JPH08266600A - Deodorant - Google Patents

Abstract

PURPOSE: To make it possible to increase the compounding ratio of the other components of a deodorant and to increase the degree of freedom in compsn. design as the deodorant by incorporating amorphous calcium phosphate as a deodorizing active material, thereby preparing the deodorant. CONSTITUTION: An ammonium triacrylate salt is added to a suspension of calcium hydroxide (ACP) under stirring in such a manner that the content thereof attains, for example, 0.5wt.% of the weight of the ACP to obtain a soln. mixture; thereafter, the soln. mixture is adjusted to, for example. pH10 under dropping of an aq. phosphate soln. to obtain a slurry 3 contg. ACP particulates 1 of a grain size of, for example, about <=0.1μm. The slurry 3 is diluted with ion exchanged water, thereby the concn. of the ACP particulates 1 is adjusted so as to attain 8wt.%. The ACP slurry 3 contg. such ACP particulates 1 and an org. dispersant 2 is supplied by a fixed delivery pump 4 to a spray driver 5, and an atomizer 6 is rotated at a high speed, by which the slurry is granulated and dried. The resulted ACP particles 7 are classified and drawn by a cyclone 8 in such a manner that the average grain size attains, for example, 10 to 100μm.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a deodorant containing amorphous calcium phosphate as a deodorant active substance.

[0002]

2. Description of the Related Art Conventionally, many explanations for the causes of body-derived malodors such as axillary odor, sweat odor, hair odor, and physiological odor are caused by bacterial decomposition of sweat (eg, Labows and Klig).
man et al., "J. Soc. Cosmet. Chem., 34. (1982)", p. 193).
Is stated.

For this reason, there are many products on the market for treating odors derived from living bodies. These products include deodorants containing antiperspirants, bactericides, masking agents and the like.

Most of the antiperspirants are astringent aluminum compounds that suppress perspiration, and aluminum hydroxychloride is usually used. Hexachlorophene, various quaternary ammonium compounds, and the like that often prevent bacterial growth are often used as bactericides. Further, as a masking agent, a substance having a pleasant odor such as eugenol is used. These antiperspirants, bactericides and masking agents are blended in the deodorant alone or in any combination.

However, although an antiperspirant can suppress the generation of sweat, which is a source of malodor, it is impossible to completely control perspiration from a physiological viewpoint, and considering its mechanism of action. Also has the drawback that the sweat odor already generated cannot be controlled.

[0006] In addition, since it has been pointed out that the disinfectant has a safety problem with the compound having a disinfectant effect, the disinfectant should be contained in a concentration sufficient to achieve a sufficient deodorant effect. It has the drawback that it cannot be compounded.

Further, the masking agent has a drawback that it may generate an unpleasant odor when mixed with a sweat odor.

Therefore, the deodorants containing the above antiperspirants, bactericides and masking agents have a problem that they are not sufficiently satisfactory in terms of effectiveness, safety and usability.

Therefore, for example, Japanese Patent Publication No. 5-64064 discloses a "deodorant" in which a composite powder composed of a synthetic resin and hydroxyapatite is used as a deodorant active substance. Since the deodorant of the above publication uses hydroxyapatite, which constitutes a deodorant active substance, as an adsorbent that adsorbs odorous components, it can adsorb the sweat odor already generated, and hydroxyapatite is safe for living organisms. Therefore, it is satisfactory in terms of effectiveness, safety and usability.

[0010]

However, in the deodorant disclosed in the above publication, hydroxyapatite is used to adsorb odorous components, and further, one having excellent adsorption ability is required. Has been.

Further, in the above publication, although the deodorizing effect which is considered to be derived from the adsorption of the odor component of the deodorizing active substance can be obtained, in order to obtain the sufficient deodorizing effect, it is necessary to use the deodorant in the deodorant. It is necessary to incorporate an amount of deodorant active substance. Therefore, there are problems that the effects of other active ingredients other than the deodorant active substance in the deodorant are prevented from being sufficiently exerted, or that the degree of freedom in designing the blending of each component is reduced. .

