JP2003052800A - Deodorant composition suitable for deodorization of sulfur-base malodor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an effective deodorant composition of a high deodorization effect of so-called sulfur-base malodors essentially consisting of compound containing sulfur elements, such as hydrogen sulfide, and further to provide a deodorant composition effective for combined malodors mingled with several kinds or more of malodorous components containing sulfur-base malodorous components. SOLUTION: This deodorant composition is a deodorant composition consisting of a particulate zinc oxide having a specific surface area within a range of 40 to 100 m<2> /g, a hydrogen sulfide volume of >=3.0 mmol/g and a primary particle size of <=0.2 μm and further contains at least one material selected from the group consisting of a material carrying a compound having a primary amino group in the molecule, quaternary metal phosphate and hydrated zirconium oxide and the particulate zinc oxide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorant having excellent deodorizing performance against various malodors, especially so-called sulfur malodor containing a compound containing elemental sulfur as a main component, and sulfur malodor and other malodors. The present invention relates to a deodorant composition having excellent deodorizing performance against a complex malodor composed of malodor.

[0002]

2. Description of the Related Art In recent years, the demand for a comfortable life is rapidly increasing, and one of them is a deodorizing product capable of removing a bad odor generated around the user.
In particular, sulfur-based gas containing a compound containing a sulfur element such as hydrogen sulfide and methyl mercaptan as a main component is disliked because it gives a particularly strong discomfort, and a deodorant effective for these malodorous sulfur-based gas is desired. It is rare. However, a general deodorant that has been conventionally known, such as activated carbon, activated carbon impregnated with a primary amine of aromatic genus, activated carbon whose pH is adjusted,
A combination of an iron compound and ascorbic acid, a polymer compound having an amino group or a sulfone group, and the like all had low ability to eliminate sulfur malodor. Further, these deodorants are originally colored, or cause coloration or discoloration by adsorbing or chemically reacting a malodorous component, so that there is a problem that they cannot be used depending on the application.

On the other hand, as a deodorant having a function of deodorizing sulfur malodor, Japanese Patent Laid-Open No. 1-223968 discloses a deodorant containing a hydroxide or hydrous oxide of zirconium or a lanthanoid element as an active ingredient. However, Japanese Patent Laid-Open No. 10-
Japanese Patent No. 155883 proposes a deodorant composed of a tetravalent metal phosphate containing a specific metal ion. Although these deodorants have the characteristic that the deodorants themselves are not colored or discolored, their deodorizing performance against sulfur-based malodorous gases, particularly hydrogen sulfide, was not sufficient. Further, in the case of a composite malodor containing one or several malodorous components other than the sulfur malodorous component, there is a problem that the deodorizing effect is reduced. In the case of complex malodor, it is effective to combine several types of deodorants, but for example, when eliminating complex malodor composed of sulfur malodor and formaldehyde malodor, it is effective for sulfur malodor. Deodorant compound A
Even if the deodorant compound B effective against formaldehyde type malodor is simply combined, it does not always exhibit sufficient deodorant performance, but rather the deodorant performance when the A compound and the B compound are originally used alone. There were many cases where it was not possible to exhibit.

[0004]

DISCLOSURE OF THE INVENTION The present invention solves the problems of conventional deodorants and provides a deodorant having a large deodorizing effect on various malodorous components, particularly sulfurous malodorous components such as hydrogen sulfide. It is another object of the present invention to provide a deodorant composition which is effective against a complex malodor containing several malodorous components including a sulfur malodorous component.

[0005]

Means for Solving the Problems As a result of intensive investigations by the present inventors, fine particle zinc oxide having specific physical properties has excellent deodorizing performance against sulfur malodorous components, By combining various deodorant compounds, basic gas such as ammonia and trimethylamine, aldehyde gas such as acetaldehyde and formaldehyde, and mixture of multiple malodorous gases such as acetic acid and isovaleric acid. It was found that the complex type malodorous substance can be efficiently deodorized, and the present invention has been completed.

That is, the present invention has a specific surface area of 40 to 100.
It is within the range of m ² / g and the deodorizing capacity of hydrogen sulfide is 3.
The present invention relates to a deodorant composed of fine zinc oxide having a primary particle diameter of 0 mmol / g or more and a primary particle diameter of 0.2 μm or less,
Furthermore, at least one or more substances selected from the group consisting of aluminum silicate, a substance carrying a compound having a primary amino group in the molecule, a tetravalent metal phosphate, and hydrated zirconium oxide, and the above-mentioned fine particle oxidation. The present invention relates to a deodorant composition containing zinc. The substances contained in the above group which are contained together with the fine particle zinc oxide in the deodorant composition of the present invention are all deodorant substances having a deodorizing ability alone, and are useful as deodorants. .

