JP2000178881A - Processing of cellulosic cloth - Google Patents
Processing of cellulosic clothInfo
- Publication number
- JP2000178881A JP2000178881A JP35572098A JP35572098A JP2000178881A JP 2000178881 A JP2000178881 A JP 2000178881A JP 35572098 A JP35572098 A JP 35572098A JP 35572098 A JP35572098 A JP 35572098A JP 2000178881 A JP2000178881 A JP 2000178881A
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- Prior art keywords
- water
- soluble substance
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- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明はセルロース系布帛に
形態安定性を付与する樹脂加工法の改良に関し、布帛に
形態安定性を具備させる以外に布帛の引裂強力を維持さ
せるとともに、吸湿性を向上させて、むれ感や静電気の
発生といった不快感を減少させ、さらには湿潤発熱性に
よる保温効果を具備させるセルロース系布帛の加工法で
あり、その加工処理品は、肌着，シャツ等の衣料分野で
好適に利用される、セルロース系布帛の加工法を提供す
るものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improvement in a resin processing method for imparting morphological stability to a cellulosic fabric, and in addition to providing the fabric with morphological stability, maintaining the tear strength of the fabric and improving the hygroscopicity. It is a method of processing cellulosic fabrics that reduces discomfort such as unevenness and generation of static electricity, and furthermore has a heat retaining effect due to wet heat generation. The processed products are used in the field of clothing such as underwear and shirts. It is an object of the present invention to provide a method for processing a cellulosic fabric, which is suitably used.
【０００２】[0002]
【従来の技術】綿やレーヨンのようなセルロース系繊維
製品は皺になりやすく、洗濯により収縮する欠点があ
り、それを改善し、さらには繊維製品のウォッシュ＆ウ
ェア性（以下Ｗ＆Ｗ性という）を向上させるために、従
来よりグリオキザール樹脂加工，エチレン−尿素樹脂加
工，尿素−ホルマリン樹脂加工等の反応性モノマーを用
いた樹脂加工が行なわれ、その改良が計られている。2. Description of the Related Art Cellulosic fiber products such as cotton and rayon tend to wrinkle and shrink due to washing. This is improved and the wash and wear properties (hereinafter referred to as W & W properties) of the fiber products are improved. Conventionally, resin processing using a reactive monomer such as glyoxal resin processing, ethylene-urea resin processing, urea-formalin resin processing, and the like have been performed, and the improvement has been attempted.
【０００３】しかしながら、これらの樹脂加工をセルロ
ース系繊維に施すことによって、セルロースの水酸基が
疎水性の樹脂によって封鎖され、親水性が減少する結果
となり、セルロースが本来持っている吸湿性が損なわれ
る欠点があった。それとともに疎水性汚れに対する防汚
性が低下したり、また、帯電性が増加するといった欠点
も生じていた。[0003] However, when these resin treatments are applied to cellulosic fibers, the hydroxyl groups of the cellulose are blocked by the hydrophobic resin, resulting in a decrease in the hydrophilicity, thereby impairing the inherent hygroscopicity of the cellulose. was there. At the same time, there have been disadvantages such as a decrease in antifouling property against hydrophobic stains and an increase in charging property.
【０００４】また、樹脂加工による布帛の親水性の低下
は、布帛の吸放湿性を低下させ、布帛を構成する繊維が
水分の吸着により発熱し、水分の放出により吸熱するこ
とによる身体保護機能の減少にもつながっている。この
親水性の減少を補うために、各種処理剤の使用等が試み
られているが、耐洗濯性の面から根本的な解決には至っ
ていないのが現状である。[0004] In addition, the decrease in hydrophilicity of the fabric due to the resin processing lowers the moisture absorption and desorption properties of the fabric, and the fibers constituting the fabric generate heat due to the adsorption of moisture, and absorb heat due to the release of moisture, thereby exerting a function of protecting the body. This has led to a decrease. In order to compensate for the decrease in hydrophilicity, use of various treatment agents has been attempted, but the present situation has not reached a fundamental solution from the viewpoint of washing resistance.
【０００５】更に、このような樹脂加工によりセルロー
ス系布帛の引裂強力が低下するので、これを補うために
布帛中にポリエステル等の合成繊維を混紡した糸を用い
ることが行われているが、この場合にも布帛の親水性の
低下は明らかであり、上記した欠点が残されたままであ
る。Further, since the tear strength of a cellulosic fabric decreases due to such resin processing, a yarn obtained by blending a synthetic fiber such as polyester into the fabric is used to compensate for this. Even in this case, the decrease in the hydrophilicity of the fabric is evident, and the above-mentioned drawbacks remain.
【０００６】樹脂加工時に第三成分を添加する加工法に
ついては、特開平４−１５３３６９号公報に、アミノ系
樹脂と多価アルコールと酸性触媒とで処理する加工法に
より、高度の防皺効果に加えて、強度低下が少なく、遊
離ホルムアルデヒドの発生量も少なくできることが開示
されてるいるが、水酸基のみを多数有する多価アルコー
ルのみの添加では湿潤発熱性が弱く、十分な保温効果を
得ることはできない。また、特開平４−５７９７２号公
報には、Ｎ−メチロール系樹脂等の架橋剤とリン酸アミ
ド系化合物の併用により、セルロース繊維に防縮性能を
付与すると共に強力低下の少ない加工法が開示されてい
るが、セルロース繊維に防縮効果を付与する加工法であ
り形態安定性に関する記載はなく、またリン酸アミドの
添加では湿潤発熱性による保温効果を得ることはできな
い。Japanese Patent Application Laid-Open No. 4-153369 discloses a processing method in which a third component is added at the time of processing a resin. In addition, it is disclosed that a decrease in strength is small and the amount of free formaldehyde generated can be reduced, but addition of only a polyhydric alcohol having only a large number of hydroxyl groups has a weak heat build-up property, and a sufficient heat retaining effect cannot be obtained. . JP-A-4-57972 discloses a processing method in which a crosslinking agent such as an N-methylol resin and a phosphoric acid amide compound are used in combination to impart a shrink-proofing property to cellulose fibers and reduce the strength. However, it is a processing method for imparting a shrinkage-preventing effect to cellulose fibers, and there is no description about morphological stability. Addition of phosphoric amide cannot provide a heat retention effect due to wet heat generation.
【０００７】[0007]
【発明が解決しようとする課題】本発明は、上述のよう
な欠点を解決し、強力低下が少なく、形態安定性，吸湿
性，湿潤発熱性，防汚性，帯電防止性に優れ、中でも吸
湿性，湿潤発熱性の特に優れたセルロース系布帛を容易
な処理で得るための加工法を提供するものである。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned drawbacks, has a small decrease in strength, and is excellent in form stability, moisture absorption, wet heat generation, antifouling properties and antistatic properties. It is intended to provide a processing method for obtaining a cellulosic fabric having particularly excellent heat resistance and wet heat generation property by an easy treatment.
【０００８】[0008]
【課題を解決するための手段】本発明の一つの発明は、
セルロース系布帛を、Ｎ−メチロール系樹脂加工剤とそ
の反応触媒と分子中に水酸基とアミノ基および／または
カルボキシル基を有する水溶性物質を水に混合溶解した
混合水溶液で処理し、さらに加熱処理するセルロース系
布帛の加工法であり、該分子中に水酸基とアミノ基およ
び／またはカルボキシル基を有する水溶性物質が、アミ
ノ糖，糖酸，ヒドロキシアミノ酸，タンパク質，セルロ
ース誘導体，ムコ多糖またはムコ多糖誘導体から選ばれ
るセルロース系布帛の加工法である。そしてもう一つの
発明は、セルロース系布帛を、Ｎ−メチロール系樹脂加
工剤とその反応触媒と分子中に２個以上の水酸基を有す
る水溶性物質と分子中に２個以上のアミノ基および／ま
たはカルボキシル基を有する水溶性物質を水に混合溶解
した混合水溶液で処理し、さらに加熱処理するセルロー
ス系布帛の加工法であり、該分子中に２個以上の水酸基
を有する水溶性物質が、糖アルコール，ポリアルコー
ル，単糖，オリゴ糖，多糖から選ばれ、該分子中に２個
以上のアミノ基および／またはカルボキシル基を有する
水溶性物質が、アミノ酸，ポリアミン，ポリアミノ酸，
ポリカルボン酸から選ばれるセルロース系布帛の加工法
である。Means for Solving the Problems One invention of the present invention is as follows.
