JP2022135699A - Deodorant - Google Patents

Abstract

To provide a deodorant that can efficiently catch aldehyde, ammonia, amine, hydrogen sulfide, and thiol.SOLUTION: A deodorant contains: at least one salt selected from the group consisting of gluconate, paraphenol sulfonate, and sulfate; ampholytic surfactant; and carboxylated O-substituted monohydroxylamine or chemically acceptable salt thereof.SELECTED DRAWING: Figure 1

Description

The present invention relates to deodorants.

Aldehydes such as acetaldehyde and formaldehyde are representative odorous substances in the living environment, and since they have extremely low odor thresholds, they cause unpleasant odors even at low concentrations. These aldehydes are known to be generated from synthetic resins, plywood, cigarette smoke, etc. indoors or in automobiles, and cause sick house syndrome and sick car syndrome. These aldehydes are also suspected to be carcinogenic, and there is a risk of harming health if people are exposed to them on a daily basis. Therefore, the Ministry of Health, Labor and Welfare has set indoor concentration guideline values of 0.03 ppm or less for acetaldehyde and 0.08 ppm or less for formaldehyde. Therefore, means for rapidly and continuously removing aldehydes are desired.

Since lower aldehydes such as acetaldehyde and formaldehyde have a low boiling point, their capture efficiency is low with inorganic porous materials such as silica gel and activated carbon, which are commonly used as deodorants. Therefore, a method of capturing aldehydes by chemically reacting deodorants such as hydrazine derivatives, amines, amino acids, or urea derivatives with aldehydes has been disclosed (see, for example, Patent Documents 1 to 3).

However, the methods described in these patent documents have problems such as insufficient trapping efficiency, the deodorant itself becoming an odor source, or even once trapping aldehydes, the aldehydes are re-released over time. was there. In addition, when the deodorant described in these patent documents is used in a house or a car for the purpose of preventing sick house syndrome or sick car syndrome, these places become hot in summer, etc., so the performance is lowered. was a problem.

Major odorous substances other than aldehydes in the living environment of humans include ammonia, amines, hydrogen sulfide, and thiols, and many reports have reported effective methods for trapping these odorous substances. On the other hand, as described above, there is much room for improvement in methods for capturing aldehydes, and a deodorant capable of efficiently capturing aldehydes, ammonia, amines, hydrogen sulfide, and thiols is desired.

JP-A-4-358536 JP-A-11-4879 Japanese Patent Application Laid-Open No. 2012-120708

The present invention has been made in view of the above background art, and an object of the present invention is to provide a deodorant capable of efficiently capturing aldehydes, ammonia, amines, hydrogen sulfide, and thiols. .

The present inventors have made intensive studies to solve the above problems, and found that one or more salts selected from the group consisting of specific gluconates, paraphenolsulfonates, and sulfates, amphoteric surfactant and a carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof efficiently trap aldehydes, ammonia, amines, hydrogen sulfide, and thiols. , have completed the present invention.

That is, the present invention has the following gists.

[1] One or more salts selected from the group consisting of gluconates, paraphenolsulfonates, and sulfates, an amphoteric surfactant, and a carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable A deodorant characterized by containing a salt.

[2] The deodorant according to [1], wherein the one or more salts selected from the group consisting of gluconates, paraphenolsulfonates, and sulfates are zinc salts.

[3] The deodorant according to [1] or [2], wherein the amphoteric surfactant is a compound represented by the following general formula (1) or (2).

(In the formula, R ¹ represents an alkyl group having 8 to 18 carbon atoms.)

(In the formula, R ² represents an alkyl group having 8 to 18 carbon atoms.)
[4] The deodorant according to [1] to [3], wherein the carboxy group-containing O-substituted monohydroxylamine is a compound represented by the following general formula (3).

(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. n represents an integer of 1 to 6. Plural R may be the same or different.)
[5] In general formula (3), R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a benzyl group, or a phenyl group. The deodorant according to [4], characterized in that it is either

[6] A method for deodorizing, which comprises using the deodorant according to [1] to [5] to remove odorous substances.

