JP2009011821A - Deodorant containing glyoxylic acid esters - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deodorant which exhibits more excellent odor-eliminating effect according to a change in living conditions and can be formed in various dosage forms depending on applications. <P>SOLUTION: A glyoxylic acid ester, glyoxylic acid hemiacetal ester, glyoxylic acid ester dimer and diglyoxylic acid ester have excellent effect of eliminating malodor derived from hydrogen sulfide or ammonia, and can be made into a water-based, oil-based or gelled form. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a deodorant containing glyoxylic acid esters. More specifically, it contains one or more of glyoxylic acid ester, glyoxylic acid hemiacetal ester, diglyoxylic acid ester, and glyoxylic acid dimer, and is a liquid and gel that effectively removes malodors such as ammonia and hydrogen sulfide. It relates to a deodorant.

  In recent years, the need for more effective deodorizing means has increased with changes in the living environment. For example, in order to keep the living space comfortable, there is an increasing need to more effectively remove bad odors generated in the kitchen, indoors, toilets, shoe boxes, automobiles, and the like. In order to keep the environment comfortable, there is a demand for a deodorant that is more effective against bad odors generated from garbage, sewage, septic, garbage disposal facilities, and factory wastewater.

In order to meet these needs, a deodorant has been proposed in which glyoxylic acid is used as an active ingredient, the pH is adjusted between 2.4 and 9, and a surfactant is further added (Patent Document 1). However, although this technology improves the deodorizing effect against sulfurous malodor, it cannot necessarily be said that the deodorizing effect is strong against ammonia and hydrogen sulfide. Further, the present technology has a drawback that it cannot be applied to oily liquid and gel preparations.
JP 2001-137323 A

（Ｘは−ＣＨＯ、−ＣＨＯＨＯＲ^１、−ＣＨＯＨＣＯＣＯＯＲ^２を、ＹはＲ^３、Ｒ^４ＯＣＯＸを、Ｒ^１、Ｒ^２及びＲ^３はそれぞれ同一または異なって炭素数１〜２２のアルキル基、炭素数３〜１５のアルコキシアルキル基を、Ｒ^４は炭素数２〜６のアルキレン基、又は炭素数４〜１６のポリエチレングリコール、ポリプロピレングリコール、ブチレングリコール残基を表す。）
で示されるグリオキシル酸エステル類の１種又は２種以上を含有する消臭剤、
（２）一般式（Ｉ）で示されるグリオキシル酸エステル類の１種又は２種以上とシリカ、アルミナ、ゼオライト、酸性白土からなる固体酸の１種又は２種以上を含有する消臭剤、
（３）一般式（Ｉ）で示されるグリオキシル酸エステル類がグリオキシル酸エステル、グリオキシル酸ヘミアセタールエステル、グリオキシル酸エステルダイマー、及びジグリオキシル酸エステルの１種又は２種以上である（１）又は（２）の消臭剤
（４）さらに加えて界面活性剤、溶剤又はゲル化剤の１種又は２種以上を含有する（１）又は（２）の消臭剤、
（５）界面活性剤が炭素数８〜２２の陰イオン界面活性剤、非イオン界面活性剤、陽イオン界面活性剤、両性界面活性剤の１種又は２種以上である（４）の消臭剤、
（６）溶剤が水、流動パラフィン、イソパラフィン、植物精油、アルコールのいずれか１種、又は２種以上である（４）の消臭剤、
（７）ゲル化剤が硬化ひまし油脂肪酸、ゼラチン、ケルコゲル、Ｎ−ラウロイルーＬ−グルタミン酸−α、γ−ジーｎ−ブチルアミドの１種又は２種以上である（４）の消臭剤、
である。The present inventors have found a glyoxylic acid compound having a stronger deodorizing effect and eagerly researched to develop an oily liquid and a gel-like deodorant in addition to an aqueous liquid deodorant using this compound. As a result, the present inventors have found that a deodorant containing glyoxylic acid esters represented by the following general formula (I) solves this problem.
That is, the present invention
(1) General formula (I)

