JP7412732B2 - Blended yarns and fiber structures - Google Patents

Description

The present invention relates to a blended yarn and a fiber structure using this blended yarn.

Fibers containing fine powder of graphite silica are described in, for example, Patent Document 1. Patent Document 1 describes that ``a fiber containing 0.2 to 25% by weight of fine powder of graphite silica, in which 1 g of graphite silica particles having an average particle size of 70 to 80 μm is sandwiched between upper and lower electrodes, and 350 g of graphite silica is used. A fiber having a resistance value of 9×10 ¹⁰ Ω or less under a load of 9×10 10 Ω or less” is disclosed, whereby “a fiber with excellent heat storage and heat retention performance can be stably obtained.” be. Underwear and clothing made of graphite-silica stone-containing fibers have the excellent feature of being warm even though they are thin due to far-infrared rays.

JP 2017-020141 (Claims)

As mentioned above, underwear and clothing made of fibers containing graphite silica have excellent heat storage properties and are warm even when thin. However, although graphite silica itself is porous and has adsorption properties, graphite silica stone-containing fibers have insufficient deodorizing properties.

The present invention solves the above problems, and aims to provide a blended yarn that has sufficient deodorizing properties while maintaining the excellent characteristics of graphite-silica-containing fibers, such as excellent heat storage properties and warmth even when thin. purpose. Another object of the present invention is to provide a fiber structure using this blended yarn.

In order to solve the above problems, we developed a deodorizing material made of graphite silica stone-containing short fibers containing fine powder of graphite silica stone, and a thermoplastic polymer containing a tetravalent metal phosphate, a divalent metal hydroxide, and a photocatalyst. It was made into a blended yarn consisting of short fibers.

The inventors of the present invention have conducted intensive research and development to impart deodorizing properties while taking advantage of the excellent characteristics of graphite-silica-containing fibers, such as excellent heat storage properties and warmth even when thin. Then, the above problem was solved by a blended yarn consisting of graphite silica stone-containing short fibers and deodorizing short fibers made of a thermoplastic polymer containing a tetravalent metal phosphate, a divalent metal hydroxide, and a photocatalyst. I discovered that.
In addition, clothing made of the above-mentioned blended yarn has a less stuffy feeling than clothes made of the blended yarn made of the deodorizing short fibers. The detailed reason why the feeling of stuffiness is reduced in this way is unknown, but it is speculated that the far infrared rays emitted from graphite silica stone cause a change in the state of sweating.
As described above, the blended yarn obtained by blending the graphite silica stone-containing short fibers and the deodorizing short fibers has both deodorizing properties and heat storage properties, and has the remarkable effect of reducing the feeling of stuffiness.

Further, the graphite silica stone-containing short fibers have a core-sheath type composite structure consisting of a core part and a sheath part, and contain fine powder of graphite silica stone only in the core part, and the content of graphite silica stone is It can be a blended yarn containing 0.5 to 5% by weight of the fibers contained.

This blended yarn maintains the excellent characteristics of graphite-silica-containing fibers, such as excellent heat storage properties and warmth even though it is thin, for a long period of time, and has sufficient deodorizing properties.
Graphite silica itself is porous and adsorbent. However, if impurities were adsorbed to graphite silica, there was a risk that the far-infrared effect would deteriorate. Therefore, the graphite-silica stone-containing short fibers were made into a core-sheath type composite structure consisting of a core part and a sheath part, and fine powder of graphite-silica stone was contained only in the core part. This has resulted in a structure in which graphite silica is less likely to adsorb impurities. Note that even if the fine powder of graphite silica is contained only in the core, the excellent characteristics of graphite silica-containing fibers, such as excellent heat storage properties and warmth even when thin, can be maintained.
Further, the content of graphite silica is preferably 0.5 to 5% by weight, more preferably 0.5 to 4% by weight of the graphite silica-containing fiber.

Further, a blended yarn containing 10 to 30% by weight of graphite silica stone-containing short fibers and 10 to 90% by weight of deodorizing short fibers can also be used.

This blended yarn can realize the excellent characteristics of graphite-silica stone-containing fibers and sufficient deodorizing properties at a high level. It is preferable to use a blended yarn containing 15 to 30% by weight of graphite silica stone-containing short fibers and 30 to 85% by weight of deodorizing short fibers.

The deodorant short fiber has a core-sheath type composite structure consisting of a core part and a sheath part, the core part is made of a thermoplastic polymer with a melting point of 150°C or higher, the sheath part is made of polybutylene terephthalate, and the It is also possible to form a blended yarn in which the sheath contains a tetravalent metal phosphate, a divalent metal hydroxide, a photocatalyst, and an antioxidant.

This blended yarn can also achieve the excellent characteristics of graphite-silica-containing fibers and sufficient deodorizing properties at a high level. In addition, since tetravalent metal phosphates, divalent metal hydroxides, photocatalysts, and antioxidants are contained in the sheath, tetravalent metal phosphates, divalent metal hydroxides, and photocatalysts are contained in the sheath. A great deodorizing effect can be obtained even if the amount used is small.

