JP2001070422A - Deodorant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make it possible to simultaneously eliminate acidic malodors and basic malodors and to obtain a deodorization effect even for sulfureous compounds by incorporating a copolymer of the polyalkylene glycol acrylate monomer and methacrylate monomer expressed by specific formulas into a deodorant. SOLUTION: The copolymer of the polyalkylene glycol mono(meth)acrylate monomer expressed by formula I and the (meth)acrylate monomer expressed by formula II and/or the copolymer obtained by neutralizing this copolymer with an alkaline material is incorporated into the deodorant. In the formulas, R1 denotes a hydrogen atom or methyl group; R2 denotes 2-4C alkylene group. In the formulas, R3 denotes a hydrogen atom, 1-5C alkyl group or phenyl group; n denotes 1 to 200; R4 denotes a hydrogen atom or methyl group and X denotes a hydrogen atom, univalent metal atom, bivalent metal atom, ammonium group or organic amine group.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel deodorant, and more particularly to an unpleasant body odor such as sweat odor, armpit odor, bad breath, foot odor, socks, shoes, shoe boxes, air conditioners, toilets, and sewage. ,
Efficiently eliminates foul odors from pets, tobacco, garbage, filth, etc. in homes and cars, and odors emitted from livestock, sewage treatment plants, food processing plants, pulp plants, feed plants, waste cleaning plants, etc. For odorants.

[0002]

2. Description of the Related Art In order to eliminate body odors, odors in homes and vehicles, and odors discharged from factories and the like, it is effective to appropriately select an elimination method according to the components of the odors. Various odor components are known, for example, lower fatty acids such as butyric acid and isovaleric acid, ammonia and amines such as ammonia and methylamine, and sulfur-containing compounds such as hydrogen sulfide and methyl mercaptan. And the like. The main odor components such as sweat odor, armpit odor, foot odor, socks, shoes, and shoe boxes are lower fatty acids, and similarly, the main odor components of pet odor are lower fatty acids. In addition, malodorous components such as tobacco, toilets, sewage, garbage, filth, and garbage are ammonia / amines, lower fatty acids, sulfur-containing compounds, and the like.

[0003] As a method for eliminating these odors, there are sensory deodorizing methods represented by camphor and the like, odor neutralizing action and masking of fragrance, neutralization reaction of acid and base, oxidation reaction, reduction reaction, polymerization reaction. , Condensation reaction, chelation reaction, chemical deodorization method by hydrolysis, silica gel, activated carbon, zeolite,
Physical deodorization method using an adsorption reaction with a porous material such as cyclodextrin, a high boiling solvent, a surfactant, etc., biological oxidation using microorganisms or enzymes, biochemical deodorization using a bactericide, etc., plant extract A deodorizing method using such a method is known.

[0004]

However, in the sensory deodorizing method, the quality of malodor is changed by a fragrance, and since the malodor itself still exists, its deodorizing effect is limited. In addition, a fragrance and a bad smell may be mixed to further promote the bad smell. Since the physical adsorption deodorization method does not directly deodorize, it is difficult to obtain a sufficient effect. In the biochemical deodorization method using a bactericide or the like, the bacteria causing the malodor can be killed, but the malodor cannot be directly deodorized.

[0005] The chemical deodorization method is a very effective method for directly acting on malodorous components and eliminating odor. For example, lower fatty acids such as isovaleric acid can be deodorized by a neutralization reaction with sodium hydroxide or the like, while ammonia and amines can be deodorized by an acid such as hydrochloric acid. However, malodorous components vary depending on the subject, and their components are also complex. For example, bad smells such as tobacco, toilets, sewage, garbage, filth, and garbage are composed of ammonia / amines, lower fatty acids, sulfur-containing compounds, and the like. Even when trying to deodorize both lower fatty acids and ammonia / amines, bases and acids cannot be mixed at the same time, and at present there are few known deodorants that can simultaneously deodorize acidic malodorous components and basic malodorous components. Absent. In addition, even if it is known, the effect is insufficient, and there is a problem in persistence of the effect.

Accordingly, an object of the present invention is to simultaneously deodorize acidic malodors such as lower fatty acids and basic malodors such as ammonia and amines, and furthermore, it is also effective against sulfur-containing compounds such as hydrogen sulfide and mercaptans. An object of the present invention is to provide a deodorant having a deodorizing effect.