(X is —CHO, —CHOHOR ¹ , —CHOHCOCOOR ² ; Y is R ³ , R ⁴ OCOX; R ¹ , R ^2, and R ³ are the same or different and each is an alkyl group having 1 to 22 carbon atoms; 3 to 15 alkoxyalkyl groups, R ⁴ represents an alkylene group having 2 to 6 carbon atoms, or a polyethylene glycol, polypropylene glycol, or butylene glycol residue having 4 to 16 carbon atoms.)
A deodorant containing one or more glyoxylic acid esters represented by:
(2) A deodorizer containing one or more glyoxylic acid esters represented by the general formula (I) and one or more solid acids composed of silica, alumina, zeolite, and acid clay,
(3) The glyoxylic acid ester represented by the general formula (I) is one or more of glyoxylic acid ester, glyoxylic acid hemiacetal ester, glyoxylic acid ester dimer, and diglyoxylic acid ester (1) or ( 2) deodorant (4) (1) or (2) deodorant further containing one or more of a surfactant, solvent or gelling agent,
(5) Deodorant according to (4), wherein the surfactant is one or more of an anionic surfactant having 8 to 22 carbon atoms, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant. Agent,
(6) The deodorizer according to (4), wherein the solvent is any one of water, liquid paraffin, isoparaffin, plant essential oil, and alcohol, or two or more thereof.
(7) The deodorizer according to (4), wherein the gelling agent is one or more of hardened castor oil fatty acid, gelatin, kelcogel, N-laureuil L-glutamic acid-α, and γ-di-n-butyramide,
It is.

In the glyoxylic acid esters represented by the general formula (I) of the present invention, examples of the glyoxylic acid ester represented by X = —CHO and Y = R ³ include methyl glyoxylate, ethyl glyoxylate, and n-propyl glyoxylate. Isopropyl glyoxylate, n-butyl glyoxylate, isobutyl glyoxylate, n-amyl glyoxylate, isoamyl glyoxylate, hexyl glyoxylate, heptyl glyoxylate, n-octyl glyoxylate, 2-ethylhexyl glyoxylate, nonyl glyoxylate, glyoxyl Decyl acid, lauryl glyoxylate, myristyl glyoxylate, stearyl glyoxylate, methoxyethyl glyoxylate, ethoxyethyl glyoxylate, methoxypropyl glyoxylate, Examples of the ester include ethoxypropyl roxylate, propoxypropyl glyoxylate, methoxybutyl glyoxylate, ethoxybutyl glyoxylate, propoxybutyl glyoxylate, ethoxyhexyl glyoxylate, propoxyhexyl glyoxylate and the like. Examples of the diglyoxylic acid ester represented by X = —CHO and Y = R ⁴ OCOX include, for example, ethylene glycol diglyoxylate, propylene diglyoxylate, butylene diglyoxylate, hexylene diglyoxylate, diglyoxylic acid 1,1, Each ester of 3-trimethylpropylene, diglyoxylic acid and diethylene glycol, diglyoxylic acid and triethylene glycol, diglyoxylic acid and tetraethylene glycol, diglyoxylic acid and dipropylene glycol, diglyoxylic acid and tripropylene glycol, diglyoxylic acid Examples include tetrapropylene glycol, diglyoxylic acid and dibutylene glycol, and esters of diglyoxylic acid and tributylene glycol. Examples of the glyoxylic acid hemiacetal ester represented by X = -CHOHOR ¹ and Y = R ³ include, for example, ethyl glyoxylate, n-propyl glyoxylate, isopropyl glyoxylate, n-butyl glyoxylate, isobutyl glyoxylate, and glyoxylic acid n. Examples include hemiacetal esters such as amyl, isoamyl glyoxylate, n-octyl glyoxylate, 2-ethylhexyl glyoxylate, lauryl glyoxylate, ethoxyethyl glyoxylate, ethoxypropyl glyoxylate, and ethoxybutyl glyoxylate. Examples of the glyoxylic acid ester dimer represented by X = —CHOHCOCOOR ² and Y = R ³ include, for example, methyl glyoxylate, ethyl glyoxylate, n-propyl glyoxylate, isopropyl glyoxylate, n-butyl glyoxylate, isopropyl glyoxylate, N-amyl glyoxylate, isoamyl glyoxylate, hexyl glyoxylate, heptyl glyoxylate, n-octyl glyoxylate, 2-ethylhexyl glyoxylate, nonyl glyoxylate, decyl glyoxylate, lauryl glyoxylate, methoxyethyl glyoxylate, ethoxy glyoxylate Ethyl, methoxypropyl glyoxylate, ethoxypropyl glyoxylate, propoxypropyl glyoxylate, methoxybutyl glyoxylate Le, ethoxy butyl glyoxylate, propoxycarbonyl glyoxylate carboxybutyl, glyoxylic acid ethoxy-hexyl, dimers of the esters, such as glyoxylic acid propoxy hexyl.

