JP2003070890A - Deodorant dispersion and deodorizing spray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a deodorant dispersion which achieves excellent dispersion stability and re-dispersibility by accomplishing handy and highly efficient deodorizing of various bad smells and a deodorizing spray which eliminates clogging even under prolonged preservation. SOLUTION: In a deodorant dispersion which has a solid deodorant dispersed into a dispersion medium, colloidal particles are used as a dispersion stabilizer. Moreover, the solid deodorant employs substances having electric charges in the dispersion medium.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a deodorant dispersion liquid capable of effectively and easily deodorizing various malodors while maintaining stable liquid properties for a long period of time, and a deodorant dispersion liquid and a propellant thereof. Deodorant spray consisting of.

[0002]

2. Description of the Related Art Generally, substances having deodorant properties include those in solid, liquid, and gas states, and the product forms of deodorants using these substances are powdery, granular, gel, and liquid. Sprays (including those in which solid particles are dispersed in a dispersion medium) and sprays are used. Among them, the liquid or spray deodorant is excellent in the immediate effect of the deodorizing effect. In addition, since it can be dripped or sprayed directly on the malodor generating source, it has a feature that it can easily and effectively deodorize. Therefore, a deodorant liquid or a deodorant spray in which a deodorant substance is dispersed or dissolved in a solvent such as water or alcohol has been proposed.

However, deodorant substances that can be dissolved in a solvent are generally highly volatile, and many of them are liquids that volatilize the substance at the same time when the solvent dries, and the deodorizing performance is not good enough. have. Many deodorant substances with excellent deodorant performance are solid deodorant substances that are insoluble in solvents, but in general, this substance has a high specific gravity and tends to have poor dispersibility. When it is dispersed in a liquid as a raw material, it is liable to settle and separate, and once separated, there is a problem that it is difficult to redisperse even if it is stirred. Further, when this dispersion liquid is sprayed, there is a problem that the injection nozzle is clogged.

In order to solve these problems, a calcium phosphate compound powder having a specific average particle diameter and a surfactant,
Deodorizing liquid containing alcohol (JP-A-5-115538), deodorant aerosol composition (JP-A-8-291023) in which spherical silicone having specific physical properties is mixed, corn starch octenyl succinate ester and inorganic powder Deodorant aerosol composition in which a nonionic surfactant is added to a system composed of, etc. (JP-A-10-158139), Nε-
Although a deodorant aerosol composition (JP-A-11-29456) in which a nonionic surfactant is added to a system composed of lauroyl-L-lysine and an inorganic powder has been proposed,
In a dilute dispersion system used as a deodorant or deodorant spray, the dispersion stability is improved, but the dispersion stability of the solution is insufficient when left standing for a long time, and the hard cake on the bottom. Was generated, which made it impossible to use as a deodorant liquid or deodorant spray. This tendency tends to increase as the particles become finer and the concentration becomes lower. Once formed, the hard cake does not redisperse even when shaken.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems of the conventional deodorant dispersions, can easily and efficiently deodorize various malodors, and improves dispersion stability and redispersibility. An object is to provide an excellent deodorant dispersion liquid and a deodorant spray that does not clog even when stored for a long period of time.

[0006]

Means for Solving the Problems As a result of intensive studies by the present inventors, dispersion stability was improved by adding colloidal particles as a dispersion stabilizer to a deodorant liquid containing a dispersion medium and a deodorant.
The present invention has been accomplished by finding that redispersibility is remarkably improved. That is, the present invention relates to a solid deodorant, a deodorant dispersion containing a dispersion medium as an essential component, wherein deodorant dispersion is characterized by using colloidal particles as a dispersion stabilizer, and this deodorant dispersion. And a propellant.

DETAILED DESCRIPTION OF THE INVENTION

The present invention will be described in detail below. ○ Colloidal particles Colloid is a state of a substance in a special dispersed state, such as Brownian motion and the Tyndall phenomenon. Colloidal particles are particles in that state, generally 1 to 50
Refers to particles with a diameter of 0 nm, which carry a positive or negative charge in a solvent. Types of colloidal particles include molecular colloidal particles in which a polymer is itself, and hydrophilic colloidal particles in which low molecules are associated.

The colloidal particles in the present invention are not particularly limited to organic substances and inorganic substances, but colloidal particles made of inorganic substances are preferable. The colloidal solution used in the present invention varies depending on the type of the dispersion medium and the deodorant, and further the application, but in order to disperse the deodorant dispersion more stably, the solid deodorant is dispersed. It is desirable that it is the same as the pH of the liquid. Specifically, when the colloidal solution is added to the deodorant liquid in which the deodorant component is dispersed, it is preferable that the pH does not change by ± 3 or more. Particularly preferred colloidal particles in the present invention are silica sol, alumina sol,
Examples thereof include zirconia sol.

