WO2021187426A1 - Method for producing fiber material, and fiber material - Google Patents

Abstract

The present invention provides a method for producing a fiber material, said method being capable of performing a scouring treatment without using sodium hydroxide that is strongly alkaline, while being also capable of performing the scouring treatment and a bleaching treatment at the same time in a single bath. A method for producing a fiber material that contains at least one kind of fibers selected from among natural fibers and regenerated cellulose fibers, said method comprising: preparation of a fiber material that is to be subjected to a scouring treatment and a bleaching treatment; and treatment of the fiber material with a treatment liquid that has an initial pH of from 9 to 11, while containing (1) a chelating agent, (2) a surfactant, (3) a bleaching agent, and (4) an alkali treatment agent that does not contain sodium hydroxide.

Description

Fabric material manufacturing method and textile material

This disclosure relates to a method for manufacturing a fiber material and a fiber material.

In the production of fiber materials (eg, raw cotton, yarn, woven fabrics, knitted fabrics, etc.) using natural fibers and / or regenerated cellulose fibers as raw materials, metals, pectic substances, and waxes (including wax) adhering to the fibers are produced. ) And a scouring process to remove fats and the like are generally performed. By performing the refining treatment, the water absorption of the fiber material is improved, so that the fiber material can be easily dyed.

Here, taking cotton as an example, the general refining treatment of cotton is carried out using a strongly alkaline treatment liquid in which a surfactant is added to an aqueous solution containing sodium hydroxide. According to this method, although the desired water absorption can be imparted to the treated cotton, embrittlement and hardening of the cotton are likely to occur. Further, when the scouring treatment with a strong alkaline treatment liquid is applied to a blended product of cotton and protein fibers (for example, wool, silk, cashmere hair), the protein fibers tend to be damaged or dissolved. Further, the strongly alkaline treatment liquid needs to be neutralized with a large amount of neutralizing agent at the time of wastewater treatment, which imposes a heavy burden on the user.

In view of these problems, Patent Document 1 uses an acidic treatment liquid containing an amylase enzyme and a surfactant to remove the glue adhering to the fiber material, and at the same time, refine the fiber material. The pectic metal contained in the fibrous material is attacked with a proton by using the acidic treatment liquid having a pH in the range of 3 to 6 and containing an acid capable of donating a proton. We have proposed a method for treating a fibrous material, which comprises converting the pectic acid into a pectic acid and eluting the metal contained in the pectic metal as an ion during an acidic treatment.

Also, the refined fiber material is usually subjected to bleaching treatment. The bleaching treatment is generally a method of treating with a bleaching agent in a bath different from the bath in which the refining treatment is carried out (two bath method), or a method of adding the bleaching agent to the bath in which the refining treatment is carried out after the completion of the refining treatment (two bath method). It is carried out by the one-bath two-stage method). In these methods, the refining treatment and the bleaching treatment are performed separately, which causes a problem of high cost and time. Therefore, in order to solve this problem, Patent Document 2 describes a glue containing a surfactant, a transition metal complex, a building bath agent containing at least an amine compound, an alkaline component, and a bleaching oxidizing agent. We are proposing a one-bath bleaching / scouring / bleaching treatment agent. Patent Document 3 describes degluing and bleaching at a predetermined pH in a bath containing hydrogen peroxide, sodium hydroxide, a chelating agent, an enzyme preparation based on a starch degrading enzyme, and a surface activator. We are proposing to implement it within the scope.

Japanese Patent No. 5554172 JP-A-2007-9365 Tokuhei No. 2-2989

Provided is a method for producing a fiber material, which can carry out a refining treatment without using sodium hydroxide showing strong alkalinity, and can carry out a refining treatment and a bleaching treatment at the same time in one bath.

The present disclosure is a method of producing a fiber material containing at least one selected from natural fibers and regenerated cellulose fibers.
Preparing fiber materials for scouring and bleaching, and containing 1) chelating agent, 2) surfactant, 3) bleaching agent, and 4) sodium hydroxide-free alkaline treatment agent, initial pH 9 Treating the fibrous material with a treatment liquid of ~ 11
To provide a method for producing a fiber material, including.

The production method of the present disclosure removes a metal from a pectic metal of a fiber material by simultaneously acting a chelating agent, a surfactant and a bleaching agent under the conditions of an initial pH of 9 to 11 without using sodium hydroxide. It is possible to reduce the labor required for wastewater treatment. Further, according to the manufacturing method of the present disclosure, bleaching can be carried out at the same time as refining of the fiber material, and efficient production of the fiber material becomes possible.

It is a micrograph which shows the residual state of wool in the knitting obtained in Example 2-1. It is a micrograph which shows the residual state of wool in the knitting obtained in the reference example. 6 is a photomicrograph showing a residual state of wool in the knitted fabric obtained in Comparative Example 2-1. 6 is an electron micrograph (SEM image) showing the state of the fiber surface in the knitted fabric obtained in Example 1-4. 6 is an electron micrograph (SEM image) showing the state of the fiber surface in the knitted fabric obtained in Example 1-5. 6 is an electron micrograph (SEM image) showing the state of the fiber surface in the knitted fabric obtained in Example 1-6. It is an electron micrograph (SEM image) which shows the state of the fiber surface in the unrefined bleached knit.

(Background to this embodiment)
In order to avoid damage to the fiber material, the present inventors can obtain a refining effect equal to or higher than that of using strongly alkaline sodium hydroxide without using strongly alkaline sodium hydroxide, and can obtain a refining effect in one bath. We examined a method that can carry out refining treatment and bleaching treatment by treatment. As a result, according to the treatment liquid having an initial pH of 9 to 11 in which the chelating agent is combined with the alkaline treatment agent, the surfactant and the bleaching agent, scouring and bleaching can be carried out at the same time, and the water absorption and diffusivity are excellent. We have found that a fiber material having a small amount of residual metal can be obtained, and have reached this embodiment.

The chelating agent has a track record of being generally used in the refining treatment using sodium hydroxide for the purpose of removing metal ions contained in the water used in the refining treatment. Further, instead of refining using sodium hydroxide, a refining treatment of cellulose fibers in which an enzyme and a chelating agent are combined has also been proposed. However, no method has been proposed in which a chelating agent is used as the main refining agent and a method of performing refining bleaching in one bath using the chelating agent. The present inventors have found that refining and bleaching treatment can be carried out in one bath by using a chelating agent that has been used as an auxiliary with a bleaching agent under certain conditions.

<Embodiment 1: Manufacturing method of fiber material>
The method for producing a fiber material of the present embodiment is a method for producing a fiber material containing at least one selected from natural fibers and regenerated cellulose fibers.
Preparing fiber materials for scouring and bleaching, and containing 1) chelating agent, 2) surfactant, 3) bleaching agent, and 4) sodium hydroxide-free alkaline treatment agent, initial pH 9 Treating the fibrous material with a treatment liquid of ~ 11
including.

[Preparation of fiber material]
The fibrous material produced in this embodiment comprises at least one selected from natural fibers and regenerated cellulose fibers. Natural fibers include, for example, cotton, capoc, flax, ramie, cannabis, yellow hemp, Manila hemp, sisal hemp, shrofiber, coconut fiber, plant fiber such as pulp (wood pulp, etc.), silk, wool, cashmere hair. , Angora hair, alpaca hair and the like, and examples of the regenerated cellulose fiber include biscous rayon, cupra, and solvent-spun cellulose fiber (for example, lenting lyocell (registered trademark) and tencel (registered trademark)). Be done.

The fiber material produced in the present embodiment broadly includes those composed of fibers, and includes, for example, raw cotton, yarn (including paper yarn), tow, top, skein, woven fabric (including mixed woven fabric), non-woven fabric, and knitted fabric. (Including mixed knitting) and products using woven fabrics, non-woven fabrics or knitted fabrics (hereinafter, these are collectively referred to as "fabric products"). Fabric products may be, for example, clothing (including socks and hats), duvet covers, mattresses, towels, blankets. Woven fabrics, knitted fabrics, and fabric products may contain two or more fibers and may be, for example, made of blended or twisted yarns. According to this embodiment, embrittlement of protein fibers that are weak against alkali such as animal fibers can be suppressed. Is also applicable.

In this case, the combination of two or more fibers is a combination of two or more natural fibers, a combination of natural fibers and synthetic fibers, a combination of natural fibers and regenerated cellulose fibers, a combination of two or more regenerated cellulose fibers, a combination of regenerated cellulose fibers and synthetic fibers. It may consist of a combination of fibers. Examples of the combination of two or more natural fibers include a combination of plant fiber / animal fiber (for example, cotton / wool, cotton / silk) and a combination of two or more plant fibers (for example, cotton). (Cotton) / flax), and combinations of two or more animal fibers (wool / silk). An example of these combinations can be an example of a combination of yarn materials constituting a blended spinning or mixed weaving.

