JPH0332672A - deodorant composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a deodorant composition that has excellent deodorizing power and can be used in a wide range of ways against bad odors generated from the human body, home, environment, etc. .

With the urbanization and diversification of living environments, people are becoming increasingly concerned about the smells around them, and in particular, bad odors are being criticized more harshly. Currently, the following methods are generally known as methods for treating bad odors.

■Sensory deodorization...masking with fragrance.

■Physical deodorization: Adsorption using activated carbon, etc. Absorption and inclusion by cyclodextrin.

■Chemical deodorization...neutralization with acids and alkalis.

Oxidation, oxidation with reducing agents, reduction, addition with lauryl methacrylates, etc.

■Biological deodorization: Deodorization due to the bactericidal action of disinfectants and the effect of microorganisms or enzymes.

However, in the sensory deodorization method (2), the quality of the bad odor is changed by the fragrance, and the bad odor itself exists, and if it loses its balance with the fragrance, it may even create a feeling of disgust.

The physical deodorizing method (2) adsorbs or absorbs and includes malodors, but there is a problem in that the adsorption capacity for various malodorous gases is insufficient.

■Chemical deodorization has some safety issues, and although it is effective against a single type of bad odor, it cannot be a panacea against the complex odors of today's daily life. .

Biological deodorization (2) has shortcomings in terms of speed and sustainability, and a single deodorization method alone is not sufficient.

Activated carbon is the most commonly used deodorant and is known to adsorb various malodorous components. However, it has poor deodorizing power against hydrogen sulfide and ammonia among malodorous components.

In order to improve this point, activated carbon is made to support a halide (Japanese Patent Application Laid-Open No. 55-51421), a metal is supported (Japanese Patent Application Laid-Open No. 53-137089),
Research has been carried out on impregnating acids and alkalis, but this has not yet been sufficient.

Furthermore, the above-mentioned publications generally describe the deodorizing performance against various types of bad odors, but when considering the use of deodorants, the deodorizing speed and the amount of deodorizing are also important factors.

The present inventors previously proposed the use of an aluminosilicate having a composition containing Sin, MOIIL, and AM, O, in specific amounts as a deodorant as a three-component ratio expressed as an oxide (especially No. 63-220874).

DISCLOSURE OF THE INVENTION The present invention provides a deodorizing composition that exhibits excellent deodorizing effects against various types of bad odors and is highly safe.

The present invention also provides a deodorizing composition that exhibits an excellent deodorizing effect against various types of bad odors and has an excellent long-lasting effect.

The first deodorant composition of the present invention comprises the following (a) and (b).
) and/or (C).

(a) Porous material.

(b) Plant extract.

(c) Fungicide.

The present invention will be explained in more detail below.

(a) Component porous materials include activated carbon, silica gel,
Typical examples include aluminosilicates and clay minerals. Activated carbon is obtained by treating coal 1 petroleum residue, charcoal, fruit grains, etc. with water vapor, carbon dioxide, etc. by a gas activation method, or by a chemical activation method such as zinc chloride, and has a BET specific surface area of 500 to 2000 m/ g is preferably used.

The aluminosilicate is preferably one having a three-component composition ratio value expressed as a zeolite and an oxide below.

SiO,: 5-80 mol%, preferably 25-75 mol% MO,: 5-65 mol%, preferably 15-60 mol% AQ, 03: 1-60 mol%, preferably 1-45 mol% ( M is at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin, and zirconium.

(n represents the valence of the metal) Among the porous materials of component (a), aluminosilicates in particular are said to have the characteristics of solid acids and solid acid groups, and silica
The acidity of alumina-based catalysts changes depending on the content of alumina, and it is also said that the acidity changes depending on the ratio of the alumina and silica contents [Kozo Okabe, Acid-Base Catalyst, p. 183 (1967) ] Furthermore, since this aluminosilicate has a structure in which acidic Sin and basic metal oxide are combined, it has basic and acidic polarity, and is mainly chemically adsorbed for both malodorous components. , it is thought to have a deodorizing effect based on a chemical reaction.

Aluminosilicate is obtained as a white or light-colored powder, and water-soluble silicate, water-soluble metal salt, water-soluble aluminum salt and/or water-soluble aluminate, etc. are added to water in an amount corresponding to the above composition ratio. It is produced by reacting in the presence of water and, if necessary, heating the resulting precipitate in the presence of water.

This reaction easily proceeds by the so-called double decomposition method.

That is, an alkali silicate such as sodium silicate is used as the silica component, a water-soluble metal salt such as chloride, nitrate, or sulfate is used as the metal oxide component, and sodium aluminate and/or aluminum chloride is used as the alumina component. A water-soluble aluminum salt such as aluminum sulfate is used, and these are mixed in the presence of water to cause a reaction to occur by metathesis.

In order to carry out this metathesis reaction homogeneously, it is preferable to carry out the reaction while simultaneously separating an aqueous silicate solution, an aqueous metal salt solution, and an aqueous solution containing an alumina component into water in which silica has been dispersed.

The reaction by metathesis is sufficient at room temperature, but it can also be carried out under heating, for example, it is of course possible to carry out the reaction under heating up to about 95°C.

The pH of the reaction system during simultaneous sex is 5-IO1, especially 6-
It is best to keep it within the range of 9. For this purpose, if necessary, an acid or alkali is added to the reaction system to maintain the pH of the liquid within the above range.

Simultaneous sex produces an aluminosilicate precipitate whose composition approximately corresponds to the aqueous solution composition.

By separating this precipitate or, if necessary, heating it in the presence of moisture, it is obtained as a white to light-colored powdery substance.

(b) Ingredients include red algae, brown algae, gymnosperms,
Extracts of angiosperms are used, and those having a deodorizing effect are preferred. Specific examples of these plants include the following.