A fiber structure containing at least a portion of these blended yarns has sufficient deodorizing properties while maintaining the excellent characteristics of graphite-silica-containing fibers, such as excellent heat storage properties and being warm even when thin.

According to the present invention, it is possible to provide a blended yarn having sufficient deodorizing properties while maintaining the excellent characteristics of graphite-silica-containing fibers, such as excellent heat storage properties and being warm even when thin. Furthermore, it is also possible to provide a fiber structure using this blended yarn.

FIG. 2 is a diagram illustrating a heat storage evaluation device.

Hereinafter, the blended yarn will be exemplified and explained. The blended yarn consists of graphite silica stone-containing short fibers and deodorizing short fibers.
Note that the following embodiments and examples are merely for illustrating the present invention, and the present invention is not limited to the following specific embodiments and examples. First, graphite silica stone-containing short fibers will be exemplified and explained.

[Short fiber containing graphite silica]
Graphite silica stone-containing short fibers are short fibers containing fine powder of graphite silica stone. The graphite silica stone-containing short fibers are obtained by shortening graphite silica stone-containing fibers. The graphite silica stone-containing fiber is disclosed in, for example, Japanese Patent Application Publication No. 2017-020141.

1. Graphite silica Graphite silica is thought to be the product of diatoms that have been deposited on the ocean floor for hundreds of millions of years and have risen to the surface. Graphite silica is mainly composed of SiO ₂ and contains graphite crystals (usually about 5%). Graphite silica also contains aluminum, potassium, titanium, iron dioxide, and magnesium. Graphite silica is sometimes referred to as black silica.

2. Pulverization of graphite silica Pulverization of graphite silica. At this time, it is preferable to pulverize the graphite silica stone so that the average particle size (d50: cumulative 50% particle size) is 3 μm or less.

3. Fiberization (long fiberization)
A graphite-silica stone-containing fiber (long fiber) containing a predetermined amount of the graphite-silica fine powder is produced.

The polymer constituting the graphite-silica-containing fiber, that is, the polymer into which the graphite-silica fine powder is kneaded, is not particularly limited. Considering spinnability and yarn physical properties during spinning, polyethylene terephthalate, nylon 6, nylon 66, etc. are preferred. In addition, in the case of making a core-sheath type fiber with a fiber cross section consisting of a core part and a sheath part, for example, select two types of polymers from the above, and use one as the polymer for the core part and the other as the polymer for the sheath part. I can do it.

At this time, the graphite silica fine powder may be added to either the core polymer or the sheath polymer. It can also be added to both the core and sheath polymers. Further, it is preferable to add the fine powder of graphite silica stone only to the core polymer and cover the core with the sheath polymer, thereby forming a so-called core-sheath type fiber.

In the case of a core-sheath type fiber, the ratio (weight ratio) of the sheath part to the core part is preferably in the range of 4:1 to 1:4, more preferably in the range of 3:1 to 1:3, A range of 2:1 to 1:1 is most preferred. Further, the core need not be one core in the fiber, but may be two or more multi-core. Furthermore, a portion of the core may be exposed on the fiber surface, or the core may be covered with a sheath.

There are no particular restrictions on the method of adding the fine powder of graphite silica to the thermoplastic polymer. From the viewpoint of uniform dispersion, it is preferable to form a master chip using a twin-screw extruder.
The timing of adding the fine powder of graphite silica is also not particularly limited. It can be added to the reaction system at the initial stage of polymerization and directly spun. It is also possible to use a so-called post-addition method in which fine powder of graphite silica is kneaded into the polymer in a molten state. Furthermore, a so-called masterbatch method using a master chip containing fine powder of graphite silica at a high concentration can also be used.

The amount of the fine powder of graphite silica stone added is preferably 0.5 to 8.0% by weight of the graphite silica stone-containing fiber (graphite silica stone-containing short fiber), more preferably 0.5 to 5.0% by weight of the graphite silica stone-containing fiber. 0% by weight, more preferably 0.5 to 4.0% by weight of the graphite-silica-containing fiber.

In order to form fibers into graphite-silica-containing fibers, it is possible to use the above-mentioned materials and use ordinary fiber manufacturing processes as they are. The thickness of the fibers is preferably in the range of 0.5 to 15 decitex (dtex).

The cross-sectional shape of the graphite-silica-containing fiber is not particularly limited. In addition to a round cross section, it may have a polygonal cross section such as a trigonal to hexagonal cross section, a T-shaped cross section, or a U-shaped cross section.

Note that as the graphite-silica-containing fiber, it is also possible to use ordinary fibers with a resin coating layer containing fine powder of graphite-silica stone formed on the surface of the fibers. However, in consideration of friction durability and the like, it is preferable to use graphite-silica-containing fibers in which fine powder of graphite-silica stone is mixed into the fiber polymer.

