JP2017104030A - Method for manufacturing desized denim products - Google Patents
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- JP2017104030A JP2017104030A JP2015239179A JP2015239179A JP2017104030A JP 2017104030 A JP2017104030 A JP 2017104030A JP 2015239179 A JP2015239179 A JP 2015239179A JP 2015239179 A JP2015239179 A JP 2015239179A JP 2017104030 A JP2017104030 A JP 2017104030A
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Landscapes
- Enzymes And Modification Thereof (AREA)
- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Chemical Or Physical Treatment Of Fibers (AREA)
Abstract
Description
本発明は、酵素を使用して糊抜きをする糊抜きデニム製品の製造方法に関する。 The present invention relates to a method for producing a desizing denim product in which desizing is performed using an enzyme.
デニム生地を使用した衣料品としてジーンズパンツ、ジーンズシャツ、ジーンズジャケット等が普及している。デニム生地は、インジゴ染料で染色後に糊付された経糸と、未染色の緯糸とを織成してなるものである。経糸を糊付けすることで、経糸の毛羽立ちが抑制される、経糸の強度を保持できる、織成時に経糸をさばきやすくなり開口させやすいなどの利点がある。一方でデニム生地に糊が残存していると、製品を使用する際に肌触りが硬くなる。このため、デニム生地の糊を抜く作業が一般的に行われている。 Jeans pants, jeans shirts, jeans jackets, etc. are widely used as clothing using denim fabric. The denim fabric is formed by weaving warps glued after dyeing with an indigo dye and undyed wefts. By pasting warp, there are advantages such as suppression of fuzz of warp, retention of warp strength, and ease of opening and opening of warp during weaving. On the other hand, when the paste remains in the denim fabric, the touch becomes hard when the product is used. For this reason, the operation of removing the paste from the denim fabric is generally performed.
例えば、特許文献1にはα-アミラーゼとエンドグルカナーゼとを配合し、ドラム型洗濯機(ワスケータ、登録商標)で洗浄することが記載されている。 For example, Patent Document 1 describes that α-amylase and endoglucanase are blended and washed with a drum-type washing machine (Waskater, registered trademark).
特許文献2には、ポリビニルアルコール(以下、PVAと称する。)で糊付した綿スフ糸を、Pseudomonas C-3の乾燥菌体を加えた30℃の液中に浸けて糊抜きをすることが記載されている。 Patent Document 2 discloses that a cotton suf yarn glued with polyvinyl alcohol (hereinafter referred to as PVA) is dipped in a solution at 30 ° C. to which dried Pseudomonas C-3 cells are added to remove the paste. Have been described.
特許文献1の方法は、セルラーゼの一種であるエンドグルカナーゼを配合して洗浄するため、デニム生地を構成するセルロースが部分的に分解され着心地が柔らかくなると推測される。しかし、この方法はストーンウォッシュのための方法であってデニム生地に脱色による縞模様が現れる。 In the method of Patent Document 1, since endoglucanase, which is a kind of cellulase, is mixed and washed, it is assumed that cellulose constituting the denim fabric is partially decomposed and the comfort is softened. However, this method is a method for stone wash, and a striped pattern due to decoloration appears on the denim fabric.
特許文献2には、PVAで糊付けした綿スフ糸を糊抜きする方法が記載されているに過ぎず、デニム製品の糊抜きについては記載されていない。デニム生地の経糸はインジゴ染料で染色されPVAの他にデンプン系の糊で糊付けされているため、特許文献2の方法では、デニム生地から糊を抜くことは難しい。 Patent Document 2 only describes a method for desizing a cotton suf yarn glued with PVA, and does not describe desizing for a denim product. Since the warp of denim fabric is dyed with indigo dye and pasted with starch-based glue in addition to PVA, it is difficult to remove the glue from the denim fabric with the method of Patent Document 2.
その他、デニム製品をお湯に浸漬して撹拌式の洗浄機で洗浄することで糊抜きを行う方法もあるが、デニム生地に毛羽立ったり脱色したりするなどの問題がある。 In addition, there is a method of desizing by immersing the denim product in hot water and washing it with a stirring type washing machine, but there is a problem that the denim fabric is fluffed or decolored.
本発明は、デニム生地の脱色を防ぎつつ、デニム生地の糊を糊抜きして柔軟な糊抜きデニム製品を製造する方法を提供する。 The present invention provides a method for producing a flexible deflated denim product by removing the paste of the denim fabric while preventing the decolorization of the denim fabric.
ポリビニルアルコールを酸化可能な酵素及びアミラーゼを含有する脱糊液と、糊付けされたデニム製品とを接触させて、接触後に酵素接触後のデニム製品を洗浄し、洗浄後のデニム製品を乾燥して糊抜きされたデニム製品を得る糊抜きデニム製品の製造方法によって、上記の課題を解決する。この方法によれば、デニム生地を糊抜きして肌触りを軟らかくし、しかもデニム生地の脱色を防ぐことができる。 A desizing solution containing an enzyme capable of oxidizing polyvinyl alcohol and amylase is brought into contact with the pasted denim product. After the contact, the denim product after the enzyme contact is washed, and the washed denim product is dried and glued. The above-described problems are solved by a method for manufacturing a paste-free denim product to obtain a punched denim product. According to this method, the denim fabric can be desalted to soften the touch and the denim fabric can be prevented from being discolored.
