JP2009297202A - Deodorant, spray deodorant, deodorant article, deodorant kit, and manufacturing method of deodorant - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deodorant which has a deodorant effect even when an amount of titanium oxide and silver used is small, and to provide technique related thereto. <P>SOLUTION: The deodorant uses a component containing titanium oxide and silver chlorocomplex. The titanium oxide is titanium oxide fine particle. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a deodorant, and particularly relates to a deodorant using a metal compound.

  Techniques for dealing with unpleasant odors include fragrances, deodorants, deodorants, and deodorants (see Non-Patent Document 1). The fragrance imparts fragrance to the space and masks malodors with the fragrance. The deodorant removes or reduces odor by a chemical action such as decomposition. The deodorizer removes or mitigates the odor by a physical action or the like, and for example, activated carbon, zeolite or the like is used. The deodorant is a substance that adds other substances to the odor element to prevent the generation and divergence of the odor. For example, an antibacterial agent is used.

  However, fragrances do not remove unpleasant odors. Deodorizers can also cause odor re-release. Deodorants cannot cope with the odor that flows from the outside. Therefore, a deodorant is particularly preferably used depending on the purpose.

Until now, deodorizers using organic acids, polyphenols and the like are known. In recent years, deodorants using metal compounds have attracted attention because of their high residual effect. For example, Patent Document 1 discloses a coating material for building materials that includes titanium oxide fine particles and a silver salt and has a deodorizing function. Titanium oxide has a photocatalytic ability and generates active oxygen called a hydroxy radical and singlet oxygen. These active oxygens act as strong oxidants and decompose odor components. Silver is also known to generate active oxygen called a superoxide anion radical, and has been conventionally used as an antibacterial agent.
JP 11-315223 A (published November 16, 1999) Fragrance and Deodorant Council “Self-standards for fragrances, deodorants and deodorants for general consumers (Revised in 2004)” (released on November 11, 2004)

  However, in the deodorizer described in Patent Document 1, it is necessary to use a certain amount or more of titanium oxide and silver in order to exert a deodorizing effect. Since both titanium oxide and silver are expensive, there is a strong demand for a deodorant that can exhibit a sufficient deodorizing effect even if the amount of titanium oxide and silver used is small.

  The present invention has been made in view of the above problems, and provides a deodorant capable of exhibiting a sufficient deodorizing effect even when the amount of titanium oxide and silver used is small, and a related technique. Is the main purpose.

  As a result of intensive studies, the present inventors have surprisingly found that a mixture of titanium oxide and a silver chloro complex exhibits a sufficient deodorizing effect even when the amount of titanium oxide and silver used is small. The headline and invention were completed.

  That is, the deodorizer according to the present invention is characterized by containing titanium oxide and a silver chloro complex.

  In the deodorizer, the titanium oxide is preferably titanium oxide fine particles. The average particle diameter of the titanium oxide fine particles is preferably 1 nm or more and 100 nm or less.

  In the deodorizer, the mass ratio of the silver content to the titanium oxide content is preferably 0.05 times or more and 0.75 times or less.

  The deodorant preferably further contains a chloride. The chlorides are alkali metal chlorides, alkaline earth metal chlorides, aliphatic quaternary ammonium salts, primary amine hydrochlorides, tertiary amine hydrochlorides, aromatic amine hydrochlorides, aromatic quaternary ammonium salts. One or more chlorides selected from the group consisting of The chloride content is preferably 0.1 mol / l or more and 1 mol / l or less. Furthermore, the deodorizer may further contain a solvent in which the chloride is dissolved.

  The deodorant preferably further contains ethanol.

  The deodorizing spray agent according to the present invention is characterized by comprising the above deodorizing agent.

  The deodorant article according to the present invention is characterized in that the deodorant is applied.

  The deodorizing kit according to the present invention is characterized by comprising titanium oxide and a silver chloro complex.

  The manufacturing method of the deodorizer which concerns on this invention is characterized by including the process of mixing a titanium oxide and a silver chloro complex.

