JP4659557B2 - Deodorant composition - Google Patents

Description

  The present invention relates to a deodorant composition, and more particularly, to a deodorant composition that can reduce a composite odor derived from sweat odor and aldehydes and is safe for the human body.

A deodorant relieves an unpleasant odor together with a fragrance, and plays an important part in living a comfortable life. Recent needs regarding deodorization have changed from a fragrance that masks bad odor with a strong fragrance to a deodorant that eliminates the odor itself with a slight fragrance or no fragrance.
In addition, while there is an increasing laundry habit of wearing clothes that do not touch the skin directly, they do not wash immediately, but on the other hand, they are concerned about the smell of clothes that are not washed. Most of the unpleasant odors in the living environment are complex odors, and there is a need for a deodorant effective for these complex odors.

Conventionally, deodorizing techniques for specific malodorous components are known, but few are effective for complex odors.
For example, Patent Document 1 discloses a liquid deodorant that deodorizes sweat odor and tobacco odor by using a cationic surfactant or an amphoteric surfactant in combination with a chelating agent. A liquid deodorant that deodorizes sweat odor by using a deodorant base such as a fragrance, a cationic surfactant and a specific solvent in combination is disclosed. However, these liquid deodorizers do not have sufficient deodorizing performance for aldehydes and the like.
Patent Document 3 discloses a deodorant composition that suppresses spoilage odor by using a deodorant base material mainly composed of an extract from a plant, a fragrance, ethanol, and a surfactant. 4 discloses a deodorant fiber capable of deodorizing ammonia odor and the like by treatment with a treatment agent comprising a betaine amphoteric compound, a nonionic surfactant, and an anionic surfactant. However, these also have insufficient deodorizing performance against sweat odors and aldehydes.

Patent Document 5 discloses that an anionic surfactant containing at least one selected from triethanolamine, tris (hydroxymethyl) aminomethane, and the like as a salt can suppress a complex odor in which lower fatty acids and amines coexist. However, amine salts of anionic surfactants are not suitable for preparing a deodorant composition because they have insufficient effects on aldehydes and some have poor solubility in water.
Patent Document 6 discloses that an organic dibasic acid or a salt thereof can deodorize lower fatty acids such as acetic acid and isovaleric acid and amines such as ammonia and trimethylamine. The salt does not have a sufficient deodorizing effect on aldehydes.
Patent Document 7 discloses that ethanolamine is effective for deodorizing unsaturated aldehydes such as nonanal, which are said to be deeply involved as a causative substance of an aging odor recognized after middle-aged and older. In addition, the effect on sweat odor and aldehydes is unknown, and ethanolamine is irritating and is not suitable for use in a form that may touch the human body.
Under such circumstances, there has been a demand for the development of a deodorant that can reduce the composite odor derived particularly from sweat odor and aldehydes and is safe for the human body.

JP 2001-40581 A JP 2001-70423 A JP 2001-178806 A JP 2004-176225 A JP 2004-49889 A JP 2001-95907 A JP 2001-97838 A

  It is an object of the present invention to provide a deodorant that can reduce a composite odor derived from sweat odor and aldehydes, is easy to prepare an aqueous deodorant, and is safe even when touched by the human body. And

The present inventors have demonstrated that specific polyhydroxyamines are effective for deodorizing complex odors derived from sweat odors, aldehydes, etc., and can also be effective for amines by adjusting the pH to near neutrality. Moreover, it was found that the stimulation to the human body was alleviated. Moreover, it discovered that deodorizing performance could be improved further by using together with a polyhydric alcohol.
That is, the present invention relates to a deodorant composition containing a polyhydroxyamine compound represented by the following general formula (1) and / or a salt thereof (a), and a nonionic surfactant (b) (however, The content of the anionic surfactant is 0.3 or less in molar ratio with respect to the component (a).

（式中、Ｒ¹は、水素原子、炭素数１〜５のアルキル基、又は炭素数１〜５のヒドロキシアルキル基を表し、Ｒ²は、水素原子、炭素数１〜６のアルキル基、又は炭素数１〜５のヒドロキシアルキル基を表し、Ｒ³及びＲ⁴は、炭素数１〜５のアルキレン基を表す。Ｒ³及びＲ⁴は、同一でも異なっていてもよい。）

(In the formula, R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms, and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or represents a hydroxyalkyl group having 1 to 5 carbon atoms, R ³ and R ⁴ are, .R ³ and R ⁴ represents an alkylene group having 1 to 5 carbon atoms may be the same or different.)