The cellulose-based fabric is treated with an N-methylol-based resin processing agent, a reaction catalyst thereof, and a mixed aqueous solution in which a water-soluble substance having a hydroxyl group, an amino group and / or a carboxyl group in a molecule is mixed and dissolved in water, and further heated. A method for processing a cellulosic fabric, wherein a water-soluble substance having a hydroxyl group and an amino group and / or a carboxyl group in the molecule is formed from an amino sugar, a sugar acid, a hydroxy amino acid, a protein, a cellulose derivative, a mucopolysaccharide or a mucopolysaccharide derivative. This is the method of processing the selected cellulosic fabric. Another invention relates to a cellulose-based fabric, a N-methylol-based resin processing agent, a reaction catalyst thereof, a water-soluble substance having two or more hydroxyl groups in a molecule, and two or more amino groups and / or two or more in a molecule. A method for processing a cellulosic fabric in which a water-soluble substance having a carboxyl group is treated with a mixed aqueous solution obtained by mixing and dissolving in water, and further subjected to heat treatment, wherein the water-soluble substance having two or more hydroxyl groups in the molecule is a sugar alcohol. , Polyalcohols, monosaccharides, oligosaccharides, and polysaccharides, and the water-soluble substance having two or more amino groups and / or carboxyl groups in the molecule is an amino acid, a polyamine, a polyamino acid,
This is a method for processing a cellulosic fabric selected from polycarboxylic acids.
【０００９】[0009]
【発明の実施の形態】本発明で用いられるセルロース系
布帛とは、綿，麻等の天然セルロース繊維やレーヨン，
リヨセル等の再生セルロース繊維からなる編織物の布
帛、また、天然セルロース繊維や再生セルロース繊維と
ポリエステル，ナイロン等の合成繊維や絹，羊毛等の天
然動物繊維を混紡した繊維からなる布帛，セルロース繊
維糸と合成繊維糸および／または動物繊維糸とを交編織
した布帛である。BEST MODE FOR CARRYING OUT THE INVENTION The cellulosic fabric used in the present invention includes natural cellulose fibers such as cotton and hemp, rayon,
Knitted and woven fabrics made of regenerated cellulose fibers such as lyocell, and fabrics made of fibers obtained by blending natural cellulose fibers or regenerated cellulose fibers with synthetic fibers such as polyester and nylon, and natural animal fibers such as silk and wool, and cellulose fiber yarns And synthetic fiber yarns and / or animal fiber yarns.
【００１０】本発明で用いられるＮ−メチロール系樹脂
加工剤は、触媒を添加し、加熱処理することにより反応
性モノマーが重合し、セルロース系布帛上に三次元的な
樹脂を形成するものであり、具体的には、ジメチロール
エチレン尿素、ジメチロールウロン、ジメチロールトリ
アゾン、ジメチロールプロピレン尿素、ジメチロール−
４−メトキシ−５，５−ジメチルプロピレン尿素、ジメ
チロールジヒドロキシエチレン尿素、ジメチロールアル
キルカーバメート、メチル化ジメチロールジメトキシエ
チレン尿素、１，３−ジメチル−４，５−ジヒドロキシ
−エチレン尿素等が挙げられる。The N-methylol resin processing agent used in the present invention forms a three-dimensional resin on a cellulose-based fabric by adding a catalyst and subjecting it to heat treatment to polymerize the reactive monomer. Specifically, dimethylol ethylene urea, dimethylol urone, dimethylol triazone, dimethylol propylene urea, dimethylol-
4-methoxy-5,5-dimethylpropylene urea, dimethylol dihydroxyethylene urea, dimethylol alkyl carbamate, methylated dimethylol dimethoxyethylene urea, 1,3-dimethyl-4,5-dihydroxy-ethylene urea and the like.
【００１１】また、これらの樹脂加工剤の重合架橋反応
を促進する触媒としては、用いる樹脂加工剤に適する通
常のものを用いれば良く、例えば、住友化学工業（株）
製、商品名スミテックスアクセラレーター Ｘ−１１０
のようなものが挙げられる。As a catalyst for accelerating the polymerization crosslinking reaction of these resin processing agents, a conventional catalyst suitable for the resin processing agent to be used may be used. For example, Sumitomo Chemical Co., Ltd.
Made, trade name Sumitex accelerator X-110
And the like.
【００１２】本発明の一つの発明では、目的とする効果
を発揮させるために分子中に水酸基とアミノ基および／
またはカルボキシル基を有する水溶性物質を樹脂加工剤
及びその触媒と混合して用いる。該水溶性物質の水酸
基，アミノ基，カルボキシル基は親水性官能基であり、
これらの官能基に水分子が吸着する際に吸着熱を発生す
る。従って、これらの官能基を有する水溶性物質でセル
ロース系布帛を処理することにより該布帛は親水性が向
上し、吸湿性を発現するとともに湿潤発熱性を発現し、
保温効果を発揮するものである。該水溶性物質の有する
官能基が水酸基のみである場合、またはアミノ基および
／またはカルボキシル基のみである場合には、加工処理
したセルロース系布帛の親水性は向上するものの、湿潤
発熱性が不十分であり、目的とする保温効果が発揮でき
ない。従って、該水溶性物質の有する官能基は、水酸基
とアミノ基および／またはカルボキシル基とを同時に有
するものであることが必要であり、これらの官能基の合
計の数は少なくとも２個以上である。In one aspect of the present invention, a hydroxyl group and an amino group and / or
Alternatively, a water-soluble substance having a carboxyl group is used by mixing with a resin processing agent and its catalyst. The hydroxyl group, amino group and carboxyl group of the water-soluble substance are hydrophilic functional groups,
When water molecules are adsorbed on these functional groups, heat of adsorption is generated. Therefore, by treating the cellulosic fabric with a water-soluble substance having these functional groups, the fabric has improved hydrophilicity, exhibits moisture absorption, and exhibits wet heat generation,
It has a warming effect. When the functional group of the water-soluble substance is only a hydroxyl group or only an amino group and / or a carboxyl group, the hydrophilicity of the processed cellulose-based fabric is improved, but the wet heat generation property is insufficient. Therefore, the intended heat retaining effect cannot be exhibited. Therefore, the functional group of the water-soluble substance needs to have a hydroxyl group and an amino group and / or a carboxyl group at the same time, and the total number of these functional groups is at least two or more.
【００１３】本発明で用いられる分子中に水酸基とアミ
ノ基および／またはカルボキシル基を有する水溶性物質
としては、グルコサミンやガラクトサミン等のアミノ
糖，グルコ糖酸やマンノ糖酸等の糖酸，セリンやチロシ
ンやヒドロキシプロリン等のヒドロキシアミノ酸，ジエ
チルアミノエチルセルロースやカルボキシメチルセルロ
ース等のセルロース誘導体，キチンやヒアルロン酸等の
ムコ多糖，カルボキシメチルキチン等のムコ多糖誘導
体，タンパク質等が挙げられ、これらの１種を用いても
よいし、２種以上を混合して用いてもよい。The water-soluble substances having a hydroxyl group, an amino group and / or a carboxyl group in the molecule used in the present invention include amino sugars such as glucosamine and galactosamine, sugar acids such as glucosolic acid and mannosaccharic acid, serine and the like. Examples include hydroxyamino acids such as tyrosine and hydroxyproline, cellulose derivatives such as diethylaminoethylcellulose and carboxymethylcellulose, mucopolysaccharides such as chitin and hyaluronic acid, mucopolysaccharide derivatives such as carboxymethylchitin, and proteins. Or a mixture of two or more.
【００１４】本発明の他の発明では、目的とする効果を
発揮させるために分子中に２個以上の水酸基を有する水
溶性物質と分子中に２個以上のアミノ基および／または
カルボキシル基を有する水溶性物質の少なくとも２種類
の水溶性物質を樹脂加工剤及びその触媒と混合して用い
る。これらの水溶性物質でセルロース系布帛を処理する
ことにより該布帛は親水性が向上し、吸湿性を発現する
とともに湿潤発熱性を発現し、保温効果を発揮するもの
である。分子中に２個以上の水酸基を有する水溶性物質
のみを用いた場合、または、分子中に２個以上のアミノ
基および／またはカルボキシル基を有する水溶性物質の
みの場合には、加工処理したセルロース系布帛の親水性
は十分に向上するが湿潤発熱性の発現が十分ではなく、
目的とする保温効果が発揮できない。従って、分子中に
２個以上の水酸基を有する水溶性物質と分子中に２個以
上のアミノ基および／またはカルボキシル基を有する水
溶性物質を同時に用いることが必要である。According to another aspect of the present invention, a water-soluble substance having two or more hydroxyl groups in a molecule and two or more amino groups and / or carboxyl groups in a molecule are provided in order to exert a desired effect. At least two kinds of water-soluble substances are used by mixing with a resin processing agent and its catalyst. By treating a cellulosic fabric with these water-soluble substances, the fabric is improved in hydrophilicity, exhibits moisture absorption, exhibits wet heat generation, and exhibits a heat retaining effect. If only a water-soluble substance having two or more hydroxyl groups in the molecule is used, or if only a water-soluble substance having two or more amino groups and / or carboxyl groups in the molecule is used, processed cellulose is used. Although the hydrophilicity of the system fabric is sufficiently improved, the expression of wet heat generation is not sufficient,
The intended heat retention effect cannot be exhibited. Therefore, it is necessary to simultaneously use a water-soluble substance having two or more hydroxyl groups in the molecule and a water-soluble substance having two or more amino groups and / or carboxyl groups in the molecule.