In the phylum of red algae, the phylum Rhodophyta are of the order Cercipitridae, the family Ogonoriaceae, and the family Ceratopsinae, and the plants of the order Aeginidae, the family Ornatidae, Hanesozo, Kurotsupu, Kobusozo, and Papirasozo.

Mozuku, a member of the order Phaeophyceae of the order Phaeophyceae and the family Mozuriaceae.

Arame and Kurome of the Laminaceae family of the order Laminaria, Hijiki, Sargassum, Sargassum, Sargassum family, Sargassum, Sargassum, Sawtooth grass, Sea travesty, Sawtooth grass, Nejimoku, Narasamo, and Mamedawara of the Sargassum family.

Yatsumatamoku, Yoremoku, Isomoku, and Togemoku.

A seaweed that belongs to the order Laminaria, family Ainuwakame.

Ginkgo biloba, a member of the Ginkgo family of the order Ginkgophyta, of the phylum Gymnosperms, and metasequoia, a member of the family Cobia family of the order Pinus.

In the phylum Angiosperms, in the order Kossinaceae, in the family Kossinaceae, the birch, in the family Fagaceae, in the order Fagaceae, birch in the family Fagaceae, in the order Polygonales, in the family Polygonaceae, rhubarb, in the order Ranunculaceae, in the family Magnoliaceae, in the order Ranunculaceae, in the family Magnoliaceae, in the family Magnolia, and in the family Ranunculaceae. peony, Japanese oleracea, Akebia of the family Acaciaceae of the order Ranunculaceae, nandina of the barberry family, Epimedium, tussafras of the Lauraceae family, camphor tree, poppy of the papaver family of the order Papaveraceae, and papaver of the Brassicaceae family.

Porphyra of the order Prunusidae, Hamamelis of the family Rosaceae, wild cherry of the Rosaceae, raspberry, hawthorn, rattania of the Fabaceae family, sorcery, aspergillus, japonica of the family Rutaceae of the order Prunus, yellowfin tuna, hemruta and melium of the Meliaceae family. Cha, of the order Hymenoptera and family Camellia,
Camellia, Pomegranate (Pomegranate family), Clove (Myrtaceae family), Eucalyptus, Allspice, Celery (Umbelliferae family), Anise, Cucumber, Akebia (Ericaceae family), Forsythia (Osteraceae family), Tubular flower orders Lamiaceae sage, thyme, marjoram, rosemary, scutellariae, scutellariae, melissa, and orchid.

Black mint, perilla, basil, olein, savory, wolfberry from the nightshade family, wolfberry from the family Rubiaceae, hemium from the Rubiaceae family, strawberry from the Asteraceae family, tarragon, and arnica.

Sanna, a member of the order Zingiberaceae and family Zingiberaceae.

When obtaining solvent extracts from these plants, the whole plant or each part of the plant such as leaves, bark, flowers, pericarp, fruits, rhizomes, and roots may be used. Depending on the plant, a part of the plant containing a relatively large amount of deodorizing active ingredients can be selected and used.

In order to obtain deodorizing active ingredients from these plants, 5 known methods can be used. For example, the plants are dried and then cut and powdered, which is then mixed with water, ethyl ether, ethylene chloride,
dioxane, acetone, ethanol, n-butanol,
Ethyl acetate.

One or more polar solvents such as propylene glycol, or n-hexane, petroleum ether, ligroin,
Adopt a method of extraction with one or more non-polar solvents such as cyclohexane, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, toluene, benzene, etc., or a mixed solvent of these polar solvents and non-polar solvents. be able to. In this case, a conventional method can be used for the extraction operation, for example, a method such as digesting the plant in a solvent can be used.

The extract obtained by the above extraction procedure is usually mixed with a deodorant after the solvent has been distilled off. However, in some cases, especially when the solvent is water, ethanol, etc., the solvent may be distilled off. It can also be added directly to deodorants.

The deodorant composition of the present invention can be obtained by using the above components (,) and (b) and/or (C) as essential components, but if necessary, each of these components can be made into powder granules. Component (a) can be mixed with component (a), or component (a) can be impregnated with component (b) and/or component (C), or a carrier can be impregnated with component (b) and/or component (C). They are used by mixing, or by kneading and granulating component (a), component (b) and/or component (C) under solvent retention conditions.

(C) As a bactericidal agent, p-oxybenzoic acid ester, 0-phenylphenol, 3-methyl-4-isopropylphenol, bistributyltin oxide,
Dibutyltin naphthinate, triphenyltin oxide, benzethonium chloride, benzalkonium chloride, α-
Bromocinnamic aldehyde, alkyl di(aminoethyl)glycine salt, 2-bromo-2nitropropane-
1,3-diol, chlorhexidine, 2- (4-
Thiazolyl) benzimidazole, stearyldimethylbenzylammonium chloride, distearyldimethylammonium chloride, stearyltrimethylammonium chloride, cetylpyridium chloride, domiphene bromide.

Alkylisoquinolium bromide, 3,4.4' trichlorocarbanilide, dehydroacetic acid, sorbic acid, p-chloro-m-kynol, p-chloro-m-cresol, 2,
4.6-dribromophenol, 2,4.6-trichlorophenol, pentachlorophenol.

2.4.4'-trichloro-2'-hydroxydiphenyl ether, 3-trichloro-2'-dichloro-N,N'-diphenylurea, dimethyldithiocarbamate, 1,2-benzisothiazolin-3-one , butyl-m-cresol, α-chlorobenzaldoxime acetate, resorcinol, isopropylmethylphenol, resorcinol monoacetate, and the like.

Among these, p-chloro-m-xylenol, butyl-n-cresol, 0-phenylphenol, α-
Bromocinnamic aldehyde is preferred.

The deodorant composition of the present invention can be obtained as the above-mentioned components (a) and (c) as essential components, but if necessary, the surrounding components may be prepared as a mixture of powdery granules, or (a).
) component particles are impregnated with component (c), and further (a), (
The component c) is used in mixed form and granulated under solvent retention conditions.

