WO2012090580A1

WO2012090580A1 - Liquid deodorant composition for textile products

Info

Publication number: WO2012090580A1
Application number: PCT/JP2011/075052
Authority: WO
Inventors: 洋子浅沼; 直行江川; 英史小倉; 昌平藤村
Original assignee: ライオン株式会社
Priority date: 2010-12-27
Filing date: 2011-10-31
Publication date: 2012-07-05
Also published as: MY161136A; KR101922946B1; KR20140022373A; JP5735005B2; JPWO2012090989A1; WO2012090989A1

Abstract

The present invention provides a liquid deodorant composition for textile products, that includes: (A) zinc sulfate or copper sulfate; (B) methylglycine diacetic acid, iminobissuccinic acid, or a salt thereof; and (C) a water-soluble solvent; whereby (A)/(B)=0.01-6 (molar ratio). The liquid deodorant composition for textile products has an excellent deodorizing effect on complex odors attached to textile products.

Description

Liquid deodorant composition for textile products

The present invention relates to a liquid deodorant composition for fiber products and a liquid deodorant article for fiber products, which is excellent in deodorizing a composite odor such as tobacco odor, food odor and body odor attached to fibers.

In recent years, there is a growing tendency to worry about bad smells attached to fibers such as curtains, sofas, clothing and bedding. “Deodorization technology” has been developed for industrial filters, but the market has been increasing year by year as various companies have started to release deodorant sprays for household use. Inventions related to deodorization technology embodied in these deodorant sprays have been the subject of patents (Patent Documents 1 to 3).
Among them, as a deodorizing technique, a technique using a metal complex of a metal ion and a chelating agent has been proposed. The main purpose of this technology is to deodorize single or specific components, such as tobacco odor containing multiple malodorous components such as pyridine, nicotine and acetic acid, body odor containing oils and fatty acids such as sebum and sweat, It is not suitable for deodorizing complex odors such as excrement odors including hydrogen, methyl mercaptan and ammonia. Furthermore, since the deodorizing spray for home use has to consider damages such as discoloration and damage of fibers, it is difficult to use industrial techniques as they are (Patent Documents 4 and 5).

JP 2006-299501 A JP 2005-248372 A Japanese Patent No. 4170155 JP 2000-70351 A JP 2002-143283 A

An object of the present invention is to provide a liquid deodorant composition for a textile product and a liquid deodorant article for a textile product, which are excellent in the effect of deodorizing the composite odor attached to the textile product.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by combining zinc sulfate and methylglycine diacetic acid at a specific molar ratio. The inventors further searched for compounds that exhibit the same effect as these combinations, and completed the present invention.
That is, the present invention provides (A) a divalent water-soluble metal salt,
(B) at least one compound represented by the following formulas (I) to (IV);
(C) 5-30% by mass of water-soluble solvent
A liquid deodorant composition for textiles is provided that contains (A) / (B) = 0.01 to 6 (molar ratio).

(In the formula (I), A ^I represents an alkyl group, a sulfo group, an amino group, a hydroxyl group, a hydrogen atom or COOM ^I , and M ^I may be the same as or different from each other, and each represents a hydrogen atom, an alkali metal, or an alkaline earth. 1 type selected from the group consisting of similar metals, cationic ammonium groups and alkanolamines, and m ^I and n ^I are each an integer of 0 to 2, provided that m ^I and n ^I are both 0 , A ^I is a methyl group.
In the formula (II), X ^II-1 to X ^II-4 may be the same or different and are each independently a group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group and an alkanolamine. One selected from the above, Q ^II represents a hydrogen atom or an alkyl group, R ^II represents a hydrogen atom or a hydroxyl group, and n ^III represents an integer of 0 or 1.
In the formula (III), R ^III is a linear or branched C8-C22 alkyl and alkenyl group, A ^III is H, a methyl group, or (CH ₂ ) n ^III —COOX ^III , X ^III-1 is Each represents H, an alkali metal atom, an alkaline earth metal atom, an alkanolamine, or NH ₄ . n ^III represents any one of 1 to 3.
In the formula (IV), X ^IV represents a hydrogen atom, an alkali metal, or an alkaline earth metal. n ^IV represents an integer of 1 or 2, and when n ^IV is 2, X ^IV may be the same or different. )
The present invention also provides a liquid deodorizing article for textiles, which contains a liquid deodorant composition for textiles in a spray container.

