JPWO2014119346A1 - Deodorant and textile products - Google Patents

Abstract

The deodorant of the present invention comprises (a) 1 part by mass of zinc oxide, (b) 0.1 to 5 parts by mass of aluminum dihydrogen phosphate, (c) 3.5 to 8 parts by mass of binder resin, and (d) water. Contains 5 to 50 parts by weight.

Description

  The present invention relates to a deodorant that provides a fiber having a high deodorizing property against bad odors and hardly deteriorates even if washing is repeated, and a fiber product using the deodorant.

  Conventionally, cotton products and the like have been frequently used for clothing such as underwear, but with the development of the petrochemical industry, many are made of chemical fibers such as polyester fibers. In recent years, with the increase in population and population density in various countries around the world, particularly from the viewpoint of etiquette, clothing such as underwear has been required to have a deodorizing performance against bad odors such as sweat generated by the human body. ing.

  In order to solve the above problems, a deodorant containing aluminum tripolyphosphate, zinc oxide, smectite and water, and a fiber product containing the deodorant and dried (for example, Patent Document 1) have been studied. reference). Further, in order to obtain a deodorant effective in deodorizing human body odor, in which zinc carbonate fine particles are dispersed in water in a stable state, a deodorant obtained by dispersing zinc carbonate fine particles and a water-soluble carboxyl group-containing polymer in water. And the fiber or textiles processed with the deodorizer were examined (for example, refer patent document 2).

Japanese Patent Publication “JP 2009-90012 A” Japanese Patent Publication “JP 2003-52798 A”

  However, the deodorizers described in Patent Document 1 and Patent Document 2 cannot be said to be sufficient as deodorizers having the following performance, which has recently been increasing in demand. That is, it cannot be said to be sufficient as a deodorant that provides a fiber product that has a high deodorizing property against bad odors and does not easily deteriorate even after repeated washing. In particular, the deodorizers described in Patent Document 1 and Patent Document 2 are used in chemical fibers such as polyester fibers and polyester blended fibers, which have recently been used in an increased amount, and it is difficult to maintain the deodorant properties after washing. It was inadequate as a deodorant which can maintain deodorant property after washing with respect to a fiber blend fiber.

  The problem to be solved by the present invention is a deodorant that gives a fiber product that is highly deodorant against bad odors and does not easily deteriorate even if washing is repeated, particularly for polyester fibers and polyester blended fibers. Is providing a deodorant capable of providing the same effect. Another problem to be solved by the present invention is to provide a fiber product obtained by drying the fiber impregnated with the deodorant.

  As a result of intensive studies, the inventors of the present invention have found that a specific amount of (a) zinc oxide, a specific amount of (b) aluminum dihydrogen tripolyphosphate, a specific amount of (c) a binder resin and a specific amount of (d) water. It has been found that a deodorant containing odors has a high deodorizing property against bad odors and gives a fiber product that does not easily deteriorate even after repeated washing. It has been found that it is possible to provide a fiber product having the same effect as when other fibers such as cotton are used for chemical fibers and chemical fiber blended fibers such as polyester fiber and polyester blended fiber, which are difficult to perform, It came to complete the deodorizer and textiles of this invention.

  That is, the deodorizer of the present invention comprises (a) 1 part by mass of zinc oxide, (b) 0.1 to 5 parts by mass of aluminum dihydrogen tripolyphosphate, (c) 3.5 to 8 parts by mass of binder resin and (d ) Contains 5 to 50 parts by weight of water.

  The fiber product of the present invention is obtained by drying the fiber impregnated with the deodorant of the present invention.

  The deodorizer of the present invention has a high deodorizing property against bad odors, and gives a fiber product in which the deodorizing property is not easily lowered even if washing is repeated. In particular, the same effects as other fibers such as cotton can be imparted to polyester fibers and polyester blended fiber chemical fibers and chemical fiber blended fibers that have been difficult to maintain deodorant after washing. Can do. The fiber product of the present invention has a high deodorizing property against bad odors, and even if the washing is repeated, the deodorizing property is not easily lowered.

The deodorant of this invention contains (a) zinc oxide. (A) Zinc oxide is effective against acidic malodors such as acetic acid and isovaleric acid and basic malodors such as ammonia. (A) Zinc oxide is not limited to a specific one. (A) The primary average particle diameter of zinc oxide is preferably 0.001 μm to 100 μm, more preferably 0.002 μm to 50 μm, still more preferably 0.003 μm to 10 μm, particularly preferably. , 0.005 μm to 2 μm. (A) BET specific surface area of the zinc oxide is ^{preferably, 0.1m 2 / g~100m 2 / g} , more ^preferably from 1m ² / g~100m 2 / g, more preferably, 5 m ² / G to 100 m ² / g. The use of (a) zinc oxide having a BET specific surface area of the primary average particle size (a) zinc oxide or 0.1m ² / g~100m ² / g of 0.001Myuemu～100myuemu, deodorant of the present invention Inside (a) precipitation of zinc oxide can be prevented, and the deodorizer of the present invention can exhibit excellent deodorizing performance against basic malodors such as ammonia.

  The primary average particle diameter of zinc oxide is determined by measuring the tangential diameter of Feret constant direction of 50 or more particles based on a photograph by a transmission electron microscope (TEM), and calculating by simple arithmetic average.