The deodorant composition contains (a) a porous substance and (c) a disinfectant in a weight ratio of (a)/(c) = 1/99-9.
9.9910.01, more preferably 50150-99
．． It is preferable that they coexist within the range of G.910.1.

In addition to component (a), component (b), and/or component (c), the composition of the present invention may optionally include a surfactant, an alkaline agent, and an acid substance.

It can also be blended with pigments, ultraviolet absorbers, antioxidants, polymeric substances, etc.

The foul-smelling gases generated in daily life are generally made up of many components.6 Typical foul-smelling components include ammonia, nitrogen-based gases such as amines, hydrogen sulfide, mercaptans, etc. sulfur-based gases are known. However, since these nitrogen-based malodorous components and sulfur-based malodorous components behave differently, there has been no deodorizing base material that is effective against both malodorous components.

In addition, bad odors are always generated from food waste, leftover garbage, etc., and if the deodorizing speed and amount are insufficient, there is a problem in terms of the sustainability of the deodorizing effect.

In the present invention, it is possible to deodorize various malodorous components by using the porous material as the component (a) together with the plant extract as the component (b) and/or the disinfectant as the component (c). And so.

In addition, by using it in combination with the plant extract of component (b),
In addition to being effective against various bad odors, we have achieved a deodorizing composition that has a fast deodorizing speed, a large amount of deodorizing, and is highly safe.

On the other hand, by combining component (a) with a bactericide as component (c), the deodorizing speed and the amount of deodorizing can be further improved, and a deodorant with excellent long-lasting effects can be obtained.

Synthesis examples of aluminosilicate used as the porous material of component (a), examples of deodorant compositions, and evaluation results thereof will be described below in sequence.

The amount of inspection is double. Synthesis example 1 No. 3 sodium silicate (S i O,: 22.0%.

Na, O: 7.0%) 109g and sodium hydroxide 94g
(NaOH content: 2.35 mol) was dissolved in water to make a total volume of 1, and this was used as solution A (S i O, min: 0.4 mol).

On the other hand, 95 g of zinc chloride (anhydrous salt) and aluminum chloride (
Dissolve 97 g of hexahydrate salt in water to make the total amount IQ, and add this to Solution B (Zn0 min: 0.7 mol, Afi, O.

minute: 0.2 mol).

Water LQ was placed in a 5Q beaker, and while stirring, liquids A and B were simultaneously added at a rate of about 25 cc/min. After completion of sex, ρ[1 of this reaction solution was 6.9.

After further stirring and aging for 30 minutes, 85~
The reaction solution heated at 90°C for 2 hours was suction filtered, washed with water, and dried at 110°C. The resulting cake was sorted through a sieve to obtain white granules of zinc aluminosilicate as granules of 8 to 16 meshes.

The three-component composition ratio and BET specific surface area of the obtained granules are shown together with the subsequent synthesis examples after the synthesis examples.

Synthesis Example 2 As in Synthesis Example 1, No. 3 sodium silicate (S i O2:2
2%, Na, O: 7.0%) 139 g and 88 g of sodium hydroxide (NaOH content = 2.2 mol) were dissolved in water to make the total amount IQ, and this was used as solution A (Sin, min: O,
St mol).

On the other hand, 65 g of zinc chloride (anhydrous salt) and aluminum chloride (
126g of hexahydrate salt is used as one flood, and this is used as solution B (Zn0 min:
0.48 mol, AQ, 03 minutes: 0.26 mol).

Water IQ was placed in a 5Q beaker, and while stirring, liquids A and B were simultaneously added at a rate of about 25 cc/min. After sex, the pH of the reaction solution was 8.6.

Thereafter, the same treatment as in Example 1 was carried out to obtain zinc aluminosilicate as granules of 8 to 16 meshes.

Synthesis example 3 No. 3 sodium silicate (S i O,: 22.0%.

Na, O: 7.0%) 273 g and sodium hydroxide 6
Dissolve 0 g (NaOH content: 1.5 mol) in water to make the total amount IQ, and use this as Solution A (Sins content = 1.0 mol).

On the other hand, 34 g of silver nitrate and aluminum nitrate (9 hydrate)
Dissolve 225g in water, make the total amount IQ, and add this to liquid B (
AgzO content: 0.1 mols A Q s Os content = 0.
3 moles).

One volume of water was poured into a beaker No. 52, and while stirring, liquids A and B were simultaneously separated at a rate of about 25 cc/min. After completion of Ebetsu, the pH of this reaction solution was 8.9.

Stirring was continued and the mixture was aged for 1 hour. The resulting cake was sorted through a sieve to obtain silver aluminosilicate as granules of 8 to 16 meshes.

Table 1 shows the measurement results of the three-component composition ratio and specific surface area of the granular materials obtained in Synthesis Examples 1 to 3.

Table 1 Apex" 1: Two Example 1 20g of dried leaves of 0-Zumary were crushed with a cutter, placed in a Soxhlet extraction container, 180g of water was added, heat extraction was performed for 15 hours, and this extract was extracted with a 10% rose Marie extract.

10 for 100g of aluminosilicate obtained in Synthesis Example 1
% rosemary extract and dried at 80°C.

The obtained cake was sieved through an 8 to 16 mesh sieve to obtain a deodorant composition.

Example 2 20 g of whole thyme plants were crushed, 180 g of water was added to a Soxhlet oil extraction container, and hot water extraction was carried out for 13 hours to obtain an extract. Thereafter, the same treatment as in Example 1 was carried out to obtain a deodorant composition.

Example 3 10 g of dried sage leaves were crushed, placed in a Soxhlet extraction vessel, added with 190 g of 50% ethanol, and subjected to heat extraction for 15 hours to obtain a 5% sage extract. Synthesis example 2
100 g of the obtained aluminosilicate was impregnated with 10 g of 50% sage extract obtained by concentrating with an evaporator.
Dry at 10°C. The obtained cake was sieved through an 8 to 16 mesh sieve to obtain a deodorant composition.

