JP4115880B2 - Special cross-section fiber - Google Patents

Description

【００９０】
【表２】

【００９１】
【発明の効果】
本発明の繊維は、表面溝構造に起因するさまざまな特徴を発揮し、高濃度の臭気成分の消臭のみならず、低濃度の臭気成分をほとんど完全に消臭することができ、さらに抗菌性能・ワイピング性をも合わせ持った繊維を提供することができる。また、衣料用としては良好なキシミ風合を有する。したがって、本発明の繊維は衣料用素材・生活資材素材など様々な用途に有用である。
【図面の簡単な説明】
【図１】 本発明の繊維の形態を示す電子顕微鏡写真。
【図２】 本発明の繊維の横断面の一例を示す模式図。
【図３】 本発明の繊維を得るための複合繊維の形態の一例を示す繊維断面写真。[0001]
BACKGROUND OF THE INVENTION
The present invention has a surface structure that could not be formed by conventional fiber manufacturing technology made of thermoplastic polymer, and hates odors such as masks, carpets, curtains, hospital sheets, diapers, wiping cloths, clothing materials, etc. It relates to deodorant and antibacterial fibers that can be used for various purposes.
[0002]
[Prior art]
Among synthetic fibers, polyester fibers, polyamide fibers, and the like are indispensable not only as clothing materials but also as daily life materials from the viewpoint of excellent dimensional stability, chemical resistance, strength, durability, and the like. However, depending on the intended use, it has been desired to provide a special function. For example, in the living environment such as homes, offices, hospitals, etc., interest in various bad odors is increasing, and bad odors (nitrogen containing ammonia, amines, etc.) that cause as much as possible in carpets, curtains, hospital sheets, diapers, etc. Compounds, sulfur-containing compounds such as hydrogen sulfide and methyl mercaptan, aldehydes such as formaldehyde and acetaldehyde, and lower fatty acids such as formic acid, acetic acid, propionic acid and valeric acid) And textile products were desired.
[0003]
However, there are various odor components such as basic odor components such as nitrogen-containing compounds, neutral odor components such as sulfur-containing compounds, aldehydes, and acidic odor components such as lower fatty acids in the living environment. It was difficult to effectively remove these components. In order to remove these odor components, various deodorizing fibers have been proposed. For example, a method has been proposed in which an extract from natural conifers, broad-leaved trees, or an extract from green tea is attached to the surface of a textile product by post-processing. However, there is a problem in durability because functions are added by post-processing. was there. In particular, there has been a problem that the deodorizing performance is extremely lowered when repeated washing is performed, or when a textile product is dyed.
[0004]
Further, a deodorizing fiber in which an adsorbent is supported on the fiber has been proposed. However, since the adsorption capacity of the adsorbent is limited in such a deodorizing fiber, the deodorization cannot be performed when the adsorption amount of the odor component reaches the saturated adsorption amount, and there is a problem in sustainability of the deodorization performance. In addition, a technique for catalytically degrading malodorous components with deodorant fibers carrying metal phthalocyanine has been proposed (see Patent Documents 1 and 2). However, since the catalytic activity of metal phthalocyanine is small, the deodorizing effect is not sufficient. There wasn't.
[0005]
Furthermore, for the purpose of improving the durability, there is a deodorant kneaded in the resin, which is a combination of an iron divalent ion compound and L-ascorbic acid, but the heat resistance is insufficient or a malodorous component. There is a problem that discoloration occurs after deodorizing and can only be used as a fiber material for specific purposes. In addition, deodorant fibers in which zirconium phosphate particles are kneaded into fibers as a deodorant component (see Patent Document 3), and zinc silicate particles having an amorphous structure composed of zinc oxide and silicon dioxide are kneaded in fibers. There have been proposed deodorized fibers (see Patent Document 4) and deodorized fibers (see Patent Document 5) in which white fine powders of hydrated oxides of Ti and Zn are kneaded into the fibers. Further, a deodorant fiber in which an adsorbent composition containing a water-insoluble phosphate of a tetravalent metal and a hydroxide of a divalent metal is combined or blended in the fiber has been proposed (see Patent Documents 6 and 7). However, these deodorizing fibers do not exhibit excellent deodorizing performance with respect to all odor components such as acidic odor components, basic odor components and neutral odor components.
[0006]
In addition, even if it has a certain level of deodorizing performance, if the contact area with the air containing odorous components is small, the odorous components cannot be completely deodorized, and the odor (bad odor) will be felt for those who are sensitive to odors. ) Will remain, and discomfort will not be wiped away.
[0007]
Conventionally, a type using ultrafine fibers has been proposed that has a certain degree of deodorization performance and increases the contact area with air (see Patent Document 8), but the fiber diameter is originally extremely thin. The ultrafine fibers are easily cut, and it is difficult to obtain ultrafine fibers having a desired tensile strength. Furthermore, since the tension was insufficient when the fabric was used, mixing with other fibers was necessary.
Many of these past proposals have not been sufficient to meet the demands of modern consumers who want a higher quality.
[0008]
[Patent Document 1]
JP-A-62-6985 Patent Claim
[Patent Document 2]
Japanese Patent Application Laid-Open No. 62-6986
[Patent Document 3]
JP 63-29571 A Claims
[Patent Document 4]
Japanese Patent Laid-Open No. 2-91209 Patent Claim
[Patent Document 5]
JP-A-2-80611 Patent Claim
[Patent Document 6]
Japanese translation of PCT publication No. 5-504091
[Patent Document 7]
JP, 6-47276, A Claims
[Patent Document 8]
JP, 10-204727, A Claims
[0009]
[Problems to be solved by the invention]
The object of the present invention is a fiber that can remove various odor components such as basic odor components, neutral odor components, and acidic odor components extremely efficiently and over a long period of time, and also removes a trace amount of odor components. It is to provide a deodorant fiber that can be used. In addition, another object is to provide a deodorant fiber having antibacterial and wiping properties.
[0010]
[Means for Solving the Problems]
That is, the present invention comprises a thermoplastic polymer containing a tetravalent metal phosphate, a divalent metal hydroxide and a photocatalyst, and has 20 or more grooves on the fiber surface along the length direction of the fiber. When the linear distance from the center of gravity of the cross section of the fiber to the farthest point on the outer periphery of the fiber is A, the outer peripheral length B of the fiber cross section is more than 10 times the linear distance A. The fiber is characterized in that the width of the groove is 1/50 or less of the outer peripheral length B, and has a groove depth more than twice the width of the groove.
[0011]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, unless otherwise specified, it is referred to as “containing” including inclusion in the fiber by kneading the photocatalyst and adsorbent and loading on the fiber surface by post-processing. The group numbers in the periodic table are based on the IUPAC (International Union of Pure and Applied Chemistry) Inorganic Chemical Nomenclature Commission naming convention 1970 edition. As described above, a composition composed of a tetravalent metal phosphate and a divalent metal hydroxide may be simply referred to as an “adsorbent”, and the adsorbent and other adsorbents as necessary. The composition composed of the adsorbent may be simply referred to as “adsorbent component”. Further, the photocatalyst and the adsorbent may be collectively referred to as “deodorant”.
