JP2016094352A - Pol soluble metallic compound and oil soluble deodorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a technology for oil dissolving a hydrazide compound with low oil solubility, to provide a novel hydrazide compound with oil solubility and to provide an oil soluble deodorant soluble in an organic solvent with low polarity, maintaining high deodorant effects on a sulfur compound, a nitrogen compound, an organic acid or the like and excellent in deodorant effects on bad odor derived from aldehydes.SOLUTION: There are provided an oil soluble metal hydrazide compound obtained by reacting a hydrazide compound (A) with an oil soluble metallic compound obtained by reacting zinc oxide and an N-acyl sarcosine compound in an organic solvent or without solvent at mass ratio of 1:5 to 1:100 (B), and a deodorant containing the oil soluble metallic hydrazide compound.SELECTED DRAWING: None

Description

  The present invention relates to an oil-soluble metal compound and a deodorant containing the oil-soluble metal compound. Specifically, the oil-soluble metal compound containing zinc as a metal and having oil solubility, and the oil-soluble metal compound are used. It relates to deodorants.

It is known that a hydrazide compound has a deodorizing effect, particularly effective for deodorizing aldehydes.
Patent Document 1 describes a water-soluble deodorant containing a hydrazide compound and a metal compound as active ingredients, and an aqueous solution of the deodorant is sprayed onto an object using a nebulizer.
Specifically, Patent Document 1 discloses a water-soluble aldehyde deodorant composition comprising a hydrazide compound and a metal halide, nitrate, sulfate, sulfite or hydroxide as active ingredients. Yes.
However, in addition to not being disclosed about the metal oxide, what was obtained was not oil-soluble but water-soluble, and its usage and application were limited.

Patent Document 2 describes that a metal complex of a hydrazide compound has a deodorizing effect. The “metal complex of a hydrazide compound” is dissolved in water, and the aqueous solution is supported on an inorganic porous material. It is described that
Specifically, Patent Document 2 discloses that a complex of a metal and a hydrazide compound is obtained by dissolving and stirring a metal chloride and a hydrazide compound in a solvent (for example, an alcohol / water solution), and adding it to a deodorizer. It can be used as
However, the metal salt is a chloride, and only examples of synthesis in an aqueous solvent are described, and what is obtained is not oil-soluble but water-soluble, and its usage and application are limited. It was a thing.

Patent Document 3 discloses an oil-soluble metal complex using a hydrazide compound, and discloses a technique for oil-solubilizing a hydrazide compound having no oil solubility or poor oil solubility.
Specifically, Patent Document 3 includes a hydrazide compound, a metal salt of a phosphate ester, a metal salt of a thiophosphate ester, a metal salt of a dithiophosphate ester, a metal salt of a phosphonate ester, a metal salt of a dithiophosphonic acid, An oil-soluble metal complex obtained by mixing a metal salt of carbamic acid, a metal salt of thiocarbamic acid, a metal salt of dithiocarbamic acid or a metal salt of naphthenic acid is disclosed.
However, in addition to not being disclosed about metal oxides, what is obtained is a lubricant additive rather than a deodorant.

On the other hand, Patent Document 4 describes an oil-soluble deodorant that can be dissolved in an isoparaffin solvent, and an oil-soluble metal salt is disclosed as the oil-soluble deodorant.
Specifically, Patent Document 4 discloses an oil-soluble deodorant obtained by reacting zinc oxide and N-acyl sarcosines.
However, although the deodorizer described in Patent Document 4 has a high deodorizing effect for hydrogen sulfide, ammonia, and the like, the deodorizing effect for aldehydes is insufficient.

In recent years, the use of deodorants is expanding, and there is a demand for deodorants that can absorb odor-causing substances of all systems (effective). However, as described above, Since it is water-soluble rather than oil-soluble, its use and usage are limited, and it is not effective for specific odor-causing substances.
While the use of deodorants is expanding, and the demand for deodorants is increasing, such known techniques are insufficient and there is room for further improvement.

JP 2001-149456 A JP 2007-054328 A JP 2005-139162 A JP 2014-094047 A

The present invention has been made in view of the above-described background art, and its problem is to develop a technique for oil-solubilizing a hydrazide compound that is generally not oil-soluble or low in oil-solubility, and provides a novel oil-soluble hydrazide compound. It is to provide.
It is also soluble in organic solvents with low polarity and maintains a high deodorizing effect for sulfur compounds, nitrogen compounds, organic acids, etc., and is also excellent for deodorizing effects caused by aldehydes. It is to provide an oil-soluble deodorant.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have mixed and reacted a hydrazide compound with an oil-soluble metal compound obtained by reacting zinc oxide and an N-acyl sarcosine compound. The present inventors have found that oil solubility is imparted to a hydrazide compound, and the hydrazide compound can be soluble in a low polarity organic solvent.
The obtained oil-soluble hydrazide compound has an excellent deodorizing effect, and in particular, has been found to have a high deodorizing effect even with respect to aldehydes, and the present invention has been completed.

  That is, the present invention provides an hydrazide to an oil-soluble metal compound (B) obtained by reacting zinc oxide and an N-acyl sarcosine compound in an organic solvent or without a solvent in a mass ratio of 1: 5 to 1: 100. The present invention provides an oil-soluble metal hydrazide compound obtained by reacting a compound (A).

  Moreover, this invention provides the deodorizer characterized by containing said oil-soluble metal hydrazide compound.

  Moreover, this invention provides the aldehyde odor deodorizer characterized by containing said deodorizer.