Among the glyoxylic acid esters represented by the above general formula (I) of the present invention, glyoxylic acid ester, diglyoxylic acid ester, and glyoxylic acid ester of X = —CHO, —CHOHCOCOOR ² , Y = R ³ , R ⁴ OCOX Dimer is produced by azeotropic dehydration of 50% aqueous solution of glyoxylic acid and alcohol or glycol together with an aromatic solvent such as toluene or benzene in the presence of an acid catalyst such as concentrated sulfuric acid or p-torninsulfonic acid. (Patent Document 2). In the presence of an acid catalyst, if the reaction proceeds too much, oligomers are formed, which causes turbidity and viscosity increase. Therefore, it is desirable to limit the formation of monomers and dimers. Glyoxylate is also produced by cleaving its hemiacetal ester into an ester and an alcohol with a P ₂ O ₅ catalyst (Academic Document 1).
JP 2005-170880 A

Academic literature 1

Journal of the American Chemical Society, 1941, 63, 3338

The glyoxylic acid hemiacetal ester represented by X = —CHOHOR ¹ and Y = R ³ in the general formula (I) of the present invention can be obtained by reacting a 50% aqueous solution of glyoxylic acid with an alcohol in the absence of an acid catalyst. (Patent Document 3). If the reaction proceeds too much, a fluacetal ester is produced, so it is desirable to limit the production to the hemiacetal ester production.
JP-A-53-116319

  The glyoxylic acid ester and diglyoxylic acid ester of the present invention have a stronger deodorizing effect on ammonia and hydrogen sulfide than glyoxylic acid. When the CHO group of glyoxylic acid ester is acetalized by reaction with alcohol, hemiacetal ester exhibits a weaker deodorizing effect than ester, but full acetal ester exhibits little deodorizing effect. However, dealcoholization in the presence of an acidic catalyst can cleave the fluacetal ester into a hemiacetal ester and then the hemiacetal ester into an ester to enhance the deodorizing effect. In general, glyoxylic acid ester is easily polymerized, which not only increases the viscosity but also decreases the deodorizing effect. This tendency is particularly strong with diglyoxylate. Similarly, the polymerization can be delayed by utilizing the depolymerization effect of the acidic catalyst. This is particularly effective in the case of glyoxylate dimer. Such an acidic catalyst desirably acts slowly on the glyoxylic acid ester contained in the deodorant, and is preferably a solid acid such as silica, alumina, zeolite, or acidic clay. The solid acid is added in an amount of 0.1 to 20% by weight, preferably 1 to 10% by weight, based on glyoxylic acid esters.

When the glyoxylic acid esters of the present invention are water-soluble, such as ethyl ester, propyl ester, isoamyl ester, diester with ethylene glycol, diester with propylene glycol, diester with dipropylene glycol, It is used as a 30% by weight, preferably 1-5% by weight, water-soluble preparation. When the glyoxylic acid esters of the present invention are oil-soluble, for example, lauryl ester, 2-ethylhexyl ester, ethoxypropyl hemiacetal ester, isoamyl hemiacetal ester, 0.1 to 30% by weight, preferably 1 to Used as a 5% by weight oil-soluble formulation.
The demand for indoor deodorants has increased due to the recent increase in the number of households that keep pets indoors, but oil-based deodorants and gel-type deodorants that have a longer life than aqueous deodorants are desired. Yes. Furthermore, the oil-soluble deodorant component can be applied to interior materials and chemical cloths for general houses and automobiles, and new applications can be considered.
In addition, by using an oil-soluble glyoxylic acid ester of the present invention as an active ingredient, an oily liquid deodorant or a gel-like deodorant that has not been found in conventional glyoxylic acid deodorants can be obtained.

