式会社製の酸化亜鉛)を170g添加した。さらに撹拌しながらイオン交換水150gを添加し、徐々に加熱しながら温度を130℃まで上昇させた。加熱を継続して水分を揮発させ、ネオデカン酸亜鉛を得た。このネオデカン酸亜鉛をエタノールに溶解し、2%の溶液とした。
[Example 7]
170 g of zinc white (zinc oxide manufactured by Toei Chemical Co., Ltd.) was added to 340 g of neodecanoic acid (Versatic acid manufactured by Shell Co., Ltd.) while stirring. Further, 150 g of ion-exchanged water was added while stirring, and the temperature was raised to 130 ° C. while gradually heating. Heating was continued to volatilize water, and zinc neodecanoate was obtained. This zinc neodecanoate was dissolved in ethanol to give a 2% solution.
[実施例8]
ヘキサン酸(和光純薬工業株式会社製)6gをイオン交換水30gに混合し、撹拌しながら10%水酸化ナトリウム水溶液を20g添加した。さらに硫酸銅五水和物(和光純薬工業株式会社製)を12.5g添加し、撹拌しながら100〜130℃に加熱した。生成した青色沈殿をろ別し、水洗後に乾燥させてヘキサン酸銅を得た。このヘキサン酸銅をエタノールに溶解し、2%の溶液とした。
[Example 8]
6 g of hexanoic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed with 30 g of ion-exchanged water, and 20 g of 10% sodium hydroxide aqueous solution was added while stirring. Further, 12.5 g of copper sulfate pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated to 100 to 130 ° C. with stirring. The produced blue precipitate was filtered off, washed with water and dried to obtain copper hexanoate. This copper hexanoate was dissolved in ethanol to make a 2% solution.
[実施例9]
ラウリン酸亜鉛(和光純薬工業株式会社製)10g、ポイズ520(花王株式会社製)2.5g、ニューカルゲンCP−80(竹本油脂株式会社製)2.5gをイオン交換水85gに添加し、直径1mmのガラス製ビーズを用いて湿式粉砕を行い、30メッシュの金網でビーズを取り除き、ラウリン酸亜鉛の10%フロアブル剤を調製した。
[Example 9]
10 g of zinc laurate (manufactured by Wako Pure Chemical Industries, Ltd.), 2.5 g of Poise 520 (manufactured by Kao Corporation), 2.5 g of New Calgen CP-80 (manufactured by Takemoto Yushi Co., Ltd.) are added to 85 g of ion-exchanged water, Wet grinding was performed using glass beads having a diameter of 1 mm, and the beads were removed with a 30-mesh wire mesh to prepare a 10% flowable agent of zinc laurate.
[実施例10]
アジピン酸(和光純薬工業株式会社製)7.3gをイオン交換水20gに混合し、撹拌しながら10%水酸化ナトリウム水溶液を38g添加しアジピン酸を溶解した。60℃に加熱し、さらに塩化亜鉛(和光純薬工業株式会社製)6.8gを撹拌しながら添加した。生成した白色沈殿をろ別し、水洗後に乾燥させてアジピン酸亜鉛を得た。このアジピン酸亜鉛をニューカルゲンCP−120(竹本油脂株式会社製)の2%水溶液に分散させ、2%の分散液を調製した。
[Example 10]
7.3 g of adipic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was mixed with 20 g of ion-exchanged water, and 38 g of 10% aqueous sodium hydroxide solution was added with stirring to dissolve adipic acid. The mixture was heated to 60 ° C., and 6.8 g of zinc chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was further added with stirring. The produced white precipitate was filtered off, washed with water and dried to obtain zinc adipate. This zinc adipate was dispersed in a 2% aqueous solution of New Calgen CP-120 (manufactured by Takemoto Yushi Co., Ltd.) to prepare a 2% dispersion.
[比較例1]
2−エチルヘキサン酸(田岡化学株式会社製オクチル酸)2gをイオン交換水約30gに溶解し、10%水酸化ナトリウム水溶液を添加して中和し、さらにイオン交換水を添加して2%の水溶液とした。
[Comparative Example 1]
2 g of 2-ethylhexanoic acid (octyl acid manufactured by Taoka Chemical Co., Ltd.) is dissolved in about 30 g of ion-exchanged water, neutralized by adding a 10% aqueous sodium hydroxide solution, and further added with ion-exchanged water to give 2% An aqueous solution was obtained.
