JP2001353208A - Deodorant - Google Patents

Abstract

(57) [Summary] [Problem] It is possible to easily and quickly deodorize unpleasant odors generated from sludge, manure, etc. by simply foaming and covering the odor generation source, and for a long time. To provide a deodorant that lasts long. SOLUTION: The deodorant is characterized by containing a polymer compound such as a cationic polyamine compound, an amphoteric surfactant and water, and further containing a polybasic acid compound or a fluorine surfactant as required. Agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel and useful deodorant. Specifically, it relates to a specific deodorant composed of a water-soluble polymer compound, an amphoteric surfactant and water, and emits an unpleasant odor emitted during treatment of sludge, manure, etc., exclusively at the time of treatment, The present invention relates to a deodorant that can be easily and quickly deodorized.

[0002]

2. Description of the Related Art In general, as foul odors and odors, smoke and waste liquid from factories, cigarettes and manure, kitchen garbage and the like are sources, and the types of odors and odors are various. Substances that cause these odors include amines such as trimethylamine, which is a putrefactive smell of fish and meat; hydrogen sulfide, which is a putrefactive smell of eggs and milk; mercaptans, such as methyl mercaptan, which is a putrid smell of vegetables and garbage; Organic acids such as odor of ammonia, tobacco odor, and butyric acid, which is a odor of sweat and body odor, and the like.

[0003] Of these, the simple toilets used in homes with children and elderly people, hospitals, nursing homes, and the like are particularly problematic. Since such a simplified toilet does not have a facility for treating waste such as a stool unlike a flush toilet, it is necessary to manually discard the waste every time it is used.

However, for example, in a hospital or the like,
Because of the small number of nurses, it is often not possible to discard filth every time it is used, and the filth may be left in the toilet for several hours or even a day. In such a state, a bad smell drifts in the room where the toilet is left, and the state becomes unpleasant.

[0005] Once an odor / offensive odor is diffused into the air from its source, the sensory threshold concentration of the odorous substance at the source is very low. Large amounts of energy and deodorants are required. Therefore, in order to achieve an effective deodorizing effect, it is important to control the off-flavor from the source and to exert the deodorizing effect of the deodorizing component.

Heretofore, physical and chemical methods have been adopted as methods for eliminating such malodors and off-flavors. Physical methods include a washing method, a cooling method, and an adsorption method. However, the water washing method and the cooling method require a large amount of water and a large-scale apparatus, and thus cannot be said to be general methods. The adsorption method of adsorbing and deodorizing a malodorous or off-flavor component by using the adsorbing power of activated carbon or the like has a drawback that the malodorous or off-flavor component is reversely released from the activated carbon or the like after the adsorption of the malodor or off-flavor component.

As a chemical method, there are a combustion method, a chemical treatment method, and a masking method. However, the combustion method is not general because it requires a large-scale apparatus and increases running costs. In the chemical treatment method, the odor is deodorized by acid-alkali washing or the like. However, the target malodorous component is limited, and the handling of the used chemicals requires attention, and a large-scale apparatus is required. The masking method is a method that is mainly used in ordinary households, and deodorizes by masking offensive odors and unpleasant odors by the odor of the deodorant itself. However, in this case, it is hard to say that this is a general method because there is a preference of a person for the scent possessed by the deodorant itself, and some scents have an aversion.

By the way, effervescent deodorants containing carbonates, surfactants and the like are already known.
-288267, JP-A-2-147061, JP-A-4-30855, JP-A-5-50056, JP-A-6
-105893, JP-A-7-8546, JP-A-7-
278598, and JP-A-10-54068.

However, these foaming deodorants are:
Basically, a spray of the deodorant composition is sprayed onto the surface of the offensive odor source, foamed and covered with a foam-like protective film, which blocks odors from the outside air and neutralizes odors with a deodorant etc. In Although,
The foaming and swelling action during treatment is weak, and the deodorant does not penetrate and contact the details of the odorous substances, it cannot be said that it is a method to fundamentally eliminate the odor source, and it is difficult to maintain the foam for a long time. There is a problem that the sustainability of the deodorant effect is poor.

[0010]

The present deodorant provides an effect of easily and quickly deodorizing unpleasant odors emitted during the treatment of sludge, manure, etc., and maintains the effect for a long time. It is intended to provide a deodorant that can be used.

[0011]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies while paying attention to the above problems, and as a result, sprayed an aqueous solution containing a water-soluble polymer compound, an amphoteric surfactant and water. The present invention was found to exhibit an even more excellent deodorizing effect as compared with the prior art by foaming and covering the odor generation source, and completed the present invention.

That is, [I] The present invention provides a deodorant comprising a water-soluble polymer compound (A), an amphoteric surfactant (B) and water.