DETAILED DESCRIPTION OF THE INVENTION

Fine Particle Zinc Oxide The fine particle zinc oxide used in the deodorant of the present invention has a specific surface area within the range of 40 to 100 m ² / g. When the specific surface area is less than 40 m ² / g, the deodorizing performance against sulfur-based malodor such as hydrogen sulfide is not sufficient. Again 100m ²
If it exceeds / g, particles tend to aggregate with each other, making it difficult to handle as a powder. The specific surface area can be easily measured by the BET method calculated from the nitrogen adsorption amount.

The fine particle zinc oxide used in the present invention has a hydrogen sulfide gas deodorizing capacity of 3.0 m / g.
It must be at least mol. The hydrogen sulfide deodorizing capacity is the maximum amount of hydrogen sulfide that can be deodorized, absorbed and adsorbed by a compound, and the measuring method is as follows. A test bag such as a Tedlar bag, which is a material that is hard to adsorb hydrogen sulfide gas and is impermeable to air, is filled with particulate zinc oxide and then sealed, and hydrogen sulfide gas is injected into the sealed test bag. The residual hydrogen sulfide concentration in the test bag is measured immediately after hydrogen sulfide gas injection and after a certain period of time. At this time, the point at which the residual gas concentration after a certain period of time became 1/10 or less of the initial gas concentration was taken as the point at which the deodorant performance passed, and the difference between the residual gas concentration at this time and the initial gas concentration was The amount of hydrogen sulfide gas deodorized and absorbed by the particulate zinc oxide. Fine particulate zinc oxide having a hydrogen sulfide gas deodorizing capacity of less than 3.0 mmol / g has a low deodorizing performance for sulfur malodors and complex malodors including sulfur malodors.
Not a satisfactory deodorant.

The primary particle diameter of the particulate zinc oxide in the present invention is preferably 0.2 μm or less, particularly preferably 0.1 μm or less. Primary particle size is 0.2
When it exceeds μm, the deodorizing performance is deteriorated. The primary particle diameter indicates the size of particles that have not aggregated, and is a numerical value that can be easily measured by a scanning electron microscope. In addition,
When the primary particles are large, the specific surface area tends to be small.

In the deodorant of the present invention, surface-treated fine particle zinc oxide can also be used. Specific examples of the surface treatment include those surface-treated with organopolysiloxane,
Some of them have their surfaces coated with oxides or hydroxides of aluminum, silicon, zirconium, or tin, but surface treatment with organic materials such as organopolysiloxane is more effective than surface treatment with inorganic materials. It is preferable because it has high deodorizing performance against sulfur-based odor such as. Further, the amount of the surface treatment agent in the surface treatment is usually 1 to 20% by mass with respect to the particulate zinc oxide. The amount of surface treatment agent is 1% by mass
When the amount is less, the various effects obtained by the surface treatment are not sufficient, and when the amount exceeds 20% by mass, the deodorizing performance of the original fine particle zinc oxide is significantly impaired, which is not preferable. The fine particle zinc oxide used in the deodorant of the present invention is obtained by steam-oxidizing electric zinc metal or water obtained by neutralizing an aqueous solution of a water-soluble salt such as zinc sulfate and zinc chloride. The production method is not particularly limited, such as those obtained by firing zinc oxide, zinc carbonate, zinc sulfide, zinc oxalate and the like.

The deodorant composition of the present invention is constituted by combining with the above-mentioned fine particle zinc oxide in order to efficiently remove the complex malodor in which several malodorous sources including sulfur malodorous gas are mixed. The deodorant substances belonging to the group of specific substances that will be described below will be described in detail.

Aluminum silicate In order to eliminate complex malodors including basic malodors such as ammonia and trimethylamine, it is preferable that aluminum silicate is mixed in the deodorant composition of the present invention. The aluminum silicate used in the deodorant composition of the present invention may be natural or synthetic as long as it has an alkali adsorption capacity. For example, synthetic aluminum silicate is a compound represented by the following formula.

## STR1 ## _{Al 2 0 3 · nSiO 2 ·} mH 2 O In the formula, n is 6 or more integer, m is an integer. In the present invention, aluminum silicate in which n is 6 ≦ n ≦ 50 and m is 1 ≦ m ≦ 20 in the above formula is preferable,
Aluminum silicate in which n is 8 ≦ n ≦ 15 and m is 3 ≦ m ≦ 15 is particularly preferable.