前記のPVAを酸化可能な酵素は第2級アルコールオキシダーゼを含むことが好ましい。当該酵素は菌体外に分泌される可溶性酵素であるため取り扱いが容易である点で好ましい。 The enzyme capable of oxidizing PVA preferably includes a secondary alcohol oxidase. Since the enzyme is a soluble enzyme secreted outside the cells, it is preferable in terms of easy handling.
脱糊液は酸化されたPVAを加水分解可能な酵素を含有することが好ましい。当該酵素を用いることにより酸化されたPVAを速やかに低分子化することができる。 The desizing solution preferably contains an enzyme capable of hydrolyzing oxidized PVA. By using the enzyme, oxidized PVA can be rapidly reduced in molecular weight.
前記の酸化されたPVAを加水分解可能な酵素はβ‐ジケトンヒドロラーゼを含むものであることが好ましい。当該酵素は菌体外に分泌される可溶性酵素であるため取り扱いが容易である点で好ましい。 The enzyme capable of hydrolyzing oxidized PVA preferably contains β-diketone hydrolase. Since the enzyme is a soluble enzyme secreted outside the cells, it is preferable in terms of easy handling.
脱糊液及び糊付けされたデニム製品を接触させるに際しては、脱糊液に糊付けされたデニム製品を浸漬した状態で0.5〜12時間接触させることが好ましい。これにより、比較的に短い時間、かつ簡便な操作でデニム製品を糊抜きすることが可能である。 When the desizing liquid and the denim product pasted are brought into contact with each other, it is preferable that the denim product pasted in the desizing liquid is contacted for 0.5 to 12 hours. As a result, it is possible to desizing the denim product in a relatively short time and with a simple operation.
脱糊液と糊付けされたデニム製品とを接触させるときの温度は15℃〜60℃であることが好ましい。これにより、比較的に低温でデニム製品を糊抜きすることが可能である。 It is preferable that the temperature when the desizing solution and the pasted denim product are brought into contact is 15 ° C to 60 ° C. As a result, it is possible to desizing the denim product at a relatively low temperature.
脱糊液及び糊付けされたデニム製品を接触させるに際しては、pH4.0〜9.0の脱糊液を糊付けされたデニム製品に接触させることが好ましい。強酸性又は強塩基性などの厳しい反応条件ではなく、穏やかな反応条件とすることができるので操作が簡易であり、デニム製品へのダメージも少なくすることが可能である。 When the desizing solution and the pasted denim product are brought into contact, it is preferable to contact the desizing solution having a pH of 4.0 to 9.0 with the pasted denim product. Since the reaction conditions are not severe, such as strong acidity or strong basicity, but gentle reaction conditions, the operation is simple, and damage to the denim product can be reduced.
本発明の製造方法によれば、デニム生地の脱色を防ぎつつ、デニム生地の糊を糊抜きして柔軟な糊抜きデニム製品を製造することができる。 According to the manufacturing method of the present invention, it is possible to manufacture a flexible paste-free denim product by removing the paste of the denim fabric while preventing decolorization of the denim fabric.
以下、本発明を実施するための形態について説明する。 Hereinafter, modes for carrying out the present invention will be described.
本発明は、PVAを酸化可能な酵素及びアミラーゼを含有する脱糊液と、糊付けされたデニム製品とを接触させて、接触後に酵素接触後のデニム製品を洗浄し、洗浄後のデニム製品を乾燥して糊抜きされたデニム製品を得る糊抜きデニム製品の製造方法である。 In the present invention, a desizing solution containing an enzyme capable of oxidizing PVA and amylase is brought into contact with a pasted denim product, the denim product after contact with the enzyme is washed after the contact, and the washed denim product is dried. This is a method for producing a paste-free denim product.
