JP2004232093A - Bleaching ingredient-containing cellulose fiber or fiber product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a cellulose fiber and a cellulose fiber product designed to make a bleaching ingredient contained in the cellulose fiber transfer to perspiration, etc., and contact the skin. <P>SOLUTION: The cellulose fiber or cellulose fiber product is composed so as to be bound with at least one kind of bleaching ingredient selected from the group consisting of ferulic acid and its ester and hydroquinone through a chemical bond selected from an ester bond, an acetal bond, an ether bond and a urethane bond. The cellulose fiber or cellulose fiber product is produced by applying and/or impregnating with (1) the bleaching ingredient and (2) a compound binding the bleaching ingredient to the cellulose fiber or cellulose fiber product with the chemical bond selected from the ester bond, acetal bond, ether bond and urethane bond into the cellulose fiber or cellulose fiber product and then carrying out a heat treatment. <P>COPYRIGHT: (C)2004,JPO&NCIPI

Description

【００３３】
［式中、Ｒは−Ｏ−Ｒ^１−Ｏ−又は−Ｏ（Ｒ^２Ｏ）_ｎ−を示す。ここでＲ^１は炭素数２〜１２の直鎖又は分枝鎖状アルキレン基を示す。Ｒ^２は−ＣＨ_２ＣＨ_２−、−ＣＨ_２−ＣＨ（ＣＨ_３）−又は−（ＣＨ_２）_４−を示し、ｎは４〜５０の整数を示す。］
で表されるジグリシジルエーテルを挙げることができ、具体的にはエチレングリコールジグリシジルエーテル、ジエチレングリコールジグリシジルエーテル、トリエチレングリコールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル（ｎ＝４〜５０）、プロピレングリコールジグリシジルエーテル、ジプロピレングリコールジグリシジルエーテル、トリプロピレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル（ｎ＝４〜５０）、ネオペンチルグリコールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、グリセロールジグリシジルエーテル、ジグリシジルポリシロキサン等が挙げられる。
【００３４】
トリグリシジル化合物としては、例えばグリセロールトリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル等が挙げられる。
【００３５】
ポリトリグリシジル化合物としては、例えばポリグリセロールポリグリシジルエーテル、ソルビトールポリグリシジルエーテル、ポリグリシジルポリシロキサン等が挙げられる。
【００３６】
脂環式エポキシ化合物としては、例えば３，４−エポキシシクロヘキシルメチル−３’，４’−エポキシシクロヘキサンカルボキシレート等が挙げられる。
【００３７】
異節環状型エポキシ化合物としては、例えばトリグリシジルイソシアヌレート等が挙げられる。
【００３８】
上記一般式（１）で表されるジグリシジルエーテルの中でも、Ｒ^１がエチレングリコール系、ポリエチレングリコール系、グリセリン系であるものが好ましい。
【００３９】
市販品としては、ナガセ化成工業社製のデナコールＥＸシリーズ等が挙げられる。
【００４０】
活性ビニル化合物としては、分子内にジアクリロイル基を有する化合物、分子内にジメタクリロイル基を有する化合物、分子内にトリアリル基を有する化合物、分子内にテトラアリル基を有する化合物、分子内にペンタアリル基を有する化合物等を挙げることができる。
【００４１】
分子内にジアクリロイル基を有する化合物としては、具体的にはエチレングリコールジアクリレート、ジエチレングリコールジアクリレート、ポリエチレングリコールジアクリレート（ｎ＝３〜５０）、１，４−ブタンジオールジアクリレート、１，６−ヘキサンジオールジアクリレート、１，９−ノナンジオールジアクリレート、ネオペンチルグリコールジアクリレート、ジメチロールトリシクロデカンジアクリレート、トリプロピレングリコールジアクリレート、ビスフェノールＡのエチレンオキシド付加物ジアクリレート、ビスフェノールＡのプロピレンオキシド付加物ジアクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジアクリレート等を例示できる。
【００４２】
分子内にジメタクリロイル基を有する化合物としては、具体的にはエチレングリコールジメタクリレート、ジエチレングリコールジメタクリレート、ポリエチレングリコールジメタクリレート（ｎ＝３〜５０）、１，３−ブタンジオールジメタクリレート、１，４−ブタンジオールジメタクリレート、１，６−ヘキサンジオールジメタクリレート、１，９−ノナンジオールジメタクリレート、１，１０−デカンジオールジメタクリレート、グリセリンジメタクリレート、ネオペンチルグリコールジメタクリレート、ジメチロールトリシクロデカンジメタクリレート、トリプロピレングリコールジメタクリレート、ビスフェノールＡのエチレンオキシド付加物ジメタクリレート、ビスフェノールＡのプロピレンオキシド付加物ジメタクリレート、ヒドロキシピバリン酸ネオペンチルグリコールジメタクリレート、ヘキサヒドロフタル酸ジアリル、ジアリルオルソフタレート、ジアリルイソフタレート、ジアリルテレフタレート、ジビニルベンゼン、１，１’−ビフェニル−２，２’−ジカルボン酸ジアリル、ジアリルクロレンデート、Ｎ，Ｎ−メチレンビスアクリルアミド等を例示できる。
【００４３】
分子内にトリアリル基を有する化合物としては、具体的にはトリメチロールプロパントリアリルエーテル、トリメチロールプロパントリアクリレートとそのエチレンオキシド変性物、トリメチロールプロパントリメタクリレート、ペンタエリスリトールトリアリルエーテル、ペンタエリスリトールトリアクリレート、ペンタエリスリトールトリメタクリレート、トリアリルトリメリテート、トリアリルイソシアヌレート、トリアリルシアヌレート、トリアクリルホルマール、トリメタアリルイソシアヌレート等を例示できる。
【００４４】
分子内にテトラアリル基を有する化合物としては、具体的にはジトリメチロールプロパンテトラアクリレート、ペンタエリスリトールテトラアクリレート等を例示できる。
【００４５】
分子内にペンタアリル基を有する化合物としては、具体的にはジペンタエリスリトールヘキサアクリレート等を例示できる。
【００４６】
活性ビニル化合物としては、分子内にジアクリロイル基を有する化合物や分子内にジメタクリロイル基を有する化合物が好ましく、特にポリエチレングリコールジアクリレート（ｎ＝３〜５０）やポリエチレングリコールジメタクリレート（ｎ＝３〜５０）が好ましい。
【００４７】
ウレタン結合（−ＮＣＯＯ−）により美白成分とセルロース繊維又はセルロース繊維製品とを結合させることができる化合物としては、例えばジイソシアネート化合物、トリイソシアネート化合物、ポリイソシアネート化合物等の他、ｍ−イソプロペニル−α，α−ジメチルベンジルイソシアネート等を挙げることができる。
【００４８】
ジイソシアネート化合物としては、具体的にはトリレンジイソシアネート、４，４−ジフェニルメタンジイソシアネート、キシリレンジイソシアネート、１，３−ビス（イソシアナトメチル）シクロヘキサン、ヘキサメチレンジイソシアネート、ドデカメチレンジイソシアネート、テトラメチルキシリレンジイソシアネート、イソホロンジイソシアネート、１，５−ナフタレンジイソシアネート、ｏ−トリジンジイソシアネート、ジシクロヘキシルメタンジイソシアネート等を例示できる。
【００４９】
トリイソシアネート化合物としては、具体的にはトリフェニルメタントリイソシアネート等を例示できる。
【００５０】
ポリイソシアネート化合物としては、具体的にはポリメチレンポリフェニルポリイソシアネート等を例示できる。
【００５１】
本発明では、上記ジイソシアネート化合物、トリイソシアネート化合物、ｍ−イソプロペニル−α，α−ジメチルベンジルイソシアネート等は、活性イソシアネート基がブロック剤によりブロックされたものであってもよい。ブロック剤としては、例えばオキシム（アセトオキシム、シクロヘキサノンオキシム）、ラクタム（ε−カプロラクタム）、ジエチルマロネート、アセト酢酸エチル、アセチルアセトン、重亜硫酸塩等を挙げることができる。
