JP2006152469A - Treating agent for dyed fibrous product and method for finish-treating dyed product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a treating agent for a bio-wash processing which is a finish-treatment for the dyed color of dyed fibrous products such as a denim, etc., and effectively inhibiting the coloration at the reverse side of a fabric, caused by the re-soiling of a dyestuff. <P>SOLUTION: This method for treating the dyed fibrous products is provided by performing an enzyme treatment by using treating liquid consisting of an aqueous dispersion of the enzyme and a smectite-based clay. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a treatment agent and a treatment method for a dyed fiber product such as denim, and more particularly to a treatment agent and a treatment method used for a dyeing finish treatment of a dyed fiber product called biowash processing.

  Denim products typified by jeans usually use 10-16 single yarn dyed with indigo dye as warp, and bleached yarn slightly thinner than warp as weft, 3/1 or 2/1 twill structure A lot of warps appear on the front side, dark blue frosting, and the back side is whitish pale amber. Dyeing is hard and the geology is strong, so it is often used in work clothes, children's clothes, and everyday trousers.

  By the way, denim products made of cotton cloth dyed in this way have become fashionable from the viewpoint of fashionability. For this reason, recently, a finishing process of dyeing called bio-wash processing has been performed, and it has been troublesome to sell after partially removing the color on the front side.

  The above bio-washing process uses an aqueous dispersion containing an enzyme that breaks down the molecules that make up the fiber (for example, cellulose), thereby partially decolorizing the surface of the textile product being dyed. It is done by. That is, the surface of the fabric is partially decolored by decomposing the fiber surface with an enzyme and partially removing the dye dyeing the fiber surface together with the surface fiber.

However, when the surface of the dyed fiber product is partially decolored by the bio-washing process as described above, the tag ( There is a problem that the display label) is colored. That is, in products such as denim, the fabric must be a pale amber color close to white, and if this back side is colored, it will be indistinguishable from a used product and the commercial value will be significantly reduced. It becomes. As means for solving such a problem, for example, Non-Patent Document 1 proposes to add the nonionic surfactant to the enzyme aqueous dispersion and perform the above-described biowash processing.
TheInternational Conference on Dying and Finishing EXCO, Daegu, Korea Nov. 20-21, 2003, 207-209

  When the bio-wash process is performed using the enzyme aqueous dispersion proposed in Non-Patent Document 1, it is certainly more fabric than when the enzyme aqueous dispersion to which a nonionic surfactant is not added is used. Coloring on the back side of the film is prevented to some extent, but the degree is still not sufficient.

  Therefore, the object of the present invention is to be used for bio-washing, which is a finishing process for dyeing dyed textile products such as denim, and effectively suppresses coloring (contamination) due to transfer of detached dye on the back side of fabric and pockets. Another object of the present invention is to provide a treating agent that can be used and a dyeing finishing method using the treating agent.

According to the present invention, there is provided a dyed fiber product treating agent comprising an aqueous dispersion of an enzyme and a smectite clay.
In addition, according to the present invention, an enzyme and smectite clay are added to water to prepare a dyeing finishing solution having an enzyme concentration of 0.1 to 10 g / L, and a dyed fiber product is put into the processing solution. The fabric surface of the dyed fiber product is partially decolored by stirring, the dyed fiber product is separated from the dyeing finish treatment liquid, and the dyeing finish treatment is performed by rinsing and drying. A method for treating dyed fiber products is provided.

In the treatment agent of the present invention,
(1) The enzyme and smectite clay are each composed of a mixture in the form of a dry product or an aqueous dispersion,
(2) containing 10 to 500 parts by weight, particularly 20 to 200 parts by weight of smectite clay per 100 parts by weight of the enzyme;
(3) The dyed fiber product is denim,
(4) using cellulase as the enzyme,
Is preferred.

In the processing method of the present invention,
(5) Prior to the rinsing, the partially decolored dyed fiber product is heated to 65 ° C. or higher, particularly in the range of 70 to 100 ° C., and enzyme deactivation treatment is performed.
Is preferred.