[0012]
The structure of the fiber of the present invention will be described with reference to the drawings. FIG. 1 is a photograph showing one embodiment of the fiber of the present invention. FIG. 2 is a schematic diagram showing the shape of the cross section of the fiber of the present invention.
In the present invention, the first requirement is that the X component containing the deodorant is A, where the linear distance from the center of gravity (G) of the fiber cross section to the farthest point on the outer periphery of the fiber cross section is A. It is important that the outer peripheral length B of the fiber cross section is 10 times or more than A. By setting the perimeter length B in this way, odorous components can be removed very efficiently, the amount of deodorant used can be reduced, and a large deodorizing effect can be achieved with a small amount of deodorant. .
Furthermore, in the present invention, the fiber cross section can be an irregular cross section or a hollow cross section depending on the application.
[0013]
In the present invention, the center of gravity G of the fiber cross section can be obtained by mass property calculation on a computer using an enlarged photograph of the fiber cross section. Also, if the cross-sectional shape is simple, cut out an enlarged photo along the cross-sectional shape of the fiber, for example, place it on a needle, etc., and simply find the point of balance as the center of gravity G, farthest from the fiber periphery A straight line distance to the point may be A. Also for the fiber outer peripheral length B, the above enlarged photograph is used, and appropriate yarns are stacked along the outer periphery of the fiber cross section to make the total yarn length simply the outer peripheral length B, and the ratio between A and B can be obtained. it can.
[0014]
The second requirement of the fiber of the present invention is that the groove having a width not more than 1/50 of the outer peripheral length B of the fiber cross section and having a depth not less than 2 times, preferably not less than 3 times the width. There are many. By forming grooves having such a size on the fiber surface, odorous components can be removed very efficiently. When the groove width C exceeds 1/50 of the outer peripheral length B, or when the groove depth D is less than twice the groove width C, it is difficult to obtain a deodorizing performance with high immediate effect. From this viewpoint, in the present invention, the groove width C is preferably 1/100 or less of the outer peripheral length B, more preferably 1/200 or less, and even more preferably 1/250 or less. Although a lower limit is not specifically limited, For example, it is preferable that it is 1 / 10,000 or more.
The groove depth D is preferably 3 times or more of the groove width C, and the upper limit is preferably 30 times or less, more preferably 20 times or less, and particularly preferably 15 times or less.
The ratio of the groove width C to the groove depth D is the linear distance of the perpendicular line extending from the center point of the straight part of the groove width C to the deepest point of the groove as shown in the enlarged view of FIG. This is obtained as the groove depth D.
In the present invention, the first requirement and the second requirement are combined to achieve the desired performance synergistically.
[0015]
The third requirement in the present invention is that 20 or more groove structures having the above sizes are formed in the fiber cross section. When the number of grooves is less than 20, the deodorizing performance with high immediate effect is not sufficient, and as a result, the intended performance is not sufficiently exhibited. Therefore, the number of grooves is preferably 25 or more, more preferably 45 or more. The upper limit of the number of grooves is not particularly limited, but is preferably 200 or less, more preferably 150 or less, and still more preferably 100 or less.
[0016]
The polymer constituting the fiber of the present invention can be basically used as long as it is a thermoplastic polymer. For example, polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, polyhexamethylene terephthalate, polyethylene naphthalate. , Polyester polymers such as polylactic acid, aliphatic polyamides such as nylon 6, nylon 66, nylon 12 and the like, vinyl polymers such as polyethylene, polypropylene, polyvinyl chloride, polystyrene, polymethyl methacrylate, polycarbonate, polyoxymethylene, polyphenylene Condensation polymers such as sulfides and polyurethanes, and molten liquid crystalline polymers such as polyarylates can be applied. Preferably, polyesters, polyamides, polyolefins, etc. System, a thermoplastic crystalline polymer of the polycondensation polymers are preferred.
[0017]
As a polymer used by this invention, the glass transition temperature (Tg) of 65 degrees C or less is preferable from the point of the deodorizing effect. The polyester polymer will be described in detail. In the case of a modified polyester (sometimes referred to as a copolyester), examples of the modified species include aliphatic dicarboxylic acids such as adipic acid and sebacic acid, and the amount of modification constitutes the polyester. 3 mol% to 15 mol% is preferable, more preferably 7 mol% to 10 mol%, based on the total acid component. When the amount of modification is less than 3 mol%, the glass transition temperature (Tg) does not reach 65 ° C. or less, making it difficult to exhibit the desired deodorizing performance, and when it exceeds 15 mol%, the fiberization processability deteriorates. Furthermore, polyesters such as polybutylene terephthalate (PBT), polylactic acid, and polytrimethylene terephthalate are used, preferably polybutylene terephthalate and polylactic acid, and polybutylene terephthalate is particularly preferable. 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 typical examples thereof are composed only of terephthalic acid units and 1,4-butanediol units. And polybutylene terephthalate (hereinafter sometimes referred to as “PBT”).
[0018]
The polyester is preferably further modified with an aromatic dicarboxylic acid containing a sulfonate group effective for deodorizing ammonia. Specific examples of the sulfonate group-containing compound include 5-sodium sulfoisophthalic acid, 5-sodium sulfoisophthalic acid dimethyl ester, 5-sodium sulfoisophthalic acid diethyl ester, 5-potassium sulfoisophthalic acid, and 5-potassium sulfoisophthalic acid dimethyl ester. Benzenedicarboxylic acid having a metal sulfonate group such as 5-potassium sulfoisophthalic acid diethyl ester, 5-lithium sulfoisophthalic acid, 5-lithium sulfoisophthalic acid dimethyl ester, 2-sodium sulfoterephthalic acid or the like; Sodium sulfo-2,6-naphthalenedicarboxylic acid, 4-sodium sulfo-2,6-naphthalenedicarboxylic acid dimethyl ester, 6-sodium sulfo-1,4-naphthalenedicarboxylic acid Bon acid, naphthalene dicarboxylic acid or a lower alkyl ester having a metal sulfonate group such as 5-sodium sulfo-1,4-naphthalenedicarboxylic acid. Only one kind of the sulfonate group-containing compound may be used, or two or more kinds thereof may be used. The content of the compound is 0.5 mol% to 7.7% with respect to the total acid components constituting the copolymer polyester. An amount in the range of 0 mol% is preferred, more preferably in an amount in the range of 1.2 mol% to 5.0 mol%, in particular in an amount in the range of 1.5 mol% to 3.0 mol%. It is preferable. If the compound component is less than 0.5 mol%, the deodorizing performance of ammonia tends to be insufficient, whereas if it exceeds 7.0 mol%, the fiber physical properties of the resulting fiber tend to decrease. .
