JP4773727B2 - Fabric with dyeing and deodorizing functions - Google Patents

Description

The present invention relates to a fabric imparted with a dyeing and deodorizing function using indigo, a fiber product using the fabric as a material, and a method for dyeing and deodorizing a fabric using indigo.

Conventionally, as a method of deodorizing a fabric, a method in which an antibacterial substance such as silver-substituted zeolite is contained in the fiber and deodorizing by an antibacterial action against microorganisms (see, for example, Patent Document 1), a part of cellulosic fibers is used. There is a method of obtaining a deodorant cellulosic fabric by copper carboxymethylation or zinc carboxymethylation (for example, see Patent Document 2). There is also a report explained from the viewpoint of malodorous substances (for example, see Non-Patent Document 1). Typical malodorous substances include sulfur compounds such as methyl mercaptan and ethyl mercaptan, nitrogen compounds such as ammonia and methylamine, and butyric acid. And the like are listed.

Japanese Patent Publication No. 8-1003 JP 2002-371462 A New deodorization technology, Susumu Kokubu, published by Industrial Research Committee

A fiber product using a metal chlorophyllin derivative-based green dye has also been reported by utilizing the antibacterial and deodorant properties of a natural pigment chlorophyllin compound (see, for example, Patent Document 3). When wool is mordanted with an acid dye, when ethyl mercaptan is used as a malodorous substance, it was reported that a deodorizing effect was observed (for example, see Non-Patent Document 2). It has been reported that the deodorizing effect was recognized (see, for example, Non-Patent Document 3). When indigo dyeing is employed as the dye, it has been reported that the dyed cloth or paper has bactericidal properties, so that it was used for sanitary paper (see, for example, Patent Document 4). As a similar application example, in order to impart antibacterial properties, an example of indigo dyeing a paper cloth processed product that prevents floor slippage (see, for example, Patent Document 5), to impart antibacterial properties, grass is made of indigo and titanium oxide. There is an example of staining (for example, see Patent Document 6). On the other hand, when dyeing indigo on cotton, there has been a report that ultrasonic waves were used to disperse and infiltrate the blue and blue particles into the gaps between the fiber elements, but the effect was not obtained (for example, non-patent literature) 4).

JP-A-9-48925 Japanese Patent Laid-Open No. 61-28077 JP-A-4-176460 JP 2004-224027 A Textile Res. J. et al. 72 (2), 125-31 (2002) Textile Res. J. et al. 72 (12), 1088-92 (2002) Occupational Chemistry Magazine Vol. 60, No. 6, 40-43 (1957)

It is known that deodorizing effect can be obtained by mordanting with copper using some kinds of acid dyes and some kinds of direct dyes, but deodorizing methods for dyeing with indigo have not been established yet. Absent.

The present invention does not require an antibacterial substance or the like to be contained in the fiber, and does not require the introduction of a reactive group such as a carboxyl group in a part of the fiber in order to impart deodorizing properties. An object of the present invention is to provide a dyed fabric having an excellent deodorizing effect by mordanting using a shampoo.

Although the effect of ultrasonic waves was not recognized for the purpose of dispersing and penetrating indigo into the gaps between the fiber elements, the present inventors dyed the fabric by irradiating ultrasonic waves when mordanting indigo. Was found to exhibit a remarkable deodorizing effect, and the present invention was completed.

That is, the present invention is a fabric imparted with a dyeing and deodorizing function by dyeing using indigo and then mordanting with a metal salt solution of copper salt. Moreover, this invention is a textile product which uses as a material the fabric provided with the above-mentioned dyeing | staining and deodorizing function. Furthermore, the present invention is a method of simultaneously dyeing and imparting a deodorizing function to a fabric by dyeing using indigo and then post-mordanting with a metal salt solution of a copper salt.

Since the fabric imparted with the dyeing and deodorizing function of the present invention is also imparted with a deodorizing effect by dyeing with indigo, it does not require a step for containing an antibacterial substance or the like in the fiber. Since a process for introducing a reactive group into a part of the fiber is not required in order to impart deodorant properties, it can be manufactured very simply and inexpensively.

The apparatus for ultrasonic irradiation used in the present invention does not require a special apparatus, and for example, a small-scale apparatus used for an ultrasonic cleaner can sufficiently function.

The fabric imparted with the dyeing and deodorizing functions of the present invention is not required to be dyed according to the present invention over the entire fibers constituting the fabric in order to exhibit this deodorizing effect. It is necessary that at least 2% of the total fibers constituting the fabric are dyed according to the present invention.