[比較例2]
塩化セリウム七水和物(和光純薬工業株式会社製)をイオン交換水に溶解し、2%水溶液とした。
[Comparative Example 2]
Cerium chloride heptahydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in ion exchange water to make a 2% aqueous solution.
[比較例3]
ステアリン酸亜鉛(和光純薬工業株式会社製)10g、ポイズ520(花王株式会社製)3g、ニューカルゲンCP−80(竹本油脂株式会社製)3gをイオン交換水84gに添加し、直径1mmのガラス製ビーズを用いて湿式粉砕を行い、30メッシュの金網でビーズを取り除き、ステアリン酸亜鉛の10%フロアブル剤を調製した。
[Comparative Example 3]
10 g of zinc stearate (manufactured by Wako Pure Chemical Industries, Ltd.), 3 g of poise 520 (manufactured by Kao Corporation), 3 g of New Calgen CP-80 (manufactured by Takemoto Yushi Co., Ltd.) are added to 84 g of ion-exchanged water, and a glass having a diameter of 1 mm. Wet pulverization was performed using the beads made, and the beads were removed with a 30 mesh wire netting to prepare a 10% flowable agent of zinc stearate.
[比較例4]
酢酸亜鉛(和光純薬工業株式会社製)をイオン交換水に溶解し、2%水溶液とした。
[Comparative Example 4]
Zinc acetate (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in ion exchange water to make a 2% aqueous solution.
[試験例1]
アレルゲン低減化組成物によるダニアレルゲンの低減化効果の測定
ダニアレルゲンDer f2を含有する、タンパク質量として約900ng/1mL{リン酸緩衝液(pH7.2)}のアレルゲン液1mLに対し、実施例1〜10(実施例2、4、5,9についてはあらかじめ水で5倍に希釈した液を使用)、比較例1〜4(比較例3についてはあらかじめ水で5倍に希釈した液を使用)と対照として蒸留水をそれぞれ100μL反応させた。これら試料について Der f2酵素免疫測定法(ELISA)のサンドイッチ法にてダニアレルゲン低減化効果の測定を行った。まず、リン酸緩衝液(pH7.4)で2μg/mLに希釈した抗Der f2 モノクローナル抗体15E11を、F16 MAXISORP NUNC−IMMUNO MODULEプレート(NUNC社製)の1ウェルあたり100μLずつ添加し、4℃にて3日以上感作させた。感作後、液を捨て、ブロッキング試薬{1重量%牛血清アルブミン+リン酸緩衝液(pH7.2)}を1ウェルあたり200μLずつ添加し、37℃、60分間反応させた。反応後、リン酸緩衝液(pH7.2)にてプレートを洗浄した。
[Test Example 1]
Measurement of the mite allergen reducing effect of the allergen-reducing composition Example 1 with respect to 1 mL of an allergen solution containing mite allergen Der f2 and having a protein amount of about 900 ng / 1 mL {phosphate buffer (pH 7.2)}. 10 (for Examples 2, 4, 5 and 9 use a solution diluted 5 times with water in advance), Comparative Examples 1 to 4 (for Comparative Example 3 use a solution diluted 5 times with water in advance) As a control, 100 μL each of distilled water was reacted. About these samples, the mite allergen reduction effect was measured by the sandwich method of Der f2 enzyme immunoassay (ELISA). First, anti-Der f2 monoclonal antibody 15E11 diluted to 2 μg / mL with phosphate buffer (pH 7.4) was added in an amount of 100 μL per well of an F16 MAXISORP NUNC-IMMUNO MODULE plate (manufactured by NUNC), and then added to 4 ° C. Sensitized for more than 3 days. After sensitization, the solution was discarded, and 200 μL of a blocking reagent {1 wt% bovine serum albumin + phosphate buffer (pH 7.2)} was added per well and reacted at 37 ° C. for 60 minutes. After the reaction, the plate was washed with a phosphate buffer (pH 7.2).