[II] The present invention provides the deodorant according to the above [I] containing the polybasic acid compound (C),

[III] The present invention also provides a deodorant according to the above [I] or [II] containing a fluorine-containing surfactant (D),

[IV] The present invention provides the deodorant according to any one of the above [I] to [III], wherein the water-soluble polymer compound (A) is a cationic polyamine polymer compound. To do

[V] The present invention relates to a polybasic acid compound (C)
Is a dibasic acid compound having 4 to 18 carbon atoms, wherein the deodorant according to any one of the above [I] to [IV] is provided,

[VI] The present invention provides the deodorant according to any one of the above [I] to [V], wherein the fluorine-containing surfactant (D) contains an anionic hydrophilic group. Things,

[VII] The present invention provides the deodorant according to any one of the above [I] to [VI], wherein the water-soluble polymer compound (A) is polyethyleneimine or a derivative thereof.

[VIII] The present invention provides any one of the above [I] to [VII], wherein the fluorosurfactant (D) has a fluorinated aliphatic group having 3 to 20 carbon atoms as a hydrophobic group. Or to provide the deodorant described,

[IX] The above-mentioned [I] to [V], wherein the amphoteric surfactant (B) is an alkylamidopropylbetaine and / or an alkyldimethylaminoacetate betaine.
III].

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION The water-soluble polymer compound (A) used in the present invention is an amphoteric surfactant (B) described later.
Long-term stabilization of foam foamed by ionic interaction with
In other words, it is an essential component in suppressing defoaming at the time of contact with the odor source.

Particularly typical examples of the water-soluble polymer compound (A) include cellulose derivatives such as methylcellulose and hydroxyethylcellulose, starch and denatured starch, proteins such as glue and egg protein, and gum arabic. Gums, or polyethylene glycol, polyvinyl alcohol, polyamine, acrylic,
Various water-soluble synthetic polymers, such as urethane and polyester, may be used alone or in combination of two or more.

Among them, polyethyleneimine is representative in terms of foam stabilization and interaction with an amphoteric surfactant (B), a polybasic acid compound (C), a fluorine-based surfactant (D) and the like, which will be described later. It is preferable to use a cationic polyamine polymer compound.

The cationic polyamine polymer refers to a polymer containing a cationic group such as an amino group, an ammonium group, a pyridinium group or a quaternary ammonium group, and usually has a solubility in water of 0.1% by weight. % Or more. The above cationic group is
There are primary, secondary and tertiary types, and these cationic groups may be present in the main chain or side chain of the polyamine polymer compound.

The quantitative ratio of primary, secondary and tertiary cationic groups is not particularly limited, but is not limited to cationic polyamines in which the primary cationic groups are 40% by weight or less with respect to the total cationic groups. A polymer compound is preferred, and a cationic compound in which a primary cationic group accounts for 40% by weight or less based on the entire cationic group and a secondary cationic group accounts for 35% by weight or more based on the entire cationic group. Polyamine polymer compounds are particularly preferred.

The degree of polymerization of the water-soluble polymer compound is regulated by the solubility in water, but the degree of polymerization is tens of thousands or more from the oligomer region, that is, the molecular weight is 1,000 to 1,1 in terms of number average molecular weight.
It is preferably about 1,000,000, more preferably 4,000 to 300,000, and particularly preferably 5,000 to 50,000 in terms of the degree of polymerization for exhibiting the deodorant effect.

The following are specific examples of the cationic polyamine polymer compound, but the present invention is not limited by these specific examples.

A-I Polyethyleneimine A-II N-substituted product As polyethyleneimine N-substituted product, for example, -C_nH_{2n + 1}, -CONHC_nH
_{2n + 1 ,}-COC_nH_{2n + 1 ,} Or-(CH_TwoCH_TwoO)_n-H (where n is 1 to 6
Represents an integer. ).

[0029]

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AX Melamine-formaldehyde condensate A-IX Guanidine-formaldehyde condensate The method for producing the cationic polyamine-based polymer compound is not particularly limited. For example, the method for producing polyethyleneimine in the presence of a catalyst There is a method of synthesizing ethyleneimine by directly dehydrating and opening monoethanolamine in a gas phase. Polyethyleneimine is synthesized by subjecting the ethyleneimine produced by this method to ring-opening polymerization in the presence of an acid catalyst.

The polyethyleneimine produced by this method is not obtained as a completely linear polymer due to the reaction kinetics, and has a high branched structure containing primary, secondary and tertiary amines as shown by the following formula. A molecular compound is obtained.

As the catalyst, an organic metal catalyst, an organic catalyst,
Any of inorganic catalysts and the like can be used, but a compound having a different branched structure depending on the catalyst used and naturally having a different ratio of primary, secondary and tertiary amines in the molecule can be obtained.

[0033]

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The deodorant according to the present invention is characterized in that an amphoteric surfactant (B) is added from the viewpoint of stabilizing foam by interaction with the water-soluble polymer compound (A). As the amphoteric surfactant (B) used in the present invention, any known and commonly used compounds can be used, and of course, the compounds may be used alone or in combination of two or more. It is.

Specific examples of the amphoteric surfactant (B) include:
Amphoteric hydrocarbon surfactants such as alkyldimethylaminoacetate betaine, alkyldimethylamine oxide, alkylcarboxymethylhydroxyethylimidazolium betaine, alkylamidopropylbetaine, alkylhydroxysulfobetaine, amphoteric fluorine surfactant, silicone surfactant Agents and the like, but the present invention is not limited to these specific examples at all.