Solid deodorant The solid deodorant usable in the present invention is not particularly limited as long as it is a solid having deodorant performance,
For example, activated carbon, ascorbic acid, cyclodextrin,
Catechin, zeolite, calcium phosphate, clay mineral and the like can be used. Among these, it is preferable to use a deodorant composed of an inorganic material or a deodorant containing an inorganic material as a main component because the deodorizing effect can be maintained.

The solid deodorant used in the deodorant dispersion of the present invention is a deodorant composed of a substance having a positive or negative charge in the dispersion medium, and the stability of the dispersion. Is particularly preferable in that In general, there are various methods for measuring the surface charge of particles, but as a potential that can be particularly easily measured, there is a colloidal vibration potential (CVP) or an ultrasonic vibration potential (UVP). According to Debye's law, this method is a method of measuring the potential difference caused by the difference in mobility between the particle and the particle surface (interface) at the location shifted by 1/2 wavelength when the particle is vibrated by ultrasonic waves. Is. The measurement conditions are as follows: particles are dispersed in a medium to form a slurry.
Stir for 0 minutes or more to equilibrate, and after confirming that solid precipitation does not occur, measure. Since CVP changes depending on the solid concentration and PH, pay attention to the adjustment of the slurry during measurement. As a measuring device, for example, PEN-KEM7 manufactured by PEN-KEM
000 (hereinafter referred to as the present apparatus).

The solid deodorant having a positive or negative charge in the dispersion medium, which can be preferably used in the present invention, is a substance in which the above CVP or UVP shows positive or negative in a state of being dispersed in the dispersion medium. Refers to. For example, when CVP is measured by this device, aluminum silicate (at 1 mass% and pH 6.1, as an inorganic deodorant having a positive charge in an aqueous medium,
430 μV), hydrotalcite (1% by mass, pH
In the case of 8.9, 42 μV) and the like, and as an inorganic deodorant having a negative charge in an aqueous medium, zirconium phosphate (1
% By mass at pH 3.4, -860 μV), zirconium hydroxide (at 1% by mass, pH 6.6, -93 μV)
0 μV), zirconium phosphate carrying copper ions by ion exchange (1 mass%, pH 4.0, -390
μV) etc.

The solid deodorant having particularly high deodorant performance and excellent dispersion stability includes zirconium phosphate, titanium phosphate, hydrotalcite and its fired product, zinc oxide, aluminum silicate, One or more substances selected from the group consisting of zirconium hydroxide, silica, and porous silicon dioxide supporting a polyamine compound can be preferably used.

The above-mentioned polyamine which can be used in the present invention is a compound having two or more amino groups in the same molecule and is also called a polyvalent amine. In the present invention, the specific polyamine represented by the following formula is preferred. _{H 2 N- (CH 2 CH 2} -NH) n- CH 2 CH 2 NH 2 (n is 0 to 3 integer) Further, the porous silicon dioxide supporting the polyamine in the present invention, the specific surface area is 200 ˜900 m ² / g of silicon dioxide, which includes, for example, silica gel and commercially available nip seal (fine particle hydrous silicon dioxide). Furthermore, the amount of polyamine supported on the porous silicon dioxide is 0.02 to 2 mm per 1 g of silicon dioxide.
It is preferably ol.

As for the solid deodorant, it is preferable to appropriately select the type of deodorant depending on the component to be deodorized and to combine several kinds of solid deodorants. For example, with respect to a bad odor containing an aldehyde compound as a main component, as a solid deodorant, porous silicon dioxide carrying a polyamine compound, hydrotalcite and its fired product, and zirconium hydroxide are preferable. Zirconium hydroxide is also referred to as zirconium oxyhydroxide, hydrous zirconium oxide, hydrated zirconium oxide, and zirconium oxide hydrate, and includes all of these. Examples of the aldehyde compound to be deodorized include acetaldehyde, which is a main component of tobacco odor, formaldehyde that causes sick house syndrome, nonenal that causes aging odor, and compounds having an aldehyde group such as benzaldehyde and nonanal.

Preferred solid deodorants for deodorizing ammonia odor and amine odor include aluminum silicate, zirconium phosphate, titanium phosphate, zinc oxide and the like.
Examples of the malodor source containing ammonia and amine as main components include nightmarine odor, manure odor, sweat odor, pet odor, and the like. Acetic acid,
Preferred solid deodorants for eliminating acidic malodors such as caproic acid and isovaleric acid include zirconium hydroxide, hydrotalcite, and anion exchangers such as fired products thereof. Isovaleric acid and caproic acid are main components of sole odor and sweat odor, and acetic acid is a component contained in tobacco odor.

