JP2003247174A - Method for modifying fiber containing polyester by enzyme - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for degrading or modifying a high-molecular polymer by an enzyme. <P>SOLUTION: The method for modifying a polyester involves a step for reacting an oxidation-reduction enzyme with the fiber. The method can also involve a step for reacting a hydrolytic enzyme of a carboxylate with the fiber. The oxidation-reduction enzyme can be a laccase or a polyphenol oxidase. The hydrolytic enzyme of a carboxylate can be a lipase or an esterase. The step for reacting the hydrolytic enzyme of a carboxylate is carried out before the step for reacting the oxidation-reduction enzyme. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for decomposing or modifying a high-molecular polymer with an enzyme. More particularly, the present invention relates to enzymatically degrading or modifying aromatic polyester fibers.

[0002]

2. Description of the Related Art Currently, about 70% of all synthetic fibers are manufactured in the world, and about 60,000 tons of polyester fibers are used for woven and knitted fabrics in Japan. .

Polyester, typically 100% polyester garments, are generally processed by caustic soda alkali weight reduction. This method provides a drape and imparts a silky feel to the polyester fibers by using a concentrated caustic soda solution and reducing the polyester fibers by up to about 30%. However, according to this method, a large amount of high-concentration caustic soda waste liquid containing a polyester decomposition product is generated, and the treatment thereof is a big problem. Further, even by this method, the defects such as sticky feeling (low water absorption) and clinging (chargeability), which are found in polyester clothing, are not yet improved.

On the other hand, as a technique for improving the functionality of the polyester fiber, the development of a technique for improving the dye stability, the water absorption property, the cooling property, the antistatic property, and the electroconductivity in addition to the morphological stability is active. . This is because polyester fibers have the drawbacks of being difficult to dye (not easy to dye), being hydrophobic and easily generating static electricity (which causes clinging).

As a processing technique for imparting easy dyeability, 1) a cation dyeing technique, 2) an atmospheric pressure dyeing technique, 3) a high pressure dyeing method for ultrafine fibers, 4) a vivid deep coloration technique, etc. have been devised. ing. The vivid and deep-coloring technology is a method in which minute irregularities are formed on the surface of a polyester fiber to facilitate structural dyeing, and at the same time, an optically vivid or deep color is obtained.

[0006] Other methods for improving the functionality of polyester fibers include texture processing, uneven processing, moisture absorption processing, antistatic processing and the like, and these techniques use various finishing agents in order to impart desired properties. To use. For example, the antistatic treatment is a method in which an antistatic agent is used in combination with a resin or the like and applied to the fiber surface. However, the fibers to which the finishing agent is added have a drawback that they have poor durability against washing and the like. In other words, this is, so to speak, only a temporary reforming method.

As a technique aiming at permanent modification by directly decomposing and changing the surface of the polyester fiber, You-Lo Hsieh and Lisa has been proposed.
A. Cram "Enzymatic Hydroly
sis to Improving Wetting an
d Absorbency of Polyester
Fabris "Textile Res. J. , 6
8, (5), 311 to 319 (1988) describe a method for modifying a polyester fiber using an enzyme.

Japanese Patent Application Laid-Open No. 2001-502014 (Japanese Patent Application No. 9-2014) entitled "Enzymatic treatment for improving wettability and absorbability of fabric".
-531905) describes a method of treating textile fibers with pectinases, cellulases, proteases, lipases or mixtures thereof.

Japanese Unexamined Patent Publication (Kokai) No. 5-34489 entitled "Method for Degrading Aliphatic Polyester and Surface Treatment Using Enzyme"
7 describes a method of treating an aliphatic polyester with a lipase.

Japan Society for the Promotion of Science 12
0 Committee 96th Lecture Material “Potential for Enzymatic Weight Loss Processing” Yoshiharu Kimura, “Developing Enzymatic Polyester Weight Loss Processing-Successful Cultivation of Polyester Degrading Bacteria-” Processing Technology, Vol.34, No. 5, 302 (1999)
Describes polyester-degrading bacteria.

The above prior art describes the effectiveness of the action of lipases on aliphatic polyester fibers.

[0012]

As described above, the present polyester processing is mainly carried out by concentrated alkali processing. The above-mentioned conventional polyester processing technology using an enzyme is a method of allowing a lipase to act on an aliphatic polyester or an aromatic polyester partially containing the aliphatic polyester. At present, none of the research examples relating to the decomposition and modification of 100% aromatic polyester which is mainly used or a blended product thereof has reached a practical level.

The inventors of the present invention have researched a better method for modifying an aromatic polyester from the viewpoint of modifying the surface of the aromatic polyester fiber by modifying the properties thereof, and have studied the method for modifying the aromatic polyester fiber such as laccase (or polyphenol oxidase).
The oxidoreductase is effective in decomposing and modifying the aromatic polyester, and further, the oxidoreductase is a lipase,
The inventors have found that the effect is enhanced by the combined use with a carboxylic acid ester hydrolase such as esterase, and completed the present invention.

