JP2002113081A - Deodorant and its using method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant having high deodorization activity against aldehyde and not discharging the adsorbed aldehyde at high humidity. SOLUTION: The amino acid having an α-amino acid structure coupled with nitrogen atom having unsubstituted hydrogen with β- or γ-carbon atom or hetero- atom is used as the deodorization component of this deodorant. The deodorant is used in the high-humidity environment by this using method.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a deodorizing material and a method for using the same, and more particularly, to a deodorizing material containing a deodorizing component having an .alpha.-amino acid structure satisfying specific conditions, and an effective method for using the deodorizing material. About.

[0002]

2. Description of the Related Art Aldehydes are originally ammonia,
Compared to basic odor components such as trimethylamine and acidic odor components such as hydrogen sulfide, methyl mercaptan and acetic acid,
There are few suitable deodorants. However, in recent years, in relation to sick house syndrome and tobacco odor unpleasant for non-smokers,
Formaldehyde, acetaldehyde and other aldehydes have been identified as problems.

[0003] From such a point, many deodorizing materials mainly targeting aldehydes have recently been proposed. Among them, deodorizing materials using an amino acid, particularly an α-amino acid, as a deodorizing component have attracted attention from the viewpoints of odorlessness, excellent deodorizing performance for aldehydes, and harmlessness to the human body. These deodorizing materials are used in various forms suitable for the purpose of use, for example, supported on various carriers.

For example, in the invention of "Deodorizing / Deodorizing Agent" disclosed in Japanese Patent Application Laid-Open No. Sho 60-129054, a deodorizing material comprising lysine, glutamic acid, aspartic acid or the like or a complex amino acid thereof or salts thereof as a deodorizing component. Is disclosed. In the invention of "gas adsorbent" disclosed in JP-A-62-186939, a deodorant comprising a polymer having a polyamino acid and an amino sugar as a deodorant component is disclosed.

[0005]

According to the study of the present inventor, the amino acids specifically disclosed in the above prior art show good aldehyde deodorizing performance under ordinary humidity conditions, It has been found that the adsorbed aldehyde may be reversibly re-emitted under humidity conditions.

For example, a case where formaldehyde is adsorbed by lysine will be described. As shown in FIG. 1, lysine adsorbs formaldehyde by a dehydration reaction to form imine. However, this imine is not necessarily a stable compound, and can be hydrolyzed to the original lysine and formaldehyde in a high humidity environment such as a relative humidity of 95% or more where there is a possibility of dew condensation. As a result, a problem occurs that formaldehyde once adsorbed is released again.

Accordingly, the present invention provides a deodorizing material utilizing an amino acid having excellent odorlessness, deodorizing performance, harmlessness, etc., in terms of moisture resistance, which means that aldehyde once adsorbed is not re-released even under high humidity conditions. Assigning is an issue to be solved. The present inventor has found that incorporating an adsorbed aldehyde into a stable cyclic chemical structure by a ring-closing reaction is extremely effective in preventing aldehyde from being re-released, and completed the present invention.

[0008]

Means for Solving the Problems The structure of the first invention of the present application (the invention described in claim 1) for solving the above-mentioned problems has an α-amino acid structure and a β structure. A deodorizing material comprising, as a deodorizing component, an amino acid having a structure in which a nitrogen atom with unsubstituted hydrogen is bonded to a carbon atom or a hetero atom at the-or γ-position.

(Structure of the Second Invention) The structure of the second invention of the present application (the invention according to claim 2) for solving the above problems is as follows.
The amino acid according to the first invention is an acid deodorant.

(Structure of Third Invention) The structure of the third invention of the present application (the invention according to claim 3) for solving the above problems is as follows.
An acid constituting the acid salt according to the second invention binds to an amino group constituting the α-amino acid structure, and / or
It is a deodorizing material bonded to a nitrogen atom bonded to a carbon atom or a hetero atom at the β-position or the γ-position.

(Structure of the Fourth Invention) The structure of the fourth invention of the present application (the invention according to claim 4) for solving the above problems is as follows.
A deodorizing material, wherein the amino acid according to any one of the first to third inventions is histidine.