The manufacturing method of the present embodiment includes preparing a fiber material to be subjected to a refining process. "Preparing a fiber material to be subjected to a smelting treatment" is a step of preparing a fiber material that has not yet been smelted and requires a smelting treatment. In this preparatory process, in addition to manufacturing raw cotton, raw yarn, woven fabric, knitting, and woven and knitted products, those distributed in the form of yarn, woven fabric, knitted fabric, or fabric products (however, they have not been refined). It is also included to obtain the thing) and carry out the work or processing necessary for the scouring process described later. Such work or processing may be, for example, arranging the fibrous material in an apparatus, or cutting the fibrous material or the like to appropriate dimensions.

[Treatment of fiber materials with treatment liquid]
In the production method of the present embodiment, as described above, the initial pH is 9 to 11, which includes 1) a chelating agent, 2) a surfactant, 3) a bleaching agent, and 4) an alkaline treatment agent containing no sodium hydroxide. The fibers are treated with a treatment solution.

(Chelating agent)
Chelating agents are used to capture and remove metals contained in fibers. The chelating agent is selected from, for example, an aminocarboxylic acid chelating agent, a polyacrylic acid chelating agent, an acrylic acid / maleic acid copolymer chelating agent, a dicarboxylic acid chelating agent, a phosphonic acid chelating agent, and a gluconic acid chelating agent. It may be at least one. These chelating agents may be provided as salts. The salts are, for example, metal salts and ammonium salts. The metal salt is, for example, a sodium salt or a potassium salt, and in particular, the sodium salt is preferably used from the viewpoint of metal trapping property and solubility in water. In addition, since the sodium salt is easily removed as a base in the treatment solution, when the sodium salt is used, the chelating agent from which the sodium salt has been removed binds / captures the metal in the fiber, and the removed base binds to the pectin of the fiber. And promotes the detachment of pectin.

Examples of the aminocarboxylic acid-based chelating agent include ethylenediamine tetraacetic acid, diethylenetriamine pentaacetic acid, glutamate diacetic acid, nitrotriacetic acid, hydroxyethyliminodiacetic acid, dihydroxyethylglycine, (S, S) -ethylenediamine disuccinic acid, and ethylenediamine hydroxy. There are ethyl triacetic acid, and triethylenetetramine hexaacetic acid, methylglycine diacetate trisodium salt and salts thereof.

The aminocarboxylic acid-based chelating agent preferably used in the present embodiment is ethylenediaminetetraacetic acid and its salt, diethylenetriaminetetraacetic acid and its salt, and glutamate diacetic acid and its salt. Since these aminocarboxylic acid-based chelating agents have many ligands in one molecule, they are preferable in that they produce stable chelating compounds for metals having a large number of coordination numbers.

Examples of the polyacrylic acid-based chelating agent include ALBATEX AD-01 (trade name) sold by Huntsman Japan Corporation and Aquaric FH (trade name) sold by Nippon Shokubai Co., Ltd. be. Examples of the acrylic maleic acid-based chelating agent include Dekol SN-S liq (trade name) sold by Arkroma Japan Co., Ltd., Aquaric TL400 (trade name) sold by Nippon Shokubai Co., Ltd., etc. There is. Phosphonic acid-based chelating agents include hydroxyethylidiene diphosphonic acid, nitrilotris (methylenephosphonic acid), 2-phosphonobutane-1,2,4-tricarboxylic acid, ethylenediaminetetramethylenephosphonic acid, and metal salts and ammonium thereof. There is salt etc. Further, as a phosphonic acid-based chelating agent, there is KWB-25 (trade name) sold by Senka Co., Ltd.

Among the chelating agents exemplified above, the aminocarboxylic acid-based chelating agent, the polyacrylic acid-based chelating agent, and the acrylic acid / maleic acid copolymer chelating agent do not contain phosphorus. Is preferably used when the involvement of is not desired.

Among the chelating agents exemplified above, those used as cosmetic raw materials or edible raw materials (for example, food additives) are included. For example, ethylenediaminetetraacetic acid, diethylenetriaminetetraacetic acid, ethylenediaminehydroxyethyl triacetic acid, hydroxyethylidiene diphosphonic acid, gluconic acid, and metal salts thereof (particularly sodium salts) are used as raw materials for cosmetics. Further, for example, a disodium salt of ethylenediamine tetraacetic acid and a sodium salt of gluconic acid are used as edible raw materials (food additives). Therefore, textile materials produced using these chelating agents can give consumers a sense of security in that they are treated with agents that are also used in cosmetics and foods.

Other chelating agents used as cosmetic raw materials or edible raw materials include methylglycine trisodium diacetate, sodium polyacrylic acid salt, sodium metaphosphate salt, 1-hydroxyethylidene-1,1-diphosphonic acid, and L-glutamic acid. Examples thereof include tetrasodium diacetate and tetrasodium 3-hydroxy-2.2'-iminodicosuccinate. These can also be used as chelating agents in this embodiment.

From the viewpoint of metal trapping property, a chelating agent having a pH of 4 to 13, preferably pH 5 to 12, particularly pH 7 to 10, is preferably used. According to the chelating agent having a pH in the above range, the initial pH of the treatment liquid containing an alkaline treatment agent containing no sodium hydroxide can be set to 9 to 11 when the fiber material is scoured and bleached.

(Surfactant)
As the surfactant, those usually used in the refining treatment can be arbitrarily used. In this embodiment, at least one surfactant selected from a nonionic surfactant and an anionic surfactant is preferably used. This is because these surfactants are superior in dispersion and desorption to cellulose fibers as compared with cationic surfactants and amphoteric surfactants, and are less likely to be reattached.

Nonionic surfactants include, for example, higher alcohol alkylene oxide adducts, fatty acid alkylene oxide adducts, fatty acid esters of glycerol, and sucrose fatty acid esters such as glucamido-based surfactants, alkyl polyglycosides, and the like. Glutamine, sorbitan fatty acid ester and the like are also classified as nonionic surfactants. Examples of anionic surfactants include higher alcohol sulfate esters, sulfated fatty acid esters, α-olefin sulfonates, alkylbenzene sulfonates and the like.

The surfactant may be selected according to the type of chelating agent. For example, chelating / surfactant combinations include diethylenetriamine pentaacetate / nonion and / or anionic surfactant, ethyleneamine tetraacetate / nonion and / or anionic surfactant, hydroxyetylidene diphosphonate / nonion and / Or anionic surfactant, dicarboxymethyl glutamate / nonion and / or anionic surfactant, 3-hydroxy-2,2'iminodicosuccinate / nonion and / or anionic surfactant, diethylenetriamine pentaacetate / glucamide , Ethyleneamine tetraacetate / glucamide, hydroxyetilidene diphosphonate / glucamide, dicarboxymethyl glutamine / glucamide, diethylenetriamine pentaacetate / glucamide, alkylpolyglucoside / glucamide, diethyleneamine pentaacetate / glucamide, diethylenetriamine5 Acetate / alkyl polyglucoside, ethyleneamine ein tetraacetate / alkyl polyglucoside, hydroxyetylidenate / alkyl polyglucoside, phosphonate / alkyl polyglucoside, methyl dicarboxylic acid polyglucoside / alkyl polyglucoside, diethylenetriamine pentaacetate / When the alkyl polyglucoside is used, the refining treatment is carried out more efficiently, and there is a tendency that a fiber material having better water absorption and diffusivity can be obtained.

Some surfactants are used as cosmetic raw materials or edible raw materials (for example, food additives). For example, sucrose fatty acid esters such as glucamido and sugar-based surfactants, alkyl polyglucosides, sorbitan fatty acid esters, higher alcohol alkylene oxide additives, fatty acid alkylene oxide additives, higher alcohol sulfate esters, sulfated fatty acid esters, α- Olefin sulfonate is used as a raw material for cosmetics. Further, sucrose fatty acid ester and sorbitan fatty acid ester are edible and are used as food additives. When these surfactants are combined with the above-mentioned cosmetic raw material or chelating agent which is an edible raw material, it is possible to provide a fiber material which can give a more secure feeling to consumers.

Examples of the glucamide-based surfactant used as a raw material for cosmetics include lauroyl glucamide, lauroyl / myristyl methyl glucamide, cocoyl methyl glucamide, and sunflower fatty acid methyl glucamide. These can also be used as surfactants for refining and bleaching treatments in this embodiment.