  According to the present invention, by performing partial decoloring treatment on the fabric surface of the dyed fiber product using the aqueous dispersion to which the smectite clay is added together with the enzyme, coloring by migration of the release dye on the back side of the fabric is performed. (Contamination) can be effectively prevented.

The degree of coloring (contamination) on the back side of the fabric and the pockets is as follows. The surface reflectance R (λmax: 660 nm) of the white cloth after the treatment is measured, and the following formula called the Kubelka-Munk formula:
K / S = (1-R) ² / 2R
In the formula, R: surface reflectance
K: Absorbance coefficient
S: Can be evaluated by the K / S value calculated by the scattering coefficient. The smaller this value, the lower the degree of coloration (contamination) due to dye transfer of the white fabric, and thus the more effective the coloring of the back side of the fabric. It can be seen that it can be prevented. That is, when the treatment agent of the present invention is used, the K / S value is compared with the case where treatment is performed using an aqueous dispersion containing only an enzyme or an aqueous dispersion containing an enzyme and a surfactant. Is low, and coloring of the back side of the fabric due to dye transfer can be effectively prevented.

(Dyeing fiber product treatment agent)
The dyed fiber product treating agent of the present invention will be described in detail in the (dye finishing treatment) described later, and is composed of a dried product (powder, granules, etc.) or an aqueous dispersion (liquid, paste, etc.) of enzyme and smectite clay. The treatment agent is appropriately diluted with water during the treatment described later, and used in a dyeing finishing process called biowashing.

  As described above, the enzyme in this treatment agent has an activity of decomposing fibers on the surface of the fabric, which is a dyed fiber product, and is a dye that is dyed on the surface fibers by the decomposition of the surface fibers. (E.g. indigo dye) is removed, thereby performing partial decolorization of the fabric surface. As understood from this, as such an enzyme, an appropriate one is used depending on the kind of fiber, but it is generally cotton denim that such a dyeing finish is performed. As such an enzyme, cellulase which is a cellulolytic enzyme is generally used.

  There are various cellulases depending on the purpose, such as those derived from animals, those derived from plants (fungi / yeast), those obtained as a single component by cloning techniques, and those that exhibit activity on the acidic or alkaline side. However, in the biowash process of the present invention, an acidic or neutral type showing activity is effectively used.

  In addition, the smectite clay used together with the enzyme is used as a so-called migration (contamination) inhibitor, and by using the smectite clay, the back surface of the fabric with the dye removed together with the surface fibers that have been enzymatically decomposed is used. Transfer can be effectively prevented.

Smectite generally has a layered structure composed of SiO ₄ tetrahedral layer-AlO ₆ octahedral layer (or MgO ₆ octahedral layer) -SiO ₄ tetrahedral layer, or these tetrahedral layers and octahedral layers are of the same type with different metals. have substituted basic skeleton, a part of Al atoms AlO ₆ octahedral layer of the basic three-layer structure is in such Mg atoms and divalent Fe atoms, the Si atoms in the SiO ₄ tetrahedral layers Some of them are substituted with Al atoms. As a result, hydrogen ions, sodium ions, and the like are ion-bonded between layers so as to compensate for the insufficient valence. That is, the SiO ₄ tetrahedron layer in the above layered structure has a high affinity for dye molecules and enzymatically decomposed fiber components (fiber waste), and Al atoms in the AlO ₆ octahedron layer at the end of the layer and SiO ₄ tetrahedrons. Hydroxyl groups and interlayer ions coordinated to Si atoms in the layer show high affinity for water. That is, this smectite exhibits a very high surface-active effect on fiber wastes stained with indigo dye, etc., forming micelle-like particles surrounding such fiber wastes, becoming a kind of protective colloid. Dyeing (that is, transfer) of the back side of the fabric with the dye removed from the fabric surface is effectively prevented.

  Examples of such smectites include montmorillonite, beidellite, nontronite, saponite, iron saponite, hectorite, soconite, stevensite, and the like. Naturally-produced clays such as acid clay, fuller's earth, bentonite, sub-bentonite, activated bentonite, and the like containing beidellite as main components are suitable. Moreover, the activated clay etc. which acid-treated the acidic clay can also be used.