That is, when the present inventors have made laccase (or polyphenol oxidase) and lipase act on an aromatic polyester, a remarkable fibrillation which is not found by the conventional enzyme treatment method using only lipase is detected. We found that it occurs on the surface, and at the same time confirmed that the fiber is given more excellent properties (improvement of flexibility, antistatic effect, water absorption, wrinkle prevention effect, improvement of dyeing density, etc.), Furthermore, they have found that these effects are enhanced by the coexistence of mediators during enzyme treatment. The present invention is the first disclosure to show that redox enzymes such as laccase (or polyphenol oxidase) are effective in degrading and modifying aromatic polyesters.

[0015]

According to the present invention, an aromatic polyester is treated with an oxidoreductase (typically laccase (or polyphenol oxidase)) or a carboxylate degrading enzyme (typically lipase). Provide a method of modifying a fabric fiber surface that is environmentally friendly and has a lasting effect and that can be carried out on an industrial scale.

The present invention relates to a method for modifying a fiber containing polyester, which method comprises a step of causing a redox enzyme to act on the fiber.

Preferably, the above method may further include a step of causing a carboxylic acid ester hydrolase to act on the above fiber.

Preferably, the redox enzyme may be laccase or polyphenol oxidase.

Preferably, the laccase may be laccase Daiwa.

[0020] Preferably, the carboxylic acid ester hydrolase may be a lipase or an esterase.

Preferably, the lipase is lipase P
It can be S.

Preferably, the step of causing the carboxylic acid ester hydrolase to act may be carried out before the step of causing the oxidoreductase to act.

[0023] Preferably, the surface of the fiber containing polyester can be fibrillated by the above method.

Preferably, the flexibility, water absorbency, antistatic property, anti-wrinkle property or deep dyeing property of the polyester-containing fiber can be modified by the above method.

[0025] Preferably, the step of allowing the redox enzyme to act may be carried out in the presence of a laccase mediator.

Preferably, the step of allowing the redox enzyme to act may be carried out in the presence of a reagent selected from the group consisting of a surfactant, a wetting agent, and a dispersant.

The present invention also relates to a method for modifying a fiber containing polyester, which comprises the step of allowing a carboxylic acid ester hydrolase to act on the fiber in the presence of a laccase mediator.

[0028] Preferably, the step of causing the carboxylic acid ester hydrolase to act may be carried out in the presence of a reagent selected from the group consisting of a surfactant, a wetting agent, and a dispersant.

[0029] Preferably, the carboxylic acid ester hydrolase may be a lipase or an esterase.

Preferably, the lipase is Lipase P
It can be S.

Preferably, the polyester-containing fiber may be a blended product of animal hair fiber and polyester fiber.

Preferably, the fibers containing the polyester may be alkali-treated fibers.

[0033]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described in detail below.

The present invention relates to a method for modifying a fiber containing polyester, which method comprises a step of causing a redox enzyme to act on the fiber. This method may further include the step of causing a carboxylic acid ester hydrolase to act on the fiber.

Representative examples of the carboxylic acid ester hydrolase include lipase and esterase. As the lipase and esterase, any lipase and esterase that decomposes an aliphatic polyester, that is, a carboxylic acid ester can be used. As a source of such carboxylic acid ester hydrolase,
Absidia, Achromobacter, A
genus eromonas, genus Alternaria, Asp
genus ergillus, genus Alcaligenes, Au
genus reobasidium, genus Bacillus, Be
Auveria, Brochothix, Can
genus dida, genus Chromobacter, copri
genus nus, Fusarium genus, Geotricum
Genus, Hansenula, Humicola, Hy
genus phozyme, genus Lactobacillus, M
genus etarhizium, genus Mucor, Paecil
genus omyces, genus Penicillium, Pseu
genus domonas, genus Rhizoctonia, Rhi
genus zomucor, genus Rhodosporidium,
Rhodotorula genus, Sporobolomyc
es genus, Thermomyces genus, Thiarosp
orella, Trichoderma, Vert
Microorganisms belonging to the genus icillum can be mentioned. As
genus pergillus, Achromobacter
Genus, Bacillus, Candida, Chro
genus mobacter, genus Fusarium, humic
ola genus, Hyphozyma genus, Pseudomon
As genus, Rhizomucor genus, Rhizopus
Microorganisms belonging to the genus Thermomyces are used as suitable sources. For example, Aspergill
us niger, Bacillus pumilu
s, Bacillus stearothermoph
ilus, Candida cylindracea,
Candida antarctica, Humicol
a insolens, Pseudomonas ce
pacia, Pseudomonas fluores
sense, Thermomyces lanugin
The enzyme produced by Osus is preferably used. Commercially available enzyme preparations are also preferably used. For example, lipase PS (Amano Enzyme Inc.) can be effectively used.

