JP2003024424A - Deodorant composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique for suppressing the growth of bacteria of fungi without affecting an adsorbent in a deodorant comprising the adsorbent dispersed in a gel. SOLUTION: This deodorant composition comprising the adsorbent dispersed in the gel is characterized in that at least two or more of composite metal compounds represented by the following formulas are blended thereto as antibacterial agents and fungicides: (M1 <2+> )1- X(M2 <2+> )X(OH)2 (I), (M1 <2+> )1- X(M2 <2+> )XO (II), MY<m+> Om Y/2 .Al2 O3 .nSiO2 .aH2 O (III), and bZnO.Al2 O3 (IV) wherein M1 is Mg or Ca; M2 is Cu or Zn; X is a number satisfying 0.0001<=X<0.9; M<m+> is an m-valent ion exchangeable metal (m=1 or 2) selected from Ag<+> , Cu<2+> and Zn<2+> ; Y, m, n, and (a) are numbers satisfying 0<Y<=2, 1<=m<3, 4<n<15, 0<=a, respectively; and b is a number satisfying 20<=b<=30.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a deodorant composition, and more particularly to a deodorant composition capable of suppressing the generation and growth of fungi and mold in a base gel.

[0002]

2. Description of the Related Art Hitherto, many deodorants and deodorants have been proposed for removing bad odors generated in toilets, rooms, refrigerators, cars and the like. Among these, as the deodorant, there is a type of a granular material having a physical adsorption property such as activated carbon or zeolite, which is stored in a bag having air permeability, and a malodor is adsorbed and removed by the granular material. Is commonly known.

However, although such a deodorant has an excellent deodorizing effect, there is a problem in that the life of the deodorant, that is, the end time of the deodorant is not known, and the replacement time of the deodorant is missed.

As a solution to such a problem, the present applicant has previously developed and applied for a patent for a "deodorant obtained by dispersing an adsorbent in a gel (hereinafter referred to as" gel deodorant "). . (JP 2000-157706 A). This product was very easy to use due to its high deodorizing effect and the end time being easy to understand, but depending on the environment of use, there was a problem that fungi propagated to the gel deodorant itself and mold grew. This problem not only impairs aesthetics,
This is a serious problem because the gel is destroyed by the action of fungi and fungi, causing water separation and impairing the product performance.

On the other hand, although many gel preparations such as gel-like fragrances and deodorants have been proposed so far, the problem that molds grow also has been known. As a means for solving the problem, usually, an antibacterial / antifungal agent such as paraben or sodium benzoate is blended in the gel deodorant.

However, even if these fungicides used for conventional gel-like fragrances and deodorants were blended with the gel-like deodorant, no effect was observed. It has been speculated that the reason for this is that antibacterial and antifungal agents such as paraben and sodium benzoate are adsorbed by the adsorbent dispersed in the gel deodorant.

[0007] As described above, the gel deodorant cannot use the antibacterial and antifungal method adopted in other gel formulations, and suppresses the growth of bacteria and the growth of mold by another method. Therefore, there has been a demand for technological development for suppressing the generation and reproduction of germs and mold of the gel deodorant.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and in a deodorant obtained by dispersing an adsorbent in a gel, the growth of fungi and mold without affecting the adsorbent. The problem is to provide a technique for suppressing the proliferation of the.

[0009]

Means for Solving the Problems The inventors of the present invention have made an earnest search for a gel deodorant which has an antibacterial and antifungal effect with little effect of the adsorbent dispersed in the gel. Meanwhile, it was found that a specific complex metal compound has such a property, and by incorporating this into a gel deodorant, it is possible to effectively suppress the generation of fungi and mold in the gel, and the present invention Completed

That is, according to the present invention, a deodorant obtained by dispersing an adsorbent in a gel contains one or more of the following complex metal compounds as an antibacterial / antifungal agent. A composition is provided.

