JP5695288B2 - Basic deodorant - Google Patents

Description

  The present invention relates to a deodorant having a deodorizing effect on basic malodor and a deodorizing method using the deodorant.

  Deodorization is broadly divided into sensory methods, chemical methods, physical methods, and biological methods. Conventional efforts have been made to significantly reduce the odors generated from toilets, garbage, and tobacco. .

  In recent years, it can be said that the odor itself of toilets, garbage, cigarettes, etc. has been considerably reduced by improvements in housing, air conditioning equipment, and sanitary environment such as garbage collection. However, consumers' sense of odor has become rather more sensitive, and consumer demand for odor remains high.

  There are various types of bad odors. Examples include alkylamines such as methylamine, ethylamine, trimethylamine, and triethylamine; pyridines such as pyridine, ethylpyridine, and vinylpyridine; pyrazines such as pyrazine, and indoles such as skatole and indole. There are many things that accompany it.

  Alkylamines are often contained in animal and plant septics and excreta and are key components of complex odors. Specific examples include raw garbage odor, rag odor, cloth odor, fish odor, drainage odor, urine odor, and fecal odor. Among them, the threshold value of trimethylamine is 0.000032 ppm, which is particularly low even when compared with other malodors, and is the most important deodorizing object. Pyridines and pyrazines are also key components of a complex odor accompanied by combustion, and specific examples include tobacco odor, grilled meat odor, and odor during cooking.

  For basic malodor, there is a method of neutralizing and deodorizing using an acidic deodorant. For example, in the industrial field, there is acid cleaning using a large amount of acidic deodorant (Non-patent Document 1). However, for home use, use has been restricted from the viewpoint of safety.

  Today's consumers are quicker to use deodorant ingredients that have both masking and chemical deodorant functions than to make great efforts to eliminate malodors using unscented deodorants. We want products that can deodorize. Examples of the deodorant component having both functions include a fragrance material and a plant extract.

  As a fragrance material having a chemical deodorizing effect on basic malodors, especially amines, a fragrance material having an α, β-unsaturated carbonyl structure such as cinnamaldehyde, citral, carvone and other carbonyl groups in the molecule Perfume materials such as Citronellal are known (Non-Patent Documents 1 and 2). Moreover, methyldihydrojasmonate etc. are known as a fragrance | flavor raw material which has a chemical deodorizing effect with respect to an ammonia odor (patent document 1). As plant extracts having a deodorizing effect, essential oils such as cinnamon oil, citronella oil and peppermint oil (Non-patent Document 1) and solvent extracts of Lamiaceae plants such as rosemary (Patent Document 2) are known. It has been.

  However, although cinnamon aldehyde and cinnamon oil have a high deodorizing effect, their use is restricted from the viewpoint of safety, and citronellal and citronella oil have a unique odor and are not very versatile. Then there was a problem. Other substances were not satisfactory in terms of deodorizing effect.

  Therefore, in order to meet the consumer demand for the above-mentioned basic malodor, particularly trimethylamine, it is desired to develop a deodorant having a mild deodorant and a chemical deodorant effect. It was.

Konosuke Nishida “Deodorizing and Deodorizing” Fragrance No.168 (1990) p65-87 Tetsuro Horiuchi “Perfume compounds and deodorization” Fragrance Journal No.72 (1985) p64-67 JP 2002-159565 A JP-A-57-204278

  An object of the present invention is to provide a deodorant that has a mild aroma and is not concerned about safety, and a method for deodorizing a basic malodor using the same, by chemically or physically reducing basic malodor. There is to do.

  From the above-mentioned viewpoints, the present inventors have investigated the chemical or physical deodorizing effect on basic malodors, particularly trimethylamine and pyridine, with respect to a plant extract having a fragrance material and a fragrance by the test method described later. The present inventors have found a fragrance material and a plant extract that have a remarkably higher deodorizing effect than conventionally known compounds.