[0007]

Means for Solving the Problems The present inventor has proposed a polyalkylene glycol mono (meth) acrylate monomer represented by the following general formula (1) of the following [formula 3] (same as the above [formula 1]). a) and a copolymer (A) of the following [Chemical Formula 4] (same as the above [Chemical Formula 2]) and a (meth) acrylic acid monomer (b) represented by the general formula (2) and / or the copolymer. The object has been attained by providing a deodorant containing a copolymer (B) obtained by neutralizing the union (A) with an alkaline substance.

[0008]

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[0009]

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[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the deodorant of the present invention will be described in detail based on preferred embodiments. The polyalkylene glycol mono (meth) acrylate monomer (a) represented by the general formula (1) used in the present invention.
[Hereinafter referred to as monomer (a)] is obtained by a known method, and includes, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polybutylene glycol mono (meth) acrylate, and these. Examples of the monomer include a monomer in which the polyethylene glycol terminal of the monomer is alkoxylated such as methoxylation, and one or more of these can be used.

The degree of polymerization n of the polyalkylene glycol in the monomer (a) is preferably from 2 to 30, preferably from 4 to 10.
Is particularly preferred.

By using such a monomer (a), even when a (meth) acrylic acid salt is contained in the structural unit of the copolymer, it can be made soluble in a solvent such as water or ethanol.

Examples of the (meth) acrylic acid monomer (b) represented by the general formula (2) used in the present invention (hereinafter referred to as monomer (b)) include acrylic acid, methacrylic acid, And monovalent metal salts, divalent metal salts, ammonium salts and organic amine salts.
More than one species can be used.

In the present invention, in addition to the monomer (a) and the monomer (b), a monomer (c) copolymerizable therewith, for example, a C ₁ -C ₂₀ aliphatic alcohol and (meth) acrylic acid ester, (meth) acrylamide, maleic acid, fumaric acid, vinyl acetate, propenyl, styrene, p- methyl styrene, styrene sulfonic acid, vinyl chloride, and C ₁ -C ₂₀ aliphatic alcohols or C ₂ -C ₄ Or a monoester or diester of maleic acid, fumaric acid, or the like, or a polyalkylene glycol having 2 to 200 added moles of these glycols.

The ratio (weight ratio) of the amount of the monomer (a) to the amount of the monomer (b) used is such that the ratio of monomer (a) / monomer (b) ≧ 1/2 from the viewpoint of solubility in a solvent such as water or ethanol.
9 is preferred, and from the viewpoint of the deodorizing effect, the monomer (a) /
It is preferable that the monomer (b) ≦ 9/1. Further, the ratio of monomer (a) / monomer (b) is particularly preferably 1/1 to 9/1.

By polymerizing the monomer (a), the monomer (b) and, if necessary, the monomer (c),
The copolymer (A) which is an active ingredient of the deodorant of the present invention is obtained. The polymerization method of the copolymer (A) can be performed by solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization, or the like. Examples of the solvent used for the solution polymerization include water, methanol, ethanol, isopropanol, benzene, toluene, xylene, cyclohexane, hexane, ethyl acetate, acetone, MEK and the like. Water, methanol, ethanol, and isopropanol are preferred in terms of the solubility of the monomer and the solubility of the copolymer (A).

In the polymerization of the copolymer (A), a polymerization initiator is used. For example, in an aqueous system, a water-soluble polymerization initiator such as ammonia or an alkali metal persulfate or hydrogen peroxide is used. In the solvent system, polymerization initiators such as peroxides (benzoyl peroxide, lauroyl peroxide, etc.), hydroperoxides (cumene hydroperoxide, etc.) and aliphatic azo compounds (azobisisobutylnitrile) are used. In the polymerization of the copolymer (A), a polymerization accelerator may be used in combination. For example, in an aqueous system, sodium hydrogen sulfite or the like is used, and in a solvent system, an amine compound or the like is used. Water-
When performing solution polymerization using an alcohol mixed solvent, it is appropriately selected from the above-mentioned various polymerization initiators or a combination of the polymerization initiator and the polymerization accelerator. The polymerization temperature is appropriately determined depending on the solvent and the polymerization initiator.

The weight average molecular weight of the copolymer (A) is 50
0 to 1,000,000, further 2000 to 500,000, especially 10,000 to 20
10,000 is preferred.

In the deodorant of the present invention, a copolymer obtained by neutralizing the copolymer (A) with an alkaline substance together with or instead of the copolymer (A). Coalescing (B) is used.

Examples of the alkaline substance used for obtaining the copolymer (B) include, for example, aqueous solutions of sodium hydroxide, calcium hydroxide, potassium hydroxide, ammonia, calcium hydroxide, magnesium hydroxide and the like; And organic amines such as diethanolamine, triethanolamine and diethylenetriamine.

