JP4976930B2 - Liquid laundry aid composition - Google Patents

Description

  The present invention relates to a liquid laundry aid composition.

Conventionally, at the time of washing, the washing object is washed, and at the same time, as a method of imparting a sterilization effect or antibacterial effect to the washing object, a cleaning composition and an oxygen-based or chlorine-based bleaching composition A method using both of these methods, or a method using a cleaning composition containing a bleaching component, a bactericidal component or an antibacterial component is used.
Here, “disinfecting” means removing germs already proliferating on an object to be washed by sterilization, washing or the like before washing.
“Antibacterial” refers to inhibiting the growth of bacteria in an object after washing.

However, in actual laundry, the above-described method can be used to adsorb bleaching components, bactericidal components or antibacterial components to the object to be washed in the presence of a high concentration surfactant, or to have an antibacterial effect particularly on the item to be washed. It was difficult to maintain after rinsing and drying.
On the other hand, for example, as a method of imparting an antibacterial effect to an object to be washed, a method of imparting an antibacterial effect together with a flexibility imparting effect using a softener composition in a rinsing stage after washing is generally used. Has been done.

In addition, as a method for imparting a sterilizing effect or an antibacterial effect to an object to be washed, it has been proposed to use a laundry composition containing a compound containing silver ions (for example, patents). References 1 and 2).
In addition, many techniques using a compound containing silver ions as an antibacterial component and a laundry composition containing the antibacterial component have been proposed (see, for example, Patent Documents 3 to 9).
JP 09-3492 A JP 2001-238937 A JP 2001-335405 A JP 2000-256365 A International Publication No. 95/07913 Pamphlet JP 2005-145923 A Japanese Patent Laid-Open No. 11-209209 JP 2000-16905 A Special table 2003-521472 gazette

However, in the laundry composition containing the silver ion-containing compound described in Patent Documents 1 and 2, when washing the object to be washed and sun-dried, the silver ion is reduced by the influence of ultraviolet irradiation. The fiber of the article to be washed is discolored due to deterioration, or the storage stability of the composition is poor (for example, the compound itself containing silver ions in the composition precipitates or precipitates over time or under high temperature storage) ) Etc. have problems in practical use.
Moreover, when the antimicrobial component of patent documents 3-9 is used with the conventional cleaning composition, the antimicrobial effect with respect to a to-be-washed object is still inadequate. Furthermore, there is a problem that the fibers of the object to be washed discolor due to the influence of silver ions.
Therefore, when using a laundry composition containing a compound containing silver ions, in addition to sufficiently exhibiting a sterilizing effect and an antibacterial effect, the compound containing silver ions can be stably added to the laundry composition. It is necessary to reduce the adverse effects caused by silver ions such as blending and discoloration of the fibers of the washing object after washing and drying.

  The present invention has been made in view of the above circumstances, and is used together with a detergent composition, which is excellent in sterilizing effect and antibacterial effect, can suppress discoloration of fibers, and has good storage stability. It is an object to provide an agent composition.

As a result of intensive studies, the present inventors provide the following means in order to solve the above problems.
That is, the liquid laundry assistant composition of the present invention contains a water-soluble silver salt (a), an imidazole derivative (b) represented by the following general formula (b1), and water, and the water-soluble silver salt The molar ratio (b) / (a) between the silver ion in (a) and the imidazole derivative (b) is (b) / (a) = 5-50 and the pH is 5-11. It is characterized by.

［式（ｂ１）中、Ｒ^１〜Ｒ^４はそれぞれ独立して水素原子または炭素数１〜４のアルキル基を表す。ただし、当該アルキル基の水素原子はアミノ基、カルボキシ基およびヒドロキシ基からなる群から選択される少なくとも１種の基で置換されていてもよい。］

[In Formula (b1), R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, the hydrogen atom of the alkyl group may be substituted with at least one group selected from the group consisting of an amino group, a carboxy group, and a hydroxy group. ]

The liquid laundry aid composition of the present invention preferably further contains a polycarboxylic acid or a salt (c) thereof.
Moreover, in the liquid laundry adjuvant composition of this invention, it is preferable to further contain magnesium sulfate (d).

  ADVANTAGE OF THE INVENTION According to this invention, it can use with a cleaning composition and can provide the liquid washing adjuvant composition which is excellent in a microbe elimination effect and an antibacterial effect, can suppress discoloration of a fiber, and has favorable storage stability.