  The present invention also provides an oil-soluble metal compound (B) by reacting zinc oxide and an N-acyl sarcosine compound in an organic solvent or without solvent at a mass ratio of 1: 5 to 1: 100, The present invention provides a method for producing an oil-soluble metal hydrazide compound comprising a step of reacting an oil-soluble metal compound (B) with a hydrazide compound (A) at 20 ° C. or higher and 150 ° C. or lower in a solvent.

  According to the present invention, the above problems and the above-mentioned problems can be solved and a novel oil-soluble metal hydrazide compound can be provided.

Hydrazide compounds are a group of compounds that are used in many fields, including deodorants, but are generally highly polar and have no oil solubility or at least low oil solubility (into water, which is a polar solvent). Some of them are soluble), and few of them are soluble in solvents with low polarity such as isoparaffinic solvents, paraffinic solvents, and aromatic hydrocarbon solvents.
According to the present invention, the functional group of the hydrazide compound (chemical structure that determines physical properties) is hardly impaired, that is, it can be made oil-soluble while maintaining the physical properties of the hydrazide compound to some extent. Can be greatly expanded.

Conventionally, in general, it has been difficult to make oil-soluble while maintaining the physical properties of the hydrazide compound.
According to the present invention, “an oil-soluble metal compound (B) obtained by reacting zinc oxide and an N-acyl sarcosine compound” is added with a solvent, if necessary, and a hydrazide compound is added to the “isoparaffin”. It was possible to obtain a novel oil-soluble metal hydrazide compound that can be dissolved in a solvent having extremely low polarity such as a system solvent.

Moreover, according to this invention, the oil-soluble deodorizer which melt | dissolves in a low polarity solvent as mentioned above and has the outstanding deodorizing effect can be provided.
The hydrazide compound is known to have a deodorizing effect on aldehydes. However, according to the present invention, not only an oil-soluble deodorant having an excellent deodorizing effect is provided, but in particular an aldehyde It is possible to provide an oil-soluble deodorant that is extremely excellent in the deodorizing effect on the product.

  Aldehydes, for example, emit bad odors such as nonenal, octanal, hexanal and the like, and are mostly water-insoluble aldehydes. The deodorizer of the present invention is particularly effective for deodorizing odors caused by these oil-soluble aldehydes. Can be demonstrated.

The oil-soluble metal hydrazide compound of the present invention is obtained by reacting a hydrazide compound (A) with an “oil-soluble metal compound (B) obtained by reacting zinc oxide and an N-acyl sarcosine compound”. However, such an oil-soluble metal compound (B), which can be said to be an intermediate, has a high deodorizing effect on sulfur compounds, nitrogen compounds, organic acids and the like.
If the oil-soluble metal hydrazide compound of the present invention is used as a deodorant, it is possible to further add a deodorizing effect to aldehydes while maintaining the deodorizing effect of the oil-soluble metal compound (B).

  Therefore, according to the present invention, sulfur compounds such as hydrogen sulfide and alkyl mercaptans; nitrogen compounds such as ammonia and amines; organic acids such as lower fatty acids and carboxylic acids (for example, acetic acid, propionic acid, isovaleric acid, butyric acid, etc.) ); And the like, and at the same time, to provide an oil-soluble deodorant having an excellent deodorizing effect against bad odor caused by aldehydes such as formaldehyde, acetaldehyde and benzaldehyde. Can do.

  Moreover, if the oil-soluble metal hydrazide compound of the present invention is dissolved in a diluent, an aerosol deodorant or an aldehyde odor deodorant having an excellent deodorizing effect can be provided.

  Hereinafter, the present invention will be described, but the present invention is not limited to the following specific embodiments, and can be arbitrarily modified within the scope of the technical idea.

<Oil-soluble metal hydrazide compound>
The oil-soluble metal hydrazide compound of the present invention is “an oil-soluble metal compound obtained by reacting zinc oxide and an N-acyl sarcosine compound in an organic solvent or without solvent in a mass ratio of 1: 5 to 1: 100 ( B) "is obtained by reacting the hydrazide compound (A).

In the present invention, “reaction” includes all those whose physical properties change thereby, and includes not only a covalent bond but also a coordination bond, and also includes a weaker interaction such as coordination and orientation.
The oil-soluble metal compound (B) in the present invention and the oil-soluble metal hydrazide compound of the present invention have a certain chemical structure (a chemical structure in a broad sense including coordination and orientation in a solvent). Furthermore, although the oil-soluble metal hydrazide compound of the present invention has a novel and constant chemical structure, the chemical structure is not clear or cannot be clearly expressed by a simple chemical formula. These “things” are defined by the manufacturing method.

  In the present invention, “oil-soluble” means a property of dissolving 5 mass% or more at 20 ° C. in IP solvent or dipropylene glycol monomethyl ether (hereinafter sometimes abbreviated as “DPGMME”) which is an isoparaffin solvent. Say that.

<< Hydrazide Compound (A) >>
The “hydrazide compound (A)” used for obtaining the oil-soluble metal hydrazide compound of the present invention and subject to oil solubilization is not particularly limited, and organic acid hydrazides such as carboxylic acid hydrazide and sulfonic acid hydrazide may be used. Can be mentioned. Among these, carboxylic acid hydrazide is preferable from the viewpoint of oil solubility, deodorizing effect, safety, cost, and the like.