[0019]
The polyamide-based polymer used as a suitable polymer of the present invention will be described. As the aliphatic polyamide, polyamides mainly composed of the above-described nylon 6, nylon 66, metaxylenediamine nylon, and nylon 12 are preferable. Depending on the purpose, a polyamide having a high melting point or glass transition point may be used. In that case, a semi-aromatic polyamide having thermoplasticity is preferably used. Examples of such polyamide include a dicarboxylic acid and a diamine component, wherein 60 mol% or more of the dicarboxylic acid component is an aromatic dicarboxylic acid and 60 mol% or more of the diamine component is an aliphatic alkylene having 6 to 12 carbon atoms. Polyamide which is diamine is mentioned.
[0020]
As the aromatic dicarboxylic acid, terephthalic acid is preferable, and isophthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,4-phenylenedioxydiacetic acid, 1 , 3-phenylenedioxydiacetic acid, diphenic acid, dibenzoic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4 ′ -Aromatic dicarboxylic acids such as biphenyldicarboxylic acid can be used alone or in combination of two or more. The content of the aromatic dicarboxylic acid is preferably 60 mol% or more of the dicarboxylic acid component, and more preferably 75 mol% or more.
[0021]
Examples of dicarboxylic acids other than the aromatic dicarboxylic acids include malonic acid, dimethylmalonic acid, succinic acid, 3,3-diethylsuccinic acid, glutaric acid, 2,2-dimethylglutaric acid, adipic acid, 2-methyladipic acid, and trimethyl. Aliphatic dicarboxylic acids such as adipic acid, pimelic acid, azelaic acid, sebacic acid, and suberic acid; and alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, These acids can be used alone or in combination of two or more. Among these, in order to increase the glass transition point of the polymer, it is preferable that the dicarboxylic acid component is 100% aromatic dicarboxylic acid.
Furthermore, a polyvalent carboxylic acid such as trimellitic acid, trimesic acid, pyromellitic acid or the like can be contained within a range where fiberization is easy.
[0022]
Further, 60 mol% or more of the diamine component is preferably composed of an aliphatic alkylene diamine having 6 to 12 carbon atoms. Examples of the aliphatic alkylene diamine include 1,6-hexanediamine and 1,8-octanediamine. 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2-methyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine And the like. Of these, 1,9-nonanediamine alone or a combination of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is preferred from the standpoint of fiberizing process properties and desired yarn quality.
The content of the aliphatic alkylene diamine is preferably 60 mol% or more of the diamine component, more preferably 75 mol% or more, and particularly preferably 90 mol% or more from the viewpoint of fiberizing process and yarn quality. preferable.
[0023]
Examples of diamines other than the above aliphatic alkylene diamines include aliphatic diamines such as ethylene diamine, propylene diamine, and 1,4-butane diamine; fats such as cyclohexane diamine, methyl cyclohexane diamine, isophorone diamine, norbornane dimethyl diamine, and tricyclodecane dimethyl diamine. Cyclic diamines; aromatic diamines such as p-phenylenediamine, m-phenylenediamine, xylylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylether, or the like The mixture of these can be mentioned, These can use not only one type but 2 or more types.
[0024]
In the present invention, as long as the effect is not impaired, a stabilizer such as a copper compound, a colorant, an ultraviolet absorber, a light stabilizer, an antioxidant, an antistatic agent, a flame retardant, and a plasticizer are added to the polyamide component. In addition, a lubricant and a crystal acceleration retarder can be added during the polymerization reaction or in a subsequent step. Addition of an organic stabilizer such as hindered phenol, a copper halide compound such as copper iodide, and an alkali metal halide compound such as potassium iodide as heat stabilizers improves the melt retention stability during fiberization. Therefore, it is preferable.
[0025]
The deodorant comprising a photocatalyst and an adsorbent can be added to the modified polyester by (1) a method of adding a deodorant during or immediately after the polymerization of the modified polyester, and (2) a deodorant in the modified polyester. A masterbatch is prepared by adding an agent, and a method of using the masterbatch, and (3) erasing at any stage until the modified polyester is spun (for example, polymer pellet preparation stage, melt spinning stage, etc.). There is a method of adding an odorant. Among these, in the method (1), a method of adding a deodorant to the raw slurry of the fiber-forming polymer, a method of adding a deodorant immediately after the prepolymer is produced and immediately before the prepolymer is further polycondensed, fiber A method of adding a deodorant immediately after polymerization of the forming polymer and still in a liquid state can be adopted, but the deodorant used in the present invention has a very high catalytic activity, so depending on the type of polymer. In some cases, the polymerization reaction may proceed, so care must be taken.
[0026]
The deodorant is added in the form of fine particles, but if the particles are added to the polymer as they are, fiber aggregation may be difficult due to aggregation of the particles, or only low strength can be obtained even if fiberized. Therefore, it is preferable to add it to the polymer in a slurry state dispersed in an appropriate dispersion medium.
[0027]
The photocatalyst constituting the deodorant used in the present invention refers to a photocatalyst that functions as a photooxidation catalyst by generating active radicals upon irradiation with light rays such as ultraviolet rays and oxidizing and decomposing many harmful substances and malodorous substances. For this reason, photocatalysts often belong to the category of oxidizing photocatalysts. When such a photocatalyst is used, deodorization can be performed over a long period of time because deodorization can be achieved using catalytic decomposition rather than a simple adsorption action. Furthermore, this photocatalyst not only decomposes harmful substances and malodorous substances, but also has a bactericidal action, an antibacterial action and the like.
[0028]
As a photocatalyst, various optical semiconductors can be used regardless of whether they are inorganic or organic, but they are often inorganic optical semiconductors. As the photocatalyst, for example, a sulfide semiconductor (CdS, ZnS, In ₂ S _Three , PbS, Cu ₂ S, MoS _Three , WS ₂ , Sb _Three S _Three , Bi _Three S _Three ZnCdS ₂ Etc.), metal chalcogenite (CdSe, In, etc.) ₂ Se _Three , WSe _Three HgSe, PbSe, CdSe, etc.), oxide semiconductor (TiO ₂ , ZnO, WO _Three , CdO, In ₂ O _Three , Ag ₂ O, MnO ₂ , Cu ₂ O, Fe ₂ O _Three , V ₂ O _Five , SnO ₂ Etc.), and semiconductors other than sulfides and oxides include GaAs, Si, Se, CdP _Three , Zn ₂ P _Three Etc. are also included. These photocatalysts can be used alone or in combination of two or more.
[0029]
Among these photocatalysts, sulfide semiconductors such as CdS and ZnS, TiO ₂ ZnO, SnO ₂ , WO _Three Oxide semiconductors such as ₂ ZnO and the like are preferable. There is no particular limitation on the crystal structure of the optical semiconductor constituting the above-described photocatalyst. For example TiO ₂ May be any of anatase type, brookite type, rutile type, amorphous type and the like. Particularly preferred TiO ₂ Includes anatase-type titanium oxide.