  Gel preparations are roughly classified into aqueous and oily. The following is an example of how to make it. In the case of an aqueous solution, the glyoxylic acid esters of the present invention, a surfactant and the like are dispersed in water in a container and heated to 85 ° C., and kelcogel swollen in glycerin is added and stirred. When the kelcogel is dissolved, the heating is stopped and the desired container is filled and cooled. If oily, the solvent isoparaffin is placed in a container and heated to 110 ° C. Subsequently, N-lauroyl-L-glutamic acid α, γ-di-n-butyramide as a gelling agent is added and stirring is continued while maintaining at 110 ° C. to completely dissolve the gelling agent. Subsequently, glyoxylic acid esters and a surfactant are added and dissolved, and then filled into a desired container to be cooled and gelled.

  The glyoxylic acid ester, glyoxylic acid hemiacetal ester, glyoxylic acid ester dimer, and diglyoxylic acid ester of the present invention have a strong deodorizing effect especially on ammonia, but are also balanced against organic acids such as acetic acid. In order to have a good effect, it may be used in combination with a metal oxide such as zinc oxide or copper (II) oxide. For example, a mixture of the same amount with zinc oxide exhibits a deodorizing effect that is almost balanced with respect to ammonia and acetic acid.

The deodorant containing the glyoxylic acid ester, glyoxylic acid hemiacetal ester, glyoxylic acid ester dimer, and diglyoxylic acid ester of the present invention exhibits a stronger deodorizing effect when combined with a surfactant. The surfactant used for this purpose may be any of anionic, nonionic, cationic, and amphoteric, with nonionic and amphoteric being more preferred. Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate ester, dialkyl sulfosuccinate, and nonionic surfactants include fatty acid polyethylene glycol and polyoxyethylene alkyl. Ethers, polyoxyethylene glycerides, polyoxyethylene sorbitan fatty acid esters include cationic surfactants such as alkyl quaternary ammonium salts and alkylbenzyl quaternary ammonium salts, and amphoteric surfactants include, for example, fatty acid amides. Examples include propyl betaine and 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazolinium betaine.
The surfactant of the water-soluble preparation is desirably one having an HLB of 10 to 16, and the amount added is 0.2 to 3 times, preferably 1 to 2.5 times in terms of weight relative to glyoxylic acid esters. is there. The surfactant of the oil-soluble preparation is desirably one having an HLB of 4 to 6, and the addition amount is 0.2 to 3 times, preferably 1 to 3 times in terms of weight with respect to glyoxylic acid esters. In particular, when coconut oil fatty acid amidopropyl betaine is added to a water-soluble preparation, an increase in deodorizing effect can be obtained by adding 0.2 to 1.5 times in terms of weight with respect to glyoxylic acid esters.

  Examples of the solvent used in the deodorant of the present invention include water, alcohol suitable for water-soluble preparations, liquid paraffin, isoparaffin, and plant essential oils suitable for oil-soluble preparations. Among these, the boiling point of isoparaffin is over a wide range of 70 to 350 ° C. depending on the grade, and can be properly used depending on the application. Examples of the gelling agent include hardened castor oil fatty acid, gelatin, Kelco gel, N-lauroilu L-glutamic acid-α, and γ-di-n-butyramide. The amount of gelling agent added to the gel deodorant is preferably 0.8 to 1.2% by weight. If it is 0.8% by weight or less, gelation is difficult, and even if it is 1.2% by weight or more, the gel strength does not change.