【００５２】
これらの中でも、ジイソシアネート化合物が好ましく、ヘキサメチレンジイソシアネートが特に好ましい。
【００５３】
市販品としては、第一工業製薬社製のエラストロンシリーズ等が挙げられる。
【００５４】
エステル結合、アセタール結合、エーテル結合及びウレタン結合から選ばれた化学結合により美白成分とセルロース繊維又はセルロース繊維製品とを結合させることができる化合物（以下これらの化合物を「化学結合形成化合物」という）としては、上記に例示した化合物を１種単独で使用してもよいし、２種以上混合して使用してもよい。
【００５５】
美白成分とセルロース繊維又はセルロース繊維製品との間の化学結合は、エステル結合、アセタール結合又はエーテル結合（Ｎ−メチロール化合物によるエーテル結合）であるのが好ましい。これらの化学結合の場合、セルロース繊維又はセルロース繊維製品が汗等と接触すると、加水分解を受けた美白成分が徐々に放出され、美白効果を長期に亘って発現できる。
【００５６】
本発明では、化学結合形成化合物は、セルロース繊維又はセルロース繊維製品中に０．１〜２０重量％、好ましくは０．５〜１０重量％含有されているのがよい。
【００５７】
本発明のセルロース繊維又はセルロース繊維製品の製造方法
方法Ａ：
本発明のセルロース繊維又はセルロース繊維製品は、セルロース繊維又はセルロース繊維製品に美白成分及び化学結合形成化合物を付着及び／又は含浸させ、次いで熱処理することにより製造される。
【００５８】
セルロース繊維又はセルロース繊維製品へ美白成分及び化学結合形成化合物を付着及び／又は含浸させるに当たっては、従来公知の方法、例えば浸漬法、スプレー法、コーティング法等従来公知の各種の方法を広く適用することができる。
【００５９】
本発明では、美白成分及び化学結合形成化合物を含有する処理液中に処理すべきセルロース繊維又はセルロース繊維製品を浸漬する、いわゆる、浸漬法を採用するのが好ましい。尚、化学結合形成化合物としてＮ−メチロール化合物を用いる場合には、触媒を配合しておくのが好ましい。このような触媒としては、例えば塩化アルミニウム 、硫酸アルミニウム 、塩基性塩化アルミニウム、硫酸マグネシウム、塩化マグネシウム 、リン酸二水素マグネシウム 、ホウフッ化亜鉛 、硝酸亜鉛 、塩化亜鉛 、ホウフッ化マグネシウム 、過塩素酸マグネシウム等の各種金属塩（結晶水含有物も含む）類、硫酸、塩酸、硝酸、りん酸等の強酸のアンモニウム塩類、２ −アミノ−２ −メチル−１ −プロパノールの塩酸塩等の各種アルカノールアミンの酸性塩及びこれらの混合物等が挙げられる。
【００６０】
以下、浸漬法につき詳述する。
【００６１】
処理液中の美白成分濃度及び化学結合形成化合物濃度は、処理液の絞り率と必要とする担持量より算出した濃度に設定すればよい。
【００６２】
本発明では、一つの処理液中に所定濃度の美白成分及び化学結合形成化合物が全て含有されていてもよいし、これら美白成分及び化学結合形成化合物が別個の処理液中に含有されていてもよい。
【００６３】
上記処理液のｐＨは０〜６、好ましくは２〜５に調整されていることが好ましい。処理液のｐＨがこの範囲であれば、本発明で所望するセルロース繊維又はセルロース繊維製品を得ることができる。当該範囲のｐＨは処理液に対して中和剤、即ち適当なアルカリ又は塩を添加することにより調整できる。
【００６４】
ｐＨの調整に使用される中和剤として、例えば水酸化ナトリウム、重炭酸ナトリウム、炭酸ナトリウム、過炭酸ナトリウム、ホウ酸ナトリウム、メタホウ酸ナトリウム、水素化ホウ素ナトリウム、ケイ酸ナトリウム、メタケイ酸ナトリウム、亜硫酸ナトリウム、チオ硫酸ナトリウム、リン酸ナトリウム、リン酸水素ナトリウム、メタリン酸ナトリウム、ポリリン酸ナトリウム、ピロリン酸ナトリウム、亜リン酸ナトリウム、次亜リン酸ナトリウム、ギ酸ナトリウム、酢酸ナトリウム、リンゴ酸ナトリウム、酒石酸ナトリウム、乳酸ナトリウム等が挙げられる。また、上記のナトリウム塩に代わり、カリウム塩、アンモニウム塩、メチルアミン、ジメチルアミン、トリメチルアミン、トリエチルアミン等の揮発性の低級アミンの塩も使用できる。これらの中和剤は、単独で又は２種以上を組み合わせて使用してもよい。
【００６５】
上記中和剤の添加量は、使用される美白成分及び化学結合形成化合物の溶解量や種類にもよるが、処理液中の濃度として通常０．１〜１０重量％程度とするのがよい。
【００６６】
上記処理液を構成する溶媒としては有機溶媒でも差支えないが、安全、価格を考慮すれば水を溶媒にするのが好ましい。上記化学結合形成化合物が水不溶性のものであれば、適当な界面活性剤を使用するのがよい。処理液の形態は、所定の効果が得られる限り特に限定されるものではなく、溶液の形態であっても乳化液の形態であってもよいが、処理効率及び安全性の観点から水溶液又は水分散液であることが好ましい。
【００６７】
上記処理液のセルロース繊維又はセルロース繊維製品に対する浸透速度は充分に速く、浸漬時間、浴温度に特に制限はない。通常、浸漬時間０．１〜３００秒、浴温は１０〜４０℃で行われる。絞りは加工する製品によって異なり、夫々に適当な絞り方法、絞り率が採用できる。通常、絞り率は３０〜２００％で行うのが好ましい。
【００６８】
浸漬、絞りを行った後、乾燥を行う。工業的には、乾燥温度は４０〜１５０℃、時間は温度に応じて選定すればよい。
【００６９】
本発明においては、美白成分及び化学結合形成化合物を付着及び／又は含浸させたセルロース繊維又はセルロース繊維製品を次いで加熱処理する。
【００７０】
加熱処理の温度は、通常１００〜２５０℃、好ましくは１２０〜２００℃、処理時間は２０秒〜１時間である。これより穏やかな条件では、加工処理されたセルロース繊維又はセルロース繊維製品の美白成分保持性能が洗濯を繰り返すことにより低下する傾向になり、厳しすぎる条件では繊維の劣化を引き起こし、強度低下や繊維黄変として表れる傾向が生ずるので、いずれも好ましくない。
【００７１】
方法Ｂ：
本発明のセルロース繊維製品は、セルロース繊維に美白成分を付着及び／又は含浸させ、次いで乾燥した後、縫製等によりセルロース繊維製品とし、最後に該セルロース繊維製品を気相ホルマリン加工処理することによっても製造される。
【００７２】
セルロース繊維に美白成分を付着及び／又は含浸させる工程、及び乾燥工程の各手段や条件は、方法Ａと同じでよい。
【００７３】
気相ホルマリン加工処理につき、以下に説明する。
【００７４】
ホルマリンを吸着させるために適度な水分率に調節した後、気相ホルマリン加工処理すべきセルロース繊維製品にホルムアルデヒドガスを吸着させ、熱処理してホルムアルデヒドを架橋せしめる。
【００７５】
架橋反応をさせる際に用いる触媒は、予めセルロース繊維製品に触媒溶液をパディングした後に気相処理を行ってもよいし、触媒溶液又は液化している触媒を気化又はミスト化してセルロース繊維製品に吸着させてもよい。或いは、セルロース繊維に美白成分を付着及び／又は含浸させる際に、触媒をセルロース繊維に吸着させておいてもよい。
【００７６】
触媒としては、例えば塩化水素ガス、亜硫酸ガス等のガス、塩酸、硝酸、硫酸、りん酸等の無機酸、グリコール酸、マレイン酸、乳酸、クエン酸、酒石酸、蓚酸等の有機酸等を挙げることができる。また、例えば塩化アルミニウム 、硫酸アルミニウム 、塩基性塩化アルミニウム、硫酸マグネシウム、塩化マグネシウム 、リン酸二水素マグネシウム 、ホウフッ化亜鉛 、硝酸亜鉛 、塩化亜鉛 、ホウフッ化マグネシウム 、過塩素酸マグネシウム等の各種金属塩（結晶水含有物も含む）類、硫酸、塩酸、硝酸、りん酸等の強酸のアンモニウム塩類、２ −アミノ−２ −メチル−１ −プロパノールの塩酸塩等の各種アルカノールアミンの酸性塩及びこれらの混合物等のルイス酸も触媒として使用可能である。
【００７７】
ホルムアルデヒドガスを吸着させた後、セルロース繊維製品を熱処理して架橋反応を行うが、この熱処理は、１００〜１８０℃の範囲の温度、０．５〜１０分間の処理を行うことにより架橋反応を完結することができる。
【００７８】
方法Ｃ：
本発明のセルロース繊維製品は、セルロース繊維製品に美白成分を付着及び／又は含浸させ、必要に応じて乾燥した後、該セルロース繊維製品を気相ホルマリン加工処理することにより製造される。
【００７９】
セルロース繊維製品に美白成分を付着及び／又は含浸させる工程、及びホルマリン加工処理工程の各手段や条件は、方法Ａ及び方法Ｂと同じでよい。
【００８０】
本発明では、方法Ａに従いセルロース繊維又はセルロース繊維製品を製造するのが特に好ましい。方法Ａに従い製造されたセルロース繊維又はセルロース繊維製品は、一段と優れた美白成分保持性能を発現する。
【００８１】
【発明の効果】
本発明によれば、美白成分を含有するセルロース繊維及びセルロース繊維製品が提供される。
【００８２】
本発明のセルロース繊維又はセルロース繊維製品は、セルロース繊維又はセルロース繊維製品に含まれる美白成分が徐々に汗等に移行し、皮膚に接触できるようなるので、美白効果を長期に亘って発現できる。
【００８３】
本発明のセルロース繊維又はセルロース繊維製品は、洗濯を繰り返し行っても美白成分が繊維から殆ど脱落しない性能（耐洗濯性）を備えている。
【００８４】
本発明のセルロース繊維又はセルロース繊維製品は、皮脂の酸化を防止する性能を備えており、防臭性能に優れている。