【００１５】また、分子中に２個以上の水酸基を有する
水溶性物質と分子中に２個以上のアミノ基および／また
はカルボキシル基を有する水溶性物質を混合して用いる
場合は、それぞれの水溶性物質は分子中に少なくとも２
個以上の官能基を有することが必要であり、該官能基の
数が２個以上ないと、樹脂加工剤と該官能基が反応して
しまい、官能基が残存しなくなることが推論でき、親水
性や湿潤発熱性を発揮できなくなるため好ましくない。When a water-soluble substance having two or more hydroxyl groups in the molecule and a water-soluble substance having two or more amino groups and / or carboxyl groups in the molecule are used as a mixture, the respective water-soluble substances are mixed. The substance has at least 2
It is necessary to have at least two functional groups, and if the number of the functional groups is not two or more, it can be inferred that the resin processing agent reacts with the functional groups, and that the functional groups do not remain. It is not preferable because the heat resistance and wet heat generation cannot be exhibited.
【００１６】本発明で用いられる分子中に２個以上の水
酸基を有する水溶性物質としては、エリスリトールやソ
ルビトール等の糖アルコール，ポリビニルアルコールや
ポリエチレングリコール等のポリアルコール，グリコー
スやフラノース等の単糖，スクロースやマルトース等の
オリゴ糖，デンプン等の多糖が挙げられ、これらの１種
を用いてもよいし、２種以上を混合して用いてもよい。
また、本発明で用いられる分子中に２個以上のアミノ基
および／またはカルボキシル基を有する物質としては、
グリシンやアラニン等のアミノ酸，ポリグルタミンやポ
リアスパラギン酸等のポリアミノ酸，ポリアミン，ポリ
カルボン酸等が挙げられ、これらの１種を用いてもよい
し、２種以上を混合して用いてもよい。Examples of the water-soluble substance having two or more hydroxyl groups in the molecule used in the present invention include sugar alcohols such as erythritol and sorbitol, polyalcohols such as polyvinyl alcohol and polyethylene glycol, monosaccharides such as glucose and furanose. Examples thereof include oligosaccharides such as sucrose and maltose, and polysaccharides such as starch. One of these may be used, or two or more thereof may be used in combination.
Examples of the substance having two or more amino groups and / or carboxyl groups in the molecule used in the present invention include:
Examples include amino acids such as glycine and alanine, polyamino acids such as polyglutamine and polyaspartic acid, polyamines, polycarboxylic acids, and the like. One of these may be used, or two or more may be used in combination. .
【００１７】本発明は、上述の樹脂加工剤とその反応触
媒と水溶性物質を混合溶解した混合水溶液としてセルロ
ース系布帛を処理し加工を行うものである。該混合水溶
液は、樹脂加工剤、その反応触媒，水溶性物質を含んで
いれば良く、その調整法は特に制限されない。一例を挙
げると、樹脂加工剤，触媒，水溶性物質それぞれを水に
溶解して水溶液とした後、各水溶液を混合して混合水溶
液とすればよい。According to the present invention, a cellulose-based fabric is processed and processed as a mixed aqueous solution obtained by mixing and dissolving the above-mentioned resin processing agent, its reaction catalyst and a water-soluble substance. The mixed aqueous solution only needs to contain a resin processing agent, a reaction catalyst thereof, and a water-soluble substance, and the method of preparing the mixed aqueous solution is not particularly limited. For example, a resin processing agent, a catalyst, and a water-soluble substance may be dissolved in water to form aqueous solutions, and the aqueous solutions may be mixed to form a mixed aqueous solution.
【００１８】該混合水溶液中の樹脂加工剤の濃度は通常
用いられている１〜２０重量％の範囲でよく、上述の樹
脂加工剤を単独のみかまたは２種以上を併用することも
できることはもちろんである。また、該混合水溶液中の
触媒の濃度は通常用いられている１〜１０重量％の範囲
であればよい。The concentration of the resin processing agent in the mixed aqueous solution may be in the range of usually used 1 to 20% by weight, and the above-mentioned resin processing agents may be used alone or in combination of two or more. It is. The concentration of the catalyst in the mixed aqueous solution may be in the range of usually used 1 to 10% by weight.
【００１９】また、該混合水溶液中の水溶性物質の濃度
は、２〜１２重量％であることが必要であり、２重量％
に満たない場合には、加工したセルロース系布帛の吸湿
性が十分ではなく、湿潤発熱性を十分に発揮することが
できない。また、１２重量％を越える場合には、樹脂加
工が十分に行われなく、形態安定性に劣ることから好ま
しくない。水溶性物質の２種以上を併用した場合にはそ
の合計の濃度が上記した濃度範囲であればよい。該混合
水溶液によるセルロース系布帛の処理は、通常の方法、
すなわち浸漬法やバッチ法等により行えばよく、スプレ
ー法も採用することができる。The concentration of the water-soluble substance in the mixed aqueous solution must be 2 to 12% by weight, and 2% by weight.
If less than the above, the processed cellulose-based fabric does not have sufficient hygroscopicity and cannot sufficiently exhibit wet heat generation. On the other hand, when the content exceeds 12% by weight, the resin processing is not sufficiently performed and the form stability is poor, which is not preferable. When two or more water-soluble substances are used in combination, the total concentration thereof may be within the above-mentioned concentration range. The treatment of the cellulosic fabric with the mixed aqueous solution is performed by a usual method,
That is, it may be performed by an immersion method, a batch method, or the like, and a spray method can also be employed.
【００２０】セルロース系布帛は、該混合水溶液で処理
後必要により絞りを行うが、その場合には通常行われて
いる絞り率約９０％以上で絞れば良い。次いで加熱処理
を行うが、該加熱処理は１００℃〜２５０℃、好ましく
は１２０℃〜２００℃で３０秒〜５分間行うことが好ま
しい。また、加熱処理の前に、８０℃〜１２０℃で１〜
３分間予備乾燥した後、上記した温度、時間で加熱処理
してもよい。その後十分水洗し乾燥を行い、必要に応じ
て本発明の目的とする吸湿性，湿潤発熱性等を阻害しな
い仕上げ剤処理を行ってもよい。The cellulose-based cloth is squeezed as required after the treatment with the mixed aqueous solution. In this case, the squeezing may be performed at a squeezing ratio of about 90% or more, which is usually performed. Next, a heat treatment is performed, and the heat treatment is preferably performed at 100 ° C to 250 ° C, preferably 120 ° C to 200 ° C, for 30 seconds to 5 minutes. In addition, before the heat treatment, 1 to 80 ° C ~ 120 ° C
After preliminary drying for 3 minutes, heat treatment may be performed at the above-described temperature and time. Thereafter, the film may be sufficiently washed with water and dried, and if necessary, may be subjected to a finishing agent treatment which does not impair the hygroscopicity and the exothermic heat generated by the present invention.