≪Liquid laundry aid composition≫
The liquid laundry aid composition of the present invention comprises a water-soluble silver salt (a) (hereinafter referred to as component (a)) and an imidazole derivative (b) represented by the general formula (b1) (hereinafter referred to as (b) ) Component)) and water.

<(A) component>
In the present invention, the “water-soluble silver salt” as the component (a) is a salt composed of silver ions and anionic ions, and refers to a compound capable of releasing silver ions when dissociated in water.
Further, the term “water-soluble” is not particularly limited as long as it is contained in the liquid laundry aid composition of the present invention and the composition is uniform in appearance and can maintain transparency, and is 20 ° C. The solubility in water is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and particularly preferably 0.1% by mass or more.
Specific examples of the component (a) include silver sulfate, silver nitrate, silver acetate, silver fluoride, and silver perchlorate. Silver sulfate, silver nitrate, and silver acetate are preferable, and safety is high and odor is good. Therefore, silver sulfate is particularly preferable.
(A) A component may be used individually by 1 type and may use 2 or more types together.
In the content of the component (a) in the liquid laundry assistant composition, the lower limit is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and further preferably 0.02% by mass or more. The upper limit is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, and further preferably 0.05% by mass or less.
When the content of the component (a) is 0.001% by mass or more, the sterilization effect is further improved. In addition, the antibacterial effect is further improved. If content of (a) component is 0.5 mass% or less, the storage stability of a liquid laundry adjuvant composition will improve more. In addition, a sterilization effect and an antibacterial effect are sufficiently obtained, which is preferable from an economic viewpoint.

<(B) component>
In the present invention, the component (b) is an imidazole derivative represented by the general formula (b1).
In the general formula (b1), R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, part or all of the hydrogen atoms of the alkyl group may be substituted with at least one group selected from the group consisting of an amino group, a carboxy group and a hydroxy group.
Specifically, R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may be substituted with at least one group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
Specifically, R ² is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may be substituted with at least one group, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
Specifically, R ³ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may be substituted with at least one group, and is selected from the group consisting of a hydrogen atom, an amino group and a carboxy group. C1-C2 alkyl groups substituted with at least one group are more preferred, and C1-C2 alkyl groups substituted with hydrogen atoms, amino groups and carboxy groups are more preferred.
Specifically, R ⁴ is preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms which may be substituted with at least one group, and is selected from the group consisting of a hydrogen atom, an amino group and a carboxy group. C1-C2 alkyl groups substituted with at least one group are more preferred, and C1-C2 alkyl groups substituted with hydrogen atoms, amino groups and carboxy groups are more preferred.

The component (b) is preferably a water-soluble imidazole derivative.
The term “water-soluble” as used herein means that the solubility in water at 20 ° C. is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and more preferably 1% by mass or more. Particularly preferred.

Suitable examples of component (b) include imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, α-amino-1H-imidazole-4-propanoic acid (histidine), and imidazole. 1-methylimidazole and α-amino-1H-imidazole-4-propanoic acid (histidine) are more preferable, imidazole and α-amino-1H-imidazole-4-propanoic acid (histidine) are more preferable, and α-amino- 1H-imidazole-4-propanoic acid (histidine) is particularly preferred.
The steric structure of component (b) is not particularly limited, and any optical isomer can be used.

(B) A component may be used individually by 1 type and may use 2 or more types together.
In the content of the component (b) in the liquid laundry assistant composition, the lower limit is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and further preferably 0.1% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 3% by mass or less, and further preferably 1% by mass or less.
When the content of the component (b) is 0.01% by mass or more, the disinfection effect, the antibacterial effect, and the fiber discoloration suppressing effect are further improved. If content of (b) component is 10 mass% or less, the storage stability of a liquid laundry adjuvant composition will improve more. In addition, a sterilizing effect, an antibacterial effect, and a fiber discoloration suppressing effect are sufficiently obtained, which is preferable from an economic viewpoint.

In the liquid laundry assistant composition of the present invention, the molar ratio (b) / (a) between the silver ions in the component (a) and the component (b) is (b) / (a) = 5-50. .
In the molar ratio (b) / (a), the lower limit is 5 or more, preferably 10 or more, more preferably 15 or more, and still more preferably 20 or more. The upper limit is 50 or less, preferably 45 or less, more preferably 40 or less, and even more preferably 35 or less.
When the molar ratio (b) / (a) is 5 or more, the disinfection effect, the antibacterial effect, and the fiber discoloration suppressing effect are improved. When the molar ratio (b) / (a) is 50 or less, a sterilizing effect, an antibacterial effect, and a fiber discoloration suppressing effect are sufficiently obtained, which is preferable from an economic viewpoint.