4. Making short fibers The obtained graphite-silica stone-containing fibers are made into short fibers to obtain graphite-silica stone-containing short fibers. The graphite silica stone-containing fiber can be made into short fibers by a conventionally known method. The fiber length of the graphite silica stone-containing short fibers is preferably 25 to 150 mm, more preferably 35 to 100 mm, and most preferably 40 to 60 mm. For example, in the case of 3.3 dtex, the number of crimp is preferably 12 to 15 per inch, and the crimp rate is preferably approximately 10%.

Next, examples of deodorant short fibers will be explained.
[Deodorant short fiber]
Deodorant short fibers are obtained by shortening deodorant fibers. The deodorizing fiber consists of a thermoplastic polymer containing a tetravalent metal phosphate, a divalent metal hydroxide, and a photocatalyst. Such deodorizing fibers are disclosed in, for example, JP-A No. 2004-169218, JP-A No. 10-37023, and JP-A No. 10-219520. Further, such deodorizing fibers are sold, for example, as "Shine Up" (registered trademark) manufactured by Kuraray Co., Ltd.
Note that a composition composed of a tetravalent metal phosphate and a divalent metal hydroxide may be simply referred to as an "adsorbent." Moreover, this adsorbent and photocatalyst are sometimes collectively referred to as a "deodorant."

1. Tetravalent metal phosphates Tetravalent metals that form phosphates include Group 4 elements of the periodic table, such as Group 4A elements (titanium, zirconium, hafnium, thorium, etc.) and Group 4B elements (germanium, tin, lead, etc.). ) is included. Among these metals, metals belonging to Group 4A elements of the periodic table, such as titanium, zirconium, and hafnium, and metals belonging to Group 4B elements, such as tin, are preferred, and titanium and zirconium are particularly preferred.

The phosphoric acid constituting the phosphate salt includes various phosphoric acids, such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, and tetraphosphoric acid. The phosphoric acid is often orthophosphoric acid, metaphosphoric acid or pyrophosphoric acid. Phosphates also include hydrogen phosphates such as hydrogen orthophosphate. In this specification, unless otherwise specified, phosphoric acid means orthophosphoric acid.

These tetravalent metal phosphates are usually water-insoluble or poorly water-soluble. Furthermore, although the tetravalent metal phosphate may be a crystalline salt, it is preferably an amorphous salt. These tetravalent metal phosphates can be used alone or in combination of two or more.

2. Divalent metals that form hydroxides Divalent metals that form hydroxides include elements of group 1B of the periodic table such as copper, elements of group 2A of the periodic table such as magnesium, calcium, strontium, and barium, zinc, cadmium, etc. Examples include elements of group 2B of the periodic table, elements of group 6A of the periodic table such as chromium and molybdenum, elements of group 7A of the periodic table such as manganese, and elements of group 8 of the periodic table such as iron, ruthenium, cobalt, rhodium, nickel, and palladium. These divalent metal hydroxides may be used alone or in combination of two or more.

Preferred divalent metals include transition metals, such as elements of group 1B of the periodic table such as copper, group 2B elements of the periodic table such as zinc, group 7A elements of the periodic table such as manganese, and elements of group 8 of the periodic table such as iron, cobalt, and nickel. included. Preferred are copper, zinc, iron, cobalt and nickel.

These divalent metal hydroxides are generally insoluble or poorly soluble in water in the weakly acidic to weakly alkaline range (pH 4 to 10). Furthermore, although the hydroxide of a divalent metal may be crystalline, it is often amorphous.

3. Photocatalyst The photocatalyst that constitutes the deodorant functions as a photooxidation catalyst by generating active radicals by irradiation with light such as ultraviolet rays, oxidizing and decomposing many harmful substances and malodorous substances. When such a photocatalyst is used, it is possible to deodorize using catalytic decomposition rather than mere adsorption, so that the deodorizing or deodorizing effect can be maintained for a long period of time. Furthermore, this photocatalyst not only decomposes harmful substances and malodorous substances, but also has bactericidal and antibacterial effects.

As the photocatalyst, various optical semiconductors can be used, regardless of whether they are inorganic or organic. As the photocatalyst, for example, sulfide semiconductors such as CdS and ZnS, and oxide semiconductors such as TiO ₂ , ZnO, SnO ₂ and WO ₃ are preferable, and oxide semiconductors such as TiO ₂ and ZnO are particularly preferable. The crystal structure of the optical semiconductor constituting the photocatalyst described above is not particularly limited. For example, TiO ₂ may be anatase type, brookite type, rutile type, amorphous type, etc. Particularly preferred TiO ₂ is anatase type.

The photocatalyst can be used in the form of a sol, gel, or powder. When the photocatalyst is used in the form of powder, the average particle diameter of the photocatalyst can be selected within a range that does not impair photoactivity and deodorizing efficiency, and is, for example, 0.05 to 5 μm, preferably 0.05 to 1 μm.