  That is, the present invention provides a basic malodor deodorant comprising component (a) or (b) and a method for deodorizing basic malodor using component (a) or (b).

Ingredient (a); amylcinnamic aldehyde, ethyl cinnamate, nootkatone, cis-jasmon, acetyl cedrene, 2-methyl-3- (4-tert-butylphenyl) -propanal (Givaudan trade name; Lilyal), 2-cyclohexylpropanal (trade name of Kao Corporation; Polenal II), dimethyltetrahydrobenzaldehyde (trade name of IFF; product name of Tripar, Quest Corporation; Ligstral), geranylacetone, 6-methyl-5-hepten-2-one (conventional) Name: methylheptenone), methylhexyl ketone, cis-3-hexenyl formate, cis-3-hexenyl butyrate, cis-3-hexenyl lactate, cis-3-hexenyl hexanoate, cis-3-hexenyl heptanoate, 2-methylbutyric acid Cis-3-hexenyl, trans-2-hexenyl isobutyrate, heptyl isobutyrate, benzyl acetate, 3-methyl 2,2-dimethylpropionate One or more fragrance substances selected from -3-butenyl (trade name of Kao Corporation; Romirat), trans-3-hexenol, geraniol, valencene and orange recovery flavor. Ingredient (b); Orchidaceae, Algeriaceae, Pterodaceae and Dipterocarp Extract of one or more plants selected from the family

  The deodorizer of the present invention reduces the amount of basic malodor in the gas phase, particularly alkylamines, pyridines and pyrazines, and exhibits an excellent deodorizing effect. Therefore, by using this, basic malodors such as urine odor, fish odor, tobacco odor and the like can be deodorized safely and effectively.

  In the deodorant of the present invention, the component (a) contains an α, β-unsaturated carbonyl compound, but even a compound having these structures is ineffective for deodorizing basic malodors. There are compounds, and the deodorizing effect cannot be explained only by chemical reaction.

The fragrance material as component (a) is chemically classified as follows.
(a1) α, β-unsaturated carbonyl compound: amylcinnamic aldehyde, ethyl cinnamate, nootkatone, cis-jasmon, acetyl cedrene.
(a2) Ketone or aldehyde [except (a1)]: 2-methyl-3- (4-tert-butylphenyl) -propanal, 2-cyclohexylpropanal, dimethyltetrahydrobenzaldehyde, geranylacetone, 6-methyl-5 -Hepten-2-one, methyl hexyl ketone.
(a3) Esters [except (a1) and (a2)]: cis-3-hexenyl formate, cis-3-hexenyl butyrate, cis-3-hexenyl lactate, cis-3-hexenyl hexanoate, cis-heptanoate 3-hexenyl, cis-3-hexenyl 2-methylbutyrate, trans-2-hexenyl isobutyrate, heptyl isobutyrate, benzyl acetate, 3-methyl-3-butenyl 2,2-dimethylpropionate.
(a4) Alcohols or ethers: trans-3-hexenol, geraniol.
(a5) Hydrocarbons: Valencene.
(a6) Recovery flavor: Orange recovery flavor. Here, the recovered flavor is further concentrated by distilling water (oil content of the oil layer in the case of citrus fruits) containing aroma components that evaporate with moisture when concentrating the juice to produce concentrated juice, by steam distillation or solvent extraction. It is a thing.

  As these perfume substances, those isolated from natural products can also be used. For example, Nootkaton can be isolated mainly from grapefruit and Valensen can be isolated mainly from orange.

  Among these components (a), from the viewpoint of the deodorizing effect on basic malodor, ethyl cinnamate, 2-cyclohexylpropanal, geranylacetone, trans-2-hexenyl isobutyrate, cis-3-methylbutyrate Hexenyl, cis-3-hexenyl heptanoate, cis-3-hexenyl formate, cis-3-hexenyl hexanoate, 3-methyl-3-butenyl 2,2-dimethylpropionate, nootkatone, 2-methyl-3- (4 -tert-Butylphenyl) -propanal, 6-methyl-5-hepten-2-one, cis-3-hexenyl butyrate are preferred. From the overall aspect of both calmness and deodorant performance, amylcinnamic aldehyde, 2-cyclohexylpropanal, cis-3-hexenyl heptanoate, cis-3-hexenyl hexanoate, 2,2- Preference is given to 3-methyl-3-butenyl dimethylpropionate, nootkatone, 2-methyl-3- (4-tert-butylphenyl) -propanal, orange recovery flavor.