The aluminum silicate used in the present invention may be crystalline or amorphous, but amorphous aluminum silicate is preferable because it has a high deodorizing effect. Further, preferably it has a specific surface area is 20~800m ² / g, it is particularly preferable in 200~800m ² / g. If the specific surface area is too small, the deodorizing performance becomes poor, which is not preferable. Amorphous synthetic aluminum silicate can be synthesized, for example, by the following means.

Aqueous solution of water-soluble aluminum salt and silicate
Mix with an aqueous solution of potassium metal salt, and keep it at room temperature and atmospheric pressure.
If necessary, add acid or alkali to adjust the pH to about 3-7.
Coprecipitation is carried out while maintaining the conditions, and this is, for example, about 40 ° C to
Aging at about 100 ° C or without aging
It can be synthesized by washing the precipitate with water, dehydration and drying.
it can. At this time, the above-mentioned aluminum salt and alkali gold silicate
The amount of metal salt used is SiO ₂/ Al₂O₃(Molar ratio) is 6 or more
Above, for example, a range of 6 to 50 is preferable, and a range of 8 to 15
Is more preferably selected. Also, as another synthesizing means
Is, for example, silica sol, water-soluble aluminum salt water
Add the solution, and further adjust the pH of the system with acid or alkali.
Adjust to about 3 to 7 and mix well, and further
For example, heat to about 40 ℃ ~ 100 ℃, then water
Can be produced by washing, dehydration and drying
It At this time, use of silica sol and water-soluble aluminum salt
The ratio of the amount of SiO₂/ Al₂O₃Range of (molar ratio)
It is preferable to select.

Examples of the water-soluble aluminum salt include aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum iodide, aluminum bromide, sodium aluminate, potassium aluminate and the like. Examples of the alkali metal silicates include sodium silicate, potassium silicate, and lithium silicate. Furthermore, as the alkali or acid used in the above synthesis,
It is possible to use alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia water, and acids such as hydrochloric acid, sulfuric acid and nitric acid.

Substances Carrying a Compound Having a Primary Amino Group In the deodorant composition of the present invention, in order to eliminate complex malodors including aldehyde malodors such as acetaldehyde and formaldehyde, the present invention is used. It is preferable to mix a substance carrying a compound having a primary amino group in the deodorant composition of. As the carrier for supporting the compound having a primary amino group used in the deodorant composition of the present invention, a compound having a primary amino group is supported to support an aldehyde gas such as formaldehyde or acetaldehyde. Both organic substances and inorganic substances can be used as long as they exhibit deodorizing performance. As specific examples, soybean powder, blood powder, polyester resin, organic materials such as polyacrylic resin can be used, but from the viewpoint of heat resistance,
Inorganic substances such as silicon dioxide, activated carbon, sepiolite and mica are preferable. Among these inorganic carriers, porous silicon dioxide is particularly preferable because it has excellent aldehyde gas deodorizing performance.

Porous silicon dioxide usable in the present invention;
Then, the specific surface area of 200-900m ²/ G and flat
A uniform pore size of 0.1 to 10 nm is preferable, and a specific surface
Product 500-900m²/ G and the average pore size is
Those of 2 to 8 nm are particularly preferable. Porous silicon dioxide
If the specific surface area of is too small, it will have a primary amino group.
The contact area between the compound and the malodorous gas is reduced, and the amount of gas adsorption is reduced.
Be played. If the specific surface area is too large,
Since too many compounds with amino groups are adsorbed too much, fibers, etc.
Cause of discoloration due to heating when processed into
It is easy to become. The specific surface area is BE calculated from the nitrogen adsorption amount.
It can be easily measured by the T method.

On the other hand, if the average pore diameter of the porous silicon dioxide is too large, the specific surface area decreases, the amount of the compound having a primary amino group supported decreases, and the malodorous gas adsorption performance deteriorates. If the specific surface area is to be made sufficiently large even if the average pore size is too large, the porosity of the porous body becomes too large and the mechanical strength becomes small,
There is a problem that the ability to carry the compound having a primary amino group becomes weak and the compound having a primary amino group is released by slight heating. On the other hand, if the average pore size is too small, the specific surface area of silicon dioxide increases,
It becomes difficult for the compound having a primary amino group to enter the pores, and as a result, the amount of the compound having a primary amino group supported cannot be increased, and the malodorous gas absorbing ability is reduced. The average pore diameter (D) is easily calculated from the pore volume and specific surface area determined by the BET method using the following formula.