【００８５】
本発明のセルロース繊維又はセルロース繊維製品は、優れた紫外線吸収性能を有している。
【００８６】
【実施例】
以下に実施例及び比較例を掲げて、本発明をより一層明らかにする。
【００８７】
実施例１
目付１５０ｇ／ｍ^２の綿織物を精練、漂白、シルケット処理の後、１，２，３，４−ブタンテトラカルボン酸３重量％、第二リン酸ナトリウム１．５重量％及びフェルラ酸０．２重量％を含む水溶液に浸漬後、マングルで絞り（絞り率：７０％）、１００℃で乾燥後１６０℃で２分間熱処理を行い、本発明の綿織物を得た。
【００８８】
この綿織物は、フェルラ酸を０．１４重量％含有していた。また、フェルラ酸はエステル結合を介して綿織物に強固に結合していた。
【００８９】
実施例２
目付１５０ｇ／ｍ^２の綿織物を精練、漂白、シルケット処理の後、ジメチロールジヒドロキシエチレン尿素（商品名：スミテックスＮＳ２００、住友化学工業社製）５重量％、塩化マグネシウム１重量％及びフェルラ酸０．２重量％を含む水溶液に浸漬後、マングルで絞り（絞り率：７０％）、１００℃で乾燥後１６０℃で２分間熱処理を行い、本発明の綿織物を得た。
【００９０】
この綿織物は、フェルラ酸を０．１４重量％含有していた。また、フェルラ酸はエーテル結合を介して綿織物に強固に結合していた。
【００９１】
比較例１
目付１５０ｇ／ｍ^２の綿織物を精練、漂白、シルケット処理の後、フェルラ酸０．２重量％を含む水溶液に浸漬後、マングルで絞り（絞り率：７０％）、１００℃で乾燥後１６０℃で２分間熱処理を行い、比較のための綿織物を得た。
【００９２】
比較例２
目付１５０ｇ／ｍ^２の綿織物を精練、漂白、シルケット処理の後、１，２，３，４−ブタンテトラカルボン酸３重量％及び第二リン酸ナトリウム１．５重量％を含む水溶液に浸漬後、マングルで絞り（絞り率：７０％）、１００℃で乾燥後１６０℃で２分間熱処理を行い、比較のための綿織物を得た。
【００９３】
比較例３
目付１５０ｇ／ｍ^２の綿織物を精練、漂白、シルケット処理の後、ジメチロールジヒドロキシエチレン尿素系樹脂（商品名：スミテックスＮＳ２００、住友化学工業社製）５重量％及び塩化マグネシウム１重量％を含む水溶液に浸漬後、マングルで絞り（絞り率：７０％）、１００℃で乾燥後１６０℃で２分間熱処理を行い、比較のための綿織物を得た。
【００９４】
試験例１（フェルラ酸の洗濯耐久性試験）
上記実施例１〜２及び比較例１〜３で得られた各綿織物にフェルラ酸判定液（１０％水酸化カリウムエタノール溶液）を滴下し、１分後の着色の有無を調べた。このフェルラ酸判定液を用いると、フェルラ酸があると黄色に着色し、フェルラ酸がなければ無色のままである。結果を表１に示す。
【００９５】
更に、上記実施例１〜２及び比較例１〜３で得られた各綿織物をそれぞれ１０回洗濯したものについても、上記と同様にして、着色の有無を調べた。結果を表１に併せて示す。
【００９６】
尚、洗濯は花王（株）製の花王ニュービーズを５ｇ／リットルの割合で溶解した水溶液を用い、４０℃で１０分間、家庭用洗濯機中で洗濯し、次いで水洗し、乾燥する操作を１サイクルとして、このサイクルを１０回繰り返した。
【００９７】
【表１】

【００９８】
表１から、実施例１〜２で得られた綿織物は、洗濯前は勿論のこと、洗濯を１０回行った後においてもフェルラ酸を保持していることが明らかである。
【００９９】
試験例２（フェルラ酸の汗への溶出試験）
上記実施例１〜２及び比較例１〜３で得られた各綿織物（洗濯前、５回洗濯後及び１０回洗濯後）に未処理綿布（金巾３号綿布）を重ねて縫い合わせ、綿織物面に人工汗液（ＪＩＳ Ｌ０８４８準拠の酸性汗、アルカリ汗）を１ｍｌ滴下した。汗堅牢度試験機（ＪＩＳ Ｌ０８４８準拠）にて４時間処理した後、未処理綿布側にフェルラ酸判定液（１０％水酸化カリウムエタノール溶液）を滴下し、１分後の着色の有無を調べた。結果を表２に示す。
【０１００】
【表２】

【０１０１】
表２から、実施例１〜２で得られた綿織物では、フェルラ酸が未処理綿布に移行していることがわかる。従って、実施例１〜２で得られた綿織物は、人工汗液と接触すると、フェルラ酸を徐々に放出すること、及びこれらの綿織物は、洗濯前は勿論のこと、洗濯を５回又は１０回行った後においても同様の効果を発現することがわかる。
【０１０２】
試験例３（抗菌試験）
ＪＩＳ Ｌ１９０２に規定されている繊維製品の抗菌性定量試験に従い、抗菌性能を調べた。即ち、２×１０^５個の黄色ブドウ球菌（Ｓｔａｐｈｙｌｏｃｏｃｃｕｓ ａｕｒｅｕｓ ＡＴＣＣ６５３８Ｐ）を培地と共に未処理の綿織物並びに上記実施例１〜２及び比較例１〜３で得られた各綿織物に接種し、３５℃で１８時間培養後に各綿織物上の菌数を測定した。未加工綿織物上の菌数を基準にして、実施例１〜２及び比較例１〜３で得られた各綿織物上の菌数の割合を対数値で表し、静菌活性値とした。
【０１０３】
結果を表３に示す。
【０１０４】
【表３】

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a whitening component-containing cellulose fiber or fiber product.
[0002]
[Prior art]
Whitening agents such as creams, lotions, and emulsions containing whitening components such as kojic acid are widely available. These whitening agents are usually used by applying them to exposed parts of the skin such as the face, hands and feet. However, it is inevitable that these whitening agents easily fall off the skin due to sweat or the like. Therefore, in order to maintain the effect as a whitening agent over a long period of time, there is a disadvantage that the whitening agent must be frequently applied.
[0003]
[Problems to be solved by the invention]
An object of the present invention is to provide a cellulose fiber and a cellulose fiber product containing a whitening component.
[0004]
An object of the present invention is to provide a cellulose fiber and a cellulosic fiber product in which the whitening component contained in the cellulose fiber is transferred to sweat or the like and can be brought into contact with the skin.
[0005]
An object of the present invention is to provide a cellulose fiber and a cellulosic fiber product having a performance (washing resistance) in which a whitening component hardly falls off the fiber even after repeated washing.
[0006]
An object of the present invention is to provide a method for producing the above-mentioned cellulose fiber and cellulose fiber product.
[0007]
[Means for Solving the Problems]
The present inventors have conducted intensive studies to develop cellulose fibers and cellulose fiber products in which the above-mentioned problems have been solved. As a result, cellulose fibers and cellulose fiber products have been selected from the group consisting of (1) ferulic acid and its esters and hydroquinone. Attach at least one selected whitening component and (2) a compound capable of binding the whitening component to cellulose fiber or cellulose fiber product by a chemical bond selected from an ester bond, an acetal bond, an ether bond and a urethane bond. It has been found that the above problem can be achieved by impregnation and / or subsequent heat treatment. The present invention has been completed based on such findings.