<Water>
As water, tap water, purified water, distilled water and the like can be used, and purified water and distilled water are preferred from the liquid stability (uniformity of appearance, transparency, etc.) of the liquid laundry aid composition.
In the content of water in the liquid laundry assistant composition, the lower limit is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more. The upper limit is preferably 99% by mass or less, more preferably 95% by mass or less, and still more preferably 90% by mass or less.
It is preferable for the water content to be within the above range because the liquid laundry aid composition is excellent in liquid stability or usability.

<(C) component>
The liquid laundry aid composition of the present invention preferably further contains polycarboxylic acid or a salt thereof (c) (hereinafter referred to as component (c)). (C) By containing a component, the fiber discoloration suppression effect improves more.
As the component (c), for example, citrate, polyacrylate, ethylenediaminetetraacetate, and methylglycine diacetate are preferable. Of these, citrate, ethylenediaminetetraacetate, and methylglycine diacetate are more preferable, and citrate is more preferable.
Examples of the salt of polycarboxylic acid include metal salts such as sodium, potassium, magnesium, and calcium, ammonium salts, and lower alkanolamine salts of either mono, di, or tri, and metal salts are preferable, sodium salts Is particularly preferred.
(C) A component may be used individually by 1 type and may use 2 or more types together.
In the content of the component (c) in the liquid laundry assistant composition, the lower limit is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.
When the content of the component (c) is 0.01% by mass or more, the fiber discoloration suppressing effect is further improved. (C) If content of a component is 10 mass% or less, the storage stability of a liquid laundry adjuvant composition will improve more.

<(D) component>
The liquid laundry aid composition of the present invention preferably further contains magnesium sulfate (d) (hereinafter referred to as component (d)). By containing the component (d), the antibacterial effect is further improved. Moreover, (d) component can be mix | blended stably, without producing a precipitate also in coexistence with (a) component. For example, when magnesium chloride is used instead of the component (d), silver chloride is generated and becomes a precipitate, so that the storage stability of the liquid laundry aid composition is deteriorated.
As the component (d), a hydrated salt such as magnesium sulfate heptahydrate can also be used.
In the content of the component (d) in the liquid laundry assistant composition, the lower limit is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and further preferably 0.5% by mass or more. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.
When the content of component (d) is 0.01% by mass or more, the antibacterial effect is further improved. If content of (d) component is 10 mass% or less, the storage stability of a liquid laundry adjuvant composition will improve more.

<Other ingredients>
In addition to the components (a) to (d) and water, the liquid laundry assistant composition of the present invention has a viscosity, wrinkle, and the like that do not impair the effects and liquid stability of the present invention. Surfactant, solvent (excluding water), fragrance, pH adjuster for the purpose of adjusting liquid properties such as stringiness, improving liquid stability, or improving sterilization effect by improving detergency. Etc. can be suitably blended.

(Surfactant)
Nonionic surfactants such as polyoxyethylene alkyl ethers, methoxy polyoxyalkylene alkanoates, fatty acid diethanolamides, fatty acid monoethanolamides, alkyl polyglycosides, alkyl polyglyceryl ethers, alkyl polyglyceryl esters; polyoxyethylene alkyls Anionic surfactants such as ether sulfate, linear alkylbenzene sulfonate, and α-olefin sulfonate are preferred. Among these, nonionic surfactants are more preferable, and polyoxyethylene alkyl ethers are more preferable.

(solvent)
As the solvent (excluding water), lower alcohols such as ethanol and isopropanol; glycol solvents such as ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polyalkylene glycol butyl ether, and polyalkylene glycol phenyl ether are preferable. It is mentioned as a thing.

(Fragrance)
As a fragrance | flavor, the fragrance | flavor composition containing a fragrance | flavor component, a solvent, a stabilizer, etc. as described in Unexamined-Japanese-Patent No. 2002-146399 is mentioned as a suitable thing, for example.

(PH adjuster)
Suitable examples of the pH adjuster include sulfuric acid and sodium hydroxide.

  The liquid laundry aid composition of the present invention comprises the above component (a), component (b), and water, preferably component (c) and / or component (d), and other components as necessary. Can be prepared by mixing in a conventional manner.