  The deodorant, deodorant article, and deodorization kit according to the present invention exhibit a sufficient deodorizing effect even if the amount of titanium oxide and silver contained is small.

  Moreover, according to the manufacturing method of the deodorizer which concerns on this invention, even if the quantity of the titanium oxide and silver to contain is slight, the deodorizer which can exhibit sufficient deodorizing effect can be manufactured. .

(Deodorants)
The present invention provides a deodorant. As used herein, the term “deodorant” refers to a composition that removes or reduces odor by chemical action. The term “composition” refers to a form in which various components are contained in one substance.

  The deodorant according to the present invention may be liquid or solid, and can be used in various forms and applications. That is, the deodorant according to the present invention can be used, for example, as a liquid, gel, granule or solid standing or hanging type deodorant, spray agent, and a coating agent having deodorant properties, It can also be used as an additive, a resin film, a resin molded product, a fiber and the like.

  The odor that the deodorant according to the present invention removes or mitigates is not particularly limited, for example, feces odor, tobacco odor, solvent odor, body odor, sweat odor, foot odor, aging odor, pet odor, rot odor, cooking odor It may be a foul odor such as fragrance, or a fragrance from perfume, incense or the like. The deodorant object of the deodorant according to the present invention is not particularly limited, and for example, for automobiles, refrigerators, indoors, toilets, kitchens, trash cans, entrances, shoeboxes, tobacco odors, pet odors It can be used as a deodorant for use.

  The deodorizer according to the present invention contains titanium oxide and a silver chloro complex. According to the original knowledge of the present inventors, the use of a combination of titanium oxide and silver chloro complex can provide a deodorizing effect much stronger than that obtained by simply mixing titanium oxide and silver. Therefore, the deodorizer according to the present invention exhibits a sufficient deodorizing effect even if the contents of titanium oxide and silver are small.

  As the titanium oxide, for example, anatase type, rutile type, brookite type, or amorphous type can be used, and in particular, anatase type, rutile type, or a mixture thereof is used because of its high photocatalytic activity. Is preferred.

  As titanium oxide, it is preferable to use titanium oxide fine particles. The average particle diameter of the titanium oxide fine particles is not particularly limited, but is preferably 1 nm or more and 100 nm or less, more preferably 3 nm or more and 50 nm or less, and still more preferably 5 nm or more and 20 nm or less. Such titanium oxide fine particles easily form a colloid in the dispersion medium.

  The shape of the titanium oxide fine particles is not particularly limited, and various shapes such as a spherical shape, a fiber shape, a plate shape, and a polyhedron shape can be used.

  Furthermore, the titanium oxide may be one in which an inorganic oxide such as zirconium oxide, iron oxide, silicon oxide, silver oxide, or zinc oxide is adhered. In particular, a material to which zirconium oxide is attached has the function of generating active oxygen in zirconium oxide, and therefore the deodorizing effect of the deodorant can be improved.

  The method for producing such titanium oxide fine particles is not particularly limited. For example, a well-known and commonly used method such as hydrolysis of titanium oxide may be used, or commercially available titanium oxide fine particles may be purchased. In addition, when manufacturing titanium oxide microparticles | fine-particles, an average particle diameter can be adjusted to the target value by using an ultrafiltration membrane etc.

  Although content of the titanium oxide in the said deodorizer is not specifically limited, It is preferable that it is 0.001 mass% or more and 0.2 mass% or less, and is 0.002 mass% or more and 0.1 mass% or less. More preferably, it is the range of 0.004 mass% or more and 0.01 mass% or less most preferably. If content of titanium oxide is 0.001 mass% or more and 0.2 mass% or less, a big deodorizing effect can be acquired, suppressing cost.

In this specification, the “silver chloro complex” refers to [AgCl ₂ ] ⁻ , [AgCl ₃ ] ²⁻ , [AgCl ₄ ] ³⁻ , or salts thereof, which are silver chloro complex ions.

  The cation that forms a silver chloro complex salt together with the silver chloro complex ion is not particularly limited, and can be appropriately selected according to the use, production method, and the like of the deodorant according to the present invention.

