Liquid detergent composition for fiber product and washing method for fiber product

Abstract

To provide a liquid detergent composition for a fiber product which includes an aminocarboxylic acid chelator and is free of, or includes only a small amount of, a surfactant, and which can achieve both good washing performance and storage stability.SOLUTION: A liquid detergent composition for a fiber product includes 5 to 50 mass% of (A) a salt of an aminocarboxylic acid chelator and 0.2 to 5 mass% of (B) an acid, and is free of, or includes 3 mass% or less of, (C) a surfactant. The ratio (Z), which is calculated by the expression (Z)={(valence of component (B)×molar concentration of component (B)) / molar concentration of component (A)}, is 0.5 to 0.8.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a liquid detergent composition for textile products and a method for cleaning textile products. [Background technology]

[0002] As an environmentally friendly technology, there are high expectations for detergent compositions that can exert their cleaning power without using surfactants. For example, Patent Document 1 proposes a method of washing clothes using a laundry liquid containing a surfactant-free, phosphorus-free detergent composition that contains an aminocarboxylic acid-based organic chelating agent as an essential component and further contains a redeposition inhibitor, and the pH of the laundry liquid is adjusted to a specific alkaline range and the hardness component is adjusted to a specific amount or less. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 2009-132934 Summary of the Invention [Problem to be solved by the invention]

[0004] According to the findings of the present inventors, when attempting to create a liquid detergent composition that contains an aminocarboxylic acid chelating agent but no surfactant, it is difficult to ensure storage stability, and for example, if a dye is added, the liquid is likely to discolor during storage. The present invention aims to provide a liquid detergent composition for textile products that contains an aminocarboxylic acid chelating agent, does not contain a surfactant or contains only a small amount of a surfactant, and has both good cleaning performance and storage stability. [Means for solving the problem]

[0005] The present invention has the following aspects. [1] A liquid detergent composition for textile products, comprising 5 to 50 mass% of a salt of an aminocarboxylic acid chelating agent (A) and 0.2 to 5 mass% of an acid (B), and containing no surfactant (C) or 3 mass% or less of a surfactant (C), wherein the ratio (Z) calculated by the following formula (1) is 0.5 to 0.8. Ratio (Z) = {valence of component (B) × molar concentration of component (B)} / molar concentration of component (A) (1) [2] The liquid detergent composition for fabric products described in [1], wherein the salt (A) of the aminocarboxylic acid chelating agent comprises one or more selected from the group consisting of methylglycine diacetate, ethylenediaminetetraacetate, and hydroxyiminodisuccinate. [3] The liquid detergent composition for textile products according to [1] or [2], wherein the pH of the liquid detergent composition for textile products at 25°C is X and the pH of a diluted solution obtained by diluting 1.8 g of the liquid detergent composition for textile products with 1000 mL of 2°DH water at 25°C is Y, the value of YX is 0.4 or more. [4] A method for cleaning textile products using a cleaning liquid obtained by diluting the liquid detergent composition for textile products according to any one of [1] to [3] above with water, comprising: The content of the liquid detergent composition for textile products relative to the total mass of the cleaning liquid is 500 to 5000 ppm, The method for cleaning textile products, wherein the pH of the cleaning liquid at 25°C is higher than the pH of the liquid detergent composition for textile products at 25°C before dilution, and the difference therebetween is 0.4 or more. [Effects of the Invention]

[0006] According to the present invention, a liquid detergent composition for textile products can be provided which contains an aminocarboxylic acid chelating agent, does not contain a surfactant or contains only a small amount of a surfactant, and has both good cleaning performance and storage stability. DETAILED DESCRIPTION OF THE INVENTION

[0007] <Liquid detergent composition for textile products> The liquid detergent composition for textile products of the present invention (hereinafter sometimes simply referred to as "liquid detergent composition") is a composition containing components (A) and (B) as essential components. Component (C), which is a surfactant, may be absent or may be contained in a small amount. In this specification, a numerical range expressed by "to" means a numerical range in which the numbers before and after "to" are the lower and upper limits. In this specification, "ppm" is based on mass.

[0008] <Component (A)> Component (A) is a salt of an aminocarboxylic acid chelating agent. Component (A) may be a salt of an aminocarboxylic acid having an amino group and a carboxy group, such as an alkali metal salt such as a sodium salt.

[0009] Examples of aminocarboxylic acids include: DEG (dihydroxyethylglycine: N-(2-hydroxylethyl)glycine), HEIDA (N-(2-hydroxyethyl)iminodiacetic acid), HEDTA (hydroxyethylethylenediaminetetraacetic acid: N-(hydro xyethyl)ethylenediamine tetraacetic acid), NTA (Nitrilo Triacetic Acid), DT PA (Diethylene Triamine Pentaacetic Acid), HEDTA (Hydroxyethyl Ethylene Diamine Triacetic Acid), EDTA (Ethylenediaminetetraacetic Acid), MGDA (Methyl Glycine Diacetic Acid), GLDA (L-glutamic acid diacetic acid: Di carboxymethyle glutamic acid), ASDA (Aspartate Diacetic Acid), EDDS (Ethylenediamine Disuccinic Acid), HIDS (Hydroxyiminodisuccinic Acid), Examples include IDS (iminodisuccinic acid).