1. The present invention relates to a cellulose to which at least one whitening component selected from the group consisting of ferulic acid and its ester and hydroquinone is bonded via a chemical bond selected from an ester bond, an acetal bond, an ether bond and a urethane bond. Fiber or cellulosic fiber products.
2. The present invention provides a cellulose fiber or a cellulose fiber product comprising at least one whitening component selected from the group consisting of (1) ferulic acid and its ester and hydroquinone; and (2) an ester bond, an acetal bond, an ether bond, and a urethane bond. The cellulose fiber or the cellulose fiber product according to the above 1, which is obtained by adhering and / or impregnating a compound capable of binding the whitening component to the cellulose fiber or the cellulose fiber product by a selected chemical bond, and then heat-treating. .
3. The present invention is the cellulose fiber or the cellulose fiber product according to the above 1, wherein the whitening component is at least one selected from the group consisting of ferulic acid and esters thereof.
4. The present invention is the cellulose fiber or the cellulose fiber product according to the above 1, wherein the compound capable of binding the whitening component to the cellulose fiber or the cellulose fiber product by a chemical bond is a polycarboxylic acid.
5. The present invention is the cellulose fiber or the cellulose fiber product according to the above item 4, wherein the polycarboxylic acid is 1,2,3,4-butanetetracarboxylic acid.
6. The present invention is the cellulose fiber or the cellulose fiber product according to the above item 1, wherein the compound capable of binding the whitening component to the cellulose fiber or the cellulose fiber product by a chemical bond is an N-methylol compound.
7. The present invention is the cellulose fiber or cellulose fiber product according to the above item 6, wherein the N-methylol compound is dimethylol dihydroxyethylene urea.
8. The present invention provides a cellulose fiber or a cellulose fiber product comprising at least one whitening component selected from the group consisting of (1) ferulic acid and its ester and hydroquinone; and (2) an ester bond, an acetal bond, an ether bond, and a urethane bond. 2. Cellulose fiber or cellulose fiber product according to the above item 1, wherein the compound capable of binding the whitening component to cellulose fiber or cellulose fiber product by a selected chemical bond is attached and / or impregnated, and then heat-treated. Is a manufacturing method.
[0008]
BEST MODE FOR CARRYING OUT THE INVENTION
Cellulose fiber or cellulose fiber product of the present invention
In the present invention, the cellulose fiber is a conventionally known cellulose fiber, for example, natural cellulose such as cotton and hemp, regenerated cellulose such as rayon, or a blend of these. The cellulose fibers of the present invention include, in addition to these fibers, primary processed products of these fibers, such as yarn, knit, woven fabric, knitted fabric, and nonwoven fabric. In particular, in the case of cotton, raw cotton itself, caustic mercerized cotton, cotton treated with liquid ammonia, and the like are also included in the cellulose fibers of the present invention.
[0009]
In the present invention, the cellulose fiber of the present invention can be blended, twisted and knitted with non-cellulosic synthetic fibers.
[0010]
As the non-cellulosic synthetic fiber, conventionally known synthetic fibers can be widely exemplified, and examples thereof include polyester, liquid crystal polyester, polyamide, liquid crystal polyamide, acryl, polyethylene, polypropylene, and spandex. Among the above synthetic fibers, polyester, polyamide, acrylic and polypropylene are preferred, and polyester is particularly preferred.