  The deodorant composition of the present invention can deodorize a composite odor derived from sweat odor, aldehydes, etc., is easy to prepare an aqueous deodorant, and is safe to touch the human body. In addition, it exhibits an excellent deodorizing effect on the composite odor adhering to a solid surface such as a space or a textile product.

  The deodorant composition of the present invention may be referred to as a polyhydroxyamine compound represented by the following general formula (1) and / or a salt thereof (a) (hereinafter simply referred to as “polyhydroxyamine compounds (a)”). ) As a main component.

In General Formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 5 carbon atoms may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, and various pentyl groups. Examples of the hydroxyalkyl group having 1 to 5 carbon atoms include hydroxymethyl group, 2-hydroxyethyl group, 2-hydroxypropyl group, 3-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, 4- Examples thereof include a hydroxybutyl group.
R ¹ is preferably a hydrogen atom, a methyl group, an ethyl group, a hydroxymethyl group, or a 2-hydroxyethyl group from the viewpoint of deodorizing performance and availability, and particularly a hydrogen atom, a hydroxymethyl group, or 2-hydroxy An ethyl group is preferred.

R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms.
The alkyl group having 1 to 6 carbon atoms may be linear, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, cyclopentyl groups, and cyclohexyl groups.
The above-mentioned thing is mentioned as a C1-C5 hydroxyalkyl group.
From the viewpoints of deodorizing performance and availability, R ² is preferably a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or a hydroxyethyl group, and particularly preferably a hydrogen atom.
R ³ and R ⁴ represent an alkylene group having 1 to 5 carbon atoms. R ³ and R ⁴ may be the same or different. The alkylene group having 1 to 5 carbon atoms is preferably a methylene group, an ethylene group, a propylene group or a butylene group, and particularly preferably a methylene group.

Specific examples of the polyhydroxyamine compounds (a) include, for example, tris (hydroxymethyl) aminomethane, 2-amino-2-methyl-1-propanol, 2-amino-1,3-propanediol, 2-amino 2-methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxy Ethyl-1,3-propanediol, 4-amino-4-hydroxypropyl-1,7-heptanediol, 2- (N-ethyl) amino-1,3-propanediol, 2- (N-ethyl) amino- 2-hydroxymethyl-1,3-propanediol, 2- (N-decyl) amino-1,3-propanediol, 2- (N-decyl) amino- - hydroxymethyl-1,3-propanediol, and mixtures thereof with hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, salts with carbonate.
Among these, from the viewpoint of deodorizing performance and the like, tris (hydroxymethyl) aminomethane, 2-amino-2-methyl-1-propanol, 2-amino-1,3-propanediol, 2-amino-2- Methyl-1,3-propanediol, 2-amino-2-ethyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-hydroxyethyl-1 1, 3-propanediol and one or more selected from salts thereof with hydrochloric acid or the like are particularly preferable.

When the polyhydroxyamine compound represented by the general formula (1) is used as a salt such as hydrochloric acid, the pH can be adjusted by adding a base. Examples of the base that can be used include sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like, as well as monoethanolamine, diethanolamine, triethanolamine, methylethanolamine, dimethylethanolamine and the like. Among these, sodium hydroxide and potassium hydroxide are preferable.
The polyhydroxyamine compounds (a) can be produced by a conventional method.

Said polyhydroxyamine compound (a) can be used individually or in mixture of 2 or more types. Even with a single or mixture of polyhydroxyamine compounds (a), they exhibit deodorizing performance against complex odors derived from fatty acids, aldehydes and amines, but when used in combination with surfactant (b) Further, the deodorizing performance can be further enhanced.
That is, odor components usually adhere to solid surfaces such as suits, sweaters, curtains, sofas and other textile products, but surfactants not only suppress the volatilization of odor components adhering to the solid surfaces, but also deodorize. It is possible to stably disperse the component polyhydroxyamine compounds (a), improve the contact with the odor component, and further improve the deodorization performance.

  The surfactant (b) used in the present invention is not particularly limited as long as it exhibits a function of allowing the polyhydroxyamine compound (a) to penetrate into the fiber, and is a nonionic surfactant or a cationic surfactant. 1 type (s) or 2 or more types chosen from amphoteric surfactant and anionic surfactant are mentioned. However, if the content of the anionic surfactant exceeds 0.9 in terms of molar ratio with respect to the polyhydroxyamine compounds (a), it is considered that the deodorizing performance is inhibited. Content of an agent is 0.9 or less by molar ratio with respect to polyhydroxyamine compounds (a).