【００２１】[0021]
【実施例】以下、本発明について実施例により具体的に
説明するが、本発明はこの範囲に限定されるものではな
い。尚、実施例に記載した各測定値の測定は次の方法で
行った。 （洗濯処理）ＪＩＳ Ｌ ０２１７（１９９５）「繊維
製品の取り扱いに関する表示方法」２．１．（１）洗い
方番号１０３に準じて行った。 （吸湿率の測定）４．５ｃｍ×４．５ｃｍの試験布をふ
たを開けた秤量瓶に入れてふたと一緒に温度３５℃、湿
度９０％にセットした恒温恒湿機内に入れ、６０分後に
秤量瓶のふたを閉めて取り出し、重量を測定した。あら
かじめ試験布を入れない秤量瓶で同じ条件で操作したと
きの重量を測定しておき、これらの重量の差から吸湿量
を求め、試験布の絶乾重量の比から次式で吸湿率を求め
た。 吸湿率（％）＝（（Ｗ60−Ｗ0 ）／Ｗ0 ）×１００ 但し、Ｗ0 ＝絶乾時の試料重量、Ｗ60＝６０分後の試料
重量 （帯電圧）ＪＩＳ Ｌ １９０４ Ｂ法「摩擦帯電圧測
定法」に従い、試料の帯電圧を調べた。 （防汚性）１０ｃｍ×１０ｃｍの試験布を２枚づつ採取
し、平らな面に置きそれぞれの中央に汚れとして油を１
ｍｌ垂らし付着させた。２４時間放置後、１枚を上記洗
濯処理を１回行い、自然乾燥した。未洗濯の試料と洗濯
処理後の試料を並べておき、汚れの脱落程度を次のよう
に判定した。 ５級−完全に脱落する ４級−かなり脱落する ３級−脱落する ２級−僅かに脱落する １級−脱落しない （湿潤発熱量）試験布または比較用のセルロース系布帛
の表面に自動記録装置と接続した温度センサーをつけ、
ガラス製容器内に吊してセットした。容器内をシリカゲ
ル及び塩化カルシウム中を通過させた乾燥空気で充満し
て低湿度状態にし、温度が安定した後、水中を通過させ
た高湿度空気を急激に容器内に送り込み、容器内を高湿
度状態にした。このとき発生する吸着熱による試験布ま
たは比較用布帛の温度上昇を測定し、比較用布帛に対す
る温度差を湿潤発熱量とした。 （Ｗ＆Ｗ性）ＪＩＳ Ｌ １０５９「織布の防しわ試験
法」に従い、試験布のウォッシュアンド ウェア性（Ｗ
＆Ｗ性）を測定した。 （引裂強力）ＪＩＳ Ｌ １０９６（１９９０）「一般
織物試験方法」６．１５．５Ｄ法（ペンジュラム法）に
準じて測定した。EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these ranges. In addition, the measurement of each measured value described in the Example was performed by the following method. (Washing treatment) JIS L 0217 (1995) "Display method for handling textile products" 2.1. (1) Performed according to washing method number 103. (Measurement of Moisture Absorption) A 4.5 cm × 4.5 cm test cloth was put into a weighing bottle with an open lid, and put together with the lid in a thermo-hygrostat set at a temperature of 35 ° C. and a humidity of 90%. The lid of the weighing bottle was closed and taken out, and the weight was measured. Measure the weight when operating under the same conditions in a weighing bottle without a test cloth in advance, determine the moisture absorption from the difference between these weights, and determine the moisture absorption from the ratio of the absolute dry weight of the test cloth using the following formula. Was. Moisture absorption (%) = ((W 60 −W 0 ) / W 0 ) × 100, where W 0 = weight of sample when absolutely dry, W 60 = weight of sample after 60 minutes (charge potential) JIS L 1904 B method The charged voltage of the sample was examined according to the "friction charged voltage measuring method". (Anti-fouling property) Two test cloths of 10 cm × 10 cm were sampled and placed on a flat surface, and oil was applied to the center of each of the test cloths as dirt.
ml and allowed to adhere. After standing for 24 hours, one of the sheets was subjected to the above-mentioned washing treatment once and air-dried. The unwashed sample and the sample after the washing treatment were arranged, and the degree of dirt removal was determined as follows. Grade 5-Drop off completely Grade 4-Drop off considerably Grade 3-Drop off Grade 2-Drop off slightly Grade 1-Do not drop off (Wet heat generation) Automatic recording device on the surface of test cloth or cellulosic cloth for comparison Attach the temperature sensor connected to
It was set suspended in a glass container. The inside of the container is filled with dry air passed through silica gel and calcium chloride to make it a low humidity state, and after the temperature stabilizes, the high humidity air passed through the water is suddenly sent into the container, and the inside of the container becomes high humidity State. The temperature rise of the test cloth or the comparative cloth due to the heat of adsorption generated at this time was measured, and the temperature difference with respect to the comparative cloth was defined as the wet heat value. (W & W property) According to JIS L 1059 "Wrinkle prevention test method for woven fabric", wash and wear property (W
& W property) was measured. (Tear Strength) Measured in accordance with JIS L 1096 (1990) "General Fabric Testing Method" 6.15.5D method (Pendulum method).
【００２２】〔実施例１〕ジメチロールジヒドロキシエ
チレン尿素１００ｇと触媒（住友化学製、商品名スミテ
ックスアクセラレーター Ｘ−１１０）１０ｇを約８０
０ｍｌの水に溶解した水溶液を６個調製し、それぞれの
水溶液にグルコサミン塩酸塩の１０ｇ，２０ｇ，４０
ｇ，８０ｇ，１２０ｇ，１６０ｇを添加し攪拌溶解し、
更にそれぞれに水を加えて各１Ｌの混合水溶液６種を得
た。EXAMPLE 1 About 100 g of dimethylol dihydroxyethylene urea (100 g) and 10 g of a catalyst (Sumitex Accelerator X-110, manufactured by Sumitomo Chemical Co., Ltd.) were used.
Six aqueous solutions dissolved in 0 ml of water were prepared, and 10 g, 20 g, 40 g of glucosamine hydrochloride was added to each aqueous solution.
g, 80 g, 120 g, and 160 g, and stirred and dissolved.
Further, water was added to each of them to obtain six kinds of 1 L mixed aqueous solutions.
【００２３】該６種の混合水溶液それぞれに大きさが３
０ｃｍ×３０ｃｍに裁断したポリエステル／綿＝５０／
５０のブロード織物〔（５０／１×５０／１）／（１４
４×８３）〕試料を浸漬した後、絞り率９０％で絞り、
１１０℃で３分間予備乾燥した後に１５０℃で１．５分
間加熱処理した。次いで十分に水洗し、約１１０℃で乾
燥して、Ｎｏ．１〜Ｎｏ．６の試料を得た。また、樹脂
と触媒のみを加え、グルコサミン塩酸塩を加えない水溶
液で同じように処理した試料を比較例試料Ｎｏ．１とし
た。得られた各試料の洗濯前の吸湿率，帯電圧，防汚
性，Ｗ＆Ｗ性，湿潤発熱量，引裂強力を測定した結果を
表１に、１０回洗濯後の測定結果を表２にそれぞれ示し
た。Each of the six mixed aqueous solutions has a size of 3
Polyester cut into 0 cm × 30 cm / cotton = 50 /
50 broad fabrics [(50/1 × 50/1) / (14
4 × 83)] After immersing the sample, squeezing was performed at a squeezing ratio of 90%.
After preliminarily drying at 110 ° C. for 3 minutes, heat treatment was performed at 150 ° C. for 1.5 minutes. Then, it was thoroughly washed with water and dried at about 110 ° C. 1 to No. 6 samples were obtained. In addition, a sample treated in the same manner with an aqueous solution to which only the resin and the catalyst were added and to which glucosamine hydrochloride was not added was used as a comparative sample No. It was set to 1. Table 1 shows the results of measuring the moisture absorption rate, charge potential, antifouling property, W & W property, wet calorific value, and tear strength of each sample before washing, and Table 2 shows the measurement results after washing 10 times. Was.
【００２４】[0024]
【表１】 [Table 1]
【００２５】[0025]
【表２】 [Table 2]
【００２６】表１および表２の結果から、グルコサミン
塩酸塩を１％添加した試料Ｎｏ．１は未添加の比較例試
料Ｎｏ．１より吸湿性が僅かに向上しているものの不十
分であり、帯電性，防汚性，湿潤発熱性の向上も不十分
であり、また、グルコサミン塩酸塩を１６％添加した試
料Ｎｏ．６は吸湿性は上がるもののＷ＆Ｗ性が劣るため
好ましくない。グルコサミン塩酸塩を添加していない比
較例試料Ｎｏ．１は湿潤発熱性が認められない。From the results in Tables 1 and 2, Sample No. 1 containing 1% glucosamine hydrochloride was added. No. 1 is a comparative sample No. Sample No. 1 in which 16% glucosamine hydrochloride was added, although the hygroscopicity was slightly improved from that of Sample No. 1, but was insufficient, and the improvement in chargeability, antifouling property and wet heat generation was also insufficient. No. 6 is not preferable because the W & W property is inferior although the hygroscopicity is increased. Comparative Example Sample No. to which glucosamine hydrochloride was not added. No. 1 shows no exothermic heat generation.