According to the present invention, it is possible to effectively deodorize complex odors such as tobacco odor, food odor and body odor adhering to the fiber. Even if the composition of the present invention is applied to a textile product, it does not cause discoloration such as a stain or cause fabric damage, and exhibits a high effect in a small amount. According to the present invention, a textile product can be easily deodorized even at home.

(A) Divalent water-soluble metal salt (A) Component is a salt of the above specific metal, specifically, water-soluble zinc salts such as zinc sulfate and zinc chloride; water-soluble copper such as copper sulfate and copper chloride Salts; water-soluble iron salts such as iron sulfate; and water-soluble manganese salts such as manganese chloride. The component (A) includes these hydrates. From the viewpoint of deodorizing performance, a water-soluble zinc salt or a water-soluble copper salt is preferable. As the water-soluble zinc salt, zinc sulfate and zinc chloride are preferable. As a water-soluble copper salt, copper sulfate and these hydrates are preferable, copper sulfate hydrate is more preferable, and copper sulfate pentahydrate is still more preferable.
(A) A component can be used individually by 1 type or in combination of 2 or more types as appropriate. When using 2 or more types together, it is preferable that a zinc salt is included.
In the present specification, the “water-soluble metal salt” means a metal salt that dissolves 10 g or more in 1 liter of water at 25 ° C.
The content of the component (A) in the composition of the present invention is preferably 0.01 to 10% by mass, and more preferably 0.05 to 5% by mass. However, when the component (A) is a hydrate, it means the blending amount as an anhydride. If the proportion of component (A) is less than 0.01% by mass, the deodorizing effect will be insufficient. If it exceeds 10% by mass, the storage stability of the composition deteriorates, and there is a high possibility that defects such as blotting and discoloration will occur in the target fiber.

The component (B) in the present invention is a compound represented by the following formulas (I) to (IV). (B) A component can be used individually by 1 type or in combination of 2 or more types as appropriate.

In the formula (I), A ^I represents a linear or branched alkyl group having 8 to 22 carbon atoms, a sulfo group, an amino group, a hydroxyl group, a hydrogen atom, or COOM ^I. As A ^I , CH ₃ , OH, H, and COOM ^I are preferable, CH ₃ and H are more preferable, and CH ₃ is particularly preferable.
M ^I may be the same or different from each other, and each represents one selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group, and an alkanolamine. As an alkali metal, sodium and potassium are preferable. As the alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable. As M ^I , an alkali metal is preferable, and sodium is particularly preferable.
m ^I and n ^I are each an integer of 0-2. m ^I is preferably 0 or 1. n ^I is preferably 0 or 1. When both m ^I and n ^I are 0, A ^I is CH ₃ .

Among the compounds represented by the formula (I), preferred are methylglycine diacetate (MGDA), aspartate diacetate (ASDA), isoserine diacetate (ISDA), β-alanine diacetate (ADAA), serine diacetate. Examples include acetic acid (SDA), glutamic acid diacetate (GLDA), or salts thereof. Of these, MGDA or a salt thereof is preferable.

In the formula (II), X ^II-1 to X ^II-4 may be the same or different and are each selected from the group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group, and an alkanolamine. Represents a species. As an alkali metal, sodium and potassium are preferable.
As the alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable. The M ^II, alkali metals are preferred, sodium being particularly preferred.
Q ^II represents a hydrogen atom or a linear or branched alkyl group having 8 to 22 carbon atoms.
R ^II represents a hydrogen atom or a hydroxyl group. n ^II represents 0 or 1.

Preferred examples of the compound represented by the formula (II) include iminodisuccinic acid (IDS), hydroxyiminodisuccinic acid (HIDS), and salts thereof. Among them, IDS or a salt thereof is more preferable. preferable.

In the formula (III), R ^III represents a linear or branched alkyl or alkenyl group having 8 to 22 carbon atoms, preferably 12 to 18 carbon atoms.
A ^III represents H, a methyl group or (CH ₂ ) m ^III -COOX ^III . A ^III is preferably (CH ₂ ) m ^III -COOX ^III .
m ^III represents any number of 1 to 3.
X ^III represents H, an alkali metal, an alkaline earth metal, an alkanolamine or NH ₄ . As an alkali metal, sodium and potassium are preferable. As the alkanolamine, monoethanolamine, diethanolamine, and triethanolamine are preferable.
n ^III represents any one of 1 to 3.

