JP2024050135A - Fiber composition and method for producing the same - Google Patents

Abstract

To provide a dyed fiber composition containing polyamide-based fibers excellent in deodorizing function and hardly causing color bleeding, and a method for producing the same.SOLUTION: A dyed fiber composition containing polyamide-based fibers and phosphate is characterized in that the intensity ratio A/B of the diffraction peak a having a crystal plane spacing within the range of 1.30 nm to 1.80 nm to the diffraction peak b having a crystal plane spacing within the range of 0.60 nm to 0.85 nm in X-ray diffraction analysis of the phosphate is 0 or more and less than 1.0, and the color bleeding in a color bleeding test by Daimaru method for the dyed fiber composition is grade 4 or higher.SELECTED DRAWING: None

Description

The present invention relates to a fiber composition and a method for producing the same.

In recent years, due to the increasing demand for comfort, attention has been focused on textile products with deodorizing functions in the field of clothing. For example, the following Patent Document 1 discloses a processing recipe for recovering the deodorizing function reduced by processing in a textile product with deodorizing function containing phosphate.
Meanwhile, fiber compositions containing polyamide fibers are generally dyed with acid dyes, and metal-containing dyes, which are a type of acid dye, are used particularly in the field of dark colors. In addition, in order to prevent discoloration and staining due to the fall-off of the dye, a fixing agent is generally used to carry out a fixing treatment after dyeing. However, while fiber compositions containing polyamide fibers dyed by such a method have excellent deodorizing function, washing fastness, sweat fastness, water fastness, etc., there are still problems such as "friction fastness" which indicates the ease of staining due to contact or rubbing between textile products, and so-called "bleeding" in which the dye moves from the dark dyed part to the white or light colored part when the product gets wet by washing.

In recent years, a method of dyeing a fiber composition containing polyamide fibers using a reactive dye and then carrying out a fixing treatment under alkaline conditions has become widespread as a means of improving the friction fastness and suppressing bleeding. For example, the following Patent Documents 2 and 3 disclose dyeing and fixing treatment recipes using reactive dyes to solve problems with washing fastness, sweat fastness, and bleeding.

JP 2021-181670 A Chinese Patent No. 109112854 JP 2011-001652 A

However, Patent Documents 1 to 3 do not disclose any technology for preventing color bleeding in dyed fiber compositions containing polyamide fibers and for allowing the compositions to fully exhibit their deodorizing function.
In view of the above-mentioned conventional state of the art, the problem to be solved by the present invention is to provide a dyed fiber composition containing polyamide-based fibers, which has excellent deodorizing function and is less likely to cause color bleeding, and a method for producing the same.

As a result of intensive research and repeated experiments to solve the above problems, the inventors unexpectedly discovered that the above problems can be solved when a phosphate contained in a dyed fiber composition containing polyamide-based fibers, which is less prone to bleeding, has a specific crystal plane spacing and diffraction peak intensity ratio in X-ray diffraction analysis, and thus completed the present invention.

That is, the present invention is as follows.
[1] A dyed fiber composition comprising a polyamide fiber and a phosphate, characterized in that in an X-ray diffraction analysis of the phosphate, the intensity ratio A/B of a diffraction peak a having a crystal plane spacing in the range of 1.30 nm to 1.80 nm and a diffraction peak b having a crystal plane spacing in the range of 0.60 nm to 0.85 nm is 0 or more and less than 1.0, and the dyed fiber composition has a bleeding level of grade 4 or higher in a bleeding test using the Daimaru method.
[2] The fiber composition described in [1], wherein the intensity ratio A/B is 0.
[3] The fiber composition according to [1] or [2], comprising polyurethane elastic fibers containing a phosphate.
[4] The fiber composition according to any one of [1] to [3], wherein the ammonia gas reduction rate according to the ISO 17299-2 detection tube method is 70% or more before and after 10 home washings.
[5] The fiber composition according to any one of [1] to [4], which has a fastness of grade 4 or higher in a dry and wet friction fastness test according to JIS L 0849.
[6] the steps of:
A dyeing step of dyeing a fiber composition containing a polyamide fiber and a phosphate with a reactive dye;
A method for producing a fiber composition according to any one of [1] to [5] above, comprising:
[7] The steps of:
a fixing step in which fixing is carried out in an acidic solution after the dyeing step;
The method according to [6] above, further comprising:
[8] The method according to [6] above, wherein no fixing treatment is carried out after the dyeing step.