【００２７】グルコサミン塩酸塩を２〜１２％添加した
本発明の試料Ｎｏ．２〜Ｎｏ．５では表１の結果から吸
湿率の増加と帯電圧の減少、湿潤発熱量の増加が見ら
れ、本発明の処理によって引裂強力が低下することな
く、形態安定性を具備するとともに、吸湿性，帯電防止
性，防汚性，湿潤発熱性の向上が認められ、更に、表２
の結果から洗濯後もこれらの性能向上の効果が維持され
ることが明らかである。Sample No. 1 of the present invention containing 2 to 12% of glucosamine hydrochloride was added. 2-No. 5, the results in Table 1 show an increase in the moisture absorption rate, a decrease in the charged voltage, and an increase in the amount of heat generated by wetting. The treatment according to the present invention does not reduce the tear strength, has morphological stability, and has good hygroscopicity. Improvements in antistatic properties, antifouling properties and wet heat generation were observed.
From the results, it is clear that these effects of performance improvement are maintained even after washing.
【００２８】〔実施例２〕ジメチロールジヒドロキシエ
チレン尿素１００ｇと触媒（住友化学製、商品名スミテ
ックスアクセラレーター Ｘ−１１０）１０ｇを約８０
０ｍｌの水に溶解した水溶液を５個調製し、それぞれの
水溶液にそれぞれ４０ｇのグルコン酸ナトリウム、ヒド
ロキシプロリン、コラーゲン（酵素分解物、分子量２，
０００、和光純薬工業製）、キトサン酢酸塩（脱アセチ
ル化度８０％、分子量４５，０００）、カルボキシメチ
ルセルロースを添加し攪拌溶解し、更にそれぞれに水を
加えて各１Ｌの混合水溶液５種を得た。[Example 2] 100 g of dimethylol dihydroxyethylene urea and 10 g of a catalyst (Sumitex Accelerator X-110, manufactured by Sumitomo Chemical Co., Ltd.) were added to about 80 g.
Five aqueous solutions dissolved in 0 ml of water were prepared, and 40 g of sodium gluconate, hydroxyproline and collagen (enzyme degradation product, molecular weight 2,
000, manufactured by Wako Pure Chemical Industries, Ltd.), chitosan acetate (deacetylation degree 80%, molecular weight 45,000), carboxymethylcellulose, and dissolved by stirring. Further, water was added to each of them to obtain 5 kinds of 1L mixed aqueous solution. Obtained.
【００２９】５種の混合水溶液それぞれに実施例１と同
じ織物試料を浸漬した後、絞り率９０％で絞り、１１０
℃で３分間予備乾燥した後に１５０℃で１．５分間加熱
処理した。次いで十分に水洗し、約１１０℃で乾燥し
て、Ｎｏ．７〜Ｎｏ．１１の試料を得た。得られた各試
料の洗濯前の吸湿率，帯電圧，防汚性，Ｗ＆Ｗ性，湿潤
発熱量，引裂強力を測定した結果を表３に、１０回洗濯
後の測定結果を表４にそれぞれ示した。The same woven fabric sample as in Example 1 was immersed in each of the five kinds of mixed aqueous solutions, and then squeezed at a squeezing ratio of 90%.
After preliminarily drying at 150 ° C. for 3 minutes, heat treatment was performed at 150 ° C. for 1.5 minutes. Then, it was thoroughly washed with water and dried at about 110 ° C. 7-No. Eleven samples were obtained. Table 3 shows the results of measuring the moisture absorption rate, charging voltage, antifouling property, W & W property, wet calorific value, and tear strength of each of the obtained samples before washing, and Table 4 shows the measurement results after washing 10 times. Was.
【００３０】[0030]
【表３】 [Table 3]
【００３１】[0031]
【表４】 [Table 4]
【００３２】表３の結果から、試料Ｎｏ．７〜Ｎｏ．１
１は本発明による処理を行うことによりいずれも吸湿率
の増加，帯電圧の減少，湿潤発熱量の増加が見られ、引
裂強力が低下することなく、形態安定性を具備するとと
もに、優れた吸湿性を示し、帯電防止性，防汚性，湿潤
発熱性の向上が認められ、更に表４の結果から洗濯後で
もこれらの性能が十分維持されることが明らかである。From the results shown in Table 3, the sample No. 7-No. 1
No. 1 shows an increase in moisture absorption rate, a decrease in charged voltage, and an increase in wet calorific value by performing the treatment according to the present invention. The antistatic properties, the antifouling properties, and the improvement in wet heat generation were observed, and the results in Table 4 clearly show that these properties are sufficiently maintained even after washing.
【００３３】〔実施例３〕ジメチロールジヒドロキシエ
チレン尿素１００ｇと触媒（住友化学製、商品名スミテ
ックスアクセラレーター Ｘ−１１０）１０ｇを約８０
０ｍｌの水に溶解した水溶液を５個調製し、それぞれの
水溶液にエリスリトール２０ｇを添加して攪拌溶解し、
次いでそれぞれの水溶液にそれぞれ２０ｇのエチレンジ
アミン，ポリエチレンイミン（エポミンＳＰ−０１２、
日本触媒製）、ポリアリルアミン（ＰＡＡ−１０Ｃ、日
東紡績製）、ポリリジン（分子量２，０００〜４，００
０、和光純薬工業製）、第４級アンモニウム塩型カチオ
ン系水溶性高分子（ナガセ化成工業製、商品名ワイステ
ックスＴ−１０１）を添加し、攪拌溶解してさらにそれ
ぞれに水を加えて各１Ｌの混合水溶液５種を得た。Example 3 100 g of dimethylol dihydroxyethylene urea and 10 g of a catalyst (Sumitex Accelerator X-110, manufactured by Sumitomo Chemical Co., Ltd.) were added to about 80 g.
Five aqueous solutions dissolved in 0 ml of water were prepared, and 20 g of erythritol was added to each aqueous solution and dissolved by stirring.
Next, 20 g of ethylenediamine and polyethyleneimine (Epomin SP-012,
Nippon Shokubai), polyallylamine (PAA-10C, manufactured by Nitto Boseki), polylysine (molecular weight 2,000 to 4,000)
0, manufactured by Wako Pure Chemical Industries, Ltd.) and a quaternary ammonium salt type cationic water-soluble polymer (manufactured by Nagase Kasei Kogyo Co., Ltd., trade name: WISTEX T-101), and dissolved by stirring. Water is further added to each. Five 1-L mixed aqueous solutions were obtained.
【００３４】該５種の混合水溶液それぞれに実施例１と
同じ織物試料を浸漬した後、絞り率９０％で絞り、１１
０℃で３分間予備乾燥した後に１５０℃で１．５分間加
熱処理した。次いで十分に水洗し、約１１０℃で乾燥し
て、Ｎｏ．１２〜Ｎｏ．１６の試料を得た。また、樹脂
と触媒を加え、ポリエチレンイミン４０ｇを加えてエリ
スリトールを加えない水溶液で同じように処理した試料
を比較例試料Ｎｏ．２とした。得られた各試料の洗濯前
の吸湿率，帯電圧，防汚性，Ｗ＆Ｗ性，湿潤発熱量，引
裂強力を測定した結果を表５に、１０回洗濯後の測定結
果を表６にそれぞれ示した。The same woven fabric sample as in Example 1 was immersed in each of the five kinds of mixed aqueous solutions, and then squeezed at a squeezing ratio of 90%.
After pre-drying at 0 ° C. for 3 minutes, heat treatment was performed at 150 ° C. for 1.5 minutes. Then, it was thoroughly washed with water and dried at about 110 ° C. 12-No. Sixteen samples were obtained. A resin and a catalyst, 40 g of polyethyleneimine was added, and a sample treated in the same manner with an aqueous solution without erythritol was prepared. And 2. Table 5 shows the measurement results of the moisture absorption rate, charge potential, antifouling property, W & W property, wet calorific value, and tear strength of the obtained samples before washing, and Table 6 shows the measurement results after washing 10 times. Was.
【００３５】[0035]
【表５】 [Table 5]
【００３６】[0036]
【表６】 [Table 6]
【００３７】表５および表６の結果から、本発明の試料
Ｎｏ．１２〜Ｎｏ．１６は、引裂強力が低下することな
く、形態安定性を具備するとともに、優れた吸湿性を示
し、帯電防止性，防汚性，湿潤発熱性の向上が認めら
れ、洗濯後でもこれらの性能が十分認められることが明
らかである。また、アミノ基のみを有するポリエチレン
イミンを添加し水酸基のみを有するエリスリトールを添
加していない比較例試料Ｎｏ．２では、本発明によりポ
リエチレンイミンとエリスリトールを添加した試料Ｎ
ｏ．１３の結果と比較して湿潤発熱量は優れているもの
の吸湿性が十分でなく、また、帯電圧の減少が少く防汚
性に劣る結果となり好ましくない。From the results of Tables 5 and 6, the sample No. 12-No. No. 16 has morphological stability without deteriorating tear strength, exhibits excellent hygroscopicity, and has improved antistatic properties, antifouling properties, and moist heat generation properties. It is clear that it is well recognized. Further, Comparative Example Sample No. in which polyethyleneimine having only an amino group was added and erythritol having only a hydroxyl group was not added. In Sample 2, sample N to which polyethyleneimine and erythritol were added according to the present invention was used.
o. As compared with the result of No. 13, the exothermic calorific value is excellent, but the hygroscopicity is not sufficient, and the reduction of the charged voltage is small and the antifouling property is inferior.