(bleach)
In this embodiment, the bleaching agent may be an oxidizing agent or a reducing agent. Bleaching agents that are oxidizing agents include chlorine-based bleaching agents such as sodium hypochlorite and sodium dichloroisocyanurate (or potassium), as well as sodium perborate, sodium perborate, sodium monopersulfate, and peroxidation. There are oxygen bleaches such as hydrogen. Examples of the bleaching agent, which is a reducing agent, include hydrosulfite (sodium dithionite dihydrate), sodium dithionite (sodium acid sulfite), and thiourea dioxide. In particular, when sodium carbonate or sodium hydrogen carbonate is used as the alkali treatment agent, bleaching treatment with an oxygen-based bleaching agent such as hydrogen peroxide or sodium percarbonate, or a reducing bleaching agent such as thiourea dioxide or hydrosulfite. Is easy to obtain the pH (specifically, 8 to 13) in which the bleaching treatment is preferably carried out, so that the bleaching treatment can be carried out efficiently.

When hydrogen peroxide is used as the bleaching agent, a hydrogen peroxide stabilizer may be used in combination, if necessary. As the hydrogen peroxide stabilizer, for example, poly-α-hydroxyacrylic acid or a salt thereof, gluconic acid or a salt thereof or the like having a mass average molecular weight of 2000 to 1000,000, particularly 5000 to 800,000 can be used. These salts may be sodium salts, potassium salts, or lithium salts.

(Alkaline treatment agent)
In the present embodiment, the alkaline treatment agent plays a role of adjusting the initial pH of the treatment liquid, and when the above oxygen-based bleaching agent or the reduced bleaching agent is used as the bleaching agent, the pH of the treatment liquid is used for the bleaching treatment. It serves to make the pH suitable. In the present embodiment, an alkaline treatment agent containing no sodium hydroxide is preferably used. Sodium hydroxide is strongly alkaline, which tends to cause more damage to the fiber material and requires the use of large amounts of neutralizer to drain the treated solution after treatment. This is due to the increased burden of wastewater treatment.

For example, the alkali treatment agent may be sodium carbonate (soda ash), sodium hydrogen carbonate (baking soda), sodium percarbonate, or the like. Sodium carbonate may be anhydrous or liquid. These alkaline treatments release less hydroxide ions than sodium hydroxide, allowing for mild refining and bleaching with less damage to the fiber material.

In this embodiment, amine compounds such as ammonia, monoamine, diamine, and triamine are not used as the alkali treatment agent. Since amine compounds have a strong odor, they release odors during scouring and bleaching treatments and adversely affect the treatment environment, and unreacted amine compounds may remain in the fiber material and emit an amine odor.

(Treatment liquid)
The treatment liquid used in the present embodiment is a liquid containing the above-mentioned chelating agent, surfactant, bleaching agent, and alkali treatment agent in a dissolved or dispersed form. The treatment liquid may be prepared by adding these agents to water.

The treatment liquid may be prepared so that the initial pH is 9 to 11. In particular, the initial pH may be adjusted to 10 to 11. By setting the pH within this range, when an oxygen-based bleach or a reduced bleach is used, the function of the bleach can be efficiently exerted, and the alkalinity does not become excessively strong, so that the treatment is completed. The amount of neutralizing agent required for neutralizing the subsequent treatment liquid can be reduced, and the burden of wastewater treatment can be reduced.

The chelating agent, surfactant, etc. used in the preparation of the treatment liquid may be provided in a form containing sodium hydroxide for adjusting the pH of the agent, but the amount thereof is an alkaline treatment agent. Usually considerably smaller than the amount used. Therefore, it is permissible that the sodium hydroxide contained in these agents is contained in the treatment liquid.

Specifically, in the treatment liquid, each agent may be contained in the following amount with respect to 1 liter of the liquid (particularly water) serving as a solvent or a dispersion medium.
Chelating agent: for example 0.2 g / liter to 20 g / liter, preferably 0.3 g / liter to 10 g / liter, more preferably 0.4 g / liter to 5.0 g / liter, particularly 0.5 g / liter to 2 .5 g / liter.
Surfactant: for example 0.5 g / liter to 10.0 g / liter, preferably 1.0 g / liter to 5.0 g / liter, particularly 1.5 g / liter to 2.5 g / liter.
Bleach: When hydrogen peroxide is used, for example, 3 g / liter to 20 g / liter, especially 5 g / liter to 15 g / liter.
Hydrogen peroxide stabilizer (optional): For example, 1 g / liter to 20.0 g / liter, particularly 2 g / liter to 10.0 g / liter.
Alkaline treatment agent: For example, 1.0 g / liter to 25.0 g / liter, particularly 5.0 g / liter to 10.0 g / liter.

In the present embodiment, soft water having a hardness of 7 ° DH or less, particularly 6 ° DH or less, more particularly 5 ° DH or less may be used as the solvent of the treatment liquid. When water with high hardness is used in the scouring and bleaching treatment and the subsequent dyeing, the hardness component (metal ions (calcium ion, magnesium ion) contained in the water binds to the surfactant and loses its activity. In addition, the hardness component may promote the aggregation of dirt and the adhesion of dirt. Therefore, in the present embodiment, it is preferable to use water having a low hardness. As the soft water, the hardness of tap water is as described above. If the hardness is in the range, tap water may be used as it is. If the hardness of the tap water is out of the above range, the hardness is reduced by using a water softener, and then this is used as a solvent for the treatment liquid. It is preferable to use it.

(Processing conditions, etc.)
In the present embodiment, the treatment with the treatment liquid is carried out by putting the treatment liquid in a bath, bringing the fiber material into contact with the treatment liquid, and reacting with the treatment liquid. The reaction treatment is carried out under the conditions of, for example, a bath ratio of 1: 5 to 1:20, a reaction treatment temperature of 80 ° C. to 110 ° C., and a reaction treatment time of 20 minutes to 100 minutes, preferably 30 minutes to 60 minutes. It may be carried out by immersing the fiber material in the water. The bath ratio may be particularly 1:10 to 1:18, the reaction treatment temperature may be particularly 90 ° C to 100 ° C, and the reaction treatment time may be particularly 30 minutes to 45 minutes.

It is preferable that the treatment method using the treatment liquid is a batch method in which the treatment is carried out in a closed space. According to the batch method, the vapor of the treatment liquid is present in the space due to the heating of the treatment liquid, and the treatment proceeds while the fiber material is moving out of the treatment bath, so that the treatment time can be relatively shortened. Alternatively, a cold batch method or a continuous method may be adopted as long as the treatment with the treatment liquid proceeds and the desired fiber material is finally obtained.

In this embodiment, the treatment with the treatment liquid is carried out in one bath. That is, after the refining treatment, the bleaching treatment is performed in one treatment bath without changing the treatment bath or the treatment liquid (including adding a bleaching agent or the like to the treatment liquid after the refining treatment). The refining bleaching treatment is carried out by a single treatment using the liquid. Therefore, according to the present embodiment, the labor required for scouring and bleaching can be reduced.

Since the fiber material treated by the production method of this embodiment is alkaline, it is preferable to neutralize it with a neutralizing agent. The neutralizing agent is an acid, such as acetic acid, citric acid, formic acid and the like. Neutralization may be carried out after the treatment liquid is discharged from the treatment bath, and then an aqueous solution containing a neutralizing agent is added to the treatment bath so that the pH of the fiber material becomes 3.5 to 4.5.

[Washing]
After the refining and bleaching treatments are completed with the above treatment liquid, the fiber material is subjected to a washing step. In the cleaning step, for example, in the case of the batch method, the treatment liquid is drained from the treatment bath, and in the case of the continuous method, the treated fiber material is passed through a drawing roller to allow the liquid adhering to the fiber material. As much as possible, and then the fibrous material may be washed with water and / or with hot water. Washing with water means washing with water at 20 ° C to 40 ° C, and washing with hot water means washing with hot water at 60 ° C to 100 ° C. The washing with water and the washing with hot water may be carried out in combination, and in that case, the time of the washing step can be shortened.

[staining]
The production method of this embodiment may further include a dyeing step. Dyeing is performed after the treatment and washing with the above treatment liquid are completed. Dyeing may be carried out by a commonly used method (eg, dyeing or printing). The type of dye is selected from direct dyes, reactive dyes, sulfur dyes, bat dyes, acid dyes, metal-containing acid dyes, disperse dyes, and cationic dyes, depending on the type of fiber constituting the fiber material. Alternatively, the dyeing step may be carried out by a pigment printing method or a dyeing method.