[0030]
The photocatalyst can be used in the form of a sol or gel and may be used in the form of a powder. When the photocatalyst is used in the form of powder, the average particle size of the photocatalyst can be selected within a range that does not impair the photoactivity and deodorization efficiency, and is, for example, 0.05 to 5 μm, preferably 0.05 to 1 μm. When the particle diameter exceeds 5 μm, for example, filter clogging and fluff cutting are likely to occur during melt spinning. In particular, when the fiber of the present invention is used as a fiber material for various garments, a fine yarn having a single yarn fineness of about 1 dtex is required, and when the particle size of the photocatalyst is increased, yarn breakage during stretching tends to be severe. .
[0031]
The amount of the photocatalyst used can be selected from a wide range that does not impair the catalytic activity depending on the fiber structure. For example, the photocatalyst is used in an amount of 0.1 to 25% by mass, preferably 0.3 to 20% by mass, and more preferably Is in the range of 0.5 to 15% by mass, particularly preferably in the range of 0.5 to 10% by mass.
[0032]
On the other hand, the adsorbent (tetravalent metal phosphate, divalent metal hydroxide) constituting the deodorant will be described. The group in the periodic table is not particularly limited as long as the tetravalent metal forming the phosphate is a tetravalent metal. Tetravalent metals include group 4 elements of the periodic table, for example, group 4A elements (titanium, zirconium, hafnium, thorium, etc.) and group 4B elements (germanium, tin, lead, etc.). Of these metals, metals belonging to Group 4A elements of the periodic table such as titanium, zirconium, hafnium, and Group 4B elements such as tin are preferable. Titanium and zirconium are particularly preferable.
[0033]
The phosphoric acid constituting the phosphate includes various phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid, tetraphosphoric acid and the like. The phosphoric acid is often orthophosphoric acid, metaphosphoric acid or pyrophosphoric acid. Further, the phosphate includes a hydrogen phosphate such as hydrogen orthophosphate. In the present specification, unless otherwise specified, phosphoric acid means orthophosphoric acid.
[0034]
These tetravalent metal phosphates are usually water-insoluble or sparingly soluble. Furthermore, the phosphate may be a crystalline salt, but is preferably an amorphous salt. These tetravalent metal phosphates can be used alone or in combination of two or more.
[0035]
The divalent metal forming the hydroxide may be a divalent metal regardless of the group of the periodic table. Examples of the divalent metal include periodic table 1B elements such as copper, periodic table 2A elements such as magnesium, calcium, strontium and barium, periodic table 2B elements such as zinc and cadmium, periodic table 6A such as chromium and molybdenum. Examples include periodic group 7A elements such as group elements and manganese, and periodic group 8 elements such as iron, ruthenium, cobalt, rhodium, nickel and palladium. These divalent metal hydroxides may be used alone or in admixture of two or more.
[0036]
Preferred divalent metals include transition metals such as periodic table 1B elements such as copper, periodic table 2B elements such as zinc, periodic table 7A elements such as manganese, and periodic table 8 elements such as iron, cobalt and nickel. included. Copper, zinc, iron, cobalt and nickel are preferred.
[0037]
These divalent metal hydroxides are usually insoluble or hardly soluble in a weakly acidic to weakly alkaline region (pH 4 to 10). The hydroxide may be crystalline, but is often amorphous.
[0038]
The ratio of the tetravalent metal phosphate to the divalent metal hydroxide can be selected within a range that does not impair the catalytic activity, adsorption capacity for odorous components and deodorization capacity. For example, the metal atomic ratio ( (Divalent metal / tetravalent metal) = 0.1 to 10, preferably 0.2 to 7, and more preferably 0.2 to 5. In addition, when using combining a some phosphate and / or hydroxide, the metal atomic ratio based on the total amount of each metal should just be in the above-mentioned range. Further, a composition composed of a tetravalent metal phosphate and a divalent metal hydroxide may be combined by coprecipitation such as a mixed gel. In particular, when an adsorbent composed of a combination of a tetravalent metal phosphate and a divalent metal hydroxide and the above-mentioned photocatalyst are combined or used by coprecipitation, high catalytic activity is exhibited. In addition, various compounds such as odor components can be efficiently removed over a long period of time.
[0039]
The use amount of the adsorbent can be appropriately selected according to the structure of the fiber, similarly to the use amount of the photocatalyst. For example, 0.1 to 25% by mass, preferably 0.5 to 20% by mass, and further 1 The range of -10 mass% is preferable. In addition, the quantity of a photocatalyst is 1-1000 mass parts with respect to 100 mass parts of adsorbents, Preferably it is 10-750 mass parts, Furthermore, the range of 20-500 mass parts is preferable.
[0040]
The above deodorant may further contain another adsorbent (hereinafter referred to as an additional adsorbent). Such an additional adsorbent may be either an inorganic adsorbent or an organic adsorbent, and may be black, but it is a non-black adsorbent, preferably a light or white or colorless adsorbent such as blue. In many cases, an agent is used. Inorganic adsorbents include metal oxides such as aluminum oxide (alumina), silica (silicon dioxide), copper oxide, iron oxide, cobalt oxide and nickel oxide; silicates such as silica gel, silica sol and zeolite; montmorillonite, allophane, Examples include clay minerals such as sepiolite. The other adsorbent may be an adsorbent in which these components are combined by coprecipitation. Organic adsorbents include various ion exchange resins having ion-exchange functional groups such as carboxyl groups, sulfone groups, amino groups, organic acid adsorbents having the acidic functional groups, porous polyethylene, porous polypropylene, porous And porous resins such as porous polystyrene and porous polymethyl methacrylate.
[0041]
The type of the additional adsorbent can be appropriately selected according to the use of the fiber and the odor component. For example, when the fiber is exposed to a high temperature during the production or use of the fiber, the use of an inorganic adsorbent is preferable. Further, the additional adsorbent can be used alone or in combination of two or more, and mixed or coprecipitated with at least one component selected from a photocatalyst, a tetravalent metal phosphate and a divalent metal hydroxide. It may be combined by such as.
[0042]
The adsorbent constituting the deodorant described above may be combined with silicon dioxide useful for increasing the specific surface area and increasing the adsorption capacity. Examples of silicon dioxide include an inorganic polymer having a high molecular weight, a composite compound of silicon dioxide and tetravalent metal phosphate, and the like. The silicon dioxide may be hydrous silicon dioxide. Such silicon dioxide may be crystalline, but is preferably amorphous. The content of silicon dioxide can be selected within a range in which the catalytic activity and adsorption performance of the photocatalyst are not lowered. For example, the metal / silicon adsorbent metal is 0.2 to 10 in terms of metal atomic ratio with respect to the adsorbent, preferably 0. The range of .5 to 8, more preferably 1 to 7 is preferable.