  The mass ratio of the silver content to the titanium oxide content in the deodorizer according to the present invention is preferably in the range of 0.05 to 0.75 times. When the mass ratio of the silver content to the titanium oxide content is within the above range, a large deodorizing effect can be obtained while suppressing costs.

  Further, for example, JP-A-10-182326 (published July 7, 1998, hereinafter referred to as “Patent Document 2”) describes that a silver chloro complex is more stabilized in the presence of chloride. Yes. Therefore, it is preferable that the deodorizer according to the present invention further contains a chloride.

  Although it does not specifically limit as said chloride, The chloride (alkali metal chloride) which contains alkali metal ions, such as lithium ion, sodium ion, and potassium ion as a counter ion; Alkali, such as magnesium ion and calcium ion Chloride containing earth metal ion as counter ion; Aliphatic quaternary such as aliphatic quaternary ammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride having one or two long chain alkyl groups having 12 to 18 carbon atoms Ammonium salts; polyamine hydrochlorides such as ethylenediamine hydrochloride, hexamethylenediamine hydrochloride, hexamethylenetriamine hydrochloride; primary amine hydrochlorides such as methylamine hydrochloride and ethylamine hydrochloride; dimethylamine hydrochloride, diethylamine hydrochloride, etc. 2nd class Tertiary amine hydrochlorides such as trimethylamine hydrochloride and triethylamine hydrochloride; aromatic amine hydrochlorides such as pyridine hydrochloride and aniline hydrochloride; triethylbenzylammonium chloride, benzalkonium chloride, benzethonium chloride, pyridinium chloride, Aromatic quaternary ammonium salts such as imidazolinium chloride can be suitably used.

  The chloride may be in a state dissolved in a solution or in a solid state such as a crystal. In any state, the chloride supplies chloride ions to the silver chloro complex to stabilize the silver chloro complex. In addition, as a solvent for dissolving the chloride, in addition to water and a protic solvent exhibiting the same behavior as water, for example, an aprotic solvent such as N, N-dimethylformamide and dimethyl sulfoxide; propylene carbonate Polyvinyl pyrrolidone and the like.

  The content of the chloride in the deodorant is not particularly limited, but is preferably 0.1 mol / l or more and 1 mol / l or less, preferably 0.2 mol / l or more and 0.5 mol / l. The following is more preferable. The chloride has a function of stabilizing the silver chloro complex, and also has a function of corroding metals, gypsum and the like. Therefore, if the content of chloride is large, for example, when used as a deodorizing spray agent, a metal coating agent, an additive to a gypsum board, etc., an undesirable result is brought about. Moreover, when chloride is contained in the deodorant spray agent, the point that precipitation of the chloride occurs on the surface to be sprayed is also not preferable. When the content of the chloride is 0.2 mol / l or more and 0.5 mol / l or less, the silver chloro complex in the deodorant is stabilized, but the chloride is attributed to the chloride as described above. Adverse effects can be suppressed.

  The silver chloro complex can be produced, for example, by dissolving silver or a silver compound in an aqueous chloride solution as described in Patent Document 2. Although the silver compound used for manufacture of a silver chloro complex will not be specifically limited if it is a substance used as the supply source of silver, Silver chloride, silver nitrate, silver sulfate, especially silver chloride can be used preferably. Moreover, as said chloride aqueous solution, what melt | dissolved the above chlorides in the above-mentioned solvent can be used, for example.

  In addition, as described in Patent Document 2, silver chloro complexes are often produced in a form containing chloride. Therefore, in view of the adverse effects caused by chlorides as described above, it is considered difficult to use a silver chloro complex as a deodorant, particularly a deodorant spray. The present invention dares to obtain a deodorizing effect that has not been obtained in the past by using such a silver chloro complex.

  In addition to the above composition, the deodorant according to the present invention can be used in addition to the above-mentioned composition, solvent, deodorant aid, preservative, surfactant, water-absorbing polymer, discoloration inhibitor, precipitation inhibitor, oxidation An inhibitor, a colorant, a fragrance, a resin, a plasticizer, a coagulant, and the like may be further included.