The amount of the photocatalyst to be used can be selected from a wide range that does not impair the catalytic activity, for example, 0.1 to 25% by weight, preferably 0.3 to 20% by weight, more preferably 0.5 to 20% by weight, based on the entire deodorant fiber. It is often in the range of 15% by weight, and generally in the range of 0.5 to 10% by weight.

4. Adsorbent, deodorant The ratio of tetravalent metal phosphate and divalent metal hydroxide can be selected within a range that does not impair catalyst activity, adsorption capacity for odor components, and deodorization capacity. The metal atomic ratio (divalent metal/tetravalent metal) is in the range of 0.1 to 10, preferably 0.2 to 7, more preferably 0.2 to 5. When using a plurality of phosphates and/or hydroxides in combination, the metal atomic ratio based on the total amount of each metal may be within the above range. Further, the composition composed of a phosphate of a tetravalent metal and a hydroxide of a divalent metal may be in a composite state by coprecipitation, such as a mixed gel. In particular, when a deodorizing agent composed of a combination of a tetravalent metal phosphate and a divalent metal hydroxide is used in combination with the above-mentioned photocatalyst by mixing or coprecipitation, high catalytic activity is exhibited. , various compounds such as odor components can be efficiently removed over a long period of time.

The total amount of tetravalent metal phosphates and divalent metal hydroxides can be selected as appropriate depending on the structure of the fiber, and is, for example, 0.1 to 25% by weight, preferably 0.5% by weight based on the entire fiber. The range is preferably from 1 to 10% by weight, more preferably from 1 to 10% by weight.
The amount of the photocatalyst is 1 to 1000 parts by weight, preferably 10 to 750 parts by weight, and more preferably 20 to 500 parts by weight based on 100 parts by weight of the total amount of tetravalent metal phosphate and divalent metal hydroxide. A range of 50% is preferred.

Tetravalent metal phosphates and divalent metal hydroxides may be combined with silicon dioxide, which is useful in increasing specific surface area and adsorption capacity.

The deodorant is preferably amorphous, particularly a coprecipitated substance produced by coprecipitation. The amorphous deodorant produced by coprecipitation usually has a BET specific surface area of 10 to 1000 m ² /g, preferably 30 to 1000 m ² /g, and more preferably 50 to 1000 m ² /g. Therefore, fibers containing such deodorants function as deodorizing fibers with high deodorizing properties, and also have antibacterial properties.

Deodorants can be obtained by various conventional methods. For example, a deodorant can be easily obtained by mixing a tetravalent metal phosphate, a divalent metal hydroxide, and a photocatalyst with other deodorants (silicon dioxide, etc.) as necessary. . In the above-mentioned mixing, respective powder components obtained by pulverization or the like may be mixed. Methods for obtaining deodorants are described, for example, in the aforementioned Japanese Patent Application Laid-Open Nos. 2004-169218, 10-37023, and 10-219520.

5. Deodorizing fiber Examples of the thermoplastic polymer constituting the deodorant fiber include polyamides such as nylon 6 and nylon 66, and polyesters such as polyethylene terephthalate and polybutylene terephthalate. Moreover, the polyamide and the polyester may contain a third component.

Moreover, the deodorizing fiber may be not only a single fiber made of a single thermoplastic polymer, but also a composite fiber made of a plurality of thermoplastic polymers. The composite form is not particularly limited, and examples include a normal core-sheath type, a multicore-sheath type, a laminated type, a multilayer laminated type, an island-in-the-sea type, a random composite type, a hollow core-sheath type, and the like. Alternatively, one component may be removed by alkali treatment or the like to produce irregular cross-section fibers or ultrafine fibers. Further, the fibers may be hollow fibers or solid fibers, and there are no particular limitations on the cross-sectional shape of the fibers.

Methods of incorporating a deodorizing agent consisting of a photocatalyst and an adsorbent into the short fibers or composite fibers include methods of adding and incorporating the deodorizing agent during or immediately after polymerization of the thermoplastic polymer; A method of preparing a masterbatch by adding an odor agent and using it, deodorizing at any stage until the thermoplastic polymer is spun (for example, at the stage of making polymer pellets, melt spinning stage, etc.) There are methods of adding agents.

In addition, deodorants are added in the form of fine particles, but if the particles are added to the polymer as they are, it may be difficult to form fibers due to agglomeration of the particles, or even if fibers can be formed, they may only have low strength. Therefore, it is preferable to add it to the polymer in the form of a slurry dispersed in a suitable dispersion medium.

When a deodorant is added to a spinning raw material made of a thermoplastic polymer and then spun, the state of its dispersion can vary depending on the cross-sectional form of the fibers. For example, when the fiber is a single fiber, the deodorant is uniformly dispersed in the cross section, and when the fiber is a single hollow fiber, the concentration of the deodorant is gradient from the fiber surface to the hollow part. A state in which there is or is uniformly dispersed.
When the fiber is a composite fiber, the state of dispersion of the deodorant differs depending on its composite form. For example, in the case of a core-sheath type composite fiber, there is a dispersion state in which the deodorant is contained only in either the core or the sheath, or the concentration of the deodorant is different between the core and the sheath. In the case of sea-island composite fibers, there is a dispersion state in which the deodorant is contained only in either the sea or the island, or the concentration of the deodorant is different between the sea and the island. In the case of a side-by-side type or a multilayer laminated type (when it consists of two types of polymers), only one component contains the deodorant, or the concentration of the deodorant is different between one component and the other component. There is a distributed state.