  Further, if desired, for the purpose of imparting fragrance to the deodorant of the present invention and, if necessary, eliminating the ester-specific ester or hemiacetal ester odor, for example, menthol, linalool, peppermint oil, limonene, orange oil, Appropriate amounts of fragrances such as geraniol, thymol, methyl salicylate, cypress oil, camphor, rosemary oil, carvone, geraniol, citral, and natural essential oils are added. In addition, for the purpose of exhibiting a deodorizing effect over a wide range against bad odors, deodorizing components such as polyphenols and polyether derivatives extracted from natural products such as green tea and strawberries may be added.

The invention's effect

  The deodorizer containing one or more of glyoxylic acid ester, glyoxylic acid hemiacetal ester, glyoxylic acid ester dimer and diglyoxylic acid ester represented by the general formula (I) of the present invention is ammonia, hydrogen sulfide Exhibits excellent deodorizing effects against bad odors.

  The present invention will be specifically described below with reference to examples.

Synthesis of 2-ethylhexyl glyoxylate 83.3 g (0.64 mol) of 2-ethylhexyl alcohol, 104.2 g (0.74 mol) of 50% aqueous solution of glyoxylic acid, 200 mL of toluene, 0.54 mL (1.0 g) of concentrated sulfuric acid It put into the flask with a reflux tube, and azeotropic dehydration was performed at 95-122 degreeC under argon stream for 7 hours. The separated water was 67 mL. After cooling, a small amount of black solid was removed by filtration, the filtrate was placed in a still, and toluene was distilled off under reduced pressure. Concentrated sulfuric acid (0.54 mL, 1.0 g) was further added to the distillation residue, and the mixture was slowly heated in an oil bath until the oil bath temperature reached 165 ° C., and 56.0 g of an oily substance was distilled at 85 to 102 ° C. . The obtained oily substance, toluene (200 mL), and water (50 mL) were put into a reactor, heated and stirred at 80 ° C. under reduced pressure of an argon stream, cooled, and water and toluene were distilled off with an evaporator. The distillation residue was 52.6 g of an oily substance. The oily substance thus obtained was used as a Schiff base, and the presence of an aldehyde group was confirmed by thin layer chromatography. Further, the gas chromatograph of the obtained oily substance had one peak. From this, it was estimated that this was 2-ethylhexyl glyoxylate.

Synthesis of 1,1,3-trimethylpropylene diglyoxylate 3,7.8 g (0.32 mol) 1,1,3-trimethyl-1,3-propanol (hexylene glycol), 300 mL benzene, 50% aqueous solution of glyoxylic acid 104. 2 g (0.74 mol) and 1.0 g of p-toluenesulfonic acid monohydrate were put into a flask equipped with a reflux tube, and azeotropic dehydration was performed at 73 to 81 ° C. for 5 hours under an argon stream. The separated water was 62 mL. After cooling, a small amount of red candy-like precipitate was removed by decantation, and the liquid was placed in a distiller and distilled to obtain 53.3 g of a distillation residue. This was dissolved in 400 mL of water, 1 g of activated carbon was added, and a small amount of insoluble paste was adsorbed and filtered. 60 g of sodium chloride was added to the filtrate to separate the oily substance, followed by extraction with 200 mL of ethyl acetate and then with 100 mL of ethyl acetate, and the solution was separated into an organic layer and an aqueous layer. The organic layer was dried over anhydrous sodium sulfate, and ethyl acetate was distilled off with an evaporator. The residue after distillation was a slightly yellowish-brown viscous liquid, and showed almost one spot on the thin layer chromatograph. From the formation of Schiff base and the rapid absorption of ammonia gas, it was estimated that the liquid material obtained was 1,1,3-trimethylpropylene diglyoxylate.

Synthesis of isoamyl glyoxylate 42 g (0.48 mol) of isoamyl alcohol, 50% aqueous solution of glyoxylic acid (0.42 mol), 180 mL of toluene, and 0.14 mL of concentrated sulfuric acid were placed in a flask equipped with a reflux tube, and 7 hours 93 hours under an argon stream. Azeotropic dehydration was performed at ˜119 ° C. The separated water was 39.5 mL.
After cooling, a small amount of black precipitate was removed by filtration, the filtrate was put into a still, and toluene was once distilled off under reduced pressure. Further, 0.4 mL of concentrated sulfuric acid was added to 70.4 g of the distillation residue and 73 to 76. Distillation under reduced pressure was performed at 5 ° C. to obtain 43.1 g of distillation residue. To this, 200 mL of toluene and 50 mL of water were added and heated to 80 ° C. After cooling, the organic layer was separated to obtain 42.8 g of an oily substance. The presence of an aldehyde group was confirmed by the same method as in Example 1.

