JPH10131020A - Deodorant melt-blown nonwoven fabric and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a deodorant melt-blown nonwoven fabric able to remove different odoriferous ingredients effectively for a long period of time, and provide a method for producing the non-woven fabric. SOLUTION: This melt-blown nonwoven fabric contains a photocatalyst, preferably titanium dioxide, which is an oxide semiconductor, and absorbents, preferably phosphates of tetravalent metals and hydroxides of divalent metals, respectively in a quantity of 0.1-5wt.% to the total weight of the non-woven fabric.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant melt blown nonwoven fabric useful for rapidly decomposing and removing odorous components and harmful components emitted from cigarettes, sweat, building materials and the like, and a method for producing the same.

[0002]

2. Description of the Related Art Recently, there has been a growing interest in various malodors in the living environment such as homes, offices and hospitals. Many compounds are included in these odorous components and harmful components,
For example, ammonia, nitrogen-containing compounds such as amines (eg, trimethylamine, triethylamine), hydrogen sulfide, sulfur-containing compounds such as methyl mercaptan, aldehydes such as formaldehyde and acetaldehyde, lower fatty acids such as formic acid, acetic acid, propionic acid, and valeric acid. Includes types. Thus, various odor components such as acidic odor components such as lower fatty acids, basic odor components such as nitrogen-containing compounds, sulfur odor components, and neutral odor components such as aldehydes are present in the living environment. However, it is difficult to effectively decompose and remove a plurality of different kinds of components.

In order to remove these substances, various deodorant fibers, for example, deodorant fibers having an adsorbent supported on the fibers have been proposed. However, since such a deodorant fiber does not have a function of decomposing and removing a malodorous component as in the present invention, the adsorption capacity of the adsorbent is limited, and it becomes impossible to deodorize when the adsorption amount of the odorous component reaches the saturated adsorption capacity. .. JP 62-6985
JP-A-62-6986 and JP-A-62-6986 disclose that a malodorous component is catalytically decomposed by a deodorant fiber carrying a metal phthalocyanine. However, since the catalytic activity of metal phthalocyanine is small, the deodorizing effect is not sufficient.

Further, Japanese Patent Application Laid-Open No. 63-295711 proposes a deodorant fiber in which zirconium phosphate particles are kneaded into the fiber as a deodorant component, and Japanese Patent Application Laid-Open No. 2-91209 discloses zinc oxide and silicon dioxide. A deodorant fiber obtained by kneading amorphous zinc silicate particles composed of and into a fiber has been proposed. JP-A-2-80611 discloses a white fine powder of a hydrated oxide of Ti and Zn. Deodorant fibers kneaded in have been proposed. Furthermore, special table flat 5-504
No. 091 and Japanese Patent Application Laid-Open No. 6-47276 describe a deodorant fiber obtained by compounding or admixing an adsorbent composition containing a water-insoluble phosphate of a tetravalent metal and a hydroxide of a divalent metal in the fiber. Proposed. However, these deodorant fibers do not show excellent deodorizing performance with respect to all of the acidic odor components, basic odor components and neutral odor components.

On the other hand, in the melt blown nonwoven fabric, the melt blown nonwoven fabric is prepared by adding additives such as pigments, flameproofing agents, antistatic agents, antioxidants, ultraviolet absorbers and heat resistance agents to the raw materials in the manufacturing process. It is already known to produce ##STR1## and to deposit these additives on the fiber surface, such as by post-processing.

Japanese Unexamined Patent Publication (Kokai) No. 1-187918 discloses a method of imparting deodorizing performance by supporting activated carbon as a odor component adsorbent on a meltblown nonwoven fabric fiber. However, all of these have a limit in the adsorption capacity of the adsorbent as described above, and when the saturated adsorption capacity is reached, deodorization cannot be achieved.

Further, in JP-A-7-163818, similarly, a single metal, a metal oxide, a metal chloride, zeolite, kaolin, sepiolite, silica gel, activated carbon and the like are used alone or mixed and fixed on a fiber sheet. The method to do is proposed. Among them, simple metals, metal oxides, and metal chlorides may catalytically decompose odorous components, but the purpose of the present invention is "how to fix deodorizing components on a fiber sheet". That is to say, the functions and functions of these deodorizing components are not specifically touched upon, and what kind of metal simple substance, metal oxide, or metal chloride is specifically effective is also touched upon. Has not been done. Zeolite, kaolin, sepiolite, silica gel and activated carbon all have a limited adsorption capacity.

Further, Japanese Patent Application Laid-Open No. 8-70981 proposes a clothes cover using a deodorant spunbonded nonwoven fabric carrying a metal phthalocyanine derivative. However, although the metal phthalocyanine derivative itself catalytically decomposes the malodorous component, the deodorizing effect is not sufficient because the catalytic activity is small as described above.

Furthermore, the above invention is not intended to produce a meltblown nonwoven fabric having deodorant properties as in the present invention.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a deodorant melt blown nonwoven fabric capable of efficiently removing various odorous components over a long period of time and a method for producing the same. Another object of the present invention is to provide a deodorant meltblown nonwoven fabric having a high ability to remove not only acidic odor components and basic odor components but also neutral odor components, and a method for producing the same. Still another object of the present invention is to provide a deodorant melt blown nonwoven fabric capable of efficiently removing odorous components regardless of the presence or absence of light irradiation, and a method for producing the same. Another object of the present invention is to provide a deodorant melt-blown nonwoven fabric capable of effectively removing odorous components without impairing the properties of the melt-blown nonwoven fabric, and a method for producing the same.

[0011]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that a photocatalyst having an adsorbent and a photocatalytic function, particularly an adsorbent composed of a specific phosphate and hydroxide and oxidation. The melt blown non-woven fabric can remove various odorous components by incorporating a deodorant composition in combination with a photocatalyst having a photocatalytic function such as titanium or zinc oxide into the fiber and the ability to remove the odorous components for a long period of time. The present invention has been completed by discovering that it lasts.