As mentioned above, in the present embodiment, one or both of the chelating agent and the surfactant used in the scouring and bleaching treatment can be used as an agent also used in cosmetics and foods, whereby consumers are more relieved. It is possible to provide a fiber material that gives a feeling. In addition, in the dyeing step after the scouring and bleaching treatment, at least one selected from the dye, the fixing agent, and the surfactant used in the soaping step is used as a cosmetic raw material or an edible raw material. As a result, it becomes possible to manufacture the fiber material as an agent in which more of the chemicals used in the production of the fiber material are directly applied or ingested to the human body, and the consumer can be further relieved.

Examples of dyes and the like that can be used in the dyeing step and are also used as a raw material for cosmetics or an edible raw material are as follows.
Dyes: Vinyl sulfone type (VS type), triazine type (DCT type, MCT type, MFT type), pyrimidine type (TCP type, DFCP type), and heterologous bifunctional system (VS-MFP2 functional) depending on the combination of these reactive groups. Base type, VS-MCT2 functional group type, VS-MCT2 functional group type, etc.), azo type, anthraquinone type, copper formazan type, copper phthalocyanine type Fixing agent: polyoctanium, sodium carbonate Surface active agent: glucamido, sucrose fatty acid Estel, glucoside, propylbetaine, undecylate, isostearate, oleate, capricate, tortate, behenate, myristate, polyethylene glycol Promoting agent: Ginseng (sodium sulfate)

[Other processing processes]
The production method of the present embodiment may include other treatment steps in place of or in addition to the dyeing step. Other treatment steps include, for example, water absorption processing for imparting water absorption to the fiber material, soft processing for making the fiber material more flexible, and functions such as deodorant, antibacterial, and antiviral properties for the fiber material. It may be a finishing process such as functional processing for imparting properties. In these treatment steps as well, agents that are also used as cosmetic raw materials or edible raw materials may be used, which can give consumers a sense of security, as explained in relation to the dyeing step.

Water absorbents, fabric softeners, and antibacterial and / or antiviral agents that are also used as cosmetic or edible ingredients are:
Water Absorbent; Amino Modified Silicone Softener: Maltotetraose, Alkyltrimethylammonium Chloride, Polyethylene Polyamine, Chitosan Antibacterial and / or Antiviral Agent: Monoglyceride Undecylenic Acid, Grapefruit Seed Extract, Bamboo Extract

[Action and effect of this embodiment]
In the production method of the present embodiment, the fiber material is scoured and bleached using a treatment liquid containing a chelating agent, a surfactant, a bleaching agent and an alkali treating agent (however, sodium hydroxide is not contained). do. It is presumed that the pectin, waxy substance and fat, and the metal adhering to or forming the cell wall of the cells constituting the fiber material are removed by the treatment with this treatment liquid by the following mechanism.
-Pectic metals (metals that form a complex with pectin) are removed by being trapped by a chelating agent.
-The pectin after the metal has been removed is converted into a water-soluble salt by an alkaline treatment agent to promote the desorption of pectin and suppress the reattachment of pectin.
-Surfactants emulsify and disperse pectin, as well as waxes and fats.
When the bleaching agent is hydrogen peroxide, the chelating agent also functions as a stabilizer for hydrogen peroxide.

In addition, if the chelating agent is in the form of a sodium salt, this sodium salt, along with the alkaline treatment agent, also removes pectin from the fiber material, causes the pectin to form a water-soluble salt with sodium, and redistributes the pectin. It is thought to contribute to suppression.
More specifically, the chelating agent which is a sodium salt tends to generate a state in which the sodium salt of the chelating agent is removed when the treatment liquid is prepared. The chelating agent from which the sodium salt has been removed captures the metal salt contained in the first cell membrane of cellulose. At the same time, it is thought that the sodium salt removed from the chelating agent binds to pectin to produce water-soluble sodium pectinate, or the pectin is reduced to a low molecular weight and eluted in water, thereby promoting the removal of pectin. Be done. Pectic substances eluted in water are effectively removed by a surfactant.

However, these mechanisms are based on speculation and do not limit the manufacturing method of this embodiment in any way.

In the manufacturing method of this embodiment, the refining treatment and the bleaching treatment can be carried out at the same time in one treatment. Therefore, in the production method of the present embodiment, before and after the above treatment, for example, treatment with a chelating agent and a surfactant (treatment without using a bleaching agent) or treatment with a bleaching agent and an alkaline treating agent is not performed. Well, scouring and bleaching treatments can be carried out in one bath and one step to complete. Further, in the production method of the present embodiment, the fiber material can be refined and bleached without using an enzyme as described in Patent Document 3 (that is, by a treatment liquid containing no enzyme).

Further, when a cosmetic raw material or an edible raw material is used as a treatment agent in the manufacturing method of the present embodiment, the manufactured fiber material comes into direct contact with the human body (particularly a delicate part of the human body) such as underwear or underwear and a mask. Suitable for composing textile products.

[Fiber material obtained in this embodiment]
The fiber material produced by the production method of the present embodiment can be provided, for example, so that the amount of residual metal measured by IPC spectroscopic analysis satisfies at least one of the following.
Residual amount of magnesium: 150 mg / kg or less Residual amount of calcium: 600 mg / kg or less

The residual amount of magnesium may be particularly 150 mg / kg or less, and more particularly 100 mg / kg or less. The residual amount of calcium may be particularly 600 mg / kg or less, and more particularly 500 mg / kg or less.

According to the production method of the present embodiment, it is possible to obtain a fiber material having a particularly small residual amount of calcium as compared with the fiber material obtained by the conventional production method including a refining treatment. The metal remaining in the fiber material tends to inhibit dyeing during dyeing and cause dyeing unevenness. In addition, the metal remaining on the fiber material easily adsorbs dirt. The amount of residual metal in the fiber material obtained by the production method of the present embodiment is about the same as or smaller than the amount of residual metal in the fiber material obtained by the conventional production method. Therefore, in the fiber material obtained in the present embodiment, problems of uneven dyeing and stain adsorption are not likely to occur as compared with the conventional ones.

In the production method of this embodiment, the refining treatment and the bleaching treatment are carried out at the same time without using sodium hydroxide, which is strongly alkaline. Therefore, according to the present embodiment, since the neutralization treatment with a strong acid is not required, the waste liquid treatment with less environmental load becomes possible, which is advantageous in terms of cost. Further, according to the present embodiment, since the refining treatment step can be carried out without using a strong alkali, embrittlement and hardening of the fiber material can be suppressed, and the texture of the fiber material can be made soft and smooth. Further, by not using sodium hydroxide, which is strongly alkaline, it becomes easy to produce a fiber material containing protein fibers.

According to the manufacturing method of this embodiment, the measurement is performed according to JIS L 1907 7.1.1 (water absorption rate dropping method). A fiber material having a water absorption (water absorption rate) of, for example, 0 to 30 seconds, particularly 0 to 10 seconds can be obtained. A fiber material having such water absorption exhibits excellent dyeability. A fiber material having high water absorption can be obtained by the present embodiment because a chelating agent, a surfactant, a bleaching agent and an alkali treating agent are contained in one treatment liquid, and not only for removing metals but also for removing fats and oils. It is thought that this is due to the synergistic contribution.

The water absorption and diffusion area of the fiber material measured by the following method ^{is preferably 20 cm 2 or more for woven fabrics, 5 cm 2} or more for knitted fabrics, more preferably 10 cm ² or more, and 15 cm ² or more. Is the most preferable. When the water absorption / diffusion area is within the above range, the fiber material has high water absorption and is also excellent in quick-drying property, which is preferable.
[Water absorption and diffusion area]
The water absorption and diffusion area is measured by dropping 0.2 ml of the test solution (pH 7 standard water) onto the surface of a fiber material such as a woven fabric or knitted fabric, and then measuring the wet and spread area (vertical x horizontal) 1 minute later.

<Embodiment 2: Fiber treatment agent>
A fiber treatment agent will be described as Embodiment 2 of the present disclosure. The fiber treatment agent of the present embodiment can be used in the fiber production method described as the first embodiment, and is an alkali treatment that does not contain A) a chelating agent, B) a surfactant, and C) sodium hydroxide. Contains agents. When the fiber treatment agent of the present embodiment is used together with a bleaching agent, it is possible to carry out smelting and bleaching treatment at the same time in one bath.