In the present invention, the pH of the liquid laundry aid composition is 5-11.
In the pH of the liquid laundry assistant composition, the lower limit is 5 or more, preferably 5.5 or more, more preferably 6.0 or more, and still more preferably 6.5 or more. The upper limit is 11 or less, preferably 10 or less, more preferably 9 or less, and still more preferably 8 or less.
When the pH is 5 or more, the fiber discoloration suppressing effect is particularly improved. If the said pH is 11 or less, the storage stability of a liquid laundry adjuvant composition will improve. Moreover, the safety | security in handling the said liquid laundry adjuvant composition becomes high.
In the present invention, the “pH of the liquid laundry assistant composition” refers to a liquid laundry assistant composition adjusted to 25 ° C. directly by a glass electrode type pH meter (product name: HM-30G, manufactured by Toa DKK Corporation). ) Shows the value measured.

The liquid laundry aid composition of the present invention is stored and transported in a plastic container or the like.
Examples of the plastic container include a bottle container and a standing pouch for refilling. As a bottle container, what was described in Unexamined-Japanese-Patent No. 2001-3100 is mentioned suitably, for example, As resin, resin, such as polyethylene, a polypropylene, or a polyethylene terephthalate, is mentioned. In addition, it is preferable from the viewpoint of storage stability of the liquid laundry aid composition that these resins are kneaded with a pigment, an ultraviolet absorber, or the like so that transmission of ultraviolet rays is suppressed as much as possible. As the standing pouch, for example, those described in Japanese Patent Application Laid-Open No. 2000-72181 are preferably exemplified, and the material is linear low density polyethylene having a thickness of about 100 to 250 μm or stretched nylon having a thickness of about 15 to 30 μm. Etc. In particular, it is preferable from the viewpoint of storage stability of the liquid laundry aid composition that an aluminum vapor-deposited layer or the like is sandwiched between layers and ultraviolet light transmission is suppressed as much as possible.

The liquid laundry assistant composition of the present invention is suitable for an auxiliary use during washing with a laundry detergent when washing.
The method of use is not particularly limited. For example, the method of adding the liquid laundry aid composition together with the laundry detergent to water used for washing; the liquid laundry aid composition of water. A method of preparing diluted water by putting an object, pre-soaking the object to be washed in this diluted water, and then washing it as usual with a laundry detergent; this liquid on the part of the object to be cleaned with bacteria, dirt, etc. For example, a method of directly applying the laundry assistant composition and then laundering the article to be washed as usual.
Among the above-mentioned exemplified methods of use, when the liquid laundry aid composition is used in water as in the former two methods, the concentration of the water, that is, the liquid laundry aid composition in the washing liquid is The lower limit is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.10% by mass or more, and the upper limit is preferably 1% by mass. % Or less, more preferably 0.5% by mass or less, and still more preferably 0.2% by mass or less. When the concentration of the liquid laundry assistant composition in the cleaning liquid is within this range, the sterilization effect and the antibacterial effect are excellent, which is preferable from the economical viewpoint.

The liquid laundry assistant composition of the present invention described above is used together with the detergent composition, is excellent in sterilizing effect and antibacterial effect, can suppress discoloration of fibers, and has good storage stability.
The reason why such an effect can be obtained is assumed as follows.
The liquid laundry assistant composition of the present invention contains a water-soluble silver salt (a), an imidazole derivative (b) represented by the general formula (b1), and water. When the liquid laundry assistant composition is used for washing, silver ions released from the component (a) or “complexes” formed by the silver ions and the component (b) in water are adsorbed on the object to be washed. To do. Thereby, the disinfection effect and the antibacterial effect are obtained in the washing object after washing.
Moreover, in the said liquid laundry adjuvant composition, the molar ratio (b) / (a) of the silver ion in (a) component and (b) component is (b) / (a) = 5-50. And pH is 5-11. Thus, the molar ratio (b) / (a) is set to a specific ratio in which the ratio of the component (b) is excessive with respect to silver ions, and the pH is adjusted to a specific range ( A “complex” having a good balance between the strength of capturing the silver ions released from the component (a) by the component b) and the water solubility (liquid stability) of the complex is formed. As a result, even when a liquid dosage form is used, suppression of fiber discoloration of the object to be washed due to the influence of silver ions (deterioration such as reduction of silver ions) as described above, and component (a) in the composition Alternatively, precipitation of the complex and suppression of precipitation can be realized together.
For these reasons, it is estimated that the effects of the present invention can be obtained.