The content of the copolymer (A) and / or the copolymer (B) in the deodorant of the present invention is preferably 0.01 to 100% by weight, more preferably 0.1 to 100% by weight in the deodorant. 1 to
50% by weight.

The deodorant of the present invention may further contain a conventionally known deodorant component. For example, aluminum chloride, aluminum sulfate, aluminum acetate, chlorohydroxyaluminum, propylene glycol composite, aligned inclohydroxyaluminum, aluminum phenylsulfonate, zinc chloride, zinc p-phenolsulfonate, citric acid, boric acid, tannic acid Antiperspirants such as ferric chloride, fungicides such as trichlorohydroxydiphenyl ether (triclosan), benzalkonium chloride, halocarpan, zinc white, etc., as well as perfumes, oils, surfactants, preservatives, sugars and anti-inflammatory agents , A thickener, a pigment, a humectant, and the like can be added in appropriate amounts.

The deodorant of the present invention must have a neutralization degree of 0.1 to 1.1, and more preferably 0.5 to 1.0, in order to exhibit a deodorizing function for acidic malodors such as lower fatty acids. It is preferable that the degree of neutralization is 0 to 0.9, more preferably 0 to 0.5, in order to exhibit a deodorizing function against basic odors such as ammonia and amines. When a malodorous component is present, the degree of neutralization is usually adjusted in the range of 0.1 to 0.9. Here, the degree of neutralization means, in the deodorant of the present invention,
The ratio of the equivalent of the alkaline substance used based on the neutralization equivalent of the alkaline substance to the copolymer (A) [equivalent / equivalent neutralization]. In the deodorant of the present invention, when the copolymer (A) is not neutralized with an alkaline substance, that is, when the copolymer (B) is not contained and only the copolymer (A) is contained, , And the degree of neutralization is 0.

The deodorant of the present invention is not particularly limited in its use form, and is used as a spray, an aerosol, a lotion, a roll-on, a cream, a powder, a stick, etc., and is particularly preferably used as an aerosol spray. Further, the deodorant of the present invention is used for various applications, and is particularly suitably used as a deodorant for shoes and socks.

Here, the deodorizing mechanism of the offensive odor by the deodorant of the present invention will be described. When the monomer (b) is a salt, the salt site exhibits a deodorizing function against acidic malodors such as lower fatty acids. When the monomer (b) is a free acid, the acid moiety exhibits a deodorizing function against basic malodors such as ammonia and amines. The expression of these deodorizing functions is due to a neutralization reaction between the monomer (b) and the malodorous component (a neutralization reaction between a strong acid and a strong base). Therefore, by controlling the degree of neutralization, acidic malodors such as lower fatty acids,
Basic odors such as amines can be eliminated simultaneously. However, the salt site of the monomer (b) is hydrogen sulfide,
Sulfur-containing odor, which is a relatively weak acid such as mercaptans, and the neutralization reaction do not proceed. However, the deodorant of the present invention
It has an excellent deodorizing effect on sulfur-containing malodors such as hydrogen sulfide and mercaptans. This is presumed that the polyalkylene glycol at the ester site of the monomer (a) plays an important role in deodorizing sulfur-containing compounds. For example, polyethylene glycol (PEG), one of the polyalkylene glycols, can make hydrogen bonds due to its ether bond site or provide a large hydrophobic field. Although details are unknown, it is presumed that these effects are effective in the deodorizing effect.

[0026]

EXAMPLES In the following examples, unless otherwise specified.
"Parts" and "%" are "parts by weight" and "% by weight", respectively.
Means

Example 1 A stirrer, a cooling pipe, a thermometer,
300 parts of isopropyl alcohol (hereinafter abbreviated as IPA) was charged into a four-necked flask equipped with a nitrogen gas inlet tube, and heated to a reflux state while introducing nitrogen with stirring. Next, 282 parts of methoxypolyethylene glycol monomethacrylate monomer (average number of moles of ethylene oxide added: 23, manufactured by Shin-Nakamura Chemical Co., trade name “NK Ester M-230G”) was placed in the flask.
A monomer initiator solution composed of 51 parts of methacrylic acid, 190 parts of IPA and 5.0 parts of benzoyl peroxide was dropped by a dropping funnel over 2 hours. After completion of the dropwise addition, a solution composed of 1.67 parts of benzoyl peroxide and 10 parts of IPA was added in two portions every 30 minutes. After completion of the addition, aging was performed for 60 minutes under reflux conditions to obtain an unneutralized product (neutralization degree 0). An aqueous solution of sodium hydroxide was further added thereto to obtain a preparation having a neutralization degree of 0.5. The average molecular weight of the copolymer (measured by GPC under the following conditions, the same in the following Examples and Comparative Examples) was 55,000.