[0043]
The above-mentioned deodorant may contain an antibacterial metal component (for example, silver, copper, zinc, lead, etc.), particularly a silver component, together with or without the additional adsorbent. . A composition containing a silver component among antibacterial metal components has high antibacterial performance and also has a broad antibacterial spectrum. The silver component may be metallic silver, AgCl, AgF, AgF ₂ Silver halide such as Ag, Ag ₂ Silver oxide such as O and AgO, AgS ₂ Sulfides such as Ag ₂ SO _Four , Ag ₂ CrO _Four , Ag _Three PO _Four , Ag ₂ CO _Three , Ag ₂ O _Three It may be an inorganic compound such as an oxyacid salt. The silver component may be an adsorbent or a complex with an additional adsorbent. The silver component may be water-soluble, but is preferably water-insoluble or poorly water-soluble. These silver components can be used alone or in combination. The silver component can be easily introduced into a photocatalyst, an adsorbent, an additional adsorbent and the like by a conventional method such as an ion exchange method or a coprecipitation method. The content of the silver component is 0.1 to 10% by mass, preferably 0.5 to 8% by mass, and more preferably 0.5 to 7% by mass in terms of metallic silver with respect to the entire deodorant and additional adsorbent. A range is preferred.
[0044]
In the present invention, the total amount of the deodorant, additional adsorbent and silver component added as necessary is within a range that does not impair the properties of the fiber and the fiber forming process, for example, 0.1 to 30 with respect to the entire fiber. The range of mass%, preferably 0.5 to 25 mass%, more preferably 1 to 20 mass% is preferable.
[0045]
The deodorant component can be obtained by various conventional methods. For example, by mixing tetravalent metal phosphates, divalent metal hydroxides and photocatalysts with additional adsorbents (such as silicon dioxide) and / or silver components as necessary, deodorant components Can be easily obtained. At the time of mixing, the respective granular components obtained by pulverization or the like may be mixed.
[0046]
The photocatalyst can be adjusted according to a conventional method, for example, a method for producing a water-insoluble precipitate from an aqueous solution containing metal ions corresponding to the photocatalyst, a method for preparing from a metal alkoxide, a gas phase method for oxidizing at a high temperature, .
[0047]
In producing the photocatalyst, a compound containing a component corresponding to the catalyst can be used. A description will be given by taking titanium oxide as an example. TiCl as such component _Four TiF _Four , TiBr _Four Titanium halide such as Ti (SO _Four ) ₂ , TiOSO _Four Sulfates such as (CH _Three O) _Four Ti, [CH _Three (CH ₂ O] _Four Ti, [(CH _Three ) ₂ CHO] _Four Ti, [CH _Three (CH ₂ ) _Three O] _Four Ti, [(CH _Three ) ₂ CHCH ₂ O] _Four C such as Ti _1-6 Alkoxy titanium or the like can be used. In addition, a titanium oxide sol adjusted in advance may be used.
[0048]
Further, the deodorant component is a solution containing a component corresponding to a tetravalent metal ion, a divalent metal ion and a photocatalyst, or an aqueous solution containing two or more kinds of metal ions among these metal ions. It can also be obtained by a method of forming a mixed precipitate of insoluble substances. The mixed precipitate obtained by this method is usually gel-like and becomes a mixture having an amorphous structure upon drying. In this method, the component corresponding to the photocatalyst is preferably adjusted in advance to an appropriate crystal structure and added to the aqueous solution.
[0049]
Various aqueous solution metal compounds are used for the preparation of an aqueous solution containing tetravalent metal ions, divalent metal ions and silver ions. Examples of such water-soluble metal compounds of divalent metals, tetravalent metals, and silver include various metal salts and metal alkoxides. As a metal salt, in addition to a normal metal salt (normal salt), an acid salt, an oxy salt, another double salt, or a metal salt in the form of a complex salt may be used. The metal salt may be a compound that dissolves in an acidic solution, even if it is an insoluble compound in the vicinity of a neutral pH of an aqueous solution. Specific examples include the following compounds.
[0050]
(1) Halides such as metal fluorides, chlorides, bromides, iodides, (2) sulfates, ammonium sulfates, other sulfates (inorganic acid salts), (3) nitrates (inorganic acid salts), ( 4) Other inorganic acid salts such as chlorate, perchlorate, thiocyanate, diammine silver sulfate, diammine nitrate, chromate, (5) Organics such as acetate, formate, oxalate, etc. Examples thereof include acid salts, (6) oxymetal salts (oxymetal salts in the form of halides, inorganic acid salts, and organic acid salts), and (7) metal alkoxides.
[0051]
Of these metals, inorganic acid salts, particularly strong acid salts such as sulfates and nitrates, are often used. Of the tetravalent metal compounds, oxymetal salts are often used as titanium compounds and zirconium compounds.
[0052]
Water-soluble silicate compounds that are the source of silicate ions for silicon dioxide include alkali metal silicates such as sodium silicate and potassium silicate, and alkaline earth silicates such as calcium silicate and barium silicate. Examples thereof include metal salts and ammonium silicate. Silicon dioxide does not need to be water-soluble. For example, silicon dioxide xerogel (silica gel), hydrosol or hydrogel can be used as a raw material. As the silicate ion source, alkali silicates, preferably alkali metal silicates, hydrosols, and hydrogels are usually used. In particular, sodium silicate is preferable in terms of cost and handling.
[0053]
To produce tetravalent metal phosphates and divalent metal hydroxides, the divalent metal hydroxides can be produced in the presence of tetravalent metal phosphates and divalent metal ions. . For example, (i) a tetravalent metal phosphate may be produced in an aqueous solution in which a tetravalent metal ion and a divalent metal ion coexist, and then a divalent metal hydroxide may be produced, and (ii) A tetravalent metal phosphate may be generated in advance in an aqueous solution not containing a divalent metal ion, and then an aqueous solution containing a divalent metal ion may be added to generate a divalent metal hydroxide.
[0054]
In the method (i), when the composition is formed using an aqueous solution in which tetravalent metal ions and divalent metal ions coexist, the divalent metal is stirred while stirring the aqueous solution containing the tetravalent metal compound and the divalent metal compound. It is only necessary to add phosphoric acid or a phosphate while producing a precipitate of a tetravalent metal phosphate while suppressing the formation of the insoluble hydroxide. In this method, the pH of the aqueous solution containing the tetravalent metal compound and the divalent metal compound is usually in the acidic range, for example, the pH is in the range of 0 to 6, and if necessary, the formation of the divalent metal hydroxide is suppressed. Therefore, an acid may be added to adjust the pH to 4 or lower, which is an acidic range, and phosphoric acid or phosphate may be added.
[0055]
When adjusting the pH of the aqueous solution, an appropriate alkali or acid can be used. As the alkali, alkali metal or alkaline earth metal hydroxides (sodium hydroxide, potassium hydroxide, calcium hydroxide and the like), inorganic bases such as ammonia, and organic bases such as trimethylamine, triethylamine and triethanolamine can be used. As the acid, inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, and organic acids such as acetic acid, trichloroacid, trifluoroacetic acid, formic acid and oxalic acid can be used.
[0056]
Examples of the phosphoric acid or phosphate used for the production of the insoluble phosphate include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, and alkali metal salts (sodium salt, potassium salt, etc.) and ammonium salts thereof. Specifically, the phosphate includes monobasic sodium phosphate, dibasic sodium phosphate, tribasic sodium phosphate [these are simply referred to as sodium phosphate], potassium phosphate, ammonium phosphate, sodium metaphosphate. , Potassium metaphosphate, sodium pyrophosphate, potassium pyrophosphate and the like.
