JPWO2000058535A1 - Acrylic synthetic fibers, their uses, and manufacturing method for acrylic synthetic fibers - Google Patents

Abstract

(57) [Abstract] The present invention provides an acrylic synthetic fiber characterized by containing 0.5 to 20.0 weight % of a fine powder having an apparent specific gravity of 0.5 g/cm3 or ^less and an average particle size of 0.5 to 10 μm, the active ingredient of which is a metal silicate or a metal aluminosilicate. The present invention combines three functions highly desired by consumers: deodorizing performance, antibacterial/antimicrobial performance, and water/sweat absorption, thereby providing a higher quality, safer, more hygienic, healthier, and more comfortable lifestyle.

Description

[Detailed Description of the Invention] TECHNICAL FIELD The present invention relates to a composite high-performance acrylic synthetic fiber that combines three functions, namely, deodorizing performance, antibacterial/antimicrobial performance, and water/sweat absorption performance, and has excellent washing durability, as well as a method for producing the same and a nonwoven fabric.

BACKGROUND ART Acrylic synthetic fibers are widely used in clothing, bedding, and interior decoration.
In these applications, deodorizing, antibacterial/antimicrobial, and water- and sweat-absorbing properties are essential for a comfortable and healthy lifestyle. Up until now, products have been marketed that claim to combine deodorizing fibers, antibacterial/antibacterial fibers, and water- and sweat-absorbing fibers through blending, blending, interweaving, and interknitting, as well as products that claim to combine functions by post-processing single-functional materials. However, these require special equipment and production technology, and are therefore expensive and not economical.

Conventionally, acrylic synthetic fibers having both antibacterial and deodorizing properties and textile products containing the same are described in Japanese Patent Laid-Open Nos. 9-87924 and 9-157978. These relate to acrylic synthetic fibers containing metal silicates or metal aluminosilicates, but the water absorbency and sweat absorbency of the textile products described in these publications alone are insufficient.

The present inventors have worked to improve the above technology and have discovered that an acrylic synthetic fiber containing a fine powder containing, as an active ingredient, a metal silicate or metal aluminosilicate having a specific apparent specific gravity has better antibacterial and fungicidal properties and deodorizing properties than conventional acrylic synthetic fibers, and further has excellent water and sweat absorption properties, leading to the invention of the present application.

The object of the present invention is to provide a composite high-performance acrylic synthetic fiber that combines deodorizing performance, antibacterial/antimicrobial performance, and water/sweat absorption performance, which are highly demanded by consumers for a safe, hygienic, healthy, and comfortable lifestyle, and that has excellent washing durability, as well as a method for producing the same, and a nonwoven fabric therefrom.

DISCLOSURE OF THE INVENTION The gist of the present invention is to provide an acrylic synthetic fiber having an apparent specific gravity of 0.
The acrylic synthetic fiber is characterized by containing 0.5 to 20.0% by weight of fine powder of metal silicate or metal aluminosilicate having an average particle size of 0.5 to 10 μm and a density of 5 g/cm ³ or less as an active ingredient.

In addition, in the production of acrylic synthetic fibers, a method for ^producing acrylic synthetic fibers is provided, which comprises uniformly dispersing 10 to 40% by weight of a fine powder containing, as an active ingredient, a metal silicate or a metal aluminosilicate having an apparent specific gravity of 0.5 g/cm3 or less and an average particle size of 0.5 to 10 μm in a solvent solution, adding the dispersed powder to a solution of a copolymer containing acrylonitrile, and spinning the resulting mixture.

Furthermore, a fine powder containing a metal silicate or metal aluminosilicate having an apparent specific gravity of 0.5 g/cm ³ or less and an average particle size of 0.5 to 10 μm as an active ingredient is used in an amount of 0.5 to 20.0 μm.
% by weight of acrylic synthetic fibers.
It is a nonwoven fabric containing the above.

Best Mode for Carrying Out the Invention The present invention is described in detail below.

The acrylic synthetic fiber used in the present invention is made of an acrylonitrile copolymer containing at least 40% by weight of acrylonitrile, and any other copolymerizable monomers can be used in combination. For example, alkyl acrylate esters such as methyl acrylate and ethyl acrylate, alkyl methacrylate esters such as methyl methacrylate and ethyl methacrylate, neutral monomers such as styrene, vinyl acetate, vinyl chloride, vinylidene chloride, vinyl ethyl ether, and methacrylonitrile, acrylic acid, methacrylic acid, allyl sulfonic acid, methallyl sulfonic acid,
Examples of suitable acrylic copolymers include copolymers of 60% by weight or less of acidic monomers such as styrenesulfonic acid and 2-acrylamido-2-methylpropanesulfonic acid and the ammonium salts, alkali metal salts, etc. of these monomers. The acrylic copolymers may be produced by any method, such as suspension polymerization, solution polymerization, or emulsion polymerization.