Example 4 The 10% rosemary extract obtained in Example 1 was sprayed onto 100 g of the aminosilicate obtained in Synthesis Example 3 to obtain a powder deodorant composition.

Example 5 The 10% rosemary extract obtained in Example 1 was sprayed onto activated carbon (Diasolve (G-6-10) manufactured by Mitsubishi Kasei ■) to obtain a powder deodorant composition.

Example 6 The sage extract obtained in Example 3 was sprayed onto spherical silica to obtain a deodorant composition.

Example 7 30 g of pine needles were crushed, placed in a Soxhlet extraction vessel, 150 g of acetone was added, and heat extraction was performed for 10 hours to obtain an extract. Thereafter, the same treatment as in Example 1 was carried out to obtain a deodorant composition.

1 to 7) The deodorizing effects of the deodorant compositions of Examples 1 to 7 and comparative samples described above were evaluated using the following evaluation method (Method A),
The results are shown in Table-2.

[Evaluation method of deodorizing effect (Method A)]

Meat, vegetables, fish, etc. were placed in a 6Q desiccator and left for two weeks to create an artificial garbage odor.

A sample was prepared by wrapping 5 g of the deodorant composition in a nonwoven fabric and placing it in a 1.8-inch wide-mouth bottle.

Furthermore, 10 mQ of headspace gas with an artificial garbage odor was put into a wide-mouthed bottle from a 612 desiccator, and the odor intensity over time was sensory evaluated using the following criteria.

Vaginal knee 1 (-one grain base) Oodorless 1 Very faint odor 2 Slight odor 3 Easily felt odor 4
Strong odor 5 The evaluation was done by a panel of 5 people, and the top and bottom two were cut out.
The average of the names was rounded off.

A deodorant composition was prepared by mixing the aluminosilicate obtained by the methods of Synthesis Examples 1 to 3 and activated carbon (Diasorb G-6-10) manufactured by Mitsubishi Kasei ■ with the various disinfectants shown in Table 3. was prepared.

These were evaluated according to the following evaluation method (Method B), and the evaluation results are shown in Table 3 along with comparative examples.

[Evaluation method of deodorizing effect (Method B)]

Meat, vegetables, fish, etc. were placed in a 6Q desiccator and left for one week to create artificial garbage.

30 g of the prepared garbage was placed in a 1.8 Q wide-mouthed bottle, 10 g of the deodorant composition was sprinkled thereon, and the odor intensity over time was sensory evaluated using the following criteria.

Criteria Odorless Very faint odor Faint odor Easily felt odor Strong odor
The average of the names was rounded off.

(Left below) For 100 g of aluminosilicate obtained in Synthesis Example 1,
0.2% of 2-(4-thiazolyl)benzimidazole
It was impregnated with 50 g of ethyl alcohol solution and dried at 80° C. for 1 hour to obtain a powder deodorant composition.

Loss of Salmon U Activated carbon (manufactured by Mitsubishi Kasei ■, Diasolp G-6-10) 5
10 g of a 30% aqueous solution of benzalkonium chloride was sprayed onto 0 g to obtain a powder deodorant composition.

The deodorizing effects of the deodorant compositions of Examples 16 and 17 were evaluated according to Method B, and the results are shown in Table 4.

(Hereinafter, blank space) 1011 For 100 g of aluminosilicate obtained in Synthesis Example 3, 0
-10% ethyl alcohol solution of phenylphenol 3
0 g was impregnated and dried at 80° C. for 30 minutes to obtain a powdery deodorant composition.

This deodorant composition was sprinkled on a plastic garbage bucket containing food waste and a triangular corner.

Odors generated from food waste or leftover food waste have been suppressed.

A total of 19 IU of wastewater was collected into 1.8Q glass bottles.

Drainage A: Cleaning wastewater from a pigpen (87 pigs kept) Drainage B: Septic tank wastewater from a standard home with four family members To this, 10g of the deodorizing composition shown in Table 1-5 was added, and the odor intensity was measured over time. Sensory evaluation was performed.

The evaluation criteria were based on Method B.

The deodorant composition was a powder product obtained by impregnating the aluminosilicate obtained in each synthesis example with an ethanol solution of a disinfectant and drying it at 80°C for 1 hour, and impregnated with 1% disinfectant. I let it happen.

(Left below) 10 g of aluminosilicate obtained by the method of Inuzaki U Moxibustion Biheel Synthesis Examples 1 to 3
to 2.0% of the 10% rosemary extract obtained in Example 1.
0.3 g of fungicide was applied to the sample which was sprayed and dried at 80°C for 3 hours.
g to obtain a deodorant composition.

These were evaluated according to the deodorizing effect evaluation method (Method B), and the evaluation results are shown in Table 6 along with comparative examples.

(The following is a blank space) Description 1, Title of the invention Deodorant composition 2, Claim 1, Containing (a) a porous substance, and (b) a plant extract and/or a bactericide Deodorant composition 2 characterized in that the porous material of the component (a) has a three-component composition ratio expressed as the following oxides: SiO2: 5 to 80 mol%, MO: 5 to 65 mol%, 几AQ, O,: l ~ f5o mol% (M corresponds to at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin, and zirconium, and n represents the valence of the metal) The deodorant composition according to claim 1, which is an aluminosilicate having a composition.

3. The deodorant composition according to claim 1 or 2, wherein the bactericidal agent as the component (b) is a sublimable substance. 4. The plant extract as the component (b) is a red algae plant.

The claim is an extract of a plant selected from brown algae, gymnosperms and angiosperms, and the fungicide is p-chloro-m-xylenol, butyl-m-cresol, 0-phenylphenol or α-bromocinnamic aldehyde. Item 3. The deodorant composition according to item 1 or 2.