The BET specific surface area of zinc oxide is measured according to the BET method defined in ASTM D3037-89. First, a mixed gas of nitrogen and helium is introduced into a BET specific surface area measuring apparatus, and a sample cell containing a sample (an object to be measured for BET specific surface area) is immersed in liquid nitrogen to adsorb nitrogen onto the sample surface. After reaching adsorption equilibrium, the sample cell is placed in a water bath and warmed to room temperature, and nitrogen adhering to the sample is desorbed. Since the mixing ratio of nitrogen gas and helium gas before and after passing through the sample cell at the time of adsorption and desorption of nitrogen gas changes, this change is compared with a gas with a constant mixing ratio of nitrogen and helium as a thermal conductivity detector ( TCD) to detect the amount of adsorption and desorption of nitrogen gas. Before the measurement, a unit amount of nitrogen gas is introduced into the apparatus for calibration, and the surface area value corresponding to the value detected by TCD is obtained to obtain the surface area of the sample. Then, the BET specific surface area (unit: m ² / g) is obtained by dividing the obtained surface area by the mass of the sample.

  It is known that the BET specific surface area is influenced by the shape of the particles and has a large correlation with the primary average particle diameter. In general, the smaller the primary average particle size, the larger the BET specific surface area.

  The deodorizer of the present invention contains (b) aluminum dihydrogen phosphate 0.1 to 5 parts by mass with respect to 1 part by mass of (a) zinc oxide. (B) Aluminum dihydrogen tripolyphosphate is effective against basic malodor such as ammonia. (B) Aluminum dihydrogen phosphate is poorly soluble in water and is not included in (g) water-soluble aluminum salt described later. (B) Aluminum dihydrogen phosphate is not limited to a specific one. (B) The primary average particle diameter of aluminum dihydrogen tripolyphosphate is preferably 0.01 μm to 100 μm, more preferably 0.01 μm to 50 μm, and still more preferably 0.01 μm to 10 μm. By using (b) aluminum dihydrogen tripolyphosphate having a primary average particle size of 0.01 μm to 100 μm, (b) precipitation of aluminum dihydrogen tripolyphosphate can be prevented in the deodorizer of the present invention, and The deodorizer of the present invention can exhibit excellent deodorizing performance against basic malodors such as ammonia.

  The primary average particle diameter of aluminum dihydrogen tripolyphosphate is obtained by measuring the Feret fixed direction tangent diameter of 50 or more particles based on a photograph taken by a scanning electron microscope (SEM), and calculating by simple arithmetic average.

  (B) The content of aluminum dihydrogen tripolyphosphate with respect to 1 part by mass of (a) zinc oxide is 0.1 to 5 parts by mass, the preferred content is 0.3 to 3 parts by mass, and the more preferred content is 0.5 to 1.2 parts by mass.

  (B) When the content of aluminum dihydrogen tripolyphosphate is 0.1 to 5 parts by mass with respect to 1 part by mass of (a) zinc oxide, the amount balance with zinc oxide is excellent. The deodorizer can exhibit excellent deodorizing performance against bad odor. Furthermore, it can prevent that the textiles of this invention whiten by (a) excessive zinc oxide.

  The deodorizer of this invention contains (c) binder resin 3.5-8 mass parts with respect to 1 mass part of (a) zinc oxide. By using 3.5 to 8 parts by mass of the binder resin (c) based on 1 part by mass of (a) zinc oxide, the fiber product of the present invention has excellent deodorizing properties even after repeated washing such as washing. It can be.

  (C) The binder resin is not limited to a specific one.

  (C) Specific examples of the binder resin include acrylic resin, silicone resin, urethane resin, fluorine resin, vinyl chloride resin, polyamide resin, polyester resin, polyether resin, polyvinyl alcohol resin, ethylene-vinyl alcohol copolymer resin, rosin. Examples thereof include a resin, a terpene resin, a cellulose resin, and starch. Among these, those having water solubility or those finely dispersed in water are preferable because each deodorant component can be evenly adhered to the fiber. (C) The binder resin is more preferably at least one selected from the group consisting of acrylic resins, silicone resins, and urethane resins, and more preferably at least one selected from the group consisting of acrylic resins and silicone resins. It is a seed, and particularly preferred is an acrylic resin or a mixture of an acrylic resin and a silicone resin, and the most preferred is an acrylic resin. (C) Binder resin can be used individually by 1 type or in combination of 2 or more types.

  (C) The content of the binder resin with respect to 1 part by mass of (a) zinc oxide is 3.5 to 8 parts by mass, the preferable content is 3.6 to 7.5 parts by mass, and the more preferable amount is 3 7 to 7 parts by mass.

  (C) When the content of the binder resin is 3.5 to 8 parts by mass with respect to 1 part by mass of (a) zinc oxide, the fiber product of the present invention (c) the amount of the binder resin is not excessive. (C) Since the binder resin does not cover and invalidate the deodorizing component, the deodorizing property is not hindered, and (c) the amount of the binder resin is not excessively reduced. Since the component can be firmly adhered to the fiber, it can be excellent in deodorizing property even if washing such as washing is repeated.

  The deodorant of this invention contains 5-50 mass parts of (d) water with respect to 1 mass part of (a) zinc oxide. By using 5 to 50 parts by mass of (d) water with respect to 1 part by mass of (a) zinc oxide, each deodorant component is dissolved or finely dispersed, and the exposed surface area of each deodorant component is increased. Deodorizing efficiency can be increased. (D) It does not specifically limit as water, Hard water, soft water, ion-exchange water, distilled water, etc. can be used. It is preferable to use ion-exchanged water because it is inexpensive and the adverse effect on the deodorant component can be minimized.