That is, the deodorant melt blown nonwoven fabric of the present invention is composed of fibers containing a photocatalyst and an adsorbent. The deodorant melt blown nonwoven fabric may be composed of a fiber containing a composition in which the adsorbent is composed of a tetravalent metal phosphate and a divalent metal hydroxide and a photocatalyst. The photocatalyst includes a photo semiconductor, for example, an oxide semiconductor such as titanium oxide. The content of the photocatalyst can be selected from the range of about 0.1 to 5% by weight with respect to the whole nonwoven fabric, and the content of the adsorbing component can be selected from the range of about 0.1 to 5% by weight with respect to the entire nonwoven fabric. In the deodorant component, the ratio of the photocatalyst to 100 parts by weight of the adsorbent is about 10 to 750 parts by weight.

The constituent fibers of the deodorant melt-blown nonwoven fabric are composites having various structures, for example, a phase having a high concentration of photocatalyst and an adsorbent and a phase having a lower concentration of the above components than the high concentration phase. It may have a structure (for example, a sheath-core structure, a side-by-side structure, etc.). Further, the constituent fibers of the deodorant non-woven fabric may have a modified cross-sectional shape such as a hollow cross section.

The constituent fibers of the deodorant melt blown nonwoven fabric can be obtained by incorporating a photocatalyst and an adsorbing component into the nonwoven fabric. As a means for containing the photocatalyst and the adsorbing component in the nonwoven fabric, for example, a method of supporting the photocatalyst and the adsorbing component on the fiber surface, a resin composition containing the photocatalyst, the adsorbing component and the fiber-forming resin is formed into a nonwoven fabric by the melt blown method. The method of making it contain in the fiber is mentioned.

Unless otherwise specified in this specification, a resin composition containing the above-mentioned photocatalyst and an adsorbing component is melt-blended.
The method of carrying out and the inclusion by loading are collectively referred to simply as “inclusion”. The group number of the periodic table is IUPAC(In
international Union of Pure
and Applied Chemistry) Inorganic Chemistry Nomenclature Commission Nomenclature Rule 1970 Edition. Further, a composition composed of a tetravalent metal phosphate and a divalent metal hydroxide may be simply referred to as an "adsorbent", and this "adsorbent" and another adsorbent may simply be referred to as "adsorbent component". ". The composition composed of the photocatalyst and the adsorbent and optionally another adsorbent may be simply referred to as "deodorant component". Further, a composition composed of the deodorant component and, if necessary, an antibacterial component may be simply referred to as "deodorant composition".

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION The nonwoven fabric of the present invention is a deodorant meltblown having an ability to remove various odor components (acid odor component, basic odor component and neutral odor component) efficiently and for a long time. It is a non-woven fabric. This melt blow
The non-woven fabric uses a thermoplastic fiber-forming polymer, and is usually called a melt blown nonwoven fabric manufacturing method, that is, a thermoplastic fiber-forming polymer is melt-spun and finely pulverized with a gas injected at high temperature and high speed. Use a fiber flow and then this
A method for producing a non-woven fabric by collecting it in the shape of a tongue, for example, Japanese Patent Application Laid-Open No. Sho 4
It can be produced by a method already known in JP-A-9-10258, JP-A-49-48931, JP-A-50-121570 and the like.

The deodorant component may be contained in the fibers constituting the melt blown nonwoven fabric, and the deodorant component may be blended with the thermoplastic fiber-forming polymer, and the resulting melt blown
There is a method of supporting on the surface of fibers constituting the nonwoven fabric.

The fiber-forming polymer in the present invention means, for example, polyethylene, ethylene/propylene copolymer, ethylene/butylene copolymer, ethylene/octene copolymer, ethylene-based polymer, polypropylene or propylene copolymer, Polyolefin such as polybutylene, 6
-Nylon, 66-nylon, 6/66-copolymerized polyamide, 610-nylon, 11-nylon, 12-nylon or other polyamide or copolyamide, polyethylene terephthalate, ethylene terephthalate copolymer, polybutylene Polyester such as terephthalate,
Aliphatic polycarbonate, urethane elastomer,
It is at least one polymer selected from polyester elastomers, styrene elastomers, polyamide elastomers, polyvinyl chloride or copolymers, wholly aromatic polyesters, polyphenylene sulfide, and the like.

Particularly in the present invention, the fiber-forming polymer is preferably polypropylene or polyethylene. The reason why these polymers are preferable is that they are excellent in melt blown moldability and low in cost. Further, as will be described later, when particles made of an inorganic substance are mixed in a resin as in the present invention, melt blown
During the production of the nonwoven fabric, so-called "shot" polymer beads are very likely to occur. When this non-woven fabric is used for a filter or the like, the "shot" may cause "leakage" and significantly reduce the performance of the product. Therefore, its incorporation is not preferable and should be avoided as much as possible. Polypropylene or polyethylene is preferably used because this possibility is extremely low.

The photocatalyst used in the present invention means that many harmful substances are generated by generating active oxygen by irradiation with light such as ultraviolet rays.
A substance that oxidizes and decomposes malodorous substances and functions as a photooxidation catalyst. Therefore, photocatalyst often belongs to the category of oxidizing photocatalyst. When such a photocatalyst is used, deodorization can be achieved by utilizing catalytic decomposition rather than mere adsorption action, so that the deodorizing or deodorizing effect continues for a long period of time. Furthermore, the photocatalyst not only decomposes harmful substances and malodors, but also has a bactericidal action.

As the photocatalyst, various photo-semiconductors, organic or inorganic, can be used, but inorganic photo-semiconductors are often used. As the photocatalyst, for example, a sulfide semiconductor (CdS, Z
nS, In ₂ S ₃ , PbS, Cu ₂ S, MoS ₃ , WS
₂ , Sb ₃ S ₃ , Bi ₃ S ₃ , ZnCdS _2, etc.), metal chalcogenite (CdSe, In ₂ Se ₃ , Wse)
₃ , HgSe, PbSe, CdTe, etc.), oxide semiconductors (TiO ₂ , ZnO, WO ₃ , CdO, In ₂ O ₃ ,
Ag ₂ O, MnO ₂ , Cu ₂ O, Fe ₂ O ₃ , V ₂ O
₅ , SnO _2, etc.), and GaAs, Si, Se, Cd ₂ P ₃ , semiconductors other than sulfides and oxides,
Zn ₂ P _{3 and the} like are also included. These photocatalysts can be used alone or in combination of two or more.