次に、ダニアレルゲン液に上記試料を添加した液を1ウェルあたり100μLずつ滴下し、37℃、60分間反応させた。反応後、リン酸緩衝液(pH7.2)にてプレートを洗浄した。ペルオキシダーゼ標識した抗Der f2モノクローナル抗体をリン酸緩衝液{pH7.2、1重量%牛血清アルブミンおよび0.05重量%ポリオキシエチレン(20)ソルビタンモノラウレート含有}で200μg/mLに溶解し、それをリン酸緩衝液(pH7.2、1重量%牛血清アルブミンおよび0.05重量%ポリオキシエチレン(20)ソルビタンモノラウレート含有)で1200倍希釈した液を、1ウェルあたり100μLずつ添加した。37℃、60分間反応させた後、リン酸緩衝液(pH7.2)でプレートを洗浄した。0.1mol/Lリン酸緩衝液(pH6.2)6.5mLにオルト−フェニレンジアミンジヒドロクロライド(13mg Tablet、和光純薬工業株式会社製)一錠と30%過酸化水素水6.5μLを加えたものを1ウェルあたり100μLずつ添加し、37℃、3分間反応させた。その後直ちに、1mol/L H2SO4を50μLずつ入れて反応を停止させ、マイクロプレート用分光光度計(テカンジャパン株式会社製)で吸光度(OD490nm)を測定した。結果を表1に示した。 Next, a solution obtained by adding the above sample to a mite allergen solution was added dropwise by 100 μL per well and reacted at 37 ° C. for 60 minutes. After the reaction, the plate was washed with a phosphate buffer (pH 7.2). Peroxidase-labeled anti-Der f2 monoclonal antibody was dissolved in phosphate buffer {pH 7.2, containing 1% by weight bovine serum albumin and 0.05% by weight polyoxyethylene (20) sorbitan monolaurate} at 200 μg / mL, A solution obtained by diluting it with phosphate buffer (pH 7.2, containing 1% by weight bovine serum albumin and 0.05% by weight polyoxyethylene (20) sorbitan monolaurate) 1200 times was added at 100 μL per well. . After reacting at 37 ° C. for 60 minutes, the plate was washed with a phosphate buffer (pH 7.2). To 6.5 mL of 0.1 mol / L phosphate buffer (pH 6.2), add 1 tablet of ortho-phenylenediamine dihydrochloride (13 mg Table, manufactured by Wako Pure Chemical Industries, Ltd.) and 6.5 μL of 30% hydrogen peroxide solution. 100 μL was added per well and reacted at 37 ° C. for 3 minutes. Immediately thereafter, 50 μL of 1 mol / L H 2 SO 4 was added to stop the reaction, and the absorbance (OD 490 nm) was measured with a spectrophotometer for microplate (manufactured by Tecan Japan Co., Ltd.). The results are shown in Table 1.
[試験例2]
アレルゲン低減化組成物によるスギ花粉アレルゲンの低減化効果の測定
スギ花粉アレルゲンCry j1として約12.5ng/1mL{リン酸緩衝液(pH7.2)}のアレルゲン液1mLに対し、実施例1〜10(実施例2、4、5,9についてはあらかじめ水で5倍に希釈した液を使用)、比較例1〜4(比較例3についてはあらかじめ水で5倍に希釈した液を使用)と対照として蒸留水をそれぞれ100μL反応させた。これら試料についてCry j1酵素免疫測定法(ELISA)のサンドイッチ法にてスギ花粉アレルゲン低減化効果の測定を行った。まず、リン酸緩衝液(pH7.4、0.1重量%NaN3含有)で2μg/mLに希釈したCry j1 モノクローナル抗体013を、F16 MAXISORP NUNC−IMMUNO MODULEプレート(NUNC社製)の1ウェルあたり100μLずつ添加し、4℃にて1日以上感作させた。感作後、液を捨て、ブロッキング試薬{1重量%牛血清アルブミン+リン酸緩衝液(pH7.2、0.1重量%NaN3含有)}を1ウェルあたり200μLずつ添加し、37℃、60分間反応させた。反応後、リン酸緩衝液{pH7.2、0.1重量%ポリオキシエチレン(20)ソルビタンモノラウレート含有}にてプレートを洗浄した。
[Test Example 2]
Measurement of reduction effect of cedar pollen allergen by allergen-reducing composition Examples 1 to 10 with respect to 1 mL of allergen solution of about 12.5 ng / 1 mL {phosphate buffer solution (pH 7.2)} as cedar pollen allergen Cry j1 (For Examples 2, 4, 5, and 9, use a solution diluted five times with water in advance), Comparative Examples 1 to 4 (for Comparative Example 3, use a solution diluted five times with water in advance) As a result, 100 μL of distilled water was reacted. These samples were measured for the effect of reducing cedar pollen allergen by the sandwich method of Cry j1 enzyme immunoassay (ELISA). First, Cry j1 monoclonal antibody 013 diluted to 2 μg / mL with phosphate buffer (pH 7.4, containing 0.1 wt% NaN 3 ) was added per well of F16 MAXISORP NUNC-IMMUNO MODULE plate (manufactured by NUNC). 100 μL each was added and sensitized at 4 ° C. for 1 day or longer. After sensitization, the solution was discarded, and a blocking reagent {1% by weight bovine serum albumin + phosphate buffer (pH 7.2, containing 0.1% by weight NaN 3 )} was added in an amount of 200 μL per well. Reacted for 1 minute. After the reaction, the plate was washed with a phosphate buffer (pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate).