Above all, in consideration of foam stabilization due to interaction with essential components of a water-soluble polymer compound (A), a polybasic acid compound (C) described later, and a fluorine-based surfactant (D), Alkylamidopropyl betaine and betaine alkyldimethylaminoacetate are particularly preferred.

The deodorant according to the present invention preferably further comprises a polybasic acid compound (C). The polybasic acid compound (C) of the present invention is a non-surface active compound, for example, a dibasic acid, a tribasic acid, or a tetrabasic acid having 3 to 24 carbon atoms having an aromatic group, an aliphatic group, a heterocyclic ring and the like. And pentabasic acids, hexabasic acids and the like, and their alkali metal salts and ammonium salts. The acid groups include carboxylic acid groups, sulfonic acid groups and phosphoric acid groups.

Further, these polybasic acid compounds (C) may be used alone or in combination of two or more. By adding the polybasic acid compound (C), a pseudo-crosslinked structure is formed by electrostatic interaction with the water-soluble cationic polymer compound, and the effect of prolonging the stability of the foam on the water-soluble liquid is obtained. Having

The polybasic acid compound (C) is not particularly limited as long as it has a compound having an acid group in the molecule, and there is no limitation on the kind and number of the acid group, the length of the carbon chain, the molecular weight and the like. Absent.

Among these, the polybasic acid compound (C)
May have 4 to 18 carbon atoms in terms of compatibility with other compounds.
It is desirable to use the dibasic acid compound.

Specific examples of the polybasic acid compound (C) according to the present invention include those represented by the following formulas (C-1 to 32), but the present invention is not limited by these specific examples. Not something.

[0042]

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[0043]

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[0044]

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The compounds represented by the above formulas (C-1 to 32) and their alkali metal salts (Na salt, K salt, Li salt and the like) or ammonium salts are exemplified.

Further, the deodorant according to the present invention is a fluorine-based surfactant (D) which is more excellent in surface tension lowering ability than other surfactants in terms of permeation of a foaming liquid into an odor source and improvement of a contact area. Is preferably added. As the fluorine-based surfactant (D), any known and used compounds, that is, nonionic fluorine-based surfactants represented by ethylene oxide adducts containing a perfluoroalkyl group, and the like,
Carboxylic acid, anionic type fluorinated surfactant having a terminal group of sulfonic acid, cationic type fluorinated surfactant represented by tetramethylammonium salt, or urethane skeleton, acrylic skeleton, polyester skeleton, etc. A polymeric fluorine-based surfactant in which a part or the whole of the main chain or side chain is substituted with a fluoroalkyl group can be used.

Among them, the fluorine-based surfactant (D) used in the present invention can form an electrostatic interaction with the water-soluble polymer compound (A) described above,
A compound having at least one anionic hydrophilic group of the surfactant is particularly preferable for the purpose of exhibiting not only the surface tension lowering ability of the foaming liquid but also the foam stability.

As the anionic hydrophilic group, -COOH,
Groups such as —SO ₃ H, —OSO ₃ H, and —OP (OH) ₂ are preferable, and —SO ₃ H is particularly preferable. The counter ion of the cationic group may have an organic or inorganic anionic group.

The surfactant may contain one or more anionic groups of the same or different kind as the hydrophilic group, and in addition to the anionic hydrophilic group, one or both of a cationic hydrophilic group and a nonionic group. It may be a zwitterionic surfactant containing both. Of these, zwitterionic surfactants are preferred in terms of compatibility.

The hydrophobic group of the surfactant has 3 carbon atoms.
Compounds having a fluorinated aliphatic group of from 20 to 20, preferably from 6 to 16, have the most excellent surface tension lowering ability and are particularly preferred in that they have a good penetration into malodorous substances. The surfactant may be a mixture of a surfactant having an anionic hydrophilic group and a compound having these hydrophobic groups.

As the fluorine-based surfactant (D) used in the present invention, any known and publicly-known compounds can be used. In the use thereof, a single compound or a combination of two or more compounds may be used. Needless to say, specific examples of the fluorine surfactant (D) particularly useful in the present invention include those listed in the following formulas (D-1) to (D-10).

(D-1) Fluorinated amino acid type amphoteric surfactant The following general formula (D-1)

[0053]

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Wherein Rf is a fluorinated aliphatic group having 3 to 20 carbon atoms, Y is —SO ₂ — or —CO—, and Q ₁ and Q ₂ are organic divalent linking groups. , is a combination of aliphatic hydrocarbon group, an aliphatic hydrocarbon group substituted by a hydroxy group, an aromatic hydrocarbon group, a substituted aromatic hydrocarbon group, or which such, preferably - (CH _2)
-J (j is an integer of 1 to 6),

[0055]

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(R ₂ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms), and R _{1 and} R ₂ are _a hydrogen atom or a C _{1 to} C 1
An aliphatic hydrocarbon group substituted with an aliphatic hydrocarbon group or a hydrophilic group, or R ₁ and R ₂ are connected to each other to form a ring together with an adjacent nitrogen atom;
Is an anionic hydrophilic group, for example, -COO ^- ,-
^{_{SO 3 -, -OSO 3 -,}} -OP (OH) O - and is, M
Is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic cationic group. ] The fluorine-containing amino acid type amphoteric surfactant represented by these.