Among these photocatalysts, sulfide semiconductors such as CdS and ZnS, TiO ₂ , ZnO, SnO ₂ and WO ₃
Are preferred, and oxide semiconductors such as TiO ₂ and ZnO ₂ are particularly preferred. The crystal structure of the optical semiconductor forming the photocatalyst is not particularly limited. For example, TiO ₂ may be any of anatase type, brookite type, rutile type, amorphous type and the like. Preferred TiO ₂ anatase - include zero-type titanium oxide.

The photocatalyst can be used in the form of sol or gel and may be used in the form of 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 deodorizing efficiency, and is, for example, about 0.01 to 25 μm, preferably about 0.05 to 10 μm.

The amount of the photocatalyst used can be selected from a wide range that does not impair the catalytic activity.
-5% by weight, preferably 0.3-3% by weight (e.g. 1
.About.2 wt %), and more preferably about 0.5 to 1 wt %.

In the deodorant melt-blown nonwoven fabric of the present invention, a composition (that is, deodorant) composed of the photocatalyst, a tetravalent metal phosphate and a divalent metal hydroxide (that is, an adsorbent) is used. It is advantageous to use a sex component). Such deodorant components exhibit high catalytic activity and can efficiently remove various compounds such as odorous components over a long period of time.
Therefore, the deodorant melt blown nonwoven fabric in which the photocatalyst and the adsorbent are combined can remarkably enhance the deodorant property. That is, the photocatalyst alone does not effectively exhibit the deodorizing effect under light shielding, and depending on the type of the odor component, the decomposition product may be desorbed from the catalyst to cause a new bad odor again. On the other hand, when the fiber contains a combination of a photocatalyst and an adsorbent, it is possible to obtain a deodorant melt blown nonwoven fabric capable of effectively removing odorous components over a long period of time with high efficiency regardless of the presence or absence of light irradiation. it can.

The group in the periodic table is not particularly limited as long as the tetravalent metal forming phosphoric acid is a tetravalent metal. The tetravalent metal includes an element of Group 4 of the periodic table, for example, an element of Group 4A (titanium,
Zirconium, hafnium, thorium, etc.) and Group 4B elements (germanium, tin, lead, etc.) are included. Of these metals, metals belonging to Group 4A elements of the periodic table, such as titanium, zirconium and hafnium, and Group 4B elements such as tin are preferable. Particularly, titanium and zirconium are preferable, and tin is also preferable.

The phosphoric acid which constitutes the phosphate includes various phosphoric acids such as orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, triphosphoric acid and tetraphosphoric acid. Phosphoric acid is often orthophosphoric acid, metaphosphoric acid or pyrophosphoric acid. The phosphate also includes hydrogen phosphate such as hydrogen orthophosphate. Unless otherwise specified in this specification, "phosphoric acid" means orthophosphoric acid.

These tetravalent metal phosphates are usually water-insoluble or sparingly soluble. Further, the phosphate salt 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.

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

Preferred divalent metals are transition metals, for example, elements of Group 1B of the periodic table such as copper, elements of Group 2B of the periodic table such as zinc, elements of Group 7A of the periodic table such as manganese, iron, cobalt,
Elements of Group 8 of the periodic table such as nickel are included. Particularly preferred divalent metals include copper, zinc, etc., iron, cobalt,
Nickel is also preferred.

These divalent metal hydroxides are usually insoluble or sparingly soluble in water in the weakly acidic to weakly alkaline region (pH 4 to 10). The hydroxide may be crystalline, but it is often amorphous.

The ratio between the tetravalent phosphate and the hydroxide of the divalent metal can be selected within a range that does not impair the catalytic activity and the ability to adsorb and deodorize odorous components. For example, in terms of the metal atom ratio, the metal atom ratio ( (Divalent metal/tetravalent metal)=0.1-10, preferably about 0.2-5. Note that multiple phosphates and/
Alternatively, when hydroxides are used in combination, the metal atom ratio based on the total amount of each metal may be within the above range. Further, a composition composed of a tetravalent metal phosphate and a divalent metal hydroxide may be complexed by coprecipitation or the like such as a mixed gel. In particular, when an adsorbent composed of a tetravalent metal phosphate and a divalent metal hydroxide is used in combination with a photocatalyst or by complexing them by coprecipitation, high catalytic activity is exhibited, and efficiency is improved over a long period of time. Various compounds such as odorous components can be removed well.

The amount of the adsorbent used can be appropriately selected depending on the structure of the fiber, and is, for example, 0.1 to 5 relative to the whole nonwoven fabric.
It is about 0.5% by weight, preferably about 0.5 to 3% by weight. The amount of the photocatalyst is 1 to 1000 parts by weight, preferably 10 to 750 parts by weight, and more preferably 20 to 500 parts by weight, based on 100 parts by weight of the adsorbent.

The deodorant component may further contain another adsorbent (the other adsorbent may be simply referred to as an additional adsorbent). The additional adsorbent may be an inorganic adsorbent, an organic adsorbent, or a black adsorbent, but may be a non-black adsorbent, preferably a pale color such as blue or white or colorless. Adsorbents are often used. Inorganic adsorbents include, for example, aluminum oxide (alumina), silica (silicon dioxide), copper oxide, iron oxide, cobalt oxide, metal oxides such as nickel oxide, silica gel, silica sol, silicates such as theolite, montmorillonite, Examples include clay minerals such as allophane and sepiolite. The other adsorbent may be an adsorbent in which these components are complexed by coprecipitation or the like.

Examples of the organic adsorbent include various ion exchange resins having an ion-exchange functional group such as a carboxyl group, a sulfonic acid group and an amino group, an organic acid adsorbent having the acidic functional group, porous polyethylene, and the like. Examples thereof include porous resins such as porous polypropylene, porous polystyrene, and porous polymethylmethacrylate.