The fine powder used in the present invention is a powder containing S in a three-component composition ratio expressed as oxides.
_iO2 : 5-70% by weight MOn _/2 : 5-80% by weight _Al2O3 : _1-35
% by weight (where M represents at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin, magnesium, and zirconium, and n represents the valence of the metal) of a metal silicate or a metal aluminosilicate as an active ingredient.

Such metal salts have both the properties of a solid acid and a solid base in their crystals, and exist independently on the surface of a single solid particle without neutralizing each other, forming an amphoteric adsorption surface, so they have an excellent deodorizing effect by chemical adsorption against basic malodorous substances and acidic malodorous substances, and because they have a large specific surface area and a low apparent specific gravity, they have excellent contact efficiency with malodorous substances and also have a physical adsorption action, so they are thought to be able to effectively deodorize.In addition, although the antibacterial and bacteriostatic properties are not certain, they are thought to be based on the metal ions held in at least a part of the fine powder.

The apparent specific gravity of the fine powder containing metal silicate or metal aluminosilicate as an active ingredient used in the present invention is 0.5 g/cm or ^less , preferably 0.5 to 0.2 g/cm
The apparent specific gravity of the fine powder is important for the water absorption and deodorizing performance, and is ^0.5 g/cm
If the density exceeds ³ m3, the water absorption and deodorizing performance will be extremely reduced. In this invention, by incorporating a fine powder with an (extremely) low apparent specific gravity into an acrylic synthetic fiber, water absorption performance and extremely excellent deodorizing and antibacterial performance are achieved. The fine powder with an (extremely) low apparent specific gravity forms voids around the fine powder in the fiber, and these voids provide water absorption performance. Furthermore, the contact efficiency with malodorous substances and bacterial media can also be improved, achieving a dramatic improvement in deodorizing performance and antibacterial and antibacterial performance.

The average particle size of the fine powder used in the present invention, which contains a metal silicate or a metal aluminosilicate as an active ingredient, must be 0.5 to 10 μm. If the average particle size of the fine powder is less than 0.5 μm, aggregation is likely to occur, making uniform dispersion difficult without the use of special dispersing equipment and dispersants. If the average particle size of the fine powder is more than 10 μm, an increase in filtration pressure during spinning, thread breakage, etc., occur, which is undesirable from an operational standpoint. From the viewpoints of dispersion stability of the fine powder dispersion solution and spinning operation stability, 1 to 6 μm is more preferable. There are no particular restrictions on the particle size distribution of the fine powder, but it goes without saying that a fine powder distributed in a narrower range is preferable in terms of quality stability and production stability.

The specific surface area of the fine powder containing metal silicate or metal aluminosilicate as an active ingredient used in the present invention is preferably 100 m ² /g or more, particularly 150 m ² /g or more, in terms of BET specific surface area. If this BET specific surface area is lower than 100 m ² /g, the contact efficiency between the fine powder and malodorous substances decreases, and the powder cannot exhibit sufficient deodorizing ability.

The amount of the fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient used in the present invention is 0.5 to 20.0 times the amount of the acrylonitrile copolymer.
The content of the fine powder is 0.0 wt %, preferably 1.0 to 15.0 wt %.
If it is less than 5% by weight, it is not possible to impart sufficient deodorizing, antibacterial and fungicidal properties, and water and sweat absorbing properties, and if it exceeds 20.0% by weight, the spinnability, single fiber properties, and spinnability in spinning will be extremely reduced, which is not preferable.

The solvent used in the present invention may be any solvent capable of dissolving the acrylonitrile copolymer, such as dimethylformamide, dimethylacetamide, dimethylsulfoxide, or acetone, which are preferred in terms of solubility, solvent recovery, and handling.

When the fine powder containing the metal silicate or metal aluminosilicate salt as an active ingredient used in the present invention is stirred and dispersed in a solvent, it is preferable to use a dispersant in combination to maintain the dispersion stability of the fine powder and prevent the fine powder from settling. The dispersant is not particularly limited, but when the solvent to be dispersed is a highly proton polar solvent, zwitterionic surfactants or anionic surfactants are preferred to nonionic surfactants or cationic surfactants.

When the fine powder containing metal silicate or metal aluminosilicate as an active ingredient used in the present invention is dispersed in a solvent solution, the wettability becomes an issue.
Since the larger the BET specific surface area and the larger the average particle size, the poorer the wetting characteristics of the solvent solution, it is preferable to hydrophilize the surface of the fine powder to be dispersed. There are no particular restrictions on the hydrophilization method, but examples include surface treatment with a hydrophilic surfactant or hydrophilization treatment of the fine powder surface.

