JP6514604B2 - Deodorant fiber and deodorant cloth - Google Patents

Description

  The present invention is a deodorizing fiber having a function of deodorizing not only a sulfur-based malodorous substance such as hydrogen sulfide and methyl mercaptan but also a malodorous substance such as lower fatty acid and body odor component as well as having a long-lasting deodorizing effect. And deodorant cloth.

  Deodorant fibers having a deodorizing function are conventionally known as materials for underwear, socks and towels. Many of them are those that hold on the fiber an agent that exerts a deodorizing effect by a chemical adsorption reaction with neutralization with an offensive odor component or an adsorbent that physically adsorbs the offensive odor component to exert a deodorizing effect. . However, since both chemical adsorption and physical adsorption depend on the surface exposure amount of the adsorbent, the durability of the deodorizing effect depends on the exposure amount, and the deodorization limit is determined by the exposure amount. Therefore, there is a problem that the deodorizing effect by the chemical adsorption reaction or physical adsorption is poor in sustainability. Moreover, there are concerns about safety issues as many products are in direct contact with the skin.

  In order to solve such problems, the present applicant has developed a deodorant fiber holding a water-soluble glassy deodorant consisting of silver-containing phosphate glass, as disclosed in Patent Document 1 and Patent Document 2 As suggested. This vitreous deodorant releases silver ions gradually when it comes in contact with moisture, and therefore has the advantage of being able to exert its deodorizing effect over a relatively long period of time.

However, since the vitreous deodorant retained in the fiber is a fine powder having a particle size of D ₉₆ = 40 μm or less, the total content of silver is also small, and the effect depends on the surface exposure amount. For this reason, in the deodorant fibers of Patent Document 1 and Patent Document 2, it is inevitable that the deodorizing effect gradually decreases as the release of silver ions progresses.

  In addition, silver ions have the effect of preventing the offensive odor generated by bacteria because they have an antibacterial effect, but there is no deodorizing effect on malodorous substances such as lower fatty acid and body odor components, such as underwear, socks and towels with these odors. There is a problem that it can not cope with the fiber material sufficiently. Therefore, there is also a problem that it is not suitable for use in the field of care and the like.

Unexamined-Japanese-Patent No. 5-339810 Japanese Patent Application Laid-Open No. 6-93565

  Accordingly, the object of the present invention is to solve the above-mentioned conventional problems, and it is excellent in the durability of the deodorizing effect, and not only sulfur-based malodorous substances such as hydrogen sulfide and methylmercaptan but also malodorous substances such as lower fatty acid and body odor component Another object of the present invention is to provide a deodorant fiber and a deodorant cloth having a deodorizing function.

The deodorant fiber of the present invention made to solve the above-mentioned problems is a deodorant fiber having a deodorizing function by a vitreous deodorant, and the vitreous deodorant comprises a copper component And a borosilicate glass containing 2 to 7 mol% of R′O (R ′ = Mg, Ca, Sr, Ba), or a silicate glass containing a copper component and 2 to 10 mol% of R′O It is characterized in that it has a function of decomposing an offensive odor component by the catalytic action of the copper component retained in the glass while the copper component is retained in the glass .

  As described in claim 2, it is preferable that the vitreous deodorant is held by being kneaded into the fiber material or by being supported on the surface of the fiber material. According to the third aspect, the vitreous deodorant can be fiberized.

  In addition, as described in claim 4, the odor eliminating cloth of the present invention can be formed of the above-mentioned odor eliminating fiber. Further, as described in claim 5, it is possible to make the fiber constituting the cloth hold the above-mentioned vitreous deodorant to make a deodorant cloth.

The deodorant fiber of the present invention has a deodorizing function by a vitreous deodorant, and the vitreous deodorant comprises a copper component and 2 to 7 mol% of R′O (R ′ A borosilicate glass containing Mg, Ca, Sr, Ba), or a silicate glass containing a copper component and 2 to 10 mol% of R′O, while keeping the copper component in the glass, The malodorous component is decomposed by the catalytic action of the copper component contained in the glass.