Synthesis of diglyoxylic acid 1,1'-oxydipropan-2-ol ester 1,1'-oxydipropan-2-ol (dipropylene glycol) 42.9 g (0.32 mol), benzene 300 mL, glyoxylic acid A 50% aqueous solution (0.7 mol) and 1.0 g of p-toluenesulfonic acid were placed in a flask with a reflux tube, and azeotropic dehydration was performed at 73 to 81 ° C. for 6 hours under an argon stream. The separated water was 60 mL. After cooling, the colorless candy-like substance precipitated on the bottom was separated by decantation, and the resulting paste was dissolved in 400 mL of ethyl acetate and washed three times with 300 mL of 10% brine. The organic layer was separated, dehydrated with anhydrous sodium sulfate, placed in a distiller, and distilled under reduced pressure at 60 ° C. to obtain 64.2 g of a viscous colorless liquid.

Synthesis of glyoxylic acid isoamyl hemiacetal ester 80 g (0.9 mol) of isoamyl alcohol and 52.5 g (0.35 mol) of 50% aqueous solution of glyoxylic acid were placed in a flask equipped with a reflux tube, boiled for 4 hours under an argon stream, 31.2 g was separated to obtain 44.7 g of a colorless and transparent liquid substance at 84 to 85 ° C./20 mmHg. Two peaks were obtained by gas chromatography, and parent peaks of mass numbers corresponding to isoamyl alcohol and glyoxylic acid isoamyl ester were confirmed by GC-MS (CI method), respectively. Proton NMR confirmed two H peaks of —CHOH— indicating hemiacetal.

Synthesis of glyoxylic acid ethoxypropyl hemiacetal ester 180 g (1.73 mol) of ethoxypropanol, 99.2 g of 50% glyoxylic acid and 200 mL of toluene were azeotropically dehydrated at 90 to 121 ° C. for 4 hours, and 61.2 g of water was separated. Toluene was distilled off. 53.6 g of a colorless and transparent liquid material was obtained at 81 to 91 ° C./18 mmHg.
The reason why the distillation temperature range is wide is considered that the raw material ethoxypropanol is a mixture of 1-ethoxy and 2-ethoxy. As a result of measuring GC and GC-MS (CI method) about this synthetic | combination and raw material etokin propanol, it was confirmed that one of the two peaks obtained by GC of synthetic | combination was raw material ethoxypropanol, and another Since the GC-MS parent peak mass number of the peak coincided with the molecular weight of glyoxylic acid ethoxypropyl ester, it was confirmed that the synthesized product was glyoxylic acid ethoxypropyl hemiacetal ester. In proton NMR, since the raw material ethoxypropanol is a mixture of isomers, the two H peaks of —CHOH— confirmed in Example 5 could not be clearly discriminated.

Deodorizing effect of 2-ethylhexyl glyoxylate A 20% methoxyethanol solution of 2-ethylhexyl glyoxylate was prepared and deodorized. A test sample was obtained by superimposing 5 C filter paper impregnated with 2 mL of the sample solution on 5 C filter paper impregnated with 2 mL of distilled water. The sample was placed in a 5 L Tedlar bag, degassed, and then injected with 3 L of air, hydrogen sulfide, and ammonia so that the initial concentrations were 40 ppm and 400 ppm, respectively, and sealed. The gas concentration in the Tedlar bag after 30 minutes, 2 hours and 6 hours was measured with a gas detector tube. The blank was only 5C filter paper impregnated with 2 mL of distilled water. The test results are shown below.

以上の結果から、グリオキシル酸２−エチルヘキシルは、硫化水素、アンモニアに対して優れた消臭効果を有することがわかる。

From the above results, it can be seen that 2-ethylhexyl glyoxylate has an excellent deodorizing effect on hydrogen sulfide and ammonia.