  (D) The content of water with respect to 1 part by mass of (a) zinc oxide is 5 to 50 parts by mass, the preferred content is 7 to 45 parts by mass, and the more preferred content is 10 to 45 parts by mass.

  (D) Since the content of water is 5 to 50 parts by mass with respect to 1 part by mass of (a) zinc oxide, each deodorant component is blended in a well-balanced manner without excess or deficiency. The deodorant can be excellent in deodorizing properties, and (e) the smectite concentration described later is within an appropriate range, so that the viscosity of the deodorant of the present invention is within an appropriate range. As a result, the handleability of the deodorant of the present invention can be improved.

  The deodorant of the present invention preferably contains (e) smectite in an amount of 0.01 to 1 part by mass with respect to 1 part by mass of (a) zinc oxide.

  (E) Smectite is a kind of clay mineral of layered silicate mineral. A layer composed of tetravalent silicate ions having a tetrahedral structure and a layer composed of divalent and trivalent cations having an octahedral structure are 4 layers. It is a general term for plate-like minerals having a basic crystal structure of three layers: a face layer, an octahedron layer, and a tetrahedron layer. (E) Smectite has an ion adsorbing site between layers and adsorbs various compounds, and has a swelling property that allows water to enter between layers to expand the volume ten times. In addition, (e) smectite has the characteristic of developing thixotropic properties when it is made into an aqueous solution or dispersion.

  Due to the above features, the (e) smectite can thicken the deodorant and prevent sedimentation of the deodorant component. Furthermore, the (e) smectite also has the ability to further improve the deodorizing performance against basic malodor such as ammonia.

  (E) Smectite is not limited to a specific one. Specific examples include montmorillonite, beidellite, nontronite, saponite, hectorite, soconite, and stevensite. Among them, those having hydrophilicity are preferable, and hectorite is particularly preferable. The above (e) smectite can be used alone or in combination of two or more.

  (E) The preferred content of smectite with respect to 1 part by mass of (a) zinc oxide is 0.01 to 1 part by mass, the more preferred content is 0.03 to 0.8 part by mass, and the more preferred content is It is 0.05-0.5 mass part.

  (E) When the content of smectite is 0.01 to 1 part by mass with respect to 1 part by mass of (a) zinc oxide, each deodorizing component is dispersed substantially uniformly in water without settling, The deodorizer of the present invention can exhibit excellent deodorizing performance particularly against basic malodor such as ammonia.

  The deodorant of the present invention preferably contains (f) a polymer containing an organic acid group-containing monomer unit. (F) The polymer containing an organic acid group-containing monomer unit is not limited to a specific one as long as it contains an organic acid group-containing monomer unit in the molecule. In addition, in the “organic acid group-containing monomer unit” and “organic acid group-containing monomer” described later in “organic acid” in the present invention, an organic acid anhydride, an organic acid salt, As well as mixtures thereof. Moreover, the polymer containing the (f) organic acid group-containing monomer unit is not limited by its synthesis method.

  Specific examples of the synthesis method include polymerization of an organic acid group-containing monomer such as α, β-unsaturated dicarboxylic anhydride represented by maleic anhydride alone or with a monomer copolymerizable therewith. The method of doing can be mentioned. Further, an organic acid group may be introduced into an arbitrary polymer by a known polymer reaction.

  The organic acid group-containing monomer is not particularly limited, and specific examples include unsaturated dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride; fumaric acid, maleic acid, itaconic acid, citracone Unsaturated dicarboxylic acids such as acids; monomethyl fumarate, monoethyl fumarate, mono n-butyl fumarate, monomethyl maleate, monoethyl maleate, mono n-butyl maleate, monomethyl itaconate, monoethyl itaconate, mono itaconate and unsaturated dicarboxylic acid monoesters such as n-butyl, monomethyl citraconic acid, monoethyl citraconic acid, and mono n-butyl citraconic acid; unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; and the like. Of these, unsaturated dicarboxylic acid anhydrides are preferred, α, β-unsaturated dicarboxylic acid anhydrides are more preferred, and maleic anhydride is still more preferred because of excellent polymerizability in a non-aqueous solvent. The above organic acid group-containing monomers can be used alone or in combination of two or more.

  Although the monomer copolymerizable with the organic acid group-containing monomer is not particularly limited, specific examples include aromatic vinyl monomers such as styrene, α-methylstyrene, p-methylstyrene; acrylonitrile, Unsaturated nitriles such as methacrylonitrile; acrylic acid esters such as methyl acrylate, ethyl acrylate and n-butyl acrylate; methacrylic acid esters such as methyl methacrylate, ethyl methacrylate and n-butyl methacrylate; Ethylene; α-olefins such as propylene and 1-butene; carboxylic acid unsaturated esters such as vinyl acetate and allyl acetate; vinyl ether monomers such as methyl vinyl ether; conjugated dienes such as 1,3-butadiene and isoprene; Etc. Among them, aromatic vinyl monomers and vinyl ether monomers are preferable, aromatic vinyl monomers are more preferable, and styrene is still more preferable. The above-mentioned monomers copolymerizable with the organic acid group-containing monomer can be used singly or in combination of two or more.

