JPH09291478A - Polyester fiber processed fabric and its production - Google Patents
Polyester fiber processed fabric and its productionInfo
- Publication number
- JPH09291478A JPH09291478A JP9681696A JP9681696A JPH09291478A JP H09291478 A JPH09291478 A JP H09291478A JP 9681696 A JP9681696 A JP 9681696A JP 9681696 A JP9681696 A JP 9681696A JP H09291478 A JPH09291478 A JP H09291478A
- Authority
- JP
- Japan
- Prior art keywords
- polyester fiber
- chitosan
- fabric
- cloth
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、洗濯耐久性の優れ
たポリエステル繊維加工布帛及びその加工方法に関する
ものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyester fiber-processed fabric having excellent washing durability and a method for processing the same.
【０００２】[0002]
【従来の技術】吸湿性、吸汗性、水放散性、抗菌性等の
機能をキチン系物質が付与されたポリエステル繊維加工
布帛は、特開平３−７６８７１号、特開平３−５１３６
９号公報等で知られている。この公知技術は、キチン系
物質の合成重合体のバインダー樹脂等との混合溶液を含
浸法若しくはコーテイング法等を適用して加工する物質
を固着するポリエステル繊維布帛にキチン系物質を付与
する方法を紹介している。2. Description of the Related Art Polyester fiber-processed fabrics to which a chitin-based material having functions such as hygroscopicity, perspiration absorption, water dissipation, antibacterial properties, etc. are disclosed in JP-A-3-76871 and JP-A-5136.
It is known from Japanese Patent Publication No. 9 and the like. This known technique introduces a method of imparting a chitin-based substance to a polyester fiber cloth for fixing a substance to be processed by applying a mixed solution of a synthetic polymer of a chitin-based substance with a binder resin or the like by applying an impregnation method or a coating method. are doing.
【０００３】このようなバインダーを用いる加工法は、
加工した布帛の風合いが硬くなったり、チョークマーク
が発生したりするので、高品質の繊細な加工布帛製品を
得る上で好ましい加工法ではないし、又所望の加工効果
を得るに必要なキチン質物質の使用量が多くなり、加工
費が高くなりがちである。グラフト重合法又は反応性結
合剤を利用してキチン質物質を化学結合によりポリエス
テル繊維に付与することにより、付与効果の耐久性を向
上させる試みも公知である。しかし、グラフト重合法
は、特殊な加工剤を用いて複雑、精緻な加工条件の選択
を必要とするので、加工経費も嵩み、一般の加工場で手
軽に採用できる加工方法とはいい難い。The processing method using such a binder is
Since the texture of the processed fabric becomes hard and chalk marks are generated, it is not a preferable processing method for obtaining a high-quality delicate processed fabric product, and a chitinous substance necessary for obtaining a desired processing effect. The amount of used is large, and the processing cost tends to be high. It is also known to attempt to improve the durability of the imparting effect by imparting a chitinous substance to a polyester fiber by a chemical bond using a graft polymerization method or a reactive binder. However, since the graft polymerization method requires the selection of complicated and precise processing conditions using a special processing agent, the processing cost is high, and it cannot be said that the processing method can be easily adopted in a general processing site.
【０００４】特開平７−５４２６６号公報には、ポリエ
ステル等の合成繊維又は合成繊維を含む糸、編織布等の
繊維構造物に短波長紫外線（２９０ｎｍより短い波長の
紫外線、主として１８４．９ｎｍ又は２５３．７ｎｍ）
を照射して、繊維の機械物性を損なわずに繊維表面の親
水性と吸水性を改善する方法が記載されている。特開平
７−３６７１号公報は、繊維布帛に、染色前又は染色後
に、電子線を部分的に照射して照射部分と未照射部分と
で染色度に濃淡差のある模様柄をつける方法について記
載し、公報明細書中電子線照射により生成する繊維上遊
離基の相違による染料の吸着性乃至退色性の差により染
色度に濃淡差のある模様柄が得られことが記載されてい
る。In Japanese Patent Laid-Open No. 7-54266, short wavelength ultraviolet light (ultraviolet light having a wavelength shorter than 290 nm, mainly 184.9 nm or 253) is applied to a synthetic fiber such as polyester or a fiber structure such as a yarn or a woven cloth containing the synthetic fiber. 0.7 nm)
Is irradiated to improve the hydrophilicity and water absorption of the fiber surface without impairing the mechanical properties of the fiber. Japanese Unexamined Patent Application Publication No. 7-3661 describes a method of partially irradiating a fiber cloth with an electron beam before or after dyeing to form a pattern with a difference in shade between an irradiated portion and an unirradiated portion. However, in the specification of the publication, it is described that a pattern pattern having a different shade in dyeing degree can be obtained due to the difference in the adsorption or fading of the dye due to the difference in free radicals on the fiber generated by electron beam irradiation.
【０００５】[0005]
【発明が解決しようとする課題】本発明の目的は、洗濯
耐久性に優れ、しかもチョーク・マークの発生しない柔
軟性に優れたキチン誘導体による表面改質ポリエステル
繊維加工布帛及びその製造方法の提供をすることにあ
る。本発明は特にキチン誘導体特有の親水、吸湿、抗菌
性等の改質効果を表面に耐久性よく固着したポリエステ
ル繊維加工布帛製品の提供を目的とするものである。DISCLOSURE OF THE INVENTION An object of the present invention is to provide a surface-modified polyester fiber-treated cloth with a chitin derivative which is excellent in washing durability and is excellent in flexibility without generation of chalk marks, and a method for producing the same. To do. An object of the present invention is to provide a polyester fiber-processed fabric product having a hydrophilic, hygroscopic, antibacterial and other modifying effect peculiar to a chitin derivative, which is firmly adhered to the surface.