The present invention provides a dyed fiber composition containing polyamide fibers that has good deodorizing properties and is less prone to bleeding, and a method for producing the same.

1 shows the results of X-ray diffraction analysis of the phosphate contained in the fiber composition of Example 1. 1 shows the results of X-ray diffraction analysis of the phosphate contained in the fiber composition of Comparative Example 1.

Hereinafter, an embodiment of the present invention will be described in detail.
One embodiment of the present invention is a dyed fiber composition comprising a polyamide fiber and a phosphate, wherein the phosphate has an intensity ratio A/B of a diffraction peak a having a crystal plane spacing in the range of 1.30 nm to 1.80 nm and a diffraction peak b having a crystal plane spacing in the range of 0.60 nm to 0.85 nm in an X-ray diffraction analysis of the phosphate, which is 0 or more and less than 1.0, and wherein the dyed fiber composition has a bleeding level of grade 4 or higher in a bleeding test by the Daimaru method.

[Fiber composition]
The fiber composition of the present embodiment is a composition containing fibers, and the structure and shape are not limited, and examples thereof include fabric-like, belt-like, string-like, thread-like, and composite materials containing them, but are preferably fabric-like woven or knitted fabrics or nonwoven fabrics. The fiber composition only needs to contain at least polyamide-based fibers and phosphate, and may contain other fibers depending on the purpose, for example, natural fibers, regenerated fibers, synthetic fibers, and semi-synthetic fibers. The content ratio of these fibers in the fiber composition is not particularly limited.

[Phosphate]
The phosphate contained in the fiber composition of the present embodiment is not particularly limited as long as it is a known phosphate, and examples thereof include zirconium phosphate, zirconium polyphosphate, zirconium pyrophosphate, zirconium silicate phosphate, hafnium phosphate, thorium phosphate, cerium phosphate, titanium phosphate, tin phosphate, chromium phosphate, and chromium polyphosphate.

The phosphate contained in the fiber composition of this embodiment may have a diffraction peak (hereinafter also referred to as "diffraction peak a") in the crystal plane spacing range of 1.30 nm to 1.80 nm in X-ray diffraction analysis. Diffraction peak a is preferably in the crystal plane spacing range of 1.34 nm to 1.80 nm, more preferably in the range of 1.34 nm to 1.77 nm. Since the presence of diffraction peak a reduces the deodorizing function of the fiber composition containing the phosphate, the smaller the intensity value, the more preferable, and it is most preferable that the fiber composition does not have diffraction peak a.

In addition, in X-ray diffraction analysis, the phosphate has a diffraction peak (hereinafter also referred to as "diffraction peak b") with a crystal plane spacing in the range of 0.60 nm to 0.85 nm. Diffraction peak b is preferably in the range of 0.70 nm to 0.85 nm, and more preferably in the range of 0.70 nm to 0.80 nm. By having diffraction peak b, the fiber composition containing the phosphate can exhibit good deodorizing function, so it is preferable that its intensity value is greater than that of diffraction peak a.

The intensity ratio A/B of the diffraction peak a and the diffraction peak b is preferably 0 or more and less than 1.0, 0 or more and less than 0.9, 0 or more and less than 0.8, 0 or more and less than 0.7, 0 or more and less than 0.6, 0 or more and less than 0.5, 0 or more and less than 0.4, 0 or more and less than 0.3, 0 or more and less than 0.2, or 0 or more and less than 0.1, and is most preferably 0. If the intensity ratio A/B is 0 or more and less than 1.0, the dyed fiber composition can fully exhibit its deodorizing function.

The phosphate may be contained inside the fibers constituting the fiber composition, or may be contained on the surface of the fiber composition by post-processing or the like.
The fiber composition of the present embodiment can contain an amount of phosphate according to the required deodorizing performance. For example, the phosphate content of the fiber composition can be 0.05 g/ ^m2 or more, preferably 0.08 g/ ^m2 or more, or 7.50 g/ ^m2 or less.