  (F) The content of the organic acid group-containing monomer unit in the polymer containing the organic acid group-containing monomer unit is not particularly limited, but is preferably 30 mol% or more, and 30 to 30%. 70 mol% is more preferable and 40-60 mol% is still more preferable. (F) In the polymer containing an organic acid group-containing monomer unit, the content of the organic acid group-containing monomer unit is 30 mol% or more, so that (f) organic Since it is not necessary to use a large amount of a polymer containing an acid group-containing monomer unit, it is possible to prevent adverse effects on the texture and strength of the textile product.

  (F) Although the molecular weight of the polymer containing an organic acid group containing monomer unit is not particularly limited, it is preferably 500 to 1,000,000, more preferably 1,000 to 300,000. (F) Since the molecular weight of the polymer containing an organic acid group-containing monomer unit is 500 to 1,000,000, the fiber product of the present invention has excellent deodorizing properties even after repeated washing such as washing. Can be. Further, (f) the molecular weight of the polymer containing the organic acid group-containing monomer unit is within the above range, so that the water solubility does not decrease or the solution viscosity does not increase, and the handleability during processing is improved. It becomes good.

  In the present invention, a water-soluble polymer is preferably used as the polymer (f) containing an organic acid group-containing monomer unit. (F) A polymer containing an organic acid group-containing monomer unit can generally be rendered water-soluble by neutralizing an organic acid group with a base such as sodium hydroxide. In addition, since it has a low molecular weight or a high organic acid group content, those having water solubility can be suitably used without neutralization without neutralization.

  (F) Neutralization of the polymer containing an organic acid group-containing monomer unit may be performed by a known method, whereby the organic acid group is in the form of an organic acid salt. Specific examples of the base used for neutralization include basic salts of sodium such as sodium hydroxide, sodium carbonate and sodium acetate, and alkalis such as basic salts of potassium such as potassium hydroxide, potassium carbonate and potassium acetate. Metal basic salts; and the like. (F) Among the bases used for neutralizing a polymer containing an organic acid group-containing monomer unit, an alkali metal basic salt is preferable, an alkali metal hydroxide is more preferable, and sodium hydroxide and / or water is used. Potassium oxide is more preferred, and sodium hydroxide is particularly preferred. The deodorizer of the present invention exhibits more excellent deodorizing performance by using the above-mentioned base that is obtained by neutralizing a polymer containing an organic acid group-containing monomer unit (f). Can do.

The degree of neutralization of the organic acid group is not particularly limited, but is preferably 1 × 10 ⁻¹⁰ or more and 0.8 or less. When the degree of neutralization of the organic acid group is within the above range, the high molecular weight polymer can be dissolved in water well, and has excellent deodorizing properties even after repeated washing such as washing. It can be.

  (F) The content of the polymer containing the organic acid group-containing monomer unit is preferably 0.1 to 10 parts by mass with respect to 1 part by mass of zinc oxide (a), and more preferably 1 to 5 parts by mass. is there. (F) When the polymer containing an organic acid group-containing monomer unit is 0.1 to 10 parts by mass with respect to 1 part by mass of (a) zinc oxide, the deodorant of the present invention is used for each deodorant. The components can be dispersed substantially uniformly in water without settling, and can exhibit excellent deodorizing performance against basic malodors such as ammonia. Furthermore, it is possible to prevent the fiber product of the present invention from causing problems such as a loss of texture and a decrease in strength and a problem of coloring.

  The deodorant of the present invention preferably contains (g) a water-soluble aluminum salt. (G) The water-soluble aluminum salt may be an aluminum salt having a solubility in 100 g of water in an atmosphere of room temperature 23 ° C. and humidity 50%, and is not limited to a specific one. (G) Specific examples of water-soluble aluminum salts include water-soluble aluminum phosphate salts such as primary aluminum phosphate and secondary aluminum phosphate; aluminum chloride, aluminum sulfate, aluminum nitrate, polyaluminum chloride, sodium aluminate, etc. And water-soluble aluminum salts having no phosphorus atom. Among these, water-soluble aluminum phosphate salt is preferable, and primary aluminum phosphate is more preferable. The (g) water-soluble aluminum salt can be used alone or in combination of two or more. By containing the water-soluble aluminum salt (g), the deodorizer of the present invention can exhibit excellent deodorizing performance against basic malodors such as ammonia, and the textile product of the present invention. Can be excellent in deodorizing property even when washing such as washing is repeated.

  (G) The preferable content of the water-soluble aluminum salt with respect to 1 part by mass of (a) zinc oxide is 0.01 to 5 parts by mass, the more preferable amount is 0.05 to 4 parts by mass, and the more preferable amount is Is 0.1 to 3 parts by mass. (G) When the content of the water-soluble aluminum salt is 0.01 to 5 parts by mass with respect to 1 part by mass of (a) zinc oxide, the deodorant of the present invention is effective against basic malodors such as ammonia. The fiber product of the present invention can exhibit excellent deodorizing performance, and the fiber product of the present invention can be excellent in deodorizing properties even when washing such as washing is repeated.

  The deodorizer of the present invention comprises (a) 1 part by mass of zinc oxide, (b) 0.1 to 5 parts by mass of aluminum dihydrogen phosphate, (c) 3.5 to 8 parts by mass of binder resin, and (d) water. It is an aqueous dispersion containing 5 to 50 parts by mass. The deodorizer of the present invention further comprises (e) 0.01 to 1 part by mass of smectite, (f) 0.1 to 10 parts by mass of a polymer containing an organic acid group-containing monomer unit, and / or ( g) It is preferable to contain 0.01-5 mass parts of water-soluble aluminum salts.