[0010] Among these, alkali metal salts of MGDA, alkali metal salts of EDTA, and alkali metal salts of HIDS are preferred as component (A), as the use of these components (A) further enhances detergency. The component (A) may be used alone or in combination of two or more. It is particularly preferred that component (A) contains at least one member selected from the group consisting of methylglycine diacetate, ethylenediaminetetraacetate, and hydroxyiminodisuccinate.

[0011] The content of component (A) relative to the total mass of the liquid detergent composition is 5 to 50 mass%, preferably 10 to 45 mass%, and more preferably 12 to 35 mass%. When the content is at least the lower limit of the above range, good cleaning performance is likely to be obtained. When the content is at most the upper limit, good storage stability is likely to be obtained. Storage stability at low temperatures is particularly likely to be improved.

[0012] <(B) component> Component (B) is an acid. Examples of the acid include inorganic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, and silicic acid, and organic acids such as citric acid, acetic acid, malic acid, succinic acid, lactic acid, tartaric acid, and fumaric acid. Of these, hydrochloric acid, sulfuric acid, citric acid, and lactic acid are preferred. The component (B) may be used alone or in combination of two or more.

[0013] The content of component (B) relative to the total mass of the liquid detergent composition is 0.2 to 5 mass%, preferably 0.5 to 4 mass%, and more preferably 0.8 to 2.6 mass%. When the content is at least the lower limit of the above range, the pH of the liquid detergent composition does not become too high, and good storage stability is likely to be achieved. When the content is at most the upper limit, the pH of the detergent solution (diluted liquid detergent composition) is appropriately increased, and good cleaning performance is likely to be achieved.

[0014] <(C) component> Component (C) is a surfactant, and examples of the surfactant include known surfactants such as anionic surfactants, nonionic surfactants, cationic surfactants, semi-polar surfactants, and amphoteric surfactants. A "semi-polar surfactant" is a surfactant that has a semi-polar bond (a bond with properties intermediate between a non-polar bond and a polar bond), and is cationic or nonionic depending on the pH of the solution in which it dissolves or the dispersion in which it disperses. From the viewpoint of further enhancing the detergency, anionic surfactants, nonionic surfactants, and semi-polar surfactants are preferred. The component (C) may be used alone or in combination of two or more types.

[0015] When the liquid detergent composition contains component (C), the uniformity of the liquid is improved when an oil-soluble component such as a fragrance is added. On the other hand, the lower the content of component (C), the less foam is generated during the cleaning process. When foaming is suppressed, the time and amount of rinsing water required are reduced (improved rinsing performance). The content of component (C) relative to the total mass of the liquid detergent composition is 3% by mass or less, may be 2% by mass or less, may be 1% by mass or less, or may be 0% by mass.

[0016] <(D) component> Component (D) is a pigment. From the viewpoint of aesthetics, it is preferable that the liquid detergent composition contains a pigment. The type of dye is not particularly limited, but examples include xanthene dyes, quinoline dyes, pyrene dyes, anthraquinone dyes, and the like. The component (D) may be used alone or in appropriate combination of two or more types.

[0017] From the viewpoint of color stability of the liquid detergent composition, (D) / (A), which represents the mass ratio of the content of component (D) to the content of component (A), is preferably 0.00001 to 0.001, and more preferably 0.00003 to 0.0001. When (D) / (A) is equal to or greater than the lower limit of the above range, the aesthetic appeal of the liquid detergent composition due to coloring can be sufficiently enhanced. When (D) / (A) is equal to or less than the upper limit, coloring of the washed items can be prevented.

[0018] <Water> The liquid detergent composition preferably contains water as a solvent from the viewpoints of ease of handling during production, solubility in water during use, etc. Examples of water include ion-exchanged water and pure water. The water content is not particularly limited, but is preferably 40 to 94.8 mass %, more preferably 45 to 90 mass %, and even more preferably 50 to 85 mass %, relative to the total mass of the liquid detergent.

[0019] <Other optional ingredients> In addition to the above-mentioned components, the liquid detergent may optionally contain components that are typically used in liquid detergent compositions for textile products. Examples of such optional components include fragrances, pH adjusters, enzymes, anti-soiling agents, dye transfer inhibitors, fluorescent agents, solvents, preservatives, and antioxidants. The optional components may be used alone or in combination of two or more.