Further, in the above publication, in order to make the particle size of the deodorant active substance 0.2 to 20 μm, it is necessary to combine hydroxyapatite and synthetic resin powder, and for this reason, the manufacturing process of the deodorant is required. In the above, there is a problem in that a step for complexing is required, which increases the time and cost for producing the deodorant.

[0013]

Means for Solving the Problems The present inventors have conducted various studies on substances having an odor eliminating effect in order to solve the above problems, and as a result, amorphous calcium phosphate is biologically safe, and The present invention has been completed by finding that it has a high deodorizing effect.

Therefore, the deodorant of the present invention is characterized by containing amorphous calcium phosphate as a deodorant active substance.

Examples of the deodorant include external deodorants such as aerosol, roll-on, powder, cream and stick, as well as insoles and household deodorants, as well as sol and gel. It also includes a morphology.

Amorphous Calcium Phosphate (hereinafter referred to as ACP) used as the deodorant active substance is a water-soluble polymer dispersant such as triacrylic acid in a suspension of calcium hydroxide under stirring. The ammonium salt is added in an amount of 0.1 to 10% by weight, preferably 0.1 to 3% by weight to obtain a mixed solution, and then the above mixed solution with stirring is adjusted to pH 10 to 5 by dropwise addition of an aqueous phosphoric acid solution. Obtained as a slurry containing ACP fine particles of about 0.1 μm or less.

The slurry was granulated by a spray drying granulation method or the like to obtain ACP particles.

The above ACP particles are calcium phosphate according to the pattern of the X-ray diffraction pattern by the powder X-ray diffraction method, and since the pattern is broad, the amorphous calcium phosphate (Ca ₃ (PO _{3 4} ) ₂ · nH ₂ O).

Further, it is desirable that the obtained ACP particles have a large specific surface area. Therefore, although not particularly limited, the particle size of the ACP fine particles in the slurry is preferably 0.1 μm or less. The above-mentioned slurry is preferably mixed at room temperature.

In granulation, ACP in the slurry is used.
By changing the content of the fine particles within the range of 1% by weight to 90% by weight, ACP particles having a desired average particle size can be obtained. If the content of ACP fine particles in the slurry exceeds 90% by weight, the viscosity of the slurry becomes high, which makes it unsuitable for granulation. If it is less than 1% by weight, it takes time to granulate, which is uneconomical.

The granulating method is not particularly limited as long as the obtained ACP particles are porous and can have a specific surface area of 10 m ² / g or more, but for example, spraying A spray drying method, which is a dry granulation method, can be used, and in addition, a granulation method obtained by freeze-drying and then pulverizing, or a high-speed stirring granulation method may be used.

Further, the shape of the ACP particles after granulation is not limited to any shape such as a substantially spherical shape, a plate shape and a needle shape.

The particle size of the ACP particles to be obtained is not particularly limited, but when used as a deodorant applied directly to the skin, it is preferably about 0.5 to 20 μm from the feeling of use on the skin.

The deodorant of the present invention contains the above-mentioned ACP particles as a deodorant active substance, and the content can be arbitrarily changed depending on the product form. Therefore, the content of ACP particles in the deodorant may be 100%. on the other hand,
When the ACP particles and other constituents are mixed in the deodorant and used, in order to exert the deodorizing effect, the ACP particles may be mixed in the deodorant in the range of 0.1 to 90% by weight. It may be added in an amount of preferably 0.1 to 60% by weight, more preferably 0.1 to 40% by weight.

Further, since the ACP of the present application can be adjusted to an arbitrary particle size, it can be used as a deodorant active substance in a powder form of ACP alone. However, when fine ACP particles are used as a powder, it can be used as a composite powder having a synthetic resin powder as a core in order to control the particle size, prevent aggregation, and improve dispersibility. In this case, as the synthetic resin used as a constituent component of the deodorant active substance, for example, nylon, polyvinyl alcohol, polyvinylidene chloride, polyvinyl chloride, polyester, polyacrylonitrile, polyethylene, polypropylene, polyvinylidene cyanide, polyurea, polystyrene, Examples thereof include polyurethane, polyfluoroethylene, polymethylmethacrylate, and the like. Of these synthetic resins, nylon, polyethylene,
It is preferable to use polypropylene or polymethylmethacrylate, and it is particularly preferable to use nylon among the above four synthetic resins.