脱糊液とデニム製品とを接触させる際には、振とう状態若しくは撹拌状態又は静置した状態で接触させることが好ましい。振とう状態又は静置した状態で接触させることによってデニム製品同士が擦れて脱色が生じることを防ぐことができる。振とう状態若しくは撹拌状態で接触させるには、例えば、撹拌子などを使用して弱く撹拌する方法や浸漬容器を揺らす方法が挙げられる。脱糊液が対流し、デニム製品が激しく擦れない程度に撹拌又は振とうすればよい。例えば、一実施形態として、適宜の浸漬容器に脱糊液とデニム製品とを投入して振とうしながら又は静置した状態でデニム製品と脱糊液とを接触させることができる。振とうは、3〜15rpm程度とすることが好ましい。他の実施形態として、デニム製品に脱糊液を適用した状態で所定時間静置して酵素反応を進めることができる。適用する方法としては、デニム製品に脱糊液を塗ったり、噴霧したり、浸漬後に引き上げる方法が挙げられる。 When the desizing solution and the denim product are brought into contact with each other, it is preferable to bring them into contact with each other in a shaking state, a stirring state, or a stationary state. By contacting in a shaken state or in a stationary state, it is possible to prevent denim products from rubbing against each other and causing discoloration. In order to make it contact in a shaking state or stirring state, the method of stirring weakly using a stirring bar etc. and the method of shaking an immersion container are mentioned, for example. What is necessary is just to stir or shake so that a desizing liquid may convect and a denim product may not rub vigorously. For example, as one embodiment, the denim product and denim product can be brought into contact with each other while being put in a suitable soaking container and shaking or standing still. Shaking is preferably about 3 to 15 rpm. As another embodiment, the enzyme reaction can be allowed to proceed for a predetermined period of time in a state where a desizing solution is applied to the denim product. Examples of the method to be applied include a method of applying a desizing solution to a denim product, spraying it, or pulling it up after immersion.
脱糊液は、アミラーゼ及びPVAを酸化可能な酵素を含有するものであればよく種々の方法によって得られる。例えば、PVA分解活性を有する微生物の培養液に粉末若しくは液体のアミラーゼを配合すればよい。別の例としては、アミラーゼ活性を有する微生物の培養液に粉末若しくは液体のPVA分解酵素を配合すればよい。ここでいうPVA分解酵素とは、PVAを酸化可能な酵素及び/又は酸化されたPVAを加水分解可能な酵素のことである。脱糊液には、水、緩衝液等が含まれてもよい。上記の培養液は公知のたんぱく質の精製方法によって粗精製したものでもよい。 Any desizing solution may be used as long as it contains an enzyme capable of oxidizing amylase and PVA, and can be obtained by various methods. For example, a powder or liquid amylase may be added to a culture solution of a microorganism having PVA degradation activity. As another example, a powder or liquid PVA-degrading enzyme may be added to a culture solution of a microorganism having amylase activity. The PVA-degrading enzyme here is an enzyme capable of oxidizing PVA and / or an enzyme capable of hydrolyzing oxidized PVA. The desizing solution may contain water, a buffer solution, or the like. The culture broth may be roughly purified by a known protein purification method.
PVAを分解する活性を有する微生物としては、例えば、Pseudomonas属の細菌、Acinetobacter属の細菌、Sphingomonas属の細菌が挙げられる。アミラーゼ活性を有する微生物としては、例えばBacillus subtilis Marburg、Bacillus subtilis natto、Bacillus amyloliquefaciens、Bacillus licheniformis、Bacillus cereus、Bacillus macerans、Pseudomonas stutzeri、Klebusiella aerogenes等のバチルス属を中心とする細菌、Streptomyces griseus等の放線菌、Aspergillus oryzae、Aspergillus niger等のカビ類が挙げられる。これらは公知の方法により培養し、公知の方法で酵素液を抽出することができる。 Examples of microorganisms having an activity of degrading PVA include bacteria belonging to the genus Pseudomonas, bacteria belonging to the genus Acinetobacter, and bacteria belonging to the genus Sphingomonas. Examples of microorganisms having amylase activity include bacteria such as Bacillus subtilis Marburg, Bacillus subtilis natto, Bacillus amyloliquefaciens, Bacillus licheniformis, Bacillus cereus, Bacillus macerans, Pseudomonas stutzeri, Klebusiella aerogenes, etc. And molds such as Aspergillus oryzae and Aspergillus niger. These can be cultured by a known method, and an enzyme solution can be extracted by a known method.
脱糊液は、アミラーゼ及びPVAを酸化可能な酵素に加えて、酸化されたPVAを加水分解可能な酵素を含有することが好ましい。酸化されたPVAは経時的に低分子化するが、酸化されたPVAを加水分解可能な酵素を含有させることで速やかに酸化されたPVAを低分子化することが可能になる。酸化されたPVAを加水分解可能な酵素は、前記のPVAを分解する活性を有する微生物が生産することができる。 The desizing solution preferably contains an enzyme capable of hydrolyzing the oxidized PVA in addition to the enzyme capable of oxidizing amylase and PVA. Oxidized PVA decreases in molecular weight over time, but it becomes possible to rapidly reduce the molecular weight of oxidized PVA by containing an enzyme capable of hydrolyzing oxidized PVA. An enzyme capable of hydrolyzing oxidized PVA can be produced by a microorganism having an activity of degrading the PVA.
アミラーゼとしては、加工デンプンやデンプンに含まれるグリコシド結合を加水分解することでそれらに含まれるアミロースやアミロペクチンを低分子化するものを使用することが好ましい。たとえば、α-アミラーゼ、β-アミラーゼ、グルコアミラーゼ、イソアミラーゼなどが挙げられる。 As the amylase, it is preferable to use a modified starch or a starch that hydrolyzes a glycosidic bond contained in starch to reduce the molecular weight of amylose or amylopectin contained therein. For example, α-amylase, β-amylase, glucoamylase, isoamylase and the like can be mentioned.