  In addition, smectite such as montmorillonite has different pH when suspended in water depending on the ratio between the amount of hydrogen ions and the amount of alkali ions between layers. For example, in acidic clay and activated clay, the pH is on the acidic side, and in bentonite, the pH is on the alkaline side. On the other hand, biowash processing is generally performed in a buffer solution having a liquidity in a pH range suitable for the type of enzyme so as not to inhibit the activity of the enzyme used. At the added concentration of smectite clay used in the present invention (preferably within a range of about 0.2 to 2.0 g / L), the pH of the treatment solution containing the smectite clay is optimal depending on the buffering action of a commonly used salt concentration pH buffer solution. Controlled to range. Therefore, when a general pH buffer solution is used as a pH control agent, any smectite clay having a water dispersion pH on a weakly acidic side or a weakly alkaline side (for example, pH: 4 to 11) can be used. However, for enzymes that show activity on the acidic side, smectite clay with an aqueous dispersion pH on the acidic side is used. For enzymes that show activity on the neutral or alkaline side, the pH of the aqueous dispersion is medium. Use of smectite clay on the neutral or alkaline side has the advantage that the amount of pH buffer used can be reduced or the use of pH buffer can be omitted.

  The chemical composition of smectite clay, which is mainly composed of acid clay and aqueous clay having an acidic side and bentonite having an aqueous dispersion having an alkaline side, that is, montmorillonite and the like, is mainly Al in an octahedral layer. Or the Fe atom is represented by R, and the alkali (Na, K) atom and calcium atom present mainly between the layers are represented by M and Ca, and the molar ratio composition based on the oxide mole is as follows.

[Smectite clay]
R ₂ O ₃ / SiO ₂ = 0.1 to 0.3
(M ₂ O + CaO) / SiO ₂ = 0.3 × 10 ^{−2 to} 10.5 × 10 ⁻²
<Acid clay>
(M ₂ O + CaO) / SiO ₂ = 0.3 × 10 ^{−2 to} 2.3 × 10 ⁻²
<Bentonite>
(M ₂ O + CaO) / SiO ₂ = 2.1 × 10 ^{−2 to} 10.5 × 10 ⁻²

The smectite clay as described above is generally used in the form of fine powder having an average particle diameter (volume-based median diameter: D ₅₀ ) measured by a laser diffraction scattering method of ₅₀ μm or less in order to uniformly disperse in water. It is good to do.

  Such smectite clay is usually used in an amount of 10 to 500 parts by weight, preferably 20 to 200 parts by weight, particularly preferably 60 to 120 parts by weight per 100 parts by weight of the enzyme. If the amount used is less than the above range, the effect of preventing dye transfer cannot be fully exerted, and even if it is used in a larger amount than the above range, no further effect of transferring dye can be expected, but rather in terms of cost. This is a disadvantage.

  Furthermore, in the present invention, as a contamination (transfer) inhibitor, other than the smectite clay, for example, a normal surfactant or a polymer substance having a similar action can be used in combination. As such a surfactant, both anionic and nonionic surfactants can be used, and nonionic surfactants are particularly preferable. Such a surfactant or the like can be usually used in an amount of 20 to 200 parts by weight, particularly 40 to 80 parts by weight, per 100 parts by weight of the enzyme.

  The dyeing fiber product treating agent of the present invention described above is an essential condition consisting of a combination of an enzyme and a smectite clay, but the enzyme and smectite clay each have a dried product (powder or granule form). ) Or aqueous dispersions (in the form of liquids or pastes). For example, the enzyme dry product and the smectite clay dry product can be mixed to prepare the dyed fiber product treating agent of the present invention, the enzyme dry product can be mixed with the aqueous smectite clay dispersion, or The aqueous dispersion of the enzyme can be mixed with the dried smectite clay and used as the dyeing fiber product treating agent of the present invention. Accordingly, the dyed fiber product treating agent may have a solid form such as powder or granule, or may be in a liquid or paste form.