[0057]
In the method (i), the produced tetravalent metal phosphate is usually precipitated more sufficiently than aging. As the aging method, a conventional method, for example, a method of leaving at room temperature for a long time, a method of leaving at a temperature of 100 ° C. or less for a long time, a method of heating to reflux and the like can be used.
[0058]
When the pH is adjusted to a neutral range, for example, pH 4 to 12, by addition of alkali after completion of aging, a divalent metal hydroxide can be generated. In addition, the production | generation of the said hydroxide is carried out in liquid in parallel in neutral range, for example, the range of pH 4-12, for the alkali and the solution containing the tetravalent metal phosphate after completion | finish of ripening, and a bivalent metal ion. You may carry out by adding to. In the pH range as described above, a precipitate composed of a divalent metal hydroxide is formed, and the formed hydroxide precipitate and the precipitate of a tetravalent metal insoluble phosphate precipitate, precipitate mixture, or coexist. It forms as a sediment mixture. In the production of a divalent metal hydroxide, the reaction system may be heated when the reaction at room temperature is slow. Moreover, you may make it react at the temperature of 100 degreeC or more under pressure as needed. Stirring may be performed by bubbling using air.
[0059]
In the method (ii), a tetravalent metal phosphate precipitate and a divalent metal hydroxide can be produced according to the method (i). That is, phosphoric acid or a phosphate is added to an aqueous solution containing the tetravalent metal ion and not containing the divalent metal ion to form a phosphate in advance. After aging the produced phosphate as necessary, the pH is adjusted to an acidic range of 4 or less if necessary, an aqueous solution containing a divalent metal ion (for example, an aqueous solution containing a metal salt) is added and mixed, and Similarly, a mixed precipitate may be generated by adjusting the pH to a neutral range of 4 or more. In this method, the aging of the tetravalent metal phosphate may be performed in a relatively short time.
[0060]
The photocatalyst may be added to the reaction system for generating a tetravalent metal phosphate and a divalent metal hydroxide, for example, in the form of powder, and the tetravalent metal phosphate and / or the divalent metal. After the hydroxide is produced, it may be added to the reaction system or the produced precipitate.
[0061]
Furthermore, the photocatalyst may be formed simultaneously with the formation of a tetravalent metal phosphate and / or a divalent metal hydroxide. For the production of the photocatalyst, the above methods (i) and (ii) can be used. For example, when producing titanium oxide, titanium halide such as titanium chloride, inorganic acid salt (sulfate such as titanium sulfate) or alkoxide is added to the reaction system as necessary, and the pH of the reaction system is neutral or alkaline. It can be generated by adjusting.
[0062]
In the case of preparing a composition containing silicon dioxide, silicon dioxide and / or silicate ion species may be added in at least one step of the precipitate formation reaction, and a photocatalyst component and the like are produced. A precipitate and silicon dioxide may be mixed. In addition, when producing | generating silicon dioxide with the production | generation of the said precipitate, alkaline silicate solution (For example, sodium silicate, potassium silicate, etc.) can be used instead of an alkali. When using a silicate ion species, hydrous silicon dioxide can be produced by adjusting the pH to a neutral range of 4 to 12 together with the production of a divalent metal hydroxide.
[0063]
Further, regarding the silver component, as in the case of the silicon dioxide, a deodorizing component containing a silver component by adding a silver component, for example, a silver water-insoluble compound and / or a silver ion species in at least one step of the precipitation product reaction. Can be obtained. In addition, silver components such as silver ions can be easily converted into at least one or two or more of the above-mentioned photocatalyst, phosphate, hydroxide, silicon dioxide and these components by a conventional method such as an ion exchange method or an impregnation method. Can be supported.
[0064]
The precipitate thus obtained may be purified by a conventional method as necessary. For example, the reaction liquid containing a precipitate such as the mixed precipitate is filtered, washed with a washing solvent such as warm water or water, and purified by removing impurities such as anion species of the metal salt and drying. A deodorant component can be obtained. The filtration can be performed using a filter paper, a filter cloth, or the like, under normal temperature, normal pressure, reduced pressure, or increased pressure, and may be performed using a centrifugal separation method, a vacuum filtration method, or the like. Further, when cleaning, an inclined cleaning method or the like may be used. The drying operation may be performed by a conventional method, for example, air drying, or may be performed at a temperature lower than the decomposition temperature of the deodorant component, for example, at a heating temperature of about 400 ° C. or less, preferably 200 ° C. or less. Good.
[0065]
In the deodorant fiber of the present invention, the thickness of the fiber is not particularly limited, and the shape in the length direction of the fiber is not limited. That is, it may be a fiber having the same diameter in the length direction of the fiber, may be a thick and thin thick and thin fiber, or may be a fiber other than that. Further, the fiber may be either a short fiber or a long fiber, and when the fiber product is a yarn, it may be a spun yarn, a multifilament yarn, or a composite yarn of short fibers and long fibers. Furthermore, the fiber of the present invention includes an air entanglement process such as false twisting, interlacing, and Taslan (Hebaline Fiber Technology Inc registered trademark) process, crimping process, anti-shrinking process, and anti-corrosion depending on the use and type of fiber. Arbitrary processing / processing such as processing, hydrophilic processing, waterproof processing, and anti-dyeing processing may be performed. In addition to the deodorant described above, the deodorant fiber of the present invention includes various additives used for the fiber according to the type of fiber, such as an antioxidant, a flame retardant, an antistatic agent, a colorant, a lubricant, You may contain an antibacterial agent, an insecticide / acaricide, a fungicide, an ultraviolet absorber, a matting agent, etc.
[0066]
The deodorant fiber of the present invention can be used as various fiber products, such as yarns; fabrics such as woven fabrics, knitted fabrics and nonwoven fabrics; pile fabrics such as pile woven fabrics and pile knitted fabrics; clothing formed from these fabrics. And other body-wearable products; interior products; bedding; food packaging materials. Specifically, clothing and body such as underwear, sweater, jacket, pajamas, yukata, white robe, slacks, socks, gloves, stockings, apron, mask, towel, handkerchief, supporter, head hand, hat, shoe insole, interlining Wear items: various carpets, curtains, goodwill, wallpaper, shoji paper, paper, fiber blinds, artificial ornamental plants, fabrics for upholstery such as chairs, table cloths, electrical product covers, tatami mats, futon filling Etc.), futon side, sheets, blankets, duvet covers, pillows, pillow covers, bed covers, bed filling materials, mats, sanitary materials, toilet seat covers, wiping cloths, filters such as air purifiers and air conditioners Can be mentioned.
[0067]
The deodorant fiber of the present invention and the fiber product using the fiber are a basic odor component such as ammonia and amines, an acidic odor component such as acetic acid, formalin, and acetaldehyde under irradiation of sunlight, fluorescent lamp, ultraviolet lamp, etc. The odorous component can be decomposed quickly and for a long period of time to a large amount of neutral odorous components such as non-bromide. Therefore, even tobacco odors containing a large number of odor components can be efficiently removed, and it is effective for deodorizing indoors and cars. It is also effective for deodorizing aldehydes such as formalin and acetaldehyde generated from furniture and new building materials.