As the nonionic surfactant, ethylene oxide (hereinafter referred to as “EO”) and / or propylene oxide (hereinafter referred to as “PO”) is averaged to a primary or secondary alcohol having 8 to 18 carbon atoms. Polyoxyalkylene alkyl or alkenyl ether added with -18 mol; polyoxyethylene alkylphenyl ether having an alkyl group with an average carbon number of 6-12 and EO added with an average of 6-20 mol; alkyl group with 8-18 carbon atoms Or a polyoxyalkylene fatty acid ester in which 6 to 18 moles of EO and / or PO is added to a fatty acid having an alkenyl group on average; sorbitan in which a fatty acid having an alkyl group or alkenyl group having 8 to 18 carbon atoms is linked by 1 to 3 moles 6 average EO and / or PO in fatty acid ester or glycerin fatty acid ester 30 mol added polyoxyalkylene sorbitan fatty acid ester or polyoxyalkylene glycerin fatty acid ester, or polyoxyalkylene sorbit fatty acid ester added with an average of 6 to 80 mol of EO and / or PO; average of 6 to 80 mol of EO and / or PO Polyoxyalkylene castor oil or hydrogenated castor oil added; EO added to a condensate of PO and propylene glycol (pluronic surfactant); EO added to a condensate of PO and ethylenediamine (Tetronic) Type surfactant); alkyl or alkenyl diethanol amide, alkyl amine or alkyl dimethyl amine, alkenyl amine or alkenyl dimethyl amine, alkyl amine having 10 to 20 carbon atoms or alkenyl group Polyoxyalkylene alkyl or alkenyl amine such as averaged 2 to 40 moles of EO and / or PO in the alkenyl amines may.
Among these, from the viewpoint of improving the deodorizing performance, polyoxyalkylene alkyl or alkenyl ether obtained by adding 6 to 18 mol of EO and / or PO on average to a primary or secondary alcohol having 8 to 18 carbon atoms is preferable. .

Examples of the cationic surfactant include primary amine salts, secondary amine salts, tertiary amine salts, and quaternary ammonium salts. Of these, quaternary ammonium salts are preferred.
As the quaternary ammonium salt, at least one of the four substituents is an alkyl or alkenyl group having a total carbon number of 8 to 28, and the remainder is a benzyl group, an alkyl group having 1 to 5 carbon atoms and a carbon number of 1 to 5 Examples thereof include compounds that are groups selected from hydroxyalkyl groups. An alkyl or alkenyl group having a total carbon number of 8 to 28 may be substituted with an alkoxyl group, an alkenyloxy group, an alkanoylamino group, an alkenoylamino group, an alkanoyloxy group or an alkenoyloxy group within this carbon number range. Good.
Particularly preferred quaternary ammonium salts include N-lauryl-N, N-dimethyl-N-benzylammonium chloride, N-dodecyl-N-benzyl-N, N-dimethylammonium chloride, N-tetradecyl-N-benzyl. -N, N-dimethylammonium chloride, N-tetradecyl-N, N-dimethyl-N-ethyl quaternary ammonium ethyl sulfate and the like can be mentioned.

As the amphoteric surfactant, an amidopropylamine oxide (obtained by reacting an amide compound of lauric acid and dimethylaminopropylamine with hydrogen peroxide) having an alkyl group or an alkenyl group having 10 to 20 carbon atoms, Alkyl or alkenylamine oxide, or dimethyllaurylamine oxide; dimethylaminoacetic acid betaine or imidazolinium betaine; fatty acid amidopropyldimethylaminoacetic acid betaine having an alkyl or alkenyl group having 8 to 18 carbon atoms, N-acylamino acid or Examples thereof include salts thereof and N-acylmethyl taurate.
Among these, from the viewpoint of improving the deodorizing performance, amidopropylamine oxide (obtained by reacting an amide compound of lauric acid and dimethylaminopropylamine with hydrogen peroxide) and dimethyllaurylamine oxide are preferable.

Examples of the anionic surfactant include a linear or branched alkylbenzene sulfonate having an alkyl group having 8 to 16 carbon atoms (such as dodecylbenzenesulfonic acid); an alkyl sulfate or alkenyl sulfate having 10 to 20 carbon atoms , Olefin sulfonates, alkane sulfonates, alkyl polyhydric alcohol ether sulfates such as alkyl glyceryl ether sulfonic acids, higher fatty acid salts; linear or branched alkyl or alkenyl groups having 10 to 20 carbon atoms Alkyl ether sulfate or alkenyl ether added at an average ratio of 0.5 to 8 moles of EO, PO, butylene oxide, or EO / PO = 0.1 / 9.9 to 9.9 / 0.1 Examples thereof include sulfates, alkyl ether carboxylates, and alkenyl ether carboxylates.
Among the surfactants, from the viewpoint of improving the deodorizing performance, one or two or more selected from the nonionic surfactants, cationic surfactants and amphoteric surfactants are preferable.