Specific examples of the compound represented by the formula (III) include alkyl and alkenyl amino acetates such as sodium octylaminoacetate, sodium laurylaminoacetate, sodium myristylaminoacetate, sodium palmitylaminoacetate, sodium oleylaminoacetate;
Alkyl and alkenyl aminopropionates such as sodium octylaminopropionate, sodium decylaminopropionate, sodium laurylaminopropionate, sodium myristylaminopropionate, sodium palmitylaminopropionate, sodium oleylaminopropionate;
N-alkyl and alkenyl glycine salts such as sodium N-octylglycine, sodium N-decylglycine, sodium N-laurylglycine, sodium N-myristylglycine, sodium N-palmitylglycine, sodium N-oleylglycine, etc .;
N-octyl-N-methyl-β-alanine sodium, N-decyl-N-methyl-β-alanine sodium, N-dodecyl-N-methyl-β-alanine sodium, N-myristyl-N-methyl-β-alanine N-alkyl and alkenyl-N-methyl-β-alanine salts such as sodium, sodium N-palmityl-N-methyl-β-alanine, N-oleyl-N-methyl-β-alanine sodium;
Alkyl and alkenylamino diacetates such as sodium octylaminodiacetate, sodium decylaminodiacetate, sodium laurylaminodiacetate, sodium myristylaminodiacetate, sodium palmitylaminodiacetate, sodium oleylaminodiacetate; and octylaminodipropionic acid Examples include sodium, sodium decylaminodipropionate, sodium laurylaminodipropionate, sodium myristylaminodipropionate, sodium palmitylaminodipropionate, sodium oleylaminodipropionate, and alkenylaminodipropionate. It is done.
Among these, in view of storage stability, alkyl and alkenylamino diacetates are preferable, among which decylaminodiacetic acid, laurylaminodiacetic acid, myristylaminodiacetic acid, palmitylaminodiacetic acid or salts thereof are preferable, and lauryl is particularly preferable. More preferred is aminodiacetic acid, myristylaminodiacetic acid, palmitylaminodiacetic acid or a salt thereof.

In the formula (IV), X ^IV represents a hydrogen atom, an alkali metal or an alkaline earth metal. n ^IV represents 1 or 2, and when n ^IV is 2, X ^IV may be the same or different. The substitution position of the (COOX ^IV ) n ^IV group is not particularly limited, but the α position is preferred.

As the component (B), a compound represented by the formula (I) and a compound represented by the formula (II) are particularly preferable, and MDGA, IDS and salts thereof are particularly preferable. MDGA and its salts are most preferred.

The amount of component (B) in the composition of the present invention exceeds 0% by mass, preferably 15% by mass or less, more preferably 10% by mass or less, and particularly preferably 5% by mass or less. , Preferably 0.05% by mass or more, more preferably 0.1% by mass or more. By setting the blending amount of the component (B) to 10% by mass or less, it is possible to effectively prevent discoloration such as a stain on the fiber product to which the composition of the present invention is applied.
The composition of the present invention has an odor that seems to be derived from the component (B). From the viewpoint of storage stability of odor, the pH (25 ° C.) of the composition is preferably 6.5 or less. In this case, the amount of component (B) is preferably 3% or less, more preferably 1% or less, and still more preferably 0.5% or less. Depending on the balance between the pH of the composition and the amount of component (B), the more the amount of component (B) increases, the worse the odor of the composition over time.
The composition of the present invention can obtain a deodorizing effect superior to that of a conventional deodorant composition by using the component (A) and the component (B) in combination. When the blending molar ratio of the component (A) to the component (B) is expressed by (A) / (B), it is necessary from the aspect of deodorizing effect to be 0.01 to 6. When the ratio is preferably 0.05 to 2.5, more preferably 0.3 to 1, a further deodorizing effect can be obtained.

Component (C): Water-soluble solvent As the water-soluble solvent used in the present invention, those generally used in liquid deodorant compositions for textiles can be used. The “water-soluble solvent” as used herein refers to a solvent that is mixed with water at an arbitrary ratio and mixed transparently. Specifically, primary alcohols having 2 to 3 carbon atoms such as ethanol and isopropanol; glycols having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol and dipropylene glycol; and carbon numbers such as glycerin and diethylene glycol monobutyl ether Examples thereof include 3 to 8 polyhydric alcohols. Ethanol, glycerin, and diethylene glycol monobutyl ether are preferable from the viewpoint of the influence on the aroma of the liquid deodorant composition for textiles and the price.
The content of the water-soluble solvent is preferably 5 to 30% by mass and more preferably 10 to 20% by mass in the composition of the present invention. If the amount is less than this, it may take time to dry. If it is more than this, there is a possibility that the user will be exposed.