When dispersing the fine powder containing the metal silicate or metal aluminosilicate used in the present invention as an active ingredient in a solvent, it is preferable to use physical grinding equipment such as a wet mill or sand grinder in addition to the dispersion, from the standpoints of dispersion stability, prevention of sedimentation, spinning operation, and quality stability. However, the fine powder of the present invention can be spun without using any special equipment.

A method for adding or incorporating a fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient into an acrylonitrile copolymer is to add a dispersion solution prepared by dissolving a fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient in a solvent to a spinning dope prepared by dissolving an acrylonitrile copolymer in a solvent, and mix them immediately before spinning.

As a method for dispersing or dissolving the fine powder containing the metal silicate or metal aluminosilicate used in the present invention as an active ingredient in a solvent, and a method for adding and mixing the prepared solution to a spinning dope containing an acrylonitrile-based copolymer, sufficient mixing can be performed using a conventional mixer.

In the present invention, the dispersion concentration of the fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient in the dispersion solution is 5 to 40% by weight, preferably 10 to 35% by weight. If this concentration is less than 5% by weight, the concentration of the acrylonitrile copolymer in the spinning solution will decrease, resulting in a decrease in spinnability and fiber properties.
If the amount exceeds this, a good dispersion state cannot be obtained, making it difficult to easily produce the product industrially.

In addition, titanium oxide, flame retardants, and the like, which are commonly used, may be used within the range that does not impair the characteristics of the present invention.
There is no problem in adding functional modifiers such as light resistance agents and heat storage agents in combination.

The obtained spinning dope is spun from a conventional spinneret. Any known spinning method such as wet, dry-wet, or dry spinning can be applied, and the spinning can be carried out under the same conditions as for conventional acrylic synthetic fibers.

The spinning conditions are not particularly limited as long as they allow stable operation. The total spinning draw ratio is
A higher draw ratio is preferred in order to form voids around the fine powder contained in the fiber. For example, in the case of a wet spinning method, it is preferable to select a high draw ratio in the drawing step after drying and densifying. The drawing temperature conditions after drying and densifying are not particularly limited, but the draw ratio is 1.2 times or more, preferably 1.3 times or more. A high draw ratio within a range that does not excessively deteriorate the single fiber properties and allows stable operation is preferred in terms of deodorizing performance, antibacterial/antimicrobial performance, and water/sweat absorption performance.

To the extent that the characteristics of the present invention are not impaired, a surface modifier such as a coating may be used for the metal silicate or metal aluminosilicate to improve solvent dispersion stability and solvent wetting characteristics.

The fibers of the present invention can be used in any application, product, or manufacturing method that is applicable to general acrylic synthetic fibers. In this case, other fibers (for example, natural fibers such as cotton or synthetic fibers such as modacrylic) may be mixed with the products of the present invention. Examples of blending methods include blending,
There are methods such as interlacing and interweaving.

Next, the nonwoven fabric of the present invention will be described. The nonwoven fabric of the present invention is a nonwoven fabric containing at least 10% by weight of the above-mentioned acrylic synthetic fiber. This nonwoven fabric can be a functional nonwoven fabric while retaining the functional properties of the above-mentioned acrylic synthetic fiber of the present invention, such as deodorizing performance, antibacterial/antimicrobial performance, water absorption/sweat absorption, etc.

The nonwoven fabric of the present invention has an apparent specific gravity of 0.5 g/cm ³ or less and an average particle size of 0.5 to 10
A fine powder containing metal silicate or metal aluminosilicate as an active ingredient is used.
It is necessary to contain at least 10% by weight of acrylic synthetic fibers, characterized by a content of up to 20.0% by weight. If the content is less than 10% by weight, the deodorizing performance and antibacterial and antifungal performance of the nonwoven fabric will be significantly reduced, and the desired high level of functionality will not be imparted.

From the viewpoint of cost performance and to maximize the functional properties of the composite textile and composite nonwoven fabric, a low content of the acrylic synthetic fiber of the present invention is preferred within the range that maintains the high performance of the acrylic synthetic fiber, such as deodorizing performance and antibacterial and antifungal performance. Preferably, the nonwoven fabric contains 10 to 50% by weight, more preferably 10 to 35% by weight of the acrylic synthetic fiber of the present invention.

As long as the nonwoven fabric contains 10% by weight or more of the fiber of the present invention, the fiber to be mixed may be either a natural fiber or a chemical fiber, and there is no particular limitation. Also, any known blending method may be used, and for example, a single-layer nonwoven fabric using the fiber alone or mixed with other materials, or a multi-layer nonwoven fabric, etc., as long as the fiber is contained in the nonwoven fabric at 10% by weight or more.

