JP4350536B2 - Fiber fabric treatment liquid, allergen-suppressing fiber fabric and method for producing the same - Google Patents
Fiber fabric treatment liquid, allergen-suppressing fiber fabric and method for producing the same Download PDFInfo
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- JP4350536B2 JP4350536B2 JP2004011878A JP2004011878A JP4350536B2 JP 4350536 B2 JP4350536 B2 JP 4350536B2 JP 2004011878 A JP2004011878 A JP 2004011878A JP 2004011878 A JP2004011878 A JP 2004011878A JP 4350536 B2 JP4350536 B2 JP 4350536B2
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- Prior art keywords
- fiber fabric
- allergen
- components
- component
- suppressing
- 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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- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Description
本発明は、ダニや花粉等のアレルゲンを抑制するアレルゲン抑制繊維布帛を製造する際に用いて好適な繊維布帛処理液、並びに、これを用いてなるアレルゲン抑制繊維布帛及びその製造方法に関する。 The present invention relates to a fiber fabric treatment solution suitable for use in producing an allergen-suppressing fiber fabric that suppresses allergens such as mites and pollen, an allergen-suppressing fiber fabric using the same, and a method for producing the same.
近年、アトピー性皮膚炎、気管支喘息、アレルギー性鼻炎等の多くのアレルギー疾患が問題視されている。これらはヒョウダニ等の住居内性ダニ類アレルゲン（Der1, 2等）や、スギ花粉等の花粉アレルゲン（Crij1，2等）等によって引き起こされる。ダニ類アレルゲンに関しては、死虫についてもアレルゲン物質を生活空間内に放散することが指摘されており、原因となるダニ類を単に死滅させても根本的な解決には至らない。花粉アレルゲンであるCrij1，2は分子量約３７〜４０ｋＤａの糖タンパク質であり、鼻粘膜等に付着すると生体外異物として認識され、炎症反応等を引き起こすことがある。
アレルギー疾患対策としては、生活空間からのアレルゲンの完全排除や、アレルゲンの変性等による不活性化が挙げられる。
In recent years, many allergic diseases such as atopic dermatitis, bronchial asthma, and allergic rhinitis have been regarded as problems. These are caused by residential mite allergens such as leopard mites (Der1, 2 etc.) and pollen allergens (Crij1, 2 etc.) such as cedar pollen. Concerning mite allergens, it has been pointed out that dead insects also release allergen substances into the living space, and simply killing the causative mites does not lead to a fundamental solution. Crij1,2 which is a pollen allergen is a glycoprotein having a molecular weight of about 37-40 kDa. When it adheres to the nasal mucosa, it is recognized as a foreign substance and may cause an inflammatory reaction or the like.
Examples of allergic disease countermeasures include complete elimination of allergens from the living space and inactivation by allergen degeneration.
アレルゲンの完全排除は実際には困難であり現実的ではないので、以下、アレルゲンの不活性化について言及する。
上記アレルゲンは蛋白質であるため、酸化剤、還元剤、酸、アルカリ等による処理や加熱処理で変性し不活性化すると考えられるが、比較的安定性の高い蛋白質であり、不活性化には過酷な条件が必要とされている（非特許文献１等）。
Since complete elimination of allergens is actually difficult and impractical, reference will be made below to inactivation of allergens.
Since the allergen is a protein, it is thought to be denatured and inactivated by treatment with an oxidizing agent, reducing agent, acid, alkali, etc. or heat treatment, but it is a relatively stable protein and is severely inactivated. Conditions are required (Non-Patent Document 1, etc.).
比較的穏和な条件でアレルゲンを不活性化させる手段として、（１）茶抽出物や、ヒドロキシ安息香酸系化合物又はその塩等のアレルゲン抑制成分を含む組成物を、スプレー噴霧等する技術が開示されている（特許文献１、２）。しかしながら、この技術では手間がかかる上、アレルゲン抑制効果は一時的なものであり、根本的な解決にはならない。特に、寝具（シーツやカバー、布団側等）や衣類（洋服、寝衣、肌着、帽子、手袋、靴下等）等の繊維製品では、洗濯によってアレルゲン抑制成分が脱落するため、アレルゲン抑制効果が失われやすい。 As a means to inactivate allergens under relatively mild conditions, (1) a technique of spray-spraying a composition containing an allergen-suppressing component such as a tea extract or a hydroxybenzoic acid compound or a salt thereof is disclosed. (Patent Documents 1 and 2). However, this technique is time-consuming and the allergen-suppressing effect is temporary, and is not a fundamental solution. In particular, textile products such as bedding (sheets, covers, futons, etc.) and clothing (clothes, nightclothes, underwear, hats, gloves, socks, etc.) lose their allergen-suppressing effect because allergen-suppressing components are lost by washing. Easy to break.
そこで、繊維布帛自体を改質して、アレルゲン抑制効果を持続的に得る研究がなされており、繊維布帛に、アレルゲン抑制成分であるポリビニルフェノールを化学結合させる技術が提案されている（特許文献３）。 Therefore, studies have been made to continuously improve the fiber fabric itself to obtain an allergen-inhibiting effect, and a technique for chemically bonding polyvinylphenol, which is an allergen-inhibiting component, to the fiber fabric has been proposed (Patent Document 3). ).
一方、繊維布帛には汗等を吸収する吸水・吸湿性が求められる。例えば、（メタ）アクリル酸系ビニル系単量体等を繊維布帛上で重合させることで、繰り返し洗濯等に対して安定な耐久性のある吸水・吸湿性付与処理を施すことができる。
さらに、上記単量体を重合する際に所望の特性を呈する物質を合わせて作用させることで耐久性を確保しつつ高機能化を図ることができる。例えば、繊維布帛上にアクリル酸系単量体を重合する際に、絹フィブロン水溶液を合わせて作用させることで、耐久性のある吸水・吸湿性と、絹のような柔軟性やドレープ性等の風合いを呈する改質繊維布帛が得られることが開示されている（特許文献４）。その他、繊維布帛上にアクリル酸系単量体を重合する際に、コラーゲンや抗菌剤（第四級アンモニウム塩型界面活性剤、キトサン等）の水溶液や分散液を合わせて作用させることで、耐久性のある吸水・吸湿性と、耐久性のある抗菌性を呈する改質繊維布帛が得られることが開示されている（特許文献５）。
Furthermore, when the monomer is polymerized, it is possible to achieve high functionality while ensuring durability by combining and acting a substance exhibiting desired characteristics. For example, when polymerizing an acrylic acid-based monomer on a fiber fabric, by combining the silk fibron aqueous solution and acting, it has durable water absorption / hygroscopicity, silky flexibility, drapeability, etc. It is disclosed that a modified fiber fabric exhibiting a texture can be obtained (Patent Document 4). In addition, when an acrylic acid monomer is polymerized on a fiber fabric, an aqueous solution or dispersion of collagen or an antibacterial agent (a quaternary ammonium salt surfactant, chitosan, etc.) is allowed to act on the fiber fabric for durability. It has been disclosed that a modified fiber fabric exhibiting excellent water absorption / hygroscopicity and durable antibacterial properties can be obtained (Patent Document 5).
しかしながら、特許文献３に記載の技術では、以下のような問題がある。
すなわち、ポリビニルフェノールは一般に水難溶性又は水不溶性を呈するため、繊維布帛処理液は必然的に水系の乳化液または分散液、あるいは非水系となる。ポリビニルフェノール自体が良好な水溶性を呈さず、しかも繊維布帛処理液として上記形態を採用せざるを得ないため、かかる繊維布帛処理液を用いて繊維布帛の改質を実施しようとしても、繊維布帛に対して有効成分を良好に化学結合させることが難しく、良好なアレルゲン抑制効果を安定的に得ることは難しい。加えて、繊維布帛処理液として乳化液等を用いる場合、多量に配合する乳化剤がアレルゲン抑制効果の発現を阻害する恐れもあり、非水系では工業生産上の制約も大きい。
また、同文献には、寝具や衣類等の繊維製品に不可欠な耐久性（耐繰り返し洗濯性等）に関しては一切言及されていない。さらに、アレルゲン抑制効果付与と同時に、吸水・吸湿性を付与することについても開示がない。
However, the technique described in Patent Document 3 has the following problems.
That is, since polyvinylphenol generally exhibits poor water solubility or water insolubility, the fiber fabric treatment liquid is necessarily an aqueous emulsion or dispersion, or non-aqueous. Polyvinylphenol itself does not exhibit good water solubility and must adopt the above-mentioned form as a fiber cloth treatment liquid. Therefore, even if an attempt is made to modify the fiber cloth using such a fiber cloth treatment liquid, the fiber cloth On the other hand, it is difficult to chemically bond the active ingredient well, and it is difficult to stably obtain a good allergen suppressing effect. In addition, when an emulsified liquid or the like is used as the fiber fabric treatment liquid, there is a risk that an emulsifier mixed in a large amount may inhibit the expression of the allergen suppressing effect.
In addition, the document does not mention any durability (such as resistance to repeated washing) essential to textile products such as bedding and clothes. Furthermore, there is no disclosure about providing water absorption / hygroscopicity simultaneously with the allergen suppression effect.
ここで、アレルゲン抑制効果と吸水・吸湿性付与を同時に実現するには、特許文献４、５の改質技術の適用が考えられる。また、アレルゲン抑制効果を良好に発現させるには有効成分の付着量を増すことが考えられる。
しかしながら、特許文献４、５の改質技術では、有効成分の付着量は繊維布帛の質量に対して高々５質量％である。良好なしかも耐久性のあるアレルゲン抑制効果、及び吸水・吸湿性を付与するべく、単に公知の改質技術を適用しようとしても、単なる有効成分の付着量の増加は、いわゆる糊付け状態を招き、柔軟性やドレープ性等の風合いに支障を来たすに過ぎない。
Here, in order to simultaneously realize the allergen suppressing effect and imparting water absorption and hygroscopicity, application of the reforming techniques of Patent Documents 4 and 5 can be considered. Moreover, in order to express an allergen inhibitory effect favorably, it is possible to increase the adhesion amount of an active ingredient.
However, in the modification techniques of Patent Documents 4 and 5, the amount of the active ingredient attached is at most 5 mass% with respect to the mass of the fiber fabric. Even if you try to apply a well-known modification technology to give a good and durable allergen suppression effect and water absorption / hygroscopicity, an increase in the amount of active ingredients alone will cause a so-called gluing state and flexibility. It just hinders the texture such as sex and drape.
本発明はかかる事情に鑑みてなされたものであり、繊維布帛の風合いを損なうことなく、良好でしかも耐久性のあるアレルゲン抑制効果及び吸水・吸湿性を安定的に付与する繊維布帛改質技術を提供することを目的とする。 The present invention has been made in view of such circumstances, and provides a fiber fabric modification technology that stably imparts a good and durable allergen suppressing effect and water absorption / hygroscopicity without impairing the texture of the fiber fabric. The purpose is to provide.