If a large deodorizing effect is desired even if the amount of deodorant contained in the entire fiber is low, a core-sheath type composite fiber containing the deodorant only in the sheath portion is suitable. Hereinafter, such a core-sheath type composite fiber will be explained in detail.

In the core-sheath type composite fiber, it is preferable that the deodorant is contained only in the sheath portion. This is because a large deodorizing effect can be achieved with a small amount of deodorant. In this regard, in the case of single fibers, the amount of deodorizing agent used is preferably in the range of 1 to 25% by weight, but in the case of core-sheath type composite fibers, in order to achieve the same degree of deodorizing effect as single fibers, Although the amount of deodorant used depends on the proportion of the sheath, it is 0.01 to 10% by weight, preferably 0.1 to 7.5% by weight, more preferably 0.25 to 10% by weight based on the total fiber. It can be reduced to a range of 5% by weight.
Further, the composite ratio of the sheath part and the core part of the core-sheath type composite fiber is core part/sheath part = 5/95 to 95/5 (parts by weight), preferably 10/90 to 90/10, more preferably It is 30/70 to 70/30. At this time, the type of polymer constituting the core-sheath composite fiber is not particularly limited, and the core polymer and the sheath polymer may be the same type or different types.

Polyester can be used as the polymer (A) of the sheath portion. For example, polyesters such as polybutylene terephthalate (PBT), polylactic acid, and polytrimethylene terephthalate are used, preferably polybutylene terephthalate and polylactic acid, with polybutylene terephthalate being particularly preferred. PBT is mainly composed of dicarboxylic acid units mainly composed of terephthalic acid units and diol units mainly composed of 1,4-butanediol units, and a typical example is composed of only terephthalic acid units and 1,4-butanediol units. Polybutylene terephthalate (hereinafter sometimes referred to as "PBT") can be mentioned.
The glass transition temperature (Tg) of PBT is preferably 65°C or lower, more preferably 40 to 60°C, and most preferably 45 to 55°C. Moreover, polybutylene terephthalate may contain an organic sulfonic acid compound.

As mentioned above, it is preferable that the polymer (A) of the sheath portion contains a deodorant.

The core polymer (B) is preferably a crystalline thermoplastic polymer with a melting point of 150° C. or higher, such as polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polytrimethylene terephthalate, and polyamides such as nylon 6 and nylon 66. can be mentioned. Further, in order to prevent interfacial peeling from occurring when combined with the polymer (A) of the sheath portion, it is preferable to use polyester.

The polyester is not particularly limited, but preferably has a glass transition temperature of 70 to 90°C, more preferably 75 to 85°C. Further, it is preferable that the melting point is 250 to 270°C. On the other hand, polyamides containing nylon 6, nylon 66, and nylon 12 as main components can be used as the polyamide. At this time, a small amount of a third component may be included.
Particularly preferred combinations of polymers include, for example, polybutylene terephthalate having a glass transition point temperature of 65°C or lower as the polymer (A) for the sheath, and polyethylene terephthalate having a melting point of 150°C or higher as the polymer (B) for the core. .

To suppress the generation of gel due to self-crosslinking caused by heating of the polymer (A) in the sheath when melt-spinning a composite fiber consisting of the polymer (A) in the sheath and the polymer (B) in the core. In addition to containing an antioxidant, it is preferable to contain a deodorizing agent in order to impart functionality.
The antioxidant contained in the polymer (A) of the sheath is a hydroxy tert-butylphenyl compound, in which the hydroxy group is located at the ortho position to the butyl group (hereinafter referred to as a phenol compound). ) is preferable, and it is preferable to add 0.08% by weight or more to the polymer (A) of the sheath portion. The phenolic compound is generally used as an antioxidant. A phenolic compound, particularly a compound containing a nitrogen atom, exhibits a remarkable effect in suppressing gelation of the polymer (A) in the sheath portion.
Generally, when inorganic fine particles are added, thermal decomposition or gelation of the polymer (A) in the sheath portion may be promoted, but phenolic compounds have the effect of suppressing these. There is no particular upper limit to the amount of the phenolic compound (antioxidant) added, but it is preferably 5% by weight or less, particularly preferably in the range of 0.1 to 3% by weight.

The thickness of the deodorant fibers is not particularly limited, nor is the shape of the fibers in the longitudinal direction. That is, the fibers may have approximately the same diameter in the longitudinal direction of the fibers, may be thick and thin fibers having thick and thin fibers, or may be other fibers.