The liquid deodorant composition for textiles according to the present invention can be blended with the following optional components blended in a general liquid deodorant composition for textiles within a range not impairing the effects of the present invention. .
Component (D): Quaternary ammonium compound It is preferable to include a quaternary ammonium compound in the composition of the present invention because the composition can easily penetrate into the cloth and enhance the deodorizing effect. (D) As the quaternary ammonium compound, a compound represented by the following formula (V) can be used.

In the formula, Rs may be the same as or different from each other, and each of them may be H or having 1 to 14 carbon atoms, and may contain O or a benzene ring therebetween. Preferably, it represents a hydrocarbon group having 8 to 12 carbon atoms, preferably a linear or branched alkyl group or an alkenyl group. X represents Cl, Br, CH ₃ SO ₄ or C ₂ H ₅ SO ₄ .
Examples of the compound represented by the formula (V) include didecyldimethylammonium chloride, stearyltrimethylammonium chloride, benzalkonium chloride, benzethonium chloride, and the like. Didecyldimethylammonium chloride and stearyltrimethylammonium chloride are exemplified. It is preferable from the aspect of the effect.
The amount of component (D) in the composition of the present invention is usually 0 to 20% by mass, preferably 0.01 to 20% by mass, more preferably 0.05 to 5% by mass. Even if it mixes more than this, an effect does not improve.
The mass ratio of (A) / (D) is usually 0 to 100, preferably 0.01 to 100, and more preferably 0.1 to 10. It is preferable to use both in such a ratio because the component (A) can efficiently penetrate into the fiber product.

[Nonionic surfactant]
By including a nonionic surfactant, the dispersion stability of the deodorant composition for textiles of the present invention can be enhanced.
Examples of the nonionic surfactant that can be used in the present invention include polyoxyethylene alkyl ethers having an alkyl group or alkenyl group having 10 to 22 carbon atoms and an average addition mole number of oxyethylene groups of 10 to 100 moles, Polyoxyethylene fatty acid alkyl (C1-3) esters, polyoxyethylene alkylamines having an average addition mole number of oxyethylene groups of 10 to 100 moles, alkyl polyglucosides having an alkyl group or alkenyl group of 8 to 18 carbon atoms And hydrogenated castor oil having an average addition mole number of oxyethylene groups of 20 to 100 moles. Among them, a polyoxyethylene alkyl ether having an alkyl group having 10 to 14 carbon atoms, an average addition mole number of oxyethylene groups of 5 to 20 moles, and an average addition mole number of oxyethylene groups of 30 to 50 moles Castor oil is preferred.

The blending amount of the nonionic surfactant in the liquid deodorant composition for textile products of the present invention is preferably 0.01 to 5% by mass, more preferably 0.1 to 3% by mass. Within this range, the dispersion stability of the liquid deodorant composition for textiles can be enhanced.

Other ingredients include chelating agents, anti-contamination agents, polymers, preservatives, antibacterial agents, antifungal agents, repellents, natural product extracts, dispersants, dyes, antioxidants, thickeners As long as it is highly safe and used for ordinary cleaning agents, such as a thickener and an ultraviolet absorber, any material may be used without any particular limitation. The upper limit of the amount of the optional component in the present invention is preferably 5% by mass or less, more preferably 3% by mass or less.

From the viewpoint of suppressing the growth of bacteria on textiles and suppressing the generation of unpleasant odors, one or more of organic antibacterial and antifungal agents are used alone or in combination It can be used by mixing. Organic fungicides and fungicides include alcohol, phenol, aldehyde, carboxylic acid, ester, ether, nitrile, peroxide / epoxy, halogen, pyridine / quinoline, triazine, Examples include isothiazolone, imidazole / thiazole, anilide, biguanide, disulfide, thiocarbamate, saccharide, tropolone, and organometallic. In addition, the inorganic antibacterial and fungicides include metal oxides and silver. For example, an antibacterial agent or a disinfectant such as isopropylmethylphenol is preferably blended in the liquid deodorant composition in the range of 0.05 to 1% by mass.