PVAを酸化可能な酵素は、第2級アルコールオキシダーゼ(EC 1.1.3.18)を含むことが好ましい。酸化されたPVAを加水分解可能な酵素は、β-ジケトンヒドロラーゼ(EC 3.7.1.7)を含有することが好ましい。両酵素は、可溶性かつ分泌型の酵素であるとされており、例えば、両酵素の活性を有する微生物の培養液を遠心分離して得た上清をそのまま、あるいはそれから酵素を粗精製することで酵素液とすることができる。両酵素を生産する微生物として、それぞれ公知である、Pseudomonas属の細菌、Acinetobacter属の細菌、Sphingomonas属の細菌が挙げられ、例えば、Pseudomonas vesicularis PDが挙げられる。 The enzyme capable of oxidizing PVA preferably contains secondary alcohol oxidase (EC 1.1.3.18). The enzyme capable of hydrolyzing oxidized PVA preferably contains β-diketone hydrolase (EC 3.7.1.7). Both enzymes are considered to be soluble and secretory enzymes. For example, the supernatant obtained by centrifuging the culture solution of microorganisms having the activities of both enzymes can be used as it is or by roughly purifying the enzyme from it. It can be an enzyme solution. Examples of microorganisms that produce both enzymes include known bacteria of the genus Pseudomonas, bacteria of the genus Acinetobacter, and bacteria of the genus Sphingomonas, such as Pseudomonas vesicularis PD.
第2級アルコールオキシダーゼは以下の化1の反応を触媒し、酸化されたPVA分子鎖の隣接する2個の水酸基を酸化する。β-ジケトンヒドロラーゼは以下の化2の反応を触媒し、化1で生じた産物を加水分解してPVAを低分子化させると考えられる。 The secondary alcohol oxidase catalyzes the reaction of the following chemical formula 1 and oxidizes two adjacent hydroxyl groups of the oxidized PVA molecular chain. It is considered that β-diketone hydrolase catalyzes the following reaction of Chemical Formula 2 and hydrolyzes the product produced in Chemical Formula 1 to lower the molecular weight of PVA.
上述のように、脱糊液はPVAを酸化可能な酵素及びアミラーゼを含有する。脱糊液は、酸化されたPVAを加水分解可能な酵素をさらに含有することが好ましい。各酵素は精製された酵素である必要はない。例えば、アミラーゼ活性、PVAを酸化する活性、酸化されたPVAを分解する活性を有する各種の微生物の培養液をそのまま酵素液として使用してもよいし、各種の微生物の培養液に含まれる微生物を破砕して酵素液として使用してもよいし、破砕物から酵素を精製して使用してもよい。さらに、遠心分離により菌体を除去した培養上清を酵素液として使用してもよいし、破砕物及び/又は培養上清から酵素を粗精製して使用してもよい。酵素の精製には、公知のたんぱく質の単離精製方法であれば特に限定することなく使用できる。具体的には、遠心分離、膜濃縮、透析、硫安飽和や溶媒沈澱法、イオン交換クロマトグラフィーやアフィニティクロマトグラフィー等の各種クロマトグラフィー等を組み合わせて使用すればよい。 As described above, the desizing solution contains an enzyme capable of oxidizing PVA and amylase. It is preferable that the desizing liquid further contains an enzyme capable of hydrolyzing oxidized PVA. Each enzyme need not be a purified enzyme. For example, a culture solution of various microorganisms having an amylase activity, an activity to oxidize PVA, and an activity to decompose oxidized PVA may be used as an enzyme solution as it is, or a microorganism contained in a culture solution of various microorganisms may be used. It may be crushed and used as an enzyme solution, or the enzyme may be purified from the crushed material and used. Furthermore, the culture supernatant from which the cells have been removed by centrifugation may be used as the enzyme solution, or the enzyme may be roughly purified from the crushed material and / or the culture supernatant. For the purification of the enzyme, any known protein isolation and purification method can be used without particular limitation. Specifically, centrifugal separation, membrane concentration, dialysis, ammonium sulfate saturation, solvent precipitation, various types of chromatography such as ion exchange chromatography and affinity chromatography may be used in combination.
脱糊液に接触させた後にデニム製品を洗浄、及び乾燥する工程は定法により行えばよい。例えば、公知の水洗機や乾燥機を使用して行うことができる。 The step of washing and drying the denim product after being brought into contact with the desizing solution may be performed by a conventional method. For example, it can be performed using a known water washer or dryer.
デニム製品としては、デンプンや加工デンプンなどのデンプン系の糊と、PVA糊とを併用して経糸を糊付けしたものが挙げられる。例えば、デニムシャツ、ジーンズパンツ、ジーンズジャケット、デニム生地を利用した帽子などの被服、デニム生地を使用したバッグなどの鞄類などが挙げられる。 Examples of denim products include those in which warp yarns are pasted together using starch-based pastes such as starch and modified starch, and PVA paste. Examples include clothes such as denim shirts, jeans pants, jeans jackets, hats using denim fabric, and bags such as bags using denim fabric.