The type of the additional adsorbent can be appropriately selected depending on the use of the nonwoven fabric and the odorous component. For example, when the nonwoven fabric is exposed to high temperatures during the manufacturing process or during use, it is an inorganic adsorbent among the adsorbents. Is preferred. The additional adsorbents may be used alone or in combination of two or more, and may be mixed or coprecipitated with at least one component selected from a photocatalyst, a tetravalent metal phosphate and a divalent metal hydroxide. You may compound.

The adsorbent composed of the tetravalent metal phosphate and the divalent metal hydroxide constitutes an adsorption component in combination with silicon dioxide which is useful for increasing the specific surface area and the adsorption capacity. May be. Examples of the silicon dioxide include an inorganic polymer in which silicon dioxide itself has a high molecular weight, a complex compound of silicon dioxide and a 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 ability of the photocatalyst do not decrease,
For example, in terms of metal atom ratio with respect to the adsorbent, silicon/metal of adsorbent=0.2 to 10, preferably 0.5 to 8, and more preferably about 1 to 7.

The deodorant component may further comprise an antibacterial metal component (eg, silver, with or without the additional adsorbent (eg, silicon dioxide)).
Copper, zinc, etc.), and in particular, may contain a silver component. The composition containing a silver component among the antibacterial metal components has high antibacterial properties and also has a broad antibacterial spectrum.

The silver component may be metallic silver, and may be an inorganic compound (eg, silver halide such as AgCl, AgF and AgF ₂ , oxide such as Ag ₂ O and AgO, sulfide such as Ag ₂ S and Ag _{2 ).} SO ₄ , Ag ₂ CrO ₄ , Ag ₃ PO
₄ , oxyacid salts such as Ag ₂ CO ₃ and Ag ₂ O ₃ ). The silver component is a complex compound with the adsorption component (for example, a complex compound with the tetravalent metal phosphate and silver, a complex compound with a divalent metal hydroxide and silver, a complex compound with silicon dioxide and silver). May be The silver component may be water-soluble, but is preferably water-insoluble or sparingly soluble. These silver components can be used alone or in combination of two or more. The silver component can be easily introduced into the photocatalyst, the adsorbing component or the deodorizing component 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 weight, preferably 0.5 to 10% in terms of metallic silver, based on the entire deodorant component.
It is about 8% by weight, more preferably about 0.5 to 7% by weight.

The total amount of the deodorant composition composed of the deodorant component and, if necessary, an additional adsorbent (such as silicon dioxide) and a silver component is in a range that does not impair the characteristics of the melt blown nonwoven fabric, for example, It is often about 0.1 to 5% by weight, preferably about 0.5 to 3% by weight, based on the whole nonwoven fabric.

The deodorant component is preferably an amorphous composition, particularly a coprecipitated composition formed by coprecipitation. The amorphous deodorant component produced by coprecipitation is usually 10 to 1000/g,
Preferably 30-1000/g, more preferably 50-
It has a BET specific surface area of about 1000/g. Therefore, a non-woven fabric containing such a deodorant component functions as an absorptive non-woven fabric having a high adsorptivity and is a deodorant non-woven fabric or deodorant fabric for decomposing and removing various organic compounds or inorganic compounds including odorous components. Functions as a non-woven fabric.

The deodorant component and the deodorant composition can be obtained by various conventional methods. For example tetravalent metal phosphate,
A deodorant component or deodorant composition can be easily obtained by mixing a divalent metal hydroxide and a photocatalyst with an additional adsorbent (such as silicon dioxide) and/or a silver component, if necessary. You can In the mixing, each powdery component obtained by pulverization may be included.

The photocatalyst is prepared according to a conventional method, for example, a method of forming a water-insoluble precipitate from an aqueous solution containing a metal ion corresponding to the photocatalyst, a method of preparing a metal alkoxide, a gas phase method of oxidizing at high temperature, and the like. You can

In producing the photocatalyst, a compound containing a component corresponding to the catalyst can be used. Explaining titanium oxide as an example, such components include, for example, Ti
Cl _4, TiF _4, titanium halide such as _{TiBr 4, Ti (SO 4)} 2, sulfates such as TiOSO _4,
(CH ₃ O) ₄ Ti, (C ₂ H ₅ O) ₄ Ti, [CH ₃
(CH ₂ ) ₂ O] ₄ Ti, [(CH ₃ ) ₂ CHO] ₄ T
i, [CH ₃ (CH ₂ ) ₃ O] ₄ Ti, [(CH ₃ ) ₂
C _1-6 alkoxy titanium such as CHCH ₂ O] ₄ Ti can be used. Alternatively, a titanium oxide sol prepared in advance may be used.

The deodorant component is a solution containing a tetravalent metal ion, a divalent metal ion and a component corresponding to the photocatalyst,
It can also be obtained by a method of using an aqueous solution containing two or more kinds of these metal ions to form a mixed precipitate of the water-insoluble substances. The mixed precipitate obtained by this method is usually in the form of gel and, when dried, becomes a mixture having an amorphous structure. In this method, it is preferable that the component corresponding to the photocatalyst is adjusted to an appropriate crystal structure in advance and added to the aqueous solution.

Various water-soluble metal compounds are used to prepare an aqueous solution containing a tetravalent metal ion, a divalent metal ion and a silver ion. Examples of such water-soluble metal compounds of divalent metals, tetravalent metals and silver include various metal salts and metal alkoxides. As the metal salt, in addition to a normal metal salt (regular salt), an acid salt, and other double salt or complex metal salt may be used. The metal salt may be a water-soluble compound when the pH of the aqueous solution is near neutral, or may be a compound that dissolves in an acidic aqueous solution. Specifically, the following compounds may be mentioned.