Moreover, in order to ensure the storage stability of the components contained in the liquid deodorant composition, a pH adjuster can be added to the deodorant composition. Examples of the acid include inorganic acids such as hydrochloric acid and sulfuric acid, and carboxylic acids such as acetic acid and citric acid. Examples of the alkali include alkali metal salts such as sodium hydroxide and alkanolamines such as triethanolamine.

Furthermore, in order to scent the liquid deodorant composition itself or the fiber product treated with the liquid deodorant composition, a fragrance can be added to the liquid deodorant composition. Any perfume normally used in the field of the present invention can be used, for example, a perfume composition containing a perfume component, a solvent, and a stabilizer as described in JP-A-2008-7872, and a liquid 0.005 to 5% by mass can be added to the deodorant composition. From the viewpoint of scenting effect and economy, it is preferable to blend 0.01 to 1% by mass.

In addition, a silicone compound can be blended in the liquid deodorant composition to obtain a “wrinkle removing deodorant composition” that reduces the deodorizing effect and wrinkles such as suits. Silicone compounds include dimethyl silicone, polyether modified silicone, methylphenyl silicone, alkyl modified silicone, higher fatty acid modified silicone, methyl hydrogen silicone, fluorine modified silicone, epoxy modified silicone, carboxy modified silicone, carbinol modified silicone and amino modified. Examples include silicone. In the present invention, a polyether-modified silicone is preferable as the silicone compound used, and among them, a polyether-modified silicone having an HLB of 13 or less, preferably 10 or less, more preferably 7 or less is preferable from the viewpoint of reducing wearing wrinkles. . Specifically, compounds such as SH3775C and SH3772C manufactured by Toray Dow Corning are suitable. These silicone compounds can be blended in an amount of 0.01 to 5% by mass in the liquid deodorant composition. From the viewpoint of wrinkle reduction effect and economic efficiency, it is preferable to add 0.1 to 1% by mass.

The liquid deodorant composition for textiles of the present invention can be produced by a conventional method. For example, (C) water-soluble solvent, if necessary, add (D) optional components such as quaternary ammonium compounds, silicone compounds, nonionic surfactants, etc., add water to some extent, then add component (A) Add ingredients (B) and mix. Then, if necessary, use a pH adjuster such as sodium hydroxide, hydrochloric acid, sulfuric acid, etc., and adjust the pH while stirring the mixture with a stirrer with a pH meter (for example, model number MP230 manufactured by Mettler Toledo). It can manufacture by adding water.
In addition, after adding and stirring the A and B components in an arbitrary amount of water, add a small mixture of components other than the A, B and water in advance, and add a pH adjuster such as sodium hydroxide, hydrochloric acid or sulfuric acid. There is a method of using a pH meter (for example, model number MP230 manufactured by Mettler Toledo) to adjust the pH while stirring with a stirrer, and then adding the remaining water, but this is not a limitation. Absent.

The pH of the composition of the present invention is not particularly limited. However, in order to ensure the storage stability of the liquid deodorant composition and the target odor control effect, it is preferable to adjust the pH of the liquid deodorant composition to a certain range using the pH adjustor. In such a pH range, for example, the lower limit is preferably 3 or more, and the upper limit is preferably 8 or less, more preferably 6.5 or less. In addition, when the lower limit is preferably 4 or more, more preferably 5.5 or more, and the upper limit is preferably 9 or less, it is possible to enhance the deodorizing effect of pillow cover odor, body odor and the like.
From the viewpoint of storage stability, the pH of the composition is preferably 6.5 or less, and more preferably 5 or less. When the pH of the composition is higher than 6.5, the appearance of the composition may change due to storage, but the reason is not limited by any theory, but the A component / B component It is conceivable that the greater the molar ratio of 1, the greater the amount of the component A in the composition in the ionic state in the composition, and the formation of a water-insoluble compound over time. In addition, the odor may change due to storage, but the reason is not limited by any theory, but it is conceivable that the B component is altered by high pH.

Moreover, the viscosity of the liquid deodorant composition for textiles of the present invention is preferably 10 mPa · s or less. When used in a spray container, it is more preferably 5 mPa · s or less. In addition, the viscosity shown here is a numerical value when the stock solution is measured at 25 ° C. using a B-type viscometer (manufactured by Tokimec).