The deodorant of the present invention efficiently captures aldehydes, ammonia, amines, hydrogen sulfide, and thiols, which are major odorous substances in human living environments. As a result, odors in the human living environment can be reduced, and the living environment can be improved.

FIG. 4 is a diagram showing reduction rates of acetaldehyde, hydrogen sulfide, and ammonia in Examples and Comparative Examples.

The deodorant of the present invention comprises one or more salts selected from the group consisting of gluconates, paraphenolsulfonates, and sulfates, an amphoteric surfactant, and a carboxy group-containing O-substituted monohydroxylamine or its It is characterized by containing a chemically acceptable salt.

The gluconate is not particularly limited, but cupric gluconate, zinc gluconate, calcium gluconate, ferrous gluconate, lead gluconate, aluminum gluconate, manganese gluconate and the like are exemplified as preferred compounds.

Paraphenolsulfonates are not particularly limited, but are cupric paraphenolsulfonate, zinc paraphenolsulfonate, calcium paraphenolsulfonate, ferrous paraphenolsulfonate, lead paraphenolsulfonate, and paraphenolsulfonic acid. Examples of preferred compounds include aluminum and manganese paraphenolsulfonate.

Sulfates are not particularly limited, but preferred compounds include copper sulfate, zinc sulfate, calcium sulfate, ferrous sulfate, ferric sulfate, lead sulfate, and aluminum sulfate.

The amphoteric surfactant is not particularly limited as long as it is a so-called amphoteric surfactant having both anionic and cationic hydrophilic groups in one molecule. Includes betaine types and natural products such as lecithin.

Examples of amino acid types include glycine type and alanine type such as R ³ —NHCH ₂ COO— and R ³ —NHCH ₂ CH ₂ COO— (where R ³ represents an alkyl group having 8 to 18 carbon atoms in these general formulas). ) are exemplified. Examples of the betaine type include betaine represented by the following general formula (4) and imidazolinium betaine.

(where R ⁴ is an alkyl group having 8 to 18 carbon atoms or R ⁷ CONH(CH ₂ ) ₃ group in which R ⁷ is an alkyl group having 8 to 18 carbon atoms; R ⁵ and R ⁶ are a methyl group and an ethyl group; , a hydroxyl group, an amino group, or a formyl group, and n represents an integer of 1 or 2.)
In the present invention, among the above amphoteric surfactants, it is preferable to use one represented by the above general formula (1) or (2) as the betaine type.

Any of the above amphoteric surfactants can be used alone, or two or more of them can be used in combination. A cationic surfactant, an anionic surfactant or a nonionic surfactant can also be used in combination.

In the carboxy group-containing O-substituted monohydroxylamine represented by the general formula (3), R is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 7 to 15 carbon atoms. represents an arylalkyl group. n represents an integer of 1 to 6; Plural Rs may be the same or different.

The alkyl group having 1 to 18 carbon atoms may be a linear, branched or cyclic alkyl group, and is not particularly limited, but examples include methyl group, ethyl group, propyl group, butyl group, pentyl group and hexyl. group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group (cetyl group), heptadecyl group, octadecyl group (stearyl group), oleyl group, elaidyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 3-methylbutyl group, 2,2-dimethylpropyl group, 1,1-dimethylpropyl group, 2-ethylhexyl group, cyclopropyl group, cyclobutyl group , cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group and the like.

Examples of the aryl group having 6 to 14 carbon atoms include, but are not limited to, phenyl group, naphthyl group, anthryl group, tolyl group, xylyl group, cumenyl group, vinylphenyl group, biphenylyl group and phenanthryl group.

The arylalkyl group having 7 to 15 carbon atoms is not particularly limited, but examples include benzyl group, phenylethyl group, phenylpropyl group, naphthylmethyl group, anthrylmethyl group, tolylmethyl group, xylylmethyl group, cumenylmethyl group, vinylphenyl A methyl group, a biphenylylmethyl group, a phenanthrylmethyl group and the like can be mentioned.