The three groups (atoms) bonded to the two nitrogen atoms constituting one hydrazide group in the “hydrazide compound (A)” are not particularly limited, but are hydrogen atoms; 1 to 20 carbon atoms An alkyl group or an alkenyl group that may have a branch (particularly preferably 1 to 18); an aryl group such as a phenyl group;
Among them, one of the three is preferably a hydrogen atom, two of the three are more preferably a hydrogen atom, and particularly preferably all three are hydrogen atoms.

  Further, the number of hydrazide groups in the “hydrazide compound (A)” is not particularly limited, and a monohydrazide compound having one hydrazide group in the molecule, a dihydrazide compound having two hydrazide groups in the molecule, Any of the polyhydrazide compounds having 3 or more hydrazide groups is preferred.

In the case where the “hydrazide compound (A)” is a monohydrazide compound, there is no particular limitation, but the number of carbon atoms is 2 to 22 (more preferably 4 carbon atoms) including carbon of carbonyl (—C (═O) —). A monocarboxylic acid hydrazide having a structure obtained by reacting hydrazine with a monocarboxylic acid having ˜20, particularly preferably 6 to 18 carbon atoms, is preferable from the viewpoint of deodorizing effect, safety, cost and the like.
If the lower limit of the carbon number is more than the above, the final oil-soluble metal hydrazide compound is easily made oil-soluble. On the other hand, if the upper limit of the carbon number is the above or lower, the deodorizing effect is excellent and the synthesis is easy.

  Specific examples of the monohydrazide compound include oleic acid hydrazide, propionic acid hydrazide, naphthoic acid hydrazide, salicylic acid hydrazide, acetohydrazide, benzoic acid hydrazide and the like.

In the case where the “hydrazide compound (A)” is a dihydrazide compound, there is no particular limitation, but the number of carbons is 2 to 24 (more preferably 2 to 18 carbons, particularly preferably 2 carbons) including two carbonyl carbons. Dicarboxylic acid hydrazide having a structure obtained by reacting two hydrazines with a dicarboxylic acid having 2 to 10 carbon atoms, more preferably 3 to 6 carbon atoms, from the viewpoint of deodorizing effect and production. preferable.
If the lower limit of the carbon number is more than the above, the final oil-soluble metal hydrazide compound is easily made oil-soluble. On the other hand, if the upper limit of the carbon number is the above or lower, the deodorizing effect is excellent and the synthesis is easy.

  Specific examples of the dihydrazide compound include oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide, dodecanoic acid dihydrazide, maleic acid dihydrazide, tartaric acid dihydrazide, isophthalic acid dihydrazide, Examples include acid dihydrazide.

  When the “hydrazide compound (A)” is a polyhydrazide compound, the polyhydrazide compound is preferably poly (meth) acrylic acid hydrazide.

Among the above, a carboxylic acid hydrazide compound is preferable, and among these, a carboxylic acid dihydrazide compound is particularly preferable.
Specifically, for example, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide and the like are particularly preferable from the above reasons, and succinic acid dihydrazide, adipic acid dihydrazide and the like are more preferable.

The hydrazide compound (A) may be used alone or in combination of two or more.
Two or more hydrazide compounds (A) may be reacted simultaneously with one kind of oil-soluble metal compound (B) to obtain an oil-soluble metal hydrazide compound, or two or more kinds of hydrazide compounds (A) may be separately obtained. You may make them react, after obtaining 2 or more types of oil-soluble metal hydrazide compounds, you may mix them.

<< Reaction / mixing (1) of oil-soluble metal compound (B) and hydrazide compound (A) >>
The blending ratio of the oil-soluble metal compound (B) and the hydrazide compound (A) is not particularly limited as long as the hydrazide compound (A) reacts to become oil-soluble, but the oil-soluble metal compound (B) is 100 parts by mass. On the other hand, the hydrazide compound (A) is preferably 0.5 to 20 parts by mass, more preferably 1 to 15 parts by mass, and particularly preferably 1.5 to 10 parts by mass. The mass part of the oil-soluble metal compound (B) does not include the amount of the organic solvent when the oil-soluble metal compound (B) is synthesized in the organic solvent.

  If the amount of the hydrazide compound (A) with respect to the oil-soluble metal compound (B) is too small, the oil-soluble metal compound (B) is excessively wasted, and the deodorizing effect on aldehydes may not be sufficient. On the other hand, if the amount of the hydrazide compound (A) is too large, the hydrazide compound (A) to be oil-soluble may not be all oil-soluble and the reaction solution may not be transparent (uniform).

The oil-soluble metal hydrazide compound of the present invention is obtained by reacting the oil-soluble metal compound (B) with the hydrazide compound (A). At that time, only the hydrazide compound is converted into the oil-soluble metal compound (B). The reaction may be carried out by mixing, but it is also preferred to use the hydrazide compound diluted in a solvent or mixed in a solvent.
The solvent that can be used for dilution or mixing is not particularly limited as long as it does not cause a chemical reaction with the hydrazide compound, but is an isoparaffin solvent, normal paraffin solvent, alcohol solvent, glycol solvent, glycol monoether solvent. A nonpolar hydrocarbon solvent such as an isoparaffin solvent or a normal paraffin solvent having a boiling point of 70 ° C. or more, particularly preferably a boiling point of 90 ° C. or more is desirable.