本発明者らは上記目的を達成するべく鋭意検討した結果、中性域では水難溶性又は水不溶性を呈するポリビニルフェノール等のアレルゲン抑制成分がアルカリｐＨ領域で良好な水溶性を呈し、水性の繊維布帛処理液を構成し得ること、また該成分と特定の単量体成分とを繊維布帛上で合わせて重合することで、繊維布帛の表面および内部にアレルゲン抑制成分を良好に導入でき、しかも吸水・吸湿性付与効果も合わせて得られることを見出し、本発明を完成した。 As a result of intensive studies to achieve the above-mentioned object, the present inventors have found that an allergen-inhibiting component such as polyvinylphenol that exhibits poor water solubility or water insolubility in the neutral region exhibits good water solubility in the alkaline pH region, and is an aqueous fiber fabric. The treatment liquid can be configured, and the component and the specific monomer component are combined and polymerized on the fiber fabric, whereby the allergen-suppressing component can be satisfactorily introduced into the surface and inside of the fiber fabric, and the water absorption / The inventors have found that a hygroscopicity-imparting effect can also be obtained and completed the present invention.
すなわち、本発明の繊維布帛処理液は、少なくともアルカリｐＨ領域で水溶性を呈するアレルゲン抑制成分（Ｘ）と、下記一般式（１）で示される２官能性単量体（Ａ）と、水酸基、カルボキシル基、アミノ基、スルホン酸基、リン酸基のうちいずれかの基を含む単量体（Ｂ）とを含み、前記アレルゲン抑制成分（Ｘ）としてポリビニルフェノールを含み、さらに溶媒として水及び／又は水性有機溶剤を含むｐＨ１２以上のアルカリ性水性溶液であることを特徴とする。 That is, the fiber fabric treatment liquid of the present invention comprises an allergen suppressing component (X) that exhibits water solubility at least in an alkaline pH region, a bifunctional monomer (A) represented by the following general formula (1), a hydroxyl group, A monomer (B) containing any one of a carboxyl group, an amino group, a sulfonic acid group, and a phosphoric acid group, polyvinyl alcohol as the allergen-suppressing component (X), and water and / Or it is the alkaline aqueous solution of pH 12 or more containing an aqueous organic solvent.
本発明の繊維布帛処理液はさらに、少なくとも１個のアジリジン基を含む単量体、及びポリカルボジイミド基、ポリエチレンイミン基、オキサゾリン基のうちいずれかの基を含む水溶性ポリマーから選択される架橋剤（Ｃ）を含むことが好ましい。
本発明の繊維布帛処理液は、溶媒として水及び／又は炭素数１〜３の脂肪族低級アルコールを含むことが好ましい。
本発明の繊維布帛処理液は、溶媒として、水のみを含むことが好ましい。 The fiber fabric treatment liquid of the present invention further comprises a monomer containing at least one aziridine group and a cross-linking agent selected from a water-soluble polymer containing any one of a polycarbodiimide group, a polyethyleneimine group, and an oxazoline group. It is preferable to contain (C).
The fiber fabric treatment liquid of the present invention preferably contains water and / or an aliphatic lower alcohol having 1 to 3 carbon atoms as a solvent.
The fiber fabric treatment liquid of the present invention preferably contains only water as a solvent.
本発明のアレルゲン抑制繊維布帛は、下記本発明の第１又は第２のアレルゲン抑制繊維布帛の製造方法により製造されることを特徴とする。 The allergen-suppressing fiber fabric of the present invention is manufactured by the following method for manufacturing an allergen-suppressing fiber fabric of the present invention .
本発明によれば、成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とが繊維の表面および内部に導入されたアレルゲン抑制繊維布帛を提供することができる。また、本発明によれば、繊維布帛に、これら成分がグラフト重合されたアレルゲン抑制繊維布帛を提供することができる。 According to the present invention, it is possible to provide an allergen-suppressing fiber fabric in which component (X) and components (A) and (B) or components (A) to (C) are introduced on the surface and inside of the fiber. it can. Moreover, according to this invention, the allergen suppression fiber cloth by which these components were graft-polymerized to the fiber cloth can be provided.
本発明の第１のアレルゲン抑制繊維布帛の製造方法は、上記の本発明の繊維布帛処理液を繊維布帛に接触させる接液工程と、繊維布帛上で、アレルゲン抑制成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とを重合させる重合工程とを有することを特徴とする。
本発明では、前記重合工程において、繊維布帛に、アレルゲン抑制成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とをグラフト重合させることができる。
The first method for producing an allergen-suppressing fiber fabric of the present invention comprises a liquid contact step in which the fiber fabric treatment liquid of the present invention is brought into contact with the fiber fabric, an allergen-suppressing component (X) and a component ( A) and (B), or a polymerization step of polymerizing the components (A) to (C).
In the present invention, in the polymerization step, the allergen suppressing component (X) and the components (A) and (B) or the components (A) to (C) can be graft polymerized to the fiber fabric.
本発明の第２のアレルゲン抑制繊維布帛の製造方法は、
下記一般式（１）で示される２官能性単量体（Ａ）と、水酸基、カルボキシル基、アミノ基、スルホン酸基、リン酸基のうちいずれかの基を含む単量体（Ｂ）とを含み、溶媒として水及び／又は水性有機溶剤を含む繊維布帛処理液（Ｙ１）、
又は、成分（Ａ）と（Ｂ）に加えて、さらに少なくとも１個のアジリジン基を含む単量体、及びポリカルボジイミド基、ポリエチレンイミン基、オキサゾリン基のうちいずれかの基を含む水溶性ポリマーから選択される架橋剤（Ｃ）を含み、溶媒として水及び／又は水性有機溶剤を含む繊維布帛処理液（Ｙ２）を繊維布帛に接触させる第１の接液工程と、
繊維布帛上で、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）を重合させる第１の重合工程と、
繊維布帛に、少なくともアルカリｐＨ領域で水溶性を呈するアレルゲン抑制成分（Ｘ）を含み、前記アレルゲン抑制成分（Ｘ）としてポリビニルフェノールを含み、溶媒として水及び／又は水性有機溶剤を含むｐＨ１２以上のアルカリ性水性溶液である繊維布帛処理液（Ｚ）を接触させる第２の接液工程と、
繊維布帛上で、アレルゲン抑制成分（Ｘ）を重合させる第２の重合工程とを有することを特徴とする。
The method for producing the second allergen-suppressing fiber fabric of the present invention is as follows.
A bifunctional monomer (A) represented by the following general formula (1), a monomer (B) containing any one of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphoric acid group; only containing, fiber fabric treatment solution containing water and / or aqueous organic solvent as the solvent (Y1),
Alternatively, in addition to the components (A) and (B), a monomer further containing at least one aziridine group, and a water-soluble polymer containing any one of a polycarbodiimide group, a polyethyleneimine group, and an oxazoline group look containing a crosslinking agent (C) is selected, a first wetted process water and / or the fiber fabric treatment liquid containing an aqueous organic solvent (Y2) is contacted with fiber fabric as a solvent,
A first polymerization step of polymerizing components (A) and (B) or components (A) to (C) on a fiber fabric;
A fiber fabric, at least an alkaline pH region seen containing an allergen suppression component (X) which exhibits a water solubility at the allergen suppression components as (X) comprises a polyvinyl phenol, the above pH12 containing water and / or aqueous organic solvent as the solvent A second liquid contact step in which the fiber fabric treatment liquid (Z), which is an alkaline aqueous solution, is contacted;
And a second polymerization step of polymerizing the allergen suppressing component (X) on the fiber fabric.
繊維布帛処理液（Ｙ１）、（Ｙ２）、及び（Ｚ）は、溶媒として、水及び／又は炭素数１〜３の脂肪族低級アルコールを含む水性溶液であることが好ましい。
本発明では、前記第１の重合工程と前記第２の重合工程とを同時に実施し、繊維布帛に、アレルゲン抑制成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とを同時にグラフト重合させることができる。
The fiber fabric treatment liquids (Y1), (Y2), and (Z) are preferably aqueous solutions containing water and / or an aliphatic lower alcohol having 1 to 3 carbon atoms as a solvent.
In the present invention, the first polymerization step and the second polymerization step are simultaneously performed, and the allergen suppressing component (X) and the components (A) and (B) or the components (A) to (A) to the fiber fabric. (C) and graft polymerization can be carried out simultaneously.
第１、第２の製造方法によって、成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とが重合された上記の本発明のアレルゲン抑制繊維布帛を製造することができる。なお、第１の製造方法では、繊維布帛に対して、これら成分をすべて同時に接触させ、重合させるのに対し、第２の製造方法では、アレルゲン抑制成分（Ｘ）と他の成分に分けて、２段階で接触させることを特徴としている。 By the first and second production methods, the allergen-suppressing fiber fabric of the present invention in which the component (X) and the components (A) and (B) or the components (A) to (C) are polymerized is produced. can do. In the first production method, all of these components are simultaneously contacted and polymerized with respect to the fiber fabric, whereas in the second production method, the allergen suppressing component (X) is divided into other components, It is characterized by contacting in two stages.
本発明によれば、繊維布帛の風合いを損なうことなく、良好でしかも耐久性のあるアレルゲン抑制効果及び吸水・吸湿性を安定的に付与する繊維布帛改質技術を提供することができる。 According to the present invention, it is possible to provide a fiber fabric modification technique that stably imparts a good and durable allergen suppressing effect and water absorption / hygroscopicity without impairing the texture of the fiber fabric.
以下、本発明について詳述する。
「繊維布帛処理液」
本発明の繊維布帛処理液は、繊維布帛を重合にて改質する処理液であり、少なくともアルカリｐＨ領域で水溶性を呈するアレルゲン抑制成分（Ｘ）と、特定の単量体成分とを含み、かつ、溶媒として水及び／又は水性有機溶剤（これらは「水性溶媒」と総称する。）を含むアルカリ性水性溶液である。
Hereinafter, the present invention will be described in detail.
"Fiber fabric treatment liquid"
The fiber fabric treatment liquid of the present invention is a treatment liquid for modifying a fiber cloth by polymerization, and includes an allergen suppressing component (X) that exhibits water solubility at least in an alkaline pH region, and a specific monomer component, In addition, it is an alkaline aqueous solution containing water and / or an aqueous organic solvent (these are collectively referred to as “aqueous solvent”) as a solvent.
「アレルゲン抑制成分」とは、ヒョウダニ等の住居内性ダニ類アレルゲン（Der1,2等）や、スギ花粉等の花粉アレルゲン（Crij1，2等）、犬・猫等の動物に由来するアレルゲン（Can f1, Fe d1等）等のアレルゲンを変性あるいは吸着し、アレルゲンの特異抗体に対する反応性を抑制する成分である。
アレルゲン抑制効果は、例えば、ＥＬＩＳＡ法等にてアレルゲン量を定量化することで、確認できる。ＥＬＩＳＡ法用のアレルゲン量測定キットとしては、ＬＣＤアレルギー研究所社製 商品名「ＥＬＩＳＡキット」等が市販されている。
“Allergen inhibitory components” refers to allergens derived from domestic mite allergens such as leopard mites (Der1, 2 etc.), pollen allergens such as cedar pollen (Crij1, 2 etc.), animals such as dogs and cats (Can It is a component that denatures or adsorbs allergens such as f1, Fe d1, etc.) and suppresses allergen reactivity to specific antibodies.