  The method for producing the deodorant of the present invention is not particularly limited, and (a) 1 part by mass of zinc oxide, (b) 0.1 to 5 parts by mass of aluminum dihydrogenphosphate, and (c) a binder. 3.5 to 8 parts by mass of resin, and optionally added, (e) 0.01 to 1 part by mass of smectite, (f) 0.1 to 10 parts by mass of a polymer containing an organic acid group-containing monomer unit, And (g) 0.01-5 mass parts of water-soluble aluminum salts can be obtained by stirring and mixing after putting all together in (d) 5-50 mass parts of water. Also, by mixing each of the predetermined amount of each (deodorant) component in advance separately (d) water dispersed or dissolved, (d) adjusting the total amount of water to the predetermined amount, You may obtain the deodorizer of this invention. The latter is preferable because the deodorant of the present invention having good dispersibility can be obtained in a short time.

  The deodorant of the present invention includes antiseptics; antifungal agents; antibacterial agents such as metal powders such as silver and copper; thickeners such as polyvinyl alcohol; pigments such as carbon black; dyes; alcohols such as ethanol and isopropyl alcohol. A softener for fibers; a water-absorbing agent for fibers such as a surfactant; and a crosslinking agent. The compounding amount of these additives is preferably 10 parts by mass or less, more preferably 5 parts by mass or less with respect to 100 parts by mass of the total amount of the components (a) to (d).

  Since the deodorizer of the present invention is obtained by combining (a) zinc oxide, (b) aluminum dihydrogen phosphate, (c) binder resin and (d) water in a predetermined amount, deodorant against bad odor It is possible to provide a textile product that is highly resistant and whose deodorizing property does not easily deteriorate even if washing is repeated. Moreover, the deodorizer of this invention can provide the same effect also with respect to the polyester fiber or the polyester blend fiber which is difficult to maintain a deodorizing property after washing | cleaning among fibers.

  The deodorant of the present invention includes clothing (especially underwear, socks, stockings, tights, gloves, hats, etc.), carpet, carpet, goza, toilet mat, bath mat, entrance mat, futon, bed, sofa, Fibers that make up car seats, insoles, shoes, cloth diapers, disposable diapers, and other fabrics; wallpaper; flooring; wall materials; roofing materials; etc. can do. The deodorizer of the present invention is suitable for fibers and particularly suitable for fibers constituting clothing. The deodorant of the present invention can also be used as a room deodorant, a toilet deodorant, a smoking area deodorant, an in-vehicle deodorant, a refrigerator deodorant, and the like.

  The fiber impregnated with the deodorant of the present invention is dried to obtain the fiber product of the present invention. The method of impregnating and drying the fiber with the deodorant of the present invention is not particularly limited. Specific examples of the method include (I) a method obtained by spraying or applying the deodorant of the present invention to a fiber and then drying by hot air drying, vacuum drying or the like, and (II) a fiber obtained by deodorizing the present invention. Examples of the method include a method obtained by immersing the substrate in hot air drying and vacuum drying. Although drying temperature is not specifically limited, 20-250 degreeC is preferable and 60-150 degreeC is more preferable. When the drying temperature is within the above range, the deodorant of the present invention can exhibit excellent deodorizing performance against bad odor, and the textile product of the present invention can be washed. Even if washing such as the above is repeated, it is possible to achieve excellent deodorizing properties and to prevent the fibers from being damaged.

  In obtaining the fiber product of the present invention, as described above, only the deodorant of the present invention may be used as it is, but when the fiber is impregnated, the deodorant of the present invention is used with a solvent such as water or alcohol, Preferably, it may be used together with water. The amount of the solvent used together with the deodorant of the present invention when impregnating the fiber is not particularly limited. In obtaining the textile product of the present invention, the amount ratio of the deodorant of the present invention impregnated into the fiber and the above solvent is the deodorant of the present invention when the deodorant of the present invention and the above solvent are mixed. Is preferably 0.5% by mass to 30% by mass, more preferably 1% by mass to 20% by mass, still more preferably 2% by mass to 15% by mass, and particularly preferably 3% by mass to 10% by mass. It is a quantitative ratio. By making the amount ratio of the deodorant of the present invention impregnated into the fiber and the solvent so that the concentration of the deodorant of the present invention is 0.5 mass% to 30 mass%, the fiber product of the present invention Can exhibit excellent deodorizing performance against bad odors, and can be excellent in deodorizing properties even after repeated washing such as washing, and the texture of the fibers is deteriorated. Can be prevented. The fiber product of the present invention can be obtained by impregnating the fiber with the above-mentioned solvent together with the deodorant of the present invention and drying under the above-described conditions. Thus, since the fiber product of the present invention is obtained by drying the fiber impregnated with the deodorant of the present invention, the fiber product of the present invention comprises the above (a), (b) and ( The component (c) may be included, and depending on the mode of the deodorant, the component (e), (f), and (g) may be included.

