JP5268128B2 - Deodorant composition, deodorant aqueous solution, deodorant aqueous slurry, deodorant powder composition and deodorant masterbatch - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a deodorizing composition, capable of achieving better anti-rust effect in deodorizing metal salt such as bivalent iron salt than conventionally used stabilizer, preventing deodorizing metal salt such as ferrous sulfate from rusting, and effectively eliminating ammonium, amine, hydrogen sulfide, mercaptan, etc., in which ammonium is not generated even when hydrazides such as adipic acid dihydrazide are added, ammonium and aldehydes such as formaldehyde can be effectively eliminated, and flammable fiber products can be made to be flame-retardant. <P>SOLUTION: The deodorizing composition includes a deodorizing metal salt and a phosphoric acid alkali metal salt. <P>COPYRIGHT: (C)2009,JPO&amp;INPIT

Description

  The present invention relates to a deodorant composition, and more specifically, it has excellent rust prevention properties despite containing a deodorant metal salt such as ferrous sulfate and zinc sulfate, and a hydrazide compound such as adipic acid dihydrazide. The present invention relates to a deodorant composition that does not generate ammonia even when added, and can make a paper or fiber flame retardant. Further, a deodorant aqueous solution and a deodorant aqueous slurry containing the deodorant composition It is related with a liquid, a deodorant powdery composition, and a deodorant masterbatch.

  Deodorant metal salts, especially ferrous sulfate and zinc sulfate, have excellent reactivity to odorous substances such as ammonia, amines, hydrogen sulfide, mercaptans, etc., and these odors can be removed to purify the air. It is a compound that has flame retardancy. However, deodorant metal salts such as ferrous sulfate are easily oxidized, and when oxygen is present, they oxidize and rust in less than a day and lose their deodorant properties.

  Of the deodorant metal salts, as means for preventing rusting of divalent iron salts such as ferrous sulfate, it has been proposed to add L-ascorbic acid as a stabilizer (Patent Document 1, etc.), and further L- It has been proposed to add ethylenediaminetetraacetic acid (EDTA) as a stabilizer superior to ascorbic acid (Patent Document 2, etc.). In addition, L-ascorbic acid and ethylenediaminetetraacetic acid are expected to be stable against transition metals such as zinc sulfate in addition to ferrous sulfate.

  Although it is possible to rust prevent deodorant metal salts such as ferrous sulfate by using these stabilizers, it is expected to increase the degree of rust prevention by using better stabilizers. Has been.

  On the other hand, aldehydes such as formaldehyde have recently become a problem as malodorous substances causing so-called sick house syndrome. However, deodorant metal salts are excellent in reactivity with ammonia, amines, hydrogen sulfide, mercaptans, etc., but have low reactivity with aldehydes and are not suitable for removing aldehydes.

  Therefore, in order to remove both ammonia and aldehydes, deodorizing metal salts and hydrazide compounds such as adipic acid dihydrazide have been used in combination. A hydrazide compound is a compound that does not have deodorizing properties such as ammonia, but has excellent aldehyde removal properties. Among the hydrazide compounds, adipic acid dihydrazide is a remover that is particularly excellent in reactivity with aldehydes, but has a drawback that ammonia of about 3 ppm is always generated even in a room temperature atmosphere. This problem cannot be solved only by using in combination with a deodorant metal salt such as a divalent iron salt.

  Under such circumstances, a deodorant composition that can effectively remove ammonia, amine, hydrogen sulfide, mercaptan, etc., and hydrazide compounds such as adipic acid dihydrazide are added to remove aldehydes such as formaldehyde Even so, development of a deodorant composition that does not generate ammonia is expected.

JP-A-2-211240 Japanese Patent No. 3665970

  The present invention is superior in the rust preventive effect of deodorant metal salts such as divalent iron salts than conventionally used stabilizers, and does not rust deodorant metal salts such as ferrous sulfate, Deodorant composition that can effectively remove amines, hydrogen sulfide, mercaptans, etc., and generates ammonia even when hydrazides such as adipic acid dihydrazide are added to remove aldehydes. It is an object of the present invention to provide a deodorant composition having no odor. Furthermore, an object of the present invention is to provide a deodorant aqueous solution, a deodorant aqueous slurry liquid, a deodorant powdered composition, and a masterbatch containing the deodorant composition.

  As a result of diligent research to improve the rust preventive properties of deodorant metal salts such as ferrous sulfate, the present inventors have found that when an alkali metal phosphate is used as a stabilizer for the deodorant metal salt, It has been found that the rust prevention of deodorant metal salts such as iron salts is improved over conventional stabilizers. Furthermore, the deodorant composition containing a deodorant metal salt and an alkali metal phosphate has a dehydrating property such as adipic acid dihydrazide even though it does not lose the deodorizing properties of aldehydes. It was discovered that ammonia is not generated, and further, it was discovered that the hydrazide compound further improves the rust prevention property of the deodorant metal salt, and the present invention has been achieved.

According to the present invention, the following deodorant composition, deodorant aqueous solution, deodorant aqueous slurry liquid, deodorant powder composition, and deodorant masterbatch are provided.
[1] A deodorant composition comprising ferrous sulfate and / or zinc sulfate and potassium phosphate .
[ 2 ] The deodorant composition according to [1 ] above, which contains a hydrazide compound.
[ 3 ] The deodorant composition according to [ 2 ], wherein the hydrazide compound is adipic acid dihydrazide.
[ 4 ] The deodorant composition according to any one of [1] to [ 3 ], which contains a chelating agent.
[ 5 ] The deodorant composition according to [ 4 ], wherein the chelating agent is ethylenediaminetetraacetic acid (EDTA).
[ 6 ] The deodorant composition according to any one of [1] to [ 5 ], which contains an organic acid.
[ 7 ] The deodorant composition according to any one of [ 6 ], wherein the organic acid is an acid selected from citric acid, malic acid, tartaric acid, and oxalic acid.
[ 8 ] A deodorant aqueous solution comprising the deodorant composition according to any one of [1] to [ 7 ].
[ 9 ] The deodorant aqueous solution according to claim 8 , wherein the content of the deodorant composition is 0.3 to 20% by weight.
[ 10 ] pH is 3-9, Deodorant aqueous solution of Claim 8 or 9 characterized by the above-mentioned.
[ 11 ] A deodorant aqueous slurry liquid comprising the deodorant composition according to any one of [1] to [ 7 ].
[ 12 ] The deodorant aqueous slurry according to [ 11 ] above, wherein the content of the deodorant composition is 30 to 70% by weight.
[ 13 ] A deodorant powder composition comprising the deodorant composition according to any one of [1] to [ 7 ].
[ 14 ] The deodorant powder composition according to [ 13 ], wherein the content of the deodorant composition is 10 to 100% by weight.
[ 15 ] A deodorant masterbatch comprising a thermoplastic resin containing the deodorant composition according to any one of [1] to [ 7 ].
[ 16 ] The deodorant masterbatch according to [ 15 ] above, wherein the content of the deodorant composition is 10 to 60% by weight.
[ 17 ] The above [ 15 ] or [ 16 ], wherein the thermoplastic resin is any one of a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyester resin, and a polyvinyl chloride resin. Deodorant masterbatch.