  Of the basic malodors, 2-cyclohexylpropanal, trans-2-hexenyl isobutyrate, 2-methyl-3- (4-tert-butylphenyl) -propanal, formic acid Cis-3-hexenyl, cis-3-hexenyl 2-methylbutyrate, valencene, cis-3-hexenyl heptanoate, dimethyltetrahydrobenzaldehyde, geranylacetone, 6-methyl-5-hepten-2-one, trans-3-hexenol Nootkaton is preferred.

  Among basic malodors, cis-3-hexenyl formate, 2-cyclohexylpropanal, 2-methyl-3- (4-tert-butylphenyl) -propanal, dimethyltetrahydrobenzaldehyde from the viewpoint of deodorizing effect on fish odor Trans-2-hexenyl isobutyrate, geranyl acetone, geraniol, valencene, cis-jasmon, cis-3-hexenyl 2-methylbutyrate are preferred.

  Among the basic malodors, from the viewpoint of deodorizing effect on tobacco odor, 2-cyclohexylpropanal, cis-3-hexenyl formate, dimethyltetrahydrobenzaldehyde, geranylacetone, geraniol, trans-2-hexenyl isobutyrate, cis-lactic acid Preference is given to 3-hexenyl, orange recovery flavor, cis-3-hexenyl 2-methylbutyrate, cis-3-hexenyl heptanoate, nootkatone and valencene.

  Ingredient (b) is a solvent extract of one or more plants selected from the family Orchidaceae, Anniaceae, Auroaceae and Dipterocarpaceae, and has an aroma. Examples of the orchidaceae plants include Canarium luzonicum (Elemi), Commiphora abyssinica (mil), Boswellia carterii (Olivenum), Commiphora erythraea var. Rabdanam) and the like, and Pelargonium graveolens (geranium) and the like are mentioned as a plant of the family Asteraceae, and Dipterocarpus turbinatus (Gajjun) and the like as the plant of the dipterocarpaceae.

Plant parts that can be used are flowers, leaves, fruits, stems, whole plants, trunks, roots, rhizomes, resins, and the like.
Solvents used for plant extraction include ethanol, acetone, butane, hexane, polyhydric alcohols such as propylene glycol and dipropylene glycol, carbon dioxide, etc., and mixtures with water can also be used.

  Among the components (b), an organic solvent extract is preferable, and an extract with a solvent such as ethanol, acetone, butane, hexane, or the like is preferable.

  These solvent extracts are particularly referred to in the perfume industry as resinoids, oleoresin, absolute, balsam. Resinoid and oleoresin are obtained by extracting a resin other than flowers with an extraction solvent such as acetone or ethanol and then removing the solvent, and particularly contain a soluble resin component. Those used in fragrance applications are called resinoids, and those used in flavor applications are called oleoresin. Absolute is mainly after extracting flower parts with an extraction solvent such as hexane, then removing the solvent and heating and dissolving the remaining concrete with ethanol to remove insoluble materials such as wax. In addition, ethanol is removed. The balsam is a plant-like resinous secretion, which has an aromatic carboxylic acid as a free acid or an ester with an aromatic alcohol, in which the resin component dissolves and has fluidity.

  Among the components (b), a solvent extract of mill, opoponax, labdanum, geranium, or olivenum is preferable from the viewpoint of deodorizing effect against basic malodor. From a comprehensive aspect of both mild aroma and deodorant performance, solvent extracts of opoponax, labdanum, geranium and olivenum are preferred.