[0011]
When the above synthetic fibers are blended with cellulose fibers, the blending ratio is not particularly limited. The effect of the present invention (excellent whitening effect and washing resistance) is more exhibited when the blending ratio of the cellulose fiber is higher, but the performance of the synthetic fiber such as fiber strength which is a characteristic of the blended fiber and the fiber product is improved. In order to realize it without impairing it, it is usually good to blend the synthetic fibers at a ratio of 1 to 80% by weight, preferably 20 to 66% by weight in all the fibers.
[0012]
In the present invention, the cellulose fiber product means a product obtained by further processing the above-mentioned cellulose fiber, for example, clothing such as outer garments, middle garments, and inner garments, bedding products, and interior products. Specific examples of the cellulose fiber product of the present invention include coats, jackets, pants, skirts, shirts, knitted shirts, blouses, sweaters, cardigans, nightwear, underwear, supporters, socks, tights, hats, scarves, mufflers, and collars. Rolls, gloves, lining of clothes, interlining of clothes, batting of clothes, work clothes, lab coats, uniforms, uniforms for school children, curtains, futons, futon cotton, pillowcases, sheets, mats, carpets, towels, Products such as handkerchiefs can be exemplified. Among these, those that directly touch human skin are particularly preferable. For example, in clothing, inner garments and inner garments are preferred, and inner garments are more preferred.
[0013]
The cellulose fiber or cellulose fiber product of the present invention comprises at least one whitening component selected from the group consisting of ferulic acid and its ester and hydroquinone by a chemical bond selected from an ester bond, an acetal bond, an ether bond and a urethane bond. Is a cellulose fiber or a cellulosic fiber product to which is bonded.
[0014]
In the present invention, the whitening component is ferulic acid and its ester and hydroquinone.
[0015]
In the present invention, it is preferable to use a water-soluble whitening component. These whitening components may be used alone or as a mixture of two or more.
[0016]
As the whitening component, ferulic acid and esters thereof are preferable. Examples of the ester of ferulic acid include methyl ferulate, ethyl ferulate, n-propyl ferulate, isopropyl ferulate, n-butyl ferulate, 2-methylbutyl ferulate, n-hexyl ferulate, and n-heptyl ferulate. , 2-butylhexyl ferulate, n-octyl ferulate, n-nonyl ferulate, n-undecyl ferulate, n-dodecyl ferulate, n-hexdecyl ferulate, and the like.
[0017]
These whitening ingredients may be in the form of a salt. For example, taking ferulic acid as an example, the salts of ferulic acid include, for example, alkali metal salts of ferulic acid such as sodium ferulate, potassium ferulate, lithium ferulate, magnesium ferulate, barium ferulate, calcium ferulate and the like. And the like.
[0018]
In the present invention, the whitening component is contained in the cellulose fiber or cellulose fiber product in an amount of 0.001 to 20% by weight, preferably 0.01 to 3% by weight.
[0019]
In the present invention, as the compound capable of binding the whitening component and the cellulose fiber or cellulose fiber product by a chemical bond selected from an ester bond, an acetal bond, an ether bond and a urethane bond, for example, various compounds shown below. Examples can be given.
[0020]
Examples of the compound capable of binding the whitening component to the cellulose fiber or the cellulose fiber product by an ester bond (—COO—) include, for example, polycarboxylic acid.
[0021]
As the polycarboxylic acid, for example, a polycarboxylic acid having at least three carboxyl groups in a molecule can be used. As such a polycarboxylic acid, conventionally known polycarboxylic acids having at least three carboxyl groups can be widely used, and examples thereof include various aliphatic polycarboxylic acids, alicyclic polycarboxylic acids, and aromatic polycarboxylic acids. And polycarboxylic acids. These carboxylic acids may have a hydroxyl group, a halogen group, a carbonyl group, or a carbon-carbon double bond.
[0022]
Specific examples of such a polycarboxylic acid include tricarballylic acid, aconitic acid, methylcyclohexentricarboxylic acid, tribasic acids such as citric acid, butanetetracarboxylic acid, cyclopentanetetracarboxylic acid, tetrahydrofurantetracarboxylic acid, Tetrabasic acids such as ene adducts of methyltetrahydrophthalic acid and maleic acid, aromatic polycarboxylic acids such as trimellitic acid, pyromellitic acid, biphenyltetracarboxylic acid, benzophenonetetracarboxylic acid, diphenylsulfonetetracarboxylic acid, and styrene. Tetracarboxylic acid generated by Diels-Alder reaction and ene reaction from maleic anhydride, copolymer of maleic anhydride and acrylic acid or its hydrous acid, copolymer of maleic anhydride and methacrylic acid or its water Acid, epoxidized succinic acid It can be exemplified amounts compound like. These polycarboxylic acids are used alone or in combination of two or more. Among these polycarboxylic acids, water-soluble polycarboxylic acids such as tricarballylic acid, aconitic acid, citric acid, 1,2,3,4-butanetetracarboxylic acid are preferable because of good workability, and particularly preferable. 1,2,3,4-butanetetracarboxylic acid, a water-soluble and tetrabasic acid, is the most effective and is preferred.
[0023]
Acetal bond (-OCH₂Examples of the compound capable of binding the whitening component to the cellulose fiber or the cellulose fiber product by O-) include a compound having an aldehyde group in the molecule, and specifically, an aldehyde compound and the like.
[0024]
Examples of the aldehyde compound include formaldehyde and dialdehyde (glyoxal).
[0025]
Examples of the compound capable of binding the whitening component to the cellulose fiber or the cellulose fiber product by an ether bond (-O-) include, for example, an N-methylol compound, a compound having an epoxy group (glycidyl group) or a vinyl group in a molecule, and the like. Can be mentioned.
[0026]
Examples of the N-methylol compound include dimethylol urea and its methylated product, dimethylol ethylene urea and its methylated product, dimethylol uron and its methylated product, dimethylol triazone and its methylated product, dimethylol propylene urea and its methylated product, Dimethylol dihydroxyethylene urea, methylated dimethylol dimethoxyethylene urea, 1,3-dimethyl-4,5-dihydroxyethylene urea and its methylated product, dimethylol-4-methoxy-5,5-dimethylpropylene urea and its methylated product, Examples include dimethylol alkyl carbamate and its methylated product, tetramethylol glyoxal monourein and its methylated product, and the like.
[0027]
Of these, dimethylol dihydroxyethylene urea is preferred.
[0028]
Examples of commercially available products include Sumitec Resin Series manufactured by Sumitomo Chemical Co., Ltd. and Riken Resin Series manufactured by Miki Riken Co., Ltd.
[0029]
Compounds having an epoxy group (glycidyl group) in the molecule include, for example, aliphatic epoxy compounds, diglycidyl compounds, triglycidyl compounds, polyglycidyl compounds, alicyclic epoxy compounds, heterocyclic epoxy compounds, active vinyl compounds, and the like. Bisphenol A-epichlorohydrin compound, bisphenol A-diglycidyl ether compound and its ethylene oxide adduct or propylene oxide adduct, bisphenol F-diglycidyl ether compound, hydrogenated bisphenol A-diglycidyl ether compound, hydrogenated bisphenol F-diglycidyl Ether compounds and the like.
[0030]
Examples of the aliphatic epoxy compound include epoxidized soybean oil and epoxidized oleyl oleate.