Since the deodorant composition of the present invention contains potassium phosphate as a stabilizer for a deodorant metal salt, a deodorant metal salt such as ferrous sulfate or zinc sulfate is extremely used in an aqueous solution. Since it is contained in a stable state, it is excellent in rust prevention. Moreover, the deodorant composition of this invention has a flame retardance, and can make flame-retardant (flameproofing) combustibles, such as paper.
Even if a hydrazide compound such as adipic acid dihydrazide is added to the deodorant composition of the present invention, ammonia is not generated because the hydrazide compound is stably present while retaining the deodorizing properties of aldehydes. Is. In addition, the addition of a hydrazide compound further improves the rust prevention properties of the deodorant metal salt (it is considered that ferrous sulfate, zinc sulfate, potassium phosphate, and a hydrazide compound form a conjugate). . The deodorant composition of the present invention containing a hydrazide compound can remove malodorous substances such as ammonia, amines, hydrogen sulfide, mercaptans and the like, and at the same time remove malodorous substances of aldehydes such as formaldehyde.
Since the deodorant composition of the present invention is water-soluble, it can be used as a deodorant aqueous solution and can be used as a concentrated deodorant aqueous slurry liquid. The deodorant aqueous slurry liquid is separated from moisture and dried. By doing so, a deodorant powder composition can be obtained, and if the deodorant powder composition is added to the thermoplastic resin at a high concentration, a deodorant master batch can be obtained. When these are used, deodorant paper, fibers, paints, plastic molded articles and the like can be easily obtained.

Hereinafter, the deodorant composition of the present invention will be described in detail.
The deodorant composition of the present invention contains at least a deodorant metal salt and an alkali metal phosphate. The alkali metal phosphate contained in the deodorant composition is a stabilizer for a deodorant metal salt, and conventionally, than a stabilizer that has been used for divalent iron salts such as ferrous sulfate, It has excellent rust prevention effect against deodorant metal salts. Therefore, the deodorant composition of the present invention can stably hold a deodorant metal salt in an aqueous solution for a long period of time.

Examples of the metal constituting the deodorant metal salt contained in the deodorant composition of the present invention include transition metals such as titanium, vanadium, manganese, iron, cobalt, nickel, copper, zinc, silver, etc. Also, lead, aluminum, magnesium and the like can be mentioned. Among these salts made of these metals, divalent iron and / or zinc salts are selected because they are excellent in deodorizing properties such as ammonia, amine, hydrogen sulfide, mercaptan, etc. and are inexpensive.

Salts in which the metal is divalent iron include inorganic acid salts and organic acid salts. Examples of inorganic acid salts include ferrous sulfate, ferrous chloride, ferrous bromide, and ferrous iodide. Organic acid salts include ferrous citrate, ferrous malate, ferrous ascorbate, ferrous ethylenediaminetetracarboxylic acid (EDTA), ferrous lactate, ferrous gallate, and malic acid ferrous Examples thereof include iron and ferrous fumarate. The divalent iron salt has an effect of decomposing and deodorizing odorous substances such as ammonia, hydrogen sulfide, methyl mercaptan, trimethylamine, acetic acid odor and nicotine metabolite, and further antistatic agent, hydrophilizing agent, It can also act as a flame retardant and oxygen scavenger. Of the divalent iron salts, ferrous sulfate, which can be obtained at a low cost and is excellent in safety, is selected .

Salts in which the metal is zinc include inorganic acid salts and organic acid salts. Examples of inorganic acid salts include zinc sulfate, zinc chloride, zinc phosphate, zinc nitrate, and zinc carbonate. Organic acid salts include zinc acetate, zinc oxalate, zinc citrate, zinc malate, zinc fumarate, zinc glycolate, zinc lactate, zinc gluconate, zinc benzoate, zinc salicylate, zinc glycerate, zinc tartrate, Examples include zinc aluminosilicate. Zinc salts are excellent in decomposing and deodorizing odorous substances such as ammonia, hydrogen sulfide, methyl mercaptan, and trimethylamine, acetic acid odor, and pyridine as a nicotine metabolite. It can also exhibit an action as a flame retardant and oxygen scavenger. Among the zinc salts, zinc sulfate, which can be obtained at a low cost and has excellent safety, is selected .

  A salt in which the metal is copper can also be used as a deodorant metal salt. Examples of the copper salt include inorganic acid salts such as copper sulfate, copper nitrate, and copper phosphate, copper citrate, copper malate, copper fumarate, copper glycolate, copper lactate, copper gluconate, and copper benzoate. And organic acid salts such as copper salicylate, copper glycerate, and copper tartrate. Among these, copper sulfate is preferable because it can exhibit a blue color in an aqueous solution and can also be used as a colorant.

  A salt in which the metal is magnesium is also used as a deodorant metal salt. The magnesium salt is preferably used by mixing with the divalent iron salt or zinc salt. Examples of the magnesium salt include magnesium sulfate, magnesium chloride, magnesium carbonate, magnesium carbonate hydroxide, sodium magnesium sulfate, potassium magnesium sulfate, and potassium magnesium hydrogen carbonate. Of these, magnesium sulfate is preferred.

The deodorant composition of the present invention contains an alkali metal phosphate. The alkali metal phosphate has a function of stabilizing an unstable deodorant metal salt and has flame retardancy. Examples of the alkali metal include sodium and potassium, and potassium that is more excellent in stabilizing action (preventing rust of the deodorant metal salt) is selected .