  In obtaining the fiber product of the present invention, additives used in addition to the above-described solvent such as water can be used as the deodorant of the present invention when impregnating the fiber. The additive may be used separately from the deodorant of the present invention, or may be used after being added to the deodorant of the present invention and mixed as necessary. The fiber product of the present invention can be obtained by impregnating the fiber with the above-mentioned solvent or additive together with the deodorant of the present invention and drying under the above-described conditions. Specific examples of the additives include antiseptics; antifungal agents; antibacterial agents such as metal powders such as silver and copper; thickeners such as polyvinyl alcohol; pigments such as carbon black; dyes; Examples thereof include a water-absorbing agent for fibers such as an activator; a cross-linking agent; and a curing agent. The amount of the additive added is preferably 0.1 parts by weight or more and 80 parts by weight or less, more preferably 0.5 parts by weight or more and 60 parts by weight or less with respect to 100 parts by weight of the total amount of the components (a) to (d). It is 1 part by mass or more and 40 parts by mass or less. By making the additive amount of the additive 0.1 to 80 parts by mass with respect to 100 parts by mass of the total amount of the components (a) to (d), the textile product of the present invention is deodorant against bad odors. It has the characteristics that it is highly resistant and the deodorizing property is not easily lowered even if washing is repeated, and it can have other functions according to the types of various additives.

  When the deodorant of the present invention contains (f) a polymer containing an organic acid group-containing monomer unit, when the fiber product is impregnated in obtaining the fiber product of the present invention, In addition to the above-described solvent such as water, it is preferable to use a crosslinking agent having a plurality of functional groups capable of reacting with a carboxyl group or an acid anhydride group in one molecule as an additive. When the deodorizer of the present invention includes (f) a polymer containing an organic acid group-containing monomer unit, the (f) organic acid group-containing monomer unit is better for the fiber by using the above-mentioned crosslinking agent. Thus, the fiber product of the present invention can be excellent in deodorizing properties even when washing such as washing is repeated. In addition, when the deodorant of the present invention includes (f) a polymer containing an organic acid group-containing monomer unit, the crosslinking agent preferably used is not particularly limited, but may be water-soluble. preferable.

  Specific examples of the water-soluble cross-linking agent include polyvalent epoxy compounds such as glycerin diglycidyl ether, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin triglycidyl ether; and polyvalent epoxy compounds such as ethylene glycol, glycerin and polyvinyl alcohol. Alcohol compound; etc. can be mentioned.

  Above all, the cross-linking agent is preferably a polyvalent epoxy compound.

  The addition amount of the crosslinking agent is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 15 parts by mass with respect to 100 parts by mass of the total amount of the components (a) to (d). It is below mass parts. The amount of the crosslinking agent added is 0.1 to 30 parts by mass with respect to 100 parts by mass of the total amount of the components (a) to (d). The odor property is high, and the feature that the deodorization property is hardly lowered even if washing is repeated is exhibited, and the texture of the fiber can be kept good.

  The fiber used for the textile product of the present invention is not particularly limited. Specific examples of fibers used in the textile product of the present invention include plant fibers such as cotton (cotton), jute, hemp, and wool, mohair, cashmere, camel, llama, alpaca, vicuña, angora, tenji thread, silk, etc. Natural fibers such as animal fibers; synthetic fibers such as nylon, vinylon, polyester, acrylic, polyolefin and polyurethane; regenerated fibers such as polyester made from recycled rayon, polynosic, cupra, lyocell, acetate, plastic bottles, glass Examples thereof include fibers and chemical fibers such as carbon fibers. The fibers used in the textile product of the present invention may be used singly or in combination of two or more kinds. The fiber used in the textile product of the present invention preferably includes at least one selected from chemical fibers or chemical fiber blended fibers, that is, chemical fibers, and includes at least one selected from synthetic fibers and recycled fibers. More preferably, it is a polyester fiber or a polyester blended fiber. Since the fiber used in the textile product of the present invention is a fiber of the type described above, the textile product of the present invention has a high deodorizing property against bad odor, and the deodorizing property is not easily lowered even if washing is repeated. Can be expressed.

  As explained above, the deodorant according to the present invention preferably further contains (e) 0.01 to 1 part by mass of smectite. Preferred (c) binder resin is an acrylic resin and / or a silicone resin. The deodorant preferably further contains 0.1 to 10 parts by mass of a polymer containing (f) an organic acid group-containing monomer unit. The deodorizer preferably further contains (g) 0.01 to 5 parts by mass of a water-soluble aluminum salt. In the fiber product according to the present invention, preferably, the fiber is a chemical fiber or a chemical fiber mixed fiber.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited to these Examples. Unless otherwise indicated, the part and% in an Example and a comparative example are a mass reference | standard. Moreover, the value in the compounding composition of Table 1-Table 3 is a dry mass part number except ion-exchange water.

<Washing and drying>
A washing liquid is prepared by adding 15 L of tap water adjusted to a liquid temperature of 40 ° C. and 20 ml of JAFET standard detergent (containing polyoxyethylene alkyl ether and sodium alpha olefin sulfonate) to a washing machine (JW-Z23A manufactured by Haier). Then, a deodorant fabric described later was placed therein and washed. Washing with the washing solution for 15 minutes, dehydration 3 minutes, rinsing 4 minutes, dehydration 3 minutes, rinsing 4 minutes and dehydration 4 minutes were repeated 4 times.

  The deodorant fabric after washing was spread in a thermostatic bath at 80 ° C. and dried for 30 minutes.