When a composite powder composed of amorphous calcium phosphate and the above-mentioned synthetic resin is used as the deodorant active substance to be added to the deodorant of the present invention, this composite powder should be produced by any method. You can

That is, the composite powder is, for example, a synthetic resin powder as a core powder, and an amorphous calcium phosphate powder having an average particle size of 1/5 or less of the synthetic resin powder is substantially added to the core powder. It may be manufactured by completely covering the top.

The above-mentioned composite powder can be produced by using a conventionally known solid material or any conventional mixing technique.
That is, any mixer such as a rotary ball mill, a vibration ball mill, a planetary ball mill, a sand mill, or an attritor can be used. Further, when the ball-shaped mixed medium of these mixers has a small particle diameter of 5 mm or less, for example, the surface of the synthetic resin powder is substantially completely and strongly covered with the amorphous calcium phosphate powder by compression coating. This is preferable because a composite powder having excellent desorption stability (amorphous calcium phosphate does not easily desorb from the surface of the synthetic resin powder) can be obtained.

When the deodorant active substance is a composite powder composed of amorphous calcium phosphate and synthetic resin powder, the ratio of the amount of the synthetic resin powder to the amorphous calcium phosphate used is arbitrarily changed depending on the product form. Although it is not particularly limited, for example, the weight ratio of amorphous calcium phosphate to the synthetic resin is preferably 5 to 60%.

Further, the deodorant of the present invention may be blended with components other than the above-mentioned deodorant active substance, and as the blending component, any conventionally known components can be blended. .

Examples of such compounding ingredients include avocado oil, olive oil, grape seed oil, sesame oil, southern oil, safflower oil, soybean oil, camellia oil, corn oil, rapeseed oil, persic oil, castor oil, sunflower oil. , Cottonseed oil, peanut oil, cocoa oil, palm oil, coconut oil,
Fats and oils such as beef tallow, fish oil, hydrogenated oil, turtle oil, pork oil, mink oil, egg yolk oil; waxes such as whale wax, shellac, beeswax, lanolin, liquid lanolin, carnauba wax, candelilla wax; liquid paraffin, liquid poly Isobutylene,
Hydrocarbons such as squalane, pristane, petrolatum, paraffin and ceresin; succinic acid, tartaric acid, citric acid, undecylenic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, ricinoleic acid, behenin Fatty acids such as acids; ethanol, isopropanol, lauryl alcohol, cetanol, 2-hexyldecanol, stearyl alcohol, isostearyl alcohol, oleyl alcohol,
Alcohols such as lanolin alcohol; polyhydric alcohols such as ethylene glycol, diethylene glycol monoethyl ether, triethylene glycol, polyethylene glycol, propylene glycol, 1,3-butylene glycol, glycerin and batyl alcohol; glucose,
Sugars such as sucrose, lactose, xylitol, sorbitol, mannitol, maltitol; diisopropyl adipate, hexyldecyl isostearate, cetyl isooctanoate, oleyl oleate, decyl oleate, lanolin acetate, butyl stearate, isopropyl myristate, phthal Esters such as diethyl acid and hexyl laurate; metal soaps such as aluminum stearate, magnesium stearate and zinc stearate; gum arabic, sodium alginate, casein, carrageenan,
Natural water-soluble polymer compounds such as karaya gum, agar, quince seed, gelatin, dextrin, starch, tragacanth and pectin; semi-synthetic polymer compounds such as propylene glycol alginate, ethyl cellulose, crystalline cellulose and methyl cellulose; carboxyvinyl polymer, polyvinyl methyl ether , Synthetic polymer compounds such as methoxyethylene maleic anhydride copolymers; Surfactants such as dialkyl sulfosuccinates, alkylallyl sulfonates, higher alcohol sulfate salts, phosphate ester salts; ethyl paraoxybenzoate, paraoxybenzoate Preservatives such as methyl acidate; vitamins such as vitamin A, vitamin D, vitamin E, vitamin K; hormones such as estradiol, ethinyl estradiol, cortisone; red 2, blue 1 and red 02 No., yellow No. 201, green 2
Organic dyes such as No. 04, purple No. 201; aluminum powder,
Talc, kaolin bentonite, mica, mica titanium,
Inorganic pigments such as red iron oxide, calamine; UV absorbers such as urocanic acid; anti-inflammatory agents such as allantoin, aloe powder and guaizulene; halogenated hydrocarbons (eg tetrafluoroethane, octafluorocyclobutane, methyl chloride, methylene chloride, etc.), dimethyl ether Examples include propellants such as propane, normal butane, isobutane, carbon dioxide gas, and purified water.