Nonwoven fabrics can be produced by any conventionally known production method, including, for example, dip-bonded nonwoven fabrics, heat-sealed nonwoven fabrics, needle-punched nonwoven fabrics, stitch-bonded nonwoven fabrics, spun-bonded nonwoven fabrics, and wet-laid nonwoven fabrics, and various other single-layer or multi-layer nonwoven fabrics can be produced using production equipment.

Specific uses and products of the product of the present invention include, in the field of construction and bedding, pile products such as boa sheets and blankets, cover and covering products such as sheets, pillowcases and futon covers, padding products such as futons, kotatsu futons, seat cushions, bed pads, pillows and cushions, lap blankets, throw blankets, bedspreads, bathrobes, bath towels, body towels, etc. In the field of interior design, toiletry products such as toilet seat covers, toilet lid covers and toilet mats, drapery products such as curtains, lace, casements and blind cloths, floor covering products such as entrance/bathroom/kitchen mats, rugs, carpets and hot carpet covers, cover fabric products for office chairs and upholstered furniture, kotatsu futon linings, tablecloths, etc.

In the clothing field, we have innerwear such as underwear, tights, spats, and leg warmers, outerwear such as sweaters, fleece, fake fur, and cold weather interliners, socks and other sock products, loungewear such as aprons, workwear, scarves, hooded capes, pajamas, and work uniforms such as white coats and surgical gowns, and in the material field, footwear such as slippers, animal shoes, and cold weather shoes,
The company's products include dust control products such as commercial mats and cleaning mops, as well as home building materials such as wallpaper.

In the nonwoven fabric field, for housing and building materials, we offer nonwoven fabrics such as anti-condensation sheets, protective sheets, low partitions, hyper-partitions, ceiling materials, and wallpaper; agricultural nonwoven fabrics; industrial wipers for food supply centers such as catering and delivery services, hand towels, commercial dishcloths, floor wipers, baby wipes, wet tissues, and paper towels; household wiping nonwoven fabrics; storage bags, storage sheets, wrapping cloths, packaging materials, clothing covers, and draining bags; filter nonwoven fabrics for building air conditioning filters, automobile filters, household air purifier filters, commercial air purifier filters, masks, and vacuum cleaner filters; and automotive interior covering materials. Examples of applications for auxiliary materials include nonwoven fabrics for automobiles, such as needle-punched carpets, ceiling materials, and wadding materials; medical nonwoven fabrics include surgical nonwoven fabrics such as gowns, drapes, masks, caps, sheets, towels, perforated pants, patient clothing, surgical undergarments, sterilized packaging, shoe covers, birthing packs, and gauze; and transdermal drug base fabric nonwoven fabrics such as medicinal patches and plasters; and sanitary materials include nonwoven fabrics for disposable diaper components and sanitary napkin components, disposable clothing used in medical care, nursing care, laboratories, food processing, and food manufacturing, as well as clothing nonwoven fabrics such as comforters, sweat pads, and bust pads, and nonwoven fabrics for shoe components such as shoe liners and insoles. There are no particular product or application limitations. Any known manufacturing method may be used for finished products and semi-finished products.

Examples The present invention will now be described in more detail with reference to the following examples.

In the examples, parts and percentages are by weight unless otherwise specified.

[Deodorizing property] The deodorizing performance of textile products was evaluated using the following method for representative odorous substances found in daily life, namely, basic odorous substances such as ammonia odor (the odor of rotting meat, tobacco odor, etc.), trimethylamine odor (the odor of rotting fish, etc.), and methyl mercaptan odor (the odor of rotting vegetables, etc.), and acidic odorous substances such as acetic acid odor (body odor caused by decomposition of sweat components, tobacco odor, etc.).

Trimethylamine (hereinafter referred to as TMA) removal rate measurement method: 3 g of sample was placed in a Tedlar bag (made of vinylidene fluoride film, 5 L) and sealed, and 3 L of nitrogen gas was added.
Next, TMA was added to the bag to a concentration of 100 ppm, and after leaving it for 2 hours, the TMA concentration was measured using a detector tube.
A was sealed to a concentration of 100 ppm, and after leaving it for 2 hours, TMA was detected using a detector tube.
The concentration was measured, and the removal rate of TMA was calculated from the rate of decrease in the concentration.

Ammonia removal rate measurement method: Tedlar bag (made of vinylidene fluoride film, 5
1) was placed in a container, sealed, and then 3 L of nitrogen gas was added. Next, ammonia was added to a concentration of 40 ppm, and after leaving it for 2 hours, the ammonia concentration was measured using a detector tube. As a control, an empty Tedlar bag was filled with ammonia to a concentration of 40 ppm, and after leaving it for 2 hours, the ammonia concentration was measured using a detector tube.
The ammonia removal rate was calculated from the concentration reduction rate.