[Chemical 6] (In the formula, M ₁ represents Mg and / or Ca, M ₂ represents Cu and / or Zn, and X is 0.0001 ≦ X <0.9.
A metal hydroxide represented by

[Chemical 7] (Wherein M ₁ , M ₂ and X have the above-mentioned meanings),

[Chemical 8] (In the formula, M ^{m +} represents an m-valent ion-exchangeable metal containing at least one metal selected from Ag ⁺ , Cu ²⁺ and Zn ²⁺ and having m = 1 or 2 as an essential component, Y, m,
n and a are 0 <Y ≦ 2, 1 ≦ m ≦ 3, 4 <n <, respectively.
15, which represents a number satisfying 0 ≦ a), or an amorphous aluminum silicate compound represented by:

[Chemical 9] (In the formula, b represents a number in the range of 20 ≦ b ≦ 30), and aluminum oxide / zinc is represented.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The composite metal compound used as an antibacterial / antifungal agent in the deodorant composition of the present invention is represented by the above formulas (I) to (IV). Among these, those represented by the formula (I) are disclosed in, for example, Japanese Patent Laid-Open No.
-72816 is represented by formula (II) in JP-A-6-65011, and formula (III) is represented in JP-A-2000-63219 by formula (IV). Those represented are those disclosed in, for example, JP-A-8-291011, and can be easily manufactured according to the methods described in these documents.

[0012] Among the composite metal compound, specific examples of _{preferred, Ca 0.95 Zn 0. 05 (OH} ) 2 ( Sea Bio Z (Friend manufactured Systems, _{Inc.)) Ca 0.95} Cu
_0.05 (OH) ₂ (SeaBio C (manufactured by Tomomo System Co., Ltd.)), Mg _0.93 Zn _0.07 O (Seabio ZO (manufactured by Tomomo System Co., Ltd.)), Mg _0.93 Cu _0.07 O (Seabio CO)
(Manufactured by Tomoyu System Co., Ltd.), 0.2CuO ・ Al ₂ O ₃・
9SiO ₂ (Seebio KU2 (manufactured by Tomo System Co., Ltd.)) 20-30 ZnO.Al ₂ O ₃ (Seebio Z
-24 (manufactured by Tomo System Co., Ltd.) and the like,
These may be used alone or as a mixture of two or more.

The compounding amount of the above-mentioned composite metal compound in the deodorant composition is the degree of activity of the composite metal compound used, the type of gelling agent constituting the gel, the type and amount of gelling agent in the gel, Alternatively, the actual formulation should be experimentally determined because it is affected by the types and amounts of other added components. However, in general, in a gel deodorant, 0.0
It is sufficient to mix about 1% to 10%.

The deodorant composition of the present invention can be produced by a known method except that the above-mentioned composite metal compound is added as an antibacterial / antifungal agent. That is, for example, first by dispersing the powdery adsorbent and gelling agent with a dispersant, and then adding water to this and heating and stirring,
It can be manufactured by making a homogeneous solution, and finally pouring this solution into a container and cooling.

As the adsorbent to be used, conventionally known charcoal such as activated carbon and bincho charcoal, zeolite, silica gel, composite adsorbent and the like can be used. Among these, it is preferable to use charcoal in terms of price and deodorizing ability.

On the other hand, as a gelling agent, carrageenan,
Conventionally known substances such as gellan gum, agar, gelatin, guar gum, pectin, locust bean gum, xanthan gum, sodium alginate and cellulose derivatives can be used, and carrageenan is preferable from the viewpoint of deodorizing effect and cost.

Further, in the deodorant composition of the present invention, the antibacterial spectrum varies depending on the compound metal compound to be compounded, and therefore it is desirable to compound other antibacterial and antifungal agents. Examples of other antibacterial / antifungal agents include antibacterial metal-containing antifungal agents and non-adsorptive organic antifungal agents.