Furthermore, the alkali metal phosphate in the present invention includes a partially neutralized salt in which the hydrogen group of phosphoric acid is partially replaced with an alkali metal. For example, taking potassium phosphate (K ₃ PO ₄ ) as an example, potassium phosphate in the present invention includes potassium phosphate (K ₃ PO ₄ ), dipotassium hydrogen phosphate (K ₂ HPO ₄ ), and phosphoric acid. In the case where potassium dihydrogen (KH ₂ PO ₄ ) is included, specifically potassium phosphate (K ₃ PO ₄ ) and dipotassium hydrogen phosphate (K ₂ HPO ₄ ), dipotassium hydrogen phosphate (K ₂ It includes the case of HPO ₄ ) and potassium dihydrogen phosphate (KH ₂ PO ₄ ), the composition of which depends on the pH. The aqueous solution of potassium phosphate (K ₃ PO ₄ ) is strongly alkaline with a pH of about 11, and as the pH decreases, dipotassium hydrogen phosphate (K ₂ HPO ₄ ) and further potassium dihydrogen phosphate (KH ₂ PO ₄ ). There is a tendency for the content of to increase.

  As described above, the composition of alkali metal phosphates such as potassium phosphate changes depending on the pH. This means that the alkali metal phosphate can react with an alkaline or acidic malodorous substance, and the alkali metal phosphate itself has excellent deodorizing properties.

  The deodorant composition of the present invention preferably contains 5 to 60 equivalents, more preferably 9 to 40 equivalents, and more preferably 10 to 30 equivalents of an alkali metal phosphate to 1 equivalent of the deodorant metal salt. It is more preferable to contain equivalent, and it is especially preferable to contain 13-26 equivalent. Specifically, it is preferable to contain 300 to 3000 parts by weight of potassium phosphate, more preferably 500 to 2000 parts by weight, more preferably 600 to 100 parts by weight of ferrous sulfate (7 water salt). The content is more preferably 1500 parts by weight, and particularly preferably 700 to 1300 parts by weight. If the amount of the alkali metal phosphate is too large relative to the deodorant metal salt, the deodorizing properties such as ammonia, amine, hydrogen sulfide, mercaptan may be deteriorated, and the amount of alkali metal phosphate is small. If it is too high, the rust prevention properties of the alkali metal phosphate may be deteriorated.

  In the deodorant composition of the present invention, it is considered that the deodorant metal salt and the alkali metal phosphate form a complex. For example, even if an aqueous solution of a deodorant composition containing ferric sulfate and potassium phosphate is adjusted to pH 4 to 10, and potassium ferricyanide, which is a detector for divalent iron ions, is added thereto, a substantial blue color can be obtained. No color development occurs.

  The deodorant composition of the present invention has a bad odor property such as ammonia, amine, hydrogen sulfide, mercaptan, etc., although the deodorant metal salt such as divalent iron salt forms a conjugate as described above. It can show reactivity to a substance. Therefore, when air containing these malodorous substances is brought into contact with the deodorant composition of the present invention, the malodorous substances such as ammonia react with the deodorant composition and are removed from the air. Air without odorous substances such as can be obtained.

  The deodorant composition of the present invention preferably contains a hydrazide compound. The deodorant composition containing a hydrazide compound can effectively deodorize aldehydes and further improve the stability of deodorant metal salts such as ferrous sulfate and zinc sulfate. Moreover, the deodorant composition of the present invention does not generate ammonia even when a hydrazide compound such as adipic acid hydrazide is added. Thus, since the improvement of the rust prevention property of the deodorant metal salt and the prevention of the generation of ammonia from the hydrazide compound are achieved at the same time, the alkali metal phosphate, the deodorant metal salt and the hydrazide compound are combined. It is thought that it forms. That is, it is considered that a complex (chelate) in which an alkali metal phosphate and a hydrazide compound are coordinated to deodorant metal ions is formed.

  A conventional deodorant to which a hydrazide compound has been added is not suitable as a deodorant because it can remove aldehydes but cannot prevent the generation of ammonia.

  The hydrazide compound can be appropriately selected from compounds having at least one hydrazide group in the molecule. For example, a monohydrazide compound having one hydrazide group in the molecule, a dihydrazide compound having two hydrazide groups in the molecule, a polyhydrazide compound having three or more hydrazide groups in the molecule, or a mixture thereof Can be mentioned.

Specific examples of the monohydrazide compound include a monohydrazide compound represented by the following general formula (1).
R—CO—NHNH ₂ (1)
[In the formula (1), R represents a hydrogen atom, an alkyl group or an aryl group which may have a substituent. ]

  In the general formula (1), examples of the alkyl group represented by R include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, C1-C12 linear alkyl groups, such as an n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, can be mentioned. Examples of the aryl group include a phenyl group, a biphenyl group, and a naphthyl group. Examples of the substituent for the aryl group include a halogen atom such as a hydroxyl group, fluorine, chlorine and bromine, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, and an iso group. -C1-C4 linear or branched alkyl groups, such as a butyl group, etc. can be mentioned.

  Specific examples of the monohydrazide compound include lauric acid hydrazide, salicylic acid hydrazide, form hydrazide, acetohydrazide, propionic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy-2-naphthoic acid hydrazide and the like.

Specific examples of the dihydrazide compound include a dihydrazide compound represented by the following general formula (2).
_{H 2 NHN-X-NHNH 2} (2)
[In the formula (2), X represents a group —CO— or a group —CO—A—CO—. A represents an alkylene group or an arylene group. ]

  In the general formula (2), examples of the alkylene group represented by A include a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, and a nonamethylene group. C1-C12 linear alkylene groups, such as a decamethylene group and an undecamethylene group. The alkylene group may have a substituent, and examples of the substituent include a hydroxyl group. Examples of the arylene group include a phenylene group, a biphenylene group, a naphthylene group, an anthrylene group, and a phenanthrylene group.

Specific examples of dihydrazide compounds include carbodihydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecanedioic acid dihydrazide, produced by the reaction of carbonic acid and hydrazine. Examples include dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, dimer acid dihydrazide, and dibasic acid dihydrazide such as 2,6-naphthoic acid dihydrazide. Furthermore, various dibasic acid dihydrazide compounds described in Japanese Patent Publication No. 2-4607, 2,4-dihydrazino-6-methylamino-sym-triazine and the like can be mentioned.
Specifically, the polyhydrazide compound is polyacrylic hydrazide or the like.