  While various deodorants using soluble glass have been developed, "glass agents having a catalytic deodorizing effect" have not been known conventionally. The inventors of the present invention, as a result of research over many years, the copper component contained in the glass of the above-mentioned composition functions as a catalyst to promote the decomposition reaction of sulfur-based malodorous substances, and deodorizing effect of sulfur-based malodorous substances Found new findings that

  In the present invention, as described above, since the copper component contained in the glass is used as a catalyst to promote the decomposition reaction of sulfur-based malodorous substances, compared to the prior art using chemical adsorption and physical adsorption, The deodorizing capacity can be increased, and the deodorizing effect can be exhibited stably over a long period of time. That is, although both conventional chemical adsorption and physical adsorption depend on the surface exposure amount of the adsorbent, the deodorization limit is determined by the exposure amount, but in the present invention, since the catalytic reaction is used, the exposure amount is small Even large deodorizing total amount can be obtained. Therefore, if attention is focused only on the deodorizing amount, the addition amount of the vitreous deodorant may be small.

  The vitreous deodorant used in the present invention can exhibit an excellent deodorizing effect particularly to methyl mercaptan. That is, this vitreous deodorant catalytically oxidizes and decomposes methyl mercaptan to form dimer dimethyl disulfide. At this time, radicals are generated and oxidatively decomposed. Similarly, similar oxidative decomposition is possible for other gases. However, deodorizable odors are not limited to sulfur-based odorants. Specifically, lower fatty acids, acetic acid known as body odor (sweat, foot odor), isovaleric acid, propionic acid defined by the malodor prevention method, normal butyric acid, normal valeric acid, and mid-chain fatty acid caproic acid , Enanthate and trans-2-nonenal known as age-related odor can also be deodorized. Generally, those having 2 to 4 carbon atoms are referred to as short-chain fatty acids (lower fatty acids), but in the present specification, acetic acid having 1 carbon and 5 valeric acids are also treated as lower fatty acids.

  Moreover, the deodorizing cloth of the present invention using the above-mentioned vitreous deodorant is suitable for applications where deodorizing effects such as underwear, socks and towels are desired. Sulfur-based malodorants such as methyl mercaptan, as well as lower fatty acids and body odor components and odorants such as aging odor can be exhibited over a long period of time, and are therefore preferable.

  The deodorant cloth of the present invention may be a woven cloth or a non-woven cloth, and as the nonwoven cloth, sulfur may be used as a core for clothing, interior materials for automobiles, chemical wipes, masks, carpet materials, soundproofing materials, various filters, etc. It can be applied to a wide range of applications as a system in which the deodorizing function of not only the malodorous substance but also the malodorous substance of lower fatty acid is added. In addition, duvets and pillows and their covers, blankets, carpets, curtains, sofas, wallpapers, fishing lines, fishing nets, bandages, heat insulation materials, cloth diapers, insoles, drainage nets, sanitary products, paper diapers, pet sheets, anti-condensing sheets, freshness The present invention is also applicable to a holding sheet, a water absorbing sheet, a food bag, a diaper bag, various storage bags, and the like.

  In addition, glass wool, fiber reinforced plastic, printed circuit board, sports equipment, helmets, construction materials, ship members, rubber, tires, paper, fishing rods, tennis rackets, golf clubs, cement, etc. are used as fiberization of glassy deodorant. , Base materials for aircraft, car parts, light shades, yarns, cords, tapes, cash register tapes, waterproofing materials for waterproofing films, crosses for road reinforcement, cloths, tents, unit buses, refrigerators, piping members, personal computers, digital cameras , A mobile phone, etc. can be exemplified. Glass fibers may be short fibers or long fibers.

It is a typical sectional view showing a deodorizing fiber of a 1st embodiment. It is a typical sectional view showing the deodorizing fiber of a 2nd embodiment. It is a typical sectional view of a deodorant cloth. 7 is a graph showing the results of Example E.

Hereinafter, embodiments of the present invention will be described.
The deodorant fiber of the present invention can have a structure in which a vitreous deodorant is held on the surface or in the inside of a fiber material, and a vitreous deodorant itself can be a glass fiber. . As shown in FIG. 1, the deodorant fiber of the first embodiment is a fiber material 1 into which a vitreous deodorant 2 is kneaded. As in the second embodiment shown in FIG. 2, the vitreous deodorant 2 may be held on the surface of the fiber material 1. The glassy deodorant comprises an alkali-alkaline earth-borosilicate glass containing a copper component or an alkali-alkaline earth-silicate glass containing a copper component. The particle diameter is preferably D ₉₆ = 40 μm or less.