【０００６】[0006]
【課題を解決するための手段】本発明の目的は、第４級
アンモニウム塩基を有するキトサンが繊維基質に化学結
合で固着されているポリエステル繊維加工布帛によって
達成される。そして前記のポリエステル繊維加工布帛
は、２９０ｎｍ以下（近紫外線）の波長を含む紫外線を
ポリエステル繊維布帛に照射する工程、キトサンを有機
酸又は無機酸の存在下に水溶液でポリエステル繊維布帛
に付与する工程を含む処理によりポリエステル繊維布帛
にキトサンを付与することを特徴とするポリエステル繊
維加工布帛の製造方法によって得ることができる。The objects of the present invention are achieved by a polyester fiber-treated fabric in which chitosan having a quaternary ammonium salt group is chemically bonded to a fiber substrate. The polyester fiber-treated cloth is subjected to a step of irradiating the polyester fiber cloth with ultraviolet rays having a wavelength of 290 nm or less (near ultraviolet rays), and a step of applying chitosan to the polyester fiber cloth with an aqueous solution in the presence of an organic acid or an inorganic acid. It can be obtained by a method for producing a polyester fiber-treated cloth, which comprises adding chitosan to the polyester fiber cloth by the treatment including.
【０００７】本発明において、ポリエステル繊維とは、
２価アルコールとテレフタール酸とのエステル単位が８
５％以上から構成される合成長鎖重合体を繊維形成物質
とする合成繊維であって、ポリエチレンテレフタレート
繊維、ポリブチレンフタレート繊維がその代表例として
挙げられるものであるが、染色性、耐光性等の改質を目
的として前記エステル単位に他の共重合成分を含む合成
ポリエステル長鎖重合体繊維もその範疇に含まれる。In the present invention, the polyester fiber means
8 ester units of dihydric alcohol and terephthalic acid
Synthetic fibers using a synthetic long-chain polymer composed of 5% or more as a fiber-forming substance, and typical examples thereof include polyethylene terephthalate fibers and polybutylene phthalate fibers, but dyeability, light resistance, etc. A synthetic polyester long-chain polymer fiber containing another copolymerization component in the ester unit for the purpose of modifying the above is also included in the category.
【０００８】本発明でいうポリエステル繊維布帛として
は、前記のポリエステル繊維の織物、編物、不織布が挙
げられ、これら布帛を構成する繊維は、繊維が素材とし
て使用されているあらゆる形態、例えば短繊維、長繊
維、糸条例えば紡績糸、長繊維糸のフラットヤーン、テ
クスチャードヤーン等であることができる。本発明のポ
リエステル繊維加工布帛は、布帛を構成する繊維の基質
にキトサンがそのアミンを第４級化され形成されたアン
モニウム塩基を介して化学結合して固定されているもの
である。The polyester fiber cloth referred to in the present invention includes woven fabrics, knitted fabrics and non-woven fabrics of the above-mentioned polyester fibers. The fibers constituting these fabrics are in any form in which the fibers are used as raw materials, for example, short fibers, It can be long fibers, yarns such as spun yarns, flat yarns of long fiber yarns, textured yarns and the like. The polyester fiber-treated cloth of the present invention is one in which chitosan is chemically bonded to a substrate of fibers constituting the cloth through an ammonium base formed by quaternizing the amine thereof and is fixed.
【０００９】ＥＳＣＡ（光電子分光法）解析によれば、
本発明のポリエステル繊維加工布帛はその構成繊維の基
質面上に薄いキトサン層の存在が定性的に観測すること
ができ、当該キトサンはポリエステル繊維基質に吸着し
ているだけではなく、化学的に結合している。因みに、
本発明の加工布帛は、繰り返し洗濯の後もニンヒドリン
反応により呈色反応で陽性を示し、キトサンがポリエス
テル基質に化学的に固着されていることを確かめること
ができる。このことにより、本発明のポリエステル加工
布帛は、キトサンを物理的に吸着させたポリエステル繊
維布帛と比較して繰り返しの洗濯に耐える吸水性、抗菌
性を有することが確かめられた。化学的に結合している
というのは、繊維布帛表面に紫外線を照射することによ
り、表面に−ＣＯＯＨ基、−ＯＨ基、＝ＣＯ基が生成す
ることが、ＦＴ−ＩＲ測定法を用いた測定により確認さ
れ、これらの基と前述したキトサンのアンモニウム基と
の結合が加工布帛に改質特性の耐久性が大きいことを示
している。According to ESCA (photoelectron spectroscopy) analysis,
In the polyester fiber-treated cloth of the present invention, the presence of a thin chitosan layer on the substrate surface of its constituent fibers can be qualitatively observed, and the chitosan is not only adsorbed on the polyester fiber substrate but also chemically bonded. are doing. By the way,
The processed fabric of the present invention shows a positive color reaction due to the ninhydrin reaction even after repeated washing, and it can be confirmed that chitosan is chemically fixed to the polyester substrate. From this, it was confirmed that the polyester-processed fabric of the present invention has water-absorption and antibacterial properties that can withstand repeated washing as compared with the polyester fiber fabric in which chitosan is physically adsorbed. Chemically bonded means that the surface of the fiber cloth is irradiated with ultraviolet rays to generate -COOH group, -OH group, and = CO group on the surface, which is measured by FT-IR measurement method. The bond between these groups and the above-mentioned ammonium group of chitosan shows that the modified fabric has a large durability of the modified property.