  These hydrazine compounds can be used individually by 1 type or in mixture of 2 or more types.

  Preferred hydrazide compounds include hydrazine hydrate, carbonate hydrazine, phenyl hydrazine, 2-hydroxyethyl hydrazine, carbo (di) hydrazide, acetic hydrazide, adipic acid dihydrazide, and succinic acid dihydrazide. Among these, adipic acid dihydrazide is particularly preferable because it has excellent reactivity with aldehydes and is excellent in stabilizing divalent iron salts.

The deodorant composition of the present invention preferably contains 0.5 to 5 equivalents, preferably 1 to 3.5 equivalents, of the hydrazide compound in terms of NHNH ₂ groups with respect to 1 equivalent of the deodorant metal salt. It is more preferable to contain 1.4 to 2.5 equivalents. Specifically, it is preferable to contain 50 to 250 parts by weight of adipic acid dihydrazide with respect to 100 parts by weight of ferrous sulfate, more preferably 70 to 200 parts by weight, and 90 to 150 parts by weight. More preferably.
If the amount of the hydrazide compound is too large relative to the deodorant metal salt, ammonia or the like may be generated. If the amount of the hydrazide compound is too small, the rust prevention property by the hydrazide compound against the deodorant metal salt In addition, there is a possibility that the deodorizing property of aldehydes by the hydrazide compound may not be exhibited.

  In addition, even if the aqueous solution of the deodorant composition of the present invention containing a hydrazide compound is adjusted to pH 4 to 10 and potassium ferricyanide, which is a detector for divalent iron ions, is added thereto, substantial blue color development Does not occur.

  The deodorant composition of the present invention containing a hydrazide compound can exhibit reactivity with odorous substances of aldehydes such as formaldehyde. At the same time, since it contains a deodorant metal salt, it can show reactivity to malodorous substances such as ammonia, amines, hydrogen sulfide, mercaptans and the like as described above. Therefore, when air containing both malodorous substances such as ammonia and formaldehyde is brought into contact with the deodorant composition of the present invention, these malodorous substances react with the deodorant composition and are removed from the air. Therefore, air without these malodorous substances can be obtained.

The deodorant composition of the present invention preferably contains a chelating agent because the stability of the deodorant metal salt is further increased.
Any chelating agent can be used as long as it has a chelating ability for deodorant metal ions such as divalent iron ions and zinc ions. For example, ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, diethylenetriaminepentaacetic acid, nitrilotriacetic acid, diaminopropanetetraacetic acid, hydroxyethyliminodiacetic acid, 1,2-diaminocyclohexanetetraacetic acid, hydroxyethyl Polyaminocarboxylic acids such as ethylenediaminetriacetic acid and dihydroxyethylglycine or water-soluble salts thereof; polyaminophosphoric acids such as ethylenediaminetetrakis (methylenephosphonic acid) and nitrilotris (methylenephosphonic acid) or water-soluble salts thereof; citric acid, gluconic acid, etc. Oxycarboxylic acid or a water-soluble salt thereof, alkyl diphosphonic acid or a water-soluble salt thereof, and the like. These chelating agents can be used alone or in the form of a mixture. In the present invention, it is particularly preferable to use polyaminocarboxylic acids such as EDTA and iminodiacetic acid and their water-soluble salts (sodium salt, potassium salt, etc.).

  As content of the chelating agent in the deodorant composition of this invention, 0.001-0.04 equivalent is preferable with respect to 1 equivalent of deodorant metal salt, and 0.007-0.025 equivalent is more preferable. Specifically, ethylenediaminetetraacetic acid disodium (EDTA-2Na) is preferably 0.5 to 5 parts by weight and more preferably 1 to 3 parts by weight with respect to 100 parts by weight of ferrous sulfate (7-hydrate).

  The deodorant composition of the present invention preferably contains an organic acid because the stability of the deodorant metal salt is further increased and it functions as a pH adjuster. The organic acid in the present invention refers to a compound having a carboxylic acid structure (R-COOH) as an acid component, and includes fatty acids (monovalent carboxylic acids of long chain hydrocarbons), aliphatic dicarboxylic acids, and oxocarboxylic acids. Other examples include unsaturated fatty acids and hydroxy acids having a hydroxy group.

  Specific examples of the fatty acid include formic acid (methanoic acid), acetic acid (ethanoic acid), propionic acid (propanoic acid), butyric acid (butanoic acid), valeric acid (pentanoic acid), caproic acid (hexanoic acid), enanthic acid (heptane) Acid), caprylic acid (octanoic acid), pelargonic acid (nonanoic acid), capric acid (decanoic acid), lauric acid (dodecanoic acid), myristic acid (tetradecanoic acid), pentadecanoic acid, palmitic acid (hexadecanoic acid, cetanoic acid) , Margaric acid (heptadecanoic acid), stearic acid (octadecanoic acid), oleic acid, linoleic acid, linolenic acid, arachidonic acid, docosahexaenoic acid, eicosapentaenoic acid.

  Specific examples of the aliphatic dicarboxylic acid include oxalic acid, malonic acid, and succinic acid. Specific examples of the aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, gallic acid, and melicic acid. Cinnamic acid, and specific examples of oxocarboxylic acid include pyruvic acid, and other specific examples of unsaturated fatty acid and hydroxy acid include lactic acid, malic acid, citric acid, fumaric acid, maleic acid, Examples include aconitic acid, glutaric acid, adipic acid, amino acids, and nitrocarboxylic acid. In the present invention, a mixture of two or more organic acids selected from these can be used.

  In the present invention, among the above organic acids, those which are odorless, have high solubility in water, are inexpensive and can be easily obtained, are preferable. Specifically, an acid selected from citric acid, malic acid, tartaric acid, and oxalic acid, or an acid obtained by mixing them is preferably used.