(1) Halides such as metal fluorides, chlorides, bromides and iodides: CoCl ₂ , NiCl ₂ ,
CuCl ₂ , ZnCl ₂ , FeF ₂ , FeCl ₂ , Fe
Br ₂ , FeI ₂ , Na ₂ (SnF ₆ ), K ₂ (SnF
₆ ), K ₂ (SnCl ₆ ), CaCl ₂ , BaCl ₂ ,
MgCl ₂ , MnCl ₂ , TiCl ₄ , SnCl ₄ , Z
rCl ₄ , ThCl ₄ , ThI ₄ , PbCl ₄ , GeC
l ₄ etc.

(2) Sulfate, ammonium sulfate, and other sulfates (inorganic acid salts): FeSO ₄ , CoSO ₄ ,
(NH ₄ ) ₂ Fe(SO ₄ ) ₂ , ZnSO ₄ , CdSO
₄ , Ag ₂ SO ₄ , CrSO ₄ , CuSO ₄ , NiSO
₄ , MgSO ₄ , MnSO ₄ , K ₂ Co(SO ₄ ) ₂ ,
(NH ₄ ) ₂ Mn(SO ₄ ) ₂ , Zr(SO ₄ ) ₂ , S
n(SO ₄ ) ₂ , Th(SO ₄ ) ₂ , Pb(SO ₄ )
₂ , Ti(SO ₄ ) _2, etc.

(3) Nitrate (inorganic acid salt): Zn(NO
₃ ) ₂ , Co(NO ₃ ) ₂ , Cd(NO ₃ ) ₂ , Ca
(NO ₃ ) ₂ , AgNO ₃ , Fe(NO ₃ ) ₂ , Cu
(NO ₃ ) ₂ , Ni(NO ₃ ) ₂ , Ba(NO ₃ ) ₂ ,
Mn(NO ₃ ) ₂ , Zr(NO ₃ ) ₄ , Ti(NO ₃ )
₄ , Sn(NO ₃ ) ₄ , Th(NO ₃ ) _4, etc.

(4) Various inorganic acid salts such as chlorate, perchlorate, thiocyanate, diammine silver sulfate, diammine silver nitrate and chromic acid salt: Zn(ClO ₃ ) ₂ , Ca
(ClO ₃ ) ₂ , Ag(ClO ₃ ), Ba(ClO ₃ ) ₂
, Ca(ClO ₄ ) ₂ , AgClO ₄ , Fe(ClO ₄
) ₂ , Ni(ClO ₄ ) ₂ , Ba(ClO ₄ ) ₂ , M
g(ClO ₄ ) ₂ , Co(ClO ₄ ) ₂ , Zn(SC
N) ₂ , Ca(SCN) ₂ , CaCrO ₄ , AgCrO
₄ , Ag ₂ CO _3, etc.

(5) Organic acid salts such as acetate, formate and oxalate: (CH ₃ CO ₂ ) ₂ Zn, (CH ₃ CO ₂ )
₄ Zr, C ₂ O ₄ Co, (CH ₃ CO ₂ ) ₂ Co, (C
H ₃ CO ₂ ) ₂ Fe, (CH ₃ CO ₂ )Cu, (CH ₃
C0 ₂ ) ₂ Ni, (CH ₃ CO ₂ ) ₂ Ba, (CH ₃ C
O ₂ ) ₂ Mg, (CH ₃ CO ₂ )Ag, (C ₂ O ₄ ) ₂
Th etc.

(6) Oxymetal salt (oxymetal salt in the form of halide, inorganic acid salt, organic acid salt): ZrOCl
₂ , ZrOSO ₄ , ThOCl ₂ , TiOSO ₄ , Zr
O(NO ₃ ) ₂ , ZrOCO ₃ , (NH ₄ ) ₂ ZrO
(CO ₃ ) ₂ , ZrO(CH ₃ CO ₂ ) _{2 and the} like.

(7) Metal alkoxides: Zr(OCH
₃ ) ₄ , Ti(OCH ₃ ) ₄ , Zr(OC ₂ H ₅ ) ₄ ,
C _1-6 alkoxide such as Ti(OC ₂ H ₅ ) ₄ .

Of these metal compounds, inorganic acid salts, particularly strong acid salts such as sulfates and nitrates are often used. More specifically, FeSO ₄ , Ti(SO ₄ ) ₂ , ZnSO
₄ , CuSO ₄ , AgNO ₃ , Cu(NO ₃ ) _{2 and the} like are often used. Of the tetravalent metal compounds, an oxymetal salt is often used as the titanium compound or the zirconium compound, and examples of such a compound include ZrO 2.
Cl ₂ , ZrOSO ₄ , TiOSO _{4 and the} like are included.

As the water-soluble silicate compound which is a source of silicate ions for silicon dioxide, alkali metal silicates such as sodium silicate and potassium silicate,
Examples thereof include alkaline earth metal salts of silicic acid such as calcium silicate and barium silicate, and ammonium silicate.
Silicon dioxide does not have to be water-soluble, and for example, silicon dioxide xerogel (silica gel), hydrosol or hydrogel can be used as a raw material.
Alkaline silicates, preferably alkali metal silicates, hydrosols, and hydrogels are usually used as the silicate ion source, and sodium silicate is particularly preferable in terms of price and handling.

To produce a tetravalent metal phosphate and a divalent metal hydroxide, a divalent metal hydroxide is produced in the coexistence of a tetravalent metal phosphate and a divalent metal ion. Just do it.
For example, (i) a tetravalent metal phosphate is produced in an aqueous solution in which a tetravalent metal ion and a divalent metal ion coexist, then a divalent metal phosphate is produced, and then a divalent metal hydroxide. Or (ii) a tetravalent metal phosphate is previously formed in an aqueous solution containing no divalent metal ion, and then an aqueous solution containing a divalent metal ion is added to the resulting solution to hydroxylate the divalent metal. You may generate a thing.

In the method (i), when the composition is produced using an aqueous solution in which a tetravalent metal ion and a divalent metal ion coexist, the aqueous solution containing the tetravalent metal compound and the divalent metal compound is stirred. Phosphoric acid or a phosphate may be added while suppressing the formation of an insoluble hydroxide of a divalent metal to generate a precipitate of a phosphate of a tetravalent metal. In this method, the pH of the aqueous solution containing the tetravalent metal compound and the divalent metal compound is usually in an acidic range, for example, about pH 0 to 6 (preferably 0 to 4), and if necessary, the divalent metal hydroxide. In order to suppress the generation, phosphoric acid or phosphate may be added by adding an acid to adjust it to an acidic region, for example, pH 4 or less.