  From the viewpoint of the deodorizing effect on urine odor, fish odor and tobacco odor, solvent extracts of labdanum, geranium and olivenum are preferred.

  The deodorant of the present invention can be dissolved and dispersed in a suitable solvent, and other deodorant base materials and other components can be added as appropriate to form a deodorant composition. In this case, only one of component (a) and component (b) may be used, or both components may be used in combination, and component (a) and component (b) itself may be either one. A seed may be used independently or 2 or more types may be used together. The content of the component (a) and the component (b) in the deodorant composition is 0.001 to 5% by mass, particularly 0.01 to 0.5% by mass, from the viewpoint of exerting a sufficient deodorizing effect against basic malodor. % Is preferred.

  Examples of the solvent include ethanol, butanol, isopropyl alcohol, triethyl citrate, diethyl phthalate, dioctyl phthalate, acetone, ethylene glycol, propylene glycol, liquid paraffin dimethyl ether, diethyl ether, and LPG (liquefied petroleum gas). Ethanol, isopropyl alcohol, propylene glycol, dimethyl ether, diethyl ether, LPG and the like are preferable from the viewpoint that they volatilize quickly after spraying. These may be used alone or in combination of two or more.

  Examples of other deodorizing substrates that can be used in combination include general chemical deodorizing substrates and physical deodorizing substrates (referred to as component (c)).

The following are mentioned as a chemical deodorizing base material.
(Neutralization reaction) Acetic acid, hydrochloric acid, wood vinegar, bamboo vinegar, citric acid, malonic acid, succinic acid, glutaric acid, fumaric acid, malic acid, tartaric acid, maleic acid, acrylic acid, lactic acid, adipic acid, phthalic acid, Benzoic acid, nicotinic acid and their salts, betaine compounds, etc.

(Addition reaction) Methacrylic acid ester, maleic acid ester, fumarate ester, catechin, chlorogenic acid, tea extract, koji extract, etc.

(Oxidation reaction) Zinc oxide, titanium oxide, silver oxide, oxide compounds, iron ascorbate, phthalocyanine derivatives

The following are mentioned as a physical deodorizing base material.
(Cyclodextrin) α-, β- or γ-cyclodextrin, its methyl derivatives, hydroxypropyl derivatives, glucosyl derivatives, maltosyl derivatives, etc.

(Organic porous) activated carbon, divinylbenzene polymer, acrylic acid polymer, methacrylic acid polymer, chitosan polymer

(Inorganic porous) Zeolite, high silica zeolite, silica, calcium silicate, zirconium phosphate, zirconium hydroxide, styrene polymer, acrylic acid polymer, methacrylic acid polymer, chitosan polymer

(Compatible solvent / oil agent) Ethylene glycol, diethylene glycol, dipropylene glycol, polyethylene glycol, polypropylene glycol

  The content of the component (c) in the deodorant composition is preferably 0.01 to 2% by mass, more preferably 0.05 to 1% by mass, from the viewpoint of deodorizing performance.

  For the deodorant composition, in addition to the above-mentioned fragrance materials having a deodorizing effect on the basic malodor, any of other synthetic fragrances, natural fragrances, and blended fragrances can be used. In order to maximize the odor effect, fragrances with weak odors such as benzyl alcohol and methyl dihydrojasmonate are desirable.

  In addition to the deodorant, the deodorant composition may contain a cationic, anionic, nonionic or amphoteric surfactant, an antioxidant, a preservative, a pigment, and the like.

  The deodorant composition is produced in dosage forms such as an aqueous solution, an oil agent, an emulsion, a dispersion, an aerosol agent, a transpiration agent, a fumigant, and a powder agent. As the container, a trigger spray container, a pump spray container, a squeeze bottle container, an aerosol container, a mechanical sprayer, or the like can be used.

  The aerosol agent can be used by adding a propellant such as LPG (liquefied petroleum gas), pentane, dimethyl ether, diethyl ether or the like.