Among these, examples of the antibacterial antifungal agent containing an antibacterial metal include silver antifungal agents and magnesium antifungal agents. Specific examples of the silver-based fungicides include silver citrate, silver lactate and other organic acid silver salt-based fungicides, silver-supported zeolite, silver-supported silica gel, silver-supported fungicides such as silver zirconium phosphate, Examples thereof include silver-containing inorganic antifungal agents such as silver oxide and silver nitrate. Among the silver-based fungicides, Adeka Royal Guard (manufactured by Asahi Denka Kogyo Co., Ltd.) is used as the organic acid silver salt-based fungicides, and Bactekiller (Kanebo) is used as the silver-supported fungicides. Zeomic (manufactured by Sinanen),
Bactenone (manufactured by Nippon Denshi Kyokai Co., Ltd.), Novalon (manufactured by Toagosei Co., Ltd.) and the like are commercially available, and thus these may be used. Specific examples of the magnesium antifungal agent include organic acid magnesium salt antifungal agents such as magnesium citrate and magnesium-containing inorganic antifungal agents such as magnesium oxide and magnesium sulfate. The product name is Aprek 90 (manufactured by Maruwa Biochemical Co., Ltd.).

On the other hand, as the non-adsorbing organic antifungal agent,
1,3-dimethylroll-5,5-dimethylhydantoin, 1-methylol-5,5-dimethylhydantoin,
3-dimethylol-5,5-dimethylhydantoin, 2
-Bromo-2-nitropropane-1,3-diol, hexamethylenetetramine, 1- (3-chloroallyl)-
3,5,7-triaza-1-azonia adamantan chloride, 2-chloroacetamide, the following formula,

[Chemical 10] (In the formula, R₁ Is a lower alkyl group, R₂Is lower alkyl
A group or a hydrogen atom, R₃ Is a hydroxyl group or a hydrogen atom,
R_Four Is a lower alkyl group or a lower hydroxyalkyl group
To R_FiveRepresents a lower alkyl).
You can

The antibacterial metal-containing fungicides and the non-adsorbing organic fungicides can be used alone or in combination of two or more. Further, the optimum range of the compounding amount and the mixing ratio of these can be determined experimentally.

In addition, a dispersant may be used in the production of the deodorant composition of the present invention, and examples thereof include glycols such as propylene glycol and ethylene glycol, and alcohols such as ethanol and propanol. . In addition, antibacterial fungicides such as 3-methoxybutanol, 1-methoxy-2-butanol, 1-methoxy-2-propanol, 3-methoxy-3-methylbutanol and 3-methoxy-3-methylbutylacetate are also dispersants. Can be used because it has the effect of
In that case, it acts as a dispersant and antifungal agent.

Further, various additives can be added to the deodorant composition of the present invention to the extent that they do not affect gel formation. Examples of the additive include an alkali metal salt such as sodium chloride as a gel reinforcing agent and an alkaline earth metal salt such as calcium chloride. Further, deodorant components such as antiseptics, ultraviolet absorbers, organic acids, pigments, fragrances, and other plant extracts can also be added.

[0023]

In the deodorant composition of the present invention, the complex metal compounds represented by the formulas (I) to (IV) have a fungicidal effect in the gel deodorant because they are adsorbed by the adsorbent in the gel. It is presumed that it is not done.

[0024]

EXAMPLES The present invention will be described in more detail with reference to Examples and Test Examples, but the present invention is not limited to these Examples.

Example 1 2.5 g of carrageenan as a gelling agent was dispersed in 5.0 g of propylene glycol. 2.0 g of activated carbon (average 300 mesh or more) as an adsorbent, and aluminum oxide / zinc (20 to 30 ZnO) as an antibacterial and antifungal agent.
· Al ₂ O _3: ethanol 5 and trade name Sea Bio Z-24 (Friend manufactured Systems, Inc.)) 0.5 g, a dispersing agent.
What was dispersed in 0 g was mixed and stirred. This is water 8
4.5g sodium chloride 0.5g as gel toughener
The mixture was added to the mixture prepared above, heated to 80 ° C., stirred, poured into a cup, and cooled to solidify to obtain a gel deodorant (Product 1 of the present invention).