Here, D ₉₆ is a particle size distribution measurement, and means a particle size corresponding to an integrated value of 96% when cumulative distribution is performed. Depending on the fiber diameter, when D ₉₆ exceeds 40 μm, the uniform dispersion in the resin fiber material becomes difficult, and it also leads to a decrease in fiber strength, yarn breakage during spinning and drawing. In recent years, there is a tendency of fineness, and 50 denier, 30 denier, and even 15 denier or less are not uncommon. In the case of 50 deniers or less, D ₉₆ = 25 μm or less is preferable, and further 5 μm or less, 3 μm or less is preferable in addition to the improvement of the fiber production as well as the improvement of the deodorizing effect. If the particle size is less than 0.01 μm, the efficiency of grinding and classification of the glass is extremely reduced, which is not preferable in production. The composition of the vitreous deodorant 2 will be described below.

(Alkali-alkaline earth-borosilicate glass)
The alkali-alkaline earth-borosilicate glass containing the above-mentioned copper component is SiO ₂ : 46 to 70 mol%, B ₂ O ₃ + R ₂ O (R: alkali metal): 15 to 50 mol%, R′O (R': alkaline earth metal): 2 to 7 _{mol%, Al 2 O 3: 0~6} %, CuO: 0.01~23 a glass containing mol%. _Here, B ₂ O 3: _{5~20 mol%,} R 2 O: can be 10 to 30 mol%.

The preferable composition of this vitreous deodorant 2 is SiO ₂ : 51 to 63 mol%, B ₂ O ₃ + R ₂ O: 21 to 39 mol%, R′O: 2 to 7 mol%, Al ₂ O ₃ : 0 to 5.5%, CuO: 1 to 13 mol%. Here, B ₂ O ₃ may be 8 to 17 mol%, and R ₂ O may be 13 to 22 mol%.

The most preferred composition of this vitreous deodorant _2, SiO 2: 53-62 _{mol%, B} 2 O 3: _{10~17 mol%,} R 2 O: _13~19 mol%, R'O: 3~ 6 _{mol%, Al 2 O 3: 0~4.5} %, CuO: 4~13 are mole%. Below, each glass composition is demonstrated in detail.

(SiO ₂ )
SiO ₂ is a main component that forms the structural skeleton of glass, and its content is 46 to 70 mol%, preferably 51 to 63 mol%, more preferably 53 to 62 mol%. If it is less than 46 mol%, the chemical durability of the glass becomes insufficient and the glass tends to be devitrified, which is not preferable. Furthermore, if it is less than 46 mol%, the water resistance of the glass becomes insufficient, and as a result, copper ions are easily eluted in the presence of water (including water in the air), resulting in ion elution rather than catalytic deodorizing effect. It is not preferable because the deodorizing effect by the sulfurization reaction caused by When it exceeds 70 mol%, melting point of the glass becomes difficult due to the rise of the melting point, and viscosity rise also occurs, which is not preferable.

(B ₂ O ₃ )
B ₂ O ₃ is a component that improves the solubility and clarity of glass, and in a specific composition, is also a component that forms the structural skeleton of glass. B ₂ O ₃ largely affects the stability of the glass depending on the content thereof, and in the present invention, the meaning of the glass as a fluxing agent is large. The content thereof is 5 to 20 mol%, preferably 8 to 17 mol%, and more preferably 10 to 17 mol% in consideration of the volatilized amount of B ₂ O ₃ . When it exceeds 20 mol%, B ₂ O ₃ is not preferable because it is easily volatilized in the melting process and the composition control becomes difficult.

(R ₂ O)
R ₂ O (R = Li, Na, K) breaks the bond of Si and O in the structural skeleton of glass to form non-crosslinked oxygen, and as a result, the viscosity of the glass is reduced, and the formability and solubility And a flux similar to B ₂ O ₃ . The content thereof is a total of 10 to 30 mol%, preferably 13 to 22 mol%, more preferably 13 to 19 mol%, taking into consideration the content ratio of one or two or more of R ₂ O to the multicomponent. I assume. If it exceeds 30 mol%, the chemical durability of the glass will be insufficient. Specifically, the glass agent reacts with moisture in the air to cause a whitening phenomenon called bloom. The occurrence of bloom is undesirable because the contact area with the offensive gas is reduced.