  The deodorant composition can be effectively used for deodorizing places where basic malodors are a problem, such as clothing surfaces, indoor spaces, and indoor surfaces. Specifically, it is used for deodorizing hard surfaces (wood furniture, tiles, etc.), textile surfaces (clothing, bedding, carpets, sofas, curtains, etc.), leather surfaces (leather clothing, leather furniture, etc.), etc. . Kitchen with deodorant effect against basic malodor, range, floor surface, wall surface, toilet cleaning composition, residential deodorant composition, clothing cleaning composition, finishing composition, It can also be set as a softener composition and a deodorant composition.

When the deodorant composition is applied to clothing surfaces, indoor surfaces, etc., the amount is preferably 0.05 to 20 mg / m ² as a deodorant.

  The deodorant of the present invention is impregnated with inorganic powder such as silica, silica gel and ceramic, organic powder such as paper, polypropylene, polyethylene, ethylene-vinyl acetate copolymer, activated carbon and wood powder, It can also be used after being formed into a shape or granular shape. In this case, the other deodorant can be used in combination as appropriate.

Test example 1
[Measurement of deodorizing effect on trimethylamine]
In a 50 mL glass bottle, add 3.2 μL of a 30% by mass trimethylamine aqueous solution and 3.2 μL of a 30% by mass trimethylamine aqueous solution and 50 μL of deodorant, and seal. After standing for 30 minutes, the trimethylamine concentration is measured with an amine detector tube. The blank had no deodorant, and the deodorization rate was obtained from the difference from the blank (when the bad odor was 0 ppm, the deodorization rate was 100%), and was ranked according to the following criteria. The results are shown in Table 1.

<Standard>
×: Less than 50% effect △: 50% or more effect ○: 70% or more effect ◎: 90% or more effect

The compounds used in the test were grouped according to the following criteria.
Group 1 (compound having α, β-unsaturated carbonyl structure)
Group 2 (Other compounds having a carbonyl group)
Group 3 (Ester compounds other than Groups 1 and 2)
Group 4 (alcohol and ether compounds other than Groups 1 and 2)
Group 5 (hydrocarbon)
Group 6 (Recovery flavor, plant essential oil)
Group 7 (plant solvent extract)

  As can be seen from Table 1, for example, even the α, β-unsaturated carbonyl compound (Group 1) has a deodorant effect on trimethylamine that is unpredictably different, and the product of the present invention is remarkably highly effective. It was issued.

Test example 2
[Measurement of deodorizing effect on pyridine]
In a 50 mL glass bottle, add 2.5 μL of a 0.5% by mass aqueous solution of pyridine and 30 μL of deodorizer, and mix and seal. After standing for 30 minutes, the pyridine concentration is measured with a detector tube for pyridine. The blank had no deodorant, and the deodorization rate was determined from the difference from the blank (when the bad odor was 0 ppm, the deodorization rate was 100%), and ranked according to the same criteria as in Test Example 1. The results are shown in Table 2.

Test example 3
[Measurement of deodorizing effect on skatole]
In a 20 mL vial, add 10 μL of a 50 mass% acetone solution of skatole and let stand for 1 hour, then add and drop 10 μL of deodorant and seal tightly. After stirring lightly, HS-GC analysis was performed. The deodorization rate was determined from the amount of malodorous substance volatilization in the presence of a deodorant relative to the amount of blank malodorous substance volatilization (GC abundance), and was ranked according to the same criteria as in Test Example 1. The results are shown in Table 3.

<HS-GC analysis conditions>
HS-Autosampler; HS40XL made by PERKIN ELMER
Vial incubation time: 60 ° C for 30 minutes, pressurization 2 minutes, injection 0.3 minutes
GC; HEWLETT PACKARD5890
Column liquid phase: (5% phenyl) methylpolysiloxane Nonpolar Column length: 30 m, inner diameter: 0.32 mm, film thickness: 0.25 μm
Temperature rise conditions: 40 ° C (8 ° C / min) -60 ° C (4 ° C / min) -200 ° C
The deodorization rate (%) was determined by the following formula.