[0031]
The diglycidyl compound is represented by the general formula (1)
[0032]
Embedded image

[0033]
[Wherein R is -OR¹-O- or -O (R²O)_nIndicates-. Where R¹Represents a linear or branched alkylene group having 2 to 12 carbon atoms. R²Is -CH₂CH₂-, -CH₂-CH (CH₃)-Or-(CH₂)₄And n represents an integer of 4 to 50. ]
And specific examples thereof include ethylene glycol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether (n = 4 to 50), and propylene glycol. Diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether (n = 4 to 50), neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol di Glycidyl ether, diglycidyl polysiloxane and the like can be mentioned.
[0034]
Examples of the triglycidyl compound include glycerol triglycidyl ether and trimethylolpropane triglycidyl ether.
[0035]
Examples of the polytriglycidyl compound include polyglycerol polyglycidyl ether, sorbitol polyglycidyl ether, and polyglycidyl polysiloxane.
[0036]
Examples of the alicyclic epoxy compound include 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate.
[0037]
Examples of the heterocyclic epoxy compound include triglycidyl isocyanurate.
[0038]
Among the diglycidyl ethers represented by the general formula (1), R¹Are preferably ethylene glycol-based, polyethylene glycol-based and glycerin-based.
[0039]
Examples of commercially available products include Denacol EX series manufactured by Nagase Kasei Kogyo Co., Ltd.
[0040]
Examples of the active vinyl compound include a compound having a diacryloyl group in the molecule, a compound having a dimethacryloyl group in the molecule, a compound having a triallyl group in the molecule, a compound having a tetraallyl group in the molecule, and a pentaallyl group in the molecule. And the like.
[0041]
As the compound having a diacryloyl group in the molecule, specifically, ethylene glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate (n = 3 to 50), 1,4-butanediol diacrylate, 1,6- Hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, dimethylol tricyclodecane diacrylate, tripropylene glycol diacrylate, ethylene oxide adduct of bisphenol A diacrylate, propylene oxide adduct of bisphenol A Examples thereof include diacrylate and neopentyl glycol diacrylate hydroxypivalate.
[0042]
Specific examples of the compound having a dimethacryloyl group in the molecule include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate (n = 3 to 50), 1,3-butanediol dimethacrylate, 1,4- Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9-nonanediol dimethacrylate, 1,10-decanediol dimethacrylate, glycerin dimethacrylate, neopentyl glycol dimethacrylate, dimethylol tricyclodecane dimethacrylate, Tripropylene glycol dimethacrylate, ethylene oxide adduct dimethacrylate of bisphenol A, propylene oxide adduct dimethacrylate of bisphenol A Neopentyl glycol dimethacrylate hydroxypivalate, diallyl hexahydrophthalate, diallyl orthophthalate, diallyl isophthalate, diallyl terephthalate, divinyl benzene, diallyl 1,1′-biphenyl-2,2′-dicarboxylate, diallyl chlorendate, N, N-methylenebisacrylamide and the like can be exemplified.
[0043]
As the compound having a triallyl group in the molecule, specifically, trimethylolpropane triallyl ether, trimethylolpropane triacrylate and its ethylene oxide modified product, trimethylolpropane trimethacrylate, pentaerythritol triallyl ether, pentaerythritol triacrylate, Examples thereof include pentaerythritol trimethacrylate, triallyl trimellitate, triallyl isocyanurate, triallyl cyanurate, triacryl formal, and trialmethallyl isocyanurate.
[0044]
Specific examples of the compound having a tetraallyl group in the molecule include ditrimethylolpropane tetraacrylate, pentaerythritol tetraacrylate, and the like.
[0045]
Specific examples of the compound having a pentaallyl group in the molecule include dipentaerythritol hexaacrylate.
[0046]
As the active vinyl compound, a compound having a diacryloyl group in the molecule or a compound having a dimethacryloyl group in the molecule is preferable. In particular, polyethylene glycol diacrylate (n = 3 to 50) or polyethylene glycol dimethacrylate (n = 3 to 50) is preferred.
[0047]
Examples of the compound capable of binding the whitening component to the cellulose fiber or the cellulose fiber product by a urethane bond (-NCOO-) include, for example, diisocyanate compounds, triisocyanate compounds, polyisocyanate compounds, and m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like.
[0048]
As the diisocyanate compound, specifically, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate, xylylene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, hexamethylene diisocyanate, dodecamethylene diisocyanate, tetramethyl xylylene diisocyanate, Examples include isophorone diisocyanate, 1,5-naphthalenediisocyanate, o-tolidine diisocyanate, dicyclohexylmethane diisocyanate, and the like.
[0049]
Specific examples of the triisocyanate compound include triphenylmethane triisocyanate.
[0050]
Specific examples of the polyisocyanate compound include polymethylene polyphenyl polyisocyanate.
[0051]
In the present invention, the above-mentioned diisocyanate compound, triisocyanate compound, m-isopropenyl-α, α-dimethylbenzyl isocyanate and the like may have an active isocyanate group blocked by a blocking agent. Examples of the blocking agent include oximes (acetoxime, cyclohexanone oxime), lactams (ε-caprolactam), diethyl malonate, ethyl acetoacetate, acetylacetone, and bisulfite.
[0052]
Among these, diisocyanate compounds are preferred, and hexamethylene diisocyanate is particularly preferred.
[0053]
Examples of commercially available products include Elastron series manufactured by Daiichi Kogyo Seiyaku Co., Ltd.
[0054]
As a compound capable of binding a whitening component to a cellulose fiber or a cellulose fiber product by a chemical bond selected from an ester bond, an acetal bond, an ether bond, and a urethane bond (hereinafter, these compounds are referred to as “chemical bond forming compounds”) May be used singly or as a mixture of two or more of the compounds exemplified above.
[0055]
The chemical bond between the whitening component and the cellulose fiber or cellulose fiber product is preferably an ester bond, an acetal bond, or an ether bond (an ether bond by an N-methylol compound). In the case of these chemical bonds, when the cellulose fiber or the cellulose fiber product comes into contact with sweat or the like, the whitening component that has undergone hydrolysis is gradually released, and the whitening effect can be exhibited over a long period of time.
[0056]
In the present invention, the chemical bond forming compound is contained in the cellulose fiber or cellulose fiber product in an amount of 0.1 to 20% by weight, preferably 0.5 to 10% by weight.
[0057]
Method for producing cellulose fiber or cellulose fiber product of the present invention
Method A:
The cellulosic fiber or cellulosic fiber product of the present invention is produced by adhering and / or impregnating the cellulosic fiber or cellulosic product with a whitening component and a chemical bond-forming compound, followed by heat treatment.
[0058]
In adhering and / or impregnating the whitening component and the chemical bond-forming compound to the cellulose fiber or the cellulosic fiber product, various conventionally known methods such as a dipping method, a spraying method and a coating method are widely applied. Can be.
[0059]
In the present invention, it is preferable to adopt a so-called immersion method of immersing a cellulose fiber or a cellulose fiber product to be treated in a treatment solution containing a whitening component and a chemical bond forming compound. When an N-methylol compound is used as the chemical bond forming compound, it is preferable to add a catalyst. Examples of such a catalyst include aluminum chloride, aluminum sulfate, basic aluminum chloride, magnesium sulfate, magnesium chloride, magnesium dihydrogen phosphate, zinc borofluoride, zinc nitrate, zinc chloride, magnesium borofluoride, and magnesium perchlorate. Acid salts of various alkanolamines such as various metal salts (including those containing water of crystallization), ammonium salts of strong acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, and hydrochlorides of 2-amino-2-methyl-1-propanol And salts and mixtures thereof.