次に、スギ花粉アレルゲン液に上記試料を添加した液を1ウェルあたり100μLずつ滴下し、37℃、60分間反応させた。反応後、リン酸緩衝液{pH7.2、0.1重量%ポリオキシエチレン(20)ソルビタンモノラウレート含有}にてプレートを洗浄した。ペルオキシダーゼ標識したCry j1モノクローナル抗体053を蒸留水で200μg/mLに溶解し、それをリン酸緩衝液{pH7.2、1重量%牛血清アルブミンおよび0.1重量%ポリオキシエチレン(20)ソルビタンモノラウレート含有}で1200倍希釈した液を、1ウェルあたり100μLずつ添加した。37℃、60分間反応させた後、リン酸緩衝液{pH7.2、0.1重量%ポリオキシエチレン(20)ソルビタンモノラウレート含有}でプレートを洗浄した。0.1mol/Lリン酸緩衝液(pH6.2)13mLにオルト−フェニレンジアミンジヒドロクロライド(SIGMA CHEMICAL CO.製:26mg Tablet)と過酸化水素水13μLを加えたものを1ウェルあたり100μLずつ添加し、37℃、5分間反応させた。その後直ちに、2mol/L H2SO4を50μLずつ入れて反応を停止させ、マイクロプレート用分光光度計(テカンジャパン株式会社製)で吸光度(OD490nm)を測定した。結果を表2に示した。 Next, a solution obtained by adding the above sample to the cedar pollen allergen solution was added dropwise by 100 μL per well and reacted at 37 ° C. for 60 minutes. After the reaction, the plate was washed with a phosphate buffer (pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate). Peroxidase-labeled Cry j1 monoclonal antibody 053 was dissolved in distilled water to 200 μg / mL, and then dissolved in phosphate buffer {pH 7.2, 1 wt% bovine serum albumin and 0.1 wt% polyoxyethylene (20) sorbitan mono A solution diluted 1200 times with laurate contained} was added at 100 μL per well. After reacting at 37 ° C. for 60 minutes, the plate was washed with a phosphate buffer (pH 7.2, containing 0.1 wt% polyoxyethylene (20) sorbitan monolaurate). Add 100 μL per well of 13 mol of 0.1 mol / L phosphate buffer (pH 6.2) plus ortho-phenylenediamine dihydrochloride (manufactured by SIGMA CHEMICAL CO .: 26 mg Table) and 13 μL of hydrogen peroxide. And allowed to react at 37 ° C. for 5 minutes. Immediately thereafter, 50 μL of 2 mol / L H 2 SO 4 was added to stop the reaction, and the absorbance (OD 490 nm) was measured with a spectrophotometer for microplate (Tecan Japan Co., Ltd.). The results are shown in Table 2.