The allergen inhibitory effect can be confirmed by quantifying the amount of allergen by, for example, ELISA. As an allergen amount measurement kit for the ELISA method, a product name “ELISA kit” manufactured by LCD Allergy Laboratory Co., Ltd. is commercially available.
アレルゲン抑制成分（Ｘ）としては、少なくともアルカリｐＨ領域で水溶性を呈し、アレルゲン抑制効果を呈するものであれば特に限定されないが、例えば、ポリビニルフェノール、ポリ３，４，５−ヒドロキシ安息香酸ビニル、ポリチロシン、ポリ(１−ビニル−５−ヒドロキシナフタレン)、ポリ(１−ビニル−６−ヒドロキシナフタレン) 、ポリ( １−ビニル−５−ヒドロキシアントラセン)等の芳香族ヒドロキシ化合物や、２−ヒドロキシフラン、２−ヒドロキシチオフェン、ヒドロキシベンゾフラン、３−ヒドロキシピリジン等の芳香族複素環式ヒドロキシ化合物等が挙げられる。これらは１種を単独で又は複数種を組み合わせて用いることができる。 The allergen suppressing component (X) is not particularly limited as long as it exhibits water solubility at least in the alkaline pH region and exhibits an allergen suppressing effect. For example, polyvinylphenol, poly3,4,5-hydroxyvinyl vinylate, Aromatic hydroxy compounds such as polytyrosine, poly (1-vinyl-5-hydroxynaphthalene), poly (1-vinyl-6-hydroxynaphthalene), poly (1-vinyl-5-hydroxyanthracene), and 2-hydroxyfuran And aromatic heterocyclic hydroxy compounds such as 2-hydroxythiophene, hydroxybenzofuran and 3-hydroxypyridine. These can be used individually by 1 type or in combination of multiple types.
中でも、アレルゲン抑制効果に優れることから、本発明では特にポリビニルフェノール等を用いることが好ましい。
ポリビニルフェノールとしては、ポリ−４−ビニルフェノール、ポリ−３−ビニルフェノール、ポリ−２−ビニルフェノール等が具体的に挙げられる。アレルゲンとの相互作用の際の立体障害を考えると、ポリ−４−ビニルフェノールが特に好ましい。
Especially, since it is excellent in the allergen inhibitory effect, it is preferable to use especially a polyvinyl phenol etc. in this invention.
Specific examples of the polyvinylphenol include poly-4-vinylphenol, poly-3-vinylphenol, poly-2-vinylphenol, and the like. Considering steric hindrance during the interaction with the allergen, poly-4-vinylphenol is particularly preferred.
重合による改質では、用いる繊維布帛処理液は溶媒として水及び／又は水性有機溶剤を含む水性液の形態が好ましい。また、界面活性剤等の乳化剤は繊維布帛の表面に膜を形成し、有効成分の導入や導入した有効成分の機能発現に影響を及ぼす恐れがある。したがって、乳化剤を多量に含む乳化液や水分散液は不適であり、乳化剤を含まない、若しくは効果発現に影響を及ばさない程度に少量含む水性溶液の形態が好ましい。
ここで、「発明が解決しようとする課題」の項において述べたように、ポリビニルフェノール等は一般に水難溶性又は水不溶性を呈するため、従来は、水系の乳化液または分散液、あるいは非水系で使用されている。しかしながら、本発明者は、ポリビニルフェノール等のアレルゲン抑制成分が少なくともアルカリｐＨ領域で良好な水溶性を呈し、重合による繊維布帛改質に用いて好適なものとなることを見出している。
In the modification by polymerization, the fiber fabric treatment liquid to be used is preferably in the form of an aqueous liquid containing water and / or an aqueous organic solvent as a solvent. In addition, an emulsifier such as a surfactant may form a film on the surface of the fiber fabric and may affect the introduction of the active ingredient and the function expression of the introduced active ingredient. Therefore, an emulsion or aqueous dispersion containing a large amount of an emulsifier is not suitable, and an aqueous solution containing no emulsifier or containing a small amount to the extent that the effect is not affected is preferable.
Here, as described in the section of “Problems to be Solved by the Invention”, polyvinylphenol and the like generally exhibit poorly water-soluble or water-insoluble properties, so conventionally used in aqueous emulsions or dispersions or non-aqueous systems. Has been. However, the present inventor has found that an allergen-suppressing component such as polyvinylphenol exhibits good water solubility at least in the alkaline pH region and is suitable for use in fiber fabric modification by polymerization.
本発明の繊維布帛処理液のｐＨは、アレルゲン抑制成分が水溶性を呈するアルカリ領域であれば特に限定されないが、１２以上が好ましく、１４超が特に好ましい。ｐＨをかかる強アルカリ領域とすることで、ポリビニルフェノール等のアレルゲン抑制成分が優れた水溶性を呈する。
ｐＨの調整は、アルカリ金属塩、アルカリ土類金属塩、アンモニウム塩、アミン類、アミド類等のアルカリ剤を添加することで実施できる。アルカリ強度や原料コストを考慮すれば、アルカリ剤としては、水酸化ナトリウム、水酸化カリウム等のアルカリ金属塩が特に好ましい。
The pH of the fiber fabric treatment liquid of the present invention is not particularly limited as long as the allergen suppressing component is an alkaline region exhibiting water solubility, but is preferably 12 or more, particularly preferably more than 14. By making pH into such a strong alkali region, allergen-suppressing components such as polyvinylphenol exhibit excellent water solubility.
The pH can be adjusted by adding an alkali agent such as an alkali metal salt, an alkaline earth metal salt, an ammonium salt, an amine or an amide. Considering the alkali strength and raw material cost, the alkali agent is particularly preferably an alkali metal salt such as sodium hydroxide or potassium hydroxide.
本発明では単量体成分が耐アルカリ性であることが必要である。
本発明では、単量体成分として、下記一般式（１）で示される２官能性単量体（Ａ）と、水酸基、カルボキシル基、アミノ基、スルホン酸基、リン酸基のうちいずれかの基を含む単量体（Ｂ）とを併用する。
In the present invention, the monomer component is required to be alkali resistant.
In the present invention, the monomer component is any one of a bifunctional monomer (A) represented by the following general formula (1) and a hydroxyl group, carboxyl group, amino group, sulfonic acid group, or phosphoric acid group. A monomer (B) containing a group is used in combination.
また、上記単量体成分（Ａ）及び（Ｂ）に加えて、さらに架橋剤を配合することが好ましい。架橋剤としても耐アルカリ性のものを用いることが必要である。本発明では、少なくとも１個のアジリジン基を含む単量体、及びポリカルボジイミド基、ポリエチレンイミン基、オキサゾリン基のうちいずれかの基を含む水溶性ポリマーから選択される架橋剤（Ｃ）を用いることが好ましい。 In addition to the monomer components (A) and (B), a crosslinking agent is preferably further blended. It is necessary to use an alkali-resistant crosslinking agent. In the present invention, a crosslinking agent (C) selected from a monomer containing at least one aziridine group and a water-soluble polymer containing any one of a polycarbodiimide group, a polyethyleneimine group, and an oxazoline group is used. Is preferred.
成分（Ａ）は上記一般式（１）で示される２官能性単量体であれば特に限定されないが、その具体例としては、下記一般式（２）〜（５）で表される化合物等が挙げられる。これらは１種を単独で又は複数種を組み合わせて用いることができる。 The component (A) is not particularly limited as long as it is a bifunctional monomer represented by the general formula (1). Specific examples thereof include compounds represented by the following general formulas (2) to (5). Is mentioned. These can be used individually by 1 type or in combination of multiple types.
成分（Ｂ）は水酸基、カルボキシル基、アミノ基、スルホン酸基、リン酸基のうちいずれかの基を含む単量体であれば特に限定されないが、その具体例としては、アクリル酸、メタクリル酸、スチレンスルホン酸、マレイン酸、イタコン酸、クルトン酸、ビニルスルホン酸、２−アリロキシ２−ヒドロキシプロパンスルホン酸、２−アクリルアミド２−メチルプロパンスルホン酸、２−ヒドロキシエチルメタクリレート、ヒドロキシプロピルメタクリレート、下記一般式（６）〜（８）で表される化合物等が挙げられる。これらは１種を単独で又は複数種を組み合わせて用いることができる。 Component (B) is not particularly limited as long as it is a monomer containing any one of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphoric acid group. Specific examples thereof include acrylic acid and methacrylic acid. Styrene sulfonic acid, maleic acid, itaconic acid, croutonic acid, vinyl sulfonic acid, 2-allyloxy 2-hydroxypropane sulfonic acid, 2-acrylamido 2-methylpropane sulfonic acid, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate, Examples include compounds represented by formulas (6) to (8). These can be used individually by 1 type or in combination of multiple types.
成分（Ｃ）としては、１個のアジリジン基を含む単量体もしくは２個以上のアジリジン基を含む多官能性単量体を用いることができる。その具体例としては、下記一般式（９）〜（１３）で表される化合物等が挙げられる。 As the component (C), a monomer containing one aziridine group or a polyfunctional monomer containing two or more aziridine groups can be used. Specific examples thereof include compounds represented by the following general formulas (9) to (13).
また、成分（Ｃ）としては、ポリカルボジイミド基、ポリエチレンイミン基、オキサゾリン基を含む水溶性ポリマーを用いることもできる。
かかる水溶性ポリマーとしては、例えば、日本触媒社製ＲＰ−１８Ｗ、ＲＰ−２０、ＣＫ−２００、ＮＫ−１００ＰＭおよび２００ＰＭ、ＮＫ−３５０及び３８０、ＰＺ−３３、ＤＺ−２２Ｅ、エポクロスＷＳ−５００（いずれも商品名）等が市販されている。
Moreover, as a component (C), the water-soluble polymer containing a polycarbodiimide group, a polyethyleneimine group, and an oxazoline group can also be used.
Examples of such water-soluble polymers include RP-18W, RP-20, CK-200, NK-100PM and 200PM, NK-350 and 380, PZ-33, DZ-22E, Epocross WS-500 (manufactured by Nippon Shokubai Co., Ltd.). All of them are commercially available.
成分（Ｃ）は上記単量体、水溶性ポリマーを、１種単独で又は複数種を組み合わせて用いることができる。 As the component (C), the above monomers and water-soluble polymers can be used singly or in combination.
繊維布帛処理液中の成分（Ｘ）の濃度は特に限定されず、成分（Ｘ）のアレルゲン抑制能や、所望のアレルゲン抑制効果、用いる繊維布帛等に応じて適宜設定されるが、０．１〜３０質量％が好ましい。成分（Ｘ）の濃度が低すぎると、良好なアレルゲン抑制効果を安定的に付与することが困難となる恐れがあり、濃度が高すぎると、液の粘度が高くなり、取り扱い性等が悪化する恐れがある。
繊維布帛処理液中の成分（Ａ）の濃度は特に限定されないが、１〜２０質量％が好ましい。また、成分（Ａ）、（Ｂ）、（Ｃ）の配合比も特に限定されないが、１：０．０１〜１：０．０１〜１（質量比）が好ましい。
The concentration of the component (X) in the fiber fabric treatment liquid is not particularly limited and is appropriately set according to the allergen suppressing ability of the component (X), the desired allergen suppressing effect, the fiber fabric used, etc. -30 mass% is preferable. If the concentration of component (X) is too low, it may be difficult to stably impart a good allergen-inhibiting effect. If the concentration is too high, the viscosity of the liquid will increase and handling properties will deteriorate. There is a fear.