【００１０】本発明において、キトサンとはキチンを高
濃度のアルカリで処理し、脱アセチル化して得られる遊
離アミノ基を有するものであって、脱アセチル化度が３
０〜１００％の水溶性のキトサンをいう。第４級アンモ
ニウム塩基を有するキトサンは、前記キトサンをを有機
若しくは無機の酸に溶解することで、水溶性のキトサン
のアミノ基を４級化することによって調製することがで
きる。In the present invention, chitosan has a free amino group obtained by treating chitin with a high-concentration alkali and deacetylating it, and the degree of deacetylation is 3
It refers to 0 to 100% water-soluble chitosan. Chitosan having a quaternary ammonium salt group can be prepared by dissolving the chitosan in an organic or inorganic acid to quaternize the amino group of water-soluble chitosan.
【００１１】本発明のポリエステル繊維加工布帛は、ポ
リエステル繊維布帛に近２９０ｎｍ以下の短波紫外線、
例えば２５３．７ｎｍ、１８４．９ｎｍ等の短波長の紫
外線照射する工程、第４級アンモニウム塩基を有するキ
トサンの水溶液をポリエステル繊維布帛に付与する工程
を含むポリエステル繊維布帛にキトサン処理を有する製
造方法によって得ることができる。The polyester fiber-treated cloth of the present invention is short-wave ultraviolet light having a wavelength of 290 nm or less near the polyester fiber cloth,
For example, it is obtained by a manufacturing method having a chitosan treatment on a polyester fiber cloth including a step of irradiating with short wavelength ultraviolet rays such as 253.7 nm and 184.9 nm, and a step of applying an aqueous solution of chitosan having a quaternary ammonium salt group to the polyester fiber cloth. be able to.
【００１２】紫外線照射において、使用される紫外線線
源は低圧水銀ランプを用いることができるが、照射中に
可能なかぎり熱を発散する傾向が少ないランプ、例えば
高圧水銀ランプ、炭素アーク、キセノンランプ、ハライ
ドランプ等を使用したり、照射装置もしくは加工対象物
の冷却手段等を付帯させて、照射中のポリエステル布帛
の過度の加熱を避けることが好ましい。紫外線は、加工
対象布帛の面上で数ｍｗ〜数十ｍｗ／ｃｍ2 の強度で照
射される。照射を布帛の片面もしくは両面に適用するか
は任意であり、加工布帛の使用の目的によって選べばよ
い。In the irradiation of ultraviolet rays, the ultraviolet ray source used may be a low-pressure mercury lamp, but a lamp which has the least tendency to radiate heat during irradiation, such as a high-pressure mercury lamp, a carbon arc, a xenon lamp, It is preferable to avoid excessive heating of the polyester cloth during irradiation by using a halide lamp or the like, or by providing an irradiation device or cooling means for the object to be processed. Ultraviolet rays are irradiated on the surface of the fabric to be processed at an intensity of several mw to several tens mw / cm 2 . It is arbitrary whether the irradiation is applied to one side or both sides of the cloth, and it may be selected depending on the purpose of using the processed cloth.
【００１３】紫外線照射処理に先立って、ポリエステル
繊維布帛は油剤、糊剤等を精練等で予め除去し、紫外線
照射がポリエステル繊維布帛に効果的に及ばせることが
望ましい。ポリエステル繊維布帛の紫外線の照射にあた
って、被加工布帛の構造、形態、色等表面状態を考慮し
て照射の距離、強度、時間等の条件は予め実験によって
条件を適宜決定すればよいが、目安として紫外線源は加
工対象布帛に対してできるだけ接近して、例えば１５ｍ
ｍ以下の距離を保って配置し、短時間の照射時間で長く
とも１〜２０分以内に所望の加工効果が得られるように
照射手段、布帛の搬送手段等等の条件を適宜選択するこ
とにより加工の効率を挙げる工夫をすることが好まし
い。Prior to the ultraviolet irradiation treatment, it is desirable that the polyester fiber cloth is preliminarily removed of oil agents, sizing agents and the like by scouring so that the ultraviolet irradiation can effectively reach the polyester fiber cloth. When irradiating the polyester fiber cloth with ultraviolet rays, the conditions such as irradiation distance, strength, and time may be appropriately determined in advance by experiments, taking into consideration the surface condition such as the structure, morphology, and color of the cloth to be processed. The UV source should be as close as possible to the fabric to be processed, for example 15 m
By arranging at a distance of m or less and appropriately selecting conditions such as irradiation means and cloth conveying means so that a desired processing effect can be obtained within 1 to 20 minutes at the longest in a short irradiation time. It is preferable to devise to improve the processing efficiency.