GPC measurement conditions Detector: RI Eluent: Tetrahydrofuran containing 50 mmol acetic acid Column: G4000HXL and G2000HXL manufactured by Toso Corporation

Example 2 The unneutralized product obtained in Example 1 (degree of neutralization 0) was used as Example 2.

Example 3 An aqueous solution of sodium hydroxide was added to the unneutralized product (neutralization degree 0) obtained in Example 1 to obtain a degree of neutralization of 1
The preparation was obtained.

Example 4 As a monomer initiator solution,
Polyethylene glycol monomethacrylate monomer (average number of moles of ethylene oxide added: 7-9, manufactured by NOF Corporation, trade name "Plenmer PE-350") 26
The same operation as in Example 1 was performed except that 5.1 parts, 67.9 parts of acrylic acid, 190 parts of IPA and 5.0 parts of benzoyl peroxide were used, to obtain an unneutralized product (neutralization degree 0). Was. To this, an aqueous calcium hydroxide solution and an aqueous sodium hydroxide solution are further added to prepare a preparation having a neutralization degree of 0.6 (Ca
/ Na ratio = 10/90). The average molecular weight of the copolymer was 35,000.

Example 5 As a monomer initiator solution,
Phenoxy polyethylene glycol monoacrylate monomer (average number of moles of ethylene oxide added:
6. Product name “NK Ester AMP-6” manufactured by Shin-Nakamura Chemical
0G ") 273.6 parts, methacrylic acid 59.4 parts, IP
A non-neutralized product (neutralization degree 0) was obtained by performing the same operation as in Example 1 except that 190 parts of A and 5.0 parts of benzoyl peroxide were used. An aqueous ammonia solution was further added thereto to obtain a regulated product having a neutralization degree of 0.5. The average molecular weight of the copolymer was 70,000.

Example 6 As a monomer initiator solution,
Polypropylene glycol monomethacrylate monomer (average number of moles of propylene oxide added: 5 to 5)
6. Nippon Oil & Fat, trade name "Plenmer PP 100
0 ") 219.7 parts, methacrylic acid 113.3 parts, IP
A non-neutralized product (neutralization degree 0) was obtained by performing the same operation as in Example 1 except that 190 parts of A and 5.0 parts of benzoyl peroxide were used. To this, triethanolamine was further added to obtain a product having a degree of neutralization of 1.05. The average molecular weight of the copolymer was 15,000.

Example 7 As a monomer initiator solution,
Polyethylene glycol / polypropylene glycol monomethacrylate monomer (average number of moles of polyethylene oxide added: 7, average number of moles of propylene oxide added: 3, manufactured by NOF Corporation, trade name "Plenmer 70"
PEP-370B ") 228.6 parts, acrylic acid 10
The same operation as in Example 1 was carried out except that 4.4 parts, 190 parts of IPA and 5.0 parts of benzoyl peroxide were used, to obtain an unneutralized product (degree of neutralization: 0). Diethylenetriamine was further added thereto to obtain a regulated product having a degree of neutralization of 0.5. The average molecular weight of the copolymer was 40,000.

Example 8 The same flask as in Example 1 was charged with 300 parts of methyl alcohol, and heated under reflux with stirring while introducing nitrogen. Then
In this flask, 194 parts of methoxypolyethylene glycol methacrylate monomer (average number of moles of polyethylene oxide added: 9, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester M-90G”), and 139 methacrylic acid
, A monomer initiator solution consisting of 190 parts of methyl alcohol and 5.0 parts of azobisisobutyronitrile was dropped by a dropping funnel over 2 hours. After the addition, 1.67 parts of azobisisobutyronitrile and 10 parts of methyl alcohol 10
The part solution was added in two portions every 30 minutes.
After completion of the addition, aging was performed for 60 minutes under reflux conditions to obtain an unneutralized product (neutralization degree 0). An aqueous solution of sodium hydroxide and diethanolamine were further added thereto to obtain a preparation having a degree of neutralization of 0.7 (Na / diethanolamine ratio = 50/50). The average molecular weight of the copolymer was 500000.