A typical example of the oxidoreductase is laccase. Aspe as a source of laccase
genus rgillus, genus Neurospora (eg,
N. crassa), genus Podospora, Botr
genus ytis, genus Fromes, genus Lentinus, Pl
genus eurotus, genus Trametes (eg T.
Villosa), the genus Rhizoctonia (eg R. solani), the genus Coprinus (eg C. cinereus, C. comatus, C.
friesii, C.I. plicatilis), Psa
genus thyrella (eg, P. condellea
na), the genus Panaeolus (eg P. papi)
lionaceus), Myceliophthora
Genus (eg, M. thermophila), Schy
genus T. talidium (eg, S. thermophi
lum), the genus Polyporus (eg P. pin
situs), genus Phlebia (eg, P. rad)
ita), the genus Coriolus (eg C. hirs
utus, C.I. Versicolor), Myroth
ecium (eg, M. verrucaria,
M. roridum). Commercially available laccase agents are also preferably used. For example, Denilite IIS
(Novozymes Japan Co., Ltd.) and Laccase Daiwa (Daiwa Kasei Co., Ltd.) are preferably used.

The enzymatic treatment of the polyester of the present invention can be carried out under the conditions of pH and temperature suitable for the action of the above enzyme. The enzymatic treatment of the polyester of the present invention can be enhanced by adding a mediator as shown in Table 3, for example.

The term “mediator” as used herein
And "laccase mediator" is used interchangeably and means a substance capable of enhancing the activity of the above-mentioned carboxylic acid ester hydrolase and oxidoreductase. Such substances are known to the person skilled in the art, for example 1-Nitroso-2-napht used in Example 2 below.
hol-3,6-disulfonic acid d
isodium salt, 2-Nitroso-1-
naphthol-4-sulfonic acid,
Acetosyringone, Viourrica
cid monohydrate, ABTS (2,2 '
-Azino-bis (3-ethylbenzoth
iazoline-6-Sulfonic Aci
d)), 1-Hydroxybenzotriazol
Typical examples thereof include e, and DeniLite Plus (available from Novozymes Japan KK, a phenothiazine derivative).

The enzyme treatment of the polyester of the present invention can be carried out by mixing the polyester and the enzyme solution in a bath ratio of 1: 1 to 1: 200, preferably 1: 5 to 1: 100. The amount of enzyme added may vary depending on the activity per unit weight of the preparation, reaction time, reaction conditions, etc.
1 to 10% (W / V), typically 0.1 to 2% (W / V
V) range. The enzyme reaction temperature is also in the optimum temperature range of the enzyme used, and is usually in the range of 30 to 80 ° C, typically in the range of 45 to 70 ° C. The pH of the enzyme reaction solution is usually adjusted to a range of pH 4.0 to 8.0, typically pH 5.0 to 7.0, depending on the optimum pH of the enzyme used. It The time of enzyme treatment can vary greatly depending on the reaction conditions, but usually
It is in the range of tens of minutes to 30 hours, typically about 5 hours.

The method of enzymatic treatment of polyester of the present invention is as follows:
Reagents such as surfactants, wetting agents, dispersants, etc. may be added to enhance and enhance the interaction of the hydrophobic polyester fibers with the enzyme. The amount of such a drug added is usually in the range of 0.05 to 3% (W / V), and typically in the range of 0.1 to 1% (W / V).

Preferably, the oxidoreductase and the carboxylic ester hydrolase can be used in combination. Either enzyme may be used first to modify the polyester fiber. Treatment with oxidoreductase (typically laccase) is effective in improving the flexibility and chargeability of polyester fibers, and it is first possible to use carboxylic acid ester hydrolase (typically lipase). Treatment and then treatment with a redox enzyme (typically laccase) are effective in improving wrinkle resistance.

[0042]

EXAMPLES Examples of the present invention will be described below. The following examples are illustrative of the invention and are not intended to limit the invention.

In this example, lipase P was used as the lipase.
S (available from Amano Enzyme Inc., LPS below)
), As laccase, Denilite IIS (registered trademark) (Novozymes Japan KK, hereinafter DII
S) and laccase Daiwa (available from Daiwa Kasei Co., Ltd., hereinafter referred to as LD) were used.

Table 1 summarizes the properties of these enzymes. The enzyme treatment conditions were determined based on these properties.

[0045]

[Table 1]

(Example 1) The polyester fiber used in this example is a white cloth attached to JIS polyester. This was washed with hot water at 60 ° C. for 10 minutes, then naturally dried and used for the test.

A 2% (W / V) concentration solution of the enzyme shown in Table 1 was used alone, or as shown in Table 2, LPS → DII.
S, LPS → LD, DIIS → LPS, LD → LPS were combined in this order and added to the polyester white cloth at a bath ratio of 1: 100. Place a container containing polyester white cloth and enzyme on Bio Shaker BR-30L (manufactured by Taitec) and stir at 120 rpm to add each enzyme to 5
I made it work for time. The treatment was terminated by performing a heat treatment at 90 ° C. for 20 minutes.