When adjusting the pH of the aqueous solution, a suitable alkali or acid can be used. As the alkali, inorganic bases such as alkali metal or alkaline earth metal hydroxides (sodium hydroxide, potassium hydroxide, calcium hydroxide, etc.) and ammonia, and organic bases such as trimethylamine, triethylamine and triethanolamine can be used. .. Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid and sulfuric acid, acetic acid, trichloroacetic acid, trifluoroacetic acid, formic acid,
Organic acids such as oxalic acid can be used.

Examples of the phosphoric acid or phosphoric acid salt used for producing the insoluble phosphoric acid salt include orthophosphoric acid, metaphosphoric acid, pyrophosphoric acid, and their alkali metal salts (for example, sodium salt, potassium salt, etc.) and ammonium salts. Is exemplified. More specifically, the phosphate includes, for example, sodium phosphate monobasic, sodium phosphate dibasic, sodium phosphate tribasic, [hereinafter, these are simply referred to as sodium phosphate (first, second and third). Show. ], potassium phosphate (first, second and third), ammonium phosphate (first, second and third), sodium metaphosphate, potassium metaphosphate, sodium pyrophosphate, potassium pyrophosphate and the like.

In the above-mentioned method (i), the produced tetravalent metal phosphate is usually often sufficiently precipitated by aging or the like. As the aging method, a conventional method, for example, a method of leaving it for a long time in a greenhouse, a method of leaving it for a long time while being heated to 100° C. or lower, a method of heating under reflux, etc. can be used.

After the ripening, the pH of the divalent metal can be produced by adjusting the pH to a neutral range, for example, pH 4 to 12 by adding an alkali. For the formation of the hydroxide, an alkali, a phosphate containing a tetravalent metal after completion of aging, and a solution containing a divalent metal ion are neutralized, for example, pH 4 to 12.
It may be carried out by adding in parallel to the solution within the range of. In the pH range as described above, a precipitate composed of a hydroxide of a divalent metal is formed, and the precipitate of the hydroxide formed and the precipitate of an insoluble phosphate of a tetravalent metal are precipitated or a precipitation mixture or co-precipitate. It forms as a precipitation mixture. In the formation of divalent metal hydroxide, the reaction system may be heated if the reaction at room temperature is slow. If necessary, the reaction may be performed under pressure at a temperature of 100° C. or higher. The stirring may be carried out by bubbling with air.

In the method (ii), the tetravalent metal phosphate precipitate and the 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 but not the divalent metal ion to generate the phosphate in advance. After aging the produced phosphate as necessary, the pH is adjusted to an acidic range, for example, pH 4 or less as necessary, and an aqueous solution containing a divalent metal ion (for example, an aqueous solution containing a metal salt) is added and mixed, Similarly to the above, the mixed precipitate may be generated by adjusting the pH to a neutral range, for example, pH 4 or higher. In this method, the aging of the tetravalent metal phosphate may be performed for a relatively short time.

The photocatalyst may be added to the reaction system for producing a tetravalent metal phosphate and a divalent metal hydroxide, for example, in the form of powder, and the tetravalent metal phosphate and/or divalent metal salt may be added. After the metal hydroxide is formed, it may be added to the reaction system or the formed precipitate.

Further, the photocatalyst may be formed simultaneously with the formation of the tetravalent metal phosphate and/or the divalent metal hydroxide. The above methods (i) and (ii) can be used for producing the photocatalyst. For example, in the case of producing titanium oxide, titanium halide such as titanium chloride, an inorganic acid salt (for example, sulfate such as titanium sulfate) or an alkoxide is added to the reaction system as needed to adjust the pH of the reaction system to neutral or It can be produced by adjusting the pH to be alkaline, for example, about 6 to 12.

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 above-mentioned precipitation forming reaction, and a photocatalyst component or the like may be added. The generated precipitate may be mixed with silicon dioxide. When silicon dioxide is formed together with the formation of the precipitate, an alkaline silicate solution (eg sodium silicate, potassium silicate, etc.)
Can be used instead of alkali. When a silicate ion species is used, it is possible to generate silicon dioxide-containing silicon in the reaction system by adjusting the pH to a neutral range, for example, about pH 4 to 12 with the formation of divalent metal hydroxide.

Further, regarding the silver component, like the above-mentioned silicon dioxide, a silver component, for example, a water-insoluble compound of silver and/or a silver ion species is added in at least one step of the reaction for forming a precipitate to remove the silver component. An odorous composition can be obtained. Further, silver components such as silver ions are easily supported on the photocatalyst, phosphate, hydroxide, silicon dioxide or at least one or more of these components by a conventional method such as an ion exchange method or an impregnation method. I can.

The precipitate thus obtained may be purified by a conventional method, if necessary. For example, a reaction solution containing a precipitate such as the above-mentioned mixed precipitate is filtered, washed with a washing solvent such as warm water or water, and impurities such as anion species of a metal salt are removed and dried to obtain a purified deodorant. It is possible to obtain a sex component and a deodorant composition. The filtration can be performed using a filter paper or a filter cloth at room temperature and normal pressure, under reduced pressure or under pressure, and may be performed using a centrifugal separation method, a vacuum filtration method, or the like. In addition, when cleaning, a gradient cleaning method or the like may be used. The drying operation may be carried out by a conventional method, for example, air drying, and is carried out while heating at a temperature lower than the decomposition temperature of the deodorant composition, for example, about 400° C. or lower, preferably 200° C. or lower. May be.

In the present invention, the deodorant component and the deodorant composition (these may be simply referred to as “deodorant” hereinafter) may be contained in the nonwoven fabric, and as a means for containing the deodorant, Include a method of melt-blowing a composition containing a deodorant and a fiber-forming polymer, and a method of using a binder such as an adhesive resin to adhere the composition to the surface of the fiber so as not to fall off.