The following compounds are exemplified as these specific compounds, but the present invention is not limited by these specific examples.

[0058]

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[0059]

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(D-2) Fluorinated aminosulfonate type surfactant The following general formula (D-2) Rf-ZQ ₁ -N (R) -Q ₂ -SO ₂ M ------ (D -2) [wherein, Rf is selected from the group consisting group containing a number from 3 to 20 fluorinated aliphatic group having a carbon, Z is a divalent linking _{group, -SO 2 N (R 1)} -, -
_{CON (R 1) -, -} (CH 2 CH 2) iSO 2 N (R 1)
−,

[0061]

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Or

[0063]

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(Where R ₁ is a hydrogen atom or a carbon atom
12 represents an alkyl group, i represents an integer of 1 to 10), Q _{1
Is, - (CH 2) j -} (j represents an integer of 1-6) or

[0065]

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(However, R ₂ is a hydrogen atom or carbon atom 2-3)
Represents an alkyl group). R is a hydrogen atom, carbon number 1-3
An alkyl group or a hydroxyalkyl group of —Q ₂ S
O ₃ M or — (CH ₂ ) _k COOM (where k is 1 to
4), Q ₂ is — (CH ₂ ) _l − (l is 1 to 4
Represents an integer),

[0067]

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(R ₃ is a hydrogen atom or an alkyl group having 2 to 3 carbon atoms) or

[0069]

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M is a cationic atom or atomic group, and is a hydrogen atom, an alkali metal, an alkaline earth metal, or —N (H) m (R ₄ ) n (where R ₄ is a group having 1 to 3 carbon atoms). An alkyl group or a hydroxyalkyl group;
An integer of 4 represents m + n = 4). ] A fluorine-containing aminosulfonate surfactant represented by the formula:

Examples of these specific compounds include those of the following formulas (D-2-a to p), but the present invention is not limited by these specific examples.

[0072]

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(D-3) Fluorinated aminocarboxylate type surfactant The following general formula (D-3)

[0074]

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Wherein Rf is a polyfluoroalkyl group having 3 to 20 carbon atoms, which may contain an oxygen atom;
Z is a polyfluoroalkenyl group, a polyfluorocyclohexyl group, a polyfluorocyclohexylalkyl group, a polyfluorocyclohexylalkenyl group,

[0076]

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Wherein R ₁ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group or a monovalent group containing an aromatic ring;
Or _{- (CH 2 CH 2) j} -R 2, i is assumed to be an integer comprised from 1 to 3. (However, R ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and j represents an integer of 1 to 6)].

Q is

[0079]

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Wherein l is an integer of 1 to 6, m and n are each an integer of 2 to 6, and p and q are each 2 or 3. ] Is a divalent linking group,

Q ₁ and Q ₂ each represent-(CH ₂ ) _r-
Or - (CH _{2) s} -

[However, r and s are integers of 1 to 3. And M ₁ and M ₂ each represent a hydrogen atom or an inorganic or organic cation. ]

A fluorine-containing aminocarboxylate type surfactant represented by the formula:

Specific examples of these compounds include those of the following formulas (D-3-a to k), but the present invention is not limited by these specific examples.

[0085]

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(D-4) Fluorine-containing trianionic amphoteric surfactant The following general formula (D-4)

[0087]

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[Wherein, Rf is a fluorinated aliphatic group having 3 to 20 carbon atoms, Z is a divalent linking group, and Q is-(C
H ₂ ) _l- (where l is an integer of 1 to 6),

[0089]

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[0090] _{- (CH 2) m -O- (} CH 2) n - ( where, m, n is an integer from 2 to 6.), Or _{- (CH 2) p -O- (} CH 2) 2 —O— (CH ₂ ) _q − (where p and q are 2 or 3),

Q ₁ , Q ₂ and Q ₃ are a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms, a divalent aliphatic hydrocarbon group having 1 to 8 carbon atoms substituted by a hydroxyl group, or

[0092]

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(R represents 1 or 2), A ₁ is an anionic group, —SO ₃ ⁻ , —OSO ₃ ^— , and A ₂
And A ₃ are also anionic groups, —SO ₃ ⁻ , —OSO
₃ ^-, -COO ^- or

[0094]

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Wherein M ₁ , M ₂ and M ₃ are a hydrogen atom or an inorganic or organic cation, X ⁻ is an inorganic or organic anion, and OH ⁻ , Cl ⁻ , Br ⁻ ,
^{_{I -, ClO 4 -, 1}} / 2SO 4 2-, CH 2 SO 4 -, NO 3 -, C
H ₃ COO 2 ^- or a phosphate group is preferred. ] A fluorine-containing trianionic amphoteric surfactant represented by the formula:

Specific examples of these compounds include those of the following formulas (D-4-a to p), but the present invention is not limited by these specific examples.