【００１４】ポリエステル繊維布帛に付与される第４級
アンモニウム塩基を有するキトサンについては前記した
が、好ましくは５０％以上、更に好ましくは７０％以上
である種々重合度を有するキトサンを原料として用いて
調製される。原料のキトサンは、スルホン化キトサン、
カルボキシキトサンがあるが、カルボキシキトサンの使
用がより好ましい。第４級アンモニウム基を有するキト
サンは、前記キトサンを１〜１０重量％を含む蟻酸、酢
酸、乳酸、蟻酸、琥珀酸、グルコン酸等の有機酸、硫
酸、塩酸、燐酸等の鉱酸を添加した水（ｐＨが３〜６、
好ましくは５〜７）に溶解して第４級アンモニウム基を
有するキトサンに転化することによってその水溶液を調
製することができる。ポリエステル繊維布帛への第４級
アンモニウム塩基を有するキトサンの付与は、被照射ポ
リエステル繊維布帛に０．１〜１０％の水溶液を室温下
もしくは加熱下で飽充させることによって行われる。そ
して適当な絞り率で搾液することによって所望の付与量
で付与される。例えば、布帛を拡幅状態で汎用のパッデ
イング機にとおして付着させることができる。Although the chitosan having a quaternary ammonium salt group to be applied to the polyester fiber cloth has been described above, it is preferably prepared by using as a raw material chitosan having various degrees of polymerization of 50% or more, more preferably 70% or more. To be done. The raw material chitosan is sulfonated chitosan,
There is carboxy chitosan, but the use of carboxy chitosan is more preferred. The chitosan having a quaternary ammonium group is prepared by adding 1 to 10% by weight of the chitosan to an organic acid such as formic acid, acetic acid, lactic acid, formic acid, succinic acid or gluconic acid, or a mineral acid such as sulfuric acid, hydrochloric acid or phosphoric acid. Water (pH 3-6,
The aqueous solution can be prepared by preferably dissolving in 5-7) and converting to chitosan having a quaternary ammonium group. The addition of chitosan having a quaternary ammonium salt group to the polyester fiber cloth is carried out by saturating the irradiated polyester fiber cloth with an aqueous solution of 0.1 to 10% at room temperature or under heating. Then, by squeezing the liquid with an appropriate squeezing ratio, the liquid is applied in a desired amount. For example, the cloth can be attached in a widened state through a general-purpose padding machine.
【００１５】上述した紫外線照射工程及び第４級アンモ
ニウム塩基を有するキトサン付与工程の順番はどちらか
が先でも差し支えないが、得られる加工布帛のキトサン
改質洗濯耐久性の点から、紫外線付与工程を先にするこ
とが好ましい。紫外線照射工程、第４級アンモニウム塩
基を有するキトサン付与工程を経た布帛は、次いで広幅
乾燥機等で単に乾燥するか、もしくは加熱乾燥法等を経
たのち、要すれば水洗、水洗の後再び乾燥することによ
って加工プロセスが完了する。乾燥に代えて乾熱加熱若
しくは加熱水蒸気処理を適用して固定を促進することも
できる。The order of the above-mentioned ultraviolet irradiation step and the step of applying a quaternary ammonium salt-containing chitosan may be either first. It is preferable to do it first. The cloth that has been subjected to the ultraviolet irradiation step and the step of applying a chitosan having a quaternary ammonium salt group is then simply dried in a wide dryer or the like, or after being subjected to a heat drying method or the like, washed with water, washed with water again if necessary, and then dried again. This completes the machining process. Instead of drying, dry heat heating or heated steam treatment may be applied to promote fixation.
【００１６】[0016]
【発明の実施の形態】次に実施例をあげて本発明を更に
具体的に説明する。なお、実施例における加工繊維製品
の性能は以下の方法により評価した。 （１）洗濯試験方法 ＪＩＳ−Ｌ−０２１７、１０３号による（中性洗剤：モ
ノゲンユニ） （２）布帛の吸水性試験 ＪＩＳ Ｌ １０９６ Ａ法による。BEST MODE FOR CARRYING OUT THE INVENTION The present invention will now be described more specifically with reference to Examples. The performance of the processed fiber products in the examples was evaluated by the following method. (1) Washing test method According to JIS-L-0217, 103 (neutral detergent: Monogen Uni) (2) Water absorption test of cloth According to JIS L 1096 A method.
【００１７】（３）キトサンの検出方法 ニンヒドリン反応による呈色反応による（＋：有り、
−：なし） （４）柔軟性（カンチレバー）の測定方法 ＪＩＳ−Ｌ−１０１８のカンチレバー法(mm)による（但
し、経方向のみ)。(3) Method for detecting chitosan By color reaction by ninhydrin reaction (+: Yes,
-: None) (4) Flexibility (cantilever) measuring method According to the cantilever method (mm) of JIS-L-1018 (however, only in the longitudinal direction).
【００１８】（５）抗菌性試験 菌数測定法による（抗菌防臭加工製品の加工効果評価試
験マニュアル） 試験菌： 黄色ブドウ状菌 培養温度： ３７°Ｃ（１８時間） 菌数増減比＝培養後の試験片上の生菌数／培養直前の生
菌数 菌数増減値＝Ｌｏｇ10（培養後の試験片上の生菌数／培
養直前の生菌数） 菌数増減値差＝無加工試料の菌数増減値−加工試料の菌
数増減値 （６）チョークマーク評価 ピンセットの先端で布帛の表面を軽く引っ掻いて、発生
したチョークマーの程度を視覚判定により、下記基準で
等級格付け評価した。(5) Antibacterial test By the bacterial count method (manufacturing effect evaluation test manual for antibacterial and deodorant processed products) Test bacteria: Staphylococcus aureus Culture temperature: 37 ° C (18 hours) Increase / decrease ratio of bacteria = After culture Number of viable bacteria on the test piece / Number of viable cells immediately before culturing Bacterial count increase / decrease value = Log 10 (Number of viable bacteria on the test piece after culturing / Number of viable bacteria just before culturing) The number increase / decrease value-the increase / decrease value of the number of bacteria in the processed sample (6) Chalk mark evaluation The surface of the cloth was lightly scratched with the tip of the tweezers, and the degree of the generated chokemers was visually judged and graded and evaluated according to the following criteria.