脱糊液とデニム製品とを接触させるときの温度は、15℃〜60℃であることが好ましく、15℃〜55℃であることがより好ましく、15℃〜35℃であることがさらに好ましく、常温であることが特に好ましい。常温とは加熱、冷却を行わない平常の温度のことである。比較的に低温で糊抜きを行うことができるので加熱の煩わしさを低減することができる。また、温度を低くすることでデニム製品の脱色の程度をより小さくすることができる。デニム製品を脱糊液に浸漬する場合は、脱糊液の温度を調節するとよい。デニム製品に脱糊液を適用する場合は雰囲気の温度を調節するとよい。 The temperature at the time of bringing the desizing solution into contact with the denim product is preferably 15 ° C to 60 ° C, more preferably 15 ° C to 55 ° C, further preferably 15 ° C to 35 ° C, It is especially preferable that it is normal temperature. Room temperature is a normal temperature at which heating and cooling are not performed. Since the desizing can be performed at a relatively low temperature, the troublesomeness of heating can be reduced. Further, the degree of decolorization of the denim product can be further reduced by lowering the temperature. When the denim product is dipped in the desizing solution, the temperature of the desizing solution may be adjusted. When applying a desizing solution to denim products, the temperature of the atmosphere should be adjusted.
糊液及び糊付けされたデニム製品を接触させるに際しては、pH4.0〜9.0の脱糊液を糊付けされたデニム製品に接触させることが好ましく、pH5.8〜pH7.2とすることがより好ましい。浸漬する場合と適用する場合共に、脱糊液のpHを調節するとよい。pHを当該範囲とすることにより、反応条件を穏やかにすることができ、操作を安全に行い、デニム製品へのダメージを軽減することができる。 When contacting the paste liquid and the pasted denim product, it is preferable to bring the pH 4.0 to 9.0 desizing solution into contact with the pasted denim product, and the pH is preferably set to 5.8 to pH 7.2. preferable. It is good to adjust the pH of the desizing liquid both when immersed and when applied. By making pH into the said range, reaction conditions can be made mild, operation can be performed safely, and the damage to a denim product can be reduced.
以下、本発明の実施例を挙げてさらに具体的に説明する。なお、本発明の構成は以下に挙げる実施例に限定するものではない。 Hereinafter, examples of the present invention will be described in more detail. In addition, the structure of this invention is not limited to the Example given below.
[酵素活性]
以下において、特に明記しない限り、酵素液の酵素活性は以下のように定義する。
[PVA酸化活性]
PVAを基質とし、30℃、pH7.0の条件で酵素液を作用させ、1分間に1μmolの過酸化水素を生成する酵素量を1単位(1U)とした。
[酸化されたPVAを加水分解可能な酵素の活性]
酸化されたPVAを加水分解可能な酵素は、β−ジケトン構造を有する化合物に作用するため(Agric. Biol. Chem., 48, 1093(1986))、本構造を有する3,5−ヘプタンジオンを基質とし、30℃、pH7.0の条件で酵素液を作用させ、1分間に1μmolのメチルエチルケトンを生成する酵素量を1単位(1U)とした。
〔酵素液の調製〕
Pseudomonas vesicularis PDを科学と工業 72, 112(1993)に基づく方法で培養し、培養液から菌体を除去した後、硫安で塩析した。析出物を50mmоl/lのリン酸カリウム緩衝液(pH7.0)で溶解後、透析し、酵素液を得た。本酵素液の酵素活性を以下に記載する方法で測定したところ、PVA酸化活性が約777.6mU/mlであり、酸化されたPVAを加水分解可能な酵素が約1.7mU/mlであった。
[Enzyme activity]
In the following, unless otherwise specified, the enzyme activity of the enzyme solution is defined as follows.
[PVA oxidation activity]
Using PVA as a substrate, the enzyme solution was allowed to act under conditions of 30 ° C. and pH 7.0, and the amount of enzyme that produced 1 μmol of hydrogen peroxide per minute was defined as 1 unit (1 U).
[Activity of enzyme capable of hydrolyzing oxidized PVA]
Since an enzyme capable of hydrolyzing oxidized PVA acts on a compound having a β-diketone structure (Agric. Biol. Chem., 48, 1093 (1986)), 3,5-heptanedione having this structure is used. The enzyme solution was used as a substrate under the conditions of 30 ° C. and pH 7.0, and the amount of enzyme that produced 1 μmol of methyl ethyl ketone per minute was defined as 1 unit (1 U).
(Preparation of enzyme solution)
Pseudomonas vesicularis PD was cultured by the method based on Science and Industry 72, 112 (1993), and after removing the cells from the culture solution, it was salted out with ammonium sulfate. The precipitate was dissolved in 50 mmol / l potassium phosphate buffer (pH 7.0) and dialyzed to obtain an enzyme solution. When the enzyme activity of this enzyme solution was measured by the method described below, the PVA oxidation activity was about 777.6 mU / ml, and the enzyme capable of hydrolyzing oxidized PVA was about 1.7 mU / ml. .