[0097]

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[0098]

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(D-5) Fluorine-containing tricarboxylic acid type amphoteric surfactant The following general formula

[0100]

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[In the formula, Rf is a fluorinated aliphatic group having 3 to 20 carbon atoms, and Z is -SO _2- , -CO-,-(C
_{H 2) l -SO 2 -,} - (CH 2) l -CO- ( where, l is an integer of 1 to 6).

[0102]

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Or

[0104]

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Wherein R ₁ is a hydrogen atom, —CH ₂ CH ₂ O
_{H, - (CH 2) a} -O- (CH 2) b -CH 3 ( where, a
Is an integer of 2 to 10, b is an integer of 1 to 9),
Or an alkyl group having 1 to 12 carbon atoms, and Q ₁ is-
(CH ₂ ) _n- (where n is an integer of 2 to 6),-
_{(CH 2) d -O- (CH} 2) e - ( where, d and e 2
6 to an integer. ), Or

[0106]

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Wherein X is an inorganic or organic anion, m ₁ , m ₂ , and m ₃ are integers of 1 to 3, and two of them may be the same, and M ₁ , M ₂ and M
₃ is a hydrogen atom or an inorganic or organic cation, two or all of which may be the same. ] The fluorinated tricarboxylic acid type amphoteric surfactant represented by the formula:

Examples of these specific compounds include those of the following formula (D-5-am), but the present invention is not limited by these specific examples.

[0109]

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[0110]

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(D-6) Fluorine-containing sulfobetaine type amphoteric surfactant The following general formula (D-6)

[0112]

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[In the formula, Rf is a group containing a fluorinated aliphatic group having 3 to 20 carbon atoms, Z is a divalent linking group containing a sulfamide group or a carboxamide group, and Q ₁ , Q ₂ and Q ₃ is a divalent aliphatic group having 1 to 12 carbon atoms, an aliphatic hydrocarbon group substituted with a hydroxy group, an aromatic hydrocarbon group or a combination thereof, and R is a hydrogen atom, 1 to 12 hydrocarbyl groups, or-
_{(CH 2 CH 2 O) iH} , - (CH 2 CH (CH 3) O) iH
(Where i represents an integer of 1 to 20), and A is
In anionic atomic ^{_{group, -SO 2 -, -COO -,}} -OSO 2
^- or

[0114]

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M ₁ and M ₂ are a hydrogen atom or an inorganic or organic cation, and X is an inorganic or organic anion. ] The fluorine-containing sulfobetaine type amphoteric surfactant represented by these.

The following are examples of the specific compounds, but the present invention is not limited to these specific examples.

[0117]

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(D-7) Fluorinated aminosulfate type surfactant The following general formula (D-7)

[0119]

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Wherein Rf is a fluorinated aliphatic group having 3 to 20 carbon atoms, Z is —SO ₂ —, —CO—,

[0121]

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Or-(CH ₂ ) _a -CO- (where a represents an integer of 1 to 10) R ₁ is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms,-(C
H ₂ ) _b —OR ₃ or — (CH ₂ CH ₂ O) _d —R ₂ (where b is an integer of 1 to 10, d is an integer of 1 to 20, R ₃ is a lower alkyl group or an alkoxyl group Represents.)

Y is-(CH ₂ ) _e -,-(CH ₂ ) _p -O
— (CH ₂ ) ₂ —O— (CH ₂ ) _q — or — (CH ₂ ) _g
-O- (CH _{2) h} (where, e is an integer from 2 to 12, p, q
Represents 2 or 3, g and h represent an integer of 1 to 6. ). R
₂ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an alkenyl group or a hydroxyl-substituted alkyl group,-(CH
₂ CH _{2) m} -H (where, m is an integer of _{2~20.), Q 1 OSO 3} M, Q 1 SO 2 M or (CH ₂₎ ICO
OM (where, i is an integer of 1 to 4.) Q is - (CH _{2) j} -,

[0124]

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Or — (CH ₂ CH ₂ O) _k —CH ₂ CH ₂
-, (Where j represents an integer of 2 to 12, and k represents an integer of 1 to 50)

M represents a hydrogen atom or an inorganic or organic cation].

Specific examples of these compounds include those represented by the following formulas (D-7-a to k), but the present invention is not limited by these specific examples.