(Dye finish)
In the present invention, a predetermined amount of the dyeing fiber product treating agent is diluted with water to prepare a finishing treatment liquid, and the dyeing fiber product is introduced into the finishing treatment liquid to complete the dyeing finishing process (i.e., biotechnology). Washing process) is performed, and a partially decolored dyed fiber product can be obtained.

  In this case, the enzyme and smectite clay are stored separately, and the enzyme and smectite clay are mixed immediately before biowash processing to prepare a dyed fiber product treatment agent, which is diluted and finished. A liquid can be prepared, and an enzyme and a smectite clay can be individually added to water to prepare a finishing solution, and biowash processing can be performed.

  In such a treatment method, the enzyme concentration of the finishing treatment liquid is preferably in the range of 0.5 to 5 g / L. If the enzyme concentration is higher than necessary, the damage to the fibers increases, the weight loss after treatment increases, and the commercial value is significantly reduced. Also, if the enzyme concentration of the finishing solution is too low, it will be difficult to effectively perform the intended decolorization (partial decoloration), and even if decolorization is possible, it will take a very long time, and the processability will be remarkably high. This is because it becomes lower. In addition, as described above, the concentration of smectite clay in the finishing treatment liquid is preferably about 0.2 to 2.0 g / L.

  Moreover, it is preferable to adjust the pH to the weakly acidic side, neutral, or weakly alkaline side by adding a pH buffering agent to the treatment liquid according to the activity of the enzyme used. In this case, as described above, depending on the pH of the smectite clay used, the amount of the pH buffer used can be reduced or the use thereof can be omitted.

  The dyed fiber products to be treated are those that require partial decolorization, and as already mentioned, they are generally denim, cotton dyed in dark blue with indigo dye and undyed white cotton yarn A twill weave is used to form a fabric, but a mixed yarn of cotton yarn and polyurethane yarn may be used, or it may be dyed in another color with a dye other than indigo dye. It is also applicable to

  By putting the dyed fiber product as described above into the dyeing finishing solution and stirring and rubbing for an appropriate time, some of the fibers on the surface of the fabric of the dyed fiber product are enzymatically decomposed and dyed on the fiber. The dye that had been removed is removed along with the fiber waste and the fabric surface is partially decolorized. In the present invention, as described above, at the time of such partial decolorization, the dye removed together with the fiber waste can effectively prevent coloring (i.e., transfer) from moving to the back of the fabric, A reduction in the commercial value of the partially decolored dyed fiber product can be effectively avoided.

  After the partial decolorization, the finished product can be discharged or the dyed fiber product that has been partially decolored can be removed from the finish, and rinsed and dried to obtain the final product.

  In addition, prior to rinsing, it is preferable to perform an enzyme deactivation treatment on the partially decolored dyed fiber product. That is, there is a possibility that the fiber decomposition may be continued due to the enzyme remaining on the surface, and the decolorization may proceed more than necessary or the surface may be damaged. Such inconvenience can be reliably prevented by enzyme deactivation treatment.

  Such deactivation treatment varies depending on the nature of the enzyme used, but the dyed fiber product that has been partially decolored is poured into water and heated to, for example, 65 ° C. or more, particularly about 70 to 100 ° C. for an appropriate time. By maintaining this temperature, it can be carried out easily.

  The rinsing may be performed an appropriate number of times with water, but the present invention has an advantage that fiber waste and the like can be easily removed by such rinsing. That is, the fiber waste produced by enzymatic degradation is surrounded by smectite clay used as a dye transfer inhibitor, but this smectite clay is very easy to remove by rinsing because of its extremely high affinity for water. That is, the fiber waste adhering to the surface of the fiber product is difficult to remove, but in the present invention, such fiber waste can be easily removed by using smectite clay.

Drying after rinsing is performed by air drying, heat drying or the like according to a conventional method.
In the present invention, in the dyeing finish liquid after the partial decolorization treatment, the fiber waste containing the dye produced by the enzymatic decomposition is dispersed in water in a state surrounded by the smectite clay. Smectite clay settles slowly or rapidly when the liquid is left standing or subjected to centrifugal force treatment, so that it can be easily separated from wastewater, and the burden required for wastewater treatment can be reduced. This is a great advantage.