6. Deodorizing short fibers The obtained deodorant fibers are made into short fibers to obtain deodorant short fibers. The deodorizing fiber can be made into short fibers by a conventionally known method. The fiber length of the deodorant short fibers is preferably 25 to 150 mm, more preferably 35 to 100 mm, and most preferably 40 to 60 mm. For example, in the case of 3.3 dtex, the number of crimp is preferably 12 to 15 per inch, and the crimp rate is preferably approximately 10%.

[Blended yarn]
The graphite silica stone-containing short fibers and the deodorizing short fibers are blended to obtain a blended yarn. The blending method is not particularly limited. For example, a blended yarn can be obtained by passing graphite-silica stone-containing short fibers and deodorizing short fibers through a card (carding machine) and blending them at a predetermined ratio. When blending, the graphite-silica-containing short fibers should be 10-30% by weight and the deodorizing short fibers should be 10-90% by weight to achieve the excellent characteristics of the graphite-silica-containing fibers and sufficient deodorizing properties at a high level. It is preferable that it can be done.

[Fiber structure]
The above blended yarn can be used for various fiber structures (textile products). For example, fabrics such as woven fabrics, knitted fabrics, and non-woven fabrics; pile fabrics such as pile fabrics and pile knitted fabrics; clothing and other personal items made from these; interior products; bedding; food packaging materials, etc. can be mentioned. Specifically, clothing and body items such as underwear, sweaters, jackets, pajamas, yukatas, white coats, slacks, socks, gloves, stockings, aprons, masks, towels, handkerchiefs, supporters, headbands, hats, shoe insoles, interlining, etc. Worn items: various carpets, curtains, wallpaper, shoji paper, sliding doors, textile blinds, artificial plants, upholstery fabrics for chairs, tablecloths, electrical appliance covers, tatami mats, futon filling materials (cotton stuffing, etc.) , futon side materials, sheets, blankets, duvet covers, pillows, pillowcases, bedspreads, bed filling materials, mats, sanitary materials, toilet seat covers, wiping cloths, filters for air purifiers, air conditioners, etc. be able to.
The blended yarn and fiber structure of the present invention, which can maintain excellent deodorizing and sterilizing effects and heat storage properties over a long period of time, are particularly suitable for use in the nursing care field.

Next, the present invention will be specifically explained using Examples, but the present invention is not limited thereto. The proportions and percentages in the examples are by weight.

[Example 1]
Graphite-silica-containing fiber with a core-sheath type composite structure (sheath/core ratio = 2/ 1, a stretched system of 83 dtex/24 f) was obtained. This was combined into a 400,000 denier fiber tow, which was then crimped using a push crimper and cut into 51 mm pieces.The graphite silica stone-containing short fibers (number of crimps: 12.0) had a single yarn fineness of 3 denier. /inch).

On the other hand, deodorizing fibers were obtained by the following procedure. First, a deodorant [Cu(II)-Ti(IV)-SiO ₂ -TiO ₂ ] was prepared by the following method. 43.9 g of copper sulfate crystals (CuSO ₄ 5H ₂ O, special grade reagent manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 1 liter of distilled water, and a titanium sulfate solution (approximately 30% concentration by weight, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the resulting aqueous solution. Reagent) 60g was added. This mixed solution contains 0.175 mol of Cu(II) and 0.075 mol of Ti(IV) ions. The pH of the mixture was about 1. When about 110 g of a 15% by weight phosphoric acid solution was added dropwise to the mixture at room temperature while stirring, a white precipitate was generated. The mixture containing the precipitate was stirred as it was all day and night. When 471 g of a solution containing the above precipitate (liquid A) and an aqueous solution containing sodium silicate (liquid B) were stirred in separate beakers, they were dropped in parallel into a container containing 500 ml of distilled water. A bluish-white mixed precipitate containing Cu(II)-Ti(IV) _-SiO2 was formed. The amounts of liquids A and B to be dropped were adjusted so that the pH of liquids A and B was always about 7 when mixed. For liquid B, sodium silicate (reagent manufactured by Wako Pure Chemical Industries, Ltd.) is diluted to 30% by weight with distilled water (contains 0.86 mol of SiO ₂ ), and 30ml of a 15% by weight sodium hydroxide aqueous solution is added. Adjusted by.

After the mixture of liquids A and B was further stirred at room temperature for 2 hours, the blue-white mixed precipitate was suction-filtered, thoroughly washed with heated deionized water, and then dried at 40°C. The dried product was ground in a mortar to a size of 120 μm or less to obtain a blue-white powder containing Cu(II)-Ti(IV)-SiO ₂ . 20 parts by weight of titanium oxide powder (manufactured by Ishihara Sangyo Co., Ltd., MC-90) was mixed with 80 parts by weight of the powder, and the mixture was ground with a jet mill to prepare a deodorant.