[0128]

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(D-8) Fluorine-containing sulfatobetaine type surfactant The following general formula (D-8)

[0130]

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Wherein Rf is a fluorinated aliphatic group having 3 to 20 carbon atoms, Z is —SO ₂ —, —CO—,

[0132]

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Or-(CH ₂ ) _a --CO-- (where a represents an integer of 1 to 10), and R ₁ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms,-(CH ₂ ) _b -OR _3, or _{- (CH 2 CH 2 O)} d -R 2 ( where, b is an integer of from 1 to 10, d is an integer of 1 to 20, R ₂ represents a lower alkyl group or alkoxyl group.) Y represents-(CH
_{2) e -, - (CH} 2) p -O- (CH 2) 2 -O- (C
H _{2) q} -, _{or, - (CH 2) g -O-} (CH 2) h ( where, e is an integer from 2 to 12, p, q is 2 or 3, g,
h represents an integer of 1 to 6. )

R _{2 and} R ₃ are an alkyl group having 1 to 18 carbon atoms, an alkenyl group, a hydroxyl-substituted alkyl group, or an aromatic-substituted alkyl group,-(CH ₂ CH ₂ O) i-H
(Where, i is an integer of 2 to 20.) With the nitrogen atom to which or R ₂ and R ₃ are adjacent link together, Q ₁ is - (C
H ₂ ) _j −,

[0135]

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Or — (CH ₂ CH ₂ O) _k —CH ₂ CH ₂
-, Wherein j represents an integer of 2 to 12, and k represents an integer of 1 to 50. ] The fluorine-containing sulfatobetaine type surfactant represented by these.

Specific examples of these compounds include those of the following formula (D-8-a to i), but the present invention is not limited to these specific examples.

[0138]

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(D-9) Fluorine-containing sulfobetaine type surfactant The following general formula (D-9)

[0140]

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Wherein Rf represents a fluorinated aliphatic group having 3 to 20 carbon atoms which may contain an oxygen atom, a fluorinated alicyclic group, and Z represents a divalent linking group.

Q ₁ represents-(CH ₂ ) _l -,-(CH ₂ ) _m-
O- (CH _{2) n} - or _{- (CH 2) p -O- (} CH 2) 2 -
O- (CH _{2) q} - (where, l is an integer comprised from 1 to 6,
m and n are each an integer of 2 to 6, and p and q are each 2 or 3. ) And comprising divalent linking group, Q ₂ is - (CH _{2) l} -,

[0143]

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Or — (CH ₂ CH ₂ O) _r —CH ₂ CH ₂
-(Where r is an integer of 1 to 3 and l is as described above), and a divalent linking group represented by R ₁ and R ₂
Is an alkyl group having 1 to 8 carbon atoms, an alkyl group or alkenyl group containing 1 to 3 ether oxygens,
Or a benzyl group, or — (CH ₂ CH ₂ O) _s —H
(However, s is an integer of 1 to 11). ] The fluorine-containing sulfobetaine type surfactant represented by these.

Specific examples of these compounds include those represented by the following formula (D-9-a to o), but the present invention is not limited by these specific examples.

[0146]

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[0147]

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M, M ₁ , M ₂ , and M _{3 of} D-1 to D-9 described above.
Represents a hydrogen atom or an inorganic or organic cation, for example, Li ⁺ , Na ⁺ , K ⁺ , Ca ⁺ , Mg ⁺ , [N
(H) _s (R) _t ] ⁺ (where R is an alkyl group or a hydroxylethyl group having 1 to 4 carbon atoms, and s and t are 0 to 4
S + t = 4. ) Or

[0149]

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Is preferred. Or X is an inorganic or organic anion such as OH ⁻ , Cl ⁻ , Br ⁻ , I ⁻ , ClO _{4
^{-, 1 / 2SO 4 -,}} CH 2 SO 4 -, NO 3 -, CH 3 CO
O 2 ^- or a phosphate group is preferred.

(D-10) Fluorine-containing amine oxide type surfactant The following general formula (D-10)

[0152]

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Wherein Rf is a fluorinated aliphatic group having 8 to 18 carbon atoms, a fluorinated alicyclic group having 10 to 20 carbon atoms mediated by ether oxygen or thioether,
Is -SO ₂ - or -CO-, R1 is H, alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, -
OH, -SH, an alkoxy group having 1 to 6 carbon atoms, 1 carbon atom
To 6 thioalkyl groups, -NO2, -CN, NRR'-
(R and R ′ each represent H or an alkyl group having 1 to 6 carbon atoms), R 2 and R 3 each represent H and 1 to 6 carbon atoms.
An alkyl group, a halogenated alkyl group having 1 to 6 carbon atoms,
-OH, -SH, an alkoxy group having 1 to 6 carbon atoms, a thioalkyl group having 1 to 6 carbon atoms, -NO2, -CN, NRR
'-(R and R' each represent H or an alkyl group having 1 to 6 carbon atoms), or an alicyclic group containing a hetero atom, an alicyclic group not containing a hetero atom, all or an alicyclic group An alicyclic group partially substituted with an alkyl group, n is an integer of 2 to 6. ] A fluorine-containing amine oxide surfactant represented by the formula:

Specific examples of these compounds include the following, but the present invention is not limited by these specific examples.

[0155]

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The mixing ratio of the water-soluble polymer compound (A) and the amphoteric surfactant (B) is from 4: 1 to 1: 4, preferably from 3: 1 to 1: 2. The mixing ratio of the water-soluble polymer compound (A) and the polybasic acid compound (C) is 5: 1 to 1: 3, preferably 4: 1 to 1: 1.
It is.