  The invention is illustrated by the following examples.

  In the following experimental examples, the dyed fiber product, the enzyme, the dye transfer inhibitor, and the white cloth for pollution degree evaluation are as follows. The pH of the smectite clay is a value measured with a 5% by weight aqueous suspension.

Dyed textile products: Indigo-dyed denim [denim piece], 5 x 5 cm
Enzyme: Multi-component cellulase [manufactured by Novozymes, Cellusoft L, 750EGU / g,
Derived from Trichoderma, acid activity,
Active area / pH: 4.5-5.5, temperature: 40-55 ° C.]
Anti-transfer agent:
Smectite clay [Kurosaki Shirato Kogyo Co., Ltd., dry powder of purified smectite,
Purification method: wet classification (water tank type),
Average particle diameter D ₅₀ : 21 μm, pH: 10.2]
Nonionic surfactant [C16-18 aliphatic alcohol and ethylene oxide
80 mol added]
Anionic polymer [poly (sodium α-hydroxyacrylate),
Average molecular weight: 10500]
White cloth for pollution assessment:
Cotton broad white cloth [# 40], 9x15cm
White polyester fabric [Taffeta, TR # 58], 9 x 15 cm

Example 1
In a stainless steel beaker of a tartometer, 1 liter of an aqueous dispersion of the enzyme (enzyme concentration: 1 g / L) adjusted to pH 5 using an acetic acid-sodium acetate buffer, denim pieces (10 g) and a dye transfer inhibitor As above, 0.4 g to 1.0 g of the smectite clay was added, and partial decoloring treatment was performed by stirring (100 rpm) at a temperature of 50 ° C. for 30 minutes. Next, the denim piece was transferred to a beaker containing 500 mL of water (80 ° C.), and the deactivation treatment was performed for 20 minutes while heating to 80 ° C. Thereafter, the denim pieces were taken out, rinsed with water (500 mL of water, 3 times), and air-dried (24 hours) at room temperature.

For the denim pieces treated in this way, the dye transfer state (colored state) on the back surface of the denim piece, in particular the white weft, was visually observed, and the transfer state (contaminated state) was evaluated according to the following criteria. The results are shown in Table 1.
◎:
The color density of the front side surface of the denim piece was reduced, and there was almost no transfer to the white weft on the back side, and the twill weave pattern on the back side was particularly clear and clear to the extent before the treatment.
○ to ○ ^△ :
Although the color density on the front side of the denim piece is thin, color unevenness due to transfer to the white weft on the back side is somewhat visible, but the twill pattern is relatively clear and does not impair the commercial value .
△ ^○ ~ △:
Although the color density on the front side of the denim piece is thin, color unevenness due to transfer to the white weft on the back side is seen, and the white weft part on the back side is light blue overall, the twill pattern appears blurred, Product value is impaired.

(Comparative Example 1)
About the processed denim piece which performed the partial decoloring process same as Example 1 except having replaced with the smectite clay, and using 0.4-1.0-g nonionic surfactant as a dye transfer inhibitor. The same evaluation as in the examples was performed, and the results are shown in Table 1.

(Comparative Example 2)
Instead of smectite clay, 0.4 g to 1.0 g of an anionic polymer was used as the dye transfer inhibitor, and the same partial decolorization treatment as in Example 1 was performed, and the treated denim pieces were subjected to the treatment. Evaluation similar to the example was performed, and the results are shown in Table 1.

(Comparative Example 3)
Except that no dye transfer inhibitor was used, the same partial decolorization treatment as in Example 1 was performed, and the treated denim pieces were evaluated in the same manner as in Examples, and the results are shown in Table 1.