3. Detailed Description of the Invention The present invention relates to a deodorizing composition that has excellent deodorizing power and can be widely used to treat bad odors generated from the human body, home, environment, etc. .

With the urbanization and diversification of living environments, people are becoming increasingly concerned about the smells around them, and in particular, bad odors are being criticized more harshly. Currently, the following methods are generally known as methods for treating bad odors.

■Sensory deodorization...masking with fragrance.

■Physical deodorization: Adsorption using activated carbon, etc. Absorption and inclusion by cyclodextrin.

■Chemical deodorization...neutralization with acids and alkalis.

Oxidation, oxidation with reducing agents, reduction, addition with lauryl methacrylates, etc.

■Biological deodorization: Deodorization due to the bactericidal action of disinfectants and the effect of microorganisms or enzymes.

However, in the sensory deodorization method (2), the quality of the bad odor is changed by the fragrance, and the bad odor itself exists, and if it loses its balance with the fragrance, it may even create a feeling of disgust.

The physical deodorizing method (2) adsorbs or absorbs and includes malodors, but there is a problem in that the adsorption capacity for various malodorous gases is insufficient.

■Chemical deodorization has some safety issues, and although it is effective against a single type of bad odor, it cannot be a panacea against the complex odors of today's daily life. .

Biological deodorization (2) has shortcomings in terms of speed and sustainability, and a single deodorization method alone is not sufficient.

Activated carbon is the most commonly used deodorant and is known to adsorb various malodorous components. However, it has poor deodorizing power against hydrogen sulfide and ammonia among malodorous components.

In order to improve this point, activated carbon is made to support a halide (Japanese Patent Application Laid-Open No. 55-51421), a metal is supported (Japanese Patent Application Laid-Open No. 53-137089),
Research has been carried out on impregnating acids and alkalis, but this has not yet been sufficient.

Furthermore, the above-mentioned publications generally describe the deodorizing performance against various types of bad odors, but when considering the use of deodorants, the deodorizing speed and the amount of deodorizing are also important factors.

The present inventors previously proposed the use of an aluminosilicate having a composition containing Sin, MOIIL, and AM, O, in specific amounts as a deodorant as a three-component ratio expressed as an oxide (especially No. 63-220874).

DISCLOSURE OF THE INVENTION The present invention provides a deodorizing composition that exhibits excellent deodorizing effects against various types of bad odors and is highly safe.

The present invention also provides a deodorizing composition that exhibits an excellent deodorizing effect against various types of bad odors and has an excellent long-lasting effect.

The first deodorant composition of the present invention comprises the following (a) and (b).
) and/or (C).

(a) Porous material.

(b) Plant extract.

(c) Fungicide.

The present invention will be explained in more detail below.

(a) Component porous materials include activated carbon, silica gel,
Typical examples include aluminosilicates and clay minerals. Activated carbon is obtained by treating coal 1 petroleum residue, charcoal, fruit grains, etc. with water vapor, carbon dioxide, etc. by a gas activation method, or by a chemical activation method such as zinc chloride, and has a BET specific surface area of 500 to 2000 m/ g is preferably used.

The aluminosilicate is preferably one having a three-component composition ratio value expressed as a zeolite and an oxide below.

SiO,: 5-80 mol%, preferably 25-75 mol% MO,: 5-65 mol%, preferably 15-60 mol% AQ, 03: 1-60 mol%, preferably 1-45 mol% ( M is at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin, and zirconium.

(n represents the valence of the metal) Among the porous materials of component (a), aluminosilicates in particular are said to have the characteristics of solid acids and solid acid groups, and silica
The acidity of alumina-based catalysts changes depending on the content of alumina, and it is also said that the acidity changes depending on the ratio of the alumina and silica contents [Kozo Okabe, Acid-Base Catalyst, p. 183 (1967) ] Furthermore, since this aluminosilicate has a structure in which acidic Sin and basic metal oxide are combined, it has basic and acidic polarity, and is mainly chemically adsorbed for both malodorous components. , it is thought to have a deodorizing effect based on a chemical reaction.

Aluminosilicate is obtained as a white or light-colored powder, and water-soluble silicate, water-soluble metal salt, water-soluble aluminum salt and/or water-soluble aluminate, etc. are added to water in an amount corresponding to the above composition ratio. It is produced by reacting in the presence of water and, if necessary, heating the resulting precipitate in the presence of water.

This reaction easily proceeds by the so-called double decomposition method.

That is, an alkali silicate such as sodium silicate is used as the silica component, a water-soluble metal salt such as chloride, nitrate, or sulfate is used as the metal oxide component, and sodium aluminate and/or aluminum chloride is used as the alumina component. A water-soluble aluminum salt such as aluminum sulfate is used, and these are mixed in the presence of water to cause a reaction to occur by metathesis.

In order to carry out this metathesis reaction homogeneously, it is preferable to carry out the reaction while simultaneously separating an aqueous silicate solution, an aqueous metal salt solution, and an aqueous solution containing an alumina component into water in which silica has been dispersed.

The reaction by metathesis is sufficient at room temperature, but it can also be carried out under heating, for example, it is of course possible to carry out the reaction under heating up to about 95°C.

The pH of the reaction system during simultaneous sex is 5-IO1, especially 6-
It is best to keep it within the range of 9. For this purpose, if necessary, an acid or alkali is added to the reaction system to maintain the pH of the liquid within the above range.

Simultaneous sex produces an aluminosilicate precipitate whose composition approximately corresponds to the aqueous solution composition.

By separating this precipitate or, if necessary, heating it in the presence of moisture, it is obtained as a white to light-colored powdery substance.

(b) Ingredients include red algae, brown algae, gymnosperms,
Extracts of angiosperms are used, and those having a deodorizing effect are preferred. Specific examples of these plants include the following.

In the phylum of red algae, the phylum Rhodophyta are of the order Cercipitridae, the family Ogonoriaceae, and the family Ceratopsinae, and the plants of the order Aeginidae, the family Ornatidae, Hanesozo, Kurotsupu, Kobusozo, and Papirasozo.