【００１９】 ５級 全く発生せず ４級 僅かに発生 ３級 若干発生 ２級 かなり発生 １級 著しく発生 （実施例１）ポリエステル長繊維糸（７５ｄ／３６ｆ）
使いのジャージイ（密度：４１ウエール／インチ、３２
コース／インチ：目付１７０ｇ／ｍ2 ）の生機を常法に
より精練し、分散染料スミカロンスカーレットＳＥ−３
ＧＬ（住友化学社製）で常法により通常より淡色に染色
して乾燥して染色ポリエステル繊維布帛を調製した。こ
の染色ポリエステル繊維布帛の一方の面に低圧水銀ラン
プ（セン特殊光源(株)製、主波長２５３．７ｎｍ、１８
４．９ｎｍ、照射強度 １２ｍｗ／ｃｍ2 ）を布帛面上
１０ｍｍの位置から９０秒照射した。照射後の染色ポリ
エステル繊維布帛に乳酸０．６重量％を含む水のキトサ
ン（片倉チッカリン製：脱アセチル化度８５％）の０．
２重量％溶液を室温下でパデイング法により浸漬、搾液
（絞り率１００％）して繊維に対して０．２％ｏｗｆの
キトサンを付与した後、拡幅状態で１２０°Ｃの空気で
乾燥し、水洗し再び乾燥した。Class 5 Not generated at all Class 4 Slightly generated Class 3 Slightly generated Class 2 Significantly generated Class 1 Significantly generated (Example 1) Polyester filament fiber yarn (75d / 36f)
Your jersey (density: 41 wales / inch, 32
Course / inch: 170 g / m 2 of basis weight is scoured by a conventional method, and disperse dye Sumikaron Scarlet SE-3
A dyed polyester fiber cloth was prepared by dyeing with GL (manufactured by Sumitomo Chemical Co., Ltd.) in a lighter color than usual and drying. A low-pressure mercury lamp (manufactured by Sen Special Light Source Co., Ltd., main wavelength 253.7 nm, 18
It was irradiated with 4.9 nm and irradiation intensity of 12 mw / cm 2 ) from a position of 10 mm on the fabric surface for 90 seconds. After the irradiation, the dyed polyester fiber cloth with water containing 0.6% by weight of lactic acid had a chitosan content of 0.
The 2% by weight solution was immersed at room temperature by the padding method, squeezed (100% squeezing ratio) to give 0.2% owf chitosan to the fiber, and then dried in air at 120 ° C in a widened state. , Washed with water and dried again.
【００２０】得られた加工ジャージイ（密度：４７ウエ
ール／インチ、３４コース／インチ：目付２１０ｇ／ｍ
2 ）は、表１に示す試験、評価結果で明らかなように、
未加布帛と同様の柔軟性を有し、チョークマークの発生
が観察されず、呈色法によってキトサンが固着されてい
ることが認められた。このポリエステル繊維の加工ジャ
ージイは、３０回の洗濯試験の後もキトサンの固着を示
す呈色反応が認められるものであった。加工ジャージイ
は、抗菌性( 菌数増減値差で示す) 、吸水性等について
も洗濯に耐えるものであった。そして、これらの改質効
果は、染色、洗濯の後もキトサンの脱離がない。The resulting processed jersey (density: 47 wales / inch, 34 courses / inch: basis weight 210 g / m
2 ) is, as is clear from the test and evaluation results shown in Table 1,
It had the same flexibility as the uncoated fabric, no generation of chalk marks was observed, and it was confirmed that chitosan was fixed by the coloring method. In this processed jersey of polyester fiber, a color reaction showing sticking of chitosan was observed even after 30 washing tests. The processed jersey was also washable in terms of antibacterial properties (indicated by the difference in bacterial count increase / decrease) and water absorbency. And, as for these modifying effects, there is no desorption of chitosan even after dyeing and washing.
【００２１】比較対照として、紫外線照射を省いた以外
は実施例と同じく加工して、ポリエステル繊維加工布帛
（比較例１）及び実施例１と同じ原布を下記の組成から
なる０．５％キトサン溶液を用いて液流染色機中で６０
°Ｃ、１０分間処理を行い、遠心脱水機により絞り率１
２０％になるように絞った後、１２０°Ｃで９０秒間加
熱処理をしたポリエステル繊維加工布帛（比較例２）を
調製し、実施例と同様の試験、評価し結果を表１に実施
例と対照して示す。As a comparative control, a polyester fiber-treated fabric (Comparative Example 1) and the same base fabric as in Example 1 were processed in the same manner as in Example except that UV irradiation was omitted, and 0.5% chitosan having the following composition was used. 60 in a jet dyeing machine using the solution
Treated at 10 ° C for 10 minutes and squeezed by centrifugal dehydrator 1
After being squeezed to 20%, a polyester fiber-treated fabric (Comparative Example 2) which was heat treated at 120 ° C. for 90 seconds was prepared, and the same tests and evaluations as those in Examples were carried out. Shown in contrast.