The content of the polyhydroxyamine compounds (a) and the surfactant (b) in the deodorant composition of the present invention varies depending on the concentration of malodor to be deodorized and the usage form.
(A) A component is 0.001 mass% or more normally, Preferably it is 0.001-10 mass%, More preferably, it is 0.005-5 mass%, Most preferably, it is 0.01-5 mass%.
(B) A component is 0.001 mass% or more normally, Preferably it is 0.001-30 mass%, More preferably, it is 0.01-10 mass%, Most preferably, it is 0.01-5 mass%.
However, from the viewpoint of deodorizing performance, the content of the anionic surfactant is 0.9 or less, preferably 0.7 or less, more preferably 0.8, relative to the component (a). 5 or less, more preferably 0.3 or less, particularly preferably not contained.

The pH of the deodorant composition of the present invention is 6.0 to 9.5. The effect on sweat odor and aldehydes is excellent at pH 6.0 or higher, and the effect on amines and the like is excellent at pH 9.5 or lower.
The pH is preferably 6.5 to 9.5, and more preferably 6.8 to 9.0, from the viewpoint of the effect on all the complex odors derived from sweat odor and aldehydes, and the reduction of skin irritation.
The pH of the deodorant composition of the present invention can be adjusted by adding an acid such as hydrochloric acid or an alkali such as sodium hydroxide.

The deodorant composition of the present invention further includes polyhydric alcohol, other deodorants, and various commonly added solvents, oil agents, gelling agents, sodium sulfate, N, N, N-trimethylglycine, etc. Other components such as salt, pH adjuster, antioxidant, preservative, bactericidal / antibacterial agent, fragrance, dye, ultraviolet absorber and the like can be added.
The polyhydric alcohols, like the surfactant (b), suppress the volatilization of the odor component adhering to the solid surface and stably disperse the polyhydroxyamine compounds (a) which are deodorizing components. The deodorizing performance can be further enhanced by improving the contact with the odor.
Examples of polyhydric alcohols that can be used include glycerin, ethylene glycol, propylene glycol, 1,3-propanediol, butanediol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol, and the like. Among these, diethylene glycol and dipropylene glycol are preferable.
The content of the polyhydric alcohol used varies depending on the concentration of malodor to be deodorized and the use form, but is usually 0.001% by mass or more, preferably 0.001 to 30% by mass, and more preferably 0.005 to 5%. 10% by mass.
Solvents include lower alcohols (3 to 4 carbon atoms) such as water, ethanol and isopropanol, polyhydric alcohols (2 to 12 carbon atoms) such as ethylene glycol, propylene glycol, glycerin and sorbitol, ethylene glycol and propylene glycol. Monoethyl or monobutyl ether, monoethyl or monobutyl ether of diethylene glycol or dipropylene glycol, benzyl alcohol, benzyloxyethanol, an ethylene oxide or propylene oxide adduct of a phenolic compound, and the like.

The usage form of the deodorant of this invention can be made into solid forms, such as liquid form, gel form, powder form, and a granular form. In the case of liquid, it can be used for fibers, spaces, human bodies, hair, pets and the like, particularly as sprays, lotions and the like. The deodorant of the present invention is particularly preferably a water-based deodorant filled in a mist type spray container and adjusted in a single spray amount to 0.1 to 1 ml.
In the case of gel or solid, it is suitable for partial use on the human body. Further, for example, it can be used as a stationary type, such as being used as a filter of an air purifier by being immersed and sprayed on paper or non-woven fabric.