[Polyamide fiber]
The polyamide fibers contained in the fiber composition of the present embodiment are not particularly limited as long as they are known polyamide fibers, and include those generally called nylon. Specifically, various types of polyamide resins, such as polycondensates of lactams, polycondensates of diamine compounds and dicarboxylic acids, and polycondensates of ω-aminocarboxylic acids, or copolymer polyamide resins or blends thereof, are used as the main component, and examples of the synthetic polyamide fibers include polyamide homopolymers and copolymers typified by nylon 4, 6, 11, 12, 46, 66, 610, 612, nylon 6T, nylon 6I, nylon 9T, nylon M5T, nylon MXD6, nylon MXD7, nylon MXD8, nylon MXD9, nylon MXD10, nylon MXD12, nylon PXD6, nylon PXD7, nylon PXD8, nylon PXD9, nylon PXD10, nylon PXD12, and the like, as well as blends thereof; and natural polyamide fibers, such as silk and wool, can be appropriately selected depending on the application.

The form of the polyamide fiber may be long or short, may be uniform in the length direction or may vary in thickness, and may be polygonal (e.g., round, triangular, L-shaped, T-shaped, Y-shaped, W-shaped, eight-lobed, flat, dog-bone, etc.), multi-lobed, hollow, or irregular in cross section.Furthermore, examples of the form of the yarn include spun yarns such as ring spun yarns and open-end spun yarns, multifilament raw yarns (including ultrafine yarns), loosely twisted yarns to hard twisted yarns, mixed yarns, false twisted yarns, air jet textured yarns, etc.
As long as the desired effects of the present invention are not impaired, the polyamide fiber may contain pigments such as carbon black and titanium oxide, stabilizers such as antioxidants, color inhibitors, and light fasteners, as well as other functional agents such as antistatic agents.

[Other fibers]
When the phosphate is contained inside the fiber, the fiber is not particularly limited, and examples thereof include synthetic fibers such as polyester, polyamide, polyolefin, and acrylic polymers, polyurethane elastic fibers, semi-synthetic fibers such as acetate, and regenerated fibers such as regenerated cellulose, but polyurethane elastic fibers are preferred.
The polyurethane constituting the polyurethane elastic fiber is not particularly limited as long as it has a structure polymerized from, for example, a diisocyanate component, a diol component, a chain extender component, etc., and can be appropriately selected according to the application. The chain extender component can be a generally known diamine, a low molecular weight diol, an amino alcohol having both an amino group and a hydroxyl group, etc. Examples of the polyurethane polymer can be a polyurethane urea structure polymerized from a diisocyanate, a high molecular weight diol, a diamine, etc., or a polyurethane urethane structure polymerized from a diisocyanate, a high molecular weight diol, a low molecular weight diol, etc. In addition, alcohols or isocyanates having three or more functionalities can be used according to the purpose within a range that does not interfere with the desired effects of the present invention, and the copolymer can be a copolymer containing a structure such as a tertiary amine, or a structure into which an ionic group such as a sulfo group is introduced.

Examples of diisocyanate components include, but are not limited to, aromatic diisocyanates, alicyclic diisocyanates, and aliphatic diisocyanates. Examples of aromatic diisocyanates include, but are not limited to, diphenylmethane diisocyanate (hereinafter also referred to as "MDI"), tolylene diisocyanate, 1,4-diisocyanate benzene, xylylene diisocyanate, and 2,6-naphthalene diisocyanate. Examples of alicyclic diisocyanates and aliphatic diisocyanates include methylene bis (cyclohexyl isocyanate), isophorone diisocyanate, methylcyclohexane 2,4-diisocyanate, methylcyclohexane 2,6-diisocyanate, cyclohexane 1,4-diisocyanate, hexahydroxylylene diisocyanate, hexahydrotolylene diisocyanate, and octahydro 1,5-naphthalene diisocyanate. These diisocyanates may be used alone or in combination of two or more.

The diol component is not limited to the following, but examples thereof include high molecular weight diols such as polyether diols, polyester diols, polycarbonate diols, polyacrylic diols, polythioester diols, and polyhydrocarbon diols, and low molecular weight diols such as ethylene glycol, 1,3-propanediol, 1,4-butanediol, bishydroxyethoxybenzene, bishydroxyethylene terephthalate, and 1-methyl-1,2-ethanediol. These diols may be used alone or in combination of two or more. These low molecular weight diols may also be used as chain extenders.