Next, polybutylene terephthalate (PBT) to which 5% by mass of the above deodorant was added was used as a polymer for the sheath (component A) using a twin-screw extruder, and polybutylene terephthalate (PBT) with an intrinsic viscosity of 0.70 (phenol/tetra Using polyethylene terephthalate (measured at 30 °C with a mixed solution of equal weight of chloroethane), spinning temperature 290 °C, winding speed 1000 m/min, composite ratio of core:sheath = 50:50 (weight ratio), nozzle hole diameter 0.25φ - Spinning with 24 holes and then drawing with a roller plate method to obtain a deodorizing fiber with a round cross section of 75 denier/24 filaments.

The obtained deodorant fibers were combined to form a fiber tow of 400,000 deniers, which was crimped using a push crimper and cut into 51 mm pieces. 12.0 pieces/inch).
The graphite silica stone-containing short fibers and the deodorizing short fibers were passed through a card (carding machine) and blended at a ratio of 15:85 to obtain a 20 count blended yarn. A jersey knitted fabric was created using the obtained blended yarn.

The obtained Amagasa knitted fabric was evaluated for deodorizing properties according to the following criteria.
[Deodorization evaluation]
1. Evaluation of deodorizing properties using a detection tube The obtained Amagasa knitted fabric was cut into a size of 10 x 10 cm and used as a sample for measurement weighing approximately 3 g. This measurement sample was placed in a sampling bag (capacity: 5 L), and ammonia gas adjusted to a predetermined concentration was injected, and the bag was sealed at an ammonia concentration of 40 ppm (initial concentration). Thereafter, the ammonia gas concentration after 2 hours and 24 hours in the sealed state was measured using a gas detection tube, and the rate of decrease in the ammonia gas concentration after 24 hours was evaluated based on the following criteria.
◎: Reduction rate of 90% or more ○: Reduction rate of 70% or more ×: Reduction rate of 50% or less

2. Deodorizing performance evaluation (judgment) by panelists
The obtained Amagasa knitted fabric was cut into a size of 10×10 cm to prepare a measurement sample weighing approximately 3 g. This measurement sample was placed in an Erlenmeyer flask, and ammonia gas was injected to the flask to 100 ppm and the flask was sealed. After 24 hours, 10 panelists evaluated the strength of the odor using the criteria 1 to 5 below.
0: Odorless 1: Barely detectable odor 2: Weak odor that makes it easy to tell what kind of odor it is 3: Easily detectable odor 4: Strong odor 5: Intense odor And based on the evaluations of 10 panelists, Odor properties were judged according to the following criteria: ◎: 9 or more people judged that the odor after the test was equivalent to intensity 2 or weaker. ○: 7 to 8 people judged that the odor after the test was equivalent to intensity 2 or weaker. △: 5 to 6 people judged that the odor after the test was equivalent to intensity 2 or weaker ×: 6 or more people judged that the odor after the test was equivalent to intensity 3 or higher

Furthermore, the heat storage properties of the obtained Amagasa knitted fabrics were evaluated according to the following criteria.
[Heat storage evaluation]
1. Evaluation using artificial sun Cut out two approximately 3 cm square samples C (see Figure 1) from the Amagasa knitted fabric, overlap the two obtained samples, place a thermocouple 15 between them, and place a sample stand (made of styrofoam). After fixing it with a work holder (not shown), it was irradiated with artificial sunlight (lamp 12: artificial solar lighting lamp XC-500EFSS9 manufactured by SELIC Co., Ltd.), and the temperature of the sample was measured 15 minutes later. The irradiation distance L was 35 cm, and the room temperature was 20±2°C.

The heat storage and heat retention performance was evaluated by comparing the control sample R (see Figure 1) of approximately 3 cm square using polyester Amagasa knitted fabric with the sample C made from the gloves of each example and comparative example, and how high the temperature was. The temperature difference (ΔT°C) was measured and evaluated based on the following criteria. In addition, the position of the sample (C and R in FIG. 1) was changed and the measurement was performed four times, and the average value of the data was taken as the test result.
◎: Temperature difference of 5℃ or more
○: Temperature difference of 2°C or more △: Temperature difference of 1°C or more to less than 2°C ×: Temperature difference of less than 1°C2. Evaluation by panelists The fabrics were evaluated by 10 panelists according to the following criteria.
◎: 9 or more people judged it to have excellent heat storage properties ○: 7 to 8 people judged it to have excellent heat storage properties △: 5 to 6 people judged it to have excellent heat storage properties ×: 6 or more people judged it to have excellent heat storage properties Determined to have poor heat storage properties

The evaluation results are shown in Table 1.

As a result of the evaluation, the obtained cotton jersey knitted fabric was found to have excellent deodorizing properties and heat storage properties. It was also rated as not easily stuffy even when worn for long periods of time.

[Example 2]
In the graphite silica stone-containing staple fiber of Example 1, the sheath/core ratio was changed from 2/1 to 1/1. Other than that, a blended yarn and Amagasa knitted fabric were obtained using the same materials and conditions as in Example 1. Note that by changing the sheath/core ratio from 2/1 to 1/1, the graphite silica stone content in the fiber increased from 3.3% by weight to 5.0% by weight.
The obtained jersey knitted fabric had excellent deodorizing properties and heat storage properties. It was also rated as not easily stuffy even when worn for long periods of time.