(Structure of Fifth Invention) The structure of the fifth invention of the present application (the invention according to claim 5) for solving the above problems is as follows.
The deodorizing material according to any of the first to fourth inventions, wherein the deodorizing component is carried on a carrier.

(Structure of the Sixth Invention) The structure of the sixth invention of the present application (the invention according to claim 6) for solving the above problems is as follows.
The carrier according to the fifth invention is a deodorizing material, which is a porous carrier.

(Structure of the Seventh Invention) The structure of the seventh invention (the invention according to claim 7) for solving the above problems is as follows.
A deodorizing material, wherein the porous carrier according to the sixth invention has a metal ion coordinated with water of crystallization on its surface.

(Structure of Eighth Invention) The structure of the eighth invention (the invention according to claim 8) for solving the above problems is as follows.
The porous carrier according to the sixth or seventh aspect of the present invention is a deodorizer, wherein sepiolite is used.

(Structure of the ninth invention) The structure of the ninth invention (the invention according to claim 9) for solving the above problems is as follows.
This is a method for using the deodorizing material, wherein the deodorizing material according to any one of the first to eighth inventions is used in a high humidity environment where the relative humidity may be 95% or more.

[0017]

[Action and Effect of the Invention] (Action and Effect of the First Invention) Since the deodorizing material of the first invention has an α-amino acid structure in its deodorizing component, it has no odor, excellent deodorizing performance against aldehydes, and a human body. It has various features common to α-amino acids such as harmlessness to α-amino acids.

Further, since the deodorizing component has a structure in which a nitrogen atom with unsubstituted hydrogen is bonded to a carbon atom or a hetero atom at the β- or γ-position, the adsorbed aldehyde can be reversible even under high humidity conditions. There is no fear of re-release.

That is, it is considered that the deodorizing component normally adsorbs aldehyde by the α-amino group. Then, when the carbon atom of the aldehyde takes the imine structure and bonds to the nitrogen atom of the amino group, this carbon atom is further present (bonded to a carbon atom or a hetero atom at the β or γ position). 2.) A ring-closing reaction occurs, in which the ring is bonded to a nitrogen atom with unsubstituted hydrogen, and is incorporated into a stable 5- or 6-membered cyclic chemical structure. As a result, the reversible hydrolysis reaction described above cannot occur even in a high-humidity environment rich in water, and aldehyde re-release is effectively prevented. Theoretically, the aldehyde may be adsorbed by the nitrogen atom bonded to the carbon atom or the hetero atom at the β or γ position. Even in that case, the same ring closure reaction as described above occurs.

When a nitrogen atom with unsubstituted hydrogen is bonded to a carbon atom or a hetero atom at the δ-position equidistant from the γ-position, a ring-closing reaction as described above forms a 7-membered or more cyclic chemical structure. Result. Since such a cyclic chemical structure having a 7-membered ring or more is unstable, it may cause a hydrolysis reaction in a high humidity environment to release aldehyde again.

(Action / Effect of Second Invention) As described in the second invention, when the amino acid as the deodorizing component is an acid salt, first,
An acid proton is bonded to the nitrogen atom having an imine structure by adsorbing an aldehyde to activate the nitrogen atom, so that the above-described ring closing reaction is promoted. Second, the odor of the deodorizing component itself, which is originally slight, is further reduced. Third, the solubility of the deodorizing component in a polar solvent such as water or alcohol is increased. For example, a high-concentration solution of the deodorizing component is prepared and supported on an arbitrary carrier at a high density by a spray injection method or an immersion method. In addition, various processes as a deodorizing material are facilitated.

Even when the amino acid as the deodorizing component is used as an acid salt, the lone electron pair that traps the aldehyde at the nitrogen atom constituting the acid salt is preserved, so that the deodorizing performance of the amino acid derivative is not hindered.

(Action / Effect of Third Invention) In the second invention, the acid constituting the acid salt may be bonded to the amino group constituting the α-amino acid structure, or may be in the β-position or γ. And a nitrogen atom bonded to a carbon atom or a hetero atom. Alternatively, an acid constituting an acidic salt may be bonded to both of the above.