【００３８】〔実施例４〕ジメチロールジヒドロキシエ
チレン尿素１００ｇと触媒（住友化学製、商品名スミテ
ックスアクセラレーター Ｘ−１１０）１０ｇを約８０
０ｍｌの水に溶解した水溶液を４個調製し、それぞれの
水溶液にエリスリトール２０ｇを添加して攪拌溶解し、
次いでそれぞれの水溶液にそれぞれ２０ｇのアジピン
酸、ポリアクリル酸（分子量５，０００、和光純薬工業
製）、ポリメタクリル酸、ポリグルタミン酸（分子量
８，０００、ペプチド研究所製）を添加し、攪拌溶解し
てさらにそれぞれに水を加えて各１Ｌの混合水溶液４種
を得た。Example 4 About 100 g of dimethylol dihydroxyethylene urea and 10 g of a catalyst (Sumitex Accelerator X-110, trade name, manufactured by Sumitomo Chemical Co., Ltd.) were used.
Four aqueous solutions dissolved in 0 ml of water were prepared, and 20 g of erythritol was added to each of the aqueous solutions and dissolved by stirring.
Next, 20 g of adipic acid, polyacrylic acid (molecular weight: 5,000, manufactured by Wako Pure Chemical Industries), polymethacrylic acid, and polyglutamic acid (molecular weight: 8,000, manufactured by Peptide Research Laboratories) were added to each aqueous solution, followed by stirring and dissolution. Then, water was further added to each of them to obtain four kinds of 1 L mixed aqueous solutions.
【００３９】該４種の混合水溶液それぞれに実施例１と
同じ織物試料を浸漬した後、絞り率９０％で絞り、１１
０℃で３分間予備乾燥した後に１５０℃で１．５分間加
熱処理した。次いで十分に水洗し、約１１０℃で乾燥し
て、Ｎｏ．１７〜Ｎｏ．２０の試料を得た。また、樹脂
と触媒を加え、ポリアクリル酸４０ｇを加えてエリスリ
トールを加えない水溶液で同じように処理した試料を比
較例試料Ｎｏ．３とした。得られた各試料の洗濯前の吸
湿率，帯電圧，防汚性，Ｗ＆Ｗ性，湿潤発熱量，引裂強
力を測定した結果を表７に、１０回洗濯後の測定結果を
表８にそれぞれ示した。The same woven fabric sample as in Example 1 was immersed in each of the four mixed aqueous solutions, and then squeezed at a squeezing rate of 90%.
After pre-drying at 0 ° C. for 3 minutes, heat treatment was performed at 150 ° C. for 1.5 minutes. Then, it was thoroughly washed with water and dried at about 110 ° C. 17-No. Twenty samples were obtained. A resin and a catalyst, 40 g of polyacrylic acid was added, and a sample treated in the same manner with an aqueous solution without erythritol was prepared. It was set to 3. Table 7 shows the results of measuring the moisture absorption rate, charge potential, antifouling property, W & W property, wet calorific value, and tear strength of each of the obtained samples before washing, and Table 8 shows the measurement results after washing 10 times. Was.
【００４０】[0040]
【表７】 [Table 7]
【００４１】[0041]
【表８】 [Table 8]
【００４２】表７および表８の結果から、本発明の試料
Ｎｏ．１７〜Ｎｏ．２０は、引裂強力が低下することな
く、形態安定性を具備するとともに、優れた吸湿性を示
し、帯電防止性，防汚性，湿潤発熱性の向上が認めら
れ、洗濯後でもこれらの性能が十分認められることが明
らかである。また、カルボキシル基のみを有するポリア
クリル酸を添加し、水酸基のみを有するエリスリトール
を添加していない比較例試料Ｎｏ．３では、本発明によ
りポリアクリル酸とエリスリトールを添加した試料Ｎ
ｏ．１８の結果と比較して湿潤発熱量は優れているもの
の吸湿性が十分でなく、帯電圧の減少も少く防汚性に劣
る結果となり好ましくない。From the results in Tables 7 and 8, the sample No. 17-No. No. 20 has not only a decrease in tear strength, but also morphological stability and excellent hygroscopicity. Improvements in antistatic properties, antifouling properties and wet heat buildup are recognized, and these properties are maintained even after washing. It is clear that it is well recognized. Further, Comparative Example Sample No. to which polyacrylic acid having only a carboxyl group was added and erythritol having only a hydroxyl group was not added. In Sample 3, sample N to which polyacrylic acid and erythritol were added according to the present invention was used.
o. As compared with the result of No. 18, the wet heat value is excellent, but the hygroscopicity is not sufficient, the reduction of the charged voltage is small, and the antifouling property is inferior.
【００４３】〔実施例５〕ジメチロールジヒドロキシエ
チレン尿素１００ｇと触媒（住友化学製、商品名スミテ
ックスアクセラレーター Ｘ−１１０）１０ｇを約８０
０ｍｌの水に溶解した水溶液を５個調製し、それぞれの
水溶液にポリエチレンイミン（商品名エポミンＳＰ−０
１２、日本触媒製）２０ｇを添加して攪拌溶解し、次い
でそれぞれの水溶液にそれぞれ２０ｇのグリセリン、ス
クロース、エリスリトール、ポリビニルアルコール（鹸
化度８６〜９０の部分鹸化物、重合度１，０００、和光
純薬工業製）、トウモロコシデンプン（和光純薬工業
製）を添加し、攪拌溶解してさらにそれぞれに水を加え
て各１Ｌの混合水溶液５種を得た。Example 5 About 100 g of dimethylol dihydroxyethylene urea and 10 g of a catalyst (Sumitex Accelerator X-110, manufactured by Sumitomo Chemical Co., Ltd.) were used.
Five aqueous solutions dissolved in 0 ml of water were prepared, and polyethyleneimine (trade name Epomin SP-0) was added to each aqueous solution.
12, 20 g of Nippon Shokubai) and stirred to dissolve. Then, in each aqueous solution, 20 g of glycerin, sucrose, erythritol, polyvinyl alcohol (partially saponified product having a saponification degree of 86 to 90, polymerization degree of 1,000, Wako Pure Chemical Industries, Ltd.) And corn starch (manufactured by Wako Pure Chemical Industries, Ltd.) were added and dissolved by stirring, and water was further added to each to obtain five kinds of 1 L mixed aqueous solution.
【００４４】該５種の混合水溶液それぞれに実施例１と
同じ織物試料を浸漬した後、絞り率９０％で絞り、１１
０℃で３分間予備乾燥した後に１５０℃で１．５分間加
熱処理した。次いで十分に水洗し、約１１０℃で乾燥し
て、Ｎｏ．２１〜Ｎｏ．２５の試料を得た。また、樹脂
と触媒を加え、エリスリトール４０ｇを加えてポリエチ
レンイミンを加えない水溶液で同じように処理した試料
を比較例試料Ｎｏ．４とした。得られた各試料の洗濯前
の吸湿率，帯電圧，防汚性，Ｗ＆Ｗ性，湿潤発熱量，引
裂強力を測定した結果を表９に、１０回洗濯後の測定結
果を表１０にそれぞれ示した。After the same woven fabric sample as in Example 1 was immersed in each of the five kinds of mixed aqueous solutions, squeezing was performed at a squeezing rate of 90%.
After pre-drying at 0 ° C. for 3 minutes, heat treatment was performed at 150 ° C. for 1.5 minutes. Then, it was thoroughly washed with water and dried at about 110 ° C. 21-No. 25 samples were obtained. A resin and a catalyst, 40 g of erythritol was added, and a sample treated in the same manner with an aqueous solution containing no polyethyleneimine was prepared. And 4. Table 9 shows the measurement results of the moisture absorption rate, charge potential, antifouling property, W & W property, wet calorific value, and tear strength of each of the obtained samples before washing, and Table 10 shows the measurement results after washing 10 times. Was.