  The amount of the solvent used for the reaction between the oil-soluble metal compound (B) and the hydrazide compound (A) is not particularly limited, but is 5 to 300 parts by mass with respect to 100 parts by mass of the oil-soluble metal compound (B). Preferably, 10-200 mass parts is more preferable, and 20-100 mass parts is especially preferable. When the oil-soluble metal compound (B) is synthesized in an organic solvent, the amount of the solvent includes the amount of the organic solvent at that time.

  Since the hydrazide compound (A) is often not dissolved in a nonpolar solvent, when the nonpolar solvent is used, the hydrazide compound (A) is “oil-soluble metal compound (B) and the nonpolar solvent at the initial stage of the reaction”. In the latter stage of the reaction, the hydrazide compound (A) reacts with the oil-soluble metal compound (B) to become oil-soluble. It becomes soluble in nonpolar solvents. Therefore, with this, it was proved that the reaction occurred, and it was confirmed that a novel oil-soluble metal hydrazide compound was formed.

When the oil-soluble metal compound (B) is obtained by reacting zinc oxide and an N-acyl sarcosine compound in an organic solvent, the organic solvent will be described later, but the hydrazide compound (A) In the reaction, a new solvent may not be added, or the above-mentioned solvent may be newly added.
When the organic solvent in preparing the oil-soluble metal compound (B) is a nonpolar solvent as described above, the above-described phenomenon (the hydrazide compound (A) is not dissolved at the initial stage of the reaction, but at a later stage of the reaction) The same phenomenon occurs when the oil reacts with the oil-soluble metal compound (B) to become oil-soluble and dissolve. Similarly, the reaction of (A) and (B) was proved and it was confirmed that a novel oil-soluble metal hydrazide compound was produced.

  The reaction temperature between the oil-soluble metal compound (B) and the hydrazide compound (A) is not particularly limited, but is preferably 20 ° C or higher and 150 ° C or lower, more preferably 50 ° C or higher and 120 ° C or lower, and 70 ° C or higher and 100 ° C or lower. Is particularly preferred.

  The reaction time or mixing time of the oil-soluble metal compound (B) and the hydrazide compound (A) is not particularly limited, but is preferably 10 minutes to 12 hours, more preferably 20 minutes to 5 hours, and more preferably 30 minutes to 2 hours. Is particularly preferred.

<Oil-soluble metal compound (B)>
The oil-soluble metal compound (B) in the present invention is obtained by reacting zinc oxide and an N-acyl sarcosine compound in an organic solvent or without a solvent in a mass ratio of 1: 5 to 1: 100.

<< Zinc oxide >>
Zinc oxide is a white powder and is insoluble in water and organic solvents such as nonpolar solvents at 20 ° C.
However, the oil-soluble metal compound (B) obtained by reacting the N-acyl sarcosine compound with [zinc oxide] / [N-acyl sarcosine compound] = 1/5 to 1/100 (mass ratio) is paraffinic. It dissolves at 20 ° C. in an isoparaffin solvent such as an IP solvent described later; an alcohol solvent such as ethanol; and a glycol monoalkyl ether solvent such as DPGMME.

<< Solubility >>
The solubility at 20 ° C. when the concentration of the oil-soluble metal compound (B) is 0.2 mass% and 5 mass% is as follows.
Zinc oxide alone is insoluble in any of the following solvents.

0.2% by weight Concentration 5% by weight Concentrated water Insoluble Undissolved ethanol Stirring is not clear in 5 minutes, but dissolves is slightly turbid in 5 minutes, but dissolves DPGMME Completely dissolves in less than 5 minutes Completely dissolves in less than 5 minutes Complete dissolution in less than 5 minutes Complete dissolution in less than 5 minutes IP solvent Complete dissolution in less than 5 minutes Complete dissolution in less than 5 minutes

  This indicates that when zinc oxide and an N-acyl sarcosine compound are reacted in an organic solvent or without a solvent in a mass ratio of 1: 5 to 1: 100, the oil-soluble metal compound (B) exhibiting the above-described solubility is obtained. It shows that it is made.

<< N-acyl sarcosine compound >>
The N-acyl sarcosine compound used in the present invention is not particularly limited with respect to the acyl group, but is preferably an acyl group having 8 or more and 24 or less carbon atoms including the carbon number of carbonyl. 22 or less are more preferable, 12 or more and 20 or less are particularly preferable, and 12 or more and 18 or less are more preferable.
If the carbon number of the acyl group of the N-acyl sarcosine compound is too small, the metal compound obtained by reacting zinc oxide with the N-acyl sarcosine compound may not be oil-soluble, whereas the N-acyl sarcosine compound If the acyl group has too many carbon atoms, the reactivity may be low.

The acyl group of the N-acyl sarcosine compound used in the present invention may have a carbon-carbon double bond, and may be linear or branched.
An N-acyl sarcosine compound having an “acyl group constituting a medium chain fatty acid or a long chain fatty acid” can be preferably used. Moreover, the N-acyl sarcosine compound which has "the acyl group which comprises a saturated fatty acid or unsaturated fatty acid" can be used conveniently.

Specifically, for example, N-capryloyl sarcosine, N-lauroyl sarcosine, N-myristoyl sarcosine, N-palmitoyl sarcosine, N-stearoyl sarcosine, N-oleoyl sarcosine, N-linoloyl sarcosine, N-arachizoyl sarcosine N-behenoyl sarcosine, N-lignocelloyl sarcosine and the like.
Among these, lauroyl sarcosine, myristoyl sarcosine, palmitoyl sarcosine, and oleoyl sarcosine are particularly preferable for the reason described above in terms of the number of carbon atoms.