The inventors mixed the component (a), the component (b), and water under the conditions of the above molar ratio (b) / (a) = 5 to 50 and pH 5 to 11. In this case, the present inventors have found that an aqueous solution (liquid laundry aid composition) that exhibits the above effects can be prepared without causing precipitation or precipitation. According to further studies, by ¹ H-NMR measurement, when the component (a) is added to the component (b), the chemical shift position of the imidazole moiety changes, so that formation of a complex in an aqueous solution can be confirmed. However, as a result of measuring ¹ H-NMR of the aqueous solution prepared by changing the molar ratio of silver ions to the component (b), even when an excess molar amount of the component (b) was added to the silver ions, It was found that the chemical shift position of the imidazole part changes continuously with the change of the molar ratio. From this, in the liquid laundry assistant composition of the present invention, it is presumed that a kind of molecular aggregate composed of silver ions and an excess molar amount of the component (b) is formed and dissolved. The molecular assembly is considered to be different from that dissolved in water at a pH of 1 or less as described in Patent Document 5, for example.

According to the liquid laundry aid composition of the present invention, since it is excellent in sterilization effect and antibacterial effect, it is used together with a laundry detergent at the time of washing. Sufficient disinfection and antibacterial effects can be imparted.
In the liquid laundry assistant composition of the present invention, the compound containing silver ions is stably blended in the composition without precipitation or precipitation of the compound containing silver ions over time or under high temperature storage. can do.

  The liquid laundry aid composition of the present invention can be used, for example, when the liquid laundry aid composition is applied directly to the item to be washed, or when it is put into a washing machine, the liquid laundry aid is directly applied to the item to be washed. Even if the agent composition is applied, it has an excellent fiber discoloration suppressing effect that hardly causes fiber discoloration. For example, shirts, blouses, T-shirts, polo shirts, jeans, bath towels, handkerchiefs, tablecloths , Can be used for a wide range of textile products such as placemats, curtains, sofa covers, etc. Moreover, there is no restriction | limiting in particular also in the fiber raw material of these fiber products, For example, any of natural products, such as cotton, wool, hemp; Can be used.

  Hereinafter, the present invention will be described in more detail using examples, but the present invention is not limited to these examples. “%” Means “% by mass” unless otherwise specified.

(Examples 1-27, Comparative Examples 1-5)
According to the composition shown in Tables 1-3, each component was prepared by mixing each component according to a conventional method.
In addition, the unit of the compounding quantity in a table | surface is the mass%, and shows the value on the basis of the total mass of a liquid laundry adjuvant composition. Moreover, the compounding quantity of each component in a table | surface shows the value as conversion of a pure part.
The “appropriate amount” of the pH adjuster indicates the amount of 1N-sulfuric acid or 1N-sodium hydroxide used to adjust the pH of the liquid laundry aid composition shown in the table.
“Balance” of purified water means that the total amount is adjusted to 100% by mass.
The pH of the liquid laundry assistant composition was measured directly with a glass electrode type pH meter (product name: HM-30G, manufactured by Toa DKK Corporation) for each example of the liquid laundry assistant composition adjusted to 25 ° C. Value.
(B) / (a) (molar ratio) indicates the molar ratio of silver ions in component (a) to component (b).
Below, the used raw material is demonstrated.

<Used raw material>.
・ Water-soluble silver salt (a)
Silver sulfate: reagent grade, manufactured by Toyo Chemical Co., Ltd. (molecular weight 312); solubility in water at 20 ° C. 0.79% by mass.

-Imidazole derivative (b)
Imidazole: manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (molecular weight 68).
1-methylimidazole: Nippon Synthetic Chemical Industry Co., Ltd. (molecular weight 82).
2-methylimidazole: Nippon Synthetic Chemical Industry Co., Ltd. (molecular weight 82).
1,2-dimethylimidazole: manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (molecular weight 96).
Histidine: (S) -α-amino-1H-imidazole-4-propanoic acid, trade name “L-histidine”, manufactured by Ajinomoto Co., Inc. (molecular weight 155).

Comparative component (b ′) of imidazole derivative (b)
2-Phenylimidazole: manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (molecular weight 144).

・ Polycarboxylic acid or its salt (c)
Citric acid 3Na: trisodium citrate dihydrate, trade name “purified sodium citrate”, manufactured by Fuso Chemical Industries, Ltd.
MGDA: trisodium methylglycine diacetate, trade name “Trilon M”, manufactured by BASF Japan Ltd.