  As the deodorizing aid, alcohols, particularly ethanol is preferable, and the deodorizing effect of the deodorant according to the present invention can be enhanced. When ethanol is added, the content of ethanol is not particularly limited, but may be in the range of 10% to 59%, for example.

(Production method)
The method for producing a deodorant according to the present invention includes a step of mixing titanium oxide and a silver chloro complex. Thereby, the deodorizer containing a titanium oxide and a silver chloro complex can be manufactured. A general method may be used for mixing the titanium oxide and the silver chloro complex. For example, when a wet method is used, a dispersion obtained by dispersing titanium oxide in purified water, an aqueous ethanol solution, or the like and a silver chloro complex solution may be mixed using a propeller stirring device, a ball mill, or the like. In addition, it is preferable to use titanium oxide fine particles as titanium oxide. By using titanium oxide fine particles, titanium oxide can be uniformly dispersed in the dispersion. In the case of using a dry method, titanium oxide and a silver chloro complex may be mixed with a mortar, a ball mill, or the like.

  As described above, the silver chloro complex is prepared by mixing silver or a silver compound with an aqueous chloride solution. Therefore, mixing of the titanium oxide and the silver chloro complex may be performed by mixing titanium oxide, chloride, and silver or a silver compound. Even in this case, since the silver chloro complex is formed by mixing the chloride and silver or the silver compound, the titanium oxide and the silver chloro complex are mixed.

  About the other composition contained in the deodorizer which concerns on this invention, the deodorizer which concerns on this invention can be manufactured by mixing suitably similarly.

(Deodorant spray)
In one embodiment, the deodorant according to the present invention can be used as a deodorant spray. As used herein, “deodorant spray” refers to a deodorizer for spraying by spraying. Note that “spray” refers to a device that sprays liquid in the form of mist or foam.

  The deodorant which concerns on this embodiment is a liquid, and can be used suitably as a deodorant spray agent. The spray in which the said deodorant spray agent is used is not specifically limited, It can use in can spray, electric spray, air spray, etc.

(Deodorant article)
Furthermore, in one embodiment, the deodorant according to the present invention can produce a deodorant article by processing a substrate by various processing methods. The deodorant article refers to an article having deodorant properties. For example, in a textile product, the deodorant according to the present invention can be applied to the fiber surface by dipping, padding, coating, screen processing, or the like. The deodorant according to the present invention can also be applied to metal, glass, tile, synthetic resin, gypsum board, concrete and the like. Thus, the deodorizing article provided with the deodorizing property by applying the deodorant according to the present invention is also within the scope of the present invention.

(Deodorant kit)
The present invention also provides a deodorization kit. The term “kit” is intended to mean that at least one of the various components is contained in another substance (eg, a container). In the present specification, the “deodorizing kit” refers to a kit for removing or mitigating odor by chemical action.

  The deodorizing kit according to the present invention includes titanium oxide and a silver chloro complex. As described above, the deodorant according to the present invention can be produced by mixing titanium oxide and a silver chloro complex. Therefore, if the deodorant kit which concerns on this invention is used, the deodorizer which concerns on this invention can be manufactured easily. Examples of the deodorizing kit according to the present invention include a deodorizing spray provided with a titanium oxide colloid solution container and a silver chloro complex solution container, and a mechanism for mixing the titanium oxide colloid solution and the silver chloro complex solution during spraying. Is mentioned.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention.

  Moreover, all the academic literatures and patent literatures described in this specification are incorporated herein by reference.

[Production example]
Deodorant A was prepared by mixing 500 ml of 67.8% aqueous ethanol solution with 400 ml of purified water, 18 ml of sodium chloride aqueous solution, 6 ml of silver chloro complex solution, 2 ml of titanium oxide fine particle (colloid) solution and 48 ml of purified water in this order. did.

  The concentration of the sodium chloride aqueous solution is 311 g / l. The silver chloro complex solution is prepared by dissolving silver chloride in a sodium chloride aqueous solution having a concentration of 310 g / l so that the final silver concentration is 500 mg / l. The titanium oxide fine particle liquid is obtained by dispersing titanium oxide fine particles having an average particle diameter of 10 nm in purified water. The content of titanium oxide in the titanium oxide fine particle liquid is 2% by mass.