As a solid deodorant used for deodorizing a sulfur-based gas, zinc oxide or an ion exchanger in which a metal ion is exchanged, for example, phosphorus in which a metal ion such as copper, zinc or manganese is supported. Zirconate and titanium phosphate are preferred. Typical sulfur-based malodorous gases include methyl mercaptan and hydrogen sulfide, human odor, manure odor,
It is said to be one of the main components of sweat odor and food odor.

The solid deodorant used in the deodorant dispersion of the present invention preferably has an average particle size of 0.01 to 20 μm,
0.1 to 10 μm is particularly preferable. If the average particle size is larger than the above range, sedimentation and separation may occur easily and the spray nozzle may be clogged. On the contrary, if the average particle size is smaller than the above range, the particles may aggregate in the liquid and easily solidify, which is not preferable.

The solid deodorant content in the deodorant dispersion of the present invention is preferably 0.001% by mass to 10% by mass, and particularly preferably 0.1% by mass to 5% by mass. If the deodorant is too much, whitening or the like may occur after spraying, and if it is too small, the deodorant effect becomes insufficient. The compounding amount of the colloidal particles is preferably 0.001% by mass to 5% by mass. If the amount of the colloidal particles blended is too small, the dispersing effect does not appear and there is a risk that hard cakes will be formed. On the other hand, if the amount is too large, there is no particular problem with respect to dispersibility, but it is not economical.

Dispersion medium The dispersion medium used in the deodorant dispersion liquid of the present invention is not particularly limited as long as it is a solvent which does not react with the solid deodorant, does not have an offensive odor itself, and has low toxicity. it can. In particular, as the dispersion medium when used as a spray, a solvent having high volatility and easy to dry can be preferably used. A particularly preferred dispersion medium is ethanol or water.

In the deodorant dispersion of the present invention, if necessary,
A binder component, an antibacterial agent, an antifungal agent, an aromatic agent and the like can be used in combination. In particular, when the deodorant dispersion of the present invention is applied to the surface of a substrate, dipping, or sprayed to produce a deodorant processed product, in order to prevent the deodorant component from being released from the substrate after the solvent is volatilized. It is effective to add a binder component. As the binder component, polyvinyl alcohol, polyacrylic acid ester, urethane-based binder and the like can be used.

The deodorant dispersion according to the present invention can be made into a deodorant spray by mixing it with a propellant and filling it in a spray can. The propellant that can be used in the deodorant spray of the present invention is not particularly limited, but Freon 11, Freon 12,
Freon gas such as Freon 21, Freon 113, Freon 114, Freon 134a, propane gas, isobutane, normal butane,
Hydrocarbon-based gas such as isopentane and neopentane, liquefied gas such as dimethyl ether, nitrogen gas, carbon dioxide gas and the like can be used. In the deodorant spray of the present invention, the amount of the propellant compounded is 5% by mass to 99% of the total amount.
Mass% is preferred. Further, the content of the solid deodorant in the deodorant spray of the present invention is preferably 0.001% by mass to 10% by mass, and particularly preferably 0.1% by mass to 5% by mass.

○ Uses The deodorant dispersion and deodorant spray of the present invention are used in various fields in which conventional deodorants such as activated carbon are used without impairing the original deodorant performance of the deodorant substance, For example, cigarette odor deodorant, daily odor deodorant, body odor deodorant, manure odor deodorant, dust odor deodorant,
It can be used in fields such as caregiver deodorization. The deodorant dispersion liquid and deodorant spray of the present invention can be used as a deodorant product by itself to deodorize a bad odor, and the deodorant dispersion liquid or spray is applied to the surface of other articles and sprayed. Or by imparting deodorant property to this article by a method such as dipping the article itself in the dispersion liquid.

[0023]

The present invention will be described in more detail below. [Example 1] Zirconium phosphate was used as a solid deodorant.
Zirconia sol was used as a dispersion stabilizer, and both were 0.1
It was added to pure water so as to be a mass%, and this was stirred and mixed to obtain a deodorant dispersion liquid.

Example 2 Zirconium hydroxide was used as a deodorant, and alumina sol was used as a dispersion stabilizer. Zirconium hydroxide was added to ethanol in an amount of 2% by mass and alumina sol was 1% by mass. The mixture was stirred and mixed to obtain a deodorant dispersion liquid. [Example 3] A calcined product of hydrotalcite was used as a deodorant.
Silica sol was used as a dispersion stabilizer, and the calcined product of hydrotalcite was added to pure water such that the sol was 1% by mass and the silica sol was 0.05% by mass, and the resulting mixture was stirred and mixed to obtain a deodorant dispersion liquid. .