The chelating agent, the surfactant, and the alkaline treatment agent containing no sodium hydroxide constituting the fiber treatment agent are as described in the first embodiment. These agents may be mixed at a concentration (ratio) when they are put into the bath as described in the first embodiment. For example, when the total mass of the chelating agent, the surfactant and the alkali treatment agent is 100%, the chelating agent is 0.57% by mass or more and 93% by mass or less, particularly 3.8% by mass or more and 28% by mass or less. In terms of proportion, the surfactant is 1.1% by mass or more and 89% by mass or less, particularly 11% by mass or more and 31% by mass or less, and the alkali treatment agent is 3.2% by mass or more and 97% by mass or less, particularly 50% by mass. It may be contained in a proportion of 83% by mass or less.

The fiber treatment agent of the present embodiment can be used together with a bleaching agent to enable refining and bleaching treatment to be carried out simultaneously in one bath. As the bleaching agent, those described in the first embodiment can be used, and hydrogen peroxide may be particularly used. If hydrogen peroxide is mixed with other agents in advance, hydrogen may be generated by the reduction of hydrogen peroxide, which makes the entire treatment agent unstable. Alternatively, it may be stored in a container different from the fiber treatment agent of the present embodiment and provided as a kit together with the fiber treatment agent of the present embodiment. Such kits can also be made with other bleaches.

Hereinafter, this embodiment will be specifically described with reference to Examples.
The following fiber treatment agents were prepared.
(Chelating agent)
1) IP chelate D40 (trade name, manufactured by Lion Specialty Chemicals Co., Ltd.): diethylenetriaminetetraacetic acid 2) ALBATEX AD-01 (trade name, sold by Huntsman Japan Co., Ltd.): sodium polyacrylate 3) Dekol SN -S liq (trade name, sold by Arkroma Japan Co., Ltd.): Acrylic maleic acid-based chelate copolymer 4) Kirest CMG-40 (trade name, manufactured by Kirest Co., Ltd.): L-tetrasodium diacetate L-glutamate 5) KWB-25 (trade name, manufactured by Senka Co., Ltd.): Phosphonate 6) HIDS (trade name, manufactured by Nippon Catalyst Co., Ltd.): 3-Hydroxy-2,2'iminodic succinate 7) EDTA (trade name, manufactured by Nippon Catalyst Co., Ltd.) Co., Ltd.): Ethylenediaminetetraacetic acid salt Of 1) to 7), 2), 4), 5), 6) and 7) are raw materials for cosmetics.

(Surfactant)
1) Dysurf MOL-744 (trade name, manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.): Special surfactant compounded 2) GLUCOPURE DEG (trade name, manufactured by Clariant): Lauroyl methyl glucamide 3) Pitchran L-100 (product) Name, manufactured by Nikka Kagaku Co., Ltd.): Nonionic / anionic surfactant containing poly (oxyethylene) = alkyl = ether (C = 12-15) 4) Sunmol BH230 (trade name, Nikka Kagaku Co., Ltd.) (Manufactured by): Nonion / anionic surfactant containing poly (oxyethylene) = alkyl = ether (C = 12-15) 5) Liporan LJ-441 (trade name, manufactured by Lion Specialty Chemicals Co., Ltd.): α-olefin sulfonate Acid salt 6) Chemical free score (trade name, manufactured by Rakuto Kasei Co., Ltd.): Of sucrose fatty acid esters 1) to 6), 2), 5) and 6) are raw materials for cosmetics.

(bleach)
Hydrogen peroxide (35%) (manufactured by Kishida Chemical Co., Ltd.)
(Hydrogen peroxide stabilizer)
Neorate PLC7000 (trade name, manufactured by NICCA CHEMICAL CO., LTD.): Hydrogen peroxide stabilizer containing polycarboxylic acid polymer (alkaline treatment agent 1: for normal refining treatment)
Sodium hydroxide (flakes) (manufactured by Hayashi Junyaku Kogyo Co., Ltd.)
(Alkaline treatment agent 2)
Sodium carbonate (manufactured by Kanto Chemical Co., Inc.)

(Example 1-1)
A knitted fabric made of cotton thread (30s tenjiku, basis weight 140g / m ² ) was prepared. After putting water in the treatment bath and sufficiently wetting the knitted fabric with water, the chelating agent, the surfactant, the bleaching agent and the alkali treatment agent shown in Table 1 are added into the treatment bath at the ratios shown in Table 1. A treatment liquid was obtained. The initial pH of the treatment solution was 10.6. The treatment was carried out with a bath ratio of 1:15, a liquid temperature of the treatment bath of 95 ° C., and a treatment time of 30 minutes. The pH of the treatment liquid after the treatment was 10.3. For the processing of knitted fabrics, use a pot dyeing machine (trade name UR-MINI-COLOR MCUR-V5-6N (manufactured by Texam Giken Co., Ltd.)), put the knitted fabric to be processed and the treatment liquid in a 440 cc pot, and keep it in a sealed state. This was carried out by repeatedly rotating the pot. After the treatment, the knitted fabric was neutralized with acid, washed with hot water at 95 ° C., dehydrated and dried.

(Examples 1-2 to 1-5)
Treatment of the prepared knitted fabric according to the same procedure as in Example 1-1, except that the types and ratios of the chelating agent, the surfactant, the bleaching agent and the alkaline treating agent to be put into the treatment bath are as shown in Table 1. Was carried out, and the knitted fabric was further neutralized and washed with hot water. The initial and post-treatment pH of the treatment liquid used in each example was as shown in Table 1.

(Comparative Example 1-1)
A knitted fabric made of cotton thread (30s tenjiku, basis weight 140g / m ² ) was prepared. After putting water in the treatment bath and sufficiently wetting the knitted fabric with water, the surfactant, bleach and alkali treatment agents shown in Table 1 were added to the treatment bath at the ratios shown in Table 1 without adding the chelating agent. It was put into the inside to obtain a treatment liquid. The initial pH of the treatment solution was 11.5. The treatment was carried out with a bath ratio of 1:15, a liquid temperature of the treatment bath of 95 ° C., and a treatment time of 30 minutes. The pH of the treatment liquid after the treatment was 11.4. After the treatment, the knitted fabric was neutralized with acid, washed with hot water at 95 ° C., dehydrated and dried.

(Comparative Example 1-2)
The types and proportions of the surfactants are shown in Table 1, except that the hydrogen peroxide stabilizer was added into the treatment bath at the proportions shown in Table 1 and the treatment time was 45 minutes. , The prepared knitted fabric was processed in the same procedure as in Comparative Example 1-1. After the treatment, the knitted fabric was neutralized and washed with hot water, and dehydrated and dried.

The whiteness, water absorption, and residual metal amount of the knits obtained in Examples 1-1 to 1-5 and Comparative Examples 1-1 to 1-2 were measured. The results are shown in Table 1.

The whiteness, water absorption, and residual metal content were measured according to the following procedure.
<Color scale, whiteness>
The color scale was measured with reference to JIS L 0801: 2011 Dyeing Fastness Test Method General Rules, JIS L 0805: 2005 Contamination Grayscale.
In addition, the hunter whiteness (D65) was measured using a spectrophotometer (trade name CD100, manufactured by Yokogawa Meter & Instruments Co., Ltd.).

<Water absorption: Water absorption rate>
The time (seconds) until the water dropped on the sample was absorbed was measured according to JIS L1907: 2010 7.1.1 (water absorption rate dropping method).
<Water absorption: diffusion area>
One minute after dropping 0.2 ml of water onto the sample, the area (cm ² ) of the wet portion of the sample was determined.

<Amount of residual metal>
Pretreatment (decomposition and solution of knitted fabric) was carried out in accordance with EPA3052 (microwave wet decomposition method), and approximately 0.2 g of the extracted sample was arbitrarily collected and weighed to prepare a test piece. Next, 8 ml of nitric acid was added, the mixture was hydrolyzed, the volume was adjusted with water, and the volume was quantified by ICP emission spectroscopy. For quantification, iCAP RG manufactured by Thermo Fisher Scientific Co., Ltd. was used.

(Example 1-6)
A knitted fabric made of cotton thread (30s tenjiku, basis weight 140g / m ² ) was prepared. Water having a hardness of 5 ° DH is put in the treatment bath, and after the knitted fabric is sufficiently wetted with water, the above-mentioned chelating agent 4) is used as a chelating agent at a ratio of 2 g / liter, and the above-mentioned surfactant 2) is used as a surfactant. Into the treatment bath at a ratio of 2 g / liter, the above hydrogen peroxide as a bleaching agent at a ratio of 10.0 g / liter, and the alkali treatment agent 2) as an alkali treatment agent at a ratio of 8.0 g / liter. To obtain a treatment liquid. The initial pH of the treatment solution was 10.4. The treatment was carried out with a bath ratio of 1:15, a liquid temperature of the treatment bath of 95 ° C., and a treatment time of 30 minutes. The pH of the treatment liquid after the treatment was 10.4. For the processing of knitted fabrics, use a pot dyeing machine (trade name UR-MINI-COLOR MCUR-V5-6N (manufactured by Texam Giken Co., Ltd.)), put the knitted fabric to be processed and the treatment liquid in a 440 cc pot, and keep it in a sealed state. This was carried out by repeatedly rotating the pot. After the treatment, the knitted fabric was neutralized with acid, washed with hot water at 95 ° C., dehydrated and dried.