Other additives which can be optionally added to the deodorant of the present invention include, for example, aluminum hydroxy chloride, aluminum chloride, aluminum sulfate, basic aluminum bromide, aluminum phenol sulfonic acid, tannic acid, Antiperspirants such as aluminum naphthalene sulfonic acid and basic aluminum iodide; 3,
Fungicides such as 4,4-trichlorocarbanilide (TCC), benzalkonium chloride, benzethonium chloride, alkyltrimethylammonium chloride, resorcin, phenol, sorbic acid, salicylic acid and hexachlorophene; jascent, skatole, lemon oil, lavender. oil,
Absolute, Jasmine, Vanillin, Benzoin,
Examples thereof include masking agents such as benzyl acetate and menthol.

As described above, an aromatic deodorant can be obtained by blending the above-mentioned masking agents, aromatics and the like with the deodorant.

[0034]

【Example】

[Embodiment 1] One embodiment of the present invention is shown in FIGS.
The explanation is based on the following.

First, amorphous calcium phosphate (Amorph
ous Calcium Phosphate: hereinafter referred to as ACP) A method for producing a slurry containing particles will be described first.
0.5% by weight of a weakly alkaline organic dispersant, ammonium triacrylate (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., trade name: Ceramo D-134), in the calcium hydroxide suspension with stirring, relative to the ACP. To obtain a mixed solution, and the pH of the mixed solution with stirring was adjusted to 10 by adding a phosphoric acid aqueous solution to obtain a slurry containing ACP fine particles having a particle size of about 0.1 μm or less. .

The above slurry was diluted with ion-exchanged water to obtain an ACP slurry prepared so that the concentration of ACP fine particles was 8% by weight.

Then, as shown in FIG. 1, the ACP slurry 3 containing the ACP fine particles 1 and the organic dispersant 2 is used.
Is supplied to a spray dryer (L-8, manufactured by Okawara Kakoki Co., Ltd.) 5 by a metering pump 4. The atomizer 6 of the spray dryer 5 was rotated at a high speed, and the ACP slurry 3 was sprayed into the hot air stream in the spray dryer 5 which was dried at high temperature, whereby the ACP slurry 3 was granulated and dried by the spray granulation method.

Approximately spherical ACP particles 7 made of ACP fine powder obtained by granulation and drying are converted by a cyclone 8 into
The particles were classified and collected so that the average particle size was 10 to 100 μm. At this time, ultrafine powder that could not be collected by the cyclone 8 was separately collected by a bag filter (not shown).

The operating conditions of the spray dryer 5 are as follows. ACP by metering pump 4
The supply amount of the slurry 3 to the spray dryer 5 is
The temperature of the hot air for drying set to 1 to 3 kg / h and heated by the electric heater 10 through the air filter 9 is such that the inlet temperature of the hot gas chamber 11 in the spray dryer 5 is 200 to 250 ° C. The outlet temperature at the discharge hole 12 of the spray dryer 5 connected to the cyclone 8 was controlled so as to always exceed 80 ° C, and the rotation speed of the atomizer 6 was set within the range of 10000 to 37000 rpm.