(Action / Effect of the Fourth Invention) As the amino acid satisfying the conditions of the first invention, various kinds of amino acids can be artificially synthesized. Histidine is particularly preferred. FIG. 2 shows a reaction formula of a chemical reaction in which histidine adsorbs formaldehyde and incorporates it into a stable 6-membered cyclic chemical structure by a ring closing reaction.

(Function / Effect of the Fifth Invention) By supporting the above-mentioned various amino acids as deodorizing components on a carrier, a deodorizing material of an advantageous embodiment having a wide range of applications can be provided. .

(Function / Effect of the Sixth Invention) When the carrier of the amino acid as the deodorizing component is a porous carrier, the surface area (outer surface area and inner surface area of pores) of the carrier is particularly large, and the supporting capacity of the deodorizing component is also high. Since it is large, it is possible to provide a deodorizing material having particularly high deodorizing performance.

(Function / Effect of Seventh Invention) In the seventh invention, since the porous carrier has a metal ion coordinated with water of crystallization on its surface, the amino acid as a deodorizing component is substituted with the water of crystallization. Each molecule binds to the surface of the carrier, and is supported in a highly dispersed state in a molecular state.

That is, since the deodorizing component bound to the carrier surface for each molecule does not agglomerate or crystallize in a cluster form on the carrier surface, the deodorizing activity does not decrease due to these problems, and the deodorizing component is not distributed on the carrier surface. Since they are connected by a strong force called position coupling, there is no danger of volatilization or falling off from the carrier surface due to shock such as vibration.

Furthermore, the coordination bonding group on the surface of the carrier is bonded to the deodorizing component, whereby the state of electron localization in the molecular structure of the deodorizing component is enhanced, and the reactivity of the deodorizing component to odor components such as aldehyde is further enhanced. Tends to be strengthened. (Operation and Effect of the Eighth Invention) When the porous carrier is sepiolite, the effect of the seventh invention is particularly remarkably exhibited. (Function / Effect of Ninth Invention) According to the ninth invention, a particularly effective method of using the deodorizing material according to the first to eighth inventions is provided.

[0030]

Next, embodiments of the first to ninth inventions will be described. In the following, simply "the present invention"
When it says, it points to 1st invention-9th invention collectively.

[Deodorizing Component] The deodorizing material according to the present invention contains the aforementioned predetermined amino acid as a deodorizing component. This amino acid has an α-amino acid structure, and has a structure in which a nitrogen atom with unsubstituted hydrogen is bonded to a carbon atom or a hetero atom at the β or γ position. Histidine is the most preferred example of this amino acid, and γ-aminobutyric acid is also exemplified (slightly strong). Any amino acid synthesized with a structure meeting the above conditions is also exemplified.

The above-mentioned α-amino acid structure means a structure in which an amino group and a carboxyl group are bonded to the carbon atom at the α-position. This carboxyl group can be in the form of a derivative such as an acid amide or an acid ester, thereby giving the deodorizing component heat resistance (a property that does not cause a decrease in deodorizing performance due to polyamino acid formation in a high-temperature environment). it can. A hetero atom refers to an atom other than carbon and hydrogen contained in an organic compound. In the present invention, the type of the hetero atom is not limited according to the above definition, but oxygen (O), sulfur (S), and nitrogen (N) can be particularly preferably exemplified. As described above, the nitrogen atom accompanied by unsubstituted hydrogen is bonded to the β-position or γ-position carbon atom or hetero atom. The number of unsubstituted hydrogens in this nitrogen atom may be two, but one unsubstituted hydrogen and one arbitrary organic compound may be bonded to the nitrogen atom. Further, as in the case of the histidine, the nitrogen atom bonded to the carbon atom or the hetero atom at the β- or γ-position may form a part of the cyclic chemical structure.

It is particularly preferable that the amino acid as the deodorizing component is in the form of an acidic salt for the reason described in the section "Function and effect of the second invention". The type of the acid salt is not limited, and it does not matter whether the acid is a strong acid or a weak acid or an inorganic acid or an organic acid.In particular, in the case of the hydrochloride, the ring closure reaction is promoted, the odor of the deodorizing component itself is reduced, and the deodorizing component is reduced. Great effect of improving solubility.