Deodorizing effect of 1,1,3-trimethylpropylene glyoxylate 1 g of 1,1,3-trimethylpropylene glyoxylate was impregnated into filter paper, put in a 5 L Tedlar bag, degassed, 3 L air, and 100 ppm Ammonia was injected and sealed. The ammonia gas concentration in the Tedlar bag after 0 minutes, 10 minutes, and 30 minutes was measured with a gas detector tube. The test results are shown below.

以上の結果から、ジグリオキシル酸１，１，３−トリメチルプロピレンは、アンモニアに対して優れた消臭効果を有することがわかる。

From the above results, it can be seen that diglyoxylic acid 1,1,3-trimethylpropylene has an excellent deodorizing effect on ammonia.

Effect of addition of solid acid to 1,1,3-trimethylpropylene diglyoxylate 10g of diglyoxylic acid 1,1,3-trimethylpropylene and 1g of acid clay (Wako Pure Chemical Industries, Ltd.) Each was stored at 20 ° C. for 1 month. The degree of increase in viscosity was lower with the addition of acid clay. From each of these samples, 1 g was taken as Sample A (addition of acid clay) and Sample B (no addition of acid clay), and the same deodorization test as in Example 8 was performed. The test results are shown below.

以上の結果から、ジグリオキシル酸１，１，３−トリメチルプロピレンに対する固体酸の添加効果が認められた。固体酸の重合の抑制効果と固体酸自体の消臭効果が複合化されたと推定される。

From the above results, the effect of adding a solid acid to diglyoxylic acid 1,1,3-trimethylpropylene was recognized. It is presumed that the solid acid polymerization inhibitory effect and the solid acid deodorizing effect were combined.

Deodorizing effect of isoamyl glyoxylate A 20% ethanol solution of isoamyl glyoxylate was prepared. 1 mL of this was taken, impregnated into a filter paper having a diameter of 10 cm, and placed in a 5 L Tedlar bag. After deaeration, 3 L of air and 100 ppm of ammonia were injected and sealed. After 0 minutes, 20 minutes, and 60 minutes, the ammonia gas concentration in the Tedlar bag was measured with a Kitagawa type detector tube. The test results are shown below.

以上の結果から、グリオキシル酸イソアミルは、アンモニアに対して優れた消臭効果を有することがわかる。

From the above results, it can be seen that isoamyl glyoxylate has an excellent deodorizing effect on ammonia.

Deodorizing effect of glyoxylic acid isoamyl hemiacetal ester and ethoxypropyl hemiacetal ester on ammonia A 20% ethanol solution of the above two compounds was prepared. 1 g of this product was taken and impregnated into 5A filter paper and placed in a 3 L Tedlar bag. 120 ppm of ammonia was sealed, sealed, and the ammonia gas concentration in the Tedlar bag after 0 minutes, 30 minutes, 60 minutes, and 120 minutes was measured with a Kitagawa detector tube. The test results are shown below.

Deodorizing effect of glyoxylic acid isoamyl hemiacetal ester on hydrogen sulfide A 20% ethoxyethanol solution of glyoxylic acid isoamyl hemiacetal ester was prepared. A 5C filter paper impregnated with 2 mL of sample solution was layered on 5 C filter paper impregnated with 2 mL of distilled water to obtain a test piece. In the blank test, a 5 C filter paper impregnated with 2 mL of distilled water and a 5 C filter paper impregnated with 2 mL of ethoxyethanol were used. The test results are shown below.

Effect of solid acid addition to glyoxylic acid hemiacetal ester 100 mL of 20% ethoxyethanol solution of glyoxylic acid isoamyl hemiacetal ester and 2 g of acidic clay (reagent manufactured by Wako Pure Chemical Industries, Ltd.) were placed in a 200 mL beaker and stirred at 20 ° C. for 7 days. . From this, 2 mL was taken as a sample solution, and the deodorizing effect on hydrogen sulfide was measured in the same manner as in Example 11. The test results are shown below.