Although the density | concentration of the component (A) in a fiber fabric processing liquid is not specifically limited, 1-20 mass% is preferable. Moreover, although the compounding ratio of component (A), (B), (C) is not specifically limited, 1: 0.01-1: 0.01-1 (mass ratio) are preferable.
溶媒としては、少なくとも水性溶媒を用いる。
水性溶媒としては、アレルゲン抑制成分（Ｘ）と単量体成分（Ａ）及び（Ｂ）、さらに必要に応じて架橋剤（Ｃ）を媒散するものであれば特に限定されず、水及び／又はアルコール類等の水性有機溶剤が使用できるが、肌への刺激が小さく生体への影響が小さいことから、特に水及び／又は炭素数１〜３の脂肪族低級アルコール（メチルアルコール、エチルアルコール、イソプロピルアルコール等）が好ましく用いられる。
水性溶媒は１種を単独で用いても良いし、２種以上を併用しても良い。また、必要に応じて、ジメチルホルムアミド、アセトン、ジメチルスルホキシド等の非水性溶媒を併用することも差し支えない。
As the solvent, at least an aqueous solvent is used.
The aqueous solvent is not particularly limited as long as it can disperse the allergen-suppressing component (X), the monomer components (A) and (B), and, if necessary, the crosslinking agent (C). Alternatively, aqueous organic solvents such as alcohols can be used, but since the irritation to the skin is small and the impact on the living body is small, water and / or aliphatic lower alcohols having 1 to 3 carbon atoms (methyl alcohol, ethyl alcohol, Isopropyl alcohol or the like) is preferably used.
The aqueous solvent may be used alone or in combination of two or more. Further, if necessary, a non-aqueous solvent such as dimethylformamide, acetone, dimethyl sulfoxide may be used in combination.
繊維布帛処理液には、成分（Ｘ）、及び成分（Ａ）〜（Ｃ）、溶媒の他、各種添加剤を添加しても良い。
本発明では、吸湿性化合物（Ｄ）を添加することが好ましい。吸湿性化合物（Ｄ）としては、塩化カルシルム、塩化マグネシウム、シリカゲル等の無機化合物；ポリエチレングリコール、ポリプロピレングリコール、ポリオキシメチレン等のポリエーテル；ポリビニルアルコール等のポリアルコール；ポリアクリル酸ナトリウム塩等のポリマー塩；ポリアクリル酸等のポリマー酸等が具体的に挙げられる。これらは１種を単独で用いても良いし、２種以上を併用しても良い。
アレルゲン抑制成分（Ｘ）と吸湿性化合物（Ｄ）とを併用して、繊維布帛を改質することで、より高いアレルゲン抑制効果が発現する。これは、繊維布帛上で、吸湿性化合物（Ｄ）が空気中の水分子を引き寄せて、アレルゲン抑制成分（Ｘ）とアレルゲンとの反応場を提供し、アレルゲン抑制反応を促進するためと考えられる。
吸湿性化合物（Ｄ）としては特に、吸湿性に優れ、かつ捉えた水分子を系中に放出し易いことから、ポリエーテルが好ましい。
In addition to the component (X), the components (A) to (C), and the solvent, various additives may be added to the fiber fabric treatment liquid.
In the present invention, it is preferable to add a hygroscopic compound (D). Examples of the hygroscopic compound (D) include inorganic compounds such as calcium chloride, magnesium chloride and silica gel; polyethers such as polyethylene glycol, polypropylene glycol and polyoxymethylene; polyalcohols such as polyvinyl alcohol; polymers such as sodium polyacrylate Specific examples include salts; polymer acids such as polyacrylic acid. These may be used alone or in combination of two or more.
By using the allergen suppressing component (X) and the hygroscopic compound (D) in combination to modify the fiber fabric, a higher allergen suppressing effect is exhibited. This is probably because the hygroscopic compound (D) attracts water molecules in the air on the fiber fabric to provide a reaction field between the allergen-suppressing component (X) and the allergen and promotes the allergen-suppressing reaction. .
Especially as a hygroscopic compound (D), since it is excellent in hygroscopicity and it is easy to discharge | release the captured water molecule in a system, polyether is preferable.
その他、メラミン系樹脂、グリオキサール系樹脂、エポキシ系樹脂等の反応性樹脂やイミン系架橋剤等の成分（Ｃ）以外の架橋剤をさらに添加し、成分（Ｘ）および成分（Ａ）〜（Ｃ）の重合に際し、これらを架橋させても良い。
重合反応を効率良く進行させるため、過酸化カリウム、過硫酸アンモニウム、過酸化水素、ベンゾイルパーオキシド、アゾビスイソブチロニトリル、ターシャリーブチルパーオキシド等の重合開始剤を添加することもできる。
成分（Ｘ）の溶解性向上等を目的として、各種界面活性剤等の乳化剤を添加することもできる。
また、保湿性向上等を目的として、アミノ酸類を多く含む、セリシン、コラーゲン、プロティン、リン脂質モノマー等の天然高分子保湿成分（Ｅ）を添加することもできる。
In addition, a crosslinking agent other than the component (C) such as a reactive resin such as a melamine resin, a glyoxal resin, an epoxy resin, or an imine crosslinking agent is further added, and the component (X) and the components (A) to (C) ) May be cross-linked during polymerization.
In order to advance the polymerization reaction efficiently, a polymerization initiator such as potassium peroxide, ammonium persulfate, hydrogen peroxide, benzoyl peroxide, azobisisobutyronitrile, tertiary butyl peroxide, or the like can be added.
For the purpose of improving the solubility of the component (X), emulsifiers such as various surfactants may be added.
Moreover, natural polymer moisturizing components (E) containing a large amount of amino acids such as sericin, collagen, protein, phospholipid monomer and the like can be added for the purpose of improving the moisturizing property.
本発明の繊維布帛処理液の調製方法は特に限定されず、全構成成分を一括して添加混合し調製しても良いし、複数段階に分けて添加混合しても良い。複数段階に分ける場合には、例えば、水性溶媒、アルカリ剤、アレルゲン抑制成分（Ｘ）を混合して、成分（Ｘ）のアルカリ性水性溶液（Ｚ）を調製してから、これに単量体成分（Ａ）及び（Ｂ）、必要に応じて架橋剤（Ｃ）、さらに必要に応じて他の添加剤を添加混合するなどして、調製することができる。 The method for preparing the fiber fabric treatment liquid of the present invention is not particularly limited, and all components may be added and mixed all at once, or may be added and mixed in a plurality of stages. When dividing into a plurality of stages, for example, an aqueous solvent, an alkaline agent, and an allergen-suppressing component (X) are mixed to prepare an alkaline aqueous solution (Z) of the component (X), and then a monomer component (A) and (B), a crosslinking agent (C) as necessary, and other additives as necessary may be added and mixed.
本発明の繊維布帛処理液は以上のように構成され、詳細については後記するが、これを用いることで、繊維布帛を簡易に改質し、繊維布帛の風合いを損なうことなく、良好でしかも耐久性のあるアレルゲン抑制効果及び吸水・吸湿性を安定的に付与することができる。 The fiber fabric treatment liquid of the present invention is configured as described above and will be described in detail later. By using this, the fiber fabric can be easily modified, and it is good and durable without impairing the texture of the fiber fabric. A stable allergen suppressing effect and water absorption / hygroscopicity can be stably imparted.
「アレルゲン抑制繊維布帛」
本発明のアレルゲン抑制繊維布帛は、繊維布帛上で、アレルゲン抑制成分（Ｘ）と、上記一般式（１）で示される２官能性単量体（Ａ）と、水酸基、カルボキシル基、アミノ基、スルホン酸基、リン酸基のうちいずれかの基を含む単量体（Ｂ）と、さらに必要に応じて架橋剤（Ｃ）とを重合させてなることを特徴とする。
各成分の具体例については、上記したので説明を省略する。
"Allergen-suppressing fiber fabric"
The allergen-suppressing fiber fabric of the present invention comprises an allergen-suppressing component (X), a bifunctional monomer (A) represented by the general formula (1), a hydroxyl group, a carboxyl group, an amino group, It is characterized by polymerizing a monomer (B) containing any one of a sulfonic acid group and a phosphoric acid group and, if necessary, a crosslinking agent (C).
Since specific examples of each component have been described above, description thereof will be omitted.
本発明のアレルゲン抑制繊維布帛には、
（i）繊維布帛に、成分（Ｘ）、成分（Ａ）及び（Ｂ）、必要に応じて成分（Ｃ）がグラフト重合されたもの、
（ii）繊維布帛上で、成分（Ｘ）、成分（Ａ）及び（Ｂ）、必要に応じて成分（Ｃ）のホモポリマー及び／又はこれらの複数種が共重合したコポリマーが生成されたもの、
（iii）一部の成分が繊維布帛にグラフト重合し、残りの成分が繊維布帛上でホモポリマーおよび／又はコポリマーを生成したもの等が含まれる。
これらの中でも特に、有効成分が繊維布帛に強固に結合され、耐久性に優れたアレルゲン抑制繊維布帛が得られるため、（i）繊維布帛に、成分（Ｘ）、成分（Ａ）及び（Ｂ）、必要に応じて成分（Ｃ）がグラフト重合されたものが好ましい。
The allergen-suppressing fiber fabric of the present invention includes
(I) Component (X), components (A) and (B), and if necessary, component (C) graft-polymerized on a fiber fabric,
(Ii) Component (X), components (A) and (B), and if necessary, a homopolymer of component (C) and / or a copolymer obtained by copolymerizing a plurality of these on a fiber fabric ,
(Iii) Some components are graft-polymerized onto the fiber fabric, and the remaining components are those in which a homopolymer and / or copolymer is produced on the fiber fabric.
Among these, since the active ingredient is firmly bonded to the fiber fabric and an allergen-suppressing fiber fabric having excellent durability is obtained, the component (X), the components (A) and (B) are added to the (i) fiber fabric. Those obtained by graft polymerization of the component (C) if necessary are preferred.
基材となる繊維布帛の構成繊維としては特に限定されないが、綿、羊毛、絹、麻等の天然繊維や、ナイロン、アクリル、ポリエステル、ポリプロピレン、ポリエチレン、ポリトリメチレンテレフタレート等の合成繊維、あるいはこれらから選択される複数種からなる混紡繊維や複合繊維等が挙げられる。
本発明は、ナイロン等のポリアミド繊維やポリエステル繊維、あるいはこれらの繊維を含む混紡繊維（例えば、ポリエステル／綿混紡繊維等）や複合繊維からなる繊維布帛に対して、特に顕著な効果を奏する。これらの繊維布帛は疎水性が高く、通常の繊維処理では改質が難しく、吸水・吸湿性の付与すら困難であるが、本発明はこれらの繊維布帛に対しても、効果的に吸水・吸湿性を付与し、さらには耐久性のあるアレルゲン抑制効果をも良好に付与することができる。
The constituent fibers of the fiber fabric used as the base material are not particularly limited, but natural fibers such as cotton, wool, silk and hemp, synthetic fibers such as nylon, acrylic, polyester, polypropylene, polyethylene and polytrimethylene terephthalate, or these Examples thereof include mixed fibers and composite fibers composed of a plurality of types selected from the following.