The acid constituting the above-mentioned acidic salt is bonded to the amino group forming the α-amino acid structure, or to the nitrogen atom bonded to the β- or γ-position carbon atom or hetero atom. Generally, it is considered that there is a high possibility that the former connection mode is preferentially realized, but the latter connection mode is also possible. The former and latter acid binding forms may be realized in the same amino acid.

[Deodorizing Material] The deodorizing material of the present invention is not limited as long as it contains the amino acid as a deodorizing component.
The specific material form is not limited. For example, it may be a powder material or a granular material composed of only the above-mentioned amino acids, or any suitable compounding agent added thereto, or a deodorant solution containing an amino acid solution or an alcohol solution.
It is also possible to use such a deodorizing solution by directly spraying it into the air, or to spray a spray on the deodorizing target such as clothes, curtains, carpets and the like as a carrier, or to impregnate the deodorizing target and then dry it. And other uses.

However, the most typical use form of the deodorizing material of the present invention is a deodorizing material in which an amino acid is supported on a carrier as a deodorizing material substrate, particularly a porous carrier, by any means. There is no limitation on the use of these various forms of deodorant,
For example, it can be used as a filter for an air purifier, a deodorizing sheet, a decorative material for deodorizing, etc. in a house or a car.

[0037] All of the above-mentioned forms of use of the deodorant do not depend on their use environment. However, when used in a high-humidity environment where the relative humidity may be 95% or more, where the possibility of dew condensation is considered, the moisture resistance which is a characteristic of the deodorizing material is particularly effectively exhibited. A case where the deodorizing material is used in a house room, a car room, or the like where high humidity is expected in a rainy season or the like is cited as an example of its use.

The purpose of use of the deodorizing material of the present invention is not limited. However, it is particularly preferably used for deodorizing aldehydes. [Carrier of deodorizing material] Examples of the carrier of the deodorizing material of the present invention include powder-like, granular, pellet-like, and monolith-like carriers made of various organic or inorganic materials.
It is also preferable to use a woven fabric such as a sheet fabric for automobiles or various sheet materials as a carrier and directly impart deodorizing performance thereto.

When the carrier is in the form of the powder, granules or the like,
Such a deodorizing material may be used as it is by filling it into a suitable air-permeable container or storing it in an air passage portion, or may be used by mixing with other powder components for any purpose such as increasing the amount or imparting an aroma. You can also. Also, these deodorizing materials may be used in combination with other types of deodorizing materials (for example, capable of trapping basic odor components).

Particularly preferred as the carrier used in the present invention is a porous carrier, especially a porous carrier made of an inorganic material. There is no particular limitation on the pore size of the porous carrier, but it is necessary that the pore size is large enough to allow the molecules of the deodorizing component and the odor component such as aldehyde to easily enter.On the contrary, if the pore size is too large, the performance of the deodorizing material will be high. Is smaller. As an example, about 0.1 to 10 nm is preferable.

Examples of the porous carrier include activated carbon, porous metal oxides such as alumina, titania, and zirconia;
Examples include amorphous porous silica such as silica gel, clay minerals such as sepiolite, palygorskite, smectite, and imogolite, and crystalline porous silica. or,
Clothes made of cellulose or polyester fibers,
Fabrics such as curtains, carpets and sheet fabrics,
Air-permeable carriers such as knitted fabrics, non-woven fabrics, and various fibrous inorganic materials such as glass fibers or aggregates thereof are also included in the porous carriers.

When a porous carrier such as activated carbon or sepiolite is loaded with an amino acid which is a deodorizing component, a carrier supported on the outer surface of the porous carrier can be used. It is preferable that the particles are uniformly supported on the inner surface of the pores) because the deodorizing performance is higher.
In a porous carrier, such a preferable supporting form is naturally obtained by a usual deodorizing component supporting treatment.

Among the porous carriers, particularly preferred ones are
It is a porous carrier having metal ions coordinated with water of crystallization on the surface. Typical examples thereof include clay minerals such as sepiolite, silotile, laphrinite, and palygorskite. Of these, hydrated magnesium silicate clay minerals, especially sepiolite, are preferred because the substitution reaction is likely to occur.