[0068]
Furthermore, deodorant fibers containing deodorant components effectively deodorize by adsorbing acidic odor components, basic deodorant components, etc. without irradiating light, such as sunlight, fluorescent lamps, ultraviolet lamps, etc. Under light irradiation, the synergistic effect of the oxidative decomposition action of the photocatalyst and the high adsorption action of the adsorbent not only enhances the deodorizing performance for acidic odor components and basic odor components, but also neutral odor components such as aldehydes. In contrast, it exhibits a high deodorizing effect, and the effect lasts for a long time. In addition, even if some oxidative decomposition products (for example, acetic acid is produced in the case of acetaldehyde) are released due to the action of the photocatalyst and may cause a new odor, Oxidative decomposition products can be adsorbed. Therefore, it is possible to prevent the release or detachment of oxidative decomposition products and further improve the deodorization efficiency, and the substance adsorbed on the adsorbent is further decomposed by the photocatalyst, so the deodorization effect lasts for a long time. is there.
[0069]
In the light irradiation, a light beam having a wavelength corresponding to the photocatalyst can be used. The wavelength of this light beam may be a wavelength that excites the photocatalyst, but usually it is a light beam containing ultraviolet rays. When titanium oxide is used as the photocatalyst, the catalytic function can be sufficiently effective even with sunlight or light from a fluorescent lamp. In addition, light irradiation is normally performed in presence of oxygen containing base | substrates, such as oxygen and air.
[0070]
Furthermore, in the present invention, antibacterial performance is also achieved by using a photocatalyst. That is, when a photocatalyst such as titanium oxide is irradiated with light having the band gap energy, electrons are excited from the valence band, and electrons are generated in the conductor and holes are generated in the valence band. These electrons and holes have a reducing ability and oxidizing ability rich in reactivity, respectively, and can induce a catalytic reaction on the catalyst surface. By utilizing this high reducing ability and oxidizing ability, various harmful substances can be oxidatively decomposed to be harmless and sterilized.
[0071]
The deodorizing fiber of this invention can maintain a deodorizing effect over a long period of time by the above-mentioned deodorant. However, even with this deodorant alone, even if it is possible to reduce the high concentration odor component to some extent, it is not possible to completely suppress the low concentration odor component to “zero”, and the cross section of the fiber Only by specifying the structure and containing tetravalent metal phosphates, divalent metal hydroxides and photocatalysts can efficiently remove low-concentration odor components to almost zero. Can do it.
[0072]
Next, the manufacturing method of the fiber of this invention is demonstrated. The cross-sectional photograph of the fiber of FIG. 3 shows an example of a composite fiber that is an intermediate fiber for producing the fiber of the present invention. In this example, a fiber body (gray portion in FIG. 3) made of polymer component X and polymer component Y (sharp rust-like white portion in FIG. 3) that is more soluble or decomposable than component X are present. They are compounded radially in the fiber cross section. Then, by dissolving or decomposing and removing a predetermined amount of component Y from the composite fiber, the fiber body becomes the fiber of the present invention having a chestnut-like cross section. The chestnut shape means, for example, a shape as shown in the schematic diagram of FIG.
[0073]
As the polymer component Y forming the fiber body, any polymer component Y can be adopted as long as it is relatively soluble or decomposed with respect to the solvent or the drug as compared with the polymer component X. Now, when using a polyester-type polymer for Y component, it is preferable to use polyester whose Y dissolution rate is 5 times or more, preferably 10 times or more faster than that of X component. For example, 1-5 mol% of 5-sodium sulfoisophthalic acid, 5-30 mass% of polyalkylene glycol, and a copolymerized polyester obtained by copolymerizing a diol component and a dicarboxylic acid component that have been used conventionally are employed. can do.
[0074]
In the present invention, the groove depth D can be arbitrarily controlled by changing the removal rate of the polymer component Y or appropriately setting a combination of polymers having different dissolution / decomposition rates. The groove width C can be arbitrarily controlled by changing the composite ratio of the polymer component X and the polymer component Y, or by using a nozzle component in which the number of wedge portions is changed.
[0075]
As the polymer component Y, the fiber of the present invention can also be obtained by using water-soluble thermoplastic polyvinyl alcohol instead of polyester having a high alkali dissolution rate. The polyvinyl alcohol polymer used is preferably a polyvinyl alcohol having a viscosity average polymerization degree of 200 to 500, a saponification degree of 90 to 99.99 mol%, and a melting point of 160 to 230 ° C., and even a homopolymer is a copolymer. However, from the viewpoint of melt spinnability, water solubility, and fiber physical properties, a copolymerized polyvinyl alcohol modified by 0.1 to 20 mol% with α-olefin having 4 or less carbon atoms such as ethylene and propylene is used. It is preferable. In this case, after manufacturing the radial conjugate fiber as shown in FIG. 3, the polyvinyl alcohol component can be dissolved and removed by hot water treatment to obtain the fiber of the present invention.
In addition, as long as the combination of the polymer component X and the polymer component Y is determined, the composite fiber serving as the intermediate of the present invention can be made into fiber using a conventionally known composite spinning apparatus. . However, since the stable spinning becomes more difficult as the number of grooves is increased, it is preferable to carefully set the structure of the spinning pack and the spinning conditions.
[0076]
In the present invention, as shown in FIG. 2, in addition to the round cross-sectional shape fiber having a large number of wedge-shaped grooves, the cross-sectional shape is not limited as long as it is within the range satisfying the provisions of the present invention. There may be. Specifically, the fiber cross-section has changed to a pentagonal or hexagonal-like shape by high-order processing such as false twist crimping, or by using a modified cross-section nozzle during spinning, a trilobal shape, a T-shape, Various cross-sectional shapes such as a multi-leaf shape such as a four-leaf shape, a five-leaf shape, and a six-leaf shape, and a hollow shape such as a single-hole hollow and a two-hole hollow or more are available.
[0077]
The single fiber fineness of the fiber of the present invention is not particularly limited, but is preferably 0.5 to 10 dtex. Moreover, it can be used not only as long fibers but also as short fibers.
[0078]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, unless otherwise indicated, the part and% in an Example are related with mass.
[0079]
(1) Deodorization test
a. Initial performance
Under normal incandescent fluorescent light irradiation (500 lux), 3 g of sample was placed in a Tedlar bag (volume: 3 liters) that was allowed to stand at a distance of 15 cm and sealed, and then air containing a predetermined concentration of odorous components was removed using a syringe. It poured into the Tedlar bag so that it might be 3 liters. The injected gas was ammonia 40 ppm, hydrogen sulfide 15 ppm, (acetic acid 40 ppm), and acetaldehyde 50 ppm. After injecting the gas, the gas in the Tedlar bag is sampled with a microsyringe after a specific time has elapsed, and the gas concentrations of hydrogen sulfide, acetic acid, and acetaldehyde are measured by gas chromatography (GC-7A type, manufactured by Shimadzu Corporation). The removal rate was calculated by the following formula. For ammonia, a gas detector tube (manufactured by Kitagawa, for ammonia) was used, and the gas concentration in the Tedlar bag was directly measured to calculate the removal rate of odor components. Similarly, measurement under light shielding was also performed.