(Examples 1-7 to 1-10)
Knitted fabrics prepared in the same procedure as in Examples 1-6, except that the types and proportions of chelating agents, surfactants, bleaching agents and alkaline treating agents to be added to the treatment bath were as shown in Table 1-2. Was carried out, and the knitted fabric was further neutralized and washed with hot water. The initial and post-treatment pH of the treatment liquid used in each example was as shown in Table 1-2.

The whiteness, water absorption, and residual metal amount of the knits obtained in Examples 1-6 to 1-10 were measured. The results are shown in Table 1. For Examples 1-6 to 1-10, the whiteness was measured by the method specified in JIS L1916. Therefore, the whiteness of Comparative Example 1-1 measured by the same method is shown in Table 1-2 together with other physical characteristics.

As shown in Tables 1 and 1-2, the hunter whiteness or whiteness of the knits obtained in each example using the chelating agent and not using sodium hydroxide is a comparative example using sodium hydroxide. It is almost the same as the obtained knitted fabric and does not affect the dyeability. Each example showed the same or better water absorption than each comparative example. It is considered that the low water absorption rate of Comparative Example 1 is due to the residual of some metal salts and oils (pectin, wax). Further, the amount of Ca remaining in the knitted fabric obtained in each example was considerably smaller than that in the knitted fabric of Comparative Example 2, and it was found that the treatment with a chelating agent was effective in removing Ca. The amount of residual Mg in the knitted fabric obtained in each example was almost the same as that in the knitted fabric of Comparative Example 2.
From these results, it was found that a practical fiber material can be obtained by using a chelating agent without using sodium hydroxide.

Further, the surfaces of the fiber materials (knitted fabrics) obtained in Examples 1-4, 1-5 and 1-6 were subjected to an electron microscope (3D Real Surface View Microscope VE-9800 (trade name), KEYENCE CORPORATION). The observation was performed at a magnification of 2500 times. The SEM images of each example are shown in FIGS. 4 to 6, respectively. In addition, SEM images of the surface of the unrefined bleached knit are shown in FIG. 7 for comparison. In comparison with FIG. 7, in the fiber material of the example, no contaminants existing on the surface of the fiber as seen in FIG. 7 were observed, and refining and bleaching were effectively carried out in each example. Do you get it.

The fiber materials (knits) obtained in Examples 1-7 to 1-10 were obtained by scouring and bleaching only with an agent that is also used as a raw material for cosmetics, and are equivalent to conventional textile products. While showing water absorption and whiteness higher than that, it can give a sense of security to users, and it can be easily accepted by users who do not like scouring and bleaching treatment with strong alkali. Be expected. In particular, in Examples 1-9, the diffusion area was large and the amount of residual metal was small, so it was found that refining and bleaching were effectively carried out.

(Example 2-1)
^{A knitted fabric (30 s tenjiku, basis weight 87 g / m 2} ) was prepared with a bite knitting machine using a 30-count blended yarn consisting of 80% by mass of cotton and 20% by mass of wool. After putting water in the treatment bath and sufficiently wetting the knitted fabric with water, the chelating agent, the surfactant, the bleaching agent and the alkali treatment agent shown in Table 2 are added into the treatment bath at the ratios shown in Table 2. A treatment liquid was obtained. The initial pH of the treatment solution was 10.03. The treatment was carried out with a bath ratio of 1:15, a liquid temperature of the treatment bath of 95 ° C., and a treatment time of 30 minutes. The pH of the treatment liquid after the treatment was 9.97. After the treatment, the knitted fabric was neutralized with acid, washed with hot water at 95 ° C., dehydrated and dried. After that, the knitted fabric was subjected to a dyeing treatment.

In the dyeing treatment, a dyeing solution containing 0.5% owf of Kayanol Milling Blue 2RW (trade name, manufactured by Nippon Kayaku Co., Ltd., blue acid dye) and 1.5 g / liter of acetic acid was used. The dyeing treatment was carried out by immersing the knitted fabric in the dyeing solution at 100 ° C. for 40 minutes, a soaping step, a hot water washing / washing step, and a dehydration / drying step in this order. This staining was performed to stain only wool.

(Comparative Example 2-1)
^{A knitted fabric (30 s tenjiku, basis weight 87 g / m 2} ) was prepared with a bite knitting machine using a 30-count blended yarn consisting of 80% by mass of cotton and 20% by mass of wool. After putting water in the treatment bath and sufficiently wetting the knitted fabric with water, the surfactant, bleach and alkali treatment agents shown in Table 2 were added to the treatment bath at the ratios shown in Table 2 without adding the chelating agent. It was put into the inside to obtain a treatment liquid. The initial pH of the treatment solution was 11.01. The treatment was carried out with a bath ratio of 1:15, a liquid temperature of the treatment bath of 95 ° C., and a treatment time of 30 minutes. The pH of the treatment liquid after the treatment was 10.55. After the treatment, the knitted fabric was neutralized with acid, washed with hot water at 95 ° C., dehydrated and dried. Further, the knitted fabric after dehydration and drying was dyed in the same procedure as in Example 1-1.

(Reference example)
A knitted fabric was obtained in the same procedure as in Example 2-1 except that the bleaching agent and the alkaline treating agent were not added to the treatment liquid.

The mass (mass of raw material) of the knitted fabrics obtained in Example 2-1 and Comparative Example 2-1 before being subjected to the treatment with the treatment liquid containing a chelating agent or sodium hydroxide, and the mass after the treatment with the treatment liquid. (Mass after treatment) and mass after staining (mass after staining) were measured. From these measured values, the rate of decrease of the treated mass with respect to the raw mass and the rate of decrease of the dyed mass with respect to the raw mass were determined. Further, for the knits obtained in Example 2-1 and Comparative Example 2-1 the mixing ratio of cotton and wool was determined based on JIS L 1030: 2012. Further, the surfaces of the knitted fabrics obtained in Example 2-1 and Comparative Example 2-1 and the knitted fabric of the reference example were subjected to a magnification of 100 using an optical microscope (digital microscope VHX-2000 (trade name), manufactured by Keyence Co., Ltd.). It was observed at a magnification of 2 to confirm the residual state of the dyed fiber (wool). The results are shown in Table 2 and FIGS. 1 to 3.

As shown in Table 2, in Example 2-1 the reduction rate of the treated mass and the dyed mass with respect to the raw mass was small. On the other hand, in Comparative Example 2-1 the mass reduction rate was considerably large. Further, in the observation with an optical microscope, in Example 2-1, a relatively large amount of dyed yarn (wool) remained, and the knitted fabric prepared as a reference example (those not affected by the alkaline treatment agent). It was about the same as. On the other hand, in Comparative Example 2-1, the dyed fibers (wool) were hardly confirmed, and it is considered that they were dissolved during the treatment. From these facts, it was found that the treatment using a chelating agent and not using sodium hydroxide can effectively suppress the damage to the protein fibers.

(Example 3-1)
The production of the fiber material was scaled up under the same conditions as in Example 1-1. Specifically, two types of knitted fabrics made of cotton yarn (30s Tenjiku (Metsuke 140g / m ² ) and 20s Tenjiku (Metsuke 187g / m ² )) were prepared for 5m each. After water is poured into the treatment bath to sufficiently wet the knitted fabric, the chelating agent, surfactant, bleach, alkali treatment agent and stabilizer shown in Table 3 are added to the treatment bath at the ratios shown in Table 3. It was charged to obtain a treatment liquid. The initial pH of the treatment solution was 10.2. The treatment was carried out with a bath ratio of 1:15, a liquid temperature in the treatment bath of 95 ° C., and a treatment time of 30 minutes. The pH of the treatment liquid after the treatment was 10.1. The treatment of the knitted fabric was carried out using a high-pressure small dyeing machine (capacity 20 kg) manufactured by Tace Co., Ltd., and after charging the knitted fabric to be treated and the treatment liquid, the knitted fabric was conveyed in the dyeing machine. After the treatment, the knitted fabric was neutralized with acid, washed with hot water at 95 ° C., dehydrated and dried.