  For other substances, deodorization rate was 40% or less

  As a result of measuring the deodorizing effect, it was confirmed that the product of the present invention is more effective than a known deodorant not only for trimethylamine among basic malodors but also for pyridine and skatole.

Example 1
[Measurement of deodorizing effect on dry urine]
In a 50 mL glass bottle, add 0.06 g of dry urine (mixed for 3 persons, put in a petri dish and dried in the sun) and 100 μL of deodorant, and mix tightly. After leaving still for 30 minutes, 30 μL of 1M aqueous sodium hydroxide solution is dropped into the mixed solution to make it alkaline, and then the generated urine odor is measured with an amine detector tube. The blank has no deodorant, and the deodorization rate is obtained from the difference from the blank (when the bad odor is 0 ppm, the deodorization rate is 100%). The results are shown in Table 4.

  As for other substances, the deodorization rate was 40% or less.

Example 2
[Measurement of deodorizing effect on fish odor]
Three pieces of plastic 2mL small cups containing 50μL of baked fish waste oil (diluted 5 times by mass with ion-exchanged water) 100μL, 5M sodium hydroxide aqueous solution 30mL in a 50mL glass bottle And seal tightly. After standing for 30 minutes, the generated fish odor is measured with an amine detector tube. The blank has no deodorant and the deodorization rate is determined from the difference from the blank (when the bad odor is 0 ppm, the deodorization rate is 100%). The results are shown in Table 5.

  As for other substances, the deodorization rate was 40% or less.

Example 3
[Measurement of deodorizing effect on tobacco odor]
Into a 50 mL glass bottle, inject 50 μL of deodorant and 15 mL of smoke of cigarette (mild seven original tip 1 cm) burned in a 1 L Separa flask and seal tightly. After standing for 30 minutes, the tobacco odor is measured with a detector tube for pyridine. The blank has no deodorant and the deodorization rate is determined from the difference from the blank (when the pyridine concentration is 0 ppm, the deodorization rate is 100%). The results are shown in Table 6.

  As for other substances, the deodorization rate was 40% or less.

Example 4 Softener Composition A softener composition (pH 4) containing the deodorant according to the present invention having the composition (mass%) shown in Table 7 was prepared.

Example 5 Spray-type deodorant composition A deodorant composition containing the composition (mass%) of the deodorant according to the present invention shown in Table 8 was prepared, placed in a trigger spray container, and spray-type deodorant. A composition was prepared.

Example 6 Aerosol spray type deodorant composition The stock solution of the composition (mass%) and the liquefied petroleum gas (LPG) shown in Table 9 were filled in an aerosol can at a ratio of 6: 4 to obtain an aerosol spray.

Example 7 Tableware Cleaning Composition A tableware cleaning composition containing the deodorant according to the present invention having the composition (mass%) shown in Table 10 was prepared.

Example 8 Strong detergent composition for kitchen A detergent composition for kitchen (pH 10) containing the deodorant according to the present invention having the composition (mass%) shown in Table 11 was prepared.

Example 9 Toilet Spray Cleaning Composition A toilet cleaning composition containing the deodorant according to the present invention having the composition (mass%) shown in Table 12 is placed in a container with a trigger, and the toilet spray cleaning composition is used. Was prepared.

Example 10 Toilet wet sheet A liquid mixture containing the deodorant according to the present invention having the composition (mass%) shown in Table 13 was prepared, impregnated 2.5 times (mass) into the nonwoven sheet, and used for toilets. A wet sheet was used.

Claims (1)

Trimethylamine and / or pyridine in the gas phase using a deodorant composition containing 0.001 to 5% by mass of component (a) ( excluding garment cleaning composition, finishing composition and softener composition) How to reduce.
Ingredient (a): one or more perfume substances selected from nootkaton, cis-jasmon, geranylacetone and 6-methyl-5-hepten-2-one