[0048]

[Table 2]

In Table 2, pH 7.0 is 1.0 mmo.
l / L phosphate buffer, pH 5.0 is 1.5mm
It shows that the reaction was carried out in ol / L acetate buffer.

Each of the obtained enzyme-treated polyester cloths was evaluated as follows.

(1) Surface observation by electron microscope Scanning electron microscope JSM-T330 (JEOL Ltd.)
Was used to observe the fiber surface of the polyester cloth.

(2) Texture test Using texture measuring device (Kato Tech Co., Ltd.), KES
-Handle was evaluated by performing a tensile test by FB1, a shear test, a bending test by KES-FB2, and a compression test by KES-FB3. In addition, KES is KAWABATA '
S EVOLUTION SYSTEMS, known to those skilled in the art.

(3) Water Absorption Test The water absorption rate was measured by applying the water absorption rate (appropriate method) in JIS L 1907 “Test method for water absorption of textiles” to evaluate water absorption.

(4) Charging property test Using a static Honest meter H-0110 (Shishido Electrostatic Co., Ltd.), the half-life measuring method in JIS L 1904 "Testing method for charging property of woven and knitted materials" is applied correspondingly. did.

(5) Polyester Yarn Strength Elongation Test A warp yarn and a weft yarn were taken out from the polyester cloth, and a universal tensile tester AG-500A (Shimadzu Corporation) was used.
The single yarn tensile strength and elongation in IS L 1095 "General spun yarn test method" were applied mutatis mutandis.

(6) Wrinkle resistance test JIS L 1059 "Wrinkle resistance test method for textiles"
Was used to evaluate the wrinkle prevention rate from the measurement of the wrinkle recovery angle.

(7) Dyeing test A polyester cloth was dyed and evaluated under the following conditions. Dye Kayalon Polyester T-SF
1.0% o. w. f. Auxiliary dispersant 1.0 g / L; Acetic acid 2.0% o. w. f. Sodium acetate 1.0% o. w. f. Bath ratio 1:43; temperature raising conditions It took 70 minutes to raise the temperature from 40 ° C to 130 ° C. Then, it was kept at 130 ° C. for 60 minutes and then cooled.

The tests (2) to (6) were conducted under standard conditions (temperature 20 ° C., relative humidity 65% RH).

(Evaluation Result) (1) Surface Observation by Electron Microscope FIGS. 21, 22 and 23 show electron micrographs of enzyme-treated polyester cloth. Photo B shown in FIG. 21
22 is an electron micrograph of a polyester cloth which has not been treated with an enzyme, Photo 1 shown in the upper part of FIG. 22 is an electron micrograph of a polyester cloth which is treated with laccase and then lipase, and Photo 2 shown in the lower part of FIG. 22 is a lipase. It is an electron micrograph of the polyester cloth which carried out the laccase process after a process. Beneath each photograph is shown a magnification and a scale of 5 μm.

As shown in Photo 1, when the lipase treatment was performed after the laccase treatment, the polyester fiber surface was
A finely scratched change was observed. As shown in Photo 2, a larger change was observed on the surface of the polyester fiber in the case where the lipase treatment was followed by the laccase treatment than in the case where the laccase treatment was followed by the lipase treatment. That is, fibrillation of the polyester material occurred on the surface of the polyester fiber, and the surface of the polyester fiber was turned up. It was considered that such fibrillation was one of the major causes of the improvement in texture, water absorption, charging properties, wrinkle resistance, and dyeability described later.

In FIG. 23, photographs 3 and 4 are
3 is an electron micrograph of a polyester cloth treated with laccase and lipase alone, respectively. Photo 3 and Photo 4
As can be seen in Fig. 3, even when the laccase and the lipase alone were treated, a fine modification of the surface structure was confirmed on the polyester fiber surface.

(2) Evaluation by texture measuring apparatus FIGS. 1 and 2 show shear rigidity and tensile rigidity by KES-FB1, FIG. 3 shows bending rigidity by KES-FB2, and FIG. 4 shows KES-FB3. The results of measuring the compression stiffness are shown below. In each figure, B shows the results of the enzyme-untreated polyester, and 1 to 7 are shown in Table 2.
The results of the polyesters obtained by the enzyme treatment under the conditions corresponding to the test numbers shown in are shown.

As is clear from the respective figures, in most enzyme-treated polyester cloths, the shear rigidity, tensile rigidity, bending rigidity, and compression rigidity are respectively reduced as compared with untreated polyester cloths, and the flexibility of polyester cloths is reduced. Was improved. In particular, it was shown that the bending rigidity was significantly reduced by the enzyme treatment (Fig. 3).

(3) Water Absorption Test FIG. 5 shows the results of the water absorption test. The vertical axis of FIG. 5 represents the time (seconds) when a water drop is dropped on the surface of the cloth and the water drop is absorbed by the cloth. As shown in FIG. 5, it was shown that the absorption time of water droplets was shortened and the water absorption was increased by any of the enzyme treatments.