(Example 3-2)
The production of the fiber material was scaled up under the same conditions as in Examples 1-4. Specifically, two types of knitted fabrics made of cotton thread (30 s Tenjiku (Metsuke 140 g / m ² ) and 20 s Tenjiku (Metsuke 187 g / m ² ) were prepared for 5 m each. After wetting with, a chelating agent, a surfactant, a bleaching agent, an alkali treatment agent, and a stabilizer shown in Table 3 were used and put into the treatment bath at the ratio shown in Table 3 to obtain a treatment bath. The initial pH of the treatment liquid was 10.1. The treatment was carried out with a bath ratio of 1:15, a liquid temperature in the treatment bath of 95 ° C., and a treatment time of 30 minutes. The pH of the treatment liquid after the treatment was 10. The treatment of the knitted fabric was carried out using a high-pressure small dyeing machine (capacity: 20 kg) manufactured by Tace Co., Ltd., and after charging the knitted fabric to be treated and the treatment liquid, the knitted fabric was conveyed in the dyeing machine. After the treatment, the knitted fabric was neutralized with acid, washed with hot water at 95 ° C., dehydrated and dried.

(Comparative Example 3-1)
Two types of knitted fabrics made of cotton thread (30s Tenjiku (Metsuke 130g / m ² ) and 20s Aligned Tenjiku (Metsuke 250g / m ² )) were prepared for 20m each. After putting water in the bath to sufficiently wet the knitted fabric, the surfactants, bleaching agents, alkaline treatment agents, and stabilizers shown in Table 3 are added to the treatment bath at the ratios shown in Table 3 for treatment. I got a bath. The treatment was carried out at a bath ratio of 1:10, a liquid temperature of 95 ° C. in the treatment bath, and a treatment time of 45 minutes. The treatment of the knitted fabric was carried out using a high-pressure small dyeing machine (capacity 20 kg) manufactured by Tace Co., Ltd., and after charging the knitted fabric to be treated and the treatment liquid, the knitted fabric was conveyed in the dyeing machine. After the treatment, the knitted fabric was neutralized with acid, washed with hot water at 95 ° C., dehydrated and dried.

The whiteness, water absorption, water absorption diffusivity, water absorption rate and residual metal salt of the knits obtained in Examples 3-1 to 3-2 and Comparative Example 3-1 were measured. The results are shown in Table 3.
The water absorption rate was measured by the following method.

<Water absorption: suction test>
A sample having dimensions of about 200 mm × 25 mm in the wale direction and the course direction, which was carried out according to JIS L1907: 2010.7.1.2 (Bilek method), was prepared. The prepared sample was lowered so that the course direction was parallel to the water surface, and the lower end 20 mm ± 2 mm of the sample was immersed in a water tank filled with water and left for 10 minutes. After being left to stand, the height increased by the capillary phenomenon was measured up to a scale of 1 mm.

As shown in Table 3, the hunter whiteness of the knitted fabric obtained in each example in which the chelating agent was used and sodium hydroxide was not used in the scaled-up treatment was obtained in Example 1 using a smaller processing machine. It was almost the same as -1 and 1-4, and was almost the same as the knitted fabric obtained in the comparative example using sodium hydroxide. Each example showed the same water absorption as the comparative example. Further, the amount of Ca remaining in the knitted fabric obtained in each example was extremely small as compared with that of the knitted fabric of Comparative Example 3, and the amount was extremely small in Examples 1-1 and 1-using a small processing machine. It was considerably smaller than 4. It is presumed that this is because the knitted fabric was circulated and transferred in the processing machine, and the chelating agent acted efficiently to promote the removal of Ca. Further, the amount of residual Mg was almost the same as or smaller than that of Comparative Example 3-1 and it is presumed that Mg was also efficiently removed by the chelating agent like Ca.
From these results, it was found that the chelating agent works effectively even in the scale-up treatment, a practical fiber material can be obtained without using sodium hydroxide, and in particular, the amount of residual Ca can be reduced. ..

(Example 4-1)
The fiber material obtained in Example 1-6 was subjected to a dyeing step. In the dyeing step, a dyeing solution (solvent: water having a hardness of 5 ° DH) containing the agents shown in Table 4 in the amounts shown in Table 4 was used. The dyeing step was carried out by immersing the knitted fabric in the dyeing solution at 60 ° C. for 60 minutes, a soaping step, a hot water washing / washing step, and a dehydration / drying step in this order. In the soaping step, polyethylene glycol (trade name: Scoreroll TS801C (manufactured by Kitahiro Chemical Co., Ltd.)), which is a raw material for cosmetics, was used as a soaping agent (surfactant).

(Examples 4-2 to 4-3)
The fiber materials obtained in Example 1-6 were subjected to the dyeing step in the same manner as in Example 4-1 except that the types of dyes were as shown in Table 4.
The trade names and the like of the dyes used in Examples 4-1 to 4-3 are as follows.
Dye Yellow: Brand name Kayasion Yellow CF-COMJ, manufactured by Nippon Kayaku Co., Ltd. Dye Red: Brand name Kayasion Red CF-COMJCOMJ, manufactured by Nippon Kayaku Co., Ltd. Dye Blue: Brand name Kayasion Blue CF-COMJ, Nippon Kayaku Manufactured by Co., Ltd. All of the above dyes are raw materials for cosmetics.

The fiber materials obtained in Examples 4-1 to 4-3 were evaluated for weather resistance, washing fastness, and friction fastness. The evaluation results are shown in Table 4. The weather resistance, washing fastness, and friction fastness were evaluated according to JIS L 0842 4th grade, JIS L 0844 A-2, and JIS L 0849 II, respectively.

As shown in Table 4, even when the fiber material of this example was obtained as a dyed product, the obtained fiber material had no problem in practical use. That is, when the fiber material is treated with an alkaline treatment agent that does not contain a chelating agent, a surfactant, a bleaching agent, and sodium hydroxide, the subsequent dyeing process is not affected and normal scouring and bleaching are performed. It was found that a dyed processed product similar to the case where the treatment was carried out can be obtained.

(Example 5-1)
The fiber material obtained in Example 1-1 was subjected to antibacterial treatment. For antibacterial processing, a treatment liquid prepared by mixing an aerobic carboxylic acid compound (trade name: Amorden CPC-54, manufactured by Daiwa Chemical Industry Co., Ltd.) with water so as to have a concentration of 3% by mass was used as an antibacterial agent. This was carried out by heating the fiber material at 50 ° C. for 20 minutes in this treatment liquid. The antibacterial agent used here is also used as a raw material for cosmetics.

With respect to the fiber materials obtained in Example 5-1 and Example 5-2, the antibacterial activity values after 0 times of washing and 10 times of washing were determined. The results obtained are shown in Table 5.
The antibacterial activity value was measured according to JIS L 1902.