<< Formulation and reaction of zinc oxide and N-acyl sarcosine compound >>
As for the compounding ratio of zinc oxide and N-acyl sarcosine compound, 5 to 100 parts by mass of N-acyl sarcosine compound is essential to 1 part by mass of zinc oxide, preferably 5 to 40 parts by mass, and 5 to 20 parts by mass. Part is particularly preferred.
When the lower limit of the blending amount of the N-acyl sarcosine compound with respect to zinc oxide is not less than the above, zinc oxide does not remain in the solvent as an unreacted insoluble substance.
On the other hand, if the upper limit of the blending amount of the N-acyl sarcosine compound is the above or less, the amount of zinc oxide is sufficient, so there is room for the hydrazide compound (A) to react with the oil-soluble metal compound (B) obtained. is there.

The method for preparing the oil-soluble metal compound (B) obtained by reacting zinc oxide and an N-acyl sarcosine compound in an organic solvent or in the absence of a solvent may be in the absence of a solvent, but may be reacted in an organic solvent. It is preferable from the above point.
The organic solvent is not particularly limited as long as it does not cause a chemical reaction with either zinc oxide or N-acyl sarcosine compound, but is an isoparaffin solvent, normal paraffin solvent, alcohol solvent, glycol solvent, ether solvent. Solvents and glycol monoether solvents are preferred.
The organic solvent is more preferably a hydrocarbon solvent such as an isoparaffin solvent or a normal paraffin solvent having a boiling point of 70 ° C. or higher, particularly preferably a boiling point of 90 ° C. or higher; an alcohol solvent or ether having a boiling point of 100 ° C. or higher. A solvent or a glycol monoether solvent;

  The reaction temperature when preparing the oil-soluble metal compound (B) in an organic solvent is not particularly limited, but the reaction is preferably carried out at the boiling point or lower of the organic solvent used, and the reaction temperature is preferably 50 ° C. or higher and 150 ° C. or lower. 80 ° C. or higher and 130 ° C. or lower is particularly preferable, and 90 ° C. or higher and 120 ° C. or lower is more preferable.

  The reaction temperature when preparing the oil-soluble metal compound (B) in the absence of a solvent is not particularly limited, but the reaction is preferably performed at 90 ° C. or higher and 150 ° C. or lower, more preferably 100 ° C. or higher and 140 ° C. or lower, 110 degreeC or more and 130 degrees C or less are especially preferable.

  The reaction time is not particularly limited, but the reaction is preferably carried out for 1 to 5 hours, particularly preferably 2 to 4 hours, whether it is an organic solvent or no solvent.

<Reaction and mixing of oil-soluble metal compound (B) and hydrazide compound (A) (2)>
The oil-soluble metal hydrazide compound of the present invention is obtained by reacting zinc oxide and an N-acyl sarcosine compound in an organic solvent or without a solvent in a mass ratio of 1: 5 to 1: 100 to give an oil-soluble metal compound (B). It is preferable to produce the oil-soluble metal compound (B) by a production method having a step of reacting the hydrazide compound (A) at 20 ° C. or higher and 150 ° C. or lower in a solvent.

In the present invention, the reaction between the hydrazide compound (A) and the oil-soluble metal compound (B) has been described above.
(1) The component (A) is not diluted with a solvent, and is mixed with the component (B) that is not diluted with a solvent.
(2) The component (A) is not diluted with a solvent, but is mixed with the component (B) diluted with a solvent.
(3) The component (A) is diluted with a solvent and mixed with the component (B) that is not diluted with a solvent.
(4) The component (A) is diluted with a solvent and mixed with the component (B) diluted with a solvent.
Of these, the methods (1) and (2) are particularly preferably used.
In addition, since it may not melt | dissolve at the initial stage of reaction, "dilution" does not mean dissolving in a solvent here, but means mixing with a solvent.

<Deodorant>
Additives can be appropriately added to the oil-soluble metal hydrazide compound of the present invention as long as an organometallic reaction is not caused and deodorization is not inhibited.
Examples of the additive include, but are not limited to, essential oils such as anise seed and coriander; oxidation of sodium ascorbate, BHT (di-t-butylhydroxytoluene), eugenol, isoeugenol, thymol, and the like. Antibacterial agents and fungicides such as inhibitors; benzalkonium chloride, octanol, sodium dehydroacetate and potassium sorbate; fragrances; tannins; saponins; ultraviolet absorbers such as cinnamic acid esters and salicylic acid esters;

When the oil-soluble metal hydrazide compound of the present invention is used as a deodorant, use of the oil-soluble metal hydrazide compound after further dilution with a diluent is adapted to various usage modes such as an aerosol deodorant. Therefore, it is preferable.
Such a diluent is not particularly limited, and examples thereof include hydrocarbon solvents such as isoparaffin hydrocarbons, normal paraffin hydrocarbons, and terpene hydrocarbons; alcohol solvents such as methanol, ethanol, and isopropanol; ethylene Glycol solvents such as glycol, propylene glycol, 3-propanediol, 1,3-butanediol, 1,4-butanediol; glycol monoether solvents such as diethylene glycol monoethyl ether and dipropylene glycol monomethyl ether; It is done.

  That is, the deodorant of the present invention is one kind selected from the group consisting of the oil-soluble metal hydrazide compound, and an isoparaffin solvent, a normal paraffin solvent, an alcohol solvent, a glycol solvent, and a glycol monoether solvent. Or it is preferable that it contains 2 or more types of diluents.