Mozuku, a member of the order Phaeophyceae of the order Phaeophyceae and the family Mozuriaceae.

Arame and Kurome of the Laminaceae family of the order Laminaria, Hijiki, Sargassum, Sargassum, Sargassum family, Sargassum, Sargassum, Sawtooth grass, Sea travesty, Sawtooth grass, Nejimoku, Narasamo, and Mamedawara of the Sargassum family.

Yatsumatamoku, Yoremoku, Isomoku, and Togemoku.

A seaweed that belongs to the order Laminaria, family Ainuwakame.

Ginkgo biloba, a member of the Ginkgo family of the order Ginkgophyta, of the phylum Gymnosperms, and metasequoia, a member of the family Cobia family of the order Pinus.

In the phylum Angiosperms, in the order Kossinaceae, in the family Kossinaceae, the birch, in the family Fagaceae, in the order Fagaceae, birch in the family Fagaceae, in the order Polygonales, in the family Polygonaceae, rhubarb, in the order Ranunculaceae, in the family Magnoliaceae, in the order Ranunculaceae, in the family Magnoliaceae, in the family Magnolia, and in the family Ranunculaceae. peony, Japanese oleracea, Akebia of the family Acaciaceae of the order Ranunculaceae, nandina of the barberry family, Epimedium, tussafras of the Lauraceae family, camphor tree, poppy of the papaver family of the order Papaveraceae, and papaver of the Brassicaceae family.

Porphyra of the order Prunusidae, Hamamelis of the family Rosaceae, wild cherry of the Rosaceae, raspberry, hawthorn, rattania of the Fabaceae family, sorcery, aspergillus, japonica of the family Rutaceae of the order Prunus, yellowfin tuna, hemruta and melium of the Meliaceae family. Cha, of the order Hymenoptera and family Camellia,
Camellia, Pomegranate (Pomegranate family), Clove (Myrtaceae family), Eucalyptus, Allspice, Celery (Umbelliferae family), Anise, Cucumber, Akebia (Ericaceae family), Forsythia (Osteraceae family), Tubular flower orders Lamiaceae sage, thyme, marjoram, rosemary, scutellariae, scutellariae, melissa, and orchid.

Black mint, perilla, basil, olein, savory, wolfberry from the nightshade family, wolfberry from the family Rubiaceae, hemium from the Rubiaceae family, strawberry from the Asteraceae family, tarragon, and arnica.

Sanna, a member of the order Zingiberaceae and family Zingiberaceae.

When obtaining solvent extracts from these plants, the whole plant or each part of the plant such as leaves, bark, flowers, pericarp, fruits, rhizomes, and roots may be used. Depending on the plant, a part of the plant containing a relatively large amount of deodorizing active ingredients can be selected and used.

In order to obtain deodorizing active ingredients from these plants, 5 known methods can be used. For example, the plants are dried and then cut and powdered, which is then mixed with water, ethyl ether, ethylene chloride,
dioxane, acetone, ethanol, n-butanol,
Ethyl acetate.

One or more polar solvents such as propylene glycol, or n-hexane, petroleum ether, ligroin,
Adopt a method of extraction with one or more non-polar solvents such as cyclohexane, carbon tetrachloride, chloroform, dichloromethane, 1,2-dichloroethane, toluene, benzene, etc., or a mixed solvent of these polar solvents and non-polar solvents. be able to. In this case, a conventional method can be used for the extraction operation, for example, a method such as digesting the plant in a solvent can be used.

The extract obtained by the above extraction procedure is usually mixed with a deodorant after the solvent has been distilled off. However, in some cases, especially when the solvent is water, ethanol, etc., the solvent may be distilled off. It can also be added directly to deodorants.

The deodorant composition of the present invention can be obtained by using the above components (,) and (b) and/or (C) as essential components, but if necessary, each of these components can be made into powder granules. Component (a) can be mixed with component (a), or component (a) can be impregnated with component (b) and/or component (C), or a carrier can be impregnated with component (b) and/or component (C). They are used by mixing, or by kneading and granulating component (a), component (b) and/or component (C) under solvent retention conditions.

(C) As a bactericidal agent, p-oxybenzoic acid ester, 0-phenylphenol, 3-methyl-4-isopropylphenol, bistributyltin oxide,
Dibutyltin naphthinate, triphenyltin oxide, benzethonium chloride, benzalkonium chloride, α-
Bromocinnamic aldehyde, alkyl di(aminoethyl)glycine salt, 2-bromo-2nitropropane-
1,3-diol, chlorhexidine, 2- (4-
Thiazolyl) benzimidazole, stearyldimethylbenzylammonium chloride, distearyldimethylammonium chloride, stearyltrimethylammonium chloride, cetylpyridium chloride, domiphene bromide.

Alkylisoquinolium bromide, 3,4.4' trichlorocarbanilide, dehydroacetic acid, sorbic acid, p-chloro-m-kynol, p-chloro-m-cresol, 2,
4.6-dribromophenol, 2,4.6-trichlorophenol, pentachlorophenol.

2.4.4'-trichloro-2'-hydroxydiphenyl ether, 3-trichloro-2'-dichloro-N,N'-diphenylurea, dimethyldithiocarbamate, 1,2-benzisothiazolin-3-one , butyl-m-cresol, α-chlorobenzaldoxime acetate, resorcinol, isopropylmethylphenol, resorcinol monoacetate, and the like.

Among these, p-chloro-m-xylenol, butyl-n-cresol, 0-phenylphenol, α-
Bromocinnamic aldehyde is preferred.

The deodorant composition of the present invention can be obtained as the above-mentioned components (a) and (c) as essential components, but if necessary, the surrounding components may be prepared as a mixture of powdery granules, or (a).
) component particles are impregnated with component (c), and further (a), (
The component c) is used in mixed form and granulated under solvent retention conditions.