As for content of the organic acid in the deodorant composition of this invention, 20 * 10 < ^-3 > -0.15 equivalent of organic acids is preferable with respect to 1 equivalent of the said deodorant metal salt, 2 * 10 < ^-3 > -0. 07 equivalents are more preferable, and 1 × 10 ^{−3 to} 0.1 equivalents are even more preferable. Specifically, 0.1 to 5 parts by weight of citric acid is preferable with respect to 100 parts by weight of ferrous sulfate (septahydrate), more preferably 0.5 to 3 parts by weight, and 1 to 2 parts by weight. Further preferred.

  The deodorant composition of the present invention containing various compounds including the above-mentioned deodorant metal salt has flame retardancy and can impart flame retardancy by applying to paper or fiber.

  Next, the method for producing the deodorant composition of the present invention will be described by taking as an example the case where the deodorant metal salt is ferrous sulfate and the alkali metal phosphate is potassium phosphate. Furthermore, when a hydrazide compound, a chelating agent, and an organic acid are added to the deodorant composition of the present invention as necessary, the hydrazide compound is adipic acid dihydrazide, the chelating agent is EDTA-2Na, and the organic acid The case where is citric acid will be described. However, the present invention is not limited to this combination.

First, potassium hydroxide is added to an aqueous phosphoric acid solution at room temperature to produce an aqueous potassium phosphate solution. The amount of potassium hydroxide added to the aqueous phosphoric acid solution at this time is dominant with respect to the pH of the aqueous solution of the resulting deodorant composition, and thus is desired as the pH of the aqueous solution of the resulting deodorant composition. Can be determined based on the value. Usually, the pH is preferably 3-9, more preferably 6-8.
The pH of the aqueous solution of the deodorant composition tends to be slightly smaller than the pH of the potassium phosphate solution because ferrous sulfate is weakly acidic.

Next, ferrous sulfate is added to hot water at 50 to 100 ° C. with sufficient stirring using a high-speed mixer or the like, and an amount exceeding the solubility possible at room temperature is added and dissolved in hot water. When such hot water is used, even ferrous sulfate exceeding the solubility at room temperature can be dissolved. Next, the aqueous solution of potassium phosphate is added and cooled with stirring. There is no restriction | limiting in particular in the temperature which preserve | saves the aqueous solution of potassium phosphate, It may be about room temperature.
In addition, since the temperature of hot water is easy to dissolve ferrous sulfate, the lower limit is preferably 60 ° C, more preferably 70 ° C, and still more preferably 80 ° C. Moreover, since the upper limit is easy to handle, 97 degreeC is preferable, More preferably, it is 95 degreeC.

  In addition, when enhancing the rust prevention property of deodorant metal salts such as ferrous sulfate and imparting deodorizing properties of aldehydes, adipic acid dihydrazide may be added before or after ferrous sulfate. EDTA-2Na or citric acid can be added to further enhance the rust prevention properties of the deodorant metal salt. In that case, EDTA-2Na or citric acid can be added before or after ferrous sulfate or adipic acid dihydrazide. An acid can be added.

  The amount of each component added to the hot water is, for example, 5 to 20 parts by weight of ferrous sulfate (7 water salt) and 15 to 600 parts by weight of potassium phosphate in an aqueous potassium phosphate solution with respect to 100 parts by weight of hot water. Parts, adipic acid dihydrazide 2.5 to 50 parts by weight, EDTA-2Na 0.5 to 5 parts by weight, citric acid 0.5 to 2 parts by weight.

  When the solution is cooled to room temperature and allowed to stand, the upper part thereof becomes a transparent solution state, and the lower part thereof becomes a highly viscous slurry state. If the upper supernatant liquid is taken out and diluted 3 to 10 times with water as necessary, the deodorant aqueous solution of the present invention is obtained. If the lower slurry state liquid is taken out, the deodorant aqueous slurry liquid of the present invention (hereinafter also simply referred to as deodorant slurry liquid) can be obtained. By dehydrating the slurry liquid and drying it, and then pulverizing the obtained solid, the deodorant powdery composition of the present invention (hereinafter also simply referred to as a powdery composition) can be obtained. As drying and pulverization methods, heating is performed at 110 to 120 ° C. using a dryer, and the obtained solid is pulverized using a ball mill, a hammer mill, a jet mill, or the like, or dried and powdered using a spray dryer. There is a way to make it.

  The deodorant aqueous solution of the present invention obtained as described above is excellent in rust prevention properties of divalent iron salts such as ferrous sulfate, and has a bad odor such as ammonia, amine, hydrogen sulfide, mercaptan as a deodorant. In addition to being able to remove the active substance, it can be made flame retardant by applying it to paper or fiber.

  Further, the deodorant aqueous solution contains adipic acid dihydrazide, thereby removing ammonia, amine, hydrogen sulfide, mercaptan and the like, and simultaneously removing odorous substances such as formaldehyde.

  The content of the deodorant composition in the deodorant aqueous solution is preferably 0.3 to 20% by weight, more preferably 0.5 to 15% by weight, and still more preferably 0.7 to 10% by weight. If the content of the deodorant composition is too small, effective deodorizing properties cannot be exhibited, and if the content is too large, the composition will precipitate exceeding the solubility in water.

  The pH of the deodorant aqueous solution is preferably from 3 to 9, more preferably from 6 to 8. Since malodorous substances are alkaline with a large pH or acidic with a small pH, in order for the deodorant composition to react effectively with the malodorous substances and remove the malodorous substances, the pH of the deodorant aqueous solution is Near-neutral is preferable, and a deodorant aqueous solution having a pH close to neutral is easy to handle.

  In the final adjustment of the pH of the deodorant aqueous solution, when increasing the pH, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is preferably used. More preferably, potassium is used. In order to reduce the pH, it is preferable to use phosphoric acid or the organic acid.

  To the deodorant aqueous solution, a toning agent such as the organic acid or titanium oxide or an antibacterial agent can be added as necessary.

  The deodorant aqueous solution of the present invention is used as it is or after being diluted with water as necessary, and then sprayed on a malodor source or sprayed into air containing a malodorous substance. Further, by blowing a gas containing a malodorous substance into the deodorant aqueous solution, the malodorous substance can be removed from the gas.

Further, the deodorant aqueous solution of the present invention wallpaper, leather and leather products, paper, full Irumu, nonwoven, woven, textile fibers such as steel, glass, tiles, wood, board, plastic film, plastic plate or the like When impregnated or applied to various products and dried, these products have deodorizing properties against Amminia and aldehydes, and even if they are flammable paper or textile products, they may be flame retardant. become. In this case, the coating amount as the deodorant composition is preferably 1 to 10 g / m ² .