## EQU1 ## D = 4 × V / Sc × 104 (nm) (V: pore volume [ml / g], Sc: specific surface area [m ² /
g])

The water content of the porous silicon dioxide used in the deodorant composition of the present invention is preferably 0.5 to 20% by mass, more preferably 8 to 15% by mass. When the water content is less than 0.5% by mass, the amount of silanol groups on the surface is small, so that the supporting ability for the compound having a primary amino group in the present invention is small. On the contrary, if the water content is more than 20% by mass, it may cause coloring or deterioration when processed into a fiber or the like. The water content of porous silicon dioxide is JIS K712.
It can be easily measured according to 0-7122. Commercially available products of porous silicon dioxide include silica gel and nip seal (fine particle hydrous silicon dioxide).

As the compound having a primary amino group,
The aliphatic compound is preferably a compound represented by the following formula, and the aromatic compound is preferably aniline.

Embedded image H ₂ N- (CH ₂ CH ₂ —NH) _n —CH ₂ CH ₂ NH ₂ (n is an integer of 0 or more and 3 or less) The loading amount of the compound having a primary amino group on the carrier is 0. It is preferably 0.02 to 2 mmol / g.
If the supported amount is too small, the bad odor adsorption ability is reduced, and if the supported amount is too large, the compound having a primary amino group is released from the carrier when kneading into a fiber or a resin molded body. In addition to causing discoloration, the compound having a primary amino group itself becomes a source of malodor. In addition, the amount of acetaldehyde and formaldehyde adsorbed also decreases. The supported amount of the compound having a primary amino group can be easily calculated from the nitrogen content detected by the organic elemental analysis.

Further, for the purpose of improving the odor eliminating capacity of the aldehyde gas of the substance carrying the above-mentioned compound having a primary amino group, an organosilicon compound having an amino group capable of absorbing an aldehyde gas on the surface thereof. Can also be supported. Specific examples of the organosilicon compound that can be used include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl) -γ-aminopropyltrimethoxysilane, and N-β.
(Aminoethyl) -γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane,
Dimethyltrimethyl-silylamine and the like.

In order to eliminate complex malodors including basic malodors such as tetravalent metal phosphate ammonia and trimethylamine, a tetravalent metal phosphate is mixed in the deodorant composition of the present invention. It is preferable. Examples of the tetravalent metal phosphate that can be used in the present invention include zirconium phosphate, titanium phosphate, tin phosphate and the like. These compounds include α-type crystals, β-type crystals, γ
Crystals having various crystal systems, such as type crystals and Nasicon type crystals, and amorphous ones can be used.

Further, in order to further improve the deodorizing performance of the deodorant composition of the present invention against the malodorous sulfur, the tetravalent metal phosphate described above is used in combination with copper, zinc and manganese in combination with fine particle zinc oxide. It is preferable to use one carrying one or more metal ions selected from the following. Among the metal ions supported on the tetravalent metal phosphate, the copper ion is hydrogen sulfide,
Since it has a high deodorizing effect on methyl mercaptan, etc.,
Particularly preferred. In order to support a metal ion on the tetravalent metal phosphate, a tetravalent metal phosphate having an ion exchange property should be used.
It can be supported by bringing it into contact with a salt solution of one or more metal ions selected from copper, zinc and manganese. The supported amount of metal ions can be freely adjusted up to 100% if desired within the ion exchange capacity of the tetravalent metal phosphate.

Hydrated Zirconium Oxide Further, in the deodorant composition of the present invention, when the complex malodor contains an acidic malodor such as acetic acid, hydrated zirconium oxide is mixed in the composition. It is preferable. The hydrated zirconium oxide used in the present invention can be prepared by hydrolyzing a zirconium-containing solution such as an aqueous zirconium oxychloride solution with water or an alkaline solution. The hydrated zirconium oxide may be referred to in various ways such as zirconium oxyhydroxide, zirconium hydroxide, hydrous zirconium oxide, and zirconium oxide hydrate. It is a substance.

In the deodorant composition of the present invention, all of the deodorant substances selected from the above group which can be used by mixing with fine particle zinc oxide are usually obtained in the form of powder. When used in, the preferred average particle size is 0.0
1 to 50 μm, more preferably 0.01 to 20 μm
m, and more preferably 0.1 to 5 μm. Those having an average particle size of less than 0.01 μm are not preferred because they tend to reaggregate and are difficult to handle. On the other hand, when it is larger than 50 μm, it is difficult to disperse it uniformly in the surface treatment agent when it is dispersed in the surface treatment agent such as a binder and post-processed into fibers or the like, which is not preferable. Further, in the deodorant composition of the present invention, the mixing ratio of the fine particle zinc oxide and the deodorant substance selected from the above group is not particularly limited, but depending on the type of complex malodor, fine particle zinc oxide / deodorant It is preferable to appropriately change the agent substance within the range of 1/9 to 9/1 (mass ratio).