Methyl mercaptan (hereinafter referred to as MMP) removal rate measurement method: 3 g of sample was placed in a Tedlar bag (made of vinylidene fluoride film, 5 L) and sealed. 3 g of nitrogen gas was then introduced.
Next, MMP was added to the bag to give a concentration of 100 ppm, and after leaving the bag for 2 hours, the MMP concentration was measured using a detector tube.
MP was sealed to a concentration of 100 ppm, and after leaving it for 2 hours, MM was measured using a detector tube.
The P concentration was measured, and the removal rate of MMP was calculated from the reduction rate of the concentration.

Acetic acid removal rate measurement method: 3 g of sample is placed in a Tedlar bag (made of vinylidene fluoride film, 5 L) and sealed, and then 3 L of nitrogen gas is added.
As a control, acetic acid was sealed in an empty Tedlar bag to a concentration of 100 ppm, and after being left for 2 hours, the acetic acid concentration was measured with a detector tube, and the acetic acid removal rate was calculated from the rate of decrease in concentration.

[Antibacterial and Bacteriostatic Properties] The antibacterial performance of the fibers was evaluated using a knitted product as a sample, which was made by circular knitting single yarns with a yarn count of 27, spun using a 2-inch spinning system, and the nonwoven fabric itself as a sample, in accordance with the "bacterial count measurement method" in the certification standards for antibacterial and deodorizing processed products established by the Japan Council for Sanitary Finishing of Textile Products. The evaluation was based on the bacteriostatic activity value.

[Washability and Durability] The washability test was carried out in accordance with the "household electric washing method" of JIS L 1018. Both the knitted product and the nonwoven fabric were placed in a household laundry net and washed 0 times (W0).
The samples from the fifth test (W5) were used to evaluate the deodorizing performance and antibacterial and antifungal performance.

[Water absorption rate] After immersing 0.5 g of a sample in pure water for 30 minutes, the sample was centrifuged at 3,500 RPM.
The cotton was treated with 0.5% NaOH for 2 minutes to remove the moisture between the fibers, and the weight (Wa) was measured. The cotton was then dried, and the dry weight (Wb) was measured, and the water absorption rate was calculated using the following formula.

Water absorption rate (%)=(Wa−Wb)/Wb×100 [Liquid retention rate] A test was carried out in accordance with JIS K 7223, a method for testing water absorption of superabsorbent resins, and the liquid retention rate was calculated using the following formula.

A 7 cm square nonwoven fabric sample was washed with artificial urine (sodium chloride 9 g/l, urea 2
The samples were immersed in a solution of 100g/L of artificial urine and 1g/L of creatine prepared with ion-exchanged water for 2 hours to allow the samples to retain the artificial urine. After 2 hours, the samples were left unpacked in tea bags, but instead were hung vertically by a hook and left for 15 minutes to remove any excess retained artificial urine. After 15 minutes, the weight (Wc) of the samples was measured, and the dry weight (Wd) was measured to calculate the retention rate using the following formula:

Liquid retention rate (%) = (Wc - Wd) / Wd × 100 [Apparent specific gravity] The apparent specific gravity of the fine powder containing a metal silicate or a metal aluminosilicate as an active ingredient was measured in accordance with JIS K 6220 (Testing methods for rubber compounding agents).

[BET Specific Surface Area] The BET specific surface area of the fine powder containing metal silicate or metal aluminosilicate as an active ingredient was measured using "Multisoap-12" manufactured by Yuasa Ionics Co., Ltd., and calculated from the amount of adsorbed gas according to the BET theory.

Examples 1 to 6 and Comparative Examples 1 to 6 Acrylonitrile copolymers were produced using acrylonitrile (hereinafter referred to as AN).
An acrylonitrile copolymer consisting of acrylic acid copolymer/methyl acrylate/2-acrylamido-2-methylpropanesulfonic acid sodium (hereinafter referred to as SAM) = 90/9/1 (%) was solution polymerized in dimethylformamide (hereinafter referred to as DMF) using azobisisobutyronitrile as an initiator, and the remaining monomer was then removed.
The concentration of the acrylonitrile copolymer was adjusted to 20 to 30%.

The fine powder is made of aluminosilicate metal salt, which is an active ingredient, with a three-component composition ratio of SiO
The fine powder was used in a DMF dispersion of 30% Al 2 O ₃ , 10% Al ₂ O ₃ , and 60% ZnO, with apparent specific gravity and average particle size as shown in Table 1-1. The concentration of the DMF dispersion of the fine powder was adjusted to 30% or 25%. The dispersion stability in the DMF dispersion was evaluated comprehensively based on aggregation, sedimentation, and wettability, and rated on a three-level scale of "good", "slightly poor", and "poor". The obtained DMF dispersion was added to the acrylonitrile copolymer as shown in Table 1-1.
The ingredients were added and mixed at the addition ratios shown in Table 1 to prepare a spinning dope.