〔酵素活性の測定方法〕
[PVA酸化活性]
50mmol/lのリン酸緩衝液(pH7.0)、1%PVA(重合度約2000、ナカライテスク株式会社製)、酵素液を含む全量1.0mlの反応液を、7ml容量のL型試験管に入れ、27℃で60min振とう反応した。反応液0.32mlにチタニウム試薬(硫酸チタン(IV)溶液(ナカライテスク株式会社製)を10%硫酸で25倍希釈したもの)0.8mlを加え、410nmの吸光度を測定した。
[Method for measuring enzyme activity]
[PVA oxidation activity]
A 50 ml / l phosphate buffer (pH 7.0), 1% PVA (degree of polymerization: about 2000, manufactured by Nacalai Tesque), and a total amount of 1.0 ml of the reaction solution containing an enzyme solution were added to a 7 ml L-shaped test tube. And shaken at 27 ° C. for 60 minutes. 0.8 ml of a titanium reagent (titanium sulfate (IV) solution (manufactured by Nacalai Tesque, Inc.) diluted 25-fold with 10% sulfuric acid) was added to 0.32 ml of the reaction solution, and the absorbance at 410 nm was measured.
[β−ジケトンヒドロラーゼ活性]
50mmol/lのリン酸緩衝液(pH7.0)、8mmol/lの3,5−ヘプタンジオン、酵素液を含む全量1.0mlの反応液を、2ml容量のバイアルに入れ、ふたをした後、30℃で5hインキュベートした。0.2mlの反応液、0.04mlの0.375mol/l硫酸、および1.0mlの2.5mmol/lの1,4−ジオキサンを10ml容量のバイアル内で混合し、Shimadzu GCMS−QP2010 Ultraを用い、1,4−ジオキサンを内部標準としたヘッドスペース法により生成したメチルエチルケトン測定した。
[Β-diketone hydrolase activity]
A total volume of 1.0 ml of the reaction solution containing 50 mmol / l phosphate buffer (pH 7.0), 8 mmol / l 3,5-heptanedione, and enzyme solution was placed in a 2 ml vial, capped, Incubated at 30 ° C. for 5 h. Mix 0.2 ml reaction solution, 0.04 ml 0.375 mol / l sulfuric acid, and 1.0 ml 2.5 mmol / l 1,4-dioxane in a 10 ml vial and add Shimadzu GCMS-QP2010 Ultra. The methyl ethyl ketone produced by the headspace method using 1,4-dioxane as an internal standard was measured.
〔実施例1〕
公知の方法によってインジゴ染色し、その後、加工澱粉糊及びPVAで糊付けした経糸と、無染色で糊付けをしていない緯糸とで織成したデニム生地を素材とするジーンズパンツに対して脱糊液を適用して糊抜きを行った。デニム生地は、14オンス(経糸7番手、緯糸6番手)の一般的なジーンズを使用した。糊抜き後、公知の方法により水洗・乾燥した。ジーンズパンツを糊抜き加工に供する前と、糊抜き、水洗、及び乾燥を経た後において、生地の柔軟性と色濃度を調べた。結果を表1に示す。ジーンズパンツに脱糊液を適用する作業は以下のようにして行った。浸漬槽に水と、上記のPVA分解活性を備える酵素液と、ユケンケミカル株式会社製のα-アミラーゼ(商品名マルチザイム YS-20)とを投入して泡立たないように慎重に撹拌して脱糊液とした。水の量はジーンズパンツとの浴比が、ジーンズの重量1に対して水の重量が20となるようにした(浴比1:20)。PVA分解活性を備える酵素液は、50ml/lとなるようにした。α−アミラーゼは、1ml/lとなるようにした。
[Example 1]
Dezizing solution applied to jeans pants made of denim fabric woven with warp yarns that have been indigo dyed by a known method and then glued with processed starch paste and PVA and weft yarns that have not been dyed and are not glued Then, desizing was performed. As the denim fabric, a general jeans of 14 ounces (7th warp and 6th weft) was used. After desizing, it was washed and dried by a known method. Before the jeans pants were subjected to the desizing process, and after the desizing, washing and drying, the flexibility and color density of the fabric were examined. The results are shown in Table 1. The work of applying the degliding solution to the jeans pants was performed as follows. Water, an enzyme solution having the above-described PVA decomposition activity, and α-amylase (trade name Multizyme YS-20) manufactured by YUKEN CHEMICAL CO., LTD. A paste was used. The amount of water was such that the bath ratio with jeans pants was 20 (water ratio 1:20) with respect to 1 weight of jeans. The enzyme solution with PVA decomposition activity was adjusted to 50 ml / l. α-amylase was adjusted to 1 ml / l.