(4) Charging property test FIG. 6 shows the result of the charging property test. The vertical axis of FIG. 6 is the saturation voltage (KV) of the polyester cloth or its half-life (seconds), the saturation voltage of the tested polyester cloth is shown by a diamond, and its half-life is shown by a bar graph. As shown in FIG. 6, it was shown that both enzyme treatments reduced both the saturation voltage and the half-life of the polyester cloth. In particular, laccase-only treatment (1 and 2 in FIG. 6),
The laccase → lipase (3 and 4 in FIG. 6) and lipase → laccase (6 and 7 in FIG. 6) treatments were shown to be effective.

The present inventors do not intend to be bound by any particular theory, but one of the reasons that the properties of the polyester cloth by the enzyme treatment are modified is that the polyester material on the polyester fiber surface is It was considered that this is because the fibrillation and the change in the surface structure of the polyester fiber made it a structure suitable for retaining water, and because it became easy to wet, the water retention property increased and the static electricity leakage effect increased.

Further, it was revealed that the decomposition mode peculiar to laccase is effective for improving the charging property. Such modification of the polyester is useful for permanent prevention of so-called “clinging” which is often seen in polyester clothing which cannot be improved by the concentrated alkali treatment.

(5) Strength and Elongation Test of Polyester Yarn FIG. 7 shows the result of the polyester yarn strength test, and FIG. 8 shows the result of the polyester yarn elongation test. 7 and 8, the white bar graphs show the measurement results of the warp threads, and the black bar graphs show the measurement results of the weft thread. As shown in FIGS. 7 and 8, it was shown that the strength and the elongation of the warp and the weft were slightly reduced by the enzyme treatment.

(6) Wrinkle resistance test FIG. 9 shows the test results of the wrinkle resistance test. The white bar graph shows the measurement result of the warp yarn, and the black bar graph shows the measurement result of the weft yarn. As shown in FIG. 9, in particular, it was shown that the lipase → laccase treatment (6 and 7 in FIG. 9) improves the wrinkle resistance of the polyester fiber.

(7) Staining test FIG. 10 shows the results of staining density (K / S value). In the case of laccase alone treatment (1 and 2 in Fig. 10), blank (Fig. 1
A K / S value lower than that of B) of 0 was obtained, but a K / S value higher than that of the blank was obtained when lipase alone treatment (5 in FIG. 10) or laccase and lipase were used in combination.
Particularly, when laccase Daiwa was used in combination (4 and 7 in FIG. 10), a high K / S value was obtained, and it was shown that the dyeability was remarkably improved.

Example 2 In this example, lipase PS
The effect of various mediators on the polyester treatment with (LPS) and laccase Daiwa (LD) was examined.

Of the mediators used, 1-Ni
troso-2-naphthol-3,6-disu
lfonic acid disodium sal
t, 2-Nitroso-1-naphthol-4-
sulphonic acid, acetosyring
one, Violuric acid monohyd
rate, ABTS (2,2'-Azino-bis
(3-ethylbenzothiazoline-6
-Sulfonic Acid)), 1-Hydrox
ybenzotriazole is 1 mmol each
/ L concentration, and DeniLite Plus (available from Novozymes Japan KK, phenothiazine derivative) was used at a concentration of 1% (W / V).

The combinations of each enzyme and the mediator are as shown in Table 3.

[0074]

[Table 3]

When both LPS and LD enzymes were used, LPS was allowed to act and then LD was allowed to act. The enzyme treatment was performed according to the working conditions of Example 1. The obtained enzyme-treated polyester cloth was evaluated according to the method described in Example 1.

(Evaluation Results) The evaluation results are shown in FIGS. 11 to 20 as in Example 1. B in each figure
Shows the test result of the polyester cloth not treated with enzyme, 8
31 to 31 show the evaluation results of the polyester obtained by the enzyme treatment with the combination with the mediator corresponding to the test number shown in Table 3.

The "blank" used in the following description of evaluation is the case where the "blank" was treated with the reaction system containing no mediator shown in Table 2 of Example 1 (2 or 5 in Table 2).
Or 7).

(1) Surface Observation by Electron Microscope FIGS. 24 and 25 (Photos 5 to 8) show that the polyester cloth treated with the reaction system of Test No. 30 shown in Table 3 showed a large change in the physical property test. An electron micrograph is shown.

As shown in Photo 5 and Photo 6 (Photo 6 is a magnified version of Photo 5), the polyester fabric treated with the reaction of Test No. 30 was untreated with the enzyme of Photo B shown in FIG. It was shown that the surface structure of the polyester fiber was significantly changed as compared with the polyester cloth of No. Further, as shown in Photo 7, the polyester fiber treated with this reaction system has a portion that seems to be partially cut, and Photo 8 is an enlarged end portion thereof. It is considered that this is because not only the surface of the polyester fiber but also the inside of the polyester fiber was deeply promoted by the enzyme action to be cut.