(B ₂ O ₃ + R ₂ O)
As mentioned above, both B ₂ O ₃ and R ₂ O are used as fluxes. The total content of B ₂ O ₃ and R ₂ O is in the range of 15 to 50 mol%, preferably 21 to 39 mol%, in which the deodorizing effect is safely exhibited. If it is less than 15 mol%, the meltability of the glass becomes insufficient and devitrification tends to occur during molding, which is not preferable. When it exceeds 50 mol%, the water resistance of the glass becomes insufficient, and as a result, copper ions are easily eluted in the presence of water (including water in the air), resulting in ion elution rather than catalytic deodorizing effect Since the deodorizing effect by sulfurization reaction becomes strong, it is not preferable. On the other hand, if it exceeds 50 mol%, phase separation is likely to occur during melting, and this is not preferable because the deodorizing effect of the glass agent becomes insufficient.

(R O O)
R′O (R ′ = Mg, Ca, Sr, Ba) is a component that improves the chemical durability of the glass. The total content of R'O (R '= Mg, Ca, Sr, Ba) is 2 to 7 mol%, preferably 3 to 6 mol%. More than 10 mol% and with the viscosity at the time of melting increases, undesirable because the glass tends to be devitrified.

(Al ₂ O ₃ )
Al ₂ O ₃ is a component that improves the chemical durability of the glass and affects the crystal structure stability. In addition, Al ₂ O ₃ works to suppress phase separation of glass and to improve homogeneity of glass agent. The content is 6 mol% or less, preferably 5.5 mol% or less, and most preferably 4 or less, because raising the viscosity and the addition may affect the redox state of copper ions in the glass. .5 mol% or less.

(CuO)
CuO functions as a catalyst to accelerate the decomposition reaction of the sulfur-based malodorous substance, and exhibits the deodorizing effect of the sulfur-based malodorous substance. The content thereof is 0.01 to 23 mol%, preferably 1 to 13 mol%, and more preferably 4 to 13 mol%. If it exceeds 23 mol%, undissolved matter tends to remain, and it is not preferable because metallic copper tends to precipitate during quenching or processing. Since the glass is discolored due to the deposition of metallic copper, it is not suitable for applications where discoloring of the glass is a problem. Moreover, when it precipitates as metallic copper, poisoning will advance. On the other hand, if CuO is contained as a glass component, poisoning does not easily proceed, and the catalyst function can be stably exhibited over a long period of time.

(Other trace constituents)
Besides the above components, as trace components, ZnO, SrO, BaO, TiO ₂ , ZrO ₂ , Nb ₂ O ₅ , P ₂ O ₅ , Cs ₂ O, Rb ₂ O, TeO ₂ , BeO, GeO ₂ , Bi ₂ O ₃ , La ₂ O ₃ , Y ₂ O ₃ , WO ₃ , MoO ₃ , Fe ₂ O ₃ or the like can also be included. Furthermore, F, Cl, SO ₃ , Sb ₂ O ₃ , SnO ₂ , or Ce may be added as a fining agent.

(Alkali-alkaline earth-silicate glass)
In the present invention, an alkali-alkaline earth-silicate glass containing a copper component can also be used as the vitreous deodorant 2. This _glass, SiO 2: 50-70 _mol%, R 2 O: _10~33 mol%, R'O: 2 to 10 _{mol%, Al 2 O 3: 0~6} %, CuO: 0.01~23 It is glass containing mol%.

The preferred composition of the vitreous deodorants _2, SiO 2: 55 to 70 _mol%, R 2 O: _12~24 mol%, R'O: 2 to 10 _{mol%, Al 2 O 3: 0~5} . 5%, CuO: 1 to 20 mol%. The most preferred composition of this vitreous deodorant _2, SiO 2: 55 to 65 _mol%, R 2 O: _12~20 mol%, R'O: 3 to 7 _mol%, Al ₂ O 3: _0~ 5%, CuO: 4 to 13 mol%.

Unlike alkali-alkaline earth-borosilicate glass described above, alkali-alkaline earth-silicate glass does not contain B ₂ O ₃ and the numerical range of the composition changes somewhat, but the reason for the numerical limitation is Is the same as alkali-alkaline earth-borosilicate glass.