以上の結果を実施例１１の結果と比較すると、酸性白土の添加により、消臭効果が増大したことがわかる。ヘミアセタールエステルの一部がより効果の強いエステルに変換したためと推定される。

When the above result is compared with the result of Example 11, it turns out that the deodorizing effect increased by addition of acid clay. It is presumed that part of the hemiacetal ester was converted to a more effective ester.

Water-soluble deodorant preparation A water-soluble deodorant preparation was prepared by combining the following components.
4% by weight of glyoxylic acid isoamyl ester
Polyoxyethylene oleyl ether (HLB14) 7% by weight
Palm oil fatty acid amidopropyl betaine 2% by weight
87% by weight of purified water
Total 100% by weight

Oil-soluble deodorant preparation An oil-soluble deodorant preparation was prepared by combining the following components.
Glyoxylic acid isoamyl hemiacetal ester 5% by weight
Polyoxyethylene hydrogenated castor oil ether (HLB6) 8% by weight
Isoparaffin (boiling point 140-250 ° C) 87% by weight
Total 100% by weight

Aqueous gel deodorant An aqueous gel deodorant was prepared by combining the following components.
4% by weight of glyoxylic acid isoamyl ester
Polyoxyethylene oleyl ether (HLB14) 7% by weight
Palm oil fatty acid amidopropyl betaine 2% by weight
Kelcogel 1% by weight
Glycerin 1% by weight
85% by weight of purified water
Total 100% by weight

Oily Gel Deodorant An oily gel deodorant was prepared by combining the following components.
Glyoxylic acid isoamyl hemiacetal ester 5% by weight
Polyoxyethylene hydrogenated castor oil ether (HLB6) 8% by weight
N-laureuil L-glutamic acid-α, γ-di-n-butyramide
1% by weight
Isoparaffin (boiling point 140-250 ° C) 86% by weight
Total 100% by weight

Deodorizing effect on ammonia of gel deodorant 10 g of the gel deodorant preparations of Example 16 and Example 17 were taken, put into a 5 L Tedlar bag, degassed, and then injected with 3 L of air and 100 ppm of ammonia. . The ammonia concentration in the Tedlar bag at 0 minutes, 20 minutes, and 60 minutes after sealing was measured with a Kitagawa-type detector tube.
The test results are shown below.

  The glyoxylic acid ester, glyoxylic acid hemiacetal ester, glyoxylic acid ester dimer and diglyoxylic acid ester represented by the above general formula (I) of the present invention have an excellent deodorizing effect against malodor caused by hydrogen sulfide and ammonia. So it can be used as a deodorant.

Claims (7)

Formula (I)

(X is —CHO, —CHOHOR ¹ , —CHOHCOCOOR ² ; Y is R ³ , R ⁴ OCOX; R ¹ , R ^2, and R ³ are the same or different and each is an alkyl group having 1 to 22 carbon atoms; 3 to 15 alkoxyalkyl groups, R ⁴ represents an alkylene group having 2 to 6 carbon atoms, or a polyethylene glycol, polypropylene glycol, or butylene glycol residue having 4 to 16 carbon atoms.)
A deodorant containing one or more of glyoxylic acid esters represented by the formula: A deodorant containing one or more glyoxylic acid esters represented by the general formula (I) and one or more solid acids composed of silica, alumina, zeolite, and acid clay. The glyoxylic acid ester represented by the general formula (I) is one or more of glyoxylic acid ester, glyoxylic acid hemiacetal ester, glyoxylic acid ester dimer, and diglyoxylic acid ester. Deodorants Furthermore, the deodorizer of Claim 1 or Claim 2 which contains 1 type, or 2 or more types of surfactant, a solvent, or a gelatinizer.   The deodorizer according to claim 4, wherein the surfactant is one or more of an anionic surfactant having 8 to 22 carbon atoms, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant.   The deodorizer according to claim 4, wherein the solvent is any one of water, liquid paraffin, isoparaffin, plant refined oil, and alcohol, or two or more thereof.   The deodorizer according to claim 4, wherein the gelling agent is one or more of hardened castor oil fatty acid, gelatin, Kelco gel, N-laureuil L-glutamic acid-α, and γ-di-n-butyramide.