The method of using the liquid deodorant composition of the present invention for a textile product is not particularly limited. The fiber product may be dipped in the composition and then air-dried, or the composition may be stored in a spray container and sprayed with the composition on the fiber product and then air-dried. In particular, from the point of view of simplicity that can be easily implemented at home and the economic efficiency that the required amount of the composition can act only on the part where the odor of the textile product is anxious, the composition is stored in a spray container, and the textile product. The method of spraying and using is preferable.

Examples of spray containers include aerosol spray containers, trigger spray containers (direct pressure type or accumulator type), dispenser spray containers, and the like. Examples of the aerosol spray container include those described in JP-A-9-3441 and JP-A-9-58765. Examples of the propellant include LPG (liquefied propane gas), DME (dimethyl ether), carbon dioxide gas, nitrogen gas, and the like. These may be used alone or in combination of two or more. . Examples of the trigger spray container include those described in JP-A-9-268473, JP-A-9-256272, JP-A-10-76196, and the like. Examples of the dispenser spray container include those described in JP-A-9-256272.

The amount of spray when the article of the present invention is used by spraying on the target textile product is not particularly limited because it depends on the strength of the attached odor, but the lower limit is preferable with respect to the mass of the textile product. Is 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and the upper limit is preferably 100% by mass or less, more preferably 80% by mass or less, and further preferably 50% by mass or less. . It is preferable for the spray amount to be within this range since it is excellent in deodorizing effect and economy.

The liquid deodorant composition of the present invention can be stored in a plastic container. Examples of the plastic container include a bottle container and a standing pouch for refilling. Examples of the standing pouch include those described in Japanese Patent Application Laid-Open No. 2000-72181. The material is a double layer of 100 to 250 μm linear low density polyethylene for the inner layer and 15 to 30 μm stretched nylon for the outer layer. From the viewpoint of storage stability, a standing pouch having a structure or a three-layer structure in which 15 μm stretched nylon is an intermediate layer and 15 μm stretched nylon is an outer layer is preferable.

Although it does not specifically limit as a textile product for which the liquid deodorant composition of the present invention is used, for example, Y shirt, T shirt, polo shirt, blouse, chinos, suit, slacks, skirt, table cloth, place mat, Examples include curtains, sofas, pillow covers, sheets, shoes, and toilet mats. Also, the material of the target textile product is not particularly limited. For example, natural fibers such as cotton, wool and hemp, synthetic fibers such as polyester, nylon and acrylic, semi-synthetic fibers such as acetate, rayon, tencel and polynosic. And the like, and blended products, blended fabrics, blended products of these various fibers, etc., and among them, the effect of the composition of the present invention is remarkably exhibited in wool and its blended products that are difficult to maintain regularly. Is done.

<Preparation of liquid deodorant composition for textile products>
The compositions used in Examples and Comparative Examples were prepared as follows with the blending amounts (% by mass) shown in Tables 1 to 3.
Purified water was added to a mixture of components (A), (B) and components other than purified water in advance, and then components (A) and (B) were added. Then, using a pH meter (Horiba, Ltd., pH meter model number F-52, pH electrode model number 9615-10D) in a room at room temperature of 25 ° C., 0.1 N water was measured while measuring the pH while stirring the composition. The pH was adjusted with sodium oxide or dilute sulfuric acid, and the remaining purified water was added. In Tables 1 to 3 below, the amount of purified water added is the balance when the total amount of the composition is 100% by mass. Details of each component are as follows.

(A) Component A-1: Zinc sulfate (II) (manufactured by Kanto Chemical Co., Inc.)
A-2: Copper sulfate pentahydrate (manufactured by Kanto Chemical Co., Inc.)
A-3: Zinc chloride (Kanto Chemical Co., Ltd.)
A-4: Iron (II) sulfate (manufactured by Kanto Chemical Co., Inc.)
A-5: Aluminum sulfate (III)

(B) Component B-1: Trisodium methylglycine diacetate “MGDA” (manufactured by BASF)
B-2: 2,2'-Iminodisuccinic acid tetrasodium salt (LANXESS)
B-3: Laurylaminodiacetic acid ([Product Name] Nissan Anon Powder, manufactured by NOF Corporation)
B-4: 2,3-pyridinedicarboxylic anhydride (ACR)
B-5: Ethylenediaminetetraacetic acid “EDTA” (manufactured by Kanto Chemical Co., Inc.)
B-6: Diethylenetriamine “DETA”: (manufactured by Tokyo Chemical Industry Co., Ltd.)