  The final content of each composition contained in the deodorant A is about 0.74 mass% for sodium chloride, about 0.004 mass% for titanium oxide fine particles, and about 0.0003 mass% for silver. is there.

  In addition, 500 ml of 67.8% ethanol aqueous solution, 346 ml of purified water, 18 ml of sodium chloride aqueous solution, 60 ml of silver chloro complex solution, 2 ml of titanium oxide fine particle (colloid) solution and 48 ml of purified water were mixed in this order, and deodorant B Was prepared.

  The final content of each composition contained in the deodorant B is about 2.43% by mass of sodium chloride, about 0.004% by mass of fine titanium oxide particles, and about 0.003% by mass of silver. is there.

[Test Example 1: Ammonia]
Deodorant A and deodorant B as deodorants according to the present invention prepared in Production Examples, two types of commercial products (commercial products L and K) as comparative examples, silver chloro complex solution, titanium oxide fine particles and chloride About the silver liquid mixture, the deodorizing effect with respect to ammonia was tested as follows.

  In addition, the said silver chloro complex solution was prepared so that silver concentration might be about 0.0003 mass%. The mixed liquid of titanium oxide fine particles and silver chloride is a mixed liquid of an aqueous dispersion of titanium oxide fine particles having an average particle diameter of 10 nm and a sodium thiosulfate solution of silver chloride. The content of titanium oxide and the content of silver Is prepared so that it is approximately the same amount as the above deodorant A. That is, the content of titanium oxide in the mixed solution is about 0.004% by mass, and the content of silver is about 0.0003% by mass.

  First, 10 ml of each sample of the deodorant according to the present invention and the comparative example was dropped onto a paper towel (22 cm × 21 cm, 1.0 g) placed on a stainless steel tray. At this time, each sample soaked into the entire paper towel, and was dropped so that the sample did not protrude around the paper towel. Moreover, the paper towel which does not drip a sample was prepared as a blank.

  Each paper towel to which each sample was dropped was allowed to stand for 1 hour and air-dried, and then dried on a hot plate for about 20 minutes to a weight of about 1.0 g. The dried paper towels and blank paper towels were sealed in different 5 liter Tedlar bags.

  Into the Tedlar bag, ammonia whose concentration was adjusted in advance with odorless air was injected and allowed to stand at room temperature (20 ± 3 ° C.). The humidity was 30 ± 5%. When a predetermined time had elapsed, the concentration was measured using a detector tube. The residual rate at each elapsed time was calculated according to the following formula (1).

Residual rate (%) = ammonia concentration after each elapsed time (ppm)
/ Initial ammonia concentration (ppm) x 100 (1)
Table 1 shows the residual ratio of the ammonia concentration after the elapsed time of 0, 10, 30, 60, and 120 minutes.

  As shown in Table 1, the deodorant A has a slight content of titanium oxide and silver (titanium oxide fine particles: about 0.004 mass%, silver chloride: about 0.0003 mass%). The ammonia could be completely removed. Deodorant B was also able to completely remove ammonia.

  On the other hand, the ammonia removal rate was low in the commercially available product, a mixed solution obtained by simply mixing the same amount of titanium oxide fine particles and silver chloride as the deodorant A, and the silver chloro complex solution alone.

(Test Example 2: Methyl mercaptan)
The deodorizing effect on methyl mercaptan was tested for the deodorant A, the silver chloro complex solution as a comparative example, and the mixed solution of titanium oxide fine particles and silver chloride. The test was conducted in the same manner as in Test Example 1 except that methyl mercaptan was used instead of ammonia. The results are shown in Table 2.

  As shown in Table 2, the deodorant A has a slight content of titanium oxide and silver (titanium oxide fine particles: about 0.004 mass%, silver chloride: about 0.0003 mass%). The methyl mercaptan could be completely removed.

  On the other hand, the removal rate of methyl mercaptan was low in the mixed solution obtained by simply mixing the same amount of titanium oxide fine particles and silver chloride as the deodorant A and the silver chloro complex solution alone.