The spinning dope was spun into a 58% DMF aqueous solution at 22°C, stretched while removing the solvent, washed with water, and then oil was added, dried, and dry densified. The resulting fiber was subjected to steam stretching, crimping, and wet heat setting. The results of spinning operability were evaluated on a three-point scale of "good", "slightly poor", and "poor" based on the filtration pressure, single fiber breakage, roller wrapping, yield, etc., when produced under the conditions described in the examples. In addition, the fiber quality was evaluated based on the single fiber strength and elongation, light resistance, and
The dyeability and other properties were compared with those of ordinary acrylic synthetic fibers and evaluated on a two-level scale of "○ (good)" or "△ (slightly poor)."

In Comparative Examples 1 and 2, the apparent specific gravity of the fine powder used in Examples 1 to 6 for the acrylonitrile copolymer was outside the range, in Comparative Examples 3 and 4 the average particle size of the fine powder used in Examples 1 to 6 was outside the range, and in Comparative Examples 5 and 6 the amount of fine powder added (wt%) was outside the range. Each step and each evaluation were performed in the same manner as in Examples 1 to 6.
The results are summarized in Tables 1-1 to 1-3.

As is clear from Tables 1-1 to 1-3, the fine powders shown in Comparative Examples 1 and 2, which had apparent specific gravities outside the range, had good spinning operability and fiber quality, but although they had good antibacterial performance, both the deodorizing performance and the water absorption performance were extremely poor and insufficient.

In Comparative Example 3, in which the average particle size of the fine powder was larger than the range, the filtration pressure increased during spinning and thread breakage occurred, making spinning impossible. In Comparative Example 4, the average particle size of the fine powder was too small, causing secondary aggregation during dispersion in DMF, making filtration difficult and making spinning impossible.

In Comparative Example 5, the amount of fine powder (wt%) added was outside the range, and as expected, the filtration pressure increased during spinning, fiber breakage occurred frequently, and stable operation was not possible. In Comparative Example 6, the amount of fine powder added was too small, and although the spinning operability and fiber quality were good, the functionality was completely poor.

Examples 7 to 11 and Comparative Examples 7 to 11 Acrylonitrile copolymers were produced using a copolymer of AN/vinylidene chloride/SAM=57
An acrylonitrile copolymer consisting of 1,2-dimethyl-2,4-diol/40/3 was solution polymerized in DMF using azobisisovaleronitrile as an initiator, and the residual monomer was removed. Thereafter, the concentration of the acrylonitrile copolymer was adjusted to 20 to 30%.

The fine powder used had an apparent specific gravity of 0.38 g/cm ³ , an average particle size of 3.5 μm, a BET specific surface area of 200 m ² /g, and the composition ratio of the metal aluminosilicate salt, which is the active ingredient of the fine powder, was the same as in Examples 1 to 6, and the dispersion concentration was adjusted as shown in Table 2-1. The obtained dispersion was added to and mixed with the above acrylonitrile-based copolymer at the addition ratio shown in Table 2-1 to prepare a spinning dope.

The spinning solution was spun into a 57% DMF aqueous solution at 18°C, stretched while removing the solvent, washed with water, and then dried and densified. The resulting fiber underwent stretching, shrinkage, and crimping, followed by crimp setting via heat treatment. The spinning operability results were evaluated on a three-point scale: "Good", "Slightly Poor", and "Poor" based on the filtration pressure, single fiber breakage, roller wrapping, and fiber yield when produced under the conditions described in the examples. Furthermore, the fiber quality was evaluated on a two-point scale: "Good" and "Slightly Poor", based on the single fiber strength, elongation, lightfastness, dyeability, etc., of each example compared with ordinary acrylic synthetic fibers.

In Comparative Examples 7 and 8, the fine powder used in Examples 7 to 11 was added to the above acrylonitrile copolymer at a ratio outside the range, and each step and each evaluation were carried out in the same manner as in Examples 7 to 11.

Example 12: As a fine powder, the three-component composition ratio of the active ingredient, aluminosilicate metal salt, is S.
The composition is 55% by weight of _Al2O2 , 17% by weight _{of Al2O3} , and 28% by weight of CuO, and the apparent specific gravity is 0.
Fibers were obtained in the same manner as in Examples 7 to 11, except that a powder having a density of 40 g/cm ³ , an average particle size of 3.0 μm, and a specific surface area of 185 m ² /g was used.