Further, two types of spray dryers (FOC-20, OD-25G, FOC-25, OC-25, manufactured by Okawara Kakohki Co., Ltd.), which are scale-ups of the above spray dryer 5, are used.
When the CP slurry 3 was supplied at a rate of 100 kg / hr and ACP particles were prepared under the other conditions in the same manner as above, the same ACP particles as the ACP particles 7 obtained by the spray dryer 5 were obtained. The ACP particles thus obtained were spherical.

The produced ACP particles 7 were examined for their production phase by the powder X-ray diffraction method. As a result, as shown in FIG. 2, the ACP particles 7 were identified as calcium phosphate from the pattern of the X-ray diffraction pattern. Since the pattern is broad, amorphous calcium phosphate (Ca
₃ (PO ₄ ) ₂ · nH ₂ O).

Here, a test was conducted on the ability of the ACP particles 7 to adsorb odorous components.

This test method will be described below with reference to FIG. (Odor component adsorption test method) First, a measuring device for measuring the adsorption ability of a sample odor component will be described. First, 2 ml of 25% ammonia water was dropped into 300 ml wide-mouthed Mayer 21 and a glass tube (inner diameter 5 mm) 2 was placed at the center.
It is tightly closed with the silicon stopper 22 that has passed through 3.

Next, substantially cylindrical openings 26a.2 are formed at both ends.
Into a glass sample tube 26 having 6a, 1.2 g of the ACP particles 7 as a sample is weighed and placed. afterwards,
Cotton plugs 25, 25 are applied to the openings 26a, 26a of the sample tube 26 so that the sample does not come out.

Next, both openings 26a of the sample tube 26
Silicon tubes 24, 24 are separately connected to the outer ends of the. Then, the other end of the silicon tube 24 connected to the one opening 26a is connected to the outer end of the glass tube 23 of the silicon stopper 22, and the other end of the silicon tube 24 connected to the other opening 26a. Odor sensor (manufactured by Cosmo Electric Co., Ltd. portable odor sensor XP-3
29) Connect to the intake port 27a of 27.

In the measuring apparatus having the above structure, the odor sensor 27 sucks the gas in the Mayer 21 through the sample tube 26 to measure the adsorption ability of the odorous component of the ACP particles 7 as the sample in the sample tube 26. did. The odor sensor 27 evaluates the concentration of the odor component with a digital display value, and the smaller the display value is, the better the odor component adsorption capacity of the sample is.

As a comparative example of the adsorption ability of the ACP particles 7 of this example, the adsorption ability of the odorous component was measured for hydroxyapatite, alumina and silica in the same manner as above. The hydroxyapatite, alumina, and silica used were all powders having the same particle size as the ACP particles 7.

Comparative Example 1 In the sample tube 26, instead of the ACP particles 7, hydroxyapatite (H
AP) was added in an amount of 1.2 g, and the adsorption ability of the odorous component of hydroxyapatite was measured by the odor sensor 27, and this was set as Comparative Example 1.

Comparative Example 2 1.2 g of alumina was placed in the sample tube 26 instead of the ACP particles 7, and the odor sensor 27 was used to measure the adsorption ability of the odorous component of alumina. And

Comparative Example 3 1.2 g of silica was placed in the sample tube 26 instead of the ACP particles 7, and the odor sensor 27 was used to measure the adsorption ability of silica odorous components.
This was designated as Comparative Example 3.

The measurement by the odor sensor 27 of Example 1 and Comparative Examples 1 to 3 was carried out at a stable point after the start of sampling, and the digital display value at this point was taken as the measured value. Indicated.

[0052]

[Table 1]

As described above, from Table 1 and FIG. 4, the ACP particles 7 of this example have a significantly smaller digital display value in the odor sensor 27 than the alumina and silica in Comparative Examples 2 and 3. From this, it was found that the adsorption ability was far superior to that of alumina or silica. Furthermore, the ACP particles 7 of this embodiment are the odor sensor 2
Since the digital display value in 7 is about half of the digital display value of hydroxyapatite in Comparative Example 1, it was found that it has an adsorption capacity about twice that of hydroxyapatite.