【００４５】[0045]
【表９】 [Table 9]
【００４６】[0046]
【表１０】 [Table 10]
【００４７】表９および表１０の結果から、本発明の試
料Ｎｏ．２１〜Ｎｏ．２５は、引裂強力が低下すること
なく、形態安定性を具備するとともに、優れた吸湿性を
示し、帯電防止性，防汚性，湿潤発熱性の向上が認めら
れ、洗濯後でもこれらの性能が十分認められることが明
らかである。また、水酸基のみを有するエリスリトール
を添加しアミノ基のみを有するポリエチレンイミンを添
加していない比較例試料Ｎｏ．４では、本発明によりポ
リエチレンイミンとエリスリトールを添加した試料Ｎ
ｏ．２３の結果と比較して吸湿性は優れているものの湿
潤発熱量が著しく劣り好ましくない。From the results shown in Tables 9 and 10, the sample No. 21-No. No. 25 has not only a decrease in tear strength, but also a form stability and an excellent hygroscopicity, and an improvement in antistatic property, antifouling property and wet heat build-up is recognized. It is clear that it is well recognized. In addition, Comparative Example Sample No. containing no erythritol having only a hydroxyl group and no polyethyleneimine having only an amino group was added. 4, sample N to which polyethyleneimine and erythritol were added according to the present invention.
o. As compared with the result of No. 23, although the hygroscopicity is excellent, the heat generation value due to humidity is remarkably inferior, which is not preferable.
【００４８】〔実施例６〕ジメチロールエチレン尿素、
ジメチロールウロン、ジメチロールトリアゾン、ジメチ
ロールプロピレン尿素、ジメチロール−４−メトキシ−
５，５−ジメチルプロピレン尿素、ジメチロールジヒド
ロキシエチレン尿素、ジメチロールアルキルカーバメー
ト、メチル化ジメチロールジメトキシエチレン尿素、
１，３−ジメチル−４，５−ジヒドロキシエチレン尿素
のそれぞれ１００ｇと触媒（住友化学製、商品名スミテ
ックスアクセラレーター Ｘ−１１０）１０ｇを約８０
０ｍｌの水に溶解して、９種の樹脂水溶液を得た。Example 6 Dimethylol ethylene urea
Dimethylol uron, dimethylol triazone, dimethylol propylene urea, dimethylol-4-methoxy-
5,5-dimethylpropylene urea, dimethylol dihydroxyethylene urea, dimethylol alkyl carbamate, methylated dimethylol dimethoxyethylene urea,
About 100 g of each of 1,3-dimethyl-4,5-dihydroxyethylene urea and 10 g of a catalyst (Sumitex Accelerator X-110, manufactured by Sumitomo Chemical Co., Ltd.) are mixed for about 80 g.
It was dissolved in 0 ml of water to obtain 9 kinds of aqueous resin solutions.
【００４９】該９種の樹脂水溶液それぞれに４０ｇのグ
ルコサミン塩酸塩を添加し攪拌溶解し、更にそれぞれに
水を加えて各１Ｌの混合水溶液９種を得た。該９種の混
合水溶液それぞれに実施例１と同じ織物試料を浸漬した
後、絞り率９０％で絞り、１１０℃で３分間予備乾燥し
た後に１５０℃で１．５分間加熱処理した。次いで十分
に水洗し、約１１０℃で乾燥して、Ｎｏ．２６〜Ｎｏ．
３４の試料を得た。得られた各試料の洗濯前と１０回洗
濯後の吸湿率，帯電圧，防汚性，Ｗ＆Ｗ性，湿潤発熱量
を測定し、表１１と表１２に示した。To each of the nine aqueous resin solutions, 40 g of glucosamine hydrochloride was added and dissolved by stirring, and water was further added to each of them to obtain nine 1-liter mixed aqueous solutions. The same woven fabric sample as in Example 1 was immersed in each of the nine mixed aqueous solutions, squeezed at a squeezing ratio of 90%, preliminarily dried at 110 ° C for 3 minutes, and then heat-treated at 150 ° C for 1.5 minutes. Then, it was thoroughly washed with water and dried at about 110 ° C. 26-No.
34 samples were obtained. The moisture absorption rate, charged voltage, antifouling property, W & W property, and wet calorific value of each of the obtained samples before and after washing 10 times were measured.
【００５０】[0050]
【表１１】 [Table 11]
【００５１】[0051]
【表１２】 [Table 12]
【００５２】表１１および表１２の結果から、本発明の
試料Ｎｏ．２６〜Ｎｏ．３４は、引裂強力が低下するこ
となく、形態安定性を具備するとともに、優れた吸湿性
を示し、帯電防止性，防汚性，湿潤発熱性の向上が認め
られ、洗濯後でもこれらの性能が十分認められることが
明らかであり、本発明の加工法は、各種のＮ−メチロー
ル系樹脂加工剤に対して効果のあることが判明した。From the results shown in Tables 11 and 12, the sample No. of the present invention was obtained. 26-No. No. 34 has not only a decrease in tear strength, but also morphological stability, excellent hygroscopicity, improved antistatic properties, antifouling properties, and moist heat build-up. It is clear that this is sufficiently recognized, and it has been found that the processing method of the present invention is effective for various N-methylol resin processing agents.
【００５３】〔実施例７〕綿１００％のブロード織物
〔（５０／１×５０／１）／（１４４×７６）〕を試料
として用いる以外は実施例１と同様にして、試料Ｎｏ．
３５〜Ｎｏ．４０を得た。また、樹脂と触媒のみを加
え、グルコサミン塩酸塩を加えない水溶液で処理した試
料を比較例試料Ｎｏ．５とした。得られた各試料の洗濯
前と１０回洗濯後の吸湿率，帯電圧，防汚性，Ｗ＆Ｗ
性，湿潤発熱量を測定し、表１３と表１４に示した。Example 7 Sample No. 1 was prepared in the same manner as in Example 1 except that a 100% cotton broad cloth [(50/1 × 50/1) / (144 × 76)] was used as a sample.
35-No. 40 was obtained. A sample treated with an aqueous solution to which only a resin and a catalyst were added and to which glucosamine hydrochloride was not added was used as a sample of Comparative Example No. It was set to 5. Moisture absorption rate, charged voltage, antifouling property, W & W of each sample before and after washing 10 times
The properties and wet calorific values were measured and are shown in Tables 13 and 14.
【００５４】[0054]
【表１３】 [Table 13]
【００５５】[0055]
【表１４】 [Table 14]
【００５６】表１３および表１４の結果から、グルコサ
ミン塩酸塩を１％添加した試料Ｎｏ．３５は未添加の比
較例試料Ｎｏ．５よりは吸湿性が僅かに向上しているも
のの吸湿性が不十分であり、帯電性，防汚性，湿潤発熱
性の向上も不十分であり、また、グルコサミン塩酸塩を
１６％添加した試料Ｎｏ．４０は吸湿性は上がるものの
Ｗ＆Ｗ性が劣るため好ましくない。グルコサミン塩酸塩
を添加していない比較例試料Ｎｏ．５は、湿潤発熱性が
認められない。From the results shown in Tables 13 and 14, Sample No. 1 containing 1% glucosamine hydrochloride was added. Comparative example sample No. 35 not added. Samples with slightly improved hygroscopicity but poor hygroscopicity, insufficient charging, antifouling properties, and exothermic heat build-up, and with 16% glucosamine hydrochloride added No. 40 is not preferable because the W & W property is inferior although the hygroscopicity is increased. Comparative Example Sample No. to which glucosamine hydrochloride was not added. In No. 5, no wet exothermicity is observed.
【００５７】グルコサミン塩酸塩を２〜１２％添加した
本発明の試料Ｎｏ．３６〜Ｎｏ．３９では引裂強力が低
下することなく、形態安定性を具備するとともに、優れ
た吸湿性を示し、帯電防止性，防汚性，湿潤発熱性の向
上が認められ、洗濯後でもこれらの性能が十分認められ
ることが明らかである。Sample No. 1 of the present invention containing 2 to 12% of glucosamine hydrochloride was added. 36-No. With No. 39, tear strength was not reduced, the composition had morphological stability, and exhibited excellent hygroscopicity, and improved antistatic properties, antifouling properties, and moist heat buildup were observed. It is clear that it is acceptable.
【００５８】〔実施例８〕綿１００％のブロード織物
〔（５０／１×５０／１）／（１４４×７６）〕を試料
として用いる以外は実施例５と同様にして、試料Ｎｏ．
４１〜Ｎｏ．４５を得た。また、樹脂と触媒を加え、エ
リスリトール４０ｇを加えてポリエチレンイミンを加え
ない水溶液で同じように処理した試料を比較例試料Ｎ
ｏ．６とした。得られた各試料の洗濯前と１０回洗濯後
の吸湿率，帯電圧，防汚性，Ｗ＆Ｗ性，湿潤発熱量を測
定し、表１５と表１６に示した。Example 8 Sample No. 10 was prepared in the same manner as in Example 5 except that a 100% cotton broad woven fabric [(50/1 × 50/1) / (144 × 76)] was used as a sample.