The deodorant composition of the present invention can be granulated depending on the intended use. In this case, either the method of granulating the zinc oxide or the deodorant substance of the present invention for each component and post-mixing it, or the method of granulating after mixing can be used. Any conventional granulation method can be used for producing the granules. For example, there is a method of using silica gel, alumina sol, clay or the like as a binder to form a granular body. The particle size can be variously adjusted depending on the hardness, density, crushing strength and the like of the granules, but it is preferably 0.1 mm or more for easy handling.

Uses The deodorant or deodorant composition of the present invention (hereinafter collectively referred to as “the deodorant of the present invention”) has a deodorizing effect on sulfur malodor such as hydrogen sulfide and methyl mercaptan. Is high. It also has a high deodorizing performance against complex malodors including sulfur and other malodorous gases, so it excludes various odors that occur in the living environment such as body odor, manure odor, cigarette odor, daily odor, and garbage odor. Useful for. The deodorant of the present invention can be used as a final deodorant product in a container such as a cartridge as it is in the form of powder or granules, and its effect is exhibited by leaving it in the vicinity of the source of bad odor indoors or outdoors. You can Further, the deodorant of the present invention can be incorporated into fibers, paints, sheets, molded products, etc. as described in detail below, and can be used for producing deodorant products.

One of the useful deodorant products using the deodorant of the present invention is deodorant fiber. In this case, the raw material fiber may be either a natural fiber or a synthetic fiber, or may be a short fiber, a long fiber or a composite fiber having a core-sheath structure. There is no particular limitation on the method for imparting deodorant performance to the fiber by using the deodorant of the present invention. For example, when the deodorant of the present invention is applied to the fiber by post-processing, the deodorant is A water-based or organic solvent-based suspension containing is attached to the fiber surface by a method such as coating or dipping, and the solvent can be removed to coat the fiber surface. Moreover, you may mix the binder for increasing the adhesive force to the fiber surface. The pH of the aqueous suspension containing the deodorant is not particularly limited, but it is preferable that the pH is around 6 to 8 in order to fully exhibit the performance of the deodorant.

Further, the deodorant of the present invention is kneaded into the molten liquid resin for fibers or the dissolved resin solution for fibers, and the fibers are made into fibers to obtain fibers having deodorant performance. As the fiber resin that can be used in this method, any of known chemical fibers can be used, but preferred specific examples thereof include polyester, nylon, acrylic, polyethylene, polyvinyl, polyvinylidene, polyurethane and polystyrene, and cellulose. There is. These resins may be homopolymers or copolymers. In the case of a copolymer, the polymerization ratio of each copolymer component is not particularly limited.

The ratio of the deodorant of the present invention contained in the fiber resin is not particularly limited. Generally, if the content is increased, the deodorant property can be strongly exerted and can be maintained for a long period of time, but even if it is contained in a certain amount or more, the deodorizing effect does not significantly differ, or the strength of the fiber decreases. Therefore, it is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 1 part by mass per 100 parts by mass of the fiber resin.
It is 0 part by mass. Deodorant fiber using the deodorant of the present invention can be used in various fields requiring deodorant properties,
For example, underwear, stockings, socks, duvet, duvet cover,
It can be used for many textile products such as cushions, blankets, carpets, curtains, sofas, car seats, air filters, and nursing clothes.

The second major use of the deodorant of the present invention is as a deodorant paint. When manufacturing deodorant paint, there is no particular limitation on the fat or resin or the resin that is the main component of the paint vehicle used, and it may be any of natural vegetable oil, natural resin, semi-synthetic resin and synthetic resin, and also thermoplastic It may be either a resin or a thermosetting resin. The oils and fats that can be used include, for example, linseed oil, sesame oil, soybean oil and other drying oils or semi-drying oils, rosin, nitrocellulose,
Ethyl cellulose, cellulose acetate butyrate, benzyl cellulose, novolac type or resol type phenolic resin, alkyd resin, aminoalkyd resin, acrylic resin, vinyl chloride, silicone resin, fluororesin, epoxy resin, urethane resin, saturated polyester resin, melamine resin and There is polyvinylidene chloride resin and the like.

The deodorant of the present invention can be used in both liquid paints and powder paints. In addition, the deodorant coating composition using the deodorant of the present invention may be of a type that cures by any mechanism, specifically, an oxidative polymerization type, a moisture polymerization type, a heat curing type, a catalyst curing type, an ultraviolet curing type. , And polyol curing type. Further, the pigment, dispersant and other additives used in the coating composition are not particularly limited, except for those which may chemically react with the fine zinc oxide or the deodorant substance used in combination therewith. . A coating composition using the deodorant of the present invention can be prepared very easily, and specifically, the deodorant and the coating components can be prepared by using a general mixing device such as a ball mill, a roll mill, a disper or a mixer. Well dispersed,
Just mix.