[0060]
Hereinafter, the immersion method will be described in detail.
[0061]
The concentration of the whitening component and the concentration of the chemical bond-forming compound in the treatment liquid may be set to the concentrations calculated from the squeezing rate of the treatment liquid and the required amount of the support.
[0062]
In the present invention, all of the whitening component and the chemical bond-forming compound at a predetermined concentration may be contained in one treatment liquid, or these whitening components and the chemical bond-forming compound may be contained in separate treatment liquids. Good.
[0063]
The pH of the treatment liquid is preferably adjusted to 0 to 6, preferably 2 to 5. If the pH of the treatment liquid is within this range, the cellulose fibers or cellulose fiber products desired in the present invention can be obtained. The pH in this range can be adjusted by adding a neutralizing agent, that is, an appropriate alkali or salt to the treatment solution.
[0064]
Examples of neutralizing agents used for adjusting pH include sodium hydroxide, sodium bicarbonate, sodium carbonate, sodium percarbonate, sodium borate, sodium metaborate, sodium borohydride, sodium silicate, sodium metasilicate, and sulfurous acid. Sodium, sodium thiosulfate, sodium phosphate, sodium hydrogen phosphate, sodium metaphosphate, sodium polyphosphate, sodium pyrophosphate, sodium phosphite, sodium hypophosphite, sodium formate, sodium acetate, sodium malate, sodium tartrate , Sodium lactate and the like. In place of the above sodium salts, salts of volatile lower amines such as potassium salts, ammonium salts, methylamine, dimethylamine, trimethylamine and triethylamine can also be used. These neutralizing agents may be used alone or in combination of two or more.
[0065]
The amount of the neutralizing agent to be added depends on the amount and type of the whitening component and the chemical bond forming compound to be used, but it is generally preferable that the concentration in the treatment liquid is about 0.1 to 10% by weight.
[0066]
An organic solvent may be used as a solvent constituting the treatment liquid, but water is preferably used as the solvent in consideration of safety and cost. If the chemical bond-forming compound is water-insoluble, a suitable surfactant is preferably used. The form of the treatment liquid is not particularly limited as long as a predetermined effect is obtained, and may be in the form of a solution or an emulsion, but from the viewpoint of treatment efficiency and safety, an aqueous solution or water It is preferably a dispersion.
[0067]
The rate of penetration of the treatment liquid into cellulose fibers or cellulose fiber products is sufficiently high, and there is no particular limitation on the immersion time and bath temperature. Usually, the immersion time is 0.1 to 300 seconds, and the bath temperature is 10 to 40 ° C. The drawing differs depending on the product to be processed, and an appropriate drawing method and drawing ratio can be adopted for each. Usually, it is preferable that the drawing ratio is 30 to 200%.
[0068]
After immersion and squeezing, drying is performed. Industrially, the drying temperature may be selected from 40 to 150 ° C., and the time may be selected according to the temperature.
[0069]
In the present invention, the cellulose fiber or the cellulose fiber product to which the whitening component and the chemical bond forming compound are attached and / or impregnated is then heat-treated.
[0070]
The temperature of the heat treatment is usually 100 to 250 ° C, preferably 120 to 200 ° C, and the treatment time is 20 seconds to 1 hour. Under milder conditions, the whitening component retention performance of the processed cellulose fiber or cellulose fiber product tends to decrease due to repeated washing, and under too severe conditions, the fiber deteriorates, resulting in reduced strength and yellowing of the fiber. Are not preferred.
[0071]
Method B:
The cellulose fiber product of the present invention can also be obtained by adhering and / or impregnating a whitening component to the cellulose fiber and then drying the cellulose fiber to obtain a cellulose fiber product by sewing or the like, and finally subjecting the cellulose fiber product to a gas-phase formalin treatment. Manufactured.
[0072]
The means and conditions for the step of adhering and / or impregnating the cellulose fiber with the whitening component and the drying step may be the same as those in the method A.
[0073]
The gas phase formalin processing will be described below.
[0074]
After adjusting the water content to a suitable level to adsorb formalin, formaldehyde gas is adsorbed on the cellulose fiber product to be subjected to gas-phase formalin processing, and heat treatment is performed to crosslink the formaldehyde.
[0075]
The catalyst used for the cross-linking reaction may be subjected to a gas phase treatment after padding the catalyst solution to the cellulose fiber product in advance, or the catalyst solution or the liquefied catalyst may be vaporized or mist-adsorbed to the cellulose fiber product. You may let it. Alternatively, the catalyst may be adsorbed to the cellulose fibers when the whitening component is attached and / or impregnated to the cellulose fibers.
[0076]
Examples of the catalyst include gases such as hydrogen chloride gas and sulfurous acid gas, inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid, and organic acids such as glycolic acid, maleic acid, lactic acid, citric acid, tartaric acid, and oxalic acid. Can be. In addition, various metal salts such as aluminum chloride, aluminum sulfate, basic aluminum chloride, magnesium sulfate, magnesium chloride, magnesium dihydrogen phosphate, zinc borofluoride, zinc nitrate, zinc chloride, magnesium borofluoride, magnesium perchlorate, etc. (Including those containing water of crystallization), ammonium salts of strong acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, acid salts of various alkanolamines such as hydrochloride of 2-amino-2-methyl-1-propanol and mixtures thereof And the like can also be used as a catalyst.
[0077]
After adsorbing the formaldehyde gas, the cellulose fiber product is subjected to a heat treatment to perform a crosslinking reaction. The heat treatment is performed at a temperature in the range of 100 to 180 ° C. for 0.5 to 10 minutes to complete the crosslinking reaction. can do.
[0078]
Method C:
The cellulosic fiber product of the present invention is produced by adhering and / or impregnating a whitening component to the cellulosic fiber product, drying if necessary, and then subjecting the cellulosic fiber product to a gas phase formalin treatment.
[0079]
The means and conditions of the step of adhering and / or impregnating the whitening component to the cellulose fiber product and the formalin processing step may be the same as those in the methods A and B.
[0080]
In the present invention, it is particularly preferable to produce a cellulose fiber or a cellulose fiber product according to the method A. Cellulose fibers or cellulosic fiber products produced according to Method A exhibit even more excellent whitening component retention performance.
[0081]
【The invention's effect】
According to the present invention, a cellulose fiber and a cellulose fiber product containing a whitening component are provided.
[0082]
The cellulosic fiber or the cellulosic fiber product of the present invention allows the whitening component contained in the cellulosic fiber or the cellulosic fiber product to gradually migrate to sweat or the like and come into contact with the skin, so that the whitening effect can be exhibited over a long period of time.
[0083]
The cellulosic fiber or cellulosic fiber product of the present invention has a performance (washing resistance) in which the whitening component hardly falls off the fiber even after repeated washing.
[0084]
The cellulose fiber or cellulose fiber product of the present invention has a performance of preventing sebum from being oxidized, and is excellent in deodorant performance.
[0085]
The cellulose fiber or cellulose fiber product of the present invention has excellent ultraviolet absorption performance.
[0086]
【Example】
Hereinafter, the present invention will be further clarified with reference to Examples and Comparative Examples.