Comparative Example 1 Zirconium phosphate as a deodorant was added to pure water in an amount of 1% by mass, and this was stirred and mixed to obtain a deodorant dispersion liquid. [Comparative Example 2] Zirconium hydroxide as a deodorant was added to ethanol in an amount of 2% by mass, and the mixture was stirred and mixed to obtain a deodorant dispersion liquid. [Comparative Example 3] A calcined product of hydrotalcite was used as a deodorant.
It was added to pure water so as to be 1% by mass, and this was stirred and mixed to obtain a deodorant dispersion liquid.

Ammonia deodorant test Using the deodorant solutions obtained in Example 1 and Comparative Example 1, an ammonia deodorant test was carried out. The test conditions and procedures are as follows. Each 1 g of the deodorant dispersion of Example 1 or Comparative Example 1 was poured into another Tedlar bag. 1 liter of 50 ppm-concentration ammonia gas was injected into each of the above Tedlar bags. After 2 hours, the end of the Tedlar bag was cut off and sensory evaluation was performed by 6 test subjects. Ammonia gas was injected into a Tedlar bag to which the deodorant dispersion was not added, and the same test was performed to obtain a blank.

Acetic Acid Gas Deodorant Test Using the deodorant dispersions obtained in Example 2 and Comparative Example 2, an acetic acid gas deodorant test was carried out. The test conditions and procedures are the same as the ammonia gas deodorant test. However, the acetic acid gas concentration is 5
It was set to 0 ppm.

Isovaleric Acid Gas Deodorant Test Using the deodorant solutions obtained in Example 3 and Comparative Example 3, an isovaleric acid gas deodorant test was carried out. The test conditions and procedures are the same as the ammonia gas deodorant test. However, the isovaleric acid gas concentration was 1 ppm. The evaluation results of the above three types of gas deodorizing tests are shown in Table 1 with a case of no smell at all, and a case of slightly smelling at x.

[0029]

[Table 1]

Redispersibility Test A redispersibility test was carried out using the deodorant dispersions obtained in Examples 1 to 3 and Comparative Examples 1 to 3. The test conditions and procedures are as follows. 10 ml of each deodorant dispersion was placed in a separate test tube. It was allowed to stand at room temperature for 10 days. The test tube was shaken lightly and the redispersibility was visually evaluated.
The state of the liquid was visually observed, and when it was redispersed, it was marked with ◯, and when it was not redispersed, it was marked with x.

[0031]

[Table 2]

Spray Test Using the deodorant dispersions obtained in Examples 1 to 3 and Comparative Examples 1 to 3, spraying was performed and an injection test was carried out. The test conditions and procedures are as follows. 100 ml of each deodorant dispersion and LPG as a propellant were added to a spray can to form a spray. It was allowed to stand at room temperature for 10 days. Shake the spray can to make a polyester non-woven fabric (10 cm
X 10 cm) was sprayed from a distance of 20 cm for 3 seconds. The dispersibility of the powder adhering to the surface of the sprayed nonwoven fabric was visually evaluated. Instead of the deodorant dispersion, the sprayed non-woven fabric was put in a Tedlar bag, and the same deodorization test as the above-mentioned ammonia deodorization test was performed to perform a deodorization test.

As a result of the spray injection test, the evaluation of the injection property was indicated by ◯ when it was ejected cleanly, and by X when it was not ejected cleanly because the spray can was clogged. The dispersibility was indicated by ◯ when the deodorant powder was evenly spread on the surface of the cloth, and by x when the powder was unevenly spread. In addition, the deodorant properties are shown as in Table 1. The results are shown in Table 3. In each of Comparative Examples 1 to 3, the injection holes were clogged and the injection could not be performed. Therefore, the dispersibility and the deodorizing property could not be evaluated.

[0034]

[Table 3]

[0035]

INDUSTRIAL APPLICABILITY The deodorant dispersion liquid of the present invention has good deodorant performance, excellent dispersion stability and redispersibility for a long period of time, and is used as a spray without sedimentation. The jet nozzle will not be clogged even when.

Claims (5)

[Claims] 1. A deodorant dispersion in which a solid deodorant is dispersed in a dispersion medium, wherein colloidal particles are used as a dispersion stabilizer. 2. The solid deodorant is a deodorant composed of a substance having an electric charge in a dispersion medium.
The deodorant dispersion described. 3. The solid deodorant is zirconium phosphate,
At least one substance selected from the group consisting of titanium phosphate, hydrotalcite and its fired product, zinc oxide, aluminum silicate, zirconium hydroxide, silica, and porous silicon dioxide carrying a polyamine compound. The deodorant dispersion liquid according to claim 1 or 2. 4. The deodorant according to any one of claims 1 to 3, wherein the colloidal particles are one or more sol selected from the group consisting of silica sol, alumina sol and zirconia sol. Agent dispersion. 5. A deodorant spray comprising the deodorant dispersion according to any one of claims 1 to 4 and a propellant.