The fabric imparted with the dyeing and deodorizing function of the present invention does not require a step of incorporating an antibacterial substance into the fiber for the purpose of imparting the deodorizing function, and introduces a reactive group into a part of the fiber. Since a process is not required and a large-scale ultrasonic irradiation apparatus is not required, it can be manufactured very simply and inexpensively. In addition, the ultrasonic mordanting method of dyeing using the indigo of the present invention and then mordanting with a metal salt solution of a copper salt includes a step of containing an antibacterial substance or the like in the fiber for the purpose of imparting a deodorizing function. It does not require a process for introducing reactive groups into a part of the fiber in order to have deodorant properties, and does not require a large-scale ultrasonic irradiation device, so it is extremely simple and inexpensive. is there.

Examples of fibers that can be used in the fabric of the present invention include cotton, silk, and wool. Further, the case of not being a woven fabric such as feathers is also included in the fabric of the present invention. Examples of the textile products made from the fabric of the present invention include clothing products, bedding, indoor furniture, upholstery, interior building materials, care products, sanitary equipment, medical products, and toys.

The metal salt that can be used in the mordanting method with the metal salt of the present invention is a copper salt .

As the mordanting method, there is a pre-mordanting performed before indigo dyeing and a post-mordanting performed after indigo dyeing. Hereinafter, it is referred to as superposition mordant).

The mordant was prepared by preparing a concentrated aqueous solution of the target metal salt at 0.03 to 0.3 mol / L, and separately mixing at a ratio of 16 ml of 0.1N sodium acetate to 1 ml of 0.1N acetic acid. Dilute the concentrate with the buffer solution prepared as described above. Examples of the metal salt used here include cupric sulfate, cupric nitrate, cuprous chloride, cupric chloride , and the like.

In the post-mordanting, the above-mentioned mordant is used in an amount of 30 to 100 times the fabric or fiber (bath ratio 1:30 to 1: 100), the dyed fabric or fiber is immersed in the mordant, and at 40 to 80 ° C., After the treatment for 30 minutes to 3 hours, it is thoroughly washed with ion exchange water and then air-dried at room temperature.

In the present invention, the conditions for the pre-mordanting in the case of using the pre-mordanting together (overlaid mordanting) may be the same as the conditions for the post-mordanting described above, or may be changed as necessary.

The ultrasonic irradiation performed as a preferable embodiment at the time of post-mordanting of the present invention is performed at an output of a frequency of 10 to 100 kilohertz. In this case, the ultrasonic irradiation apparatus does not require a special specification, and a normally used apparatus such as an ultrasonic cleaning machine can be used.

Hereinafter, the present invention will be described specifically by way of examples. The concentration in the examples is expressed by mass% or mol / L.
[Scouring material cloth]
The fabric was washed with 1 g / L of an aqueous surfactant solution for 1 hour, rinsed twice with ion-exchanged water, and then immersed in ion-exchanged water overnight. After removing from the ion exchange water, it was air dried at room temperature.

[Preparation of indigo dyeing bath]
(Preparation of stock solution)
0.5 g of Indigo, 1 ml of funnel oil, 1.7 ml of 35% aqueous sodium hydroxide solution and 1.5 g of hydrosulfite were dissolved in 25 ml of hot water at 60 ° C. to prepare a stock solution. It kept at 40-60 degreeC, and was used at the time of dyeing bath preparation.
(Preparation of dye bath)
A 3.5% aqueous sodium hydroxide solution (1.5 ml), hydrosulfite (0.1 g), and 60 ° C. hot water (250 ml) were mixed and kept at 40 to 60 ° C. At the time of use, this solution and the above-described stock solution were mixed at a volume ratio of 9: 1 to prepare an indigo dye bath.

[Indigo staining]
100 ml of the indigo dyeing bath prepared in [Example 2] was used, and 2 g of cotton broad was put therein and taken out after 10 minutes. After 5 minutes of color development, the fabric was returned to the dyebath again and dyed for 10 minutes. Next, air coloring for 5 minutes was performed again. The bath ratio at this time was 1:50.