Examples of the diamine component include, but are not limited to, hydrazine, ethylenediamine, 1,2-propanediamine, 1,3-propanediamine, 2-methyl-1,5-pentanediamine, 1,2-diaminobutane, 1,3-diaminobutane, 1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, 2,2-dimethyl-1,3-diaminopropane, 1,3-diamino-2,2-dimethylbutane, 2,4-diamino-1-methylcyclohexane, 1,3-pentanediamine, 1,3-cyclohexanediamine, bis(4-aminophenyl)phosphine oxide, hexamethylenediamine, 1,3-cyclohexyldiamine, hexahydrometaphenylenediamine, 2-methylpentamethylenediamine, and bis(4-aminophenyl)phosphine oxide. These diamines may be used alone or in combination of two or more.
The amino alcohol is not particularly limited as long as it has a primary amino group or a secondary amino group.

The method of polymerizing polyurethane using these raw materials is not particularly limited, and may be a melt polymerization method or a solution polymerization method. In the case of the solution polymerization method, for example, a polyurethane solution can be obtained by performing polymerization using raw materials such as diisocyanate, polymer polyol, diol, and diamine in a solvent such as DMAc, DMF, DMSO, and NMP. In addition, the reaction method when polymerizing polyurethane is not particularly limited, but examples thereof include a one-shot method in which each raw material is put into a solvent and reacted at an appropriate temperature, and a prepolymer method in which a diisocyanate and a polymer polyol are reacted to form a prepolymer, and then a chain extension reaction is performed with a diol or a diamine to synthesize polyurethane.
The method for spinning the polyurethane elastic fiber is not particularly limited, and examples of the spinning method include a method in which polyurethane is dissolved in a solvent and spun by a wet method or a dry method, and a method in which polyurethane is heated and melted and spun by a melt method.

One example of a method for producing polyurethane elastic fibers containing a phosphate is to mix a phosphate into a polyurethane polymer solution and spin the mixture by a dry spinning method.
The polyurethane elastic fiber may be externally coated with an oil agent for polyurethane elastic fiber by a conventionally known method during spinning. An example of a method for coating the oil agent is a method using an oiling roller. The oil agent components used here are not limited to the following, but may be used in combination with various kinds of oil agents, such as silicone-based oils such as dimethyl silicone, polyether-modified silicone, and polyamino-modified silicone, mineral oils, talc, silica, and mineral fine particles such as colloidal alumina, higher fatty acid metal salt powders such as magnesium stearate and calcium stearate, higher fatty acid carboxylic acids, higher aliphatic alcohols, and waxes that are solid at room temperature such as paraffin polyethylene.

The polyurethane elastic fiber may be in the form of a long fiber or a short fiber, and the fineness is not particularly limited, and may be uniform in the length direction or may vary in thickness. The cross section may be a polygonal shape such as a round shape, a triangular shape, an L shape, a T shape, a Y shape, a W shape, an eight-lobed shape, a flat shape, a dog-bone shape, a multi-lobed shape, a hollow shape, or an indefinite shape. Furthermore, the polyurethane elastic fiber may be in the form of a known covered yarn, such as a bare yarn covered with another fiber, for example, a so-called covered yarn (single or double covered), a ply-twisted yarn, a core yarn, or an intertwined yarn.
Furthermore, within the scope of not impairing the desired effects of the present invention, known organic or inorganic compounds used in polyurethane elastic fibers, such as polymers other than polyurethane, antioxidants, heat stabilizers, antistatic agents, light resistance agents, ultraviolet absorbers, gas discoloration inhibitors, dyes, activators, matting agents, colorants, fillers, anti-tack agents, lubricants, etc. may be contained.

[Rubbing fastness]
The fiber composition of the present embodiment preferably has a dry and wet friction fastness test according to JIS L 0849 of grade 4 or higher.

[Color bleeding]
The fiber composition of the present embodiment has a grade of 4 or higher in the color bleeding test by the Omaru method.

[Ammonia gas reduction rate]
The fiber composition of the present embodiment preferably has an ammonia gas reduction rate of 70% or more before washing and after 10 home washings, as measured by the ISO 17299-2 detection tube method.