The concentration of the oil-soluble metal hydrazide compound with respect to the diluent is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, and particularly preferably 0.1 to 5% by mass.
If the concentration of the oil-soluble metal hydrazide compound in the deodorant is too low, the deodorizing effect may be weakened. On the other hand, if the concentration of the oil-soluble metal hydrazide compound is too high, the deodorizing effect may be reduced. It is expensive but not economical.

  When the oil-soluble metal hydrazide compound of the present invention is used as a deodorant, the gas to be removed is removed by reaction with the oil-soluble metal hydrazide compound, which is a deodorant component, so that the once removed gas is re-released. There is a feature that there is almost no possibility of.

The form of the deodorant when the oil-soluble metal hydrazide compound of the present invention is used as a deodorant is not particularly limited, and examples include an aerosol deodorant, a granular deodorant, and a gel deodorant.
When taking the form of a granular deodorant, it is preferable to use the oil-soluble metal hydrazide compound of the present invention or a deodorant containing the compound supported on a carrier such as silica or activated carbon.

Moreover, since the oil-soluble metal hydrazide compound of the present invention has a high deodorizing effect on aldehydes, the deodorant of the present invention can be suitably used as an aldehyde odor deodorant.
In place of the oil-soluble metal hydrazide compound of the present invention, an oil-soluble metal compound (B) not having a high deodorizing effect on aldehydes and a hydrazide compound (A) having a high deodorizing effect on aldehydes are mixed at the time of use. The use form as a complex deodorant used together is not realistic. Accordingly, since the oil-soluble metal hydrazide compound of the present invention can take the form of a deodorant alone as an active ingredient, it is excellent in that it has a deodorizing effect with many kinds of malodorous gases including aldehydes. ing.

<Action and principle>
Although the action and effect of the oil-soluble metal hydrazide compound of the present invention showing an excellent deodorizing effect is not clear, the following may be considered. However, the present invention is not limited to the range of the following effects.

The oil-soluble metal compound (B) in the present invention is produced by reacting the N-acyl group (N—C (═O) —) of N-acyl sarcosine with zinc oxide. Next, it is presumed that the hydrazide compound (A) reacted with the zinc atom, and the hydrazide compound was oil-solubilized.
It is also considered that amidation of N-acyl sarcosine proceeds, zinc oxide reacts there, and then the hydrazide compound (A) acts on the zinc molecule to form an oil-soluble metal hydrazide compound.
In any case, it is considered that the oil-soluble metal hydrazide compound was produced as a result of the reaction of the hydrazide compound (A) with the zinc atom.

  EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention should not be construed as being limited by the following examples.

Example 1
1 g of zinc oxide, 10 g of N-oleoyl sarcosine, and 89 g of IP solvent 2028 (isoparaffinic solvent, initial fraction 213 ° C., manufactured by Idemitsu Kosan Co., Ltd.) are placed in a 200 mL round bottom flask equipped with a reflux condenser. The reaction was carried out by heating for 3 hours at 110 ° C. with stirring in an oil bath to obtain an “oil-soluble metal compound (B) solution” as a yellow transparent solution.

Next, 20 g of the “oil-soluble metal compound (B) solution”, which is a yellow transparent solution obtained above, is placed in a 100 mL round bottom flask containing a stir bar, and succinic dihydrazide 0 is added thereto as the hydrazide compound (A). .2 g was added, and the mixture was reacted at 100 ° C. for 30 minutes with stirring to obtain “oil-soluble metal hydrazide compound (1s)” which was a yellow transparent solution.
Since succinic acid dihydrazide is insoluble in IP solvent 2028, the liquid is not transparent immediately after addition of succinic acid dihydrazide, but after reacting at 100 ° C. for 30 minutes, it became a transparent solution. It was confirmed that the reaction was taking place.

Example 2
In the same manner as in Example 1 except that 0.2 g of adipic acid dihydrazide was added instead of adding 0.2 g of succinic acid dihydrazide in Example 1, “oil-soluble metal hydrazide compound” (2s) "was obtained.
Since adipic acid dihydrazide is insoluble in IP solvent 2028, the liquid was not transparent immediately after addition of adipic acid dihydrazide, but became a transparent solution after reacting at 100 ° C. for 30 minutes.

Example 3
In the same manner as in Example 1 except that 0.2 g of sebacic acid dihydrazide was added instead of adding 0.2 g of succinic acid dihydrazide in Example 1, “oil-soluble metal hydrazide compound” (3s) "was obtained.
Since sebacic acid dihydrazide is insoluble in IP solvent 2028, the liquid is not transparent immediately after the addition of sebacic acid dihydrazide, but became a transparent solution after reacting at 100 ° C. for 30 minutes.

Measurement example 1
The solubility of succinic acid dihydrazide, adipic acid dihydrazide and sebacic acid dihydrazide in ion-exchanged water and an isoparaffin solvent (produced by Idemitsu Kosan Co., Ltd., IP-2028) (hereinafter sometimes abbreviated as “IP solvent”) It was measured. The results are shown in Table 1 together with the results of Examples 1, 2, and 3.

  In Examples 1, 2, and 3, "succinic acid dihydrazide, adipic acid dihydrazide, sebacic acid dihydrazide" 1 g of zinc oxide, 10 g of N-oleoyl sarcosine, and 89 g of isoparaffinic solvent were heated at 100 ° C. for 3 hours. The solubility in the oil-soluble metal compound (B) solution, which is a yellow transparent solution after the reaction is performed (hereinafter, “” may be abbreviated as “ZnO-oleoyl sarcosine-IP solvent”). As described above, all became clear solutions.