The deodorant composition contains (a) a porous substance and (c) a disinfectant in a weight ratio of (a)/(c) = 1/99-9.
9.9910.01, more preferably 50150-99
．． It is preferable that they coexist within the range of G.910.1.

In addition to component (a), component (b), and/or component (c), the composition of the present invention may optionally include a surfactant, an alkaline agent, and an acid substance.

It can also be blended with pigments, ultraviolet absorbers, antioxidants, polymeric substances, etc.

The foul-smelling gases generated in daily life are generally made up of many components.6 Typical foul-smelling components include ammonia, nitrogen-based gases such as amines, hydrogen sulfide, mercaptans, etc. sulfur-based gases are known. However, since these nitrogen-based malodorous components and sulfur-based malodorous components behave differently, there has been no deodorizing base material that is effective against both malodorous components.

In addition, bad odors are always generated from food waste, leftover garbage, etc., and if the deodorizing speed and amount are insufficient, there is a problem in terms of the sustainability of the deodorizing effect.

In the present invention, it is possible to deodorize various malodorous components by using the porous material as the component (a) together with the plant extract as the component (b) and/or the disinfectant as the component (c). And so.

In addition, by using it together with the plant extract of component (b),
In addition to being effective against various bad odors, we have achieved a deodorizing composition that has a fast deodorizing speed, a large amount of deodorizing, and is highly safe.

On the other hand, by combining component (a) with a bactericide as component (c), the deodorizing speed and the amount of deodorizing can be further improved, and a deodorant with excellent long-lasting effects can be obtained.

Synthesis examples of aluminosilicate used as the porous material of component (a), examples of deodorant compositions, and evaluation results thereof will be described below in sequence.

The amount of inspection is double. Synthesis example 1 No. 3 sodium silicate (S i O,: 22.0%.

Na, O: 7.0%) 109g and sodium hydroxide 94g
(NaOH content: 2.35 mol) was dissolved in water to make a total volume of 1, and this was used as solution A (S i O, min: 0.4 mol).

On the other hand, 95 g of zinc chloride (anhydrous salt) and aluminum chloride (
Dissolve 97 g of hexahydrate salt in water to make the total amount IQ, and add this to Solution B (Zn0 min: 0.7 mol, Afi, O.

minute: 0.2 mol).

Water LQ was placed in a 5Q beaker, and while stirring, liquids A and B were simultaneously added at a rate of about 25 cc/min. After completion of sex, ρ[1 of this reaction solution was 6.9.

After further stirring and aging for 30 minutes, 85~
The reaction solution heated at 90°C for 2 hours was suction filtered, washed with water, and dried at 110°C. The resulting cake was sorted through a sieve to obtain white granules of zinc aluminosilicate as granules of 8 to 16 meshes.

The three-component composition ratio and BET specific surface area of the obtained granules are shown together with the subsequent synthesis examples after the synthesis examples.

Synthesis Example 2 As in Synthesis Example 1, No. 3 sodium silicate (S i O2:2
2%, Na, O: 7.0%) 139 g and 88 g of sodium hydroxide (NaOH content = 2.2 mol) were dissolved in water to make the total amount IQ, and this was used as solution A (Sin, min: O,
St mol).

On the other hand, 65 g of zinc chloride (anhydrous salt) and aluminum chloride (
126g of hexahydrate salt is used as one flood, and this is used as solution B (Zn0 min:
0.48 mol, AQ, 03 minutes: 0.26 mol).

Water IQ was placed in a 5Q beaker, and while stirring, liquids A and B were simultaneously added at a rate of about 25 cc/min. After sex, the pH of the reaction solution was 8.6.

Thereafter, the same treatment as in Example 1 was carried out to obtain zinc aluminosilicate as granules of 8 to 16 meshes.

Synthesis example 3 No. 3 sodium silicate (S i O,: 22.0%.

Na, O: 7.0%) 273 g and sodium hydroxide 6
Dissolve 0 g (NaOH content: 1.5 mol) in water to make the total amount IQ, and use this as Solution A (Sins content = 1.0 mol).

On the other hand, 34 g of silver nitrate and aluminum nitrate (9 hydrate)
Dissolve 225g in water, make the total amount IQ, and add this to liquid B (
AgzO content: 0.1 mols A Q s Os content = 0.
3 moles).

One volume of water was poured into a beaker No. 52, and while stirring, liquids A and B were simultaneously separated at a rate of about 25 cc/min. After completion of Ebetsu, the pH of this reaction solution was 8.9.

Stirring was continued and the mixture was aged for 1 hour. The resulting cake was sorted through a sieve to obtain silver aluminosilicate as granules of 8 to 16 meshes.

Table 1 shows the measurement results of the three-component composition ratio and specific surface area of the granular materials obtained in Synthesis Examples 1 to 3.

Table 1 Apex" 1: Two Example 1 20g of dried leaves of 0-Zumary were crushed with a cutter, placed in a Soxhlet extraction container, 180g of water was added, heat extraction was performed for 15 hours, and this extract was extracted with a 10% rose Marie extract.

10 for 100g of aluminosilicate obtained in Synthesis Example 1
% rosemary extract and dried at 80°C.

The obtained cake was sieved through an 8 to 16 mesh sieve to obtain a deodorant composition.

Example 2 20 g of whole thyme plants were crushed, 180 g of water was added to a Soxhlet oil extraction container, and hot water extraction was carried out for 13 hours to obtain an extract. Thereafter, the same treatment as in Example 1 was carried out to obtain a deodorant composition.

Example 3 10 g of dried sage leaves were crushed, placed in a Soxhlet extraction vessel, added with 190 g of 50% ethanol, and subjected to heat extraction for 15 hours to obtain a 5% sage extract. Synthesis example 2
100 g of the obtained aluminosilicate was impregnated with 10 g of 50% sage extract obtained by concentrating with an evaporator.
Dry at 10°C. The obtained cake was sieved through an 8 to 16 mesh sieve to obtain a deodorant composition.