(C) Component C-1: Synthetic ethanol 95% (Japan alcohol sales)
C-2: Glycerin Reagent Pure Chemical

(D) Component D-1: Didecyldimethylammonium chloride “AQ210” (Arcade 210-80E, manufactured by Lion Akzo Co., Ltd.)

(E) Common component E-1: Polyoxyethylene hydrogenated castor oil (HC40: Japanese emulsion): 0.5%
Polyether-modified silicone (SH3775M: manufactured by Toray Dow Corning Co., Ltd.):
0.2%
E-2: Polyether-modified silicone (same as used in E-1): 0.5%
(F) Fragrance F-1: Fragrance composition a-1-1 described in Examples of JP-A-2008-7872
F-2 to F-4: See Table 4

Next, evaluation methods performed in Examples and Comparative Examples are shown below.
<Tobacco odor deodorant evaluation method>
16 wool surge cloths (15cm x 20cm, 5g) are hung on the top of cardboard 50cm x 30cm x 50cm in height, and one lit cigarette (Mild Seven, manufactured by Nippon Tobacco Inc.) is made of cardboard. Placed on the bottom, the cardboard was sealed and left for 40 minutes. After that, the top of the cardboard was opened and left for 40 minutes to take out the cloth. 1 g of the composition described in the examples or comparative examples was sprayed uniformly onto the test cloth using a dispenser pump spray (style guard cleansing wrinkles and odors, manufactured by Lion Co., Ltd.). After leaving as it is for 10 minutes, the intensity of tobacco odor was scored according to the evaluation standard A. The evaluation was performed by sensory evaluation of the intensity of tobacco odor remaining on the cloth by 10 panelists according to the following criteria, and the average value was described in Examples or Comparative Examples according to Evaluation Criteria B.

<Evaluation criteria A>
5 points: intense odor 4 points: strong odor 3 points: odor intensity that can be easily detected 2 points: odor intensity enough to detect what odor 1 point: odor intensity that can finally be detected 0 Point: Odorless <Evaluation criteria B>
◎◎◎: Less than 0.25 points ◎◎: 0.25 or more and less than 0.5 points ◎: 0.5 or more and less than 1.5 points ○: 1.5 or more and less than 2.5 points △: 2.5 or more and less than 3.5 points ×: 3.5 or more points ○, ◎, ◎ ◎, ◎◎◎ are acceptable.

<Method for evaluating discoloration of target clothing>
Put a wool top milled cloth (30cm x 30cm, gray) on a vertically standing acrylic board (40cm x 50cm) with clothespins, and dispense the dispenser pump spray (style guard wrinkle) The odor was sprayed 3 times on the same part using a clean spray (manufactured by Lion Co., Ltd.) at a distance of 20 cm from the test cloth. After drying for 2 hours as it was, the color change such as discoloration of the sprayed part and ring stain was judged visually.
<Evaluation criteria C>
◎: No change ◎: Slightly discolored ○: Slightly discolored △: Fairly discolored ×: Clearly discolored ○, ◎, ◎◎ pass.

<Pillow cover deodorant evaluation method>
A cotton cloth (10 cm x 10 cm, Kanakin No. 3, manufactured by Japan Standards Association) was sewed on a pillow and used as a test cloth by men in their 30s and 40s for a week. 1 g of the composition described in the examples or comparative examples was sprayed uniformly onto the test cloth using a dispenser pump spray (style guard cleansing wrinkles and odors, manufactured by Lion Co., Ltd.). After standing for 10 minutes as it was, the strength of the odor of the pillow was scored according to the evaluation standard A. The evaluation was performed by sensory evaluation of the intensity of bad odor remaining on the cloth with 10 panelists according to the following criteria, and the average value was described in Examples or Comparative Examples according to Evaluation Criteria B.

<Toilet mat deodorant evaluation method>
10 g of urine collected from 5 males in their 20s to 40s was evenly applied to a toilet mat (65cm x 65cm, good dry D Nature (white), manufactured by Oka Corporation) and left at room temperature for 3 days This was used as a test cloth. 1 g of the composition described in Examples or Comparative Examples was sprayed uniformly on the above-mentioned test cloth 10 cm × 10 cm using a dispenser pump spray (style guard wrinkle and odor clean spray, manufactured by Lion Co., Ltd.). After leaving for 10 minutes as it was, the odor strength of the toilet mat was scored according to Evaluation A. The evaluation was performed by sensory evaluation of the intensity of malodor remaining on the tray mat by 10 panelists according to the following criteria, and the average value was described in Examples or Comparative Examples according to Evaluation Criteria B.