浸漬槽に蓄えられた脱糊液に対して上記の浴比となるようにジーンズパンツを投入して、30℃で10秒に1回浸漬槽を揺すりながら8時間振とうする作業を行った。脱糊液のpHは7.0である。脱糊液からジーンズパンツを引き上げて水洗、乾燥して糊抜きされたジーンズパンツを得た。 Jeans pants were added so that the above-mentioned bath ratio was obtained with respect to the desizing solution stored in the dipping bath, and the operation was performed for 8 hours while shaking the dipping bath at 30 ° C. once every 10 seconds. The pH of the desizing solution is 7.0. The jeans pants were lifted from the desizing solution, washed with water and dried to obtain a jeans pants from which the paste was removed.
柔軟性の評価は、カトーテック株式会社製の純曲げ試験機(KESFB2)を使用して、曲げ硬さと、回復性を測定し、以下の数1により柔軟性を求めた。数1においてBは曲げ硬さ(g・cm2/cm)であり、2HBは回復性(g・cm/cm)である。 Flexibility was evaluated by measuring bending hardness and recoverability using a pure bending tester (KESFB2) manufactured by Kato Tech Co., Ltd. In Equation 1, B is bending hardness (g · cm 2 / cm), and 2HB is recoverability (g · cm / cm).
色濃度については、倉敷紡績株式会社製の分光測色機によって波長360nmから780nmの分光反射率を測定し、以下の数2のKubelka−Munk式によって濃色性の指標であるtotal k/s値に換算することで色濃度を評価した。total k/s値が大きいほど色濃度が濃いことを示す。なお、数2において、kは光の吸光係数を示し、sは光の散乱係数を示し、Rは表面反射率を示す。 As for the color density, a spectral reflectance of wavelengths from 360 nm to 780 nm is measured with a spectrocolorimeter manufactured by Kurashiki Boseki Co., Ltd., and a total k / s value that is an index of darkness according to the following Kubelka-Munk equation. The color density was evaluated by converting to. A larger total k / s value indicates a higher color density. In Equation 2, k represents the light absorption coefficient, s represents the light scattering coefficient, and R represents the surface reflectance.
〔実施例2〕
ジーンズパンツに脱糊液を適用するにあたって、浸漬槽にジーンズパンツを投入した後、10秒に1回浸漬槽を揺すりながら3時間振とうする作業を行った以外は実施例1と同様にして糊抜きされたジーンズパンツを製造した。実施例1と同様の方法で柔軟性及び色濃度を求めた。結果を表1に示す。
[Example 2]
In applying the desizing solution to the jeans pants, the glue was put in the same manner as in Example 1 except that the jeans pants were put into the immersion tank and then shaken for 3 hours while shaking the immersion tank once every 10 seconds. The punched jeans pants were manufactured. Flexibility and color density were determined in the same manner as in Example 1. The results are shown in Table 1.
〔比較例1〕
ジーンズパンツに脱糊液を適用するにあたって、実施例1の脱糊液をα-アミラーゼに変更し、α-アミラーゼとジーンズパンツとの接触を撹拌式の洗浄機(ウォッシャー)による洗浄に変更し、さらに洗浄時の温度及び時間を90℃で20分に変更し、α-アミラーゼ酵素液による洗浄を行った後60℃の温水で5分洗浄した点以外は実施例1と同様の方法で糊抜きされたジーンズパンツを製造した。α-アミラーゼは実施例1と同様のものを使用し、水200lに対しα-アミラーゼを200ml及び界面活性剤としてマルチトールHK−200(ユケンケミカル株式会社製)200mlを投入して混合した。比較例1について、実施例1と同様の方法で柔軟性及び色濃度を求めた。結果を表1に示す。
[Comparative Example 1]
In applying the desizing solution to the jeans pants, the desizing solution of Example 1 is changed to α-amylase, and the contact between the α-amylase and the jeans pants is changed to washing with a stirring type washer (washer). Further, the temperature and time at the time of washing were changed to 90 ° C. for 20 minutes, washed with an α-amylase enzyme solution, and then washed with 60 ° C. warm water for 5 minutes. Manufactured jeans pants. The same α-amylase as in Example 1 was used, and 200 ml of α-amylase and 200 ml of maltitol HK-200 (manufactured by Yuken Chemical Co., Ltd.) were added to 200 l of water and mixed. For Comparative Example 1, flexibility and color density were determined in the same manner as in Example 1. The results are shown in Table 1.
〔比較例2〕
実施例1の脱糊液を使用せず60℃のお湯に変更し、このお湯とジーンズパンツとの接触を撹拌式の洗浄機による洗浄に変更し、お湯による洗浄時の温度及び時間を60℃で10分に変更した点以外は実施例1と同様の方法で糊抜きされたジーンズパンツを製造した。比較例2について、実施例1と同様の方法で柔軟性及び色濃度を求めた。結果を表1に示す。
[Comparative Example 2]
The hot water and the jeans pants were changed to hot water without using the desizing solution of Example 1 and the contact between the hot water and the jeans pants was changed to washing with a stirring type washing machine, and the temperature and time at the time of washing with hot water were 60 ° C. In the same manner as in Example 1 except that the time was changed to 10 minutes, a jeans pants deflated was produced. For Comparative Example 2, flexibility and color density were determined in the same manner as in Example 1. The results are shown in Table 1.