Example 2 2.5 g of carrageenan as a gelling agent was dispersed in 5.0 g of propylene glycol. To this, 2.0 g of activated carbon (over 300 mesh on average) as an adsorbent, and magnesium oxide / copper (Mg _0.93 Cu) as an antibacterial and antifungal agent were _added.
0.07 O: Product name SeaBio CO (manufactured by Tomo System Co., Ltd.)
A mixture of 0.5 g and 5.0 g of ethanol as a dispersant was mixed and stirred. This was mixed with 84.5 g of water to which 0.5 g of sodium chloride as a gel strengthening agent was added, and then the mixture was heated to 80 ° C., stirred, poured into a cup, cooled and solidified to form a gel deodorant (the product of the present invention). 2) was obtained.

Example 3 2.5 g of carrageenan as a gelling agent was dispersed in 5.0 g of propylene glycol. 2.0 g of activated carbon (average 300 mesh or more) as an adsorbent, and aluminum oxide / zinc (20 to 30 ZnO) as an antibacterial and antifungal agent.
・ Al ₂ O ₃ : 0.5g of trade name Seabio Z-24 (manufactured by Tomo System Co., Ltd.) and 5.0g of 3-methoxy-3-methylbutanol, which is a fungicide and a dispersant, are mixed. And stirred. This was mixed with 84.5 g of water to which 0.5 g of sodium chloride as a gel strengthening agent was added, then heated to 80 ° C., stirred, poured into a cup, cooled and solidified to form a gel deodorant (the product of the present invention. 3) was obtained.

Example 4 2.5 g of carrageenan as a gelling agent was dispersed in 5.0 g of propylene glycol. To this, 2.0 g of activated carbon (over 300 mesh on average) as an adsorbent, and magnesium oxide / zinc (Mg _0.93 Zn _0.07 ) as an antibacterial and antifungal agent were _added.
O: Product name Sea Bio ZO (manufactured by Tomoyu System Co., Ltd.)
5 g and 3-methoxy-3-, which is a fungicide and dispersant
What was dispersed in 5.0 g of methyl butanol was mixed and stirred. This was mixed with 84.5 g of water added with 0.5 g of sodium chloride as a gel strengthening agent, and then mixed at 80 ° C.
After heating and stirring, the mixture was poured into a cup, cooled and solidified to obtain a gel deodorant (Product 4 of the present invention).

Example 5 2.5 g of carrageenan as a gelling agent was dispersed in 5.0 g of propylene glycol. To this, 2.0 g of activated carbon (over 300 mesh on average) as an adsorbent, and calcium hydroxide / zinc (Ca _0.95 Zn _0.05 ) as an antibacterial and antifungal agent were _added.
(OH) ₂ : 0.5 g of trade name Sea Bio Z (manufactured by Tomo System Co., Ltd.) was mixed with 5.0 g of 3-methoxy-3-methylbutanol, which is a fungicide / dispersant, and mixed, It was stirred. This was mixed with 84.5 g of water to which 0.5 g of sodium chloride as a gel strengthening agent was added, then heated to 80 ° C., stirred, poured into a cup, cooled and solidified to form a gel deodorant (the product of the present invention. 5) was obtained.

Example 6 2.5 g of carrageenan as a gelling agent was dispersed in 5.0 g of propylene glycol. 2.0 g of activated carbon (average 300 mesh or more) as an adsorbent, and aluminum silicate / copper (0.2 CuO / A) as an antibacterial and antifungal agent.
l ₂ O ₃ .9SiO ₂ : 0.5 g of trade name Seabio KU2 (manufactured by Tomo System Co., Ltd.) and 5.0 g of 3-methoxy-3-methylbutanol, which is also a fungicide and a dispersant, are dispersed. Mix and stir. This was mixed with 84.5 g of water to which 0.5 g of sodium chloride as a gel strengthening agent was added, then heated to 80 ° C., stirred, poured into a cup, cooled and solidified to form a gel deodorant (the product of the present invention. 6) was obtained.