[Example 3]
In the graphite silica stone-containing short fiber of Example 2, the graphite silica stone content ratio (in the core component) was changed from 10% by weight to 5% by weight. Furthermore, short acrylic fibers (fiber length 51 mm) were used as other fibers. A blended yarn was obtained by blending 30% by weight of graphite silica stone-containing short fibers, 30% by weight of deodorizing short fibers, and 40% by weight of acrylic short fibers. Except for the above, an Amagasa knitted fabric was obtained using the same materials and conditions as in Example 2.
The obtained cotton jersey knitted fabric had excellent deodorizing properties and excellent heat storage properties. It was also rated as not easily stuffy even when worn for long periods of time.

[Example 4]
In the graphite silica stone-containing short fiber of Example 1, the core component was changed from polyethylene terephthalate to nylon 6. In addition, short acrylic fibers (fiber length 51 mm) were used as other fibers. A blended yarn was obtained by blending 15% by weight of graphite silica stone-containing short fibers, 30% by weight of deodorizing short fibers, and 55% by weight of acrylic short fibers. Other than that, an Amagasa knitted fabric was obtained using the same materials and conditions as in Example 1.
The obtained cotton jersey knitted fabric had excellent deodorizing properties and excellent heat storage properties. It was also rated as not easily stuffy even when worn for long periods of time.

[Example 5]
In the graphite silica stone-containing short fiber of Example 2, the graphite silica stone content ratio (in the core component) was changed from 10% by weight to 2% by weight. Except for the above, an Amagasa knitted fabric was obtained using the same materials and conditions as in Example 2.
The obtained jersey knitted fabric had excellent deodorizing properties and heat storage properties. It was also rated as not easily stuffy even when worn for long periods of time.

[Comparative example 1]
In the graphite silica stone-containing short fiber of Example 2, the graphite silica stone content ratio (in the core component) was changed from 10% by weight to 50% by weight. In Comparative Example 1, many wire breaks occurred during the fiberization process. Therefore, sample evaluation was discontinued.
[Comparative example 2]
In the graphite silica stone-containing short fiber of Example 2, the graphite silica stone content ratio (in the core component) was changed from 10% by weight to 0.5% by weight. Other than that, a blended yarn and Amagasa knitted fabric were obtained using the same materials and conditions as in Example 2.
Although the obtained cotton jersey knitted fabric had excellent deodorizing properties, it had poor heat storage properties.
[Comparative example 3]
In Example 1, a blended yarn and Tenkasa knitted fabric were obtained using acrylic short fibers (fiber length 51 mm) instead of deodorant short fibers.
Although the obtained cotton jersey knitted fabric had excellent heat storage properties, it was significantly inferior in deodorizing properties. However, it was rated as not easily stuffy even when worn for long periods of time.

[Comparative example 4]
A blended yarn and Tenkasa knitted fabric were obtained using 70% by weight of deodorant short fibers and 30% by weight of acrylic short fibers (fiber length 51 mm).
Although the obtained jersey knitted fabric had very good deodorizing properties, it had very poor heat storage properties.

Although the present invention has been described above with reference to specific embodiments, the present invention is not limited to the above embodiments. Various changes and modifications are possible without departing from the scope of the invention.

The blended yarn of the present invention has excellent deodorizing properties and heat storage properties, and as described above, can be used for various fiber structures (textile products). The blended yarn and fiber structure of the present invention, which can maintain excellent deodorizing and sterilizing effects and heat storage properties over a long period of time (semi-permanently), can be particularly suitably used in the field of nursing care.

1 Heat storage evaluation device
11 Sample stage
12 lamps
15 Thermocouple

C Examples and comparative examples
R Control (using polyester Amagasa knitted fabric)

Claims (4)

Graphite silica-containing short fibers containing graphite silica fine powder;
Consisting of deodorizing short fibers made of a thermoplastic polymer containing a tetravalent metal phosphate, a divalent metal hydroxide, and a photocatalyst,
The deodorant short fiber is
It has a core-sheath type composite structure consisting of a core and a sheath.
The core portion is made of a thermoplastic polymer with a melting point of 150° C. or higher,
The sheath portion is made of polybutylene terephthalate,
The sheath contains a tetravalent metal phosphate, a divalent metal hydroxide, a photocatalyst, and an antioxidant.
Blended yarn. Graphite silica-containing short fibers are
It has a core-sheath type composite structure consisting of a core part and a sheath part, and contains fine powder of graphite silica stone only in the core part, and the content of graphite silica stone is 0.5 to 5% by weight of the graphite silica-containing fiber. %,
The blended yarn according to claim 1.
Contains 10 to 30% by weight of short fibers containing graphite silica,
Contains 10-90% by weight of deodorant short fibers.
The blended yarn according to claim 1 or 2. A fiber structure comprising at least a portion of the blended yarn according to any one of claims 1 to 3 .

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