<Deodorization evaluation (deodorization rate)>
The deodorant fabric is cut into a size of 10 cm x 10 cm, dried in an oven at 105 ° C for 2 hours, and conditioned for 15 hours or more in a standard state (room temperature 23 ° C, humidity 50%). And a 5 L sampling bag (5 L Tedlar Bag (registered trademark) manufactured by GL Sciences Inc.). The sampling bag containing the deodorant dough was evacuated with a vacuum pump, and then the ammonia bag with an ammonia concentration of 1000 ppm was placed in a 50 L sampling bag (50 L Tedlar Bag (registered trademark) manufactured by GL Sciences Inc.). 3 L of ammonia-containing gas prepared by diluting a mixed gas with nitrogen gas with dry air and having an ammonia concentration of 100 ppm by a detector tube was sealed and closed with a rubber stopper.

  The ammonia concentration in the sampling bag having a capacity of 5 L in which 3 L of the ammonia-containing gas having an ammonia concentration of 100 ppm is sealed is measured with a detector tube 2 hours after the ammonia-containing gas is sealed, A measured concentration was obtained.

  The detector tube is No. 1 manufactured by Gastec Corporation. 3 La (measurement range 2.5 ppm to 200 ppm) and No. 3 3 L (measurement range 0.5 ppm to 78 ppm) was used.

  A blank test is performed in the same manner except that no deodorant fabric is put in a sampling bag having a capacity of 5 L in which 3 L of the ammonia-containing gas is sealed, and a blank test concentration is obtained. The deodorization rate is calculated by the following formula (1). did. The larger the value, the better the deodorizing property.

Further, the deodorant fabric after washing and drying was evaluated in the same manner as the unwashed deodorant fabric.
Deodorization rate (%) = 100 × (Blank test concentration−Measured concentration) / (Blank test concentration) (1)
Example 1
To 1.475 parts by mass of ion-exchanged water, 0.025 parts by mass of Ultraxanthane VT-7 manufactured by Ina Food Industry Co., Ltd. and 1 part by mass of zinc oxide (NANOFINE W-1, manufactured by Sakai Chemical Industry Co., Ltd.) An average particle diameter of 0.01 μm and a BET specific surface area of 75 m ² / g) were added, and the mixture was vigorously stirred with a homogenizer to obtain 2.5 parts by mass of dispersion (I).

  To 2.87 parts by mass of ion-exchanged water, 0.82 parts by mass of aluminum trihydrogenphosphate (K-FRESH # 100P manufactured by Teika Co., Ltd., primary average particle size 0.5 μm to 1.5 μm) was added and stirred. 3.69 parts by mass of dispersion liquid (II) was obtained.

  0.18 parts by mass of smectite (Lucentite SWN manufactured by Corp Chemical Co., Ltd.) was added to 1.8 parts by mass of ion-exchanged water and stirred to obtain 1.98 parts by mass of dispersion (III).

  To 1.98 parts by mass of the dispersion (III), 3.69 parts by mass of the dispersion (II) was added and stirred to obtain 5.67 parts by mass of the dispersion (IV).

  To 5.67 parts by mass of the above dispersion (IV), 2.5 parts by mass of the above dispersion (I), a binder resin-containing liquid (DICNAL E-8203WH, manufactured by Dainippon Ink & Chemicals, Inc., acrylic resin, solid content 45%) 9.1 parts by mass (that is, 4.1 parts by mass of dry binder resin, 5 parts by mass of ion-exchanged water) and 22.155 parts by mass of ion-exchanged water (that is, ion-exchanged water in the deodorant) Of 33.3 parts by mass) was added and stirred, and the deodorant according to Example 1 was obtained.

  Next, 10 parts by mass of the deodorant according to Example 1 was added to 90 parts by mass of ion-exchanged water and stirred to obtain a processing liquid.

Polyester fibers with a fiber diameter of 20 μm are bundled into 190 μm, and a 100% polyester dry fabric knitted flat with a basis weight of 127 g / m ² is immersed in the above processing solution, and passed between two rolls with adjusted gaps once. Thus, the processed dough was squeezed with a constant pressure and the pick-up rate represented by the following formula (2) was adjusted to 100 ± 3%. Thereafter, the processed dough was dried in an oven at 150 ° C. for 5 minutes, and further heat-treated at 170 ° C. for 2 minutes to obtain a deodorant fabric (textile product) according to Example 1 in which the deodorant was uniformly processed. Obtained.
Pickup rate (%) = 100 × (mass of processed dough immediately after impregnated with processing liquid and squeezed at a constant pressure−mass of dried dough before processing) / (mass of dried dough before processing) (2)
About the obtained deodorant cloth, the deodorization rate (%) was calculated | required as mentioned above. The results are shown in Table 1.

(Examples 2 to 6 and Comparative Example 1)
The binder resin-containing liquid and the dry weight of the binder resin are changed as shown in Table 1, and finally added when obtaining the deodorant so that the total amount of ion-exchanged water becomes the amount shown in Table 1. Deodorant and deodorant cloth according to Examples 2 to 6 and deodorant according to Comparative Example 1 except that the amount of ion-exchanged water is changed to 22.155 parts by mass as necessary. An agent and a deodorant fabric were obtained.

  About the obtained deodorant cloth, the deodorization rate (%) was calculated | required as mentioned above. The results are shown in Table 1.

(Example 7)
In 14.4 parts by mass of ion-exchanged water heated to 50 ° C., 3.4 parts by mass of a styrene-maleic anhydride copolymer (SMA 1000P manufactured by Cray Valley Hydrocarbon Chemicals, copolymerization molar ratio 1: 1) and 0.3 parts by mass of sodium hydroxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added and stirred to obtain 18.1 parts by mass of dispersion (V).