Example 7 2.5 g of carrageenan as a gelling agent was dispersed in 5.0 g of propylene glycol. 2.0 g of activated carbon (average 300 mesh or more) as an adsorbent, and aluminum oxide / zinc (20 to 30 ZnO) as an antibacterial and antifungal agent.
・ Al ₂ O ₃ : 0.3 g of trade name Seabio Z-24 (manufactured by Tomo System Co., Ltd.) and aluminum silicate / copper (0.2 CuO ・ Al ₂ O ₃ .9SiO ₂ : trade name of Seabio KU 2 (Tomo system) 0.2 g) and 5.0 g of ethanol, which is a dispersant, were mixed and stirred. This was mixed with 84.5 g of water added with 0.5 g of sodium chloride as a gel strengthening agent, and then mixed at 80 ° C.
After heating and stirring, the mixture was poured into a cup, cooled and solidified to obtain a gel deodorant (Product 7 of the present invention).

Comparative Example As a comparative product, the antifungal agent in Example 1 was not added (Comparative Product 1), and 0.5 g of methylparaben (manufactured by Midori Kagaku Co.) was added in place of the antifungal agent of Example 1. A comparative product (Comparative product 2) and a product (Comparative product 3) produced by adding 0.5 g of sodium benzoate (Nacalai Tesque) were prepared.

Test Example 1 In a petri dish having a diameter of 9 cm, 15 ml each of the deodorant compositions of the products 1 to 6 of the present invention and the deodorant compositions of the comparative products 1 to 3 were poured in a liquid state and cooled and solidified. Apply the following 5 types of fungal suspensions on the surface of the solidified gel,
After culturing in a thermostatic chamber at 0 ° C for 1 month, the growth of mold was observed with the naked eye. The results are shown in Table 1.

(Test Mold) Mold 1: Aspergillus niger IFO 631 (Aspergillus niger IFO 631)
41) Mold 2: Penicillium citrinum IFO6532
6352) Mold 3: Cladosporium Cladosporioides IF
O6348 (Cladosporium cladosporio
idesIFO 6348) Mold 4: Environmental Isolate A * Mold 5: Environmental Isolate B * * Environmental Isolates A, B ... Growing after leaving the gel deodorant without fungicide in a temperature-controlled room at 25 ° C for 7 days. Shrimp

(Evaluation criteria) +: Mold growth is recognized. ±: Very slight mold growth is observed. -: Mold growth is not observed.

[0036]

[Table 1] As is clear from this result, the product of the present invention was able to completely prevent the generation of mold.

Example 8 Inventive products 1 to 6 obtained in Examples 1 to 6 and comparative products 1 to 3
An antibacterial effect confirmation test was carried out according to the following evaluation procedure and evaluation criteria.

(Evaluation Procedure) On a petri dish having a diameter of 9 cm,
The deodorant compositions of the present invention products 1 to 6 and the comparative products 1 to 3 were each poured in a liquid state in an amount of 15 ml and cooled and solidified.
Then, the surface of the solidified gel is treated with normal broth medium 10 ⁵
The following test bacterial solution prepared to -10 ⁶ cells / ml was added to 0.0
Apply 5 ml and incubate in a constant temperature room at 37 ° C for 48 hours,
The growth state was observed. The results are shown in Table 2.

(Test Bacteria) Bacteria 1 Escherichia coli IFO3301 (Escherichia coli IFO3301) Bacteria 2 Staphylococcus aureus IFO1446
2 (Staphylococcus Aureus IFO
14462) Bacteria 3 Pseudomonas aeruginosa IFO126
89 (Pseudomonas AeroginosaIF
O12689)

(Evaluation criteria) Criteria -: No growth of bacteria is observed ±: Very few germs are observed +: Growth of bacteria is recognized.

[0041]

[Table 2] As is clear from this result, the product of the present invention was able to completely prevent the generation of bacteria.

Example 7 A deodorization test was conducted on the products 1 to 5 of the present invention obtained in Examples 1 to 5 by the test method shown below. The results are shown in Table 3.

(Test Method) Each of the products 1 to 5 of the present invention prepared in Examples 1 to 5 was cut into a cube of 2 cm square,
This was used as a sample. One sample was placed in a 2 liter desiccator, and ammonia and hydrogen sulfide were injected as a malodorous gas. Concentration after injection of malodorous gas (initial concentration; App
m) and the concentration (Bppm) after 180 minutes were measured using a detector tube, and the deodorizing rate was calculated using the following formula.