26 and 27 (Photo 9 to Photo 12)
Shows an electron micrograph of a polyester cloth treated with the reaction system of Test No. 31 shown in Table 3, which also showed a large change in the physical property test.

As shown in Photo 9, also in this test section, a part where the polyester fiber seemed to be cut was recognized due to the action of the enzyme and the mediator. Most of them are Photo 10 (Photo 11 is Photo 10
As shown in Photo 12, there are some areas where the structure of the polyester fiber itself seems to have changed, as shown in Photo 12. Was there.

From the above, it was shown that the polyester decomposition reaction is promoted by adding the mediator. That is, it was shown that the polyester can be modified more practically and more practically by adding the mediator and controlling the addition amount and the reaction conditions.

(2) Evaluation by texture measuring device FIG. 11 shows the results of measuring the shear rigidity of the enzyme-treated polyester cloth by the reaction of each test number shown in Table 3. As shown in FIG. 11, all treatments with added mediator showed reduced shear stiffness and increased flexibility compared to “blank”. In particular, in the polyester fabrics treated with the reaction systems of Test Nos. 12 and 18, laccase alone treatment (FIG. 1, 2)
Alternatively, the shear rigidity was reduced to about 1/2 as compared with the treatment with lipase alone (5 in FIG. 1). Other, test number 1
Treatment of the polyester fabric with the 7, 19, 24 and 30 reaction systems also significantly reduced the shear stiffness. The greatest reduction in shear stiffness is with the polyester fabric treated with the combination of Lipase and Mediator of Test No. 18.

FIG. 12 shows the results of measuring the tensile stiffness of the enzyme-treated polyester cloth by the reaction of each test number shown in Table 3. As shown in FIG. 12, all treatments with added mediator were shown to reduce tensile stiffness values when compared to polyester fabrics treated with the "blank" reaction system. Test number 8, 1
Tensile stiffness was significantly reduced with polyester fabrics treated in the reactions of Nos. 9, 22, 30 and especially Test No. 30.

FIG. 13 shows the results of measuring the flexural rigidity of the enzyme-treated polyester fibers by the reaction of each test number shown in Table 3. As shown in FIG. 13, all treatments with the added mediator were shown to reduce the flexural stiffness values of the polyester fabric as compared to the polyester fabric treated with the "blank" reaction system.
The flexural rigidity was significantly reduced with the polyester fabrics treated with the test nos. 12, 18, 24, especially the test no. 30 reaction. However, surprisingly, the flexural rigidity of the polyester cloth was often higher when the mediator was added than when the mediator was not included and the enzyme was treated alone (FIG. 3).

FIG. 14 shows the results of measuring the compression stiffness of the enzyme-treated polyester cloths by the reactions of the respective test numbers shown in Table 3. As shown in FIG. 14, as compared to the polyester fabric treated with the “blank” reaction system, the compressive stiffness of the polyester fabric was determined by treatment with the addition of mediator, test numbers 10, 14, 15, 16, 1
The polyester fabrics treated with the enzyme in combination with the enzymes in the five test numbers 7 and 24 increased, whereas the compression stiffness of the polyester fabrics treated with the reaction systems in the other 19 test numbers decreased. The greatest reduction was with the polyester fibers treated with the reaction system of Test Nos. 11, 18, 21, 26, 30.

(3) Water Absorption Test FIG. 15 shows the results of measuring the water absorption of the enzyme-treated polyester cloth by the reaction of each test number shown in Table 3. As shown in FIG. 15, as compared with the polyester cloth treated with the “blank” reaction system, the water absorption time to the polyester cloth was shortened and the water absorption was increased by the treatment with the addition of the mediator. Was done. In particular, the water absorption of the polyester cloth treated with the reaction systems of test numbers 11, 19, 25, 30, and 31 was high. With the "blank" polyester cloth, the water absorption time
The water absorption times of the polyester cloths of Test Nos. 30 and 31 were 3.9 seconds and 3.8 seconds, respectively, compared with 11.9 seconds. The improvement of water absorption is useful for improving the discomfort (greasiness) of the fabric during sweating.

(4) Charging Characteristics FIG. 16 shows the results of measuring the charging characteristics of the polyester cloth treated with the enzyme by the reaction of each test number shown in Table 3. As shown in FIG. 16, when compared with “blank”, the addition of the mediator and the treatment significantly reduced both the saturation voltage and the half-life of the polyester fabric. The half-life, which is the time for static electricity to be released, was significantly smaller for the polyester fabrics treated with the reaction systems of Test Nos. 12, 18, 24, and 31. In particular, test number 3
The polyester fabric treated with the No. 1 reaction system had the smallest half-life of 0.3 seconds (the polyester fabric treated with the "blank" reaction had a half-life of 2.9 seconds). Half-life is about 1
Decrease to / 10 means "cluttering of fabric"
Help improve.