[0087]
Example 1
150g / m²After scouring, bleaching and mercerizing the cotton fabric of the above, it was converted to an aqueous solution containing 1,2,3,4-butanetetracarboxylic acid 3% by weight, dibasic sodium phosphate 1.5% by weight and ferulic acid 0.2% by weight. After immersion, it was squeezed with a mangle (squeezing ratio: 70%), dried at 100 ° C, and heat-treated at 160 ° C for 2 minutes to obtain the cotton fabric of the present invention.
[0088]
This cotton fabric contained 0.14% by weight of ferulic acid. Ferulic acid was firmly bound to the cotton fabric via an ester bond.
[0089]
Example 2
150g / m²After scouring, bleaching, and mercerizing cotton fabric, contains 5% by weight of dimethylol dihydroxyethylene urea (trade name: Sumitex NS200, manufactured by Sumitomo Chemical Co., Ltd.), 1% by weight of magnesium chloride, and 0.2% by weight of ferulic acid. After being immersed in the aqueous solution, it was squeezed with a mangle (squeezing ratio: 70%), dried at 100 ° C., and heat-treated at 160 ° C. for 2 minutes to obtain the cotton fabric of the present invention.
[0090]
This cotton fabric contained 0.14% by weight of ferulic acid. Ferulic acid was firmly bonded to the cotton fabric via an ether bond.
[0091]
Comparative Example 1
150g / m²After scouring, bleaching and mercerizing, immersing it in an aqueous solution containing 0.2% by weight of ferulic acid, squeezing with a mangle (squeezing ratio: 70%), drying at 100 ° C, and heat-treating at 160 ° C for 2 minutes Thus, a cotton fabric for comparison was obtained.
[0092]
Comparative Example 2
150g / m²After scouring, bleaching and mercerizing, the cotton fabric is immersed in an aqueous solution containing 3% by weight of 1,2,3,4-butanetetracarboxylic acid and 1.5% by weight of sodium diphosphate, and then squeezed with a mangle. Rate: 70%), dried at 100 ° C, and heat-treated at 160 ° C for 2 minutes to obtain a cotton fabric for comparison.
[0093]
Comparative Example 3
150g / m²After scouring, bleaching, and mercerizing cotton fabrics, immersion in an aqueous solution containing 5% by weight of dimethylol dihydroxyethylene urea resin (trade name: Sumitex NS200, manufactured by Sumitomo Chemical Co., Ltd.) and 1% by weight of magnesium chloride, followed by mangle , And heat-treated at 160 ° C. for 2 minutes to obtain a cotton fabric for comparison.
[0094]
Test Example 1 (Washing durability test of ferulic acid)
A ferulic acid determination solution (10% ethanol solution of potassium hydroxide) was dropped on each of the cotton fabrics obtained in Examples 1 and 2 and Comparative Examples 1 to 3, and the presence or absence of coloring after 1 minute was examined. When this ferulic acid determination liquid is used, it is colored yellow when ferulic acid is present, and remains colorless without ferulic acid. Table 1 shows the results.
[0095]
Furthermore, each of the cotton fabrics obtained in Examples 1 and 2 and Comparative Examples 1 to 3 was washed 10 times, and the presence or absence of coloring was examined in the same manner as described above. The results are shown in Table 1.
[0096]
The washing was carried out by using an aqueous solution in which Kao New Beads manufactured by Kao Corporation was dissolved at a rate of 5 g / liter at 40 ° C. for 10 minutes in a home washing machine, followed by washing with water and drying. This cycle was repeated 10 times.
[0097]
[Table 1]

[0098]
From Table 1, it is clear that the cotton fabrics obtained in Examples 1 and 2 retain ferulic acid not only before washing but also after washing 10 times.
[0099]
Test example 2 (elution test of ferulic acid into sweat)
An untreated cotton cloth (No. 3 cotton cloth) is laid on each of the cotton fabrics obtained in Examples 1 and 2 and Comparative Examples 1 to 3 (before washing, after washing 5 times and after washing 10 times), and sewed. 1 ml of artificial sweat liquid (acid sweat or alkali sweat according to JIS L0848) was dropped. After treatment with a sweat fastness tester (based on JIS L0848) for 4 hours, a ferulic acid determination solution (10% ethanol solution of potassium hydroxide) was added dropwise to the untreated cotton cloth side, and the presence or absence of coloring after 1 minute was examined. . Table 2 shows the results.
[0100]
[Table 2]

[0101]
From Table 2, it can be seen that in the cotton fabrics obtained in Examples 1 and 2, ferulic acid was transferred to untreated cotton fabric. Therefore, the cotton fabrics obtained in Examples 1 and 2 gradually release ferulic acid when they come in contact with artificial sweat, and these cotton fabrics were washed 5 or 10 times, not to mention before washing. It can be seen that the same effect is exhibited even after the test.
[0102]
Test example 3 (antibacterial test)
The antibacterial performance was examined according to the antibacterial quantification test for textile products specified in JIS L1902. That is, 2 × 10⁵Of Staphylococcus aureus ATCC 6538P together with a medium was inoculated into untreated cotton fabric and each cotton fabric obtained in Examples 1-2 and Comparative Examples 1-3, and cultured at 35 ° C for 18 hours. Was measured. Based on the number of bacteria on the raw cotton fabric, the ratio of the number of bacteria on each of the cotton fabrics obtained in Examples 1 and 2 and Comparative Examples 1 to 3 was expressed as a logarithmic value, which was defined as a bacteriostatic activity value.
[0103]
Table 3 shows the results.
[0104]
[Table 3]

Claims (8)

Cellulose fiber or cellulose fiber bonded with at least one whitening component selected from the group consisting of ferulic acid and its ester and hydroquinone via a chemical bond selected from an ester bond, an acetal bond, an ether bond and a urethane bond. Product. Cellulose fibers or cellulosic fiber products have at least one whitening component selected from the group consisting of (1) ferulic acid and its esters and hydroquinone; and (2) a chemistry selected from ester bonds, acetal bonds, ether bonds and urethane bonds. The cellulose fiber or cellulose fiber product according to claim 1, which is obtained by adhering and / or impregnating a compound capable of binding the whitening component to the cellulose fiber or cellulose fiber product by bonding, and then heat-treating the compound. The cellulose fiber or cellulose fiber product according to claim 1, wherein the whitening component is at least one selected from the group consisting of ferulic acid and esters thereof. The cellulose fiber or the cellulose fiber product according to claim 1, wherein the compound capable of binding the whitening component to the cellulose fiber or the cellulose fiber product by a chemical bond is a polycarboxylic acid. The cellulose fiber or cellulose fiber product according to claim 4, wherein the polycarboxylic acid is 1,2,3,4-butanetetracarboxylic acid. The cellulose fiber or cellulose fiber product according to claim 1, wherein the compound capable of binding the whitening component to the cellulose fiber or cellulose fiber product by chemical bonding is an N-methylol compound. The cellulose fiber or cellulose fiber product according to claim 6, wherein the N-methylol compound is dimethylol dihydroxyethylene urea. Cellulose fibers or cellulosic fiber products have at least one whitening component selected from the group consisting of (1) ferulic acid and its esters and hydroquinone and (2) a chemistry selected from ester bonds, acetal bonds, ether bonds and urethane bonds. The method for producing a cellulose fiber or a cellulose fiber product according to claim 1, wherein a compound capable of binding the whitening component to the cellulose fiber or the cellulose fiber product is bonded and / or impregnated, and then heat-treated. .