  The deodorant aqueous slurry liquid (deodorant slurry liquid) of the present invention is obtained as described above.

  The content of the deodorant composition in the deodorant aqueous slurry of the present invention is preferably 30 to 70% by weight, more preferably 35 to 50% by weight. If the content is 30% by weight or more, the viscosity does not decrease too much, so that the deodorant composition can be prevented from precipitating and a slurry liquid can be obtained. On the other hand, if the content is 70% by weight or less, the deodorant composition will not harden and become difficult to handle.

  The viscosity at 20 ° C. of the deodorant aqueous slurry having such a composition is determined by the concentration of the deodorant composition, preferably 5000 to 20000 poise, and more preferably 10,000 to 15000 poise.

  The pH of the deodorant aqueous slurry is preferably from 3 to 9, and more preferably from 6 to 8, like the deodorant aqueous solution. For final adjustment of the pH of the deodorant aqueous slurry liquid, potassium hydroxide, phosphoric acid, and the organic acid can be used.

  To the deodorant aqueous slurry liquid of the present invention, a dispersant (surfactant), a thickener (water-soluble polymer), a toning agent such as titanium oxide, or an antibacterial agent can be added as necessary. .

Further, the deodorant slurry liquid can contain a porous substance.
Examples of the porous material include crystalline silicates such as silicalite, zeolite, montmorillonite, sepiolite, or a mixture thereof; clays such as white clay, activated clay, diatomaceous earth, kaolin, bentonite, kibushi clay, and gillome clay; silica And metal oxides such as alumina, silica gel, magnesium oxide, titania, alumina, zirconia, silica / alumina, silica / titania, and the like. The average particle diameter of the porous material is 0.1 to 50 μm, preferably 0.5 to 20 μm, more preferably 0.5 to 10 μm.

The content of the porous material is preferably 0 to 90% by weight, more preferably 0 to 70% by weight in the total composition.
The porous substance is added by uniformly mixing the aqueous slurry of the present invention.

  The deodorant slurry liquid of the present invention is applied as it is or after being diluted with water as necessary, and then sprayed on a malodor source or sprayed into air containing a malodorous substance. Moreover, a malodorous substance can be removed from the gas by blowing the gas containing a malodorous substance into this deodorant slurry liquid.

  The deodorant slurry liquid of the present invention can be used as an additive for obtaining a deodorant product. For example, the deodorant slurry liquid is added to an adsorbent such as activated carbon, zeolite, alumina, silica, magnesia and kneaded, and the resulting kneaded product is molded and dried to have a deodorizing action. A molded product having heat resistance and flame retardancy can be obtained. The shape of the molded product can be various shapes such as a pellet shape, a plate shape, a block shape, and a container shape. Such products also have good deodorant properties, heat resistance and flame retardancy even in dry conditions. A fiber product having a deodorizing action can be obtained by impregnating a fiber product such as paper, nonwoven fabric, woven fabric, or fiber with the deodorant slurry liquid of the present invention and drying it.

  The deodorant slurry liquid of the present invention can be used as a blending component for obtaining a resin composition having a deodorizing action. Such compositions include paint compositions, ink compositions, molding resin compositions, and the like. The resin referred to in this specification includes not only a polymer but also a prepolymer thereof. Such resins include thermoplastic resins, thermosetting resins, photosensitive resins, natural polymers, synthetic rubbers, and the like.

  The deodorant powder composition (powder composition) of the present invention can be obtained by separating and drying moisture from the deodorant slurry liquid. This product has deodorizing properties and flame retardancy, and at the same time has excellent heat resistance and heat resistance up to 400 ° C.

  The content of the deodorant composition of the present invention in the powdery composition is 10 to 100% by weight, preferably 30 to 100% by weight, more preferably 50 to 100% by weight, still more preferably 70 to 70%. 100% by weight. In this case, the content of the deodorant composition of the present invention is reduced by including the porous material or the like.

  The powdery composition can be coated on a textile product such as a nonwoven fabric, a woven fabric, or a fiber using a binder, and can be coated on a building material by vacuum pressurization.

  The deodorant powder composition can be added to various resins as a deodorant and a flame retardant as long as it can be contained under production conditions of 400 ° C. or lower. Examples of the resin include semi-synthetic polymers, thermosetting resins, thermoplastic resins, and synthetic rubbers. Examples of the semi-synthetic polymer include cellulose resins such as cellulose acetate and cellulose nitrate, casein plastic, and soy protein plastic. Examples of the thermosetting resin include phenol resin, epoxy resin, melamine resin, urea resin (urea resin), unsaturated polyester resin, alkyd resin, polyurethane resin, and polyimide resin. Thermoplastic resins include: vinyl chloride resins; polyolefin resins such as polyethylene resins and polypropylene resins; polystyrene resins, acrylonitrile-butadiene-styrene resins, acrylic resins; polyethylene terephthalate, polybutylene terephthalate, polytrimethylene terephthalate, Polyester resins such as polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate; Polyamide resins such as various nylons and aramid resins; Polycarbonate resins, polyphenylene ether resins, polyphenylene ether resins, polyphenylene sulfide resins, polyether ether ketones, etc. Is mentioned. Examples of the synthetic rubber include isoprene-based, butadiene-based, acrylonitrile-based, chloroprene-based, styrene-based, and styrene-butadiene-based rubbers.

  Examples of the final products using these resins include non-woven fabrics, woven fabrics, fiber products such as fibers, building materials, charge products, packaging materials, furniture, household goods, and interior materials for vehicles such as automobiles and airplanes.

  There is no limitation on the method of incorporating the powdered composition of the present invention in these final products, but in the case of a thermoplastic resin, a masterbatch containing the powdered composition at a high concentration is produced, and the masterbatch is prepared. It is preferable to perform injection molding, extrusion molding or the like to produce a molded body or to spin a fiber. In addition, as a manufacturing method of a masterbatch, conventionally well-known methods, such as an extrusion method, are employable.