Examples 1-3 , Reference Examples 1-2, and Comparative Examples 1-3
<Preparation of deodorant composition>
Deodorant compositions having the formulation shown in Table 1 were prepared. As an antibacterial agent, Proxel BDN (manufactured by Avicia Co., Ltd., 10% aqueous solution) is used. Using a blended fragrance comprising 10 parts of Pride, 20 parts of phenylethylaldehyde, 10 parts of Cedar alcohol, and 20 parts of limonene, the deodorant composition is pH 8 with 1N hydrochloric acid or 1 / 10N aqueous sodium hydroxide solution. Adjusted to 0.0.
The components of the symbols in Table 1 are as follows.
(A) Component (a) -1: Tris (hydroxymethyl) aminomethane (a) -2: 2-amino-2-methyl-1,3-propanediol (a) -3: 2-amino-2-methyl -1-propanol
(B) Component (b) -1: Polyoxyethylene alkyl ether (nonionic surfactant) obtained by adding an average of 8 moles of ethylene oxide (EO) to a linear primary alcohol having 12 carbon atoms
(B) -2: Laurylamidopropylamine-N, N-dimethyl-N-oxide (obtained by reacting an amide compound of lauric acid with N, N-dimethyl-1,3-diaminopropane with hydrogen peroxide) Stuff) (amphoteric surfactant)
(B) -3: N-lauryl-N, N-dimethyl-N-benzylammonium chloride (cationic surfactant)
(B) -4: dodecylbenzenesulfonic acid (anionic surfactant)
Molar ratio of tris (hydroxymethyl) aminomethane dodecyl benzene sulfonic acid (active ingredient amount molar ratio) is 0.1 in Example 2, it was 1.1 in Comparative Example 2.

<Preparation of deodorant object>
A cotton melias cloth (10 cm × 10 cm) is sprayed once with a spray vial (Marem Co., No. 6) as a odor component using a 10 ppm ethanol solution of isovaleric acid or 1% ethanol solution of nonanal, 30 After drying for minutes, a test piece was obtained.
<Deodorization method>
The test piece obtained by the above method was sprayed 6 times using a spray vial (Marum Co., No. 6) with a deodorant composition having the formulation shown in Table 1 and dried for 1 hour.
<Deodorization performance evaluation>
A total of 10 panelists, 5 males and 5 females in their 30s, smelled the test piece, evaluated by the following 6-step odor intensity display method, and the average value was obtained.
0: Odorless 1: Strength of feeling something slightly but not knowing what odor (detection threshold level)
2: Know what odor, easily feel weak odor (recognition threshold level)
3: Obvious odor 4: Strong odor 5: Unacceptably strong odor Average value 0 to less than 1, ◎, average value 1 to less than 2 ○, average value 2 to less than 3 △, average value 3 to 5 The following was evaluated as x. The evaluation is preferably ◎ or ○. The results are shown in Table 1.

From Table 1, the deodorizers of Comparative Examples 1 to 3 have insufficient deodorizing performance against sweat odor and aldehyde odor, whereas the deodorizers of Examples 1 to 3 have sweat odor and It can be seen that the deodorizing performance is high for any aldehyde odor. Moreover, in Example 3 , the fragrance | flavor tone of the mix | blended fragrance | flavor was maintained.

  The deodorant composition of the present invention can deodorize a composite odor derived from sweat odor, aldehydes, etc., is easy to prepare an aqueous deodorant, and is safe to touch the human body. For this reason, the deodorant composition of this invention can be used conveniently as a deodorant composition of the composite odor adhering to solid surfaces, such as a space and a textile product.

Claims (6)

Deodorant composition containing a polyhydroxyamine compound represented by the following general formula (1) and / or a salt thereof (a), and a nonionic surfactant (b) (however, an anionic surfactant) Is a molar ratio of 0.3 or less with respect to the component (a)).

(In the formula, R ¹ represents a hydrogen atom, a hydroxymethyl group or a 2-hydroxyethyl group , and R ² represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl group having 1 to 5 carbon atoms. R ³ and R ⁴ represent an alkylene group having 1 to 5 carbon atoms, and R ³ and R ⁴ may be the same or different.   The deodorant composition of Claim 1 which does not contain an anionic surfactant. The polyhydroxyamine compound represented by the general formula (1) is tris (hydroxymethyl) aminomethane , 2-amino-1,3-propanediol , 2-amino-2-hydroxyethyl-1,3-propanediol and The deodorant composition according to claim 1 or 2, wherein the deodorant composition is at least one member selected from salts thereof with hydrochloric acid or the like.   The content of the polyhydroxyamine compound represented by the general formula (1) and / or its salt (a) is 0.001 to 10% by mass, and the content of the surfactant (b) is 0.001 to 0.001. The deodorant composition according to any one of claims 1 to 3, which is 30% by mass.   The deodorant composition according to any one of claims 1 to 4, wherein the deodorant is an aqueous deodorant.   The deodorant composition according to claim 5, which has a pH of 6.0 to 9.5.