[0044]

[Formula 1]

[0045]

[Table 3]

As is clear from these results, in the deodorant composition of the present invention containing the composite metal compound as an antibacterial / antifungal agent, no decrease in the deodorizing effect due to the addition of the compound was observed.

[0047]

EFFECTS OF THE INVENTION The deodorant composition of the present invention does not cause the growth of fungi or the growth of mold, and the deodorizing effect is not reduced by the addition of the composite metal compound which is an antibacterial / antifungal agent. Met.

Therefore, the deodorant composition of the present invention can be used in a wide range of fields as a gel deodorant free from the growth of fungi and mold. that's all

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) A01N 59/16 A01N 59/16 Z 59/20 59/20 Z A61L 9/16 A61L 9/16 D B01D 53/02 B01D 53/02 Z B01J 20/10 B01J 20/10 D 20/18 20/18 C 20/20 20/20 ADF Term (reference) 4C080 AA03 AA05 BB02 BB05 BB08 CC01 HH05 JJ03 JJ04 KK08 LL03 LL06 LL10 MM02 MM12 MM15 MM18 NN04 NN05 NN06 NN23 NN24 4D012 BA01 BA02 BA03 4G066 AA04A AA04B AA15D AA16D AA17D AA18D AA20D AA30A AA30B AA61A AA61B AB05D BA28 BC18 BB18 CA17 BA18 BC18 BB18 BB18 BB18

Claims (6)

[Claims] 1. A deodorant composition comprising an adsorbent dispersed in a gel, and one or more of the following complex metal compounds as an antibacterial / antifungal agent is added to the deodorant composition. [Chemical 1] (In the formula, M ₁ is Mg and / or Ca, and M ₂ is Cu.
And / or Zn, and X is 0.0001 ≦ X <0.
A metal hydroxide represented by a number in the range of 9), A metal oxide represented by the formula: wherein M ₁ , M ₂ and X have the above-mentioned meanings, (In the formula, M ^{m +} represents an m-valent ion-exchangeable metal containing at least one metal selected from Ag ⁺ , Cu ²⁺ and Zn ²⁺ and having m = 1 or 2 as an essential component, Y, m,
n and a are 0 <Y ≦ 2, 1 ≦ m ≦ 3, 4 <n <, respectively.
15, an amorphous aluminum silicate compound represented by the formula: 0 ≦ a, or (In the formula, b represents a number in the range of 20 ≦ b ≦ 30) An aluminum oxide / zinc solid solution. 2. The deodorant composition according to claim 1, wherein the adsorbent is charcoal, zeolite, silica gel or a composite adsorbent. 3. The deodorant composition according to claim 1, wherein the gelling agent is carrageenan, gellan gum, agar, gelatin, guar gum, pectin, locust bean gum, xanthan gum, sodium alginate or a cellulose derivative. 4. The deodorant composition according to claim 1, further comprising an antibacterial metal-containing antifungal agent or a non-adsorptive organic antifungal agent as another antibacterial / antifungal agent. . 5. The deodorant composition according to claim 4, wherein the antibacterial metal-containing antifungal agent is an organic acid silver salt antifungal agent, a silver-carrying antifungal agent, or a silver-containing inorganic antifungal agent. . 6. A non-adsorptive organic antifungal agent is 1,3-dimethylol-5,5-dimethylhydantoin, 1-methylol-5,5-dimethylhydantoin, 3-dimethylol-5,5-dimethylhydantoin, 2-bromo-2
-Nitropropane-1,3-diol, hexamethylenetetramine, 1- (3-chloroallyl) -3,5,7-
Triaza-1-azonia adamantan chloride, 2-chloroacetamide or the following general formula: (In the formula, R ₁ is a lower alkyl group, R ₂ is a lower alkyl group or a hydrogen atom, R ₃ is a hydroxyl group or a hydrogen atom,
R ₄ represents a lower alkyl group or a lower hydroxyalkyl group, and R ₅ represents a lower alkyl), and one or more compounds selected from the group consisting of the compounds represented by the above-mentioned. Agent composition.