INDUSTRIAL APPLICABILITY The present invention has a particularly remarkable effect on a fiber fabric made of polyamide fiber such as nylon, polyester fiber, blended fiber (for example, polyester / cotton blended fiber) containing these fibers, or composite fiber. These fiber fabrics have high hydrophobicity and are difficult to be modified by ordinary fiber treatment, and it is difficult to impart water absorption and hygroscopicity. However, the present invention also effectively absorbs water and absorbs moisture. It is possible to impart a good allergen-suppressing effect with durability.
繊維布帛の形態も特に限定されず、織物、編物、不織布等が挙げられる。また、精練、染色、抗菌加工、ＳＲ加工、防炎加工、帯電防止加工などが施されたものであっても良い。また、敷物（絨毯等）、カーテン、壁紙、シートカバー、椅子の布張り、寝具（シーツ、カバー、布団側等）、衣類（洋服、寝衣、肌着、帽子、手袋、靴下等）、マスク、空気清浄機のフィルター等の最終製品に加工されたものであっても良いし、加工する前のものであっても良い。 The form of the fiber fabric is not particularly limited, and examples thereof include woven fabrics, knitted fabrics, and nonwoven fabrics. Further, it may be subjected to scouring, dyeing, antibacterial processing, SR processing, flameproofing processing, antistatic processing and the like. Also, rugs (rugs, etc.), curtains, wallpaper, seat covers, chair upholstery, bedding (sheets, covers, futon side, etc.), clothing (clothes, nightclothes, underwear, hats, gloves, socks, etc.), masks, It may be processed into a final product such as a filter of an air purifier or may be processed before processing.
本発明者は、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）が繊維内部に容易に拡散して重合すること、アレルゲン抑制成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）との相性が格段に優れ、これらを合わせて重合することで、繊維布帛の種類等に関係なく、これらの成分を繊維布帛の表面及び内部に良好に導入・定着させることができることを見出している。
アレルゲン抑制成分（Ｘ）を、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）と合わせて重合することで、成分（Ｘ）を繊維布帛の表面及び内部に良好に導入できる理由は必ずしも定かではないが、アルカリｐＨ領域下で、アレルゲン抑制成分（Ｘ）と単量体成分（Ａ）及び（Ｂ）の二重結合部分とが化学的に結合し、重合されやすくなるものと推察される。
The present inventor makes the components (A) and (B) or the components (A) to (C) easily diffuse and polymerize inside the fiber, the allergen-suppressing component (X), the components (A) and ( B) or the compatibility with the components (A) to (C) is remarkably excellent, and these components are superposed on the surface and the inside of the fiber fabric regardless of the type of the fiber fabric by polymerization. It has been found that it can be introduced and established in Japan.
By polymerizing the allergen-suppressing component (X) together with the components (A) and (B) or the components (A) to (C), the component (X) can be satisfactorily introduced into the surface and inside of the fiber fabric. The reason is not necessarily clear, but under the alkaline pH region, the allergen-suppressing component (X) and the double bond portion of the monomer components (A) and (B) are chemically bonded and easily polymerized. It is guessed.
また、繊維布帛の表面のみならず内部へのアレルゲン抑制成分（Ｘ）の導入を実現したことで、繊維布帛の風合いを損なうことなく（いわゆる糊付け状態等を招くことなく）、アレルゲン抑制成分（Ｘ）の付着量を飛躍的に増大することができ、しかも導入した各成分は溶出や脱離し難いため、良好でしかも耐久性（耐繰り返し洗濯性等）のあるアレルゲン抑制効果を安定的に付与できることを見出している。特に、各成分がグラフト重合されたものは、繊維布帛と強固に結合するため、繊維の内部に導入されることと相俟って、より一層高い耐久性が実現できる。 Moreover, by introducing the allergen suppressing component (X) not only on the surface of the fiber fabric but also inside thereof, the allergen suppressing component (X) can be obtained without impairing the texture of the fiber fabric (without causing a so-called gluing state). ) Can be drastically increased, and the introduced components are difficult to elute and desorb, so that allergen suppression effects that are good and durable (such as resistance to repeated washing) can be stably imparted. Is heading. In particular, those obtained by graft polymerization of each component are firmly bonded to the fiber fabric, so that even higher durability can be realized in combination with being introduced into the fiber.
本発明者はまた、単量体成分（Ａ）及び（Ｂ）に加えて、架橋剤（Ｃ）を配合することで、アレルゲン抑制成分（Ｘ）と単量体成分（Ａ）及び（Ｂ）とが架橋剤（Ｃ）を介してより強固に結合された状態で、繊維布帛に導入されるので、より耐久性に優れたアレルゲン抑制繊維布帛が得られることを見出している。 The present inventor also blended the crosslinking agent (C) in addition to the monomer components (A) and (B), so that the allergen-suppressing component (X) and the monomer components (A) and (B) Is introduced into the fiber fabric in a state of being more firmly bonded via the cross-linking agent (C), and therefore, it has been found that an allergen-suppressing fiber fabric having superior durability can be obtained.
上記したように、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）は、アレルゲン抑制成分（Ｘ）の繊維布帛の表面及び内部への導入・定着を促進させる成分であるが、同時に吸水・吸湿性付与効果を与える。
すなわち、成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とが導入された本発明のアレルゲン抑制繊維布帛は、柔軟性やドレープ性等の良好な風合いを確保しつつ、繊維の表面から内部に渡って、耐久性のあるアレルゲン抑制処理及び吸水・吸湿化処理が施されたものである。
As described above, the components (A) and (B) or the components (A) to (C) are components that promote introduction and fixation of the allergen-suppressing component (X) on the surface and inside of the fiber fabric. At the same time, it gives water absorption and hygroscopicity.
That is, the allergen-suppressing fiber fabric of the present invention in which the component (X) and the components (A) and (B) or the components (A) to (C) are introduced has a good texture such as flexibility and drapeability. In this way, durable allergen suppression treatment and water absorption / moisture absorption treatment are performed from the fiber surface to the inside.
本発明のアレルゲン抑制繊維布帛は、繊維布帛に、成分（Ｘ）と、成分（Ａ）及び（Ｂ）、必要に応じて成分（Ｃ）を導入したものであるが、さらに必要に応じて他の成分を導入することは勿論差し支えない。
繊維布帛処理液で挙げた各種添加剤を用いることで、さらなる高機能化を図ることができる。例えば、吸湿性化合物（Ｄ）を付与することで、より高いアレルゲン抑制効果を発現させることができる。また、天然高分子保湿成分（Ｅ）を付与することで、保湿性を向上させることができる。
The allergen-suppressing fiber fabric of the present invention is obtained by introducing the component (X), the components (A) and (B), and the component (C) as necessary into the fiber fabric, but other components may be added as necessary. Of course, it is possible to introduce these components.
Further enhancement of functionality can be achieved by using the various additives mentioned in the fiber fabric treatment liquid. For example, by applying the hygroscopic compound (D), a higher allergen suppressing effect can be exhibited. Moreover, moisture retention can be improved by providing a natural polymer moisture retention component (E).
本発明のアレルゲン抑制繊維布帛は、良好なアレルゲン抑制効果を呈し、風合い、汗等の吸収性に優れ、耐洗濯性等の耐久性にも優れるため、アレルゲンの存在する環境で使用される繊維製品、生活用品、生活資材等、例えば、敷物（絨毯等）、カーテン、壁紙、シートカバー、椅子の布張り、寝具（シーツ、カバー、布団側等）、衣類（洋服、寝衣、肌着、帽子、手袋、靴下等）、マスク、空気清浄機のフィルター等に好適に利用することができる。 The allergen-suppressing fiber fabric of the present invention exhibits a good allergen-suppressing effect, is excellent in absorbability such as texture and sweat, and is excellent in durability such as washing resistance, so that it is used in an environment where allergen is present. , Daily necessities, life materials, etc., for example, rugs (rugs, etc.), curtains, wallpaper, seat covers, chair upholstery, bedding (sheets, covers, futon side, etc.), clothing (clothes, nightclothes, underwear, hats, Gloves, socks, etc.), masks, filters for air purifiers, and the like.
［アレルゲン抑制繊維布帛の製造方法］
次に、上記の本発明のアレルゲン抑制繊維布帛の製造方法について説明する。
（第１の製造方法）
本発明の第１の製造方法は、繊維布帛上で、成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とを同時に重合させることを特徴とする。
すなわち、成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とを含む上記の本発明の繊維布帛処理液（段落［００２４］〜［００４６］参照）を繊維布帛に接触させる接液工程と、繊維布帛上で成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）を重合させる重合工程とを有することを特徴とするものである。
[Method for producing allergen-suppressing fiber fabric]
Next, the manufacturing method of said allergen suppression fiber fabric of this invention is demonstrated.
(First manufacturing method)
The first production method of the present invention is characterized in that the component (X) and the components (A) and (B) or the components (A) to (C) are polymerized simultaneously on the fiber fabric.
That is, the fiber fabric treatment liquid of the present invention containing the component (X) and the components (A) and (B) or the components (A) to (C) (see paragraphs [0024] to [0046]). It comprises a liquid contact step for contacting the fiber fabric, and a polymerization step for polymerizing the component (X) and the components (A) and (B) or the components (A) to (C) on the fiber fabric. To do.
繊維布帛に繊維布帛処理液を接触（接液）させる方法としては特に限定されないが、浸漬処理法やパディング法等が挙げられる。例えば、パディング法では、繊維布帛に繊維布帛処理液を接触させた後、必要に応じて繊維布帛を絞り、繊維布帛処理液の付着量を調整する。さらに、必要に応じて５０〜１３０℃程度で加熱乾燥（乾熱処理）する。なお、乾熱処理だけでは重合反応は進行しにくい。 Although it does not specifically limit as a method of making a textile fabric processing liquid contact (wetted liquid) to a textile fabric, An immersion treatment method, a padding method, etc. are mentioned. For example, in the padding method, the fiber cloth treatment liquid is brought into contact with the fiber cloth, and then the fiber cloth is squeezed as necessary to adjust the amount of the fiber cloth treatment liquid attached. Furthermore, it heat-drys at about 50-130 degreeC (dry heat processing) as needed. It should be noted that the polymerization reaction is unlikely to proceed only by dry heat treatment.