  When manufacturing a masterbatch as a product, it is preferable to manufacture a masterbatch of a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyester resin, or a polyvinyl chloride resin in terms of versatility. As content of the powdery composition added to a masterbatch, 10 to 60 weight% is preferable, 20 to 55 weight% is more preferable, and 30 to 50 weight% is still more preferable. If the content is 10% by weight or more, the concentration is not too low to lose the advantage of producing a masterbatch, and if it is 60% by weight or less, the difficulty of producing a masterbatch is too high. Absent.

  Next, the present invention will be described in more detail with reference to examples. In the following, all parts and% are based on weight.

Example 1
While stirring using AIHO's high-speed mixer “MX-45”, 900 g of potassium hydroxide was added to 1000 g of 75% by weight aqueous solution of phosphoric acid to prepare a potassium phosphate aqueous solution having a concentration of 71% by weight and pH 8. (Phosphoric acid / potassium hydroxide = 7.65 mol / 16.0 mol = 1 mol / 2.1 mol).

Using a high speed mixer “MX-45” manufactured by AIHO, 50 g of ferrous sulfate (FeSO ₄ · 7H ₂ O) was added and dissolved while stirring 500 g of boiling hot water at high speed. Next, 600 g of the potassium phosphate aqueous solution at about room temperature was added to produce a solution containing a deodorant composition (a total of 1150 g of the deodorant composition 476 g).
.

After the solution containing the deodorant composition was allowed to stand for 1 week, a solution in which the upper part was in a transparent solution state and the lower part was in a slurry state having a high viscosity was obtained. The supernatant liquid of about 2/3 of the upper part was taken out and diluted 5-fold with water to obtain a deodorant aqueous solution (pH 7.5) having a deodorant composition concentration of about 8% by weight.
The liquid in the slurry state of about 1/3 of the lower part was taken out to obtain a deodorant aqueous slurry liquid having a concentration of about 50% by weight. Water was removed from the deodorant aqueous slurry using a dryer at 120 ° C. and dried, followed by pulverization with a ball mill to obtain a deodorant powder composition.

  When the deodorizing aqueous solution was allowed to stand for 6 months after production, iron rust did not precipitate, and iron rust did not float in the supernatant nor discolored.

  When 10 cc of a 10% aqueous solution of potassium ferricyanide was added to 100 cc of the aqueous solution obtained in Example 1 and stirred, no blue color was produced.

Comparative Example 1
Using a high-speed mixer “MX-45” manufactured by AIHO, 50 g of ferrous sulfate (FeSO ₄ · 7H ₂ O) is added to 500 g of boiling hot water, and ₄₀ g of EDTA-2Na is further added and dissolved. A deodorant aqueous solution was obtained.
When this product was left at room temperature for 6 months, it turned brown. From the comparison between Example 1 and Comparative Example 1, it can be seen that potassium phosphate used in the present invention is superior to EDTA as a stabilizer.

Example 2
While stirring using AIHO's high-speed mixer “MX-45”, 50 g of ferrous sulfate (FESO ₄ · 7H ₂ O) and 50 g of adipic acid dihydrazide were dissolved in 500 g of boiling hot water. I let you. Then, it was added the same aqueous potassium phosphate 600g Example 1 of approximately room temperature (total 1200g in deodorant composition 526 g).

After the solution containing the deodorant composition was allowed to stand for 1 week, a solution in which the upper part was in a transparent solution state and the lower part was in a slurry state having a high viscosity was obtained. The supernatant liquid of about 2/3 of the upper part was taken out and diluted 5-fold with water to obtain a deodorant aqueous solution (pH 7.5) having a deodorant composition concentration of about 8% by weight. The liquid in the slurry state of about 1/3 of the lower part was taken out to obtain a deodorant aqueous slurry liquid having a concentration of about 50% by weight.
Water was removed from the deodorant aqueous slurry using a dryer at 120 ° C. and dried, followed by pulverization with a ball mill to obtain a deodorant powder composition.

  Even when 10 cc of 10% aqueous solution of potassium ferricyanide was added to 100 cc of the obtained deodorant aqueous solution and stirred, no blue color was produced. Further, when the deodorant aqueous solution was allowed to stand for 6 months, the iron rust did not precipitate, and the iron rust was not floated or discolored in the supernatant.

Example 3
While stirring using AIHO's high-speed mixer “MX-45”, 45 g of ferrous sulfate (FeSO ₄ · 7H ₂ O) and zinc sulfate (ZnSO ₄ · 7H ₂ O) are added to 500 g of boiling hot water. ) 5 g and 50 g of adipic acid dihydrazide were added and dissolved. Next, 600 g of an aqueous potassium phosphate solution at room temperature was added in the same manner as in Example 1 (526 g of deodorant composition in a total of 1200 g).

  After the solution containing the deodorant composition was allowed to stand for 1 week, a solution in which the upper part was in a transparent solution state and the lower part was in a slurry state having a high viscosity was obtained. The supernatant liquid of about 2/3 of the upper part was taken out and diluted 5-fold with water to obtain a deodorant aqueous solution (pH 7.5) having a deodorant composition concentration of about 8% by weight. The liquid in the slurry state of about 1/3 of the lower part was taken out to obtain a deodorant aqueous slurry liquid having a concentration of about 50% by weight. Water was removed from the deodorant aqueous slurry using a dryer at 120 ° C. and dried, followed by pulverization with a ball mill to obtain a deodorant powder composition.

  Even when 10 cc of 10% aqueous solution of potassium ferricyanide was added to 100 cc of the obtained deodorant aqueous solution and stirred, no blue color was produced. Further, when the deodorant aqueous solution was allowed to stand for 3 months, no iron rust occurred.

Comparative Example 2
Using a high-speed mixer “MX-45” manufactured by AIHO, 50 g of ferrous sulfate (FeSO ₄ .7H ₂ O) and 50 g of adipic acid dihydrazide were added in order to 500 g of boiling hot water, and a deodorizer. An aqueous solution was obtained.
This product is left unattended for one day after production, and ferrous sulfate reacts with oxygen in the aqueous solution to become iron rust, yellows and precipitates, and cannot be used as a deodorant. there were.

Reference Comparative Example 1
Using a high speed mixer “MX-45” manufactured by AIHO, 50 g of adipic acid dihydrazide was added while stirring 500 gL of boiling hot water at high speed, and calcium chloride 50 was further added to obtain a deodorant aqueous solution.