The blending amount of the ACP particles 7 with respect to the deodorant is arbitrarily selected according to the kind of the deodorant, the purpose of use of the deodorant, the particle size of the ACP particles 7 and the specific surface area.

Examples of preparing a deodorant using the obtained ACP particles 7 as a deodorant active substance are described in Examples 2 to 4 below.
Explained.

Example 2 The following is an example of formulation in an aerosol deodorant spray in which the ACP particles 7 obtained in Example 1 above are blended with a general-purpose component of a deodorant.

[Formulation Example] [Example 3] The ACP particles 7 obtained in the above Example 1 and PVA (Poly Vinyl Alcohol) aqueous solution (0.1 to 20%) as an organic binder are mixed and granulated into a columnar shape using a pelletizer. This cylindrical granule has a diameter of, for example, 0.5 to
The height is 40 mm and the height is 0.5 to 10 mm.

This columnar granulated product was dried at 80 to 150 ° C. in a dryer.
After being dried in a dry atmosphere, the deodorant as a porous molded body composed of ACP particles 7 was obtained by heating in an oxidizing atmosphere at 450 to 800 ° C. to gasify and eliminate the binder.

Example 4 The ACP particles 7 obtained in the above Example 1 and PVA (Poly Vinyl Alc) as an organic binder were used.
ohol) aqueous solution (0.1-20%) is mixed and granulated into a column shape using a pelletizer. This cylindrical granule has, for example, a diameter of 0.5 to 40 mm and a height of 0.5 to 10 mm.

The columnar granules were granulated into a substantially spherical shape with a Marumerizer (rotation speed of the top plate was 300 to 650 rpm), dried in a dryer at 80 to 150 ° C., and then 450 in an oxidizing atmosphere. ~
By heating within the range of 800 ° C. to gasify and eliminate the binder, a deodorant as a substantially spherical porous molded body composed of ACP particles 7 was obtained.

From the above, the ACP particles 7 have an excellent ability to adsorb odorous components. Therefore, when the ACP particles 7 are incorporated into the deodorant as a deodorant active substance, the ACP particles 7 in the deodorant are The required adsorption capacity can be maintained even if the addition amount is reduced. For this reason, since other components of the deodorant can be blended in a larger amount, the degree of freedom in designing the components as the deodorant is increased. Therefore, various functions possessed by other components of the deodorant can be more sufficiently exhibited, and the deodorant becomes more suitable.

Further, since the ACP particles 7 have an excellent adsorption ability as compared with the hydroxyapatite, in order to obtain a sufficient deodorizing effect, even if it is a composite powder made of synthetic resin powder, It is not necessary to increase the amount of ACP particles 7 used in the composite powder as in hydroxyapatite. This can also reduce the cost for producing the deodorant.

[0063]

As described above, the deodorant of the first aspect of the present invention has a composition containing amorphous calcium phosphate as a deodorant active substance.

Therefore, it has an excellent ability to adsorb odorous components, which makes it possible to increase the blending ratio of other components of the deodorant, and thus the degree of freedom in designing components as a deodorant is great. Become.

Therefore, there is an effect that the deodorizing effect as the deodorant can be sufficiently exerted and various functions possessed by other components of the deodorant can be more sufficiently exerted.

[Brief description of drawings]

FIG. 1 is a schematic configuration diagram of a spray dryer used when producing ACP particles as a deodorant of one example of the present invention.

FIG. 2 is an X-ray diffraction diagram showing the composition of the ACP particles.

FIG. 3 is a schematic configuration diagram of a measuring device for measuring the adsorption ability of an odor component.

FIG. 4 is a graph showing a measurement result by the measuring device shown in FIG.

[Explanation of symbols]

 1 ACP fine particles 3 ACP slurry 7 ACP particles (amorphous calcium phosphate)

Claims (1)

[Claims] 1. A deodorant comprising amorphous calcium phosphate as a deodorant active substance.