The hydrous magnesium silicate clay mineral has hydrous magnesium silicate as a main component and a diameter of 0.05 to 0.6.
present a fibrous shape of about μm, and about 1 to 0.6
It has pores (channels) with a rectangular cross section of about nm and has replaceable crystal water coordinated to magnesium inside and outside the pores. The pores themselves have the function of adsorbing odor components and water vapor in the atmosphere.

In the hydrated magnesium silicate clay mineral, magnesium or silicon is partially aluminum, iron,
In some cases, nickel, sodium and the like are substituted, but these can also be used as a kind of hydrous magnesium silicate clay mineral.

[0046]

Advantageous Embodiments of the Invention The present invention can be implemented in the following advantageous embodiments. In the following:
The phrase “above” refers alternatively to all the embodiments corresponding to the preceding embodiment number of the corresponding content.

1) Deodorization containing an amino acid having an α-amino acid structure and having a structure in which a nitrogen atom with unsubstituted hydrogen is bonded to a carbon atom or a hetero atom at the β or γ position as a deodorizing component. Wood.

2) The amino acid is an acid salt.

3) The acidic salt is an acidic salt of a strong or weak acid, or an inorganic or organic acid. 4) The acidic salt is a hydrochloride.

5) The acid constituting the above acidic salt binds to the amino group constituting the α-amino acid structure, and / or
Or a nitrogen atom bonded to a carbon atom or a hetero atom at the γ-position or the γ-position.

6) The amino acid is histidine.

7) The deodorizing material is a powder or granule containing the amino acid as an active ingredient, or an aqueous solution or alcohol solution of the amino acid.

8) The amino acid is carried on a carrier which is a base material for a deodorant.

9) The carrier is a powdered, granular, pelletized or arbitrary shaped monolithic carrier composed of an organic material or an inorganic material;
Cloths, curtains, woven fabrics such as carpets, knitted fabrics, non-woven fabrics, and various sheet materials.

10) The powdery or granular carrier is filled in a gas permeable container or used in a gas passage portion.

11) The above-mentioned carrier is a porous carrier, and the pore size of the porous carrier is preferably about 0.1 to 10 nm.

12) The porous carrier is activated carbon, porous metal oxide, amorphous porous silica, clay mineral or crystalline porous silica.

13) The above-described porous carrier is a porous carrier having on its surface metal ions coordinated with water of crystallization.

14) The porous carrier is a hydrous magnesium silicate clay mineral.

15) The hydrous magnesium silicate clay mineral is sepiolite.

16) The above-mentioned deodorizing material is used as a filter for an air purifier, a deodorizing sheet, or a decorative material for deodorizing in a house or a car.

17) A method of using the deodorizing material used in a high humidity environment where the relative humidity may be 95% or more.

[0063]

EXAMPLES [ Preparation of deodorizing material ] Various deodorizing components (amino acids) shown in Examples 1 to 3 and Comparative Examples 1 and 2 in the column of "Drugs" in Table 1 at the end of Table 1 were used in amounts of 0.1% each. 5g
Each was weighed into a beaker, 25 mL of water was added, and the mixture was stirred and dissolved using a stirrer.

For these deodorized component solutions, Table 1
And 10 g of the porous carrier shown in the section of each of the above examples in the column of "Carrier" was added and stirred for 5 minutes. Next, the sample according to each of these examples was evaporated to dryness, dried at 105 ° C. overnight, and then pulverized in a mortar to obtain a powdery deodorizing material according to each example.

Separately from the above examples, a commercially available sepiolite was used as Comparative Example 3, a commercially available activated carbon was used as Comparative Example 4,
Prepared each.

[ Formaldehyde adsorption performance test ] 0.1 g, 0.2 g, and 0.5 g of the deodorizing materials (sepiolite or activated carbon in Comparative Examples 3 and 4) according to each of the above examples, respectively.
g and 1 g were weighed and stored in 5 L capacity gas-impermeable bags, respectively. 5 L of nitrogen containing formaldehyde at a concentration of 700 ppm was introduced into the bag.