In the present invention, the total of ((A) + (C)) of the fluorine-containing surfactant (D) and the total of the blend comprising the water-soluble polymer compound (A) and the polybasic acid compound (C) is used. The preferred range of the mixing ratio varies depending on the combination of the two components, but is generally (D): [(A) +
(C)] is 2: 1 to 1:50, more preferably,
The ratio is from 1: 1 to 1:10.

If the compounding ratio of the compounding composition with respect to the fluorine-containing surfactant (D) is too low, the complex formed with the fluorine-containing surfactant (D) becomes insoluble in water and the foaming property is remarkably increased. In addition to being impaired, the use of large amounts of expensive fluorinated surfactants is not suitable because it significantly increases product costs. Even if the compounding ratio is more than the above range, it does not significantly hinder the development of foaming properties, but the viscosity at the stage before mixing with water as a deodorant increases, and the solution becomes non-uniform at the time of aqueous solution formation. It loses commercial value.

The mixing ratio in the final preparation of a foaming liquid as a deodorant by mixing the above (A) to (D) with water is [(A) + (B) + (C) + (D)]. : Water is 90:
10: 0.1: 99.9, preferably 50:50
１ ： 1: 99, more preferably 20: 80-5: 9.
5

The deodorant of the present invention may further contain various additives. Additives include additional foam stabilizers, freezing point depressants, rust inhibitors, pH adjusters, and the like.

Additional foam stabilizers are added mainly to control foamability and foam water retention, and include, for example, glycerin fatty esters, propylene glycol fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, Nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene ether, polyethylene glycol fatty acid ester, alkyl alkanolamide, alkyl polyglucoside, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, carboxymethyl cellulose, gum arabic, and alginic acid Examples include soda, polypropylene glycol, and polyvinyl resin.

Examples of freezing point depressants include ethylene glycol, propylene glycol, cellosolves (ethyl cellosolve, butyl cellosolve), carbitols (ethyl carbitol, butyl carbitol, hexyl carbitol, octyl carbitol), lower alcohols (isopropyl alcohol, Butanol, octanol), urea, ammonium sulfamate and the like.

As the rust preventive and the pH adjuster, various ones known in the art can be used, and they are not particularly limited.

The method of using the deodorant of the present invention and the radiation method are not particularly limited. For example, a propellant such as LPG, DME (dimethyl ether), chlorofluorocarbon, carbon dioxide or air may be used alone in a spray container. Alternatively, a combination of two or more is used to fill the deodorant container so that the pressure is high enough to be sprayed in the atmosphere, to provide a device for compressing and high-pressure gas inside the deodorant container, or to introduce compressed air to the outside of the container. For example, a method of providing a device and increasing the pressure in the container is employed. Furthermore, when it is assumed that it will be used in homes, hospitals, nursing homes, etc., the trigger foaming method used as a container for household detergents and bleaching agents, rather than the spray method with increased pressure in the container, It is desirable to adopt it.

The deodorant of the present invention is suitable not only for a spraying or mousse foaming method using a high-pressure container, but also for a trigger foaming method in which a container injected at a low expansion ratio is not pressurized. . These foaming methods are merely examples, and it goes without saying that other foaming methods may be adopted.

The pressure in the container when the foaming method using high pressure is adopted may be in a pressure range for forming a spray or mousse, for example, in a range of 0.5 to ¹⁰ kg / cm ^2. You.

[0167]

Next, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited at all by the following Examples. In the following Examples and Comparative Examples, all percentages represent percent by weight.

(Formulation Example) In this example, the method for producing the deodorant of the present invention is described by using a specific example of a deodorant containing water-soluble polymer compound (A) and amphoteric surfactant (B) as main components. Will be explained.

Polyethyleneimine (AI) having a number average molecular weight of 13,000 (converted to polystyrene using gel permeation chromatography) as the water-soluble polymer compound (A), stearyl dimethylaminoacetic acid betaine as the amphoteric surfactant, freezing point As a depressant, a mixture of butyl carbitol, ethylene glycol, and water adjusted to pH 8.0 with hydrochloric acid was used as a deodorant stock solution, and a mixture of 10% stock solution and 90% water was used as a deodorant. did. Table 1 shows the types of compounds used in the stock solution of the deodorant and the compounding ratio.

Similarly, a stock solution of deodorant was prepared using the compounds shown in Tables 1 and 2, and a stock solution of 10% was prepared in the same manner as above.
The aqueous solution was finally prepared to obtain a deodorant composition. The pH value was all adjusted to 8.0 with hydrochloric acid in the same manner.

In Tables 1 and 2, SDMAB is betaine stearyl dimethylaminoacetate, LDMAB is betaine lauryl dimethylaminoacetate, LAPB is lauric amide propyl betaine, ADA is adipic acid, BC
A represents butyl carbitol, EG represents ethylene glycol, and other symbols represent the respective compound numbers described above.

[0172]

[Table 1]

[0173]

[Table 2]

(Examples 1 to 10) The composition examples shown in Table 1 were further prepared with water so as to be 10% of a stock solution to obtain deodorant compositions. An application evaluation test was performed.