[試験例3]
実施例9および比較例3を8cm×8cmのガラス板2枚に、塗布厚0.076mmのフィルムアプリケータを用いて塗布し、100℃の乾燥機で15分間、乾燥させた。このガラス板の1枚にダニアレルゲンDer f2を含有する、タンパク質量として約900ng/1mL{リン酸緩衝液(pH7.2)}のアレルゲン液1mLを載せ、直径0.3mm、長さ5mmのステンレス製の針金3本をスペーサーとして離して配置し、もう一枚のガラス板を処理面が合わさるように挟み、接触させた。1時間後のアレルゲン液について、Der f2酵素免疫測定法(ELISA)のサンドイッチ法にてダニアレルゲン濃度の測定を[試験例1]と同様の方法を用いて行った。結果を表3に示す。
[Test Example 3]
Example 9 and Comparative Example 3 were applied to two 8 cm × 8 cm glass plates using a film applicator with a coating thickness of 0.076 mm, and dried for 15 minutes with a dryer at 100 ° C. One glass plate is loaded with 1 ml of an allergen solution containing mite allergen Der f2 and about 900 ng / 1 mL {phosphate buffer solution (pH 7.2)} as a protein, and has a diameter of 0.3 mm and a length of 5 mm. Three wires made of metal were arranged apart from each other as a spacer, and another glass plate was sandwiched so that the treated surfaces were aligned and brought into contact. For the allergen solution after 1 hour, the mite allergen concentration was measured by the sandwich method of Der f2 enzyme immunoassay (ELISA) using the same method as in [Test Example 1]. The results are shown in Table 3.
[加工例1]
実施例1をエタノールで20倍に希釈し、27cm×20cmのポリプロピレン製不織布(80g/m2)にスプレー処理し、5.5gを付着させ、110℃で乾燥させた。(加工量は2−エチルヘキサン酸亜鉛として0.1g/m2)。
[Processing example 1]
Example 1 was diluted 20 times with ethanol, sprayed onto a 27 cm × 20 cm polypropylene non-woven fabric (80 g / m 2 ), 5.5 g adhered, and dried at 110 ° C. (The processing amount is 0.1 g / m 2 as zinc 2-ethylhexanoate).
[加工例2]
実施例2を0.2g採り、イオン交換水で40gに希釈し、この液に27cm×20cmのポリプロピレン製不織布(80g/m2)を浸漬し、絞り率250%で処理後、110℃で乾燥させた。(加工量は2−エチルヘキサン酸亜鉛として0.1g/m2)。
[Processing example 2]
Take 0.2 g of Example 2, dilute to 40 g with ion-exchanged water, immerse a 27 cm × 20 cm non-woven fabric made of polypropylene (80 g / m 2 ) in this solution, treat with a drawing rate of 250%, and dry at 110 ° C. I let you. (The processing amount is 0.1 g / m 2 as zinc 2-ethylhexanoate).
[加工例3]
実施例4を0.2g採りイオン交換水で40gに希釈し、この液に27cm×20cmのポリプロピレン製不織布(80g/m2)を浸漬し、絞り率250%で処理後、110℃で乾燥させた。(加工量は2−エチルヘキサン酸銅として0.1g/m2)。
[Processing example 3]
0.2 g of Example 4 was taken and diluted to 40 g with ion-exchanged water. A 27 cm × 20 cm non-woven fabric made of polypropylene (80 g / m 2 ) was immersed in this solution, treated at a drawing rate of 250%, and dried at 110 ° C. It was. (The processing amount is 0.1 g / m 2 as copper 2-ethylhexanoate).
[加工例4]
比較例2を1.0g採り、イオン交換水で40gに希釈し、この液に27cm×20cmのポリプロピレン製不織布(80g/m2)を浸漬し、絞り率250%で処理後、110℃で乾燥させた。(加工量は塩化セリウムとして0.1g/m2)。
[Processing example 4]
Take 1.0 g of Comparative Example 2, dilute to 40 g with ion-exchanged water, immerse a 27 cm × 20 cm polypropylene nonwoven fabric (80 g / m 2 ) in this solution, treat with a drawing rate of 250%, and dry at 110 ° C. I let you. (Processing amount is 0.1 g / m 2 as cerium chloride).
[加工例5]
比較例4を1.0g採り、イオン交換水で40gに希釈し、この液に27cm×20cmのポリプロピレン製不織布(80g/m2)を浸漬し、絞り率250%で処理後、110℃で乾燥させた。(加工量は酢酸亜鉛として0.1g/m2)。
[Processing Example 5]
Take 1.0 g of Comparative Example 4, dilute to 40 g with ion-exchanged water, immerse a 27 cm × 20 cm non-woven polypropylene fabric (80 g / m 2 ) in this solution, treat with a drawing rate of 250%, and dry at 110 ° C. I let you. (The processing amount is 0.1 g / m 2 as zinc acetate).