・ Magnesium sulfate (d)
Magnesium sulfate: Magnesium sulfate heptahydrate, trade name “magnesium sulfate”, manufactured by Ako Kasei Co., Ltd.

Other components E715: Polyoxyethylene (EO = 15) dodecyl ether, trade name “EMALEX 715”, manufactured by Nippon Emulsion Co., Ltd .; average added mole number of ethylene oxide 15
pH adjuster: 1N-sulfuric acid, reagent, manufactured by Kanto Chemical Co., Inc.
pH adjuster: 1N-sodium hydroxide, reagent, manufactured by Kanto Chemical Co., Inc.

・ Water Purified water.

<Evaluation>
The obtained liquid laundry assistant composition of each example was evaluated for the disinfection effect, antibacterial effect, fiber discoloration suppression effect, and storage stability shown below.

[Evaluation of sterilization effect]
Towels (100% by weight cotton, 80 g / sheet) were handed to 10 adult males one by one and rubbed evenly from the face to the neck area over the entire face every hour and used for 8 hours. In this way, the towel with almost uniform dirt adhered to the entire surface of the towel is cut into 8 equal parts, each of which is sprayed with ion exchange water until the water content becomes 100% by mass, and then sealed in a plastic bag with a zipper. It was left at 25 ° C. for 3 days.
(Cleaning process)
A sample of 10 users (1/8 x 10 towels) that had been allowed to breed for 3 days, and a small electric washing machine (product name: N-BK2, manufactured by Matsushita Electric Industrial Co., Ltd.) Using 4 L of tap water (20 ° C., 3 ° DH), a laundry detergent (trade name: Top, manufactured by Lion Co., Ltd.) and the liquid laundry aid composition of each example, each having a cleaning solution concentration of 0. It was added to 067% by mass, washed with a standard water flow for 10 minutes, dehydrated to a moisture content of 100% by mass, rinsed for another 3 minutes, and then dehydrated twice to a moisture content of 100% by mass.
(Measurement of the number of bacteria)
Subsequently, the number of bacteria remaining in the washed and dehydrated sample was measured using a food stamp (for live bacteria count: standard agar, manufactured by Nissui Pharmaceutical Co., Ltd.).
As a method for measuring the number of bacteria, the medium surface of the food stamp was lightly pressed against the center of the towel, capped, and the number of colonies after culturing at 25 ° C. for 3 days was counted and scored as follows.
1 point: The number of colonies is less than 10.
2 points: The number of colonies is 10 or more and less than 30.
3 points: The number of colonies is 30 or more and less than 100.
4 points: 100 or more colonies.
For each of the 10 samples, the score was given according to the above-mentioned criteria based on the counted number of colonies, and then the average value was obtained, and the sterilization effect was evaluated according to the following criteria. The results are also shown in Tables 1-3. When the average value was less than 3.5 points (３．５, ○, Δ), it was determined that the sterilization effect was good.
A: The average value is less than 1.5 points.
○: The average value is 1.5 points or more and less than 2.5 points.
Δ: The average value is 2.5 points or more and less than 3.5 points.
X: The average value is 3.5 points or more.

[Evaluation of antibacterial effect]
Towels (100% by weight cotton, 80 g / sheet) were handed to 10 adult males one by one and rubbed evenly from the face to the neck area over the entire face every hour and used for 8 hours. In this way, the towel with almost even dirt adhered to the entire surface of the towel is cut into 8 equal parts, and the samples for 10 users (1/8 towel x 10 sheets) are washed in the evaluation of the sterilization effect. It was washed by the same washing treatment. After washing and dehydration, 10 sample towels were each sealed in a plastic bag with a zipper and left at 25 ° C. for 3 days.
After standing for 3 days, the number of bacteria propagated in the sample was measured by the same method as the method for measuring the number of bacteria in the sterilization effect.
The antibacterial effect was evaluated according to the same standard as the standard for the sterilization effect. The results are also shown in Tables 1-3. When the average value was less than 3.5 points (３．５, ○, Δ), the antibacterial effect was determined to be good.