  The vitreous deodorant 2 consisting of the alkali-alkaline earth-borosilicate glass containing the copper component described above or the alkali-alkaline earth-silicate glass containing the copper component is made of resin as shown in FIG. The material is kneaded into the fiber material 1 or held on the surface of the fiber material 1 as shown in FIG. The type of the fiber material 1 is not particularly limited, and polyethylene, polypropylene, chlorinated polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, alkyd resin, polyvinyl acetate, vinyl acetate nylon, polyester, polyvinyl alcohol, acrylic resin Any resin such as simple fibers such as synthetic resins such as vinyl chloride / vinyl acetate copolymer resin, styrene resin, epoxy resin, polymethylpentene, polymethyl methacrylate, polyvinyl butyral, ionomer, polyurethane and cellulose derivative etc. it can. Of course, compositeable resins may be composited. Further, the method of kneading the vitreous deodorant 2 into the fiber material 1 and the method of forming the fibers are the same as in the prior art.

  Besides the above, as the fiber material 1, general purpose engineering plastic such as polyethylene terephthalate (PET), polycarbonate (PC), polyamide (PA), polyphenylene sulfide (PPS), modified polyphenylene ether (m-PPE), polyetherimide (PEI) ), Polyether sulfone (PES), polyarylate (PAR), heat resistant polyamide (nylon 6, nylon 66, nylon 12, nylon 6 T, nylon 9 T, nylon 46 T), polybutylene terephthalate (PBT), polyacetal (POM), poly Heat-resistant resins such as ether ether ketone (PEEK), liquid crystal polymer (LCP), and thermosetting resins can also be used. Although natural fibers can not be mixed with the vitreous deodorant 2 inside, they can be attached to the surface as shown in FIG. 2, and natural fibers such as cotton, hemp, silk etc. can be used as the fiber material 1 It can also be used.

  The content of the vitreous deodorant 2 in the fiber material is preferably 0.1 to 10% by mass. If the amount is less than this range, the deodorizing effect will be insufficient, and if it exceeds 10% by mass, the mechanical strength, moldability and the like inherent to the resin fiber may be lost. The preferred content is 0.1 to 5% by mass. In the present invention, since the vitreous deodorant 2 exerts a deodorizing function by the catalytic effect, the deodorizing amount does not depend on the exposed amount of the vitreous deodorant 2. Since the soluble glass can not be deodorized at the adsorption limit, the deodorizing effect depends on the exposure amount. For this reason, it has been devised to increase the deodorizing amount even if the exposure is small by, for example, making the specific surface area very large. However, glass is usually susceptible to exposure because it has a small specific surface area. On the other hand, the vitreous deodorant 2 of the present invention has a small specific surface area and the same exposure as the soluble glass, but since the catalyst continues to react until deterioration, as described above, even small amounts are exposed The amount of deodorization will increase. For this reason, in the long term, a small amount may be exposed on the fiber surface, and even if it is contained in excess of 10% by mass, an increase in the deodorizing amount can not be expected.

In addition, when the vitreous deodorant 2 is kneaded into the fiber material, a method of adding the vitreous deodorant 2 alone and a master batch of the vitreous deodorant 2 are used. It is also possible to add. If the method of making a master batch is adopted, a larger amount of kneading becomes possible. The amount of addition of the glassy deodorant 2 is preferably 0.1 to 10% by mass in the case of kneading, and 1 to 100 g / m ² per attachment (for example, non-woven fabric) in the case of attachment. . In addition, when using the glassy deodorant 2 as glass fiber, the addition amount is 100%. However, it is possible to blend it with other fibers to make a non-woven fabric or to weave it with other fibers, and the amount of vitreous deodorant 2 can be freely controlled. This glass fiber can be used as a fiber reinforced plastic and a heat insulating material.

  In the first embodiment described above, the vitreous deodorant 2 is uniformly kneaded into the fiber material 1, but as in the second embodiment shown in FIG. The deodorant 2 may be supported. In this case, for example, the vitreous deodorant 2 may be dispersed in a binder and then coated on the surface of the fiber material 1. In the case of FIG. 2, since the vitreous deodorant 2 which does not contribute to deodorization can be reduced by being buried inside the fiber material 1, the deodorizing effect can be further enhanced. As a binder, for example, an acrylic binder is used and can be attached to the surface of the fiber material 1 by a method such as roll coating, dipping, or spraying. As the binder, in addition to the acrylic binder, urethane, synthetic rubber, latex, melamine based emulsion organic solvent adhesive can be mentioned.