Among these, in general formula (3), R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a benzyl group, and a phenyl group. Carboxy group-containing O-substituted monohydroxylamines are particularly preferred.

Some or all of the hydroxylamino groups of the carboxyl group-containing O-substituted monohydroxylamine may be chemically acceptable salts with inorganic or organic acids. The type of salt is not particularly limited, but examples include hydrochloride, hydrobromide, perchlorate, silicate, tetrafluoroborate, hexafluorophosphate, sulfate, nitrate, and phosphoric acid. inorganic acid salts such as salts, and organic acid salts such as acetates, citrates, fumarates, maleates, trifluoromethanesulfonates, trifluoroacetates, benzoates, and tosylates; Inorganic acid salts are preferred because they are inexpensive, and hydrochlorides are more preferred.

In addition, the carboxy group of the above carboxy group-containing O-substituted monohydroxylamine may form an intramolecular salt with an intramolecular hydroxylamino group. Further, a part of the carboxyl group may be a carboxylate, but since the deodorant of the present invention becomes alkaline, the scavenging effect is reduced, so the carboxylate is formed within a pH range of 7 or less. is preferred. The type of carboxylate is not particularly limited, but examples thereof include alkali metal salts such as lithium salts, sodium salts, potassium salts and cesium salts, and ammonium salts.

The deodorant of the present invention can be used in any form depending on the purpose and application. For example, it can be dissolved in any solvent and used as a liquid deodorant (hereinafter referred to as the "liquid deodorant of the present invention"), or the liquid deodorant can be supported on any carrier to form a solid deodorant. agent (hereinafter referred to as "liquid deodorant of the present invention").

One or more salts selected from the group consisting of gluconate, paraphenolsulfonate, and sulfate, an amphoteric surfactant, and a carboxy group-containing O to the solvent when preparing the liquid deodorant of the present invention The dissolution amount of the substituted monohydroxylamine or its chemically acceptable salt can be arbitrarily adjusted according to the purpose and is not particularly limited, but each preferably ranges from 0.01 to 30% by weight. , more preferably in the range of 0.1 to 10% by weight.

The solvent used for preparing the liquid deodorant of the present invention is not particularly limited, but examples thereof include water, methanol, ethanol, toluene and the like. Among these, water, which is inexpensive and harmless to the human body, is particularly preferred.

As the carrier for supporting the liquid deodorant when preparing the solid deodorant of the present invention, any carrier that is insoluble in water can be used without particular limitation. Examples of polymer carriers include styrene polymers such as polystyrene and crosslinked polystyrene; polyolefins such as polyethylene and polypropylene; poly(halogenated olefins) such as polyvinyl chloride and polytetrafluoroethylene; nitrile polymers such as polyacrylonitrile; Examples include (meth)acrylic polymers such as methyl methacrylate and polyethyl acrylate, and high molecular weight polysaccharides such as cellulose, agarose, and dextran. Examples of inorganic carriers include activated carbon, silica gel, diatomaceous earth, hydroxyapatite, alumina, and titanium oxide. , magnesia, and polysiloxane.

Here, crosslinked polystyrene includes monovinyl aromatic compounds such as styrene, vinyltoluene, vinylxylene, and vinylnaphthalene, and divinylbenzene, divinyltoluene, divinylxylene, divinylnaphthalene, trivinylbenzene, bisvinyldiphenyl, bisvinylphenylethane, and the like. These copolymers may be copolymerized with methacrylic acid esters such as glycerol methacrylate and ethylene glycol dimethacrylate.

The shape of the carrier used in the preparation of the solid deodorant of the present invention is not particularly limited. Hollow fibers, membranous (e.g., flat membranes, etc.) shapes generally used as separation substrates can be used, and among these, spherical, membranous, granular, granular, or fibrous shapes can be used. is preferred. Spherical, granular, or granular carriers are particularly preferably used because the volume used can be freely set when used in a column method or a batch method.