[Evaluation of fiber discoloration suppression effect]
A towel (100% by weight, 80 g / sheet) cut into 8 equal parts was used as a sample. 0.15 g of the liquid laundry assistant composition of each example was dropped on the central portion of one sheet and left for 30 minutes under an indoor fluorescent lamp, and then a small electric washing machine (product name: N-BK2, Matsushita Electric Industrial Co., Ltd.) (Made by Co., Ltd.) was added to 4 L of tap water (20 ° C., 3 ° DH) so that the detergent concentration was 0.067% by mass. Then, after washing with a standard water flow for 10 minutes, it was dehydrated to a water content of 100% by mass, further rinsed for 3 minutes, and then dehydrated twice to a water content of 100% by mass.
Next, the washed and dehydrated sample was placed horizontally on a sunny day, and the UV irradiation amount was 0.1 MJ / m ² (UV care mate PRO (manufactured by Fuji Xerox Co., Ltd.)) at a wavelength of 280 to 410 nm. It was dried in the sun until the amount of ultraviolet rays was measured. About the sample after this sun-drying, the grade of the discoloration (stain) of the part which dripped the liquid washing adjuvant composition was visually evaluated by the following standards with 10 panelists.
1 point: No spots were observed.
2 points: Slight spots were observed.
3 points: A thin spot was observed.
4 points: A blot was clearly observed.
The average value of the scores of 10 people was determined, and the fiber discoloration suppressing effect was evaluated according to the following criteria. The results are also shown in Tables 1-3. When the average value was less than 3.5 points (３．５, ○, Δ), the fiber discoloration suppressing effect was judged to be good.
A: The average value is less than 1.5 points.
○: The average value is 1.5 points or more and less than 2.5 points.
Δ: The average value is 2.5 points or more and less than 3.5 points.
X: The average value is 3.5 points or more.

[Evaluation of storage stability]
The liquid laundry aid composition of each example was filled in a 50 mL screw screw bottle, sealed, and stored in a thermostatic bath at 50 ° C. for 1 month. The visual evaluation was performed based on the criteria. The results are also shown in Tables 1-3. When the evaluation was ○ or Δ, it was determined that the storage stability was good.
○: Almost no change.
Δ: There was no precipitation, but slight discoloration was observed.
X: Precipitation was clearly observed.

As is clear from the results in Tables 1 to 3, the liquid laundry assistant compositions of Examples 1 to 27 of the present invention are used together with the detergent composition, have excellent sterilization effect and antibacterial effect, and It was confirmed that discoloration could be suppressed.
Moreover, the liquid laundry adjuvant composition of Examples 1-27 of this invention has confirmed that storage stability was favorable.

From the comparison of Examples 7, 24 and 25, the liquid laundry assistant composition of Examples 24 and 25 containing the component (c) has a fiber discoloration inhibitory effect as compared with the liquid laundry assistant composition of Example 7. Has been confirmed to be better.
Further, in comparison with Examples 4 and 26, the liquid laundry assistant composition of Example 26 containing the component (d) has a better antibacterial effect than the liquid laundry assistant composition of Example 4. It was confirmed that there was.

On the other hand, it was confirmed that the liquid laundry assistant composition of Comparative Example 1 lacking the component (a) has both poor sterilization effect and antibacterial effect.
It was confirmed that the liquid laundry assistant composition of Comparative Example 5 containing the component (b ′) different from the component (b) in the present invention has a poor fiber discoloration suppressing effect and a poor storage stability.
It was confirmed that the liquid laundry assistant composition of Comparative Example 2 having a molar ratio (b) / (a) of less than 5 in the present invention has a poor fiber discoloration suppressing effect.
The liquid laundry assistant composition of Comparative Example 3 having a pH of less than 5 has a poor fiber discoloration suppressing effect, and the liquid laundry assistant composition of Comparative Example 4 having a pH of more than 11 has poor storage stability. confirmed.

Claims (3)

A water-soluble silver salt (a), an imidazole derivative (b) represented by the following general formula (b1), and water,
The molar ratio (b) / (a) between the silver ions in the water-soluble silver salt (a) and the imidazole derivative (b) is (b) / (a) = 5-50, and the pH is 5 A liquid laundry assistant composition, which is ˜11.

[In Formula (b1), R ^{1 to} R ⁴ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. However, the hydrogen atom of the alkyl group may be substituted with at least one group selected from the group consisting of an amino group, a carboxy group, and a hydroxy group. ]   The liquid laundry adjuvant composition according to claim 1, further comprising a polycarboxylic acid or a salt thereof (c).   The liquid laundry adjuvant composition according to claim 1 or 2, further comprising magnesium sulfate (d).