<Measurement of Foaming Ratio> The deodorant final composition (100 cc) was filled in a trigger foaming container used for a commercially available mold remover, bath detergent, etc. Jet perpendicular to
Foam weight (W, unit g) and volume (V,
The expansion ratio was determined according to the following calculation formula (unit: cc). Table 3 shows the results.

Expansion ratio (times) = V / W

<Confirmation of deodorant effect> Pour 10 cc of 25% aqueous ammonia into a 100 cc beaker, and immediately spray 4 times while rotating the beaker 90 ° at a time on the beaker wall by trigger foaming method to completely cover the liquid surface. I do. Next, in order to remove the ammonia vapor floating around the beaker before the injection, forced exhaust was performed by a local exhaust device for one minute.
After that, the beaker was removed to a volume of 2000 cc (100 W ×
The beaker was shielded by a rectangular parallelepiped of 100D x 200Hmm), and the amount of ammonia in the rectangular parallelepiped after standing for 3 minutes was quantified by a detector tube. The ammonia detector tube was a Kitagawa type gas detector tube, and its grade used a detector tube having a concentration range appropriate for the detected concentration. Table 3 shows the results.

(Examples 11 to 20) Fish (sardines) which had been left for about 2 weeks and were put down were used as a source of offensive odor. A predetermined amount of this putrefactive substance was placed in a plastic container having a capacity of 500 ml, and representative odor components (NH ₃ , H ₂ S, CH ₃ S) were measured using a Kitagawa type detector tube.

As a result, sardines (about 100 g)
H ₃ is 130 ppm, H ₂ S is 10 ppm, CH ₃ S 9
0 ppm was detected. On the other hand, a solution obtained by diluting the final composition of the deodorant shown in the above-mentioned formulation example to 20% was added in a volume of 2% each.
A 50 cc spray tube was filled with 100 cc, the pressure was adjusted to 1 kg / cm ² with LPG, and the mixture was sprayed to the source at a mousse shape, and the odor component concentration was measured immediately after the treatment was completely covered and one day after the treatment. Table 4 shows the results.

[0180]

[Table 3]

[0181]

[Table 4]

(Example 21) A solution obtained by diluting the deodorant final composition of Formulation Examples 1, 4, and 9 to 20% of the active ingredient with water was prepared.
Respectively 100cc filled to capacity 250cc spray tube, and adjusted to a pressure 1 kg / cm ² at LPG, injected at mousse portable in the toilet with a manure after defecation,
One day, the sensory test of the odor in the room confirmed the deodorant effect. As a result, it was confirmed that there was no excrement of manure in any of the compositions. However, the sensory test was performed by five panelists having the same level of smell.

(Comparative Examples 1 to 4) Experiments were carried out in accordance with Example 1 except that the stock solutions of the deodorants of Formulation Examples 11 to 14 were used. Table 5 shows the results.

(Comparative Examples 5 to 8) An experiment was conducted in accordance with Example 11 except that the stock solutions of the deodorants of Formulation Examples 11 to 14 were used. Table 6 shows the results.

[0185]

[Table 5]

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[Table 6]

[0187]

The deodorant of the present invention has an effect of simply and quickly deodorizing an unpleasant odor emitted during the treatment of sludge, manure, etc., and at the same time has an effect of maintaining its performance for a long time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/42 C08K 5/42 5/521 5/521 C08L 79/02 C08L 79/02 101/14 101 / 14 F-term (reference) 4C080 AA04 BB04 CC01 HH03 JJ10 KK06 LL02 LL13 MM12 MM14 MM18 MM28 4D059 AA01 AA08 BK01 DB06 DB22 DB40 4J002 AB031 AB041 AB051 AD001 BE021 BG001 CF001 CH021 EF020 EF021 EF021 FD316 GB00

Claims (9)

[Claims] 1. A deodorant comprising a water-soluble polymer compound (A), an amphoteric surfactant (B) and water. 2. The composition according to claim 1, which contains a polybasic acid compound (C).
The deodorant described. 3. The deodorant according to claim 1, which comprises a fluorine-containing surfactant (D). 4. The deodorant according to claim 1, wherein the water-soluble polymer compound (A) is a cationic polyamine polymer compound. 5. The polybasic acid compound (C) has 4 to 18 carbon atoms.
5. A dibasic acid compound according to claim 1, wherein
The deodorant according to any one of the above. 6. The deodorant according to claim 1, wherein the fluorinated surfactant (D) contains an anionic hydrophilic group. 7. The method according to claim 1, wherein the water-soluble polymer compound (A) is polyethyleneimine or a derivative thereof.
The deodorant according to the item. 8. The deodorant according to claim 1, wherein the fluorosurfactant (D) has a fluorinated aliphatic group having 3 to 20 carbon atoms as a hydrophobic group. 9. The deodorant according to claim 1, wherein the amphoteric surfactant (B) is an alkylamidopropyl betaine and / or a betaine alkyldimethylaminoacetate.