【００２２】[0022]
【表１】 [Table 1]
【００２３】[0023]
【発明の効果】繊維基質上に第４級アンモニウム塩基を
有するキトサンを直接化学結合で固定した本発明のポリ
エステル繊維加工布帛は、洗濯に著しく耐えるキトサン
改質（水、吸湿、抗菌性等）効果を有し、しかも未加工
布帛と遜色のない風合いを備えたするポリエステル繊維
加工布帛である。また、本発明のポリエステル繊維加工
布帛の製造方法は、近紫外線照射処理、第４級アンモニ
ウム塩基を有するキトサン溶液を付与、乾燥という極め
て簡素な加工により加工効率よく疎水性のポリエステル
繊維布帛にキトサン改質効果を簡素な加工方法で付与す
ることができる点、極めて意義がある製造方法である。EFFECTS OF THE INVENTION The polyester fiber-treated cloth of the present invention in which chitosan having a quaternary ammonium salt group is directly bonded to a fiber substrate by a chemical bond has an effect of modifying chitosan (water, moisture absorption, antibacterial property, etc.) which is extremely resistant to washing. It is a polyester fiber-processed fabric which has a texture comparable to that of an unprocessed fabric. In addition, the method for producing a polyester fiber-treated cloth of the present invention is a process in which near-ultraviolet irradiation treatment, a chitosan solution having a quaternary ammonium salt group are applied, and drying is performed to achieve a highly efficient hydrophobic polyester fiber cloth with improved processing efficiency. This is a very significant manufacturing method in that quality effects can be imparted by a simple processing method.
【手続補正書】[Procedure amendment]
【提出日】平成８年６月１１日[Submission date] June 11, 1996
【手続補正１】[Procedure amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】請求項２[Correction target item name] Claim 2
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【手続補正２】[Procedure amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００９[Correction target item name] 0009
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【０００９】ＥＳＣＡ（光電子分光法）解析によれば、
本発明のポリエステル繊維加工布帛はその構成繊維の基
質面上に薄いキトサン層の存在が定性的に観測すること
ができ、当該キトサンはポリエステル繊維基質に吸着し
ているだけではなく、化学的に結合している。因みに、
本発明の加工布帛は、繰り返し洗濯の後もニンヒドリン
反応により呈色反応で陽性を示し、キトサンがポリエス
テル基質に化学的に固着されていることを確かめること
ができる。このことにより、本発明のポリエステル加工
布帛は、キトサンを物理的に吸着させたポリエステル繊
維布帛と比較して繰り返しの洗濯に耐える吸水性、抗菌
性を有することが確かめられた。化学的に結合している
というのは、繊維布帛表面に紫外線を照射することによ
り、表面に−ＣＯＯＨ基、−ＯＨ基、＝ＣＯ基が生成す
ることが、ＦＴ−ＩＲ測定法を用いた測定により確認さ
れ、これらの基と前述したキトサンのアンモニウム塩基
との結合が加工布帛に改質特性の耐久性が大きいことを
示している。According to ESCA (photoelectron spectroscopy) analysis,
In the polyester fiber-treated cloth of the present invention, the presence of a thin chitosan layer on the substrate surface of its constituent fibers can be qualitatively observed, and the chitosan is not only adsorbed on the polyester fiber substrate but also chemically bonded. are doing. By the way,
The processed fabric of the present invention shows a positive color reaction due to the ninhydrin reaction even after repeated washing, and it can be confirmed that chitosan is chemically fixed to the polyester substrate. From this, it was confirmed that the polyester-processed fabric of the present invention has water-absorption and antibacterial properties that can withstand repeated washing as compared with the polyester fiber fabric in which chitosan is physically adsorbed. Chemically bonded means that the surface of the fiber cloth is irradiated with ultraviolet rays to generate -COOH group, -OH group, and = CO group on the surface, which is measured by FT-IR measurement method. The bond between these groups and the above-mentioned ammonium base of chitosan shows that the modified fabric has a large durability of the modified property.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１０】本発明において、キトサンとはキチンを高
濃度のアルカリで処理し、脱アセチル化して得られる遊
離アミノ基を有するものであって、脱アセチル化度が３
０〜１００％のキトサンをいう。第４級アンモニウム塩
基を有するキトサンは、前記キトサンを有機若しくは無
機の酸に溶解することで、水溶性のキトサンのアミノ基
を４級化することによって調製することができる。In the present invention, chitosan has a free amino group obtained by treating chitin with a high-concentration alkali and deacetylating it, and the degree of deacetylation is 3
It refers to 0 to 100% chitosan. Chitosan having a quaternary ammonium salt group can be prepared by dissolving the chitosan in an organic or inorganic acid to quaternize the amino group of water-soluble chitosan.
【手続補正４】[Procedure amendment 4]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１１[Correction target item name] 0011
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１１】本発明のポリエステル繊維加工布帛は、ポ
リエステル繊維布帛に２９０ｎｍ以下の短波紫外線、例
えば２５３．７ｎｍ、１８４．９ｎｍ等の短波長の紫外
線照射する工程、第４級アンモニウム塩基を有するキト
サンの水溶液をポリエステル繊維布帛に付与する工程を
含むポリエステル繊維布帛にキトサン処理を有する製造
方法によって得ることができる。The polyester fiber-treated cloth of the present invention is obtained by irradiating the polyester fiber cloth with short-wave ultraviolet rays having a wavelength of 290 nm or less, for example, ultraviolet rays having short wavelengths such as 253.7 nm and 184.9 nm, and an aqueous solution of chitosan having a quaternary ammonium salt group. Can be obtained by a production method having a chitosan treatment on a polyester fiber cloth, which comprises a step of applying to a polyester fiber cloth.