  The deodorizing fiber of the present invention has a function of decomposing an offensive odor component by the catalytic action of the copper component held in the glass of the vitreous deodorant 2. Unlike the soluble glass, the copper component decomposes the malodorous component by catalysis while being held in the glass, so the deodorizing effect is maintained for a long time, and the durability is excellent. Moreover, since the above-mentioned soluble glass is an acidic glass, there is no deodorizing effect to lower fatty acid which is an acidic malodor, but the vitreous deodorant 2 in the present invention is deodorant to malodorous substances such as lower fatty acid and body odor component. Have an effect.

  The deodorant fiber of the present invention can be used as it is, but is suitable for use as a woven fabric (including a knitted fabric) or a non-woven fabric. Since the glassy deodorant 2 is harmless to the human body, it can also be used directly on the part in contact with the skin. In addition, since it has a deodorizing effect on malodorous substances such as low-grade fatty acids and body odor components, it is widely used not only in underwear, socks and towels, etc., but also widely used in textiles and car interior materials in the care field, carpet materials, and various filters. be able to.

  The non-woven fabric is not particularly limited, and any non-woven fabric can be used, and for example, a chemical bond non-woven fabric, a thermal bond non-woven fabric, a needle punched non-woven fabric, a spun bond non-woven fabric and the like are used. The material of the non-woven fabric is also not particularly limited, and synthetic fibers such as polyester fibers, polyamide fibers, polypropylene fibers and acrylic fibers, or natural fibers such as hemp, cotton and wool can be used.

  As described above, in addition to weaving a deodorant fiber in which a glassy deodorant is retained on the surface or in the inside of a fiber material to form a deodorant cloth, as shown in FIG. The vitreous deodorant 2 can be retained to make a deodorant cloth. In this case, the glassy deodorant may be held later in a cloth made of ordinary fibers 3. For example, after immersing the cloth in the rally in which the vitreous deodorant 2 is dispersed, the cloth may be squeezed to dry the slurry so that the vitreous deodorant is retained on the surface of the fiber 3.

  Although the vitreous deodorant 2 is used alone in the above embodiment, it can be used in combination with an inorganic deodorant such as general-purpose silica gel, zeolite, activated carbon, clay mineral, photocatalyst (titanium dioxide), etc. . Moreover, it can also be used with the phosphate glass containing silver of patent document 1, 2 mentioned. Such combined use makes it possible to aim for effects such as speeding up of deodorizing speed, expansion of target gas, and cost reduction.

  Examples of the present invention are shown below. In the table, n.d. means not detected.

  The glass raw materials were prepared so as to obtain the composition shown in Table 1, and melted, shaped and crushed by a melting and quenching method to produce a powdered vitreous deodorant. The obtained vitreous deodorant was kneaded into the fiber material under the conditions shown in Table 2 or held on the surface of the fiber material to form a deodorant fiber. Moreover, the glass raw material was prepared so that it might become a composition shown in Table 1, and the sample made into glass fiber directly was also manufactured. The deodorizing effect of the obtained deodorant fiber or the molded article using the deodorant fiber was confirmed by the deodorizing test. Each sample preparation method is as follows.

Glass fiber · staple fiber and its moldings (glass wool insulation material and non-woven fabric)
A glass fiber with an average fiber diameter of 7 μm was produced by centrifugation, which is a common method of glass fiberization (for test: 1 g) (* 1). Moreover, the phenol resin binder was added to this, and it thermoformed, and shape | molded it in plate shape with a density of 16 kg / m < ³ > (for examination: 15 cm square). The glass fibers 10% by weight, polyester staple fiber 50% by weight, polyvinyl alcohol staple fibers 40% by weight of the formulation, producing a web with a random web forming apparatus, fused in the heat treatment, the basis weight about 30 g / m ² nonwoven Were prepared (for test: 15 cm square).

Glass fiber / long fiber Melted glass was wound up with a high-speed winder to produce glass fiber having an average fiber diameter of 90 μm (for test: 10 cm in length, cut to 15 cm).

A molded product of a resin obtained by kneading glass powder kneading A glassy deodorant is blended with various resins, melt-spinning, and drawn to prepare a glass-kneaded fiber. In addition, in the case of content 5 weight% or more, since it is easy to mix | blend uniformly, the masterbatch was produced with the same resin, and this was added to resin. The obtained fiber was tubular-knitted with a tubular knitting tester to prepare a sample cloth (for testing: cut into 10 cm square) (* 2). In Table 2, resin, content, and glass particle size were described. The content is the content of molded fibers.