(Pollution degree evaluation test 1)
Along with denim pieces (10 g), 5 g of cotton broad white cloth and 5 g of polyester taffeta white cloth are added as a white cloth for pollution degree evaluation. Decolorization treatment was performed. Moreover, about Example 1 and Comparative Examples 1 and 2, the amount of the dye transfer inhibitor was variously changed in the range of 0.2 to 1.2 g, and partial decoloring treatment was performed according to each example. . (In the treatment according to Comparative Example 3, the amount of dye transfer inhibitor used is zero.)

About the white cloth for evaluation after a process, the surface reflectance (R) in (lambda) max: 660nm is measured using a ultraviolet visible spectrophotometer, The following formula:
K / S = (1-R) ² / 2R
In the formula, R: surface reflectance
K: Absorbance coefficient
S: The degree of contamination (K / S) was calculated according to the scattering coefficient. The degree of contamination (K / S) for the white cloth for evaluation made of cotton broad is shown in Table 2 and FIG. 1, and the degree of contamination (K / S) for the white cloth for evaluation made of polyester taffeta is shown in Table 3 and FIG. .

  As the UV-visible spectrophotometer, a UV-240 type (double beam type, with an integrating sphere for diffuse reflection measurement) manufactured by Shimadzu Corporation was used.

  In Example 1, indigo prepared in advance by the following method in consideration of the possibility that the concentration of indigo desorbed from the denim in the treatment bath changes depending on the concentration of the purified smectite used as the antifouling agent. The test was performed using an indigo dispersion having a constant concentration.

Preparation Method of Indigo Dispersion 20 g (18 sheets) of denim pieces (5 cm × 5 cm) are put in 1 liter of water and stirred (160 rpm) at 50 ° C. for 30 minutes to extract and disperse indigo. After 24 hours, this extraction / dispersion is filtered twice with glass fiber filter paper (GA100, GC90) to obtain an indigo dispersion.

(Pollution degree evaluation test 2)
Prepared by mixing 5 ml of enzyme solution (concentration: 100 g / L), 50 mL of pH buffer solution (pH: 5) and 445 mL of the above indigo dispersion (concentration of indigo: 0.04 g / L), and this is a dyeing finishing solution (500 mL) In accordance with Example 1, in place of the denim pieces, 5 g of cotton broad white cloth and 5 g of polyester taffeta white cloth were added, and the same treatment and evaluation as in pollution degree evaluation test 1 were performed.
The results are shown in Table 4 and FIG. From these results, in the present invention, even when the dye concentration in the dyeing finishing solution is constant and high, the contamination degree (K / S) is increased when the added concentration of smectite clay is more than 0.8 g / L. It can be seen that an excellent anti-transfer effect can be achieved.

The figure which shows the test result (equivalent to Table 2) about the cotton broad white cloth in the pollution degree evaluation test 1. FIG. The figure which shows the test result (equivalent to Table 3) about the polyester broad white cloth in the pollution degree evaluation test 1. FIG. The figure which shows the test result (equivalent to Table 4) of the pollution degree evaluation test 2. FIG.

Claims (7)

  A dyed fiber product treating agent comprising an enzyme and a smectite clay.   The dyeing fiber product treating agent according to claim 1, wherein the enzyme and the smectite clay are each composed of a mixture obtained by mixing in the form of a dry product or an aqueous dispersion.   The dyed fiber product treating agent according to claim 1, comprising smectite clay in an amount of 10 to 500 parts by weight per 100 parts by weight of the enzyme.   The dyed fiber product treating agent according to any one of claims 1 to 3, wherein the dyed fiber product is denim.   The dyeing fiber product treating agent according to any one of claims 1 to 4, wherein cellulase is used as the enzyme.   Enzyme and smectite clay are added to water to prepare a dyeing finish treatment solution having an enzyme concentration of 0.1 to 10 g / L, and the dyed fiber product is put into the treatment solution and stirred. A method for treating a dyed fiber product, characterized in that the fabric surface of the fiber product is partially decolorized, the dyed fiber product is separated from the dye finish liquid, and rinsed and dried to perform the dye finish process.   The processing method according to claim 6, wherein, prior to the rinsing, the dyed fiber product that has been partially decolorized is heated to 65 ° C. or more to perform enzyme deactivation treatment.

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