Example 13 As a fine powder, the composition ratio of the active ingredient, aluminosilicate metal salt, is SiO₂
: 67%, Al₂O₃: 13%, Ag₂O: 20%, apparent specific gravity 0.38
g/cm³The average particle size is 3.3 μm and the specific surface area is 193 m²/g
Fibers were obtained in the same manner as in Examples 7 to 11 except that a cellulose acetate solution was used.

Comparative Example 9 In the case where the effective ingredient of the fine powder is not a metal silicate or a metal aluminosilicate, a silica-alumina fine powder having a composition ratio of SiO ₂ : 81% and Al ₂ O ₃ : 19%, an apparent specific gravity of 0.33 g/cm ³ , an average particle size of 3.3 μm, and a specific surface area of 22
Except for using a fiber having a specific surface area of 0 m ² /g, fibers were obtained in the same manner as in Examples 7 to 11. The above results are summarized in Tables 2-1 to 2-3.

As is clear from Tables 2-1 to 2-3, in Comparative Example 7, when the fine powder addition rate (content, wt%) was increased outside the range, spinning was not possible due to increased filtration pressure and spinneret pressure. In Comparative Example 8, when the fine powder addition rate was reduced outside the range, spinning operability and fiber quality were good, but sufficient deodorizing, antibacterial, and water-absorbing properties were not obtained. Furthermore, when metal silicate and metal aluminosilicate were not used, as in Comparative Example 9, functionality was completely poor. In Comparative Example 10, when the fine powder dispersion concentration (wt%) was increased outside the range, aggregation and sedimentation occurred, significantly deteriorating the dispersion stability and making spinning difficult. In Comparative Example 11, when the fine powder dispersion concentration was reduced outside the range, dispersion stability was good, but spinning was not possible due to the large number of macrovoids generated and single-fiber breakage caused by a decrease in the polymer concentration of the acrylonitrile copolymer. In contrast to these Comparative Examples, the Examples obtained satisfactory results in deodorizing, antibacterial, water-absorbing, washing durability, and fiber quality.

Examples 14 to 15 and Comparative Example 12 The same fiber 3.3 dtex used in Example 3 was used as fiber A, and recycled polyester staple fiber 3 manufactured by Oshima Sangyo Co., Ltd. was used as polyester staple fiber B.
10 (fineness 2.2 dtex) was used.

Three product specifications with different blending ratios of the fiber A of the present invention and the polyester staple fiber B were separately defatted and blended, and then processed through blending, air feeding, carding, needle punching, and heat embossing to obtain three types of knee-panned nonwoven fabrics weighing 200 g/ ^m2 . The blending ratios of the fiber A of the present invention and the polyester staple fiber B in these knee-panned nonwoven fabrics were, in weight %, as follows:
A:B=30:70 in Example 14, A:B=10:90 in Example 15,
B=5:95 is shown in Comparative Example 12.

Examples 16-17 and Comparative Example 13 As in Examples 14-15, the same fiber 3.3 dtex as used in Example 3 was used as fiber A, and Unitika Co., Ltd.'s heat-fusible polyester staple fiber C was used.
Heat-melting polyester staple fiber 4080 (fineness 2.2 dtex) manufactured by Epson Corporation was used.

Three types of product specifications, each containing different blending ratios of the fiber A of the present invention and the heat-melting polyester staple fiber C, were defibrated and mixed separately, and then passed through a mixed-fibering, air-feeding, carding, and thermal bonding process that combined a hot air method and a calendar method that emphasized flexibility, to produce 200g of fabric.
Three types of thermal bonded nonwoven fabrics were obtained, each having a density of ¹⁰⁰⁰ g/m². In these thermal bonded nonwoven fabrics, the blend ratio of the fiber A of the present invention to the thermal adhesive polyester staple fiber C was A:C in weight percent.
A:C=30:70 in Example 16, A:C=10:90 in Example 17, A:C=5
:95 is shown in Comparative Example 13.

Examples 18-19 and Comparative Example 14 As in Examples 14-15, the same fiber 3.3 dtex as used in Example 3 was used as fiber A, and pre-bleached cotton bleached by Nippon Sanmo Dyeing Co., Ltd. was used as cotton D.

Three product specifications were prepared with different blending ratios of the fiber A and cotton D of the present invention.
The fibers were mixed, punched, air-fed, and carded, and then subjected to a water jet process by Perfojet to obtain three types of spunlace nonwoven fabrics weighing 50 g/ ^m² . In these nonwoven fabrics, the blending ratio of the fiber A of the present invention to cotton D was A:D = 30:
Example 18 shows A:D=70, Example 19 shows A:D=10:90, and Comparative Example 14 shows A:D=5:95.