[Dyeing and processing]
The dyeing treatment for producing the fiber composition of this embodiment is preferably a dyeing treatment using a reactive dye, from the viewpoint of obtaining a fiber composition having dry and wet friction fastness of grade 4 or higher and color bleeding of grade 4 or higher.
Examples of reactive dyes include those having at least one reactive group that forms a covalent bond with a hydroxyl group or an amino group, such as a monochlorotriazine group, a monofluorotriazine group, a carboxypyridiniotriazine group, a dichlorotriazine group, a vinylsulfone group, a sulfatoethylsulfone group, a fluorochloropyrimidine group, a trichloropyrimidine group, a bromoacrylamide group, etc. Specific examples include the ERIOFAST series manufactured by HUNTSMAN.

Examples of fixing agents used in the adhesion process include, but are not limited to, CIBAFIX ECO, ERIOFAST FIX, ALBAFIX ECO, NOAHFIX NCF, SCIBATEX RN, NEOFIX KM-11, CENKA FIX 401, CENKA FIX SZ-2, CENKA FIX E-300, NYLON FIX TH, NEOFIX R-250, NEOFIX R-800, NEOFIX RD-5, NEOFIX CF-20, NEOFIX KM-11, NEOFIX RP-70, NEOFIX RP-70C, SUNLIFEX FW, SUNLIFEX TN, SUNLIFEX TN-8, SUNLIFEX E-37, SUNLIFEX E-48, SUNLIFEX EPS-3, SUNLIFEX TA200, SZ-9904, and TANNIN SS.

The conditions for dyeing with a reactive dye are not particularly limited, and known processing temperatures, heating rates, dyeing times, and the like, as disclosed in Patent Documents 2 and 3, can be applied, and the dyeing operation can be carried out using an apparatus such as a winch, jigger, beam dyeing machine, or liquid flow dyeing machine.
In addition, during dyeing, auxiliaries such as calcium chloride and various surfactants, and pH adjusters such as acetic acid may be used in combination, and the dyes and the amounts and concentrations thereof are not particularly limited.
Usually, in order to suppress the bleeding of a fiber composition containing polyamide fibers, a fixing treatment is performed under alkaline conditions after dyeing with a reactive dye. However, in the production of the fiber composition of this embodiment, from the viewpoint of obtaining a fiber composition with ammonia gas reduction rate of 70% or more after unwashed and 10 home washes, it is preferable to perform a fixing treatment under acidic conditions or not perform a fixing treatment after dyeing with a reactive dye. When performing a fixing treatment under acidic conditions, it is preferable to adjust the pH of the treatment liquid to less than 7 using a pH adjuster such as acetic acid. After the fixing treatment, washing with soda ash, hot water washing, neutralization, water washing, etc. may be performed. Even if the fixing treatment is not performed, the above-mentioned washing with soda ash, hot water washing, neutralization, and water washing can be performed arbitrarily.

In the manufacture of the fiber composition of this embodiment, in addition to the usual processing, treatments for imparting specific functionality, such as treatments using functionalizing agents such as softeners, antistatic agents, water absorbents, and sewability improvers, can be performed within the scope of not impairing the desired effects. The conditions for these treatments can be adjusted as desired depending on the type of material that constitutes the fiber composition.

The present invention will be specifically described below based on examples and comparative examples, but the present invention is not limited to these examples.
First, the test and evaluation methods used in the examples will be described.