〔比較例3〕
実施例1の脱糊液を第2級アルコールオキシダーゼ及びβ−ジケトンヒドロラーゼの酵素液に変更しアミラーゼを配合しなかった点、及び10秒に1回浸漬槽を揺すりながら3時間振とうする作業に変更した点以外は実施例1と同様の方法で糊抜きされたジーンズパンツを製造した。第2級アルコールオキシダーゼ及びβ−ジケトンヒドロラーゼの酵素液は実施例1と同様のものを使用した。比較例3について、実施例1と同様の方法で柔軟性及び色濃度を求めた。結果を表1に示す。
[Comparative Example 3]
For the work in which the desizing solution of Example 1 was changed to an enzyme solution of secondary alcohol oxidase and β-diketone hydrolase and amylase was not blended, and the work was shaken for 3 hours while shaking the immersion tank once every 10 seconds. Except for the changed points, the jeans pants were desalted in the same manner as in Example 1. The enzyme solutions of secondary alcohol oxidase and β-diketone hydrolase were the same as in Example 1. For Comparative Example 3, flexibility and color density were determined in the same manner as in Example 1. The results are shown in Table 1.
比較例3の方法で糊抜きしたジーンズパンツは、色濃度はほどんど低下しなかったが曲げ硬さと回復性の合計値が加工前と同じであり柔軟性に乏しいことが確認された。比較例1又は比較例2の方法で脱色したジーンズパンツは、曲げ硬さと回復性の合計値は加工前と比較して小さくなり柔軟性に富むことが確認されたが、加工前と比較して色濃度の値が顕著に小さくなった。実施例1又は実施例2の方法で脱色したジーンズパンツは、曲げ硬さと回復性の合計値が小さくなり適度な柔軟性を備え、色濃度の値も加工前と比較して顕著な変化は見られなかった。以上から明らかなように、PVAを酸化可能な酵素及びアミラーゼを含有する脱糊液を使用することにより、デニム生地の脱色を防ぎつつ、デニム生地の糊を糊抜きして肌触りのよい糊抜きデニム製品を製造することができることが確認された。 It was confirmed that the jeans pants with the paste removed by the method of Comparative Example 3 did not decrease in color density, but the total value of bending hardness and recoverability was the same as before processing, and the flexibility was poor. It was confirmed that the jeans pants decolored by the method of Comparative Example 1 or Comparative Example 2 had a lower bending hardness and recoverability compared to before processing and were rich in flexibility, but compared with before processing. The value of color density was significantly reduced. The jeans pants decolorized by the method of Example 1 or Example 2 have a small flexural hardness and recoverability, and have appropriate flexibility, and the color density value is not significantly different from that before processing. I couldn't. As is clear from the above, the use of a desizing solution containing an enzyme capable of oxidizing PVA and amylase prevents decolorization of the denim fabric, and removes the paste from the denim fabric to provide a comfortable touch. It was confirmed that the product could be manufactured.
実施例1の方法で糊抜きしたジーンズパンツ、加工前のジーンズパンツ、及び比較例1の方法で糊抜きしたジーンズパンツ、それぞれのデニム生地の拡大図を図1ないし図3に示す。 FIGS. 1 to 3 show enlarged views of the jeans pants removed by the method of Example 1, the jeans pants before processing, and the jeans pants removed by the method of Comparative Example 1, respectively.
図1及び図2の比較から明らかなように、実施例1の方法で糊抜きしたジーンズパンツは、加工前のジーンズパンツと比較して、感応評価では色濃度に違いは見られず、デニム生地を構成する繊維の毛羽立も見られなかった。一方、図3から明らかなように、比較例1の方法で糊抜きしたジーンズパンツは、経糸の表面が濃紺から淡い紺色に変化している部分が観察され、図1及び図2と比較してデニム生地の表面が毛羽立っていることが確認された。 As is clear from the comparison between FIG. 1 and FIG. 2, the jeans pants removed by the method of Example 1 have no difference in color density in the sensitivity evaluation compared to the jeans pants before processing, and the denim fabric There was also no fluffing of the fibers constituting the. On the other hand, as is apparent from FIG. 3, in the jeans pants removed by the method of Comparative Example 1, a portion where the surface of the warp is changed from dark blue to light dark blue is observed, compared with FIGS. 1 and 2. It was confirmed that the surface of the denim fabric was fuzzy.
Claims (7)
接触後に酵素接触後のデニム製品を洗浄し、
洗浄後のデニム製品を乾燥して糊抜きされたデニム製品を得る糊抜きデニム製品の製造方法。 Contacting a desizing solution containing an enzyme capable of oxidizing polyvinyl alcohol and amylase and a glued denim product,
After contact, wash the denim product after enzyme contact,
A method of producing a desizing denim product, which is obtained by drying the washed denim product to obtain a desizing denim product.
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