Deodorization Test 6 mL of the deodorant aqueous solution obtained in Examples 1 to 3, Comparative Example 1, and Reference Comparative Example 1 was applied to a 10 cm × 20 cm non-woven fabric and dried, and each was placed in a 5 L Tedlar bag. Next, 3 L of gas containing 25 ppm of ammonia, 50 ppm of acetic acid, 2.4 ppm of hydrogen sulfide, 30 ppm of acetaldehyde, and 20 ppm of formaldehyde is sequentially injected into each Tedlar bag, and the concentration of each gas after 1 hour has been detected for each gas. Measured by tube. The measurement results are shown in Table 1. This experiment was performed in an atmosphere at a temperature of 20 ° C. and a humidity of 65%.

From Table 1, it can be seen that the deodorizing aqueous solution of Example 1 has excellent deodorizing properties with respect to ammonia, acetic acid, and hydrogen sulfide. In addition, although the deodorizing aqueous solution of Comparative Example 1 is inferior to the stability of ferrous sulfate, it has the same deodorizing characteristics as Example 1.
Moreover, it turns out that the deodorizing aqueous solution of Example 2, 3 has shown the deodorizing characteristic outstanding with respect to all of ammonia, acetic acid, hydrogen sulfide, acetaldehyde, and formaldehyde. In contrast, the deodorizing aqueous solution of Reference Comparative Example 1 containing adipic acid dihydrazide as a main component can remove acetic acid, acetaldehyde, and formaldehyde, but has almost no deodorizing properties with respect to ammonia and hydrogen sulfide.

Ammonia gas injection repeated deodorization test 3 mL of the deodorizing aqueous solution obtained in Examples 2 and 3 and Reference Comparative Example 1 was applied to a 10 cm × 10 cm non-woven fabric and dried, and each was placed in a 5 L Tedlar bag. Next, the desired concentration in the Tedlar bag was adjusted to 100 ppm, and 100 ppm of ammonia gas was injected every 20 minutes, and the ammonia concentration was measured with a detector tube each time. The measurement results are shown in Table 2.

  From the comparison between Examples 2 and 3 in Table 2 and Reference Comparative Example 1, the aqueous solution containing the deodorant composition of the present invention does not generate ammonia even when adipic acid dihydrazide is added. I understand. On the other hand, the deodorant aqueous solution of Reference Comparative Example 1 containing adipic acid dihydrazide as a main component has no deodorizing property with respect to ammonia, and adipic acid dihydrazide itself generates ammonia from the measured value at the 0th time. I understand that.

Deodorant Characteristics of Deodorant Powdery Composition 3 g of the powdery composition obtained in Example 2 was placed in a 5 L Tedlar bag. Next, 3 L of gas containing 100 ppm of ammonia, 30 ppm of hydrogen sulfide, and 30 ppm of acetaldehyde was injected into each Tedlar bag, and the concentration of each gas after 20 minutes was measured with a detector tube. Table 3 shows the measurement results. This experiment was performed in an atmosphere at a temperature of 20 ° C. and a humidity of 65%.

  From Table 3, it can be seen that the deodorant composition of the present invention containing adipic acid dihydrazide can deodorize acetaldehyde together with ammonia and hydrogen sulfide.

80 ° C. Heat Resistance Test 3 mL of the deodorant aqueous solution obtained in Example 2 and Comparative Example 2 was applied to a 10 cm × 10 cm non-woven fabric and dried, and each was placed in a 5 L Tedlar bag. Next, after leaving in an atmosphere of 80 ° C. for 20 minutes, the ammonia concentration in the Tedlar bag was measured with a detector tube.
As a result, it was 0 ppm for the nonwoven fabric coated with the deodorant aqueous solution of Example 2, and 5 ppm for the nonwoven fabric coated with the combined deodorant aqueous solution of Reference Comparative Example 1. From this result, the deodorant composition of the present invention does not generate ammonia even under high temperature despite containing adipic acid dihydrazide, whereas adipic acid dihydrazide is the main component. It can be seen that the deodorant that generates ammonia generates ammonia at high temperatures.

Flame Retardancy Test 6 mL of the deodorant aqueous solution obtained in Examples 1 to 3 and Reference Comparative Example 1 was applied to 20 cm × 10 cm paper, dried, and then brought into contact with a lighter flame for 5 seconds. The paper coated with the aqueous solution of Example 1 showed flame retardancy without burning, but the paper coated with the deodorant of Reference Comparative Example 1 burned out and the flame did not disappear.

Claims (17)

A deodorant composition comprising ferrous sulfate and / or zinc sulfate and potassium phosphate . The deodorant composition according to claim 1, comprising a hydrazide compound. The deodorant composition according to claim 2 , wherein the hydrazide compound is adipic acid dihydrazide. The deodorant composition according to any one of claims 1 to 3 , further comprising a chelating agent. The deodorant composition according to claim 4 , wherein the chelating agent is ethylenediaminetetraacetic acid (EDTA). An organic acid is contained, The deodorant composition in any one of Claims 1-5 characterized by the above-mentioned. The deodorant composition according to claim 6, wherein the organic acid is an acid selected from citric acid, malic acid, tartaric acid, and oxalic acid. A deodorant aqueous solution comprising the deodorant composition according to any one of claims 1 to 7 . The deodorant aqueous solution according to claim 8 , wherein the content of the deodorant composition is 0.3 to 20% by weight. pH is 3-9, The deodorizing aqueous solution of Claim 8 or 9 characterized by the above-mentioned. A deodorant aqueous slurry containing the deodorant composition according to any one of claims 1 to 7 . The deodorant aqueous slurry liquid according to claim 11 , wherein the content of the deodorant composition is 30 to 70% by weight. A deodorant powder composition comprising the deodorant composition according to any one of claims 1 to 7 . The deodorant powder composition according to claim 13 , wherein the content of the deodorant composition is 10 to 100% by weight. A deodorant masterbatch comprising a thermoplastic resin containing the deodorant composition according to any one of claims 1 to 7 . The deodorant masterbatch according to claim 15 , wherein the content of the deodorant composition is 10 to 60% by weight. The deodorizing master according to claim 15 or 16 , wherein the thermoplastic resin is any one of a polyethylene resin, a polypropylene resin, a polystyrene resin, a polyester resin, and a polyvinyl chloride resin. batch.