以上の処理を行った後、重合を行う。
成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）との重合は、繊維布帛処理液が付着した繊維布帛に対して、湿熱処理、電子線照射処理、紫外線照射処理、マイクロ波照射処理等の処理を施すことによって行うことができる。湿熱処理を採用する場合には、例えば、水蒸気を満たした９０〜１４０℃程度の雰囲気中にて１〜９０分間程度処理すれば良い。また、電子線照射処理、紫外線照射処理、マイクロ波照射処理を採用する場合には、接液工程の前にあらかじめ電子線、紫外線、マイクロ波を照射しておいても良いし、接液工程の後に照射を行っても良い。また、電子線照射処理、紫外線照射処理、マイクロ波照射処理を採用する場合には、重合反応の際に周囲の雰囲気を窒素等により置換すると、発生したラジカルの消失を防ぎ、重合成分の有効利用率の向上を図ることができるので好ましい。
Polymerization is performed after the above treatment.
Polymerization of component (X) with components (A) and (B), or components (A) to (C) is performed by wet heat treatment, electron beam irradiation treatment on the fiber fabric to which the fiber fabric treatment liquid is attached. It can be performed by performing a process such as an ultraviolet irradiation process or a microwave irradiation process. When the wet heat treatment is employed, for example, the treatment may be performed for about 1 to 90 minutes in an atmosphere of about 90 to 140 ° C. filled with water vapor. In addition, when an electron beam irradiation process, an ultraviolet irradiation process, or a microwave irradiation process is adopted, an electron beam, an ultraviolet ray, or a microwave may be irradiated in advance before the liquid contact process. Irradiation may be performed later. In addition, when employing electron beam irradiation treatment, ultraviolet irradiation treatment, or microwave irradiation treatment, replacing the surrounding atmosphere with nitrogen or the like during the polymerization reaction prevents the disappearance of the generated radicals and effectively uses the polymerization components. It is preferable because the rate can be improved.
本発明では、この工程において、繊維の表面のみならず、繊維の内部でも重合反応が進行する。なお、本発明の製造方法では、
（i）繊維布帛に、成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とがグラフト重合される場合、
（ii）繊維布帛上で、成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）のホモポリマー及び／又はこれらの複数種が共重合したコポリマーが生成される場合、
（iii）一部の成分が繊維布帛にグラフト重合し、残りの成分が繊維布帛上でホモポリマー及び／又はコポリマーを生成する場合等が含まれる。
但し、（i）の繊維布帛に、成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とをグラフト重合することが特に好ましい。
In the present invention, in this step, the polymerization reaction proceeds not only on the surface of the fiber but also inside the fiber. In the production method of the present invention,
(I) When the component (X) and the components (A) and (B) or the components (A) to (C) are graft-polymerized to the fiber fabric,
(Ii) On the fiber fabric, component (X) and components (A) and (B), or homopolymers of components (A) to (C) and / or copolymers obtained by copolymerizing a plurality of these are produced. If
(Iii) The case where a part of the component is graft-polymerized on the fiber fabric and the remaining component forms a homopolymer and / or copolymer on the fiber fabric is included.
However, it is particularly preferable to graft-polymerize the component (X) and the components (A) and (B) or the components (A) to (C) to the fiber fabric of (i).
重合反応終了後、繊維布帛に付着している未反応化合物を除去するため、洗浄を行うことが好ましい。
また、本発明の製造方法では、接液工程の前、あるいは重合工程の後に、繊維布帛に対して公知の抗菌剤、ＳＲ剤、防炎剤、帯電防止剤等を付与することも可能である。
After completion of the polymerization reaction, washing is preferably performed to remove unreacted compounds adhering to the fiber fabric.
In the production method of the present invention, a known antibacterial agent, SR agent, flameproofing agent, antistatic agent, etc. can be applied to the fiber fabric before the liquid contact step or after the polymerization step. .
（第２の製造方法）
本発明の第２の製造方法は、成分（Ａ）及び成分（Ｂ）を含む繊維布帛処理液（Ｙ１）、若しくは成分（Ａ）〜（Ｃ）を含む繊維布帛処理液（Ｙ２）を繊維布帛に接触させる第１の接液工程と、繊維布帛上で、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）を重合させる第１の重合工程と、繊維布帛に、成分（Ｘ）を含むアルカリ性水性溶液である繊維布帛処理液（Ｚ）を接触させる第２の接液工程と、繊維布帛上で、成分（Ｘ）を重合させる第２の重合工程とを有することを特徴とする。
(Second manufacturing method)
In the second production method of the present invention, the fiber fabric treatment liquid (Y1) containing the component (A) and the component (B) or the fiber fabric treatment liquid (Y2) containing the components (A) to (C) is used as the fiber fabric. A first liquid contact step for contacting the fiber fabric, a first polymerization step for polymerizing the components (A) and (B) or the components (A) to (C) on the fiber fabric, and a component ( A second wetting step for contacting the fiber fabric treatment liquid (Z), which is an alkaline aqueous solution containing X), and a second polymerization step for polymerizing the component (X) on the fiber fabric. And
本発明の第２の製造方法において、第１の重合工程と第２の重合工程とは同時に実施することが好ましい。この場合には、製造工程を簡略化できるだけでなく、アレルゲン抑制成分（Ｘ）の導入促進が図られるため、好適である。 In the second production method of the present invention, it is preferable that the first polymerization step and the second polymerization step are performed simultaneously. In this case, not only the production process can be simplified, but also the allergen-suppressing component (X) can be promoted to be introduced, which is preferable.
繊維布帛処理液（Ｚ）は、上記の本発明の繊維布帛処理液（段落［００２４］〜［００４６］参照）から、成分（Ａ）〜（Ｃ）を除いたものである（段落［００４５］参照）。繊維布帛処理液（Ｙ１）、（Ｙ２）、及び（Ｚ）に用いる溶媒は、本発明の繊維布帛処理液と同様のものを用いることができる。各液の調製方法、接液方法、重合方法は、上記の第１の製造方法と同様である。 The fiber fabric treatment liquid (Z) is obtained by removing the components (A) to (C) from the above-described fiber fabric treatment liquid of the present invention (see paragraphs [0024] to [0046]) (paragraph [0045]). reference). As the solvent used for the fiber fabric treatment liquid (Y1), (Y2), and (Z), the same solvent as the fiber fabric treatment liquid of the present invention can be used. The preparation method, the liquid contact method, and the polymerization method of each solution are the same as those in the first manufacturing method.
本発明の第１、第２の製造方法によれば、良好なアレルゲン抑制効果を呈し、風合い、吸水・吸湿性に優れ、耐久性（耐洗濯性等）にも優れる本発明のアレルゲン抑制繊維布帛を簡易に製造することができる。
特に、繊維布帛上で、成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とを同時に接液・重合させる第１の製造方法は、成分（Ｘ）の重合促進効果が高く、アレルゲン抑制効果、吸水・吸湿性、耐久性により優れたアレルゲン抑制繊維布帛を製造することができる。また、工程数が少ない点からも、第１の製造方法は好適である。
According to the first and second production methods of the present invention, the allergen-suppressing fiber fabric of the present invention exhibits a good allergen-suppressing effect, is excellent in texture, water absorption / hygroscopicity, and is excellent in durability (washing resistance, etc.). Can be easily manufactured.
In particular, the first production method in which the component (X) and the components (A) and (B) or the components (A) to (C) are simultaneously wetted and polymerized on the fiber fabric is the component (X). It is possible to produce an allergen-suppressing fiber fabric that has a high polymerization promoting effect and is superior in allergen suppressing effect, water absorption / hygroscopicity, and durability. In addition, the first manufacturing method is preferable from the viewpoint that the number of steps is small.
次に、本発明に係る実施例および比較例について説明する。各例においてアレルゲン抑制繊維布帛を含む改質繊維布帛を作製し、評価を行った。 Next, examples and comparative examples according to the present invention will be described. In each example, a modified fiber fabric including an allergen-suppressing fiber fabric was prepared and evaluated.
（評価項目および評価方法）
＜アレルゲン抑制効果＞
各例において作製した改質繊維布帛を３３ｃｍ×３０ｃｍに裁断し、評価布片とした。また、エチルアルコール５０質量％水溶液１００質量部に対して、ダニアレルゲンを２ｍｇ／ｇ含む塵ゴミ５質量部を分散させたアレルゲン分散液を調製した。先の評価布片全体に、調製したアレルゲン分散液１ｍｌを均一に振り撒いたものを評価に供した。
［評価（１）］
上記処理を行った評価布片を室温下で８時間静置した後、アレルゲン判定キット「ダニスキャン」（アサヒフードアンドヘルスケア社製）を用いてアレルゲン性を測定した。「ダニスキャン」の使用説明書に基づき、下記基準にて判定した。
１：ダニアレルゲンの汚染はない（テストラインＴ＝０）
２：ややダニアレルゲンで汚染されている（Ｔ＜Ｃコントロールライン）
３：ダニアレルゲンで汚染されている（Ｔ＝Ｃ）
４：ダニアレルゲンで非常に汚染されている（Ｔ＞Ｃ）
［評価（２）］
上記処理を行った評価布片を室温下で２時間静置した後、「マイティーチェッカー」（シントーファイン社製）を用いて、アレルゲン成分を抽出し、アレルゲン量を測定した。判定基準は以下の通りとした。
＋＋：ダニアレルゲン量が３５μｇ／ｍ２超
＋ ：ダニアレルゲン量が１０μｇ／ｍ２超３５μｇ／ｍ２以下
± ：ダニアレルゲン量が５μｇ／ｍ２超１０μｇ／ｍ２以下
− ：ダニアレルゲン量が１μｇ／ｍ２以下
(Evaluation items and evaluation methods)
<Allergen suppression effect>
The modified fiber fabric produced in each example was cut into a size of 33 cm × 30 cm to obtain an evaluation fabric piece. Moreover, the allergen dispersion liquid which disperse | distributed 5 mass parts of dust containing 2 mg / g of mite allergens with respect to 100 mass parts of 50 mass% ethyl alcohol aqueous solution was prepared. An evaluation was made by uniformly sprinkling 1 ml of the prepared allergen dispersion on the whole evaluation cloth.
[Evaluation (1)]
The evaluation cloth piece subjected to the above treatment was allowed to stand at room temperature for 8 hours, and then allergenicity was measured using an allergen determination kit “Daniscan” (manufactured by Asahi Food and Healthcare). Based on the instruction manual of “tick scan”, the following criteria were used.
1: No mite allergen contamination (test line T = 0)
2: Slightly contaminated with mite allergen (T <C control line)
3: Contaminated with mite allergen (T = C)
4: Very polluted with mite allergens (T> C)
[Evaluation (2)]
After the evaluation cloth piece subjected to the above treatment was allowed to stand at room temperature for 2 hours, an allergen component was extracted using “Mighty Checker” (manufactured by Shinto Fine), and the amount of allergen was measured. The judgment criteria were as follows.