The proportion of the deodorant of the present invention contained in the deodorant paint is not particularly limited. Generally, if the content is increased, the deodorant property can be strongly exerted and can be maintained for a long time, but even if it is contained in a certain amount or more, the deodorizing effect does not make a big difference, or the gloss on the painted surface disappears. Therefore, the coating composition 1 is preferable because cracks may occur.
The amount is 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, per 100 parts by mass. The deodorant paint containing the deodorant of the present invention can be used in various fields that require deodorant properties, for example, the inner wall of buildings, vehicles, railways, etc.
It can be used on outer walls, garbage incinerator facilities, garbage containers, etc.

Further, another important use of the deodorant of the present invention is as a deodorant sheet. The sheet material as a raw material is not limited in its material, microstructure and the like. The preferred material is resin,
Paper or the like, or a composite material thereof, and a porous material is preferable. Preferable specific examples of the sheet material include Japanese paper, synthetic paper, non-woven fabric, resin film, and the like, and particularly preferable sheet material is paper made of natural pulp and / or synthetic pulp. The use of natural pulp has the advantage that the powder of deodorant particles is sandwiched between finely branched fibers, making it a practical carrier without the use of a binder. It has the advantage of excellent chemical properties. When synthetic pulp is used, it may be difficult to carry the deodorant particles by sandwiching the powder between the fibers, so that a part of the fibers is melted in the drying step after paper making It is also possible to increase the adhesive force between the fiber and the fiber, or to mix another thermosetting resin fiber in a part of the fiber. When natural pulp and synthetic pulp are mixed and used at an appropriate ratio in this way, paper having various properties adjusted can be obtained. Generally, when the ratio of synthetic pulp is increased, strength, water resistance and chemical resistance are increased. Also, it is possible to obtain a paper excellent in oil resistance and the like, and on the other hand, if the proportion of the natural pulp is increased, a paper excellent in water absorption, gas permeability, hydrophilicity, moldability, texture and the like can be obtained.

The method for supporting the deodorant of the present invention on the sheet material is not particularly limited. The carrying of the deodorant of the present invention may be carried out either during the production of the sheet or after the production of the sheet.For example, in the case of carrying it on paper, the deodorant is introduced in any step of the paper making step, or together with the binder. There is a method in which a liquid in which a deodorant is dispersed is applied, dipped or sprayed on paper manufactured in advance. Hereinafter, as an example, the method of introducing the deodorant of the present invention in the papermaking step will be described in more detail. The paper making process itself may be performed according to a known method. For example, first, a cationic and anionic flocculant is added to a slurry containing a deodorant and pulp at a predetermined ratio in an amount of 5% by weight or less based on the total weight of the slurry. To produce aggregates. Then, the aggregate is subjected to paper making by a known method, and is dried at a temperature of 100 to 190 ° C. to obtain a paper carrying the deodorant.

The amount of the deodorant of the present invention carried on the sheet material is
Generally, by increasing the loading amount, the deodorant property can be strongly exerted and can be maintained for a long period of time, but since the deodorizing effect does not make a large difference even if it is loaded to a certain degree or more, the preferred loading amount of the deodorant is When the deodorant is carried on the entire surface and inside of the sheet during the paper making process, the deodorant is 0.1 to 10 parts by mass per 100 parts by mass of the sheet, and the deodorant is applied only to the surface of the sheet by post-processing such as coating. When carrying 0.0
It is 5 to 10 g / m ² . The deodorant sheet using the deodorant of the present invention can be used in various fields requiring deodorant properties, for example, medical wrapping paper, food wrapping paper, nursing paper products, freshness-keeping paper. , Paper clothing, air purifying filter, wallpaper, tissue paper, toilet paper, etc.

Resin Molded Product One of the other major uses of the deodorant of the present invention is a resin molded product. When it is added to the resin, the resin and deodorant can be mixed as they are and put into a molding machine for molding, or pelletized resin containing a high concentration of the deodorant can be prepared in advance and mixed with the main resin. It can also be molded. In addition, various pigments, dyes, antioxidants, light stabilizers, antistatic agents, foaming agents, impact-strengthening agents, glass fibers, moisture-proofing agents, extenders, etc. may be added to the resin in order to improve physical properties. Other additives may also be added. As a molding method for producing a deodorant resin molded product using the deodorant of the present invention, general resin molding methods such as injection molding, extrusion molding, inflation molding, and vacuum molding can be used. The deodorant resin molded article using the deodorant of the present invention can be used in various fields requiring deodorant properties, for example, air purifiers, household appliances such as refrigerators, trash cans, drainers, etc. General household items,
There are various nursing care products such as portable toilets and daily necessities.