【手続補正５】[Procedure Amendment 5]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１４[Correction target item name] 0014
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１４】ポリエステル繊維布帛に付与される第４級
アンモニウム塩基を有するキトサンについては前記した
が、脱アセチル化度が好ましくは５０％以上、更に好ま
しくは７０％以上である種々重合度を有するキトサンを
原料として用いて調製される。原料のキトサンは、スル
ホン化キトサン、カルボキシキトサンがあるが、カルボ
キシキトサンの使用がより好ましい。第４級アンモニウ
ム塩基を有するキトサンは、前記キトサンを１〜１０重
量％を含む蟻酸、酢酸、乳酸、蟻酸、琥珀酸、グルコン
酸等の有機酸、硫酸、塩酸、燐酸等の鉱酸を添加した水
（ｐＨが３〜６、好ましくは５〜６）に溶解して第４級
アンモニウム塩基を有するキトサンに転化することによ
ってその水溶液を調製することができる。ポリエステル
繊維布帛への第４級アンモニウム塩基を有するキトサン
の付与は、被照射ポリエステル繊維布帛に０．１〜１０
％の水溶液を室温下もしくは加熱下で飽充させることに
よって行われる。そして適当な絞り率で搾液することに
よって所望の付与量で付与される。例えば、布帛を拡幅
状態で汎用のパッデイング機にとおして付着させること
ができる。The chitosan having a quaternary ammonium salt group which is applied to the polyester fiber cloth has been described above, but chitosan having various degrees of polymerization having a degree of deacetylation of preferably 50% or more, more preferably 70% or more is used. It is prepared by using it as a raw material. The raw material chitosan includes sulfonated chitosan and carboxychitosan, but carboxychitosan is more preferably used. The chitosan having a quaternary ammonium salt group is prepared by adding an organic acid such as formic acid, acetic acid, lactic acid, formic acid, succinic acid and gluconic acid containing 1 to 10% by weight of the chitosan, and a mineral acid such as sulfuric acid, hydrochloric acid and phosphoric acid. The aqueous solution can be prepared by dissolving it in water (pH 3-6, preferably 5-6) and converting it to chitosan having a quaternary ammonium base. The addition of chitosan having a quaternary ammonium salt group to a polyester fiber cloth is 0.1 to 10 times on the irradiated polyester fiber cloth.
% Aqueous solution at room temperature or under heating to saturate. Then, by squeezing the liquid with an appropriate squeezing ratio, the liquid is applied in a desired amount. For example, the cloth can be attached in a widened state through a general-purpose padding machine.
【手続補正６】[Procedure correction 6]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１８[Correction target item name] 0018
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００１８】（５）抗菌性試験 菌数測定法による（抗菌防臭加工製品の加工効果評価試
験マニュアル） 試験菌： 黄色ブドウ状球菌 培養温度： ３７°Ｃ（１８時間） 菌数増減比＝培養後の試験片上の生菌数／培養直前の生
菌数 菌数増減値＝Ｌｏｇ10（培養後の試験片上の生菌数／培
養直前の生菌数） 菌数増減値差＝無加工試料の菌数増減値−加工試料の菌
数増減値 （６）チョークマーク評価 ピンセットの先端で布帛の表面を軽く引っ掻いて、発生
したチョークマーの程度を視覚判定により、下記基準で
等級格付け評価した。(5) Antibacterial test By the bacteria count method (manufacturing effect evaluation test manual for antibacterial and deodorant processed products) Test bacteria: Staphylococcus aureus Culture temperature: 37 ° C (18 hours) Increase / decrease ratio of bacteria = After culture Number of viable bacteria on the test piece / Number of viable cells immediately before culturing Bacterial count increase / decrease value = Log 10 (Number of viable bacteria on the test piece after culturing / Number of viable bacteria just before culturing) The number increase / decrease value-the increase / decrease value of the number of bacteria in the processed sample (6) Chalk mark evaluation The surface of the cloth was lightly scratched with the tip of the tweezers, and the degree of the generated chokemers was visually judged and graded and evaluated according to the following criteria.
【手続補正７】[Procedure amendment 7]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２１[Correction target item name] 0021
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２１】比較対照として、紫外線照射を省いた以外
は実施例と同じく加工して、ポリエステル繊維加工布帛
（比較例１）及び実施例１と同じ原布を下記の組成から
なる０．５％キトサン溶液を用いて液流染色機中で６０
°Ｃ、１０分間処理を行い、遠心脱水機により絞り率１
２０％になるように絞った後、１２０°Ｃで９０秒間加
熱処理をしたポリエステル繊維加工布帛（比較例２）を
調製し、実施例と同様の試験、評価し結果を表１に実施
例と対照して示す。 処理液組成（重量部） ０．５％キトサン水溶液 ９００部 リケンレジンＲＪ−３６1) １０部 パラソルブ２７２2) ４０部 パラキャットＰ3) ４部 ディックシリコンソフナー２００4) ２部 水 ４４部 注：１）三木理研製、２）大原パラジウム社製、３）大
原パラジウム社製、４）大日本インキ化学工業社製As a comparative control, a polyester fiber-treated fabric (Comparative Example 1) and the same base fabric as in Example 1 were processed in the same manner as in Example except that UV irradiation was omitted, and 0.5% chitosan having the following composition was used. 60 in a jet dyeing machine using the solution
Treated at 10 ° C for 10 minutes and squeezed by centrifugal dehydrator 1
After being squeezed to 20%, a polyester fiber-treated fabric (Comparative Example 2) which was heat treated at 120 ° C. for 90 seconds was prepared, and the same tests and evaluations as those in Examples were carried out. Shown in contrast. Treatment liquid composition (parts by weight) 0.5% chitosan aqueous solution 900 parts Riken resin RJ-36 1) 10 parts Parasolve 272 2) 40 parts Paracat P 3) 4 parts Dick Silicone Softener 200 4) 2 parts Water 44 parts Note: 1 ) Miki Riken, 2) Ohara Palladium, 3) Ohara Palladium, 4) Dainippon Ink and Chemicals