Removal rate (%) = [(C ₀ -C) / C ₀ ] × 100
C ₀ : Initial gas concentration
C: Gas concentration after 1 hour
[0080]
(2) Antibacterial performance evaluation
The bacterial solution of the test bacteria was dropped onto the sample, and the number of viable bacteria was measured after culturing at 35 ° C. for 8 hours under light irradiation (30 cm under 2 fluorescent lamps) or under light shielding. A standard nylon cloth was used as a control cloth.
[0081]
Example 1
As polymer component X, 2.5 mol% 5-sodium sulfoisophthalic acid dimethyl ester copolymerized polybutylene terephthalate (PBT) added with 5% by mass of the above deodorant with a twin-screw extruder was used. Using a melt-modified polyvinyl alcohol (manufactured by Kuraray, saponification degree: 98.5, ethylene content: 8.0 mol%, polymerization degree: 380), the composite ratio of component X and component Y is 3: 1 by mass. Each was melted with a separate extruder, and radial composite fibers having 50 wedge shapes formed of component Y in the cross section shown in FIG. 3 were discharged from the composite spinning nozzle. Next, after the yarn discharged from the spinneret was cooled by a 1.0 m long horizontal blowing type cooling air device, the length was continuously set at a position of 1.3 m from directly below the spinneret. , Introduced into a tube heater with an inner diameter of 30 mm (inner wall temperature 180 ° C.) and stretched in the tube heater, and then an oil agent was applied to the fiber coming out of the tube heater, followed by a take-up speed of 3500 m / min via a roller. To produce a 111 dtex / 24 filament radial composite fiber.
The fiberization processability was good and no problem. A plain woven fabric having a warp density of 90 yarns / 25.4 mm and a weft yarn density of 85 yarns / 25.4 mm was prepared using the obtained composite fibers as warp yarns and weft yarns. After scouring this plain woven fabric, the woven fabric was treated in hot water for 40 minutes, and the component Y was selectively dissolved and removed so as to have a predetermined groove depth.
Then, deodorant performance and antibacterial performance were evaluated. The results are shown in Table 2. The odor component was removed with a high removal rate. Moreover, the antibacterial performance was also excellent. In addition, when the same textile fabric was left still in the atmosphere of 18 ppm of ammonia and the deodorizing effect was measured (under light irradiation), ammonia was completely deodorized in 12 hours. An odor component having a concentration as low as 18 ppm could be completely removed.
[0082]
Examples 2-3
Except that the surface groove shape of the fiber and the cross-sectional shape of the fiber were changed as shown in Table 1, fiberization and production and evaluation of the woven fabric were performed in the same manner as in Example 1.
[0083]
Examples 4-6
Defibration, woven fabric preparation, and evaluation were performed in the same manner as in Example 1 except that the deodorant species / addition amount, the surface groove shape of the fiber, and the cross-sectional shape of the fiber were changed as shown in Table 1.
[0084]
Examples 7 and 8
Polymer component X was changed to 10 mol% sebacic acid, 1.7 mol% 5-sodium sulfoisophthalic acid dimethyl ester copolymer polyester, and the deodorant species / addition amount, fiber surface groove shape and fiber cross-sectional shape are shown in Table 1. Except for the changes as shown, fiberization, woven fabric preparation and evaluation were performed in the same manner as in Example 1.
[0085]
Example 9
The polymer Y component uses polyethylene terephthalate of [η] 0.52 obtained by copolymerizing 8% by mass of polyethylene glycol having a molecular weight of 2000 and 5 mol% of 5-sodium sulfoisophthalic acid, and the spinning oil agent includes water-containing antistatic component. And using a smoothing agent component, fiberizing was carried out in the same manner as in Example 1 except that the surface groove shape of the fiber and the cross-sectional shape of the fiber were changed as shown in Table 1, and in the same manner A woven fabric was created. Thereafter, it was immersed in an alkaline aqueous solution (liquid temperature: 100 ° C.) having a caustic soda of 20 g / l and a bath ratio of 1:30 to dissolve and remove the polymer component Y.
[0086]
Example 10
The polymer component X was changed to nylon 6 and fiberization, woven fabric preparation and evaluation were performed in the same manner as in Example 1 except that the surface groove shape of the fiber and the cross-sectional shape of the fiber were changed as shown in Table 1. .
[0087]
Comparative Examples 1-4
It implemented by the method similar to Example 1 except having set so that the surface groove | channel structure shown in Table 1 might be formed. The resulting woven fabric did not have a sufficiently good texture.
[0088]
Comparative Examples 5 and 6
Comparative Example 5 was carried out in the same manner as in Example 18 except that nylon 6 was used as the polymer component X and the surface structure was set to the structure shown in Table 1. Comparative Example 6 was carried out in the same manner as in Example 19 except that polypropylene was used as the polymer component X and the surface structure was set to the structure shown in Table 1. In any case, the wiping performance using the obtained knitted fabric was insufficient.
[0089]
[Table 1]

[0090]
[Table 2]

[0091]
【The invention's effect】
The fiber of the present invention exhibits various characteristics due to the surface groove structure, can deodorize not only high concentration odor components, but also almost completely low concentration odor components, and further antibacterial performance -It is possible to provide fibers that have both wiping properties. In addition, it has a good texture for clothing. Therefore, the fiber of the present invention is useful for various uses such as clothing materials and daily life materials.
[Brief description of the drawings]
FIG. 1 is an electron micrograph showing the form of the fiber of the present invention.
FIG. 2 is a schematic view showing an example of a cross section of the fiber of the present invention.
FIG. 3 is a fiber cross-sectional photograph showing an example of the form of a composite fiber for obtaining the fiber of the present invention.

Claims (4)

  A fiber comprising a thermoplastic polymer containing a tetravalent metal phosphate, a divalent metal hydroxide and a photocatalyst, and having 20 or more grooves on the fiber surface along the length direction of the fiber, When the linear distance from the center of gravity of the cross section of the fiber to the farthest point on the outer periphery of the fiber is A, the outer peripheral length B of the fiber cross section is more than 10 times the linear distance A, and the groove The width C of the fiber is 1/50 or less of the outer peripheral length B, and has a groove depth D that is at least twice the width of the groove. The fiber according to claim 1, wherein the thermoplastic polymer has a glass transition temperature (Tg) of 65 ° C or lower. The fiber according to claim 1, wherein the thermoplastic polymer comprises a modified polyester copolymerized with at least 0.5 mol% to 7.0 mol% of a dicarboxylic acid component containing a metal sulfonate group. A wiping cloth comprising the fiber according to claim 1.

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