[After mordanting]
A 0.1 mol / L-cupric chloride aqueous solution was used as the metal salt aqueous solution. The buffer used was a mixture of 0.1 ml of 0.1N acetic acid and 16 ml of 0.1N sodium acetate. This metal salt aqueous solution was diluted with the aforementioned buffer solution having a volume ratio of 9 times, and 100 ml was subjected to post-mordanting. This solution was heated to 60 ° C., 2 g of cotton broad dyed in [Example 3] was added, and mordanting was performed for 1 hour. The bath ratio was 1:50. After the mordanting, the cotton broad was used for the next deodorizing effect measurement after washing with ion exchange water and air drying at room temperature.

[Ultrasonic mordanting]
Except that mordanting is performed under ultrasonic irradiation, the same conditions as in [Example 4] are set, and post-mordanting under ultrasonic irradiation is performed on 2 g of cotton broad dyed in [Example 3]. Went for hours. For ultrasonic irradiation, “SHARP-UT-205HS” was used, and the mordanting container was immersed in the cleaning tank of this ultrasonic cleaning machine, and the output was 200 W and the oscillation frequency was 35 kHz. After the ultrasonic mordanting, cotton broad, washed with ion-exchanged water and air-dried at room temperature, was used for the next deodorizing effect measurement.

Cotton broad dyed in [Example 3] using 0.1 mol / L-cupric chloride aqueous solution instead of 0.1 mol / L-cupric chloride aqueous solution used in [Example 4] 2 m was post-mordanted under the same conditions as in [Example 4].

Using the 0.1 mol / L-copper sulfate aqueous solution used in [Example 6], the same conditions as in [Example 5] are applied to 2 g of cotton broad dyed in [Example 3]. Ultrasonic post-mordanting was performed.

0.5 g was collected from each of the cotton broads obtained in [Example 4] to [Example 7], placed one by one in a 2 L aluminum collection bag, and the bag was filled with air and ethyl mercaptan. . The concentration of ethyl mercaptan in the bag at this time was 100 ppm (v / v). The temperature is maintained at 20 ± 1 ° C., and after 5 minutes, 10 minutes, 20 minutes, 30 minutes, 1 hour, 2 hours, 3 hours, 100 ml of gas is sucked from the bag to detect ethyl mercaptan. The concentration of ethyl mercaptan in the bag was measured through a tube. FIG. 1 shows a schematic diagram of a 2 L aluminum collection bag and an ethyl mercaptan detector tube type gas measuring device. The reaction for detecting ethyl mercaptan using the ethyl mercaptan detector tube is as shown in the following equation. The detection limit of this ethyl mercaptan detector tube is 0.2 ppm (v / v).

  The ethyl mercaptan deodorizing effect of cotton broad dyed with indigo measured in [Example 8] is shown in [FIG. 2] to [FIG. 3]. It can be seen that the cotton broad cloth provided with the dyeing and deodorizing function of the present invention rapidly decreases the ethyl mercaptan concentration and has an excellent deodorizing function with respect to ethyl mercaptan. Moreover, it turns out that the ultrasonic mordanting further improves the deodorizing function.

[Previous mordant]
For the silk cloth (plain woven cloth) before indigo dyeing, pre- mordanting was performed using the same conditions as the post-mordanting of [Example 4]. However, cupric nitrate was used instead of cupric chloride. After completion of the pre- mordation, the silk cloth was taken out, washed with ion exchange water, and then air-dried at room temperature.

In [Example 9], the silk fabric that has undergone the pre- mordanting is subjected to indigo dyeing under the same conditions as in [Example 3], and then the post-mordanting (overlapping mordanting) under the same conditions as in [Example 4]. went. However, cupric nitrate was used instead of cupric chloride in post-mordanting. After the end of mordanting, a silk cloth washed with ion-exchanged water and air-dried at room temperature was used for the next deodorizing effect measurement .

In [Example 9], ultrasonic irradiation is applied to the silk fabric that has been subjected to the pre- mordanting, and the same conditions as in [Example 10] are set. Indigo dyeing and post-mordanting under ultrasonic irradiation (multiple mordanting) Went. After ultrasonic mordanting, silk cloth washed with ion-exchanged water and air-dried at room temperature was used for the next deodorizing effect measurement.

0.5 g was collected from each of the silk fabrics obtained in [Example 10] and [Example 11], and placed one by one in a 2 L aluminum collection bag, under the same conditions as in [Example 8]. The concentration of ethyl mercaptan was measured.

  The deodorizing effect of ethyl mercaptan on the silk cloth dyed with indigo, measured in [Example 12], is shown in FIG. It can be seen that the silk cloth to which the dyeing and deodorizing functions of the present invention have been imparted has an ethyl mercaptan concentration rapidly reduced and has an excellent deodorizing function with respect to ethyl mercaptan. Moreover, it turns out that the ultrasonic mordanting further improves the deodorizing function.