++: amount mite allergen 35 [mu] g / m 2 greater than +: amount mite allergen 10 [mu] g / m 2 Ultra 35 [mu] g / m 2 or less ±: mite allergen amount 5 [mu] g / m 2 Ultra 10 [mu] g / m 2 or less -: amount mite allergen 1μg / M 2 or less
＜吸湿性＞
下記関係式により吸湿率Ｈを求めた。
Ｈ＝｛（Ｈ１−Ｈ０）／Ｈ０｝×１００（％）
ここで、Ｈ０は絶乾質量であり、評価繊維布帛を１２０℃で３時間乾燥した後の質量である。Ｈ１は吸湿質量であり、上記乾燥処理後に、温湿度雰囲気下に２４時間静置して調湿した後の質量である。温湿度雰囲気としては、衣服内気候に相当する３０℃、９０％ＲＨと、外気に相当する２０℃、６５％ＲＨとの２種類に設定した。
＜吸水性＞
ＪＩＳ Ｌ １０９６ ６−２６−１ Ａ法（滴下法）に準拠して測定した。
<Hygroscopicity>
The moisture absorption H was determined from the following relational expression.
H = {(H1−H0) / H0} × 100 (%)
Here, H0 is the absolutely dry mass, and is the mass after the evaluation fiber fabric is dried at 120 ° C. for 3 hours. H1 is a hygroscopic mass, and is the mass after adjusting the humidity by leaving it in a temperature and humidity atmosphere for 24 hours after the drying treatment. The temperature and humidity atmosphere was set to two types of 30 ° C. and 90% RH corresponding to the climate in clothes and 20 ° C. and 65% RH corresponding to the outside air.
<Water absorption>
It measured based on JIS L1096 6-26-1 A method (drop method).
＜耐久性＞
上記のアレルゲン抑制効果（評価（１）及び（２））、吸湿性・吸水性評価を、それぞれ、初期（洗濯前）と２０回洗濯後の計２回行い、耐久性を評価した。洗濯は、洗濯試験ＪＩＳ Ｌ−０２１７ １０３法に基づいて以下のようにして行った。
試験装置の水槽の標準水量を示す水位線まで液温４０℃の水を入れ、これに標準使用量となる割合で洗濯用合成洗剤を添加して溶解し、洗濯液とする。この洗濯液に浴比が、１対３０になるように評価繊維布帛を投入して運転を開始する。５分間洗浄処理した後、運転を止め、評価繊維布帛を脱水機で脱水し、次に洗濯液を３０℃以下の新しい水に替えて、同一の浴比で２分間すすぎ洗いを行う。２分間のすすぎ洗いを行った後、運転を止め、評価繊維布帛を脱水し、再び２分間すすぎ洗いを行い、脱水し、直接日光の影響を受けない状態でつり干し又は平干しする。その後、必要に応じて素材繊維の適正温度でドライアイロン仕上げを行う。
<Durability>
The above-mentioned allergen inhibitory effect (evaluations (1) and (2)) and hygroscopicity / water absorption evaluation were performed twice in total (after washing (before washing) and after 20 washings) to evaluate durability. Washing was performed as follows based on the laundry test JIS L-0217 103 method.
Water with a liquid temperature of 40 ° C. is added to the water level line indicating the standard water amount of the water tank of the test apparatus, and a synthetic detergent for washing is added and dissolved at a ratio of standard use amount to obtain a washing liquid. The evaluation fiber fabric is added to the washing liquid so that the bath ratio is 1:30, and the operation is started. After 5 minutes of washing treatment, the operation is stopped, the evaluation fiber fabric is dehydrated with a dehydrator, and then the washing liquid is replaced with fresh water of 30 ° C. or less, and rinsed at the same bath ratio for 2 minutes. After rinsing for 2 minutes, the operation is stopped, the evaluation fiber fabric is dehydrated, rinsed again for 2 minutes, dehydrated, and suspended or laid flat without being directly affected by sunlight. Then, if necessary, dry iron finish is performed at an appropriate temperature of the material fiber.
（実施例１）
生地質量が１１０ｇ／ｍ２のポリエステル仮撚加工糸を用いたポンジ織物に対して、常法にてリラックス、精練、プレセット、アルカリ減量加工、染色を順次行った。この繊維布帛を基材として用い、改質処理を行った。
表１に示す組成の本発明の繊維布帛処理液を調製し、これをパディング法にて繊維布帛に付与した。絞り率は６０質量％とした。その後、１１０℃９８％ＲＨのスチームで５分間処理する湿熱処理を施し、重合を行った。重合反応終了後、洗浄、仕上げセットを行い、本発明のアレルゲン抑制繊維布帛を得た。
なお、成分（Ｘ）含有液であるポリ−４−ビニルフェノールアルカリ性水溶液としては、ポリ−４−ビニルフェノール（アルドリッチ社製、質量平均分子量８０００）３０質量％を含み、アルカリ剤として８Ｎ水酸化ナトリム水溶液を用いてｐＨを１４超とした調製液を用いた。
(Example 1)
Relaxing, scouring, pre-setting, alkali weight reduction processing, and dyeing were sequentially performed on a Ponji fabric using a polyester false twisted yarn having a fabric mass of 110 g / m 2 in the usual manner. Using this fiber fabric as a base material, a modification treatment was performed.
A fiber fabric treatment solution of the present invention having the composition shown in Table 1 was prepared and applied to the fiber fabric by a padding method. The drawing rate was 60% by mass. Thereafter, a wet heat treatment was performed for 5 minutes with steam at 110 ° C. and 98% RH to perform polymerization. After completion of the polymerization reaction, washing and finishing set were performed to obtain an allergen-suppressing fiber fabric of the present invention.
In addition, as poly-4-vinylphenol alkaline aqueous solution which is a component (X) containing liquid, poly-4-vinylphenol (the Aldrich company make, mass average molecular weight 8000) 30 mass% is included, and 8N sodium hydroxide is used as an alkaline agent. A prepared solution with an aqueous solution having a pH of more than 14 was used.
（比較例１）
実施例１と同じポリエステルポンジ織物を用い、常法にてリラックス、精練、プレセット、アルカリ減量加工、染色、仕上げセットを順次行い、ポリエステル１００％のタフタ織物を得た。この繊維布帛を基材として用い、改質処理を行った。
表２に示す組成の繊維布帛処理液を調製し、これをパディング法にて繊維布帛に付与した。絞り率は６０質量％とした。その後、１１０℃９８％ＲＨのスチームで５分間処理する湿熱処理を施し、重合を行った。重合反応終了後、洗浄、仕上げセットを行い、比較用の改質繊維布帛を得た。
なお、比較用のアレルゲン抑制成分含有液であるポリ−４−ビニルフェノール水分散液としては、ポリ−４−ビニルフェノール（アルドリッチ社製、質量平均分子量８０００）１０質量％、エチレングリコール（和光純薬社製）３０質量％、乳化剤（第一工業製薬社製「ノイゲンＥＡ８７」）１０質量％を含む調製液を用いた。この液のｐＨは６であった。
(Comparative Example 1)
Using the same polyester pond fabric as in Example 1, relaxation, scouring, pre-setting, alkali weight loss processing, dyeing, and finishing set were sequentially performed by a conventional method to obtain a 100% polyester taffeta woven fabric. Using this fiber fabric as a base material, a modification treatment was performed.
A fiber fabric treatment solution having the composition shown in Table 2 was prepared and applied to the fiber fabric by a padding method. The drawing rate was 60% by mass. Thereafter, a wet heat treatment was performed for 5 minutes with steam at 110 ° C. and 98% RH to perform polymerization. After completion of the polymerization reaction, washing and finishing set were performed to obtain a modified fiber fabric for comparison.
In addition, as a poly-4-vinylphenol aqueous dispersion which is a comparative allergen inhibitor component-containing liquid, poly-4-vinylphenol (manufactured by Aldrich, mass average molecular weight 8000) 10% by mass, ethylene glycol (Wako Pure Chemical Industries, Ltd.) A preparation solution containing 30% by mass and 10% by mass of an emulsifier (Daiichi Kogyo Seiyaku "Neugen EA87") was used. The pH of this solution was 6.
（実施例２）
表３に示す組成の本発明の繊維布帛処理液を調製した以外は実施例１と同様にして、本発明のアレルゲン抑制繊維布帛を得た。
An allergen-suppressing fiber fabric of the present invention was obtained in the same manner as in Example 1 except that the fiber fabric treatment liquid of the present invention having the composition shown in Table 3 was prepared.
（比較例２）
表４に示す組成の繊維布帛処理液を調製した以外は実施例１と同様にして、比較用の改質繊維布帛を得た。
A modified fiber fabric for comparison was obtained in the same manner as in Example 1 except that a fiber fabric treatment solution having the composition shown in Table 4 was prepared.
（比較例３）
表５に示す組成の繊維布帛処理液を調製した以外は実施例１と同様にして、比較用の改質繊維布帛を得た。
A modified fiber fabric for comparison was obtained in the same manner as in Example 1 except that a fiber fabric treatment solution having the composition shown in Table 5 was prepared.
（実施例１、２および比較例１〜３の評価結果）
評価結果を表６、７に示す。
繊維布帛上で、アレルゲン抑制成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とを重合して改質した実施例１、２では、表に示すように、得られた改質繊維布帛にはアレルゲン抑制成分（Ｘ）が導入されており、初期において良好なアレルゲン抑制効果を呈することが確認された。また、２０回洗濯後もアレルゲン抑制効果の低下はほとんどなく、アレルゲン抑制成分（Ｘ）が脱離し難い状態で定着していることが確認された。これはアレルゲン抑制成分（Ｘ）が繊維の表面のみならず内部にも導入されたためである。得られた改質繊維布帛は、柔軟性やドレープ性等の風合いも良好であった。さらに、この繊維布帛は、初期および２０回洗濯後の双方において、高い吸水・吸湿性を示した。このように、実施例１、２で得られた改質繊維布帛は、初期および２０回洗濯後の双方において、大きな特性変化はなく、耐久性にも優れるものであった。
架橋剤（Ｃ）を用いて重合を行った実施例１では、吸水・吸湿性、耐久性の点で、特に良好な結果が得られた。
(Evaluation results of Examples 1 and 2 and Comparative Examples 1 to 3)
The evaluation results are shown in Tables 6 and 7.
In Examples 1 and 2 in which allergen-suppressing component (X) and components (A) and (B) or components (A) to (C) were polymerized and modified on the fiber fabric, as shown in the table In addition, it was confirmed that the allergen-suppressing component (X) was introduced into the resulting modified fiber fabric and exhibited a good allergen-suppressing effect in the initial stage. Moreover, even after 20 washings, the allergen inhibitory effect was hardly reduced, and it was confirmed that the allergen inhibitory component (X) was firmly fixed. This is because the allergen suppressing component (X) was introduced not only into the fiber surface but also into the interior. The resulting modified fiber fabric had good texture such as flexibility and drapeability. Furthermore, this fiber fabric exhibited high water absorption and hygroscopicity both in the initial stage and after 20 washes. As described above, the modified fiber fabrics obtained in Examples 1 and 2 did not change significantly in both the initial stage and after the 20th washing, and were excellent in durability.
In Example 1 in which polymerization was performed using the crosslinking agent (C), particularly good results were obtained in terms of water absorption / hygroscopicity and durability.