(1) Deodorizing function (reduction rate of ammonia gas before washing and after 10 home washes using the ISO 17299-2 detection tube method)
(Washing Instructions)
In accordance with the standard washing method described in the SEK Mark Textile Product Washing Method (established by: General Incorporated Association Textile Evaluation Technology Council, Product Certification Department, revised on April 1, 2022), a household electric washing machine specified in washing method 103 described in JIS L 0217:1995 "Display symbols for handling textile products and their display methods" was used, and 40 mL of JAFET standard blended detergent (blended with polyoxyethylene alkyl ether and sodium alpha-olefin sulfonate) was added to 30 L of water at 40°C to make a washing liquid, and the sample and, if necessary, a load cloth were added so that the liquor ratio was 1:30. The process of washing for 5 minutes, spin-drying, rinsing for 2 minutes, spin-drying for 2 minutes, and spin-drying was repeated 10 times, and then air-dried.
(Sample preparation)
Test pieces of 0.1 g were taken from each of the samples before and after washing, and were conditioned at a temperature of 20° C. and a relative humidity of 65% for 24 hours before being used for measurement.
(Measuring method)
In accordance with the deodorizing test described in the SEK Mark Textile Product Certification Standard (established by: General Incorporated Association Textile Evaluation Technology Council Product Certification Department, revised on April 1, 2022), the deodorizing properties of odor components were evaluated by the detector tube method. Ammonia was used as the odor component. The initial concentration of the odor component was 100 ppm of ammonia.
For the blank test, a 5L sample bag (made of film) was filled with 3L of odorous components, sealed, and left for 2 hours, after which the remaining gas concentration was measured using a gas detector tube compatible with ammonia, and this was taken as the blank test concentration. Next, the sample to be used for the measurement (10cm x 10cm) was placed in a sample bag (made of film), filled with the odorous components of the above-mentioned predetermined concentration, sealed, and the remaining gas concentration after 2 hours was measured using a gas detector tube, and this was taken as the measured concentration. The measurement was carried out three times, and the average value was used to calculate the following formula:
Deodorizing component reduction rate (%) = ((blank test concentration - measured concentration of each sample) / blank test concentration)) x 100
The reduction rate of the residual gas concentration was calculated and expressed as the reduction rate. In the examples, a reduction rate of 70% or more of the ammonia deodorizing component was judged to be acceptable.

(2) Rubbing fastness (dry and wet rubbing fastness test according to JIS L 0849)
(Sample preparation)
A test piece of 220 cm x 30 mm was taken and conditioned for 24 hours at a temperature of 20° C. and a relative humidity of 65% before use in the measurement. In addition, a white cotton cloth of 60 mm x 60 mm conforming to JIS L 0803 was prepared as a cotton cloth for friction and conditioned in the same manner as the test piece.
(Method of Determination)
Using the above test piece and white cotton cloth, friction tests were carried out in dry and wet conditions according to the friction tester type II (Gakushin type) method. Specifically, the test piece was attached to a base, and the white cotton cloth for friction was attached to the tip of the friction element, and friction was carried out 100 times at a speed of 30 times/min over the central 100 mm of the test piece with a load of 2.0 N. After the friction test, the staining level of the attached white cotton cloth was graded using the staining gray scale. In the case of a wet condition, the white cotton cloth for friction was wetted with water to make it 100% wet, and then the friction test was carried out in the same manner as in the dry condition, and the white cotton cloth used in the friction test was air-dried before the grade was judged. In the examples, grade 4 or higher was considered to be pass.

(3) Bleeding (bleeding test using the Daimaru method)
(Sample preparation)
A sample of the fiber composition measuring 2.5 cm x 3.0 cm was taken, and overlapped by 1.5 cm on a piece of Kanakin No. 3 cotton cloth (2.5 cm x 10 cm or more) conforming to JIS 0803, and sewn together to prepare a test piece.
(Method of Determination)
A 50 ml portion of a 0.05% aqueous solution of a nonionic surfactant was prepared in a beaker, and 2.0 cm of one end of the sewn test piece was vertically immersed in the solution. The test piece was left at room temperature for 2 hours, after which the beaker was removed and the piece was dried in that state. The degree of the most severe staining of the white part of the cotton fabric was graded using a gray scale for staining. In the examples, grades 4 and above were considered to be acceptable.

(4) In the X-ray diffraction analysis of a phosphate, the intensity ratio A/B of a diffraction peak a corresponding to a crystal plane spacing of 1.30 nm to 1.80 nm and a diffraction peak b corresponding to a crystal plane spacing of 0.60 nm to 0.85 nm
(Analysis equipment and conditions)
Equipment: Rigaku Ultima-IV
X-ray source: Cu-Kα rays Filter: Ni foil Tube voltage and current: Voltage 40 kV, current 40 mA
Optical system: Concentrated optical system Detector: D/teX Ultra (one-dimensional detector)
Absorber: None Analysis method: θ/2θ method Slit: DS = 1/2°, SS = open, vertical slit = 10 mm
Camera length: 285mm
Scanning range: 5 to 35°
Scan step: 0.02°