Example 4 The 10% rosemary extract obtained in Example 1 was sprayed onto 100 g of the aminosilicate obtained in Synthesis Example 3 to obtain a powder deodorant composition.

Example 5 The 10% rosemary extract obtained in Example 1 was sprayed onto activated carbon (Diasolve (G-6-10) manufactured by Mitsubishi Kasei ■) to obtain a powder deodorant composition.

Example 6 The sage extract obtained in Example 3 was sprayed onto spherical silica to obtain a deodorant composition.

Example 7 30 g of pine needles were crushed, placed in a Soxhlet extraction vessel, 150 g of acetone was added, and heat extraction was performed for 10 hours to obtain an extract. Thereafter, the same treatment as in Example 1 was carried out to obtain a deodorant composition.

1 to 7) The deodorizing effects of the deodorant compositions of Examples 1 to 7 and comparative samples described above were evaluated using the following evaluation method (Method A),
The results are shown in Table-2.

[Evaluation method of deodorizing effect (Method A)]

Meat, vegetables, fish, etc. were placed in a 6Q desiccator and left for two weeks to create an artificial garbage odor.

A sample was prepared by wrapping 5 g of the deodorant composition in a nonwoven fabric and placing it in a 1.8-inch wide-mouth bottle.

Furthermore, 10 mQ of headspace gas with an artificial garbage odor was put into a wide-mouthed bottle from a 612 desiccator, and the odor intensity over time was sensory evaluated using the following criteria.

Vaginal knee 1 (-one grain base) Oodorless 1 Very faint odor 2 Slight odor 3 Easily felt odor 4
Strong odor 5 The evaluation was done by a panel of 5 people, and the top and bottom two were cut out.
The average of the names was rounded off.

A deodorant composition was prepared by mixing the aluminosilicate obtained by the methods of Synthesis Examples 1 to 3 and activated carbon (Diasorb G-6-10) manufactured by Mitsubishi Kasei ■ with the various disinfectants shown in Table 3. was prepared.

These were evaluated according to the following evaluation method (Method B), and the evaluation results are shown in Table 3 along with comparative examples.

[Evaluation method of deodorizing effect (Method B)]

Meat, vegetables, fish, etc. were placed in a 6Q desiccator and left for one week to create artificial garbage.

30 g of the prepared garbage was placed in a 1.8 Q wide-mouthed bottle, 10 g of the deodorant composition was sprinkled thereon, and the odor intensity over time was sensory evaluated using the following criteria.

Criteria Odorless Very faint odor Faint odor Easily felt odor Strong odor
The average of the names was rounded off.

(Left below) For 100 g of aluminosilicate obtained in Synthesis Example 1,
0.2% of 2-(4-thiazolyl)benzimidazole
It was impregnated with 50 g of ethyl alcohol solution and dried at 80° C. for 1 hour to obtain a powder deodorant composition.

Loss of Salmon U Activated carbon (manufactured by Mitsubishi Kasei ■, Diasolp G-6-10) 5
10 g of a 30% aqueous solution of benzalkonium chloride was sprayed onto 0 g to obtain a powder deodorant composition.

The deodorizing effects of the deodorant compositions of Examples 16 and 17 were evaluated according to Method B, and the results are shown in Table 4.

(Hereinafter, blank space) 1011 For 100 g of aluminosilicate obtained in Synthesis Example 3, 0
-10% ethyl alcohol solution of phenylphenol 3
0 g was impregnated and dried at 80° C. for 30 minutes to obtain a powdery deodorant composition.

This deodorant composition was sprinkled on a plastic garbage bucket containing food waste and a triangular corner.

Odors generated from food waste or leftover food waste have been suppressed.

A total of 19 IU of wastewater was collected into 1.8Q glass bottles.

Drainage A: Cleaning wastewater from a pigpen (87 pigs kept) Drainage B: Septic tank wastewater from a standard home with four family members To this, 10g of the deodorizing composition shown in Table 1-5 was added, and the odor intensity was measured over time. Sensory evaluation was performed.

The evaluation criteria were based on Method B.

The deodorant composition was a powder product obtained by impregnating the aluminosilicate obtained in each synthesis example with an ethanol solution of a disinfectant and drying it at 80°C for 1 hour, and impregnated with 1% disinfectant. I let it happen.

(Left below) 10 g of aluminosilicate obtained by the method of Inuzaki U Moxibustion Biheel Synthesis Examples 1 to 3
to 2.0% of the 10% rosemary extract obtained in Example 1.
0.3 g of fungicide was applied to the sample which was sprayed and dried at 80°C for 3 hours.
g to obtain a deodorant composition.

These were evaluated according to the deodorizing effect evaluation method (Method B), and the evaluation results are shown in Table 6 along with comparative examples.

(Margin below)

Claims (1)

[Scope of Claims] 1. A deodorant composition characterized by containing (a) a porous material, and (b) a plant extract and/or a bactericide. 2. The porous material of the component (a) has the following three component composition ratios expressed as oxides: SiO_2: 5 to 80 mol% MO_n: 5 to 65 mol% Al_2O_3: 1 to 60 mol% (M is A claim that the aluminosilicate is an aluminosilicate having a composition corresponding to at least one metal selected from zinc, copper, silver, cobalt, nickel, iron, titanium, barium, tin, and zirconium, where n represents the valence of the metal. 1. The deodorant composition according to 1. 3. The deodorant composition according to claim 1 or 2, wherein the bactericidal agent as the component (b) is a sublimable substance. 4. The plant extract of component (b) is an extract of a plant selected from red algae, brown algae, gymnosperms, and angiosperms, and the fungicide is p-chloro-m-xylenol, butyl-m The deodorant composition according to claim 1 or 2, which is -cresol, o-phenylphenol or α-bromocinnamic aldehyde.