41-No. 45 was obtained. Further, a resin and a catalyst were added, 40 g of erythritol was added, and a sample treated in the same manner with an aqueous solution without adding polyethyleneimine was used as a comparative sample N.
o. 6. The moisture absorption rate, charged voltage, antifouling property, W & W property, and wet calorific value of each of the obtained samples before and after washing 10 times were measured.
【００５９】[0059]
【表１５】 [Table 15]
【００６０】[0060]
【表１６】 [Table 16]
【００６１】表１５および表１６の結果から、本発明の
試料Ｎｏ．４１〜Ｎｏ．４５は、引裂強力が低下するこ
となく、形態安定性を具備するとともに、優れた吸湿性
を示し、帯電防止性，防汚性，湿潤発熱性の向上が認め
られ、洗濯後でもこれらの性能が十分認められることが
明らかである。また、水酸基のみを有するエリスリトー
ルを添加しアミノ基のみを有するポリエチレンイミンを
添加していない比較例試料Ｎｏ．６では、本発明により
エリスリトールとポリエチレンイミンを添加した試料Ｎ
ｏ．４３の結果と比較して吸湿性は優れているものの湿
潤発熱量が劣り好ましくない。From the results shown in Tables 15 and 16, the sample No. of the present invention was obtained. 41-No. No. 45 has not only a decrease in tear strength but also morphological stability and excellent hygroscopicity, and antistatic, antifouling and moist heat-generating properties are improved. It is clear that it is well recognized. In addition, Comparative Example Sample No. containing no erythritol having only a hydroxyl group and no polyethyleneimine having only an amino group was added. In sample No. 6, sample N to which erythritol and polyethyleneimine were added according to the present invention was used.
o. As compared with the result of No. 43, although the hygroscopicity was excellent, the amount of heat generated by moistening was inferior, which was not preferable.
【００６２】[0062]
【発明の効果】以上のように、本発明のセルロース系布
帛の加工法によれば、セルロース系布帛の引裂強力を低
下させることなく、優れた形態安定性を具備させるとと
もに、優れた吸湿性を具備させ、湿潤発熱性を発揮させ
ることができる。それとともに、防汚性，帯電防止性に
も優れ、さらに繰り返し洗濯によってもこれらの性能を
維持することができる。As described above, according to the method for processing the cellulosic fabric of the present invention, the cellulosic fabric has excellent morphological stability and excellent hygroscopicity without lowering the tear strength. It is possible to exhibit wet heat generation. At the same time, it has excellent antifouling properties and antistatic properties, and can maintain these properties even after repeated washing.
【００６３】本発明による上記効果は、Ｎ−メチロール
系樹脂による加工処理時に、分子中に水酸基とアミノ基
および／またはカルボキシル基を有する水溶性物質を混
合処理するか、又は、２個以上の水酸基を有する水溶性
物質と分子中に２個以上のアミノ基および／またはカル
ボキシル基を有する水溶性物質を混合処理することによ
って達成され、即ち、本発明の効果は、水酸基とアミノ
基および／またはカルボキシル基を有する水溶性物質を
使用するか、または、水酸基を有する水溶性物質と、ア
ミノ基および／またはカルボキシル基を有する水溶性物
質との両者を混合使用することによって得られるもので
ある。The effect of the present invention can be obtained by mixing a water-soluble substance having a hydroxyl group and an amino group and / or a carboxyl group in a molecule during processing with an N-methylol resin, or by mixing two or more hydroxyl groups. Can be achieved by mixing a water-soluble substance having a hydroxyl group and an amino group and / or a carboxyl group. It is obtained by using a water-soluble substance having a group, or by mixing and using both a water-soluble substance having a hydroxyl group and a water-soluble substance having an amino group and / or a carboxyl group.
【００６４】本発明によって得られるセルロース系布帛
は、形態安定性を具備するとともに吸湿性の向上、帯電
防止性の向上によってむれ感や静電気の発生といった不
快感をなくし、湿潤発熱性を具備させることにより保温
効果を著しく高めることができるので、衣料分野等で好
適に使用できるものである。The cellulosic fabric obtained according to the present invention has morphological stability, eliminates discomfort such as unevenness and generation of static electricity by improving hygroscopicity and antistatic properties, and has moist heat generation. Can significantly enhance the heat retention effect, and thus can be suitably used in the field of clothing and the like.
Claims (4)
樹脂加工剤とその反応触媒と分子中に水酸基とアミノ基
および／またはカルボキシル基を有する水溶性物質を水
に混合溶解した混合水溶液で処理し、さらに加熱処理す
ることを特徴とするセルロース系布帛の加工法。1. A cellulose-based fabric is treated with a mixed aqueous solution obtained by mixing and dissolving an N-methylol-based resin processing agent, a reaction catalyst thereof and a water-soluble substance having a hydroxyl group, an amino group and / or a carboxyl group in water in water. And a method of processing a cellulosic fabric, further comprising a heat treatment.
はカルボキシル基を有する水溶性物質が、アミノ糖，糖
酸，ヒドロキシアミノ酸，タンパク質，セルロース誘導
体，ムコ多糖またはムコ多糖誘導体から選ばれることを
特徴とする請求項１記載のセルロース系布帛の加工法。2. A water-soluble substance having a hydroxyl group and an amino group and / or a carboxyl group in a molecule is selected from amino sugars, sugar acids, hydroxy amino acids, proteins, cellulose derivatives, mucopolysaccharides and mucopolysaccharide derivatives. The method for processing a cellulosic fabric according to claim 1.
樹脂加工剤とその反応触媒と分子中に２個以上の水酸基
を有する水溶性物質と分子中に２個以上のアミノ基およ
び／またはカルボキシル基を有する水溶性物質を水に混
合溶解した混合水溶液で処理し、さらに加熱処理するこ
とを特徴とするセルロース系布帛の加工法。3. A cellulose-based fabric comprising an N-methylol-based resin processing agent, a reaction catalyst thereof, a water-soluble substance having two or more hydroxyl groups in the molecule, and two or more amino groups and / or carboxyl groups in the molecule. A method for processing a cellulosic fabric, comprising treating a water-soluble substance having the following formula with a mixed aqueous solution obtained by mixing and dissolving the same in water, followed by heat treatment.
性物質が、糖アルコール，ポリアルコール，単糖，オリ
ゴ糖，多糖から選ばれ、分子中に２個以上のアミノ基お
よび／またはカルボキシル基を有する水溶性物質が、ア
ミノ酸，ポリアミン，ポリアミノ酸，ポリカルボン酸か
ら選ばれることを特徴とする請求項３記載のセルロース
系布帛の加工法。4. A water-soluble substance having two or more hydroxyl groups in a molecule is selected from sugar alcohols, polyalcohols, monosaccharides, oligosaccharides and polysaccharides, and two or more amino groups and / or carboxyls in the molecule. The method for processing a cellulosic fabric according to claim 3, wherein the water-soluble substance having a group is selected from amino acids, polyamines, polyamino acids, and polycarboxylic acids.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35572098A JP2000178881A (en) | 1998-12-15 | 1998-12-15 | Processing of cellulosic cloth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP35572098A JP2000178881A (en) | 1998-12-15 | 1998-12-15 | Processing of cellulosic cloth |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2000178881A true JP2000178881A (en) | 2000-06-27 |
Family
ID=18445427
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP35572098A Pending JP2000178881A (en) | 1998-12-15 | 1998-12-15 | Processing of cellulosic cloth |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2000178881A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004018765A1 (en) * | 2002-08-19 | 2004-03-04 | Unilever Plc | Fabric care composition |
| WO2006120851A1 (en) * | 2005-05-02 | 2006-11-16 | Kyowa Hakko Kogyo Co., Ltd. | Agent for imparting functions to textile products |
| JP2014088580A (en) * | 2005-07-26 | 2014-05-15 | Knauf Insulation Gmbh | Binder and material made from binder |
-
1998
- 1998-12-15 JP JP35572098A patent/JP2000178881A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004018765A1 (en) * | 2002-08-19 | 2004-03-04 | Unilever Plc | Fabric care composition |
| WO2006120851A1 (en) * | 2005-05-02 | 2006-11-16 | Kyowa Hakko Kogyo Co., Ltd. | Agent for imparting functions to textile products |
| JP2014088580A (en) * | 2005-07-26 | 2014-05-15 | Knauf Insulation Gmbh | Binder and material made from binder |
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