However, since the deodorant is firmly held in the fibers constituting the non-woven fabric and is not easily removed from the fibers, it is advantageous in that the deodorant action can be stably exerted for a long period of time. A method of melt-blowing a composition containing a resin and a fiber-forming polymer is preferably used.

In particular, when it is difficult to melt-blown a composition containing a deodorant and a fiber-forming polymer due to the inclusion of "shots", etc., a method of adhering to the surface of the fiber with a binder is used. Good. As a method of attaching the deodorant to the surface of the fiber, a method of impregnating the fiber with a dispersion containing a deodorant and a binder as necessary, spraying the dispersion onto the fiber,
A conventional method such as a coating method can be adopted.
Examples of the binder include solvent-soluble polyolefin, polyvinyl acetate, ethylene-vinyl acetate copolymer, vinyl-based polymers such as polyvinyl chloride, acrylic resins, styrene-based resins, polyesters, polyamides, thermoplastic resins such as polyurethane, and cellulose. -Series resin, epoxy resin,
A thermosetting resin such as a vinyl ester resin or a silicone resin may be used.

In order to remove the odorous component efficiently, the fiber surface area is increased by increasing the concentration of the deodorant on the fiber surface or by making the fiber itself thin, and the probability that the deodorant is present on the fiber surface is increased. It is advantageous to do
The melt blown fibers of the present invention have an average fiber diameter of about 3-4.
Since it is very thin as compared with ordinary melt-spun fibers, the probability that the deodorant is present near the fiber surface is high, which is very advantageous in that the concentration of the deodorant can be reduced accordingly.

The time and mode of adding the deodorant in the production of the melt blown nonwoven fabric containing the deodorant in the fiber are not particularly limited, but the deodorant may be added immediately after the polymerization of the fiber-forming polymer or immediately after the polymerization. A method of adding, a master-batch is prepared in advance by adding a deodorant to the fiber-forming polymer, a method of using this master-batch, and any method until spinning the fiber-forming polymer from the spinneret. An addition method such as a method of adding a deodorant into the fiber-forming polymer in a step (for example, a step of producing polymer pellets, a spinning step, etc.) can be adopted.

In the case of the above method, for example, a method of adding to a raw material slurry for a fiber-forming polymer, a method of producing a prepolymer and then adding the prepolymer immediately before polycondensation, a fiber-forming property Immediately after the production of the polymer, a method of adding it while it is still liquid can be adopted. Since the deodorant used in the present invention has a high catalytic activity, it may affect the polymerization reaction depending on the type of the polymer, so caution is required. The preferable addition method is the above method or.

The deodorant is often added in the form of powder (for example, in the form of fine particles), but if the powder is added to the polymer as it is, it becomes difficult to form fibers due to agglomeration of the particles, or even if the fibers can be formed, the strength is low. It may become fiber. Therefore, a slurry in which a powdery deodorant is dispersed in an appropriate dispersion medium may be added to the polymer.

The deodorant non-woven fabric of the present invention and non-woven fabric products using this non-woven fabric are exposed to light rays (for example, sunlight, fluorescent lamps, ultraviolet lamps, etc.), basic odor components such as ammonia and amines, and acetic acid. Many odorous components such as acidic odorous components, sulfur-containing compounds such as hydrogen sulfide, neutral odorous components such as formalin and acetaldehyde can be rapidly and long-term decomposed to eliminate the odor. Therefore, even a cigarette odor containing a large number of odorous components can be efficiently removed, and it is effective for deodorizing the interior or the interior of a vehicle. It is also effective for deodorizing formalin and aldehydes such as acetaldehyde generated from furniture and new building materials.

Further, the deodorant melt-blown nonwoven fabric containing the deodorant component adsorbs the acidic odor component, the basic odor component, etc., effectively deodorizes even if it is not irradiated with light, and the deodorant light of sunlight or a fluorescent lamp is used. In addition to enhancing the deodorizing performance against acidic and basic odor components due to the synergistic effect of oxidative decomposition of photocatalyst and high adsorption of adsorbent under the irradiation of light such as UV lamps, It has a high deodorizing effect on odorous substances, and its effect is maintained for a long time. In addition, even if some oxidative decomposition products (for example, acetic acid is produced in the case of acetaldehyde) generated by the action of the photocatalyst are released and cause a new odor, the use of an adsorbent in combination causes oxidation. It can adsorb decomposition products. Therefore, the release or desorption of oxidative decomposition products can be prevented to further enhance the deodorizing efficiency, and the substance adsorbed by the adsorbent is further decomposed by the photocatalyst, so that the deodorizing effect is maintained for a long period of time.

In the light irradiation, a light ray 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 it is usually an ultraviolet ray or a light ray containing an ultraviolet ray. When titanium oxide is used as the photocatalyst, its catalytic function can be sufficiently exerted effectively even with sunlight or light from a fluorescent lamp. The light irradiation is usually oxygen,
It is carried out in the presence of an oxygen-containing gas such as air.

[0079]

EFFECTS OF THE INVENTION Since the deodorant melt blown nonwoven fabric of the present invention contains a photocatalyst, various odor components (acid odor component, basic odor component and neutral odor component) can be obtained by light irradiation.
Can be removed efficiently and over a long period of time. In particular, it shows high removal ability not only for acidic odor components and basic odor components but also for neutral odor components that cannot be removed by the adsorption mechanism. Further, the deodorant melt blown nonwoven fabric can well remove odorous components regardless of the presence or absence of light irradiation. According to the method of the present invention, a deodorant meltblown nonwoven fabric having the above-mentioned excellent properties can be produced by a simple operation of containing a photocatalyst and an adsorbent. Moreover, the fibers constituting the melt-blown nonwoven fabric are very thin on the average of 2 to 3 μm and have a large fiber surface area, so that a large deodorizing effect can be obtained with a small deodorant content.