[不織布の水洗]
加工例1〜4の不織布を等分に切断し(13.5cm×20cm)、一方を4Lのイオン交換水に浸漬して30分間攪拌し、取り出して室温で風乾し水洗後の試料とした。
[Washing of non-woven fabric]
The nonwoven fabrics of Processing Examples 1 to 4 were cut equally (13.5 cm × 20 cm), one was immersed in 4 L of ion exchange water, stirred for 30 minutes, taken out, air-dried at room temperature, and used as a sample after washing with water.
[試験例3](加工不織布のダニアレルゲンの低減化効果の測定)
加工例1〜5の不織布および、これらの水洗を行った不織布を5cm×5cmに切り取り、チャック付きポリ袋に投入し、標準ダニアレルゲン懸濁液(アレルゲン量900ng/mL)1mLを加え、試料とアレルゲンを接触させた。1時間後にチャック付きポリ袋からアレルゲン液を搾り出し、遠心分離後のこれら試料について Der f2酵素免疫測定法(ELISA)のサンドイッチ法にてダニアレルゲン濃度の測定を[試験例1]と同様の方法を用いて行った。結果を表4に示す。
[Test Example 3] (Measurement of reduction effect of mite allergen in processed nonwoven fabric)
Cut the nonwoven fabrics of Processing Examples 1 to 5 and these washed water nonwoven fabrics into 5 cm × 5 cm, put them in a plastic bag with a chuck, add 1 mL of a standard mite allergen suspension (allergen amount 900 ng / mL), Allergen was contacted. After 1 hour, the allergen solution was squeezed out of the plastic bag with the chuck, and the mite allergen concentration was measured by the sandwich method of Der f2 enzyme immunoassay (ELISA) for these samples after centrifugation in the same manner as in [Test Example 1]. Used. The results are shown in Table 4.
[試験例4](加工不織布のスギ花粉アレルゲンCry j1の低減化効果の測定)
加工例1〜5の不織布および、これらの水洗を行った不織布を5cm×5cmに切り取り、チャック付きポリ袋に投入し、標準スギ花粉アレルゲン液(アレルゲン量 12.5ng/mL)1mLを加え、試料とアレルゲンを接触させた。1時間後にチャック付きポリ袋からアレルゲン液を搾り出し、遠心分離後のこれら試料について Cry j1酵素免疫測定法(ELISA)のサンドイッチ法にてスギ花粉アレルゲン濃度の測定を[試験例2]と同様の方法を用いて行った。結果を表5に示す。
[Test Example 4] (Measurement of reduction effect of cedar pollen allergen Cry j1 in processed nonwoven fabric)
Cut out the nonwoven fabrics of Processing Examples 1 to 5 and these washed water nonwoven fabrics into 5 cm × 5 cm, put them into a plastic bag with a chuck, add 1 mL of standard cedar pollen allergen solution (allergen amount 12.5 ng / mL), and sample And allergens were contacted. After 1 hour, the allergen solution was squeezed out of the plastic bag with the chuck, and the samples after centrifugation were measured for the cedar pollen allergen concentration by the sandwich method of Cry j1 enzyme immunoassay (ELISA) in the same manner as in [Test Example 2]. It was performed using. The results are shown in Table 5.
本発明の1価または2価のカルボン酸の金属塩を使用することにより、ダニや花粉等のアレルゲンのアレルゲン性を低減化させることができ、また不織布、繊維または繊維製品、建築用内装材に耐水性を有するアレルゲン性を低減化させる機能を付与することができ、さらにアレルゲンを低減化できる不織布、繊維または繊維製品、建築用内装材を提供することができる。
By using the monovalent or divalent carboxylic acid metal salt of the present invention, the allergenicity of allergens such as mites and pollen can be reduced, and it can be used for nonwoven fabrics, fibers or textiles, and building interior materials. It is possible to provide a non-woven fabric, a fiber or a fiber product, and a building interior material capable of imparting a function of reducing the allergenicity having water resistance and further reducing the allergen.
Claims (5)
A non-woven fabric, a fiber or a fiber product, or an interior material for construction, which is obtained by processing the allergen-reducing composition according to any one of claims 1 to 4.
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