  Table 2 shows the total amount of water in the deodorant, and 18.1 parts by weight of the dispersion (V) was added to 5.67 parts by weight of the dispersion (IV). The deodorant according to Example 7 was the same as Example 1 except that the amount of ion-exchanged water added last when obtaining the deodorant was changed to 22.155 parts by mass. Obtained.

  Next, 10 parts by mass of the deodorant according to Example 7 and 0.25 parts by mass of polyethylene glycol diglycidyl ether (Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.) are added to 89.75 parts by mass of ion-exchanged water and stirred. Thus, a deodorant fabric according to Example 7 was obtained in the same manner as in Example 1 except that the processing liquid was obtained.

  About the obtained deodorant cloth, the deodorization rate (%) was calculated | required as mentioned above. The results are shown in Table 2.

(Examples 8 to 12, Comparative Example 2)
The binder resin-containing liquid and the dry weight of the binder resin are changed as shown in Table 2, and finally added when obtaining the deodorant so that the total amount of ion-exchanged water becomes the amount shown in Table 2. Except having changed the quantity of ion-exchange water as needed, it was carried out similarly to Example 7, and the deodorizer and deodorant cloth which concern on Examples 8-12 and the deodorizer which concerns on the comparative example 2 were obtained. .

  About the obtained deodorant cloth, the deodorization rate (%) was calculated | required as mentioned above. The results are shown in Table 2.

(Example 13)
In addition to 5.67 parts by mass of the dispersion (IV), 0.9 parts by mass (ie, primary phosphorus) of primary aluminum phosphate (Taki Alpha WR-100B manufactured by Taki Chemical Co., Ltd., solid content 33%). The total amount of ion-exchanged water in the deodorant becomes the amount shown in Table 2. Thus, the deodorizer and deodorant cloth which concern on Example 13 were obtained like Example 8 except having changed the quantity of the ion exchange water added at the end when obtaining a deodorizer.

  About the obtained deodorant cloth, the deodorization rate (%) was calculated | required as mentioned above. The results are shown in Table 2.

(Examples 14 to 15)
The binder resin-containing liquid and the dry weight of the binder resin are changed as shown in Table 2, and finally added when obtaining the deodorant so that the total amount of ion-exchanged water becomes the amount shown in Table 2. Deodorizers and deodorant fabrics according to Examples 14 to 15 were obtained in the same manner as Example 13 except that the amount of ion-exchanged water was changed as necessary.

  About the obtained deodorant cloth, the deodorization rate (%) was calculated | required as mentioned above. The results are shown in Table 2.

(Example 16)
A deodorant and a deodorant fabric according to Example 16 were obtained in the same manner as in Example 7, except that the dried fabric was changed to AIR155 (65% polyester, 35% cotton) manufactured by Masuda Co., Ltd.

  About the obtained deodorant cloth, the deodorization rate (%) was calculated | required as mentioned above. The results are shown in Table 3.

1) NANOFINE W-1 manufactured by Sakai Chemical Industry Co., Ltd. (primary average particle diameter 0.01 μm, BET specific surface area 75 m ² / g)
2) K-FRESH # 100P manufactured by Teika Co., Ltd. (primary average particle size: 0.5 μm to 1.5 μm)
3) Lucentite SWN manufactured by Corp Chemical Co., Ltd.
4) SMA1000P (copolymerization molar ratio 1: 1) made by Cray Valley Hydrocarbon Specialty Chemicals
5) Wako Pure Chemical Industries, Ltd. 6) Taki Chemical Co., Ltd. Taki Alpha WR-100B (solid content 33%)
7) DICNAL E-8203WH (Acrylic resin, solid content 45%) manufactured by Dainippon Ink & Chemicals, Inc.
8) Ultrazol K-55 (acrylic resin, solid content 46%) manufactured by Aika Industry Co., Ltd.
9) POLON-MWS (silicone resin, solid content 29%) manufactured by Shin-Etsu Chemical Co., Ltd.
The deodorant fabrics according to Examples 1 to 16 had a high deodorization rate for both unwashed and after washing.

  The deodorant fabric obtained from the deodorant according to Comparative Example 1 having too little binder resin content had a high deodorization rate when not washed, but the deodorization rate after washing was low.

  Since the deodorizer according to Comparative Example 2 in which the content of the binder resin was too large could not uniformly disperse each component, the processing for obtaining the deodorant fabric was not performed.

  The deodorizer of the present invention is useful for obtaining a fiber product that has a high deodorizing property against bad odors and is unlikely to deteriorate even after repeated washing.

Claims (7)

  (A) 1 part by mass of zinc oxide, (b) 0.1-5 parts by mass of aluminum dihydrogen phosphate, (c) 3.5-8 parts by mass of binder resin and (d) 5-50 parts by mass of water Deodorants.   Furthermore, (e) The deodorizer of Claim 1 containing 0.01-1 mass part of smectites.   The deodorizer according to claim 1 or 2, wherein the (c) binder resin is an acrylic resin and / or a silicone resin.   Furthermore, (f) The deodorizer of any one of Claims 1-3 containing 0.1-10 mass parts of polymers containing an organic acid group containing monomer unit.   Furthermore, the deodorizer of any one of Claims 1-4 containing 0.01-5 mass parts of (g) water-soluble aluminum salt.   A fiber product obtained by drying a fiber impregnated with the deodorant according to any one of claims 1 to 5.   The textile product according to claim 6, wherein the fiber is a chemical fiber or a chemical fiber blended fiber.