これに対して、アレルゲン抑制成分の水分散液を用い、繊維布帛処理液を中性とした比較例１、繊維布帛上でアレルゲン抑制成分（Ｘ）のみを重合しようとした比較例２、３では、得られた改質繊維布帛はいずれも、アレルゲン抑制効果、吸水・吸湿性、耐久性が実施例１、２に比して劣るものであった。これら比較例では、アレルゲン抑制成分が繊維の表面にのみ導入され、内部への重合が十分に行われていないものと思われる。また、比較例２、３では吸水・吸湿性が著しく不良であった。 In contrast, in Comparative Example 1 in which the aqueous dispersion of the allergen-suppressing component was used and the fiber fabric treatment solution was neutral, and in Comparative Examples 2 and 3 in which only the allergen-suppressing component (X) was polymerized on the fiber fabric, Each of the obtained modified fiber fabrics was inferior to Examples 1 and 2 in allergen suppressing effect, water absorption / hygroscopicity, and durability. In these comparative examples, it is considered that the allergen-suppressing component is introduced only on the surface of the fiber, and the internal polymerization is not sufficiently performed. In Comparative Examples 2 and 3, the water absorption and hygroscopicity were extremely poor.
（実施例３）
生地質量が１００ｇ／ｍ２のナイロンタフタに対して、常法にて精練、プレセット、染色を順次行った。この繊維布帛を基材として用い、改質処理を行った。
表８に示す組成の本発明の繊維布帛処理液を調製し、パディング法にて繊維布帛に付与した。絞り率は５０質量％とした。その後、１０５℃９８％ＲＨのスチームで５分間処理する湿熱処理を施し、重合を行った。重合反応終了後、洗浄、乾燥、仕上げセットを行い、本発明のアレルゲン抑制繊維布帛を得た。
(Example 3)
Nylon taffeta with a dough mass of 100 g / m 2 was successively subjected to scouring, presetting and dyeing in the usual manner. Using this fiber fabric as a base material, a modification treatment was performed.
A fiber fabric treatment liquid of the present invention having the composition shown in Table 8 was prepared and applied to the fiber fabric by a padding method. The drawing rate was 50% by mass. Thereafter, a wet heat treatment was performed for 5 minutes with steam at 105 ° C. and 98% RH to carry out polymerization. After completion of the polymerization reaction, washing, drying and finishing set were performed to obtain an allergen-suppressing fiber fabric of the present invention.
（比較例４）
実施例３と同じナイロンタフタを用い、常法にて精練、プレセット、染色、乾燥、仕上げセットを順次行い、ナイロン１００％のタフタ織物を得た。この繊維布帛を基材として用い、改質処理を行った。
表９に示す組成の繊維布帛処理液を調製し、パディング法にて繊維布帛に付与した。絞り率は５０質量％とした。その後、１０５℃９８％ＲＨのスチームで５分間処理する湿熱処理を施し、重合を行った。重合反応終了後、洗浄、乾燥、仕上げセットを行い、比較用の改質繊維布帛を得た。
なお、比較用のアレルゲン抑制成分含有液であるタンニン酸水溶液としては、タンニン酸（和光純薬社製）１０質量％を含む調製液を用いた。この液のｐＨは３であった。
(Comparative Example 4)
Using the same nylon taffeta as in Example 3, scouring, pre-setting, dyeing, drying, and finishing set were sequentially performed by a conventional method to obtain a 100% nylon taffeta fabric. Using this fiber fabric as a base material, a modification treatment was performed.
A fiber fabric treatment solution having the composition shown in Table 9 was prepared and applied to the fiber fabric by a padding method. The drawing rate was 50% by mass. Thereafter, a wet heat treatment was performed for 5 minutes with steam at 105 ° C. and 98% RH to carry out polymerization. After completion of the polymerization reaction, washing, drying, and finishing set were performed to obtain a modified fiber fabric for comparison.
In addition, as a tannic acid aqueous solution which is a comparative allergen inhibitor component-containing liquid, a preparation liquid containing 10% by mass of tannic acid (manufactured by Wako Pure Chemical Industries, Ltd.) was used. The pH of this solution was 3.
（比較例５）
表１０に示す組成の繊維布帛処理液を調製した以外は実施例３と同様にして、比較用の改質繊維布帛を得た。
なお、比較用のアレルゲン抑制成分含有液であるカテキン水溶液としては、三井農林社製「サンカテキン」（カテキン含有量１０質量％）を用いた。この液のｐＨは６であった。
A modified fiber fabric for comparison was obtained in the same manner as in Example 3 except that a fiber fabric treatment solution having the composition shown in Table 10 was prepared.
In addition, as a catechin aqueous solution that is a comparative allergen-suppressing component-containing solution, “Sun catechin” (catechin content: 10 mass%) manufactured by Mitsui Norinsha Co., Ltd. was used. The pH of this solution was 6.
（実施例３および比較例４、５の評価結果）
評価結果を表１１、１２に示す。
繊維布帛上で、アレルゲン抑制成分（Ｘ）および成分（Ａ）〜（Ｃ）を重合した実施例３では、実施例１と同様、得られた改質繊維布帛は、成分（Ｘ）が脱離し難い状態で定着しており、風合いが良好であり、初期および２０回洗濯後の双方において、良好なアレルゲン抑制効果および高い吸水・吸湿性を示し、耐久性に優れるものであった。
これに対して、アレルゲン抑制成分として、タンニン酸又はカテキンを用い、繊維布帛処理液を中性又は酸性とした比較例４、５では、得られた改質繊維布帛は、アレルゲン抑制効果、吸水・吸湿性、耐久性が、実施例３に比して劣るものであった。
(Evaluation results of Example 3 and Comparative Examples 4 and 5)
The evaluation results are shown in Tables 11 and 12.
In Example 3, in which the allergen-suppressing component (X) and the components (A) to (C) were polymerized on the fiber fabric, the component (X) was released from the resulting modified fiber fabric, as in Example 1. It was fixed in a difficult state, had a good texture, showed a good allergen suppressing effect and high water absorption / hygroscopicity both in the initial stage and after 20 washes, and was excellent in durability.
On the other hand, in Comparative Examples 4 and 5 in which tannic acid or catechin was used as the allergen suppressing component and the fiber fabric treatment liquid was neutral or acidic, the obtained modified fiber fabric had an allergen suppressing effect, water absorption / The hygroscopicity and durability were inferior to those of Example 3.
なお、以上の例ではダニアレルゲンについてのみ評価を行っているが、本発明者は、本発明の改質技術が、花粉アレルゲン等の他のアレルゲンに対しても同様の効果を呈することを確認している。 In the above example, only the mite allergen is evaluated, but the present inventor has confirmed that the modification technique of the present invention exhibits the same effect on other allergens such as pollen allergens. ing.
本発明の繊維布帛改質技術は、アレルゲンの存在する環境で使用される繊維製品、生活用品、生活資材等、例えば、敷物（絨毯等）、カーテン、壁紙、シートカバー、椅子の布張り、寝具（シーツ、カバー、布団側等）、衣類（洋服、寝衣、肌着、帽子、手袋、靴下等）、マスク、空気清浄機のフィルター等に好ましく適用することができる。 The fiber fabric modification technology of the present invention is used in textile products, daily necessities, living materials, etc. used in an environment where allergens exist, such as rugs (rugs, etc.), curtains, wallpaper, seat covers, chair upholstery, bedding (Sheets, covers, futon sides, etc.), clothing (clothes, nightclothes, underwear, hats, gloves, socks, etc.), masks, filters for air purifiers, and the like.
Claims (10)
下記一般式（１）で示される２官能性単量体（Ａ）と、
水酸基、カルボキシル基、アミノ基、スルホン酸基、リン酸基のうちいずれかの基を含む単量体（Ｂ）とを含み、
前記アレルゲン抑制成分（Ｘ）としてポリビニルフェノールを含み、
さらに溶媒として水及び／又は水性有機溶剤を含むｐＨ１２以上のアルカリ性水性溶液であることを特徴とする繊維布帛処理液。
A bifunctional monomer (A) represented by the following general formula (1);
A monomer (B) containing any one of a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, and a phosphoric acid group,
Polyvinylphenol is included as the allergen suppressing component (X),
Furthermore, it is an alkaline aqueous solution having a pH of 12 or more containing water and / or an aqueous organic solvent as a solvent.
繊維布帛上で、アレルゲン抑制成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とを重合させる重合工程とを有することを特徴とするアレルゲン抑制繊維布帛の製造方法。 A liquid contact step of bringing the fiber fabric treatment liquid according to any one of claims 1 to 4 into contact with the fiber fabric;
What is claimed is: 1. An allergen-suppressing fiber fabric comprising an allergen-suppressing component (X) and a polymerization step for polymerizing components (A) and (B) or components (A) to (C) on a fiber fabric. Production method.
繊維布帛に、アレルゲン抑制成分（Ｘ）と、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）とをグラフト重合させることを特徴とする請求項５に記載のアレルゲン抑制繊維布帛の製造方法。 In the polymerization step,
The fiber fabric, the allergen suppression component (X), component (A) and (B), or allergen-suppression fiber fabric according to claim 5, components (A) ~ a (C), characterized in that graft polymerization Manufacturing method.
又は、成分（Ａ）と（Ｂ）に加えて、さらに少なくとも１個のアジリジン基を含む単量体、及びポリカルボジイミド基、ポリエチレンイミン基、オキサゾリン基のうちいずれかの基を含む水溶性ポリマーから選択される架橋剤（Ｃ）を含み、溶媒として水及び／又は水性有機溶剤を含む繊維布帛処理液（Ｙ２）を繊維布帛に接触させる第１の接液工程と、
繊維布帛上で、成分（Ａ）及び（Ｂ）、若しくは成分（Ａ）〜（Ｃ）を重合させる第１の重合工程と、
繊維布帛に、少なくともアルカリｐＨ領域で水溶性を呈するアレルゲン抑制成分（Ｘ）を含み、前記アレルゲン抑制成分（Ｘ）としてポリビニルフェノールを含み、溶媒として水及び／又は水性有機溶剤を含むｐＨ１２以上のアルカリ性水性溶液である繊維布帛処理液（Ｚ）を接触させる第２の接液工程と、
繊維布帛上で、アレルゲン抑制成分（Ｘ）を重合させる第２の重合工程とを有することを特徴とするアレルゲン抑制繊維布帛の製造方法。
Alternatively, in addition to the components (A) and (B), a monomer further containing at least one aziridine group, and a water-soluble polymer containing any one of a polycarbodiimide group, a polyethyleneimine group, and an oxazoline group look containing a crosslinking agent (C) is selected, a first wetted process water and / or the fiber fabric treatment liquid containing an aqueous organic solvent (Y2) is contacted with fiber fabric as a solvent,
A first polymerization step of polymerizing components (A) and (B) or components (A) to (C) on a fiber fabric;
A fiber fabric, at least an alkaline pH region seen containing an allergen suppression component (X) which exhibits a water solubility at the allergen suppression components as (X) comprises a polyvinyl phenol, the above pH12 containing water and / or aqueous organic solvent as the solvent A second liquid contact step in which the fiber fabric treatment liquid (Z), which is an alkaline aqueous solution, is contacted;
A method for producing an allergen-suppressing fiber fabric, comprising: a second polymerization step for polymerizing the allergen-suppressing component (X) on the fiber fabric.
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