(5) Polyester Strength / Elongation Test FIGS. 17 and 18 show the results of measuring the strength / elongation test of the polyester cloth treated with the enzyme by the reaction of each test number shown in Table 3. As shown in FIGS. 17 and 18, generally, the strength and elongation of the polyester fibers were also reduced when the mediator was added and treated as compared to the polyester fabric treated with the “blank” reaction system. It was characteristic that there was a difference in the degree of strength reduction between the warp and the weft. For warp, test numbers 8, 16, 25, and 3
In the polyester fabric treated with the reaction system of No. 0, the weft yarns showed a significant decrease in strength in the polyester fabrics treated with the reaction systems of test numbers 13, 15, 20, and 31 respectively. It was the polyester cloth treated with the reaction system of Test No. 31 that contained the most warp and weft and had the greatest decrease in strength.

As shown in FIG. 18, the elongation was generally decreased by the addition of the mediator as well as the strength as compared with the "blank", and the elongation was decreased in the warp as compared with "blank". Of the polyester fabrics treated with the reaction systems of Test Nos. 8, 16, 25, and 30 and having a reduced elongation in the weft were treated with the reaction systems of Test Nos. 13, 15, 20, and 27. It was a polyester cloth. It was the polyester cloth treated with the reaction system of Test No. 16 that had the greatest decrease in elongation when the warp and weft were combined.

(6) Wrinkle resistance test FIG. 19 shows the result of the wrinkle resistance test conducted on the polyester cloth treated with the enzyme by the reaction of each test number shown in Table 3. As shown in FIG. 19, compared to “blank”, in general, when a mediator was added and treated,
Wrinkle resistance of polyester cloth is improved. It was the polyester fabrics treated with the reaction systems of Test Nos. 8, 17, 19 and 23 that had improved wrinkle resistance in the warp direction as compared to the polyester fabrics treated with the "blank" reaction system,
The wrinkle prevention rate was improved in the latitudinal direction by the test numbers 13 and 14,
The polyester fabric was treated with 16, 19, 26, and 29 reaction systems. It was considered that there is a certain degree of correlation between the improvement of the wrinkle prevention rate and the reduction of strength. This is because the destruction of the appropriate polymer structure proceeds inside the fiber,
It is considered that this is because the resilience against the bending force is improved.

(7) Dyeing test FIG. 20 shows the result of a dyeing test performed on the enzyme-treated polyester cloth by the reaction of each test number shown in Table 3. FIG. 20 shows the result of dyeing a polyester cloth, obtaining the dyeing density as a K / S value, and showing the rate of increase or decrease of the value. Evaluation of staining density in this test was carried out by enzyme alone treatment (test numbers 2, 5, 7 or "blank").
The increase / decrease rate relative to the value in the case of was used. As shown in FIG. 20, test numbers 8, 10, 12, 19, and 30
The polyester cloth treated with the reaction system of No. 19 showed a large increase in the dyeing density, and the remarkable increase rate was observed especially in the polyester cloth treated with the reaction system of Test No. 19.

[0093]

INDUSTRIAL APPLICABILITY As described above, the present invention provides a method for treating a polyester with an enzyme such as lipase or laccase to decompose it. According to this method, the surface structure of the polyester fiber is efficiently modified, and the physical properties of the polyester fiber such as flexibility, water absorption, chargeability, wrinkle resistance, and deep dyeing property are improved. Furthermore, in such enzyme treatment, by using a mediator together,
The action of the enzyme on the polyester is enhanced, at least partially destroying the polymer structure of the polyester fiber,
It is possible to further improve the physical properties of the polyester fiber such as flexibility, water absorption, chargeability, wrinkle resistance, and deep dyeing property.

The method according to the present invention, unlike the conventional method using concentrated alkali, is environmentally friendly and
It is applicable not only to 00% polyester fiber but also to a blended product of animal hair fiber and polyester fiber, and the texture such as flexibility can be effectively modified.

[Brief description of drawings]

FIG. 1 is a graph showing the shear rigidity of a polyester cloth obtained according to the present invention.

FIG. 2 is a graph showing the tensile stiffness of the polyester cloth obtained according to the present invention.

FIG. 3 is a graph showing flexural rigidity of a polyester cloth obtained according to the present invention.

FIG. 4 is a graph showing the compression stiffness of the polyester obtained according to the present invention.

FIG. 5 is a graph showing the results of a water absorption test of the polyester obtained according to the present invention.

FIG. 6 is a graph showing the results of a charging property test of the polyester obtained according to the present invention.

FIG. 7 is a graph showing the results of a strength test of the polyester obtained according to the present invention.

FIG. 8 is a graph showing the results of an elongation test of the polyester obtained according to the present invention.

FIG. 9 is a graph showing the results of a wrinkle resistance test of the polyester obtained according to the present invention.

FIG. 10 is a graph showing the results of dyeing density of polyester obtained according to the present invention.