｛式中、ｄ：結晶面間隔／ｎｍ、ｎ：回折次数、λ：Ｘ線波長／ｎｍ、θ：ブラッグ角／ｒａｄである。｝。
を用いて求めた。 (Sample preparation)
Only the fibers containing phosphate were collected from the fiber composition, placed on a sample stage so as to be as smooth as possible, and subjected to X-ray diffraction analysis under the above-mentioned conditions.
(Analysis conditions)
The obtained X-ray diffraction profile was fitted under the conditions shown below to obtain information on the crystal plane spacing.
<Diffraction peak near 2θ=6°>
The fitting range was set to 2θ=5.0-6.6°, and a straight line was drawn as the baseline, followed by a single diffraction peak, and a Gaussian function was used. This peak was designated as peak a, and its top intensity value was designated as A.
<Diffraction peak near 2θ=12°>
The fitting range was set to 2θ=10.8-12.7°, and a straight line was drawn as the baseline, followed by a single diffraction peak, and a Gaussian function was used. This peak was designated as peak b, and its top intensity value was designated as B.
The crystal plane spacing is expressed by the following Bragg formula:

{In the formula, d is the crystal plane spacing/nm, n is the diffraction order, λ is the X-ray wavelength/nm, and θ is the Bragg angle/rad.}.
was calculated using

[Example 1]
A polyurethane elastic fiber containing 4.5% by mass of phosphate was obtained by mixing α-zirconium phosphate with a polyether polyurethane urea solution and then dry spinning the mixture. A russell warp knitting machine RSE-4N-1 56 gauge/inch manufactured by Karl Mayer was used to produce a russell warp knitted fabric having the following composition.
(Grey Fabric Composition)
Nylon 6 (44 decitex 48 filaments): 72.1%
Polyurethane elastic yarn containing phosphate (44 decitex): 7.4%
Regular polyurethane elastic yarn (155 decitex): 11.1%
Regular polyurethane elastic yarn (255 decitex): 9.4%

The obtained greige fabric was scoured in a multi-tank continuous scourer at a maximum temperature of 90°C for about 1 minute, and then pre-set at 188°C for 72 seconds. Then, dyeing with reactive dyes, soaping, neutralization, and water-absorbing agent application were performed, and finally, the water-absorbing agent was padded and final setting was performed, resulting in a dyed fiber composition containing about 0.54 g/ ^m2 of phosphate. The processing conditions for each process are shown below.
(Dyeing treatment)
Dye: ERIOFAST BLACK M (manufactured by HUNTSMAN) 4.55% owf
Dye: ERIOFAST BLUE 3G (manufactured by HUNTSMAN) 0.20% owf
Auxiliary agent: ALBAFLOW FFW (manufactured by HUNTSMAN) 0.50 g/L
Auxiliary agent: NICEPOLE PRS (manufactured by Nicca Chemical Co., Ltd.) 2.00% owf
Auxiliary agent: calcium chloride 1.20% owf
pH adjuster: acetic acid 1.00 g/L
Bath ratio: 1:12
Temperature: 100°C
Duration: 40 minutes

(Soaping treatment)
Auxiliary agent: RUCOGAL PAA (manufactured by RUDOLF) 1.00 g/L
pH adjuster: soda ash 1.00g/L
Bath ratio: 1:12
Temperature: 80°C
Time: 20 minutes

(Neutralization treatment)
pH adjuster: acetic acid 0.50 g/L
Temperature: 50°C
Time: 20 minutes (water absorbing agent application treatment)
Water absorbent: NICEPOLE PRS (manufactured by Nicca Chemical Co., Ltd.) 3.00% owf
pH adjuster: acetic acid 1.00 g/L
Temperature: 50°C
Time: 20 minutes (final set)
Auxiliary agent: HV (manufactured by CLARIANT) padding 0.50 g/L
Temperature: 160°C
Time: 36 seconds

[Example 2]
The fabric was finished under the same conditions as in Example 1, except that the fixing treatment described below was added between the dyeing treatment and the soaping treatment.
(Fixing treatment)
Fixing agent: ERIOFAST FIX (manufactured by HUNTSMAN) 1.00 g/L
pH adjuster: acetic acid Adjust the pH of the treatment bath to 4.0 Bath ratio: 1:12
Temperature: 90°C
Time: 20 minutes