[0080]

[Deodorant composition Zn (II) -Ti (IV) Preparation of -TiO _2]

1) 6.64 g of titanyl sulfate powder (manufactured by Fuji Titanium Industry Co., Ltd., trade name "Taisalt", containing 32.5% by weight of TiO ₂ ) and zinc sulfate crystals (ZnSO ₄ .7H ₂
O, Wako Pure Chemical Industries, Ltd. reagent special grade) (18.1 g) was added to water (180 g). This aqueous solution contains 0.027 mol of Ti(IV) ions and 0.062 mol of Zn(II) ions.
About 35.3 g of a 15% by weight phosphoric acid aqueous solution was added dropwise to this aqueous solution with stirring at room temperature to produce a white precipitate. The mixture containing white precipitate was stirred as it was overnight. 2) Add 15% sodium hydroxide solution to the resulting mixture.
It was dripped until H became 7.0. When the pH dropped during the dropping of sodium hydroxide, a sodium hydroxide solution was further added to maintain the pH at about 7.0. p
If stirring is continued until no decrease in H is observed, Zn
A white precipitate containing (II)-Ti(IV) was formed. 3) The white precipitate formed was filtered off with suction, thoroughly washed with warm deionized water, and then dried at 120°C.
Zn(II)-Ti by grinding to 20 μm or less
A white powder containing (IV) was obtained. 4) Titanium oxide powder (manufactured by Ishihara Sangyo Co., Ltd., MC-9) against 70 parts by weight of white powder containing Zn(II)-Ti(IV)
0) 30 parts by weight are mixed, the resulting mixture is supplied to a jet mill grinder, and further pulverized into fine powder, and a deodorant composition containing Zn(II)-Ti(IV)-TiO ₂ Of fine powder was obtained. 5) The average particle size of the obtained fine powder was 1 μm.

Example 1 Two parts of the deodorant composition obtained above were prepared with respect to polypropylene of melt flow rate 700.
Master-batch pellets kneaded with 0% by weight were prepared. After mixing 5 parts of the master-batch in a pellet form with 95 parts of the polypropylene, melt extrusion was performed by an extruder, spinning temperature of 285° C., single hole discharge rate of 0.5 g/min.
Discharge from nozzle through hole, temperature 285℃, pressure 0.4kg
A polypropylene melt blown with 1% by weight of the above deodorant composition having an average basis weight of 20 g/cm ² was collected by collecting a fiber flow spun with hot air of /cm ² at a position 20 cm below the die.
An ultrafine fiber nonwoven fabric was obtained.

Example 2 The compounding ratio of the deodorant composition was 3
A melt-blown nonwoven fabric was obtained under the same conditions as in Example 1 except that the content was changed to 0.1%.

Example 3 The compounding ratio of the deodorant composition was 5
A melt-blown nonwoven fabric was obtained under the same conditions as in Example 1 except that the content was changed to 0.1%.

Comparative Example 1 A melt blown nonwoven fabric was obtained under the same conditions as in Example 1 except that polypropylene not containing the deodorant composition was used.

[Deodorizing Test] The deodorizing ability of the cloths obtained in Examples and Comparative Examples was measured for hydrogen sulfide and ammonia as follows. A non-woven fabric (3 g) was put in a Tedra bag (volume: 5 liters) and sealed. Then, using a syringe, air containing a predetermined concentration of odorous components was injected into the tedra bag so that the total gas amount was 3 liters.
The initial concentration of the injected gas was 4
It is 0 ppm and hydrogen sulfide 15 ppm. The test is 27
The tedra bag was left standing 15 cm away from the W white fluorescent lamp in a dark room, and the entire cloth was irradiated with light.

After a lapse of a fixed time after injecting the gas, in the case of hydrogen sulfide, the gas in the tedra bag was sampled with a microsyringe, and the gas concentration was measured by gas chromatography (Shimadzu GC-14A type). Then, the removal rate of the odorous components was obtained. In the case of ammonia, a gas detector tube (manufactured by Gastec Co., 3 L type for ammonia) was used to directly measure the gas concentration in the tedra bag, and the removal rate of the odorous component was determined by the following formula. The results are shown in Tables 1 and 2. Removal rate (%)=(C ₀ −C)/C ₀ ×100 (C ₀ is the initial concentration, and C is the concentration after a certain period of time.)

[0087]

[Table 1]

[0088]

[Table 2]

As is clear from the table, the use of the deodorant non-woven fabrics obtained in the examples makes it possible to remove odorous components with respect to basic odorous components and acidic odorous components. And even if the content of the deodorant is only 1%, sufficient performance can be exhibited.

Claims (10)

[Claims] 1. A deodorant meltblown nonwoven fabric containing a photocatalyst and an adsorbent. 2. The deodorant melt blower according to claim 1, wherein the adsorbent is a tetravalent metal phosphate and a divalent metal hydroxide.
Non-woven fabric. 3. The deodorant melt blown nonwoven fabric according to claim 1 or 2, wherein the photocatalyst is an optical semiconductor. 4. The deodorant meltblown nonwoven fabric according to claim 1, wherein the photocatalyst is an oxide semiconductor. 5. The photocatalyst is titanium oxide.
The deodorant melt blown nonwoven fabric described. 6. The deodorant meltblown according to claim 1 or 2, which contains 0.1 to 5% by weight of a photocatalyst with respect to the whole nonwoven fabric.
Non-woven fabric. 7. The deodorant melt-blown according to claim 1, which contains 0.1 to 5% by weight of an adsorbent with respect to the whole nonwoven fabric.
Non-woven fabric. 8. The deodorant meltblown nonwoven fabric according to claim 1, wherein the ratio of the photocatalyst to 100 parts by weight of the adsorbent is 10 to 750 parts by weight. 9. A method for producing a deodorant melt blown non-woven fabric, wherein a tetravalent metal phosphate, a divalent metal hydroxide and a photocatalyst are contained in a fiber. 10. The method for producing a deodorant melt-blown nonwoven fabric according to claim 9, wherein a composition containing a tetravalent metal phosphate, a divalent metal hydroxide, a photocatalyst and a fiber-forming resin is spun.