Thereafter, each bag was allowed to stand in a constant temperature / humidity bath at a constant temperature of 25 ° C., and after about 4 hours, the concentration of formaldehyde gas remaining in the bag was measured using a gas detector tube. Separately, a measured value of 400 ppm was obtained as a blank concentration (residual formaldehyde gas concentration when the same treatment as in each of the above examples was performed without containing a deodorant or a carrier). From the measured values of the blank concentration and the measured concentrations according to the respective examples, the amount q of formaldehyde adsorbed by the deodorizing material or the carrier according to the respective examples was calculated according to the following “Equation 1”.

[0068]

(Equation 1) Next, an adsorption isotherm representing the relationship between the equilibrium concentration and the amount of adsorption according to each example was created from the above calculation results. The adsorption amount (mg / g) of formaldehyde at an equilibrium concentration of 1 ppm on the adsorption isotherm is shown in the column of "Adsorption amount of formaldehyde (mg / g)" in Table 1.

[Rerelease Test under High Humidity ] The deodorizing agent or the carrier according to each of the examples in which the formaldehyde was adsorbed in the above test was accurately weighed in a range of 5 mg to 10 mg into a glass tube. Both ends were filled with glass wool. Next, keeping the inside of the glass tube at 50 ° C.
Air at 95 ° C. and a relative humidity of 95% was flowed at a flow rate of 100 mL / min, during which formaldehyde desorbed from the deodorant or the carrier was collected by a DNPH (dinitrophenylhydrazine) cartridge. Thereafter, the collected formaldehyde was extracted with acetonitrile, and the amount of formaldehyde in the extract was quantified by HPLC.

With respect to the amount of formaldehyde re-emitted determined as described above, the percentage of the amount of formaldehyde adsorbed on the deodorizing material or the carrier put in the glass tube was calculated, and the “re-emission rate in humid air” in Table 1 was calculated. (%) ".

A comparative re-emission test was also conducted in the same manner as above except that dry air having a relative humidity of 0% was used instead of air having a relative humidity of 95%. Table 1 shows the re-release rate in that case.
In the column of “Rerelease rate (%) in dry N ₂ ”.

According to the results shown in Table 1, each of Examples and Comparative Examples 1 and 2 has a larger “formaldehyde adsorption amount” and a lower “rerelease rate in dry N ₂ ” than Comparative Example 3. In Comparative Examples 1 and 2, the “re-emission rate in humid air” is considerably higher than in each of Examples.

[0073]

[Table 1]

[Brief description of the drawings]

FIG. 1 is a diagram showing a reaction formula of a chemical reaction at the time of aldehyde adsorption by lysine.

FIG. 2 is a view showing a reaction formula of a chemical reaction at the time of aldehyde adsorption by histidine.

Continuation of the front page (72) Inventor Kazuhiro Fukumoto 41-Cho, Yokomichi, Nagakute-machi, Aichi-gun, Aichi Prefecture F-term in Toyota Central R & D Laboratories Co., Ltd. 4C080 AA05 BB02 CC02 HH05 JJ04 KK08 LL10 MM18 NN01 NN02 NN03 NN04 NN05 NN06 NN24 NN26 4G066 AA05C AA63C AB10B AB13B BA36 CA02 CA52 DA03 FA12

Claims (9)

[Claims] 1. An amino acid having an α-amino acid structure and having a structure in which a nitrogen atom with unsubstituted hydrogen is bonded to a carbon atom or a hetero atom at the β or γ position as a deodorizing component. Deodorizing material characterized by the following. 2. The deodorizing material according to claim 1, wherein the amino acid is an acid salt. 3. An acid constituting the acid salt binds to an amino group constituting the α-amino acid structure, and / or
The deodorizing material according to claim 2, wherein the deodorizing material is bonded to a nitrogen atom bonded to the carbon atom or the hetero atom at the β-position or the γ-position. 4. The deodorizing material according to claim 1, wherein the amino acid is histidine. 5. The deodorizing material according to claim 1, wherein the deodorizing material has the deodorizing component supported on a carrier. 6. The deodorizing material according to claim 5, wherein the carrier is a porous carrier. 7. The deodorizing material according to claim 6, wherein the porous carrier has a metal ion coordinated with water of crystallization on its surface. 8. The deodorizing material according to claim 6, wherein the porous carrier is sepiolite. 9. A method for using a deodorizing material, wherein the deodorizing material according to claim 1 is used in a high humidity environment where the relative humidity may be 95% or more.