[Comparative Example 1]
The finishing was carried out under the same conditions as in Example 2, except that the fixing treatment was changed to the following conditions.
(Fixing treatment)
Fixing agent: ERIOFAST FIX (manufactured by HUNTSMAN) 1.00 g/L
pH adjuster: caustic soda 0.20g/L
Bath ratio: 1:12
Temperature: 90°C
Time: 20 minutes

[Comparative Example 2]
The preparation, scouring and presetting of the raschel warp knitted fabric were carried out under the same conditions as in Example 1, but the dyeing process and subsequent steps were changed to the following conditions using a metal-containing dye.
(Dyeing treatment)
Dye: ISOLAN BLACK 2S-LD (manufactured by DYSTER) 2.50% owf
Auxiliary agent: Ammonium sulfate 4.00% owf
Bath ratio: 1:12
Temperature: 100°C
Time: 60 minutes (fixing treatment)
Fixing agent: Nylonfix 501 (manufactured by Senka Co., Ltd.) 5.00% owf
Temperature: 90°C
Time: 20 minutes (soaping process)
Auxiliary agent: New Sunrex E (manufactured by Nicca Chemical Co., Ltd.) 2.00 g/L
Bath ratio: 1:12
Temperature: 60°C
Time: 30 minutes (final set)
Auxiliary agent: HV (manufactured by CLARIANT) padding 0.50 g/L
Temperature: 160°C
Time: 36 seconds

The results of various evaluation tests of the fiber compositions obtained in the Examples and Comparative Examples are shown in Table 1 below.

In Examples 1 and 2, peak a was not observed, the intensity ratio A/B with peak b was 0, the ammonia gas reduction rate was 70% or more before washing and after 10 home washings, the dry and wet friction fastness was grade 4 or more, and the color bleeding was grade 4 or more. In contrast, in Comparative Example 1, as shown in Figure 2, the intensity ratio A/B of peak a and peak b was 1.0 or more, and the ammonia gas reduction rate was less than 70% before washing and after 10 home washings, which was unacceptable. In Comparative Example 2, no reactive dye was used, and the ammonia gas reduction rate was 70% or more, which was acceptable, but the friction fastness and color bleeding in a wet state were less than grade 4, which was unacceptable.
From the above results, it can be seen that the fiber compositions of Examples 1 and 2 have better deodorizing properties, are less susceptible to color bleeding, and are also superior in friction fastness compared to the fiber compositions of Comparative Examples 1 and 2.

The fiber composition of the present invention has excellent deodorizing properties, is less likely to bleed when the entire fabric becomes wet due to sweat or washing, and is highly resistant to contamination caused by contact or friction between clothes when worn in layers, making it suitable for use in sportswear, underwear, etc.

Claims (8)

A dyed fiber composition comprising a polyamide fiber and a phosphate, characterized in that the intensity ratio A/B of the diffraction peak a in which the crystal plane spacing is in the range of 1.30 nm to 1.80 nm and the diffraction peak b in which the crystal plane spacing is in the range of 0.60 nm to 0.85 nm in an X-ray diffraction analysis of the phosphate is 0 or more and less than 1.0, and the dyed fiber composition has a bleeding level of grade 4 or higher in a bleeding test using the Daimaru method. The fiber composition according to claim 1, wherein the strength ratio A/B is 0. The fiber composition according to claim 1 or 2, comprising polyurethane elastic fibers containing phosphate. The fiber composition according to claim 1 or 2, in which the ammonia gas reduction rate measured before washing and after 10 home washings is 70% or more according to the ISO 17299-2 detection tube method. The fiber composition according to claim 1 or 2, which has fastness of grade 4 or higher in the dry and wet friction fastness test according to JIS L 0849. The following steps:
A dyeing step of dyeing a fiber composition containing a polyamide fiber and a phosphate with a reactive dye;
A method for producing the fiber composition according to claim 1 or 2, comprising: The following steps:
a fixing step in which fixing is carried out in an acidic solution after the dyeing step;
The method of claim 6 further comprising: The method according to claim 6, in which no fixing treatment is performed after the dyeing step.

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