As for the particle size of the spherical, granular, or granular carrier, those having an average particle size in the range of 1 μm to 10 mm are generally usable, and the range of 2 μm to 1 mm is preferable.

The carrier used in preparing the solid deodorant of the present invention may be porous or non-porous. As the average pore diameter of the porous carrier, one having an average pore diameter of 1 nm to 1 μm can be used, and a range of 1 nm to 300 nm is preferable from the viewpoint of deodorizing speed.

A method for preparing the solid deodorant of the present invention is not particularly limited, but an example thereof includes a method of immobilizing the liquid deodorant of the present invention by physically adsorbing it onto a carrier.

The method of immobilizing the liquid deodorant of the present invention by physically adsorbing it is not particularly limited, but for example, the liquid deodorant of the present invention is added with the above-described carrier, gluconate, paraphenolsulfonic acid, The carrier is impregnated with one or more salts selected from the group consisting of salts and sulfates, an amphoteric surfactant, and a carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof, and then A method of distilling off the solvent can be mentioned.

One or more salts selected from the group consisting of gluconate, paraphenolsulfonate, and sulfate, amphoteric surfactant, and carboxy group-containing O-substituted monohydroxylamine or chemically acceptable The impregnated amount of the salt can be arbitrarily adjusted according to the purpose, and is not particularly limited, but is preferably in the range of 0.01 to 30% by weight, and more preferably in the range of 0.1 to 10% by weight. preferable.

The present invention will be specifically described below, but the present invention should not be construed as being limited to these examples.

Examples 1-3 (Preparation of solid deodorants 1-3)
Example 1 uses zinc gluconate (manufactured by Fujisawa Pharmaceutical Co., Ltd.), Example 2 uses zinc sulfate (manufactured by Wako Pure Chemical Industries, Ltd.), and Example 3 uses zinc paraphenolsulfonate (manufactured by Matsumoto Trading Co., Ltd.). lauryl dimethylamino acetate betaine (manufactured by Sanyo Chemical Industries, Ltd. Levon LD-36, solid content equivalent of 40% by weight solution), aminooxyacetic acid, and ion-exchanged water as shown in Table 1. After that, the solution was dissolved with stirring under heating to prepare an amino acid-containing deodorant solution. 1 mL of these amino acid-containing deodorant solutions were evenly dropped onto a 10 cm×10 cm cloth (cellulosic bleach) and dried at 60° C. for 10 hours to obtain solid deodorants 1-3.

Examples 4-6 (Evaluation of Acetaldehyde Scavenging Performance)
In a 10 L Tedlar bag, Example 4 solid deodorant 1, Example 5 solid deodorant 2, and Example 6 solid deodorant 3 were sealed together with acetaldehyde gas (15 ppm). After standing at room temperature for 4 hours, the acetaldehyde concentration in the Tedlar bag was measured with a detector tube (Detector tube No. 92L manufactured by Gastech). The results of the measurements are listed in Table 2 and FIG.

Examples 7-9 (Evaluation of hydrogen sulfide trapping performance)
In a 10 L Tedlar bag, Example 7 contains solid deodorant 1, Example 8 contains solid deodorant 2, and Example 9 contains solid deodorant 3, together with hydrogen sulfide gas (20 ppm). After standing at room temperature for 4 hours, the concentration of hydrogen sulfide in the Tedlar bag was measured with a detector tube (Detector tube No. 4LL manufactured by Gastech). The results of the measurements are listed in Table 2 and FIG.

Examples 10-12 (Evaluation of ammonia trapping performance)
In a 10 L Tedlar bag, Example 10 solid deodorant 1, Example 11 solid deodorant 2, and Example 12 solid deodorant 3 were sealed together with ammonia gas (50 ppm). After standing at room temperature for 4 hours, the concentration of ammonia in the Tedlar bag was measured with a detector tube (detector tube No. 3L manufactured by Gastech). The results of the measurements are listed in Table 2 and FIG.