The wool before indigo dyeing was pre- mordanted under the same conditions as in [Example 9], and indigo dyeing and post-mordanting (overlaid mordanting) were carried out under the same conditions as in [Example 10]. On the other hand, indigo dyeing and post-mordanting (superposition mordanting) under ultrasonic irradiation were performed under the same conditions as in Example 11. These wools were used for the next deodorizing effect measurement .

For the wool obtained in [Example 13], the ethyl mercaptan concentration in the bag was measured under the same conditions as in [Example 12]. The measured deodorizing effect of ethyl mercaptan on wool stained with indigo is shown in FIG. It can be seen that the wool imparted with the dyeing and deodorizing function of the present invention has a reduced ethyl mercaptan concentration rapidly and has an excellent deodorizing function with respect to ethyl mercaptan. Moreover, it turns out that the ultrasonic mordanting further improves the deodorizing function.

The feathers before indigo staining were pre- mordanted under the same conditions as in [Example 9], and indigo dyeing and post-mordanting (overlapping mordanting) were performed under the same conditions as in [Example 10]. On the other hand, indigo dyeing and post-mordanting (superposition mordanting) under ultrasonic irradiation were performed under the same conditions as in Example 11. These feathers were used for the next deodorizing effect measurement .

For the feather obtained in [Example 15], the ethyl mercaptan concentration in the bag was measured under the same conditions as in [Example 12]. The measured deodorizing effect of ethyl mercaptan on feathers stained with indigo is shown in FIG. It can be seen that the feathers imparted with the dyeing and deodorizing functions of the present invention rapidly reduce the ethyl mercaptan concentration and have an excellent deodorizing function with respect to ethyl mercaptan. Moreover, it turns out that the ultrasonic mordanting further improves the deodorizing function.

As the malodorous substance, ammonia was used instead of ethyl mercaptan, the cotton broad obtained in [Example 4] to [Example 7] was used, and the 2 L aluminum collection bag shown in [FIG. 1] was used. The deodorizing effect on ammonia was measured under the same conditions as in [Example 8], with the ammonia concentration in the bag being 100 ppm (v / v). The detection limit of this ammonia detector tube is 0.5 ppm (v / v), and the color change of the detector tube is purple → yellow. Ammonia deodorizing effect after cupric chloride and ultrasonic mordanting is shown in [Fig. 7]. Ammonia deodorizing effect after copper sulfate and sonic mordanting is shown in [Fig. 8]. It can be seen that the cotton broad cloth provided with the dyeing and deodorizing functions of the present invention has an excellent deodorizing function for ammonia. Moreover, it turns out that the ultrasonic mordanting further improves the deodorizing function.

As a malodorous substance, instead of ethyl mercaptan, acetic acid was used, cotton broad obtained in [Example 4] to [Example 7] was used, and a 2 L aluminum collection bag shown in [FIG. 1] Using a 2 L Teddler bag having the same shape, the deodorizing effect on acetic acid was measured under the same conditions as in [Example 8]. The detection limit of this acetic acid detector tube is 0.2 ppm (v / v), and the color change of the detector tube is pink → yellow. The acetic acid deodorizing effect when post-mordanting with cupric chloride and ultrasonic post-mordanting is shown in [Fig. 9], and the acetic acid deodorizing effect when post-mordanting with copper sulfate and ultrasonic post-mordanting is shown in [Fig. 10]. It can be seen that the cotton broad cloth provided with the dyeing and deodorizing functions of the present invention has an excellent deodorizing function with respect to acetic acid. Moreover, it turns out that the ultrasonic mordanting further improves the deodorizing function.

[Repeated deodorizing effect]
Ultrasonic mordanting was carried out under the same conditions as in [Example 5] using ethyl mercaptan as the malodorous substance and cotton broad as the fabric. For this cotton broad, the deodorizing function for ethyl mercaptan was measured under the same conditions as in [Example 8]. After measuring for 3 hours, the cotton blow was taken out of the aluminum collection bag and left in a vacuum dryer at 105 ° C. for 3 hours. After standing, the cotton broad was again placed in an aluminum collection bag, and the deodorizing function for ethyl mercaptan was measured under the same conditions as in [Example 8]. After the measurement for 3 hours, the same operation was repeated, and the deodorizing function for ethyl mercaptan was measured.