Attachment of glass powder to non-woven fabric A glass powder is added to a urethane-based emulsion, and a non-woven fabric (face weight: 380 g / m ² ) heat-sealed with commercially available nylon is dipped in a tank of this suspension. By heat-sealing after drying, a non-woven fabric to which glass powder was attached was produced (for test: 15 cm square cut) (* 3).

(Example A: Glass fiber and its molded body)
The fibers or molded articles of Experimental Examples 1 to 17 in Table 2 were sealed in a container together with an offensive odor component, and the malodor concentration in the container with elapsed time was measured at room temperature. Hydrogen sulfide and methyl mercaptan were measured by a gas chromatograph, acetic acid and isovaleric acid were measured by a gas detection tube, and trans-2-nonenal was measured by a high performance liquid chromatograph. As a comparison, a vitreous deodorant consisting of soluble glasses 1 to 3 shown in Table 3 was produced in the same manner as * 1. In addition, a blank corresponds to Experimental example 3 using the glass (composition number 9) which does not contain a copper component. The results are shown in Table 4. As a result, it was confirmed that any offensive odor had a deodorizing effect except for the blank. Moreover, it was confirmed that the soluble glass has no deodorizing effect on acetic acid, isovaleric acid and nonenal.

Example B: Molded Product of Resin Fiber Containing Glass Powder
The molded articles of Experimental Examples 18 to 39 in Table 2 were enclosed in a container together with an offensive odor component, and the malodor concentration was measured in the same manner as Example A. As a comparison, a vitreous deodorant consisting of soluble glasses 1 to 3 shown in Table 3 was ground to D ₉₆ = 40 μm or less, and a content rate of 0.1% by mass was prepared similarly to * 2 for PET. In addition, a blank corresponds to Experimental example 23 using the glass (composition number 9) which does not contain a copper component. The results are shown in Table 5. As a result, it was confirmed that any offensive odor had a deodorizing effect except for the blank.

(Example C: Nonwoven fabric with glass powder attached)
The molded articles of Experimental Examples 40 to 50 in Table 2 were enclosed in a container together with an offensive odor component, and the malodor concentration was measured in the same manner as Example A. As a comparison, a vitreous deodorant consisting of soluble glasses 2 and 3 shown in Table 3 was formed, ground to D ₉₆ = 40 μm or less, and the content rate was 1 g / m ² to prepare as in * 3. In addition, a blank corresponds to Experimental example 49 using the glass (composition number 9) which does not contain a copper component. The results are shown in Table 6. As a result, it was confirmed that any offensive odor had a deodorizing effect except for the blank.

Example D: Persistence to soluble glass
The molded articles of Experimental Examples 20, 22 and 25 in Table 2 were enclosed in a container together with an offensive odor component, and the malodor concentration was measured in the same manner as Example A. As a comparison, a vitreous deodorant consisting of soluble glasses 2, 3 and 4 shown in Table 3 is formed, ground to D ₉₆ = 40 μm or less, and the content is 0.1% by mass to nylon 6 * 2 It produced similarly to. As a result, as shown in Table 7, while the soluble glass reached the deodorizing limit, it was confirmed that Experimental Examples 20 and 22 have a large deodorizing total amount. The deodorizing limit of the soluble glass is determined according to the amount of exposure, while the experimental example exhibits a catalytic action, so that even if a small amount is exposed, the total deodorizing can be expected. However, the glass changes continuously depending on the composition, and the effect also changes continuously from the catalytic reaction to the adsorption reaction of the soluble glass. Since the experimental example 25 had a composition with reduced durability, it was confirmed that the tendency of the adsorption reaction became strong like the soluble glass, and the deodorizing limit was reached.

(Example E: Basic characteristics and decomposition action of glassy deodorant)
1 g of glass consisting of composition number 6 in Table 2 ground to D ₅₀ = 4.2 μm and methyl mercaptan are sealed in a 5 L Tedlar bag, and at room temperature, methyl mercaptan and dimethyl disulfide in the bag with elapsed time are measured by gas chromatography. did. Moreover, the same operation was performed using the bag of the same volume formed with the fiber which does not contain a glassy deodorant as a blank. In addition, it was previously confirmed in the gas chromatograph mass spectrometer that the gas component present in the bag is the two components. As a result, as shown in FIG. 3, it was confirmed that the glassy deodorant of the present invention has an effect of decomposing methyl mercaptan to form dimethyl disulfide. The basic properties of the glassy deodorant are naturally retained even if it is kneaded into fibers.