FIG. 11 is a graph showing the shear rigidity of the polyester obtained according to the present invention.

FIG. 12 is a graph showing the tensile stiffness of the polyester obtained according to the present invention.

FIG. 13 is a graph showing flexural rigidity of the polyester obtained according to the present invention.

FIG. 14 is a graph showing the compression stiffness of the polyester obtained according to the present invention.

FIG. 15 is a graph showing water absorption of the polyester obtained according to the present invention.

FIG. 16 is a graph showing the chargeability of the polyester obtained according to the present invention.

FIG. 17 is a graph showing the strength of the polyester obtained according to the present invention.

FIG. 18 is a graph showing the elongation of the polyester obtained according to the present invention.

FIG. 19 is a graph showing the wrinkle resistance of the polyester obtained according to the present invention.

FIG. 20 is a graph showing the dyeability of the polyester obtained according to the present invention.

FIG. 21 is a photograph of enzyme-untreated polyester.

FIG. 22 is an electron micrograph of a polyester obtained according to the present invention. Photo 1 is a photo of polyester treated with laccase and then with lipase (Test No. 4). Photo 2 is a photo of the laccase-treated polyester after the lipase treatment (test number 7).

FIG. 23 is an electron micrograph of polyester obtained according to the present invention. Photo 3 is a photo of polyester treated with laccase alone (Test No. 2). Photo 4 is a photo of polyester treated with lipase alone (Test No. 5).

FIG. 24 is an electron micrograph of polyester obtained according to the present invention. Photo 6 is an enlarged photo of photo 5.

FIG. 25 is an electron micrograph of a polyester obtained according to the present invention. Photo 8 is an enlarged photo of photo 7.

FIG. 26 is an electron micrograph of polyester obtained according to the present invention.

FIG. 27 is an electron micrograph of polyester obtained according to the present invention. Photo 11 is an enlarged photo of Photo 10.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Michio Kitano             33-33 Higashiyama-dori, Chikusa-ku, Nagoya, Aichi (72) Inventor Shuji Yamamoto             Aichi Prefecture Bisai City, Yogi Three Volume 44 No. 1 Public Corporation             West housing complex 1 306 (72) Inventor Noriyuki Kitamoto             Aichi Prefecture Moriyama-ku, Nagoya Shimoshidanji Kazakoshi             1 at address 1931 (72) Inventor Shoko Yasuda             5273 Mizusato, Nakagawa-ku, Nagoya-shi, Aichi (72) Inventor Etsushi Chatani             8-11-1 Asafucho, Inazawa City, Aichi Prefecture (72) Inventor Hataya Nakatani             1-4-21 Ogaya, Otsu City, Shiga Prefecture Domirase             Field 704 (72) Inventor Yasuhiro Shimizu             741-43 Nakayabu-cho, Hikone City, Shiga Prefecture F-term (reference) 4L031 AA05 AA18 AB31 BA39 CA02                       CA03 DA05 DA08 DA14

Claims (17)

[Claims] 1. A method for modifying a fiber containing polyester, which comprises a step of causing a redox enzyme to act on the fiber. 2. The method according to claim 1, further comprising the step of causing a carboxylic acid ester hydrolase to act on the fiber. 3. The method according to claim 1, wherein the oxidoreductase is laccase or polyphenol oxidase. 4. The method according to claim 3, wherein the laccase is Laccase Daiwa. 5. The method according to claim 2, wherein the carboxylic acid ester hydrolase is a lipase or an esterase. 6. The lipase is lipase PS,
The method according to claim 5. 7. The method according to claim 2, wherein the step of allowing the carboxylic acid ester hydrolase to act is performed before the step of causing the oxidoreductase to act. 8. The method of claim 1, wherein the surface of the fiber containing polyester is fibrillated. 9. The method according to claim 1, wherein flexibility, water absorption, chargeability, anti-wrinkle property or deep dyeing property is modified. 10. The step of acting the redox enzyme is performed in the presence of a laccase mediator.
The method of claim 1. 11. The method according to claim 1, wherein the step of allowing the redox enzyme to act is carried out in the presence of a reagent selected from the group consisting of a surfactant, a wetting agent, and a dispersant. 12. A method for modifying a fiber containing a polyester, which comprises the step of allowing a carboxylic acid ester hydrolase to act on the fiber in the presence of a laccase mediator. 13. The method according to claim 12, wherein the step of allowing the carboxylate hydrolase to act is carried out in the presence of a reagent selected from the group consisting of a surfactant, a wetting agent, and a dispersant. . 14. The method according to claim 12, wherein the carboxylic acid ester hydrolase is a lipase or an esterase. 15. The method of claim 14, wherein the lipase is Lipase PS. 16. The method according to claim 1, wherein the polyester-containing fiber is a blended product of animal hair fiber and polyester fiber. 17. The method according to claim 1, 2 or 12, wherein the polyester-containing fiber is an alkali-treated fiber.