[0038]

The present invention will be described in more detail below. (Examples 1 and 2) Fine particle zinc oxide (trade name: NANOFINE K, specific surface area: 53 m ² manufactured by Sakai Chemical Industry Co., Ltd.)
/ G, hydrogen sulfide deodorizing capacity 4.0 mmol / g, primary particle diameter 0.15 to 0.001 μm, average primary particle diameter about 0.0
1 μm) as a deodorant sample A (Example 1), and organic polysiloxane surface-treated fine particle zinc oxide (trade name: NANOFINE W-1-LP, specific surface area: 75 m ² / g, hydrogen sulfide, also manufactured by Sakai Chemical Industry Co., Ltd.) Deodorant capacity 4.2 mmol /
g, primary particle size 0.15 to 0.001 μm, average primary particle size about 0.01 μm) was designated as deodorant sample B (Example 2). 0.05g of each of these two types of samples was placed in separate Tedlar bags, and the sulfur-based malodorous component 1 shown in Table 1 was placed therein.
Table 2 shows the results obtained by injecting L into different Tedlar bags and measuring the residual gas concentration in each Tedlar bag after 2 hours using a detector tube.

(Comparative Example 1) A transparent zinc oxide (specific surface area 25 m ² / g, deodorizing hydrogen sulfide, manufactured by Sakai Chemical Industry Co., Ltd., which is a zinc oxide that does not correspond to the particulate zinc oxide which is the deodorant of the present invention. Volume 1.5 mmol / g, average primary particle size 0.3μ
m) was used as sample a (Comparative Example 1). Using this sample, a deodorizing performance test for a sulfur malodorous gas was conducted in the same manner as in Example 1, and the results are shown in Table 2.

[0040]

[Table 1]

[0041]

[Table 2]

The following substances were prepared as deodorant substances selected from a specific group to be added to the deodorant composition. Reference Example 1 Tetravalent Metal Phosphate Commercial α-type layered zirconium phosphate (trade name: inorganic ion exchanger IXE-100) manufactured by Toagosei Co., Ltd. was used as it was. Reference Example 2 Hydrated Zirconium Oxide Commercially available hydrated zirconium oxide (trade name: EPD zirconium hydroxide) manufactured by Daiichi Rare Element Co., Ltd. was used as it was.

(Reference Example 3) Porous silicon dioxide carrying a primary amine compound Silica gel manufactured by Fuji Silysia K.K. (trade name: Silysia 740, average particle size: 5 μm) was mixed with 0.3 mmol of diethylenetriamine per 1 g of silica gel. And mixed. This mixture was put into a Henshal mixer and stirred, and an aqueous solution of γ-aminopropyltrimethoxysilane was added thereto while spraying so that the amount was 0.3 mmol per 1 g of the mixture, and stirring was continued for 30 minutes to prepare a primary amine-supporting porous material. A crystalline silicon dioxide was obtained.

Reference Example 4 Copper Ion-Supporting Tetravalent Metal Phosphate Commercially available Toagosei Co., Ltd. copper ion-supporting α-type layered zirconium phosphate (trade name Kesmon NS-10C) was used as it was.

(Examples 3 to 6) Sample A used in Example 1 or Example 2 so as to have the mass ratio shown in Table 3.
Alternatively, 10 parts by mass of the mixture obtained by adding the deodorant substance of Reference Examples 1 to 4 to Sample B and 100 parts by mass of pure water were shaken and stirred for 24 hours, dried at 100 ° C., and further pulverized to be erased. The odorant composition samples C to F were used. 0.05 g of each of these deodorant composition samples was placed in a separate Tedlar bag,
1 L of the malodorous gas shown in Table 4 was injected into each Tedlar bag separately for each component, and the residual gas concentration in each Tedlar bag after 2 hours was measured with a detector tube.

[0046]

[Table 3]

[0047]

[Table 4]

[0048]

[Table 5]

(Comparative Examples 2 to 3) Samples a used in Comparative Example 1 were added to Reference Examples 1 to 3 so that the mass ratios shown in Table 6 were obtained.
After stirring 10 parts by mass of the mixture containing the specific deodorant substance shown in 4 and 100 parts by mass of pure water for 24 hours with shaking and stirring,
Deodorant composition sample b dried at 100 ° C. and further pulverized
(Comparative Example 2) and Sample c (Comparative Example 3). Using these samples, the deodorizing effect of the complex malodorous gas was measured by the same method as in Example 3, and the results are shown in Table 5.