In the dissolution experiment, the hydrazide compound was put in a solvent, mixed by stirring at 100 ° C. for 30 minutes, returned to room temperature (20 ° C.), and the solubility was evaluated according to the following criteria.
In Examples 1, 2, and 3, "ZnO-oleoyl sarcosine-IP solvent" (oil-soluble metal compound (B) solution), which is a yellow transparent solution, is treated in parallel with ion-exchanged water and IP solvent. As a solvent.
The concentrations of various hydrazide compounds in various solvents were the same mass concentrations as in Examples 1, 2, and 3.
It should be noted that, even with ion-exchanged water or IP solvent, the solubility was determined after stirring at 100 ° C. for 30 minutes and returning to room temperature, which is in accordance with the conditions of Examples 1, 2, and 3.

<Criteria>
○: A transparent solution was obtained visually.
X: It did not become a transparent solution visually but produced turbidity or a precipitate.

All of the hydrazide compounds were stirred at 100 ° C. for 30 minutes and returned to room temperature to determine solubility, but were not dissolved in the IP solvent.
On the other hand, all of the hydrazide compounds were stirred at 100 ° C. for 30 minutes and returned to room temperature to determine solubility, and then dissolved in ZnO-oleoyl sarcosine-IP solvent (oil-soluble metal compound (B) solution) (Examples) 1, 2, 3). Thereby, it was confirmed that the reaction occurred.

Evaluation Example 1
<Deodorization test>
The “oil-soluble metal hydrazide compound (1s)”, which is a yellow transparent solution obtained in Example 1, is used as a “stock solution” of a deodorant, and in accordance with one of the standard use conditions as a deodorant, The stock solution was dissolved in IP solvent to 2% by mass to prepare “2% by mass IP solvent solution”.

Prepare a 3L glass separable flask equipped with a gas inlet for removal, a pressure adjustment port, a detection tube measurement port and a spare port, and use a syringe from each gas injection port to obtain a predetermined initial concentration of acetaldehyde gas. The mixture was individually injected so as to be stirred for 10 seconds. Thereafter, the initial concentration of acetaldehyde gas was measured from a gas tech detector tube.
Next, after 3 mL of deodorant was injected, the concentration (mass ppm) of acetaldehyde gas after the elapsed time shown in Table 2 was measured with a detector tube, and the deodorization rate (%) was measured from the following formula.
[Deodorization rate (%)] = 100 × [concentration after elapsed time (mass ppm)] / [initial concentration (mass ppm)]
The results are shown in Table 2 below.

  Both the “oil-soluble metal hydrazide compound (1s)” (stock solution) obtained in Example 1 and the “2% by mass IP solvent solution” in which the stock solution was dissolved in IP solvent to 2% by mass Excellent deodorizing effect on acetaldehyde gas.

Example 4
<Reaction of zinc oxide and N-oleoyl sarcosine in the absence of solvent>
Zinc oxide (2.5 g) and N-oleoyl sarcosine (50 g) were placed in a 100 mL round bottom flask equipped with a reflux condenser, and heated for 3 hours with stirring at 120 ° C. without solvent using an oil bath. A dark brown viscous transparent solution which is an “oil-soluble metal compound (B) solution” was obtained. This whole amount was dissolved in 50 g of IP solvent.

  The whole amount of the “oil-soluble metal compound (B) solution” diluted with the IP solvent obtained above is placed in a 200 mL round bottom flask, then 5 g of adipic acid dihydrazide is added, and the mixture is heated and stirred at 100 ° C. for 1 hour to obtain a brown transparent solution. An “oil-soluble metal hydrazide compound (4n)” was obtained.

Evaluation example 2
<Deodorization test>
Using the “oil-soluble metal hydrazide compound (4n)”, which is a brown transparent solution obtained in Example 4, three glass separable flasks having a volume of 3 L were prepared in the same manner as in Evaluation Example 1, and each gas injection was performed. From the inlet, three kinds of gases of acetaldehyde, hydrogen sulfide, and ammonia were separately injected as malodorous gases, and the deodorization test was conducted in the same manner as in Evaluation Example 1. The results are shown in Table 3.

The “oil-soluble metal hydrazide compound (4n)” obtained in Example 4 exhibited an excellent deodorizing effect on each gas of acetaldehyde, hydrogen sulfide, and ammonia.
In particular, the “oil-soluble metal compound (B) solution”, which is a heated reaction product of zinc oxide and N-oleoyl sarcosine, did not have a high deodorizing effect on acetaldehyde gas (described in Table 3). However, after 30 minutes, the deodorization rate was about 20%.) The “oil-soluble metal hydrazide compound (4n)” obtained in Example 4 is an acetaldehyde gas that is difficult to deodorize. Also has an excellent deodorizing effect.

Example 5
In the same manner as in Example 4, a zinc oxide-N-oleoyl sarcosine reaction product was prepared in the absence of a solvent, and then dissolved in 50 g of IP solvent. Then, instead of 5 g of adipic acid dihydrazide, 2 g of succinic acid dihydrazide and sebacic acid were used. 1 g of dihydrazide was added, and the mixture was heated and stirred at 100 ° C. for 1 hour to obtain “oil-soluble metal hydrazide compound (5n)” as a brown transparent solution.