Example 9 The same flask as in Example 1 was charged with 237 parts of water, and heated to 90 ° C. while introducing nitrogen while stirring. Next, methoxypolyethylene glycol acrylate monomer (average number of moles of polyethylene oxide added: 9, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester AM-90G”) 2 was placed in the flask.
A monomer solution consisting of 43.9 parts, 89.1 parts of acrylic acid and 127 parts of water, and a 5% aqueous solution of ammonium persulfate 10
And 0 parts were dropped with a dropping funnel over 2 hours.
After dropping, 33 parts of a 5% aqueous ammonium persulfate solution was added to 2 parts.
Added over 0 minutes. After completion of the addition, aging was performed for 100 minutes to obtain an unneutralized product (neutralization degree 0). Ethanolamine was further added thereto to obtain a preparation having a neutralization degree of 0.4.
The average molecular weight of the copolymer was 13,000.

Example 10 The same flask as in Example 1 was charged with 70 parts of water and 70 parts of IPA, and heated to 90 ° C. while introducing nitrogen while stirring. Next, methoxypolyethylene glycol methacrylate ester monomer (average number of moles of polyethylene oxide added: 4, manufactured by Shin-Nakamura Chemical Co., Ltd., trade name “NK Ester M”) was placed in the flask.
-40G "), a monomer solution consisting of 191 parts, 136.8 parts of methacrylic acid, 100 parts of water and 100 parts of IPA;
A monomer solution composed of 5.3 parts of acrylamide, 50 parts of water and 50 parts of IPA, and 50 parts of a 10% aqueous solution of ammonium persulfate were respectively dropped by a dropping funnel over 2 hours. After dropping, 10% aqueous ammonium persulfate solution 1
6.7 parts were added over 20 minutes. After the addition, 100
After aging for 5 minutes, an unneutralized product (neutralization degree 0) was obtained. To this, an aqueous solution of potassium hydroxide was further added to give a neutralization degree of 0.1.
5 preparations were obtained. The average molecular weight of the copolymer was 82,000.

With respect to the deodorants of Examples 1 to 10, the deodorizing effect was evaluated by the following method.

Deodorizing Evaluation Method 100 μl of the malodorous component (described in Table 1) diluted to each concentration was permeated into a filter paper spread on a disposable dish. There,
1 m sample prepared in 1% aqueous solution of the deodorant of each example
Insert l. About 3 hours later, five panelists conducted a sensory evaluation based on the following criteria, and the average value was rounded off. Table 2 shows the evaluation results. (Sensory evaluation criteria) 5: Very strong smell. 4: Strong smell 3: Smell clearly. 2: Smell is weak. 1; smells faintly. 0; does not smell.

[0040]

[Table 1]

[0041]

[Table 2]

[Use example] 1.0% by weight of the deodorant of Example 1
And an ethanol solution consisting of 0.1% by weight of a bactericide (isopropylmethylphenol) and LPG (3.5 kg / c)
m ² ) at a ratio of 50:50 (weight ratio) into an aerosol container by cooling to prepare a deodorant spray for shoes and socks. The shoes (No. 1 to 10) of 10 foot odor panelists are sprayed for 5 seconds using the deodorant spray for shoes and socks, and the odor of the shoes before spraying and 1 hour after spraying is measured by a specialized panel 5 The sensory evaluation was performed by a person according to the following criteria, and the average value was rounded off. Table 3 shows the evaluation results. (Sensory evaluation criteria) 5: Very strong smell. 4: Strong smell 3: Smell clearly. 2: Smell is weak. 1; smells faintly. 0; does not smell.

[0043]

[Table 3]

As a result of the evaluation, as apparent from Table 3, a clear difference was observed before and after using the deodorizing spray for shoes and socks, and it was confirmed that the deodorant of the present invention had an excellent deodorizing effect. Was.

[0045]

The deodorant of the present invention has a deodorant effect excellent in general versatility not found in conventional deodorants, that is,
It can simultaneously deodorize acidic malodors such as lower fatty acids and basic malodors such as ammonia and amines, and has a deodorizing effect on sulfur-containing compounds such as hydrogen sulfide and mercaptans.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C080 AA06 BB02 BB04 CC02 CC03 CC04 CC05 CC08 CC09 CC12 CC13 CC14 CC15 HH02 HH03 HH04 HH05 JJ01 KK06 KK08 LL03 MM26 QQ03 4C083 AC092 AD091 DD08 DD11 DD17 DD31 EE18

Claims (1)

[Claims] 1. A polyalkylene glycol mono (meth) acrylate monomer (a) represented by the following general formula (1) represented by the following general formula (1) and a polyalkylene glycol mono (meth) acrylate monomer represented by the following general formula (2): A deodorant containing a copolymer (A) with a (meth) acrylic acid monomer (b) and / or a copolymer (B) obtained by neutralizing the copolymer (A) with an alkaline substance. Embedded image Embedded image