【手続補正８】[Procedure amendment 8]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００２３[Correction target item name] 0023
【補正方法】変更[Correction method] Change
【補正内容】[Correction contents]
【００２３】[0023]
【発明の効果】繊維基質上に第４級アンモニウム塩基を
有するキトサンを直接化学結合で固定した本発明のポリ
エステル繊維加工布帛は、洗濯に著しく耐えるキトサン
による改質（吸水、吸湿、抗菌性等）効果を有し、しか
も未加工布帛と遜色のない風合いを備えたポリエステル
繊維加工布帛である。また、本発明のポリエステル繊維
加工布帛の製造方法は、近紫外線照射処理、第４級アン
モニウム塩基を有するキトサン溶液を付与、乾燥という
極めて簡素な加工により加工効率よく疎水性のポリエス
テル繊維布帛にキトサンによる改質効果を簡素な加工方
法で付与することができる点、極めて意義がある製造方
法である。EFFECTS OF THE INVENTION The polyester fiber-treated cloth of the present invention in which chitosan having a quaternary ammonium salt group is directly bonded to a fiber substrate by a chemical bond is modified by chitosan (water absorption, moisture absorption, antibacterial property, etc.) that is extremely resistant to washing. It is a polyester fiber-processed cloth that is effective and has a texture comparable to that of the unprocessed cloth. Further, the method for producing a polyester fiber-treated cloth of the present invention is a very simple processing of near-ultraviolet irradiation treatment, application of a chitosan solution having a quaternary ammonium salt base, and drying. This is a very significant manufacturing method in that the modifying effect can be imparted by a simple processing method.
Claims (2)
ンが繊維基質に化学結合で固着されているポリエステル
繊維加工布帛。1. A polyester fiber-processed fabric in which chitosan having a quaternary ammonium salt group is chemically bonded to a fiber substrate.
リエステル繊維布帛に照射する工程とキトサンを有機酸
又は無機酸の存在下に水溶液でポリエステル繊維布帛に
付与する工程を含む処理によりポリエステル繊維布帛に
キトサンを付与することを特徴とするポリエステル繊維
加工布帛の製造方法。2. The chitosan is added to the polyester fiber cloth by a treatment including a step of irradiating the polyester fiber cloth with ultraviolet rays having a wavelength of 290 nm or less and a step of applying chitosan to the polyester fiber cloth with an aqueous solution in the presence of an organic acid or an inorganic acid. A method for producing a polyester fiber-treated cloth, which comprises:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9681696A JPH09291478A (en) | 1996-04-18 | 1996-04-18 | Polyester fiber processed fabric and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9681696A JPH09291478A (en) | 1996-04-18 | 1996-04-18 | Polyester fiber processed fabric and its production |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09291478A true JPH09291478A (en) | 1997-11-11 |
Family
ID=14175117
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9681696A Pending JPH09291478A (en) | 1996-04-18 | 1996-04-18 | Polyester fiber processed fabric and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09291478A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7081139B2 (en) | 2001-05-11 | 2006-07-25 | E. I. Du Pont De Nemours And Company | Antimicrobial polyester-containing articles and process for their preparation |
| CN100458005C (en) * | 2002-05-10 | 2009-02-04 | 纳幕尔杜邦公司 | Antimicrobial polyester-containing articles and process for their preparation |
| JP2012503104A (en) * | 2008-09-22 | 2012-02-02 | レンツィング アクチェンゲゼルシャフト | Cellulose molded body processing method |
| ITPR20130020A1 (en) * | 2013-03-25 | 2014-09-26 | Nearchimica S P A | PROCEDURE AND SYSTEM FOR POLYMERIZATION OF POLYMERS IN PHOTOINIZER UNITS ON TEXTILE SUBSTRATES |
| CN104975503A (en) * | 2015-06-29 | 2015-10-14 | 安徽东锦服饰有限公司 | Processing method of anti-ultraviolet thermal-insulation clothing |
| CN105821658A (en) * | 2016-04-13 | 2016-08-03 | 江苏红豆杉科技开发有限公司 | Antibacterial finishing agent for yew fiber shell fabric and antibacterial finishing technology of antibacterial finishing agent |
-
1996
- 1996-04-18 JP JP9681696A patent/JPH09291478A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7081139B2 (en) | 2001-05-11 | 2006-07-25 | E. I. Du Pont De Nemours And Company | Antimicrobial polyester-containing articles and process for their preparation |
| CN100458005C (en) * | 2002-05-10 | 2009-02-04 | 纳幕尔杜邦公司 | Antimicrobial polyester-containing articles and process for their preparation |
| JP2012503104A (en) * | 2008-09-22 | 2012-02-02 | レンツィング アクチェンゲゼルシャフト | Cellulose molded body processing method |
| ITPR20130020A1 (en) * | 2013-03-25 | 2014-09-26 | Nearchimica S P A | PROCEDURE AND SYSTEM FOR POLYMERIZATION OF POLYMERS IN PHOTOINIZER UNITS ON TEXTILE SUBSTRATES |
| CN104975503A (en) * | 2015-06-29 | 2015-10-14 | 安徽东锦服饰有限公司 | Processing method of anti-ultraviolet thermal-insulation clothing |
| CN105821658A (en) * | 2016-04-13 | 2016-08-03 | 江苏红豆杉科技开发有限公司 | Antibacterial finishing agent for yew fiber shell fabric and antibacterial finishing technology of antibacterial finishing agent |
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