Example 6
In Example 4, except that the amount of zinc oxide was changed from 2.5 g to 1 g and the hydrazide compound was changed to 5 g of phthalic acid dihydrazide, it was prepared in the same manner as in Example 4, and the “oil-soluble metal hydrazide compound (6n ) ”.

Example 7
A yellow and transparent “oil-soluble metal compound (B) solution” was obtained in the same manner as in Example 1 except that 10 g of N-lauroyl sarcosine was used instead of 10 g of N-oleoyl sarcosine.
Of these, 50 g was put into a 200 mL round bottom flask, then 1 g of adipic acid dihydrazide was added, and the mixture was heated and stirred at 100 ° C. for 1 hour to obtain “oil-soluble metal hydrazide compound (7s)” as a brown transparent solution.

Example 8
In Example 7, except that 10 g of N-lauroyl sarcosine was replaced by 10 g of N-palmitoyl sarcosine and the hydrazide compound was replaced by 1 g of succinic acid dihydrazide, the “oil-soluble metal hydrazide, which was a brown transparent solution, was obtained in the same manner as in Example 7. Compound (8s) "was obtained.

Example 9
In Example 7, except that 10 g of N-lauroyl sarcosine was replaced with 10 g of N-myristoyl sarcosine, an “oil-soluble metal hydrazide compound (9s)” which was a brown transparent solution was obtained.

Example 10
In Example 1, an “oil-soluble metal compound (B) solution” which is a yellow transparent solution was obtained in the same manner except that 89 g of liquid paraffin was used instead of 89 g of the IP solvent.

  The obtained solution was put into a 200 mL round bottom flask, and then 50 g of the yellow transparent solution, 50 g of dipropylene glycol monomethyl ether (DPGMME) and 0.5 g of succinic dihydrazide were added, and the mixture was stirred at 100 ° C. for 30 minutes. The reaction was performed to obtain “oil-soluble metal hydrazide compound (10s)” as a yellow transparent solution.

Comparative Example 1
In a 200 mL round bottom flask, 1.0 g of zinc oxide and 1.5 g of succinic acid dihydrazide were added, and then 100 g of ion-exchanged water was added as a solvent, followed by heating and stirring at 100 ° C. for 1 hour under reflux.
As a result, the system remained white and did not become transparent.

The solution obtained above was filtered, washed several times with ionic water, filtered again, and air-dried at room temperature. Subsequently, it dried at 100 degreeC all day and night, and obtained white solid 0.9g.
This was measured by atomic absorption with reference to the document JAPAN ANALYST vol21 (1972) “Quantification of Cu, Ni and Zn in metal complexes by atomic absorption.” As a result, the amount of Zn in the white solid was 79% by mass. It was. This is close to 80.2% by mass, which is the zinc content (theoretical value) in zinc oxide.
That is, in Comparative Example 1, it was found that zinc oxide and hydrazide compound did not react.

  Moreover, since neither zinc oxide nor hydrazide compounds are dissolved in IP solvent or liquid paraffin, even if the solvent is changed from the above ion-exchanged water to IP solvent or the like, there is no change in that zinc oxide and hydrazide compound do not react.

Comparative Example 2
In a 200 mL round bottom flask, 1.6 g of oleoyl sarcosine and 1.0 g of sebacic acid dihydrazide were added, and then 100 g of IP solvent was added as a solvent, followed by heating and stirring at 100 ° C. for 1 hour.

  As a result, the system remained white and did not become transparent. Therefore, it was found that oleoyl sarcosine and hydrazide compound do not react.

  The blending table of “oil-soluble metal compound (B)” and “oil-soluble metal hydrazide compound” obtained in Example 1 to Example 10 is shown in Table 5, and “Examples obtained in Examples 5 to 10” Table 6 shows the results of evaluation of the “oil-soluble metal hydrazide compound” stock solution and the 5 mass% IP solvent solution in the same manner as the evaluation after 30 minutes in Evaluation Example 2 as a deodorant.

  From the results of Table 6, it was found that the oil-soluble metal hydrazide compound of the present invention and the deodorant using the compound have an extremely high deodorizing effect not only on ammonia and hydrogen sulfide but also on acetaldehyde. .

  Since the oil-soluble metal hydrazide compound of the present invention is a novel compound, it may be used in various fields. The deodorant using the oil-soluble metal hydrazide compound of the present invention is oil-soluble, and Since it has an excellent deodorizing effect, it is widely used in various forms for various deodorant applications as a deodorant for business use and home use.

Claims (6)

  Reaction of hydrazide compound (A) with oil-soluble metal compound (B) obtained by reacting zinc oxide and N-acyl sarcosine compound in an organic solvent or without solvent at a mass ratio of 1: 5 to 1: 100 An oil-soluble metal hydrazide compound, characterized in that it is obtained by a process.   The oil-soluble metal hydrazide compound according to claim 1, wherein the hydrazide compound (A) is a carboxylic acid hydrazide compound.   The oil-soluble metal hydrazide compound according to claim 1 or 2, wherein the N-acyl sarcosine compound has an acyl group having 10 to 22 carbon atoms.   A deodorant comprising the oil-soluble metal hydrazide compound according to any one of claims 1 to 3.   The oil-soluble metal hydrazide compound according to any one of claims 1 to 3, and a group consisting of an isoparaffin solvent, a normal paraffin solvent, an alcohol solvent, a glycol solvent, and a glycol monoether solvent. The deodorant of Claim 4 containing the selected 1 type, or 2 or more types of diluent.   An aldehyde odor deodorant comprising the deodorant according to claim 4 or 5.