(Test Example 3: Trimethylamine)
The deodorizing effect on trimethylamine was tested for the deodorant A, the silver chloro complex solution as a comparative example, and the mixed liquid of titanium oxide fine particles and silver chloride. The test was performed in the same manner as in Test Example 1 except that trimethylamine was used instead of ammonia. The results are shown in Table 3.

  As shown in Table 3, the deodorant A has a small amount of titanium oxide and silver (titanium oxide fine particles: about 0.004% by mass, silver chloride: about 0.0003% by mass). The trimethylamine could be completely removed.

  On the other hand, the removal rate of trimethylamine was low in the mixed solution obtained by simply mixing the same amount of titanium oxide fine particles and silver chloride as the deodorant A and the silver chloro complex solution alone.

(Test Example 4: Acetic acid)
The deodorizing effect on acetic acid was tested for the deodorant A, the silver chloro complex solution as a comparative example, and the mixed liquid of titanium oxide fine particles and silver chloride. The test was performed in the same manner as in Test Example 1 except that acetic acid gas was used instead of ammonia. The results are shown in Table 4.

  As shown in Table 4, the deodorant A has a small amount of titanium oxide and silver (titanium oxide fine particles: about 0.004 mass%, silver chloride: about 0.0003 mass%). The acetic acid gas could be completely removed.

  On the other hand, the removal rate of acetic acid gas was low in the mixed solution obtained by simply mixing the same amount of titanium oxide fine particles and silver chloride as the deodorant A and the silver chloro complex solution alone.

(Test Example 5: n-valeric acid)
The deodorizing effect on n-valeric acid was tested for the deodorant A, the silver chloro complex solution as a comparative example, and the mixed solution of titanium oxide fine particles and silver chloride. The test was conducted in the same manner as in Test Example 1 except that n-valeric acid was used instead of ammonia. The results are shown in Table 5.

  As shown in Table 5, the deodorant A has a slight content of titanium oxide and silver (titanium oxide fine particles: about 0.004 mass%, silver chloride: about 0.0003 mass%). , N-valeric acid could be completely removed.

  On the other hand, the removal rate of n-valeric acid was low in the mixed solution obtained by simply mixing the same amount of titanium oxide fine particles and silver chloride as the deodorant A and the silver chloro complex solution alone.

  INDUSTRIAL APPLICABILITY The present invention can be used as a deodorant for deodorizing various odors and can be used for producing various articles imparted with deodorizing properties, such as clothing, building materials, daily necessities and the like.

Claims (13)

  A deodorant comprising titanium oxide and a silver chloro complex.   The deodorizer according to claim 1, wherein the titanium oxide is titanium oxide fine particles.   The deodorant according to claim 2, wherein an average particle diameter of the titanium oxide fine particles is 1 nm or more and 100 nm or less.   The deodorizer according to any one of claims 1 to 3, wherein a mass ratio of the silver content to the titanium oxide content is 0.05 to 0.75 times.   The deodorizer according to any one of claims 1 to 4, further comprising a chloride.   The chloride is an alkali metal chloride, alkaline earth metal chloride, aliphatic quaternary ammonium salt, primary amine hydrochloride, tertiary amine hydrochloride, aromatic amine hydrochloride, aromatic quaternary ammonium salt. The deodorizer according to claim 5, wherein the deodorizer is one or more chlorides selected from the group consisting of:   The deodorizer according to claim 5 or 6, wherein the chloride content is 0.1 mol / l or more and 1 mol / l or less.   The deodorizer according to any one of claims 5 to 7, further comprising a solvent in which the chloride is dissolved.   The deodorizer according to any one of claims 1 to 8, further comprising ethanol.   A deodorant spray agent comprising the deodorizer according to any one of claims 1 to 9.   A deodorant article, wherein the deodorizer according to any one of claims 1 to 9 is applied.   A deodorizing kit comprising titanium oxide and a silver chloro complex.   A method for producing a deodorant comprising the step of mixing titanium oxide and a silver chloro complex.