Examples 20-21 and Comparative Example 15 As in Examples 14-15, the same fiber 3.3 dtex as used in Example 3 was used as fiber A, and P (Plastic Fiber) manufactured by Chisso Corporation was used as olefin-based heat-melting fiber E.
P/PE heat-fusible fiber ES 2.2 dtex and pre-bleached cotton bleached by Nippon Sanmo Dyeing Co., Ltd. were used as cotton D.

Three types of product specifications, each containing different blending ratios of the fiber A of the present invention and the olefin-based heat-fusible fiber E, were defibrated and mixed separately, and then passed through a mixed-fibering, air-feeding, carding, and thermal bonding process that combined a hot air method and a calendar method that emphasized flexibility, to produce fabrics weighing 20g.
Three types of thermal bonded nonwoven fabrics with a surface area of 1/m ² were obtained.
The blending ratio of the fiber A of the present invention to the olefin-based heat-fusible fiber E is 5% by weight, and A:E=5
Nonwoven fabric X was made up of a mixture of A:E=25:75 and nonwoven fabric Y was made up of a mixture of A:E=10:
90 was designated as nonwoven fabric Z.

These three types of thermal bonded nonwoven fabrics X, Y, and Z were each layered on a cotton web D weighing 20 g/ ^m² and jet-bonded to obtain a two-layer spunlaced nonwoven fabric. The blend ratio of the fiber A of the present invention, cotton D, and olefin-based thermal adhesive fiber E in these nonwoven fabrics was A:D:E = 25:50:25 by weight, as in Example 20.
In Example 21, A:D:E = 12.5:50:37.5 was used, and in Example 22, A:D:E = 5:
50:45 is shown in Comparative Example 15.

As can be seen from Tables 3-1 and 3-2, when obtaining a functional nonwoven fabric using the fibers of the present invention, it is necessary to mix at least 10% by weight of the fibers of the present invention into the nonwoven fabric, regardless of the type of fiber mixed. In cases where the fibers of the present invention were mixed in the nonwoven fabrics of Comparative Examples 10 to 13 at less than 10% by weight, the deodorizing performance, antibacterial and deodorizing performance, and liquid absorption and retention performance were significantly reduced. Conversely, in Examples 14 to 21, in which the fibers of the present invention were mixed into the nonwoven fabric at a low mixing ratio of 10 to 30%, deodorizing performance, antibacterial and antimicrobial performance, and water and sweat absorption (liquid and urine absorption) performance could be imparted, making the most of the characteristics of the other fibers used in the mixture, and obtaining a functional nonwoven fabric with extremely excellent cost performance.

Industrial Applicability: The present invention has realized a comfortable fiber material with excellent cost performance by combining three functions highly desired by consumers: deodorizing, antibacterial and antifungal properties, and water and sweat absorption. This will provide consumers with a higher quality, safer, more hygienic, healthier, and more comfortable lifestyle.

───────────────────────────────────────────────────── Continued from the front page (81) Designated Countries EP(AT,BE,CH,CY, DE, DK, ES, FI, FR, GB, GR, IE, I T, LU, MC, NL, PT, SE), OA (BF, BJ , CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP(GH, GM, K E, LS, MW, SD, SL, SZ, TZ, UG, ZW ), UA(AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, C R, CU, CZ, DE, DK, DM, EE, ES, FI , GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, K Z, LC, LK, LR, LS, LT, LU, LV, MA , MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, S K, SL, TJ, TM, TR, TT, TZ, UA, UG , US, UZ, VN, YU, ZA, ZW (Note) This publication is based on the international publication by the International Bureau of International Trade and Industry (WIPO). Please note that the effect of the international publication of the Japanese-language patent application (Japanese-language utility model registration application) related to this publication arises pursuant to Article 184-10, Paragraph 1 of the Patent Act (Article 48-13, Paragraph 2 of the Utility Model Act), and is unrelated to this publication.

Claims (3)

[Claims] [Claim 1] An acrylic synthetic fiber characterized by containing 0.5 to 20.0 weight % of a fine powder having an apparent specific gravity of 0.5 g/cm3 or ^less and an average particle size of 0.5 to 10 μm, the effective ingredient of which is a metal silicate or a metal aluminosilicate. Claim 2: When producing acrylic synthetic fibers, the apparent specific gravity is 0.5 g/cm
A method for producing acrylic synthetic fibers, comprising uniformly dispersing 10 to 40% by weight of a fine powder containing, as an active ingredient, a metal silicate or a metal aluminosilicate having a particle size of 0.3 or ^less and an average particle size of 0.5 to 10 μm in a solvent, adding the resulting dispersion to a solution of a copolymer containing acrylonitrile, and spinning the resulting mixture. 3. A nonwoven fabric containing at least 10% by weight of the acrylic synthetic fiber according to claim 1.