Synthesis Examples 1-3 (Preparation of deodorant cloths 1-3)
Synthesis Example 1 uses the zinc gluconate, Synthesis Example 2 uses the zinc sulfate, and Synthesis Example 3 uses the zinc paraphenolsulfonate. After blending as described above, the ingredients were dissolved while stirring under heating to prepare a deodorant solution. 1 mL of these deodorizing chemical solutions were evenly dropped onto a 10 cm×10 cm cloth (cellulosic bleach) and dried at 60° C. for 10 hours to obtain deodorizing cloths 1 to 3.

Comparative Examples 1-3 (Evaluation of Acetaldehyde Scavenging Performance)
In a 10 L Tedlar bag, the deodorant cloth 1 of Comparative Example 1, the deodorant cloth 2 of Comparative Example 2, and the deodorant cloth 3 of Comparative Example 3 were sealed together with acetaldehyde gas (15 ppm), and kept at room temperature for 4 hours. After standing still, the acetaldehyde concentration in the Tedlar bag was measured with a detector tube (Detector tube No. 92L manufactured by Gastech). The results of the measurements are listed in Table 2 and FIG.

Comparative Examples 4-6 (Evaluation of hydrogen sulfide trapping performance)
In a 10 L Tedlar bag, the deodorant cloth 1 in Comparative Example 4, the deodorant cloth 2 in Comparative Example 5, and the deodorant cloth 3 in Comparative Example 6 were sealed together with hydrogen sulfide gas (20 ppm). After standing for a period of time, the concentration of hydrogen sulfide in the Tedlar bag was measured with a detector tube (detector tube No. 4LL manufactured by Gastech). The results of the measurements are listed in Table 2 and FIG.

Comparative Examples 7-9 (Evaluation of ammonia trapping performance)
In a 10 L Tedlar bag, the deodorant cloth 1 of Comparative Example 7, the deodorant cloth 2 of Comparative Example 8, and the deodorant cloth 3 of Comparative Example 9 were sealed together with ammonia gas (50 ppm), and kept at room temperature for 4 hours. After standing still, the concentration of ammonia in the Tedlar bag was measured with a detector tube (Detector tube No. 3L manufactured by Gastech). The results of the measurements are listed in Table 2 and FIG.

The deodorizing cloths 1 to 3 shown in Comparative Examples 1 to 9 can reduce the concentration of hydrogen sulfide and ammonia, but cannot reduce the concentration of acetaldehyde. In contrast, the solid deodorants 1 to 3 shown in Examples 4 to 12 can simultaneously and efficiently remove acetaldehyde in addition to hydrogen sulfide and ammonia.

Claims (6)

One or more salts selected from the group consisting of gluconate, paraphenolsulfonate, and sulfate, an amphoteric surfactant, and a carboxy group-containing O-substituted monohydroxylamine or a chemically acceptable salt thereof A deodorant comprising: 2. The deodorant according to claim 1, wherein the one or more salts selected from the group consisting of gluconates, paraphenolsulfonates, and sulfates are zinc salts. The deodorant according to claim 1 or 2, wherein the amphoteric surfactant is a compound represented by the following general formula (1) or (2).

(In the formula, R ¹ represents an alkyl group having 8 to 18 carbon atoms.)

(In the formula, R ² represents an alkyl group having 8 to 18 carbon atoms.) The deodorant according to any one of claims 1 to 3, wherein the carboxy group-containing O-substituted monohydroxylamine is a compound represented by the following general formula (3).

(In the formula, R represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an arylalkyl group having 7 to 15 carbon atoms. n represents an integer of 1 to 6. Plural R may be the same or different.) In general formula (3), R is a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a benzyl group, or a phenyl group; The deodorant according to claim 4, characterized in that there is A method of deodorizing, comprising removing odorous substances using the deodorant according to any one of claims 1 to 5.

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