The present embodiment includes the following aspects.
(Aspect 1)
A method for producing a fiber material containing at least one selected from natural fibers and regenerated cellulose fibers.
Preparing fiber materials for scouring and bleaching, and containing 1) chelating agent, 2) surfactant, 3) bleaching agent, and 4) sodium hydroxide-free alkaline treatment agent, initial pH 9 Treating the fibrous material with a treatment liquid of ~ 11
A method for manufacturing a textile material, including.
(Aspect 2)
The method for producing a fiber material according to embodiment 1, wherein in the treatment liquid, the chelating agent is contained in an amount of 0.3 g / liter or more and 20.0 g / liter or less with respect to 1 liter of soft water as a solvent.
(Aspect 3)
The chelating agent is selected from an aminocarboxylic acid-based chelating agent, a polyacrylic acid-based chelating agent, a phosphonic acid-based chelating agent, a dicarboxylic acid-based chelating agent, a gluconic acid-based chelating agent, and an acrylic acid / maleic acid copolymer chelating agent. The method for producing a fiber material according to aspect 1 or 2, which is at least one of the above.
(Aspect 4)
The aminocarboxylic acid-based chelating agent is at least one selected from the group consisting of ethylenediaminetetraacetic acid and its salt, diethylenetriaminetetraacetic acid and its salt, and glutamic acid diacetic acid and its salt. Method.
(Aspect 5)
The aminocarboxylic acid-based chelating agent is at least one selected from the group consisting of a sodium salt of ethylenediaminetetraacetic acid, a sodium salt of diethylenetriaminetetraacetic acid, and a sodium salt of glutamate diacetic acid, for producing the fiber material of embodiment 3. Method.
(Aspect 6)
The method for producing a fiber material according to any one of aspects 1 to 5, wherein the surfactant is at least one selected from a nonionic surfactant and an anionic surfactant.
(Aspect 7)
The method for producing a fiber material according to any one of aspects 1 to 6, wherein the alkali treatment agent is at least one selected from sodium carbonate, sodium hydrogen carbonate, and sodium percarbonate.
(Aspect 8)
The method for producing a fiber material according to any one of aspects 1 to 7, wherein the bleaching agent is hydrogen peroxide.
(Aspect 9)
In the treatment of the fiber material with the treatment liquid, the treatment liquid is put in a bath, and the fiber material is subjected to a bath ratio of 1: 5 to 1:20, a treatment temperature of 80 ° C. to 110 ° C., and a treatment time of 20 minutes to 100 minutes. The method for producing a fiber material according to any one of aspects 1 to 8, which comprises immersing the fiber material in the treatment liquid under the conditions of the above.
(Aspect 10)
The method for producing a fiber material according to any one of aspects 1 to 9, wherein one or both of the chelating agent and the surfactant is a cosmetic raw material and / or an edible raw material.
(Aspect 11)
The chelating agent is from trisodium methylglycine diacetate, sodium polyacrylate, sodium metaphosphate, 1-hydroxyethylidene-1,1-diphosphonic acid, and 4-sodium 3-hydroxy-2.2'-iminodicosuccinate. The method for producing a fiber material according to embodiment 10, which is at least one selected.
(Aspect 12)
The fiber material of aspect 10 or 11, further comprising a dyeing step, wherein at least one selected from the dyeing agent, fixing agent and surfactant used in the dyeing step is a cosmetic raw material and / or an edible raw material. Manufacturing method.
(Aspect 13)
It further includes at least one finishing step selected from a water absorption processing step using a water absorbing agent, a softening processing step using a softener, and a functional processing step using a functional agent.
The water-absorbing agent, the softener, and the functional agent are cosmetic raw materials and / or edible raw materials.
A method for producing a fiber material according to any one of aspects 10 to 12.
(Aspect 14)
A fiber material containing at least one selected from natural fibers and regenerated cellulose fibers, wherein the amount of residual metal measured by IPC spectroscopic analysis satisfies at least one of the following.
Residual amount of magnesium: 150 mg / kg or less Residual amount of calcium: 600 mg / kg or less (Aspect 15)
Fiber treatment that contains A) chelating agent, B) surfactant, and C) sodium hydroxide-free alkaline treatment agent, and can be used together with bleach to simultaneously perform refining and bleaching treatment in one bath. Agent.
(Aspect 16)
The chelating agent is selected from an aminocarboxylic acid chelating agent, a polyacrylic acid chelating agent, and an acrylic acid / maleic acid copolymer chelating agent, a phosphonic acid chelating agent, a dicarboxylic acid chelating agent, and a gluconic acid chelating agent. Is at least one
The surfactant is at least one selected from nonionic surfactants and anionic surfactants.
The alkali treatment agent is at least one selected from sodium carbonate, sodium hydrogen carbonate, and sodium percarbonate.
The fiber treatment agent of aspect 15.
(Aspect 17)
The fiber treatment agent of aspect 15 or 16, wherein the bleaching agent is hydrogen peroxide, for hydrogen peroxide bleaching treatment.
(Aspect 18)
A kit of a fiber treatment agent, wherein the fiber treatment agent according to any one of embodiments 15 to 17 is contained in one container, and the bleaching agent is contained in a container different from the fiber treatment agent.

According to the production method of the present embodiment, it is possible to obtain a fiber material from which impurities have been removed without using strongly alkaline sodium hydroxide. The present embodiment can also be applied to fibrous materials containing animal fibers. Therefore, this embodiment is useful as a method for producing various fiber materials.

Claims (18)

1. A method for producing a fiber material containing at least one selected from natural fibers and regenerated cellulose fibers.
   Preparing fiber materials for scouring and bleaching, and containing 1) chelating agent, 2) surfactant, 3) bleaching agent, and 4) sodium hydroxide-free alkaline treatment agent, initial pH 9 Treating the fibrous material with a treatment liquid of ~ 11
   A method for manufacturing a textile material, including.
2. The method for producing a fiber material according to claim 1, wherein in the treatment liquid, the chelating agent is contained in an amount of 0.3 g / liter or more and 20.0 g / liter or less with respect to 1 liter of soft water as a solvent.
3. The chelating agent is selected from an aminocarboxylic acid-based chelating agent, a polyacrylic acid-based chelating agent, a phosphonic acid-based chelating agent, a dicarboxylic acid-based chelating agent, a gluconic acid-based chelating agent, and an acrylic acid / maleic acid copolymer chelating agent. The method for producing a fiber material according to claim 1 or 2, which is at least one of the above.
4. The fiber according to claim 3, wherein the aminocarboxylic acid-based chelating agent is at least one selected from the group consisting of ethylenediaminetetraacetic acid and its salt, diethylenetriaminetetraacetic acid and its salt, and glutamic acid diacetic acid and its salt. How to make the material.
5. The fiber according to claim 3, wherein the aminocarboxylic acid-based chelating agent is at least one selected from the group consisting of a sodium salt of ethylenediaminetetraacetic acid, a sodium salt of diethylenetriaminetetraacetic acid, and a sodium salt of glutamate diacetic acid. How to make the material.
6. The method for producing a fiber material according to any one of claims 1 to 5, wherein the surfactant is at least one selected from a nonionic surfactant and an anionic surfactant.
7. The method for producing a fiber material according to any one of claims 1 to 6, wherein the alkali treatment agent is at least one selected from sodium carbonate, sodium hydrogen carbonate, and sodium percarbonate.
8. The method for producing a fiber material according to any one of claims 1 to 7, wherein the bleaching agent is hydrogen peroxide.
9. In the treatment of the fiber material with the treatment liquid, the treatment liquid is put in a bath, and the fiber material is subjected to a bath ratio of 1: 5 to 1:20, a treatment temperature of 80 ° C. to 110 ° C., and a treatment time of 20 minutes to 100 minutes. The method for producing a fiber material according to any one of claims 1 to 8, which comprises immersing the fiber material in the treatment liquid under the conditions of the above.
10. The method for producing a fiber material according to any one of claims 1 to 9, wherein one or both of the chelating agent and the surfactant is a cosmetic raw material and / or an edible raw material.
11. The chelating agent is from trisodium methylglycine diacetate, sodium polyacrylate, sodium metaphosphate, 1-hydroxyethylidene-1,1-diphosphonic acid, and 4-sodium 3-hydroxy-2.2'-iminodicosuccinate. The method for producing a fiber material according to claim 10, which is at least one selected.
12. 10. The claim 10 or 11, further comprising a dyeing step, wherein at least one selected from the dyeing agent used in the dyeing step, the fixing agent and the surfactant used in the soaping step is a cosmetic raw material and / or an edible raw material. Method of manufacturing fiber materials.
13. It further includes at least one finishing step selected from a water absorption processing step using a water absorbing agent, a softening processing step using a softener, and a functional processing step using a functional agent.
    The water-absorbing agent, the softener, and the functional agent are cosmetic raw materials and / or edible raw materials.
    The method for producing a fiber material according to any one of claims 10 to 12.
14. A fiber material containing at least one selected from natural fibers and regenerated cellulose fibers, wherein the amount of residual metal measured by IPC spectroscopic analysis satisfies at least one of the following.
    Residual amount of magnesium: 150 mg / kg or less Residual amount of calcium: 600 mg / kg or less
15. Fiber treatment that contains A) chelating agent, B) surfactant, and C) sodium hydroxide-free alkaline treatment agent, and can be used together with bleach to simultaneously perform refining and bleaching treatment in one bath. Agent.
16. The chelating agent is selected from an aminocarboxylic acid chelating agent, a polyacrylic acid chelating agent, and an acrylic acid / maleic acid copolymer chelating agent, a phosphonic acid chelating agent, a dicarboxylic acid chelating agent, and a gluconic acid chelating agent. Is at least one
    The surfactant is at least one selected from nonionic surfactants and anionic surfactants.
    The alkali treatment agent is at least one selected from sodium carbonate, sodium hydrogen carbonate, and sodium percarbonate.
    The fiber treatment agent according to claim 15.
17. The fiber treatment agent according to claim 15 or 16, wherein the bleaching agent is hydrogen peroxide, for hydrogen peroxide bleaching treatment.
18. A kit of a fiber treatment agent, wherein the fiber treatment agent according to any one of claims 15 to 17 is contained in one container, and the bleaching agent is contained in a container different from the fiber treatment agent.

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