(Example F: Basic characteristics of glassy deodorant, radical generation)
0.1 mol·L ⁻¹ phosphate buffer solution of pH = 7.4 with respect to 200 mg of glass consisting of composition number 6, 9 of Table 2 and soluble glass 1 of Table 3 ground to D ₅₀ = 5.0 μm 200 μL was added. Then, 10 μL of 9.2 mol·L ^-1 DMPO (manufactured by LABOTEC., LM-2110) was added and shaken. After 10 seconds, 1 minute and 5 minutes after addition of DMPO, the shake was stopped, and only the solution was collected with a hematocrit tube, and ESR (FR-30, X band manufactured by JEOL Ltd.) measurement was performed. Moreover, what remove | eliminated glass was made into the blank. All performed at room temperature under fluorescent light. This method corresponds to the spin trap method which is a general method of radical measurement, and when DMPO captures a radical, a spin adduct is generated. The product (DMPO-OH) was detected by ESR. The unit of the detection value is the peak area value ratio (area single / area manganese, S / M) to the reference substance Mn2 +. The results are shown in Table 8. While the glass of composition No. 6 was confirmed to produce DMPO-OH, composition No. 9 and soluble glass 1 only showed a background value as well as the blank. It was confirmed that the glassy deodorant of the present invention is highly likely to generate radicals. The basic properties of the glassy deodorant are naturally retained even if it is kneaded into fibers.

(Example G: Basic characteristics of vitreous deodorant, suppression of catalyst deterioration)
0.1 g of a glass consisting of composition No. 6 in Table 2 and 0.1 g of CuO reagent (average particle diameter 4 μm) each crushed to D ₅₀ = 4.2 μm is sealed in a 1-L Tedlar bag, and at room temperature, with lapse of time The methyl mercaptan concentration in the bag was measured by gas chromatography. The initial concentration of methyl mercaptan was 55 ppm and was repeated up to 10 times. Moreover, the same operation was performed without glass as a blank. As a result, as shown in Table 9, the CuO reagent has a reduced deodorizing effect with repetition. This is the generally known catalytic degradation (sulfur adsorption) of CuO. On the other hand, it was confirmed that the glass maintained the deodorizing effect and the sustainability was high. Although the elucidation of this mechanism remains a problem, it was confirmed that vitrification suppresses the catalyst deterioration. When the glass surface at this time was analyzed by XPS (manufactured by ULVAC-PHI, Inc., PHI 5000 VersaProbe), as shown in Table 10, it was confirmed that there is no adsorption of sulfur after deodorization. The basic properties of the glassy deodorant are naturally retained even if it is kneaded into fibers.

1 Fiber material 2 Glassy deodorant 3 Fiber

Claims (5)

Deodorant fiber that has a deodorizing function with glassy deodorant,
This vitreous deodorant is a borosilicate glass containing a copper component and 2 to 7 mol% of R′O (R ′ = Mg, Ca, Sr, Ba), or a copper component and 2 to 10 mol% of R It is characterized by being composed of silicate glass containing 'O and having the function of decomposing malodorous components by the catalytic action of the copper component held in the glass while holding the copper component in the glass. With deodorant fiber.   The deodorant fiber according to claim 1, wherein the glassy deodorant is held by being kneaded into the fiber material or by being supported on the surface of the fiber material.   The deodorant fiber according to claim 1, wherein the glassy deodorant is fiberized.   It formed using the deodorizing fiber in any one of Claims 1-3, The deodorizing cloth characterized by the above-mentioned. A deodorant cloth in which a glassy deodorant is held by fibers constituting a cloth,
This vitreous deodorant is a borosilicate glass containing a copper component and 2 to 7 mol% of R′O (R ′ = Mg, Ca, Sr, Ba), or a copper component and 2 to 10 mol% of R It is characterized by being composed of silicate glass containing 'O and having the function of decomposing malodorous components by the catalytic action of the copper component held in the glass while holding the copper component in the glass. With deodorant cloth.