<Evaluation of storage stability of composition>
The blended composition was put into a screw mouth bottle (manufactured by Nichiden Science Glass Co., Ltd., SV-50 bottle), and the appearance and smell immediately after blending were evaluated. Then, after storing at 40 ° C. or −5 ° C. for 1 month, the temperature was returned to room temperature (about 25 ° C.), and the appearance and aroma after storage were evaluated.
The appearance was evaluated visually. The smell was sensory evaluated for the smell of the bottle mouth. For the odor after storage, the odor after storage at −5 ° C. was evaluated as the standard, and the odor after storage at 40 ° C. was evaluated according to the following criteria.
<Appearance criteria immediately after compounding>
○: Turbidity, poor dispersion, no precipitate Δ: Slightly opaque but no dispersion, no precipitate ×: Turbidity, poor dispersion, or precipitate <Aroma evaluation criteria immediately after blending>
○: No strange odor △: Somewhat bad odor ×: Some bad odor <Appearance criteria after storage>
◎: No change ○: If you look closely, the color is slightly cloudy.
Δ: Translucent. Alternatively, precipitation occurs, but dissolves if gently shaken.
X: It is opaque. Alternatively, precipitates are generated and do not dissolve even when shaken.
<Evaluation criteria after storage>
◎: No change ○: Slight change but odor does not change △: Slight change in odor ×: Change in odor

Claims

(A) a divalent water-soluble metal salt,
(B) at least one compound represented by the following formulas (I) to (IV);
(C) 5-30% by mass of water-soluble solvent
A liquid deodorant composition for textiles, comprising (A) / (B) = 0.01 to 6 (molar ratio).

(In the formula (I), A I represents an alkyl group, a sulfo group, an amino group, a hydroxyl group, a hydrogen atom or COOM I , and M I may be the same as or different from each other, and each represents a hydrogen atom, an alkali metal, or an alkaline earth. 1 type selected from the group consisting of similar metals, cationic ammonium groups and alkanolamines, and m I and n I are each an integer of 0 to 2, provided that m I and n I are both 0 , A I is a methyl group.
In the formula (II), X II-1 to X II-4 may be the same or different and are each independently a group consisting of a hydrogen atom, an alkali metal, an alkaline earth metal, a cationic ammonium group and an alkanolamine. One selected from the above, Q II represents a hydrogen atom or an alkyl group, R II represents a hydrogen atom or a hydroxyl group, and n III represents an integer of 0 or 1.
In the formula (III), R III is a linear or branched C8-C22 alkyl and alkenyl group, A III is H, a methyl group, or (CH 2 ) n III —COOX III , X III-1 is Each represents H, an alkali metal atom, an alkaline earth metal atom, an alkanolamine, or NH 4 . n III represents any one of 1 to 3.
In the formula (IV), X IV represents a hydrogen atom, an alkali metal, or an alkaline earth metal. n IV represents an integer of 1 or 2, and when n IV is 2, X IV may be the same or different. )
The liquid deodorant composition for textiles according to claim 1, wherein the component (B) is a compound represented by the formula (I) or the formula (II).
The liquid deodorant composition for textiles according to claim 1, wherein the component (B) is methylglycine diacetate, iminodisuccinic acid or a salt thereof.
The liquid deodorant composition for textiles according to any one of claims 1 to 3, wherein the component (A) is a water-soluble zinc salt or a water-soluble copper salt.
The component (C) is at least one selected from the group consisting of primary alcohols having 2 to 3 carbon atoms, glycols having 2 to 6 carbon atoms, and polyhydric alcohols having 3 to 8 carbon atoms. The liquid deodorant composition for textiles according to any one of the above.
The liquid deodorant composition for textiles according to any one of claims 1 to 5, wherein the pH of the composition is 6.5 or less.
Further, a polyoxyethylene alkyl ether having an alkyl group having 10 to 14 carbon atoms, an average addition mole number of oxyethylene groups of 5 to 20 moles, and an average addition mole number of oxyethylene groups of 30 to 50 moles The liquid deodorant composition for textiles according to any one of claims 1 to 6, comprising a nonionic surfactant selected from the group consisting of castor oil.
A liquid deodorant article for textiles, comprising the liquid deodorant composition for textiles according to any one of claims 1 to 7 contained in a spray container.