[0050]

[Table 6]

(Examples 7 to 8 and Comparative Examples 4 to 5) Pure water 1
Deodorant used in Examples 1 and 2 (samples A and B) and zinc oxide used in Comparative Example 1 (sample a) with respect to 100 parts by mass.
3 parts by mass of an acrylic binder (KB-1300
50 parts by weight of each suspension prepared by adding 3 parts by weight of Toagosei Co., Ltd.) and stirring, was applied to 100 parts by weight of polyester fiber, dried at 150 ° C., and then deodorized fiber. (The content of the deodorant is 1.5 parts by mass based on 100 parts by mass of the resin). 5 g of this deodorant fiber was put in a Tedlar bag, 1 L of the sulfur malodorous gas shown in Table 1 was injected, and the residual gas concentration in the Tedlar bag after 2 hours was measured. The results are shown in Table 7. In addition, the same operation as in Example 7 was performed except that the deodorant was not added to give Comparative Example 5, and the results are also shown in Table 7.

[0052]

[Table 7]

(Examples 9 to 12 and Comparative Examples 6 to 8) Using the deodorant compositions (Samples C to F and Samples b to c) used in Examples 3 to 6 and Comparative Examples 2 to 3, A deodorant fiber was prepared in the same manner as in Example 7. Using this fiber, a deodorant test was conducted in the same manner as in Example 7 except that the composite malodorous gas shown in Table 4 was used as the test malodorous gas. The results are shown in Table 8. The case where the fiber containing no deodorant composition was used as Comparative Example 8, and the results are also shown in Table 8.

[0054]

[Table 8]

(Examples 13 to 14 and Comparative Examples 9 to 10)
For 100 parts by mass of xylene solvent, acrylic resin (S
C Johnson Polymer Co., Ltd. product name J-500) 7
0 parts by mass, 3 parts by mass of a dispersant (manufactured by BYK Chemie, trade name BYK-110), 2 parts by mass of a thickener (manufactured by Wilber Els, trade name Benton SD2), Example 1 (Sample A) ), Example 2 (Sample B) and Comparative Example 1 (Sample a) were mixed with 200 parts by weight of zinc oxide, and then kneaded and dispersed by a three-roll to obtain a paste composition. This is diluted 10 times with xylene and 70 mm x
It was applied to both sides of a 150 mm galvanized steel sheet so that the film thickness would be 100 μm. One piece of this coated galvanized steel sheet was placed in a Tedlar bag, and the sulfur-based malodorous gas 1 shown in Table 1 was used.
L was injected, and the residual gas concentration in the Tedlar bag was measured 2 hours later. The results are shown in Table 9. Further, the same operation as in Example 13 was carried out except that the deodorant was not added to give Comparative Example 10, and the results are also shown in Table 9.

[0056]

[Table 9]

(Examples 15-18 and Comparative Examples 11-1)
3) A coated zinc steel sheet was prepared in the same manner as in Example 13 except that the deodorant compositions (Samples C to F and Samples b to c) prepared in Examples 3 to 6 and Comparative Examples 2 to 3 were used. Created. Table 10 shows the results of an odor eliminating test conducted in the same manner as in Example 13 except that this coated zinc steel sheet was used as the test malodorous gas and the composite malodorous gas shown in Table 4 was used. Comparative Example 13 was prepared without the deodorant composition, and the results are also shown in Table 10.

[0058]

[Table 10]

[0059]

As is clear from the evaluation of deodorant performance against various malodors in Examples and Comparative Examples, the deodorant composition of the present invention alone has excellent deodorant performance against hydrogen sulfide and methyl mercaptan. Needless to say, even when used in combination with other deodorants that show excellent deodorant performance against basic gas and acidic gas, it retains excellent deodorant performance against basic gas and acidic gas. At the same time, the deodorant performance of the sulfur-based gas originally possessed by the deodorant composition of the present invention can be sufficiently exhibited. Further, by using the deodorant of the present invention, excellent deodorant properties can be imparted to processed products such as fibers, paints, sheets and molded products.

Claims (3)

[Claims] 1. A specific surface area of 40 to 100 m ² / g and a hydrogen sulfide deodorizing capacity of 3.0 mmol / g.
A deodorant consisting of fine particles of zinc oxide having a particle size of g or more and a primary particle size of 0.2 μm or less. 2. At least one substance selected from the group consisting of aluminum silicate, a substance having a compound having a primary amino group in the molecule, a tetravalent metal phosphate, and hydrated zirconium oxide. Item 10. A deodorant composition containing the fine particle zinc oxide according to Item 1. 3. The deodorant composition according to claim 2, wherein the substance carrying a compound having a primary amino group in its molecule is porous silicon dioxide.