  The repeated deodorizing effect of cotton broad dyed with indigo measured on [Example 19] with respect to ethyl mercaptan is shown in [FIG. 11]. The ethyl mercaptan deodorizing function by the cotton broadening with the dyeing and deodorizing function of the present invention is not saturated by one use, but the deodorizing function is reversibly restored by diffusion or the like. I understand that. From this, it can be seen that the deodorizing function of the present invention is maintained for a long time.

[Comparative Example 1]
Instead of the fabric of the present invention shown in [Example 4] to [Example 18], "Dismel (manufactured by Toyobo Co., Ltd.)" and "Sunderron (Nippon Tsuji Co., Ltd.), which are commercially available deodorizing fibers, are used. The deodorizing function for ethyl mercaptan was measured under the same conditions as in [Example 8] using the same weight of fiber. The results are shown in FIG. It can be seen that the absorption of ethyl mercaptan by the deodorant fiber used in Comparative Example 1 is extremely slow compared to the absorption of the fabric of the present invention shown in [Example 4] to [Example 18].

It can be widely used as a material for clothing products that require a deodorizing effect.
It can be widely used in textile products that require deodorizing effects, such as clothing products, bedding, indoor furniture, upholstery, interior building materials, care products, sanitary equipment, medical products, and toys. .

It is the schematic diagram which showed the collection bag made from aluminum, and the detection tube type gas measuring device. It is the graph which showed the ethyl mercaptan deodorization result of the cotton broad obtained in Example 4 and Example 5. It is the graph which showed the ethyl mercaptan deodorization result of the cotton broad obtained in Example 6 and Example 7. It is the graph which showed the ethyl mercaptan deodorization result of the silk cloth obtained in Example 10 and Example 11. It is the graph which showed the ethyl mercaptan deodorization result of the wool obtained in Example 13 and Example 14. It is the graph which showed the ethyl mercaptan deodorization result of the feather obtained in Example 15 and Example 16. It is the graph which showed the ammonia deodorizing result of the cotton fabric obtained in the case of the cupric chloride of Example 17. It is the graph which showed the ammonia deodorizing result of the cotton fabric obtained in the case of the copper sulfate of Example 17. It is the graph which showed the acetic acid deodorization result of the cotton fabric obtained in the case of the cupric chloride of Example 18. It is the graph which showed the acetic acid deodorization result of the cotton fabric obtained in the case of the copper sulfate of Example 18. It is the graph which showed the ethyl mercaptan repeated deodorizing result of the cotton fabric obtained in Example 19. 2 is a graph showing the results of deodorizing ethyl mercaptan obtained in Comparative Example 1.

Claims (9)

After dyeing using Indigo, when mordanting with a metal salt solution of copper salt, imparting dyeing and deodorizing function , characterized by enhanced deodorizing function by performing ultrasonic irradiation Made fabric. The fabric with dyeing and deodorizing functions according to claim 1 , wherein a pre-morning process is added by a metal salt solution of copper salt before the dyeing. The process of post-mordanting or pre-mordanting with the metal salt solution of copper salt described above is performed at 40 to 80 ° C for 30 minutes to 3 hours, according to any one of claims 1 and 2. A fabric provided with the described dyeing and deodorizing functions. The fabric with dyeing and deodorizing functions according to any one of claims 1 to 3, wherein the fabric described above is cotton, silk, wool, or feather. After dyeing using indigo, when mordanting with a copper salt metal salt solution, by applying ultrasonic irradiation, the deodorizing function is enhanced and the deodorizing function is added. Textile products made of fabric. After dyeing using indigo, when mordanting with a metal salt solution of copper salt , the deodorizing function is enhanced by irradiating with ultrasonic waves, and the fabric is dyed and deodorized. A method of adding functions simultaneously. The method for simultaneously dyeing and imparting a deodorizing function to the fabric according to claim 6 , wherein a pre-morning process is added by a metal salt solution of copper salt before the dyeing. The treatment of post-mordanting or pre-mordanting with the metal salt solution of copper salt described above is performed at 40 to 80 ° C for 30 minutes to 3 hours , according to any one of claims 6 and 7. A method of simultaneously dyeing and imparting a deodorizing function to the fabric described. The method of performing simultaneously dyeing | staining and deodorizing function provision with respect to the fabric as described in any one of Claims 6-8 whose above described fabric is cotton cloth, silk, wool, or feather.

Images