[0020] <Manufacturing method> The method for producing the liquid detergent composition is not particularly limited, and the liquid detergent composition can be produced according to a conventional method. For example, the liquid detergent composition can be obtained by mixing all of the components constituting the liquid detergent composition.

[0021] <How to use> A preferred method for washing textile products (items to be washed) using a liquid detergent composition is to wash the items using a diluted solution prepared by dissolving the liquid detergent composition in water as a washing liquid. When the content of the liquid detergent composition relative to the total mass of the diluted solution (cleaning solution) is taken as the dilution concentration (unit: ppm), the dilution concentration is preferably 500 to 5,000 ppm, more preferably 1,000 to 3,000 ppm. When the dilution concentration is equal to or greater than the lower limit of the above range, excellent cleaning performance is achieved. When the dilution concentration is equal to or less than the upper limit, the amount of liquid detergent composition used is not too large, improving usability and cost-effectiveness for consumers. Examples of textile products (items to be washed) include clothing, fabrics, sheets, curtains, carpets, and the like.

[0022] <Ratio (Z)> In the liquid detergent composition and its diluted solution, the ratio (Z) calculated by the following formula (1) is 0.5 to 0.8. Ratio (Z) = {valence of component (B) × molar concentration of component (B)} / molar concentration of component (A) (1) By setting the ratio (Z) within the above range, both good cleaning performance and storage stability can be achieved. When the ratio (Z) is equal to or greater than the lower limit of the above range, the storage stability is excellent, and when the ratio is equal to or less than the upper limit of the above range, the cleaning performance is excellent.

[0023] To improve the stability of a liquid detergent composition, it is effective to bring the pH of the liquid detergent composition closer to the neutral range, while to improve cleaning performance, it is effective to bring the pH of the diluted cleaning solution (diluted pH) closer to the alkaline range. However, since the pH of conventional liquid detergent compositions approaches the neutral range upon dilution, it has been difficult to achieve both the pH of the liquid detergent composition closer to the neutral range and the pH of the cleaning solution closer to the alkaline range. The liquid detergent composition of this embodiment, when diluted to a dilution concentration of, for example, 500 to 5,000 ppm, can raise the pH of the cleaning solution to a more alkaline pH than the pH before dilution by using the (A) and (B) components in a specific ratio (Z). That is, the pH of the liquid detergent composition can be maintained on the neutral side while raising the pH of the cleaning solution to an alkaline range. By setting the ratio (Z) to be equal to or greater than the lower limit, the pH of the liquid detergent composition before dilution can be maintained low, ensuring stability. By setting the ratio (Z) to be equal to or less than the upper limit, the pH after dilution can be sufficiently raised, ensuring cleaning performance.

[0024] <pH of liquid detergent composition> The pH of the liquid detergent composition at 25°C is preferably 7.0 to 11.0, more preferably 8.5 to 10.0. When the pH of the liquid detergent composition is equal to or higher than the lower limit of the above range, the liquid detergent composition exhibits excellent cleaning performance when used for cleaning with a cleaning liquid prepared by diluting the liquid detergent composition. When the pH is equal to or lower than the upper limit, the liquid detergent composition exhibits excellent storage stability. For example, the color tone of a liquid detergent composition containing a dye is less likely to change over time.

[0025] <Difference in pH before and after dilution (YX)> When the pH of the liquid detergent composition before dilution at 25°C is X and the pH of a diluted solution (cleaning solution) obtained by diluting 1.8 g of the liquid detergent composition with 1000 mL of 2°DH water at 25°C is Y, the value of YX is preferably 0.4 or more, more preferably 0.6 or more. When the value of YX is equal to or greater than the above lower limit, both good cleaning performance of the diluted solution (cleaning solution) and storage stability of the liquid detergent composition before dilution can be achieved.

[0026] <pH of cleaning solution> When the liquid detergent composition is diluted and used for cleaning, the pH of the diluted solution (cleaning solution) at 25°C is preferably 9.5 to 11.5, more preferably 10.0 to 11.0. When the pH of the diluted solution (cleaning solution) is at least the lower limit of the above range, the cleaning performance is excellent. When the pH is at most the upper limit, the pH of the liquid detergent composition before dilution is not too high, and the storage stability of the liquid detergent composition is excellent. The pH of the dilution solution (cleaning solution) varies depending on the hardness of the water used for dilution. The water used for dilution is not particularly limited. For example, tap water can be used.

[0027] When diluted so that the content (dilution concentration) of the liquid detergent composition with respect to the total mass of the cleaning solution is 500 to 5000 ppm, the pH of the diluted cleaning solution at 25°C is higher than the pH of the liquid detergent composition before dilution at 25°C, and the difference is preferably 0.4 or more, and more preferably 0.6 or more. When the difference in pH before and after dilution is at least the above lower limit value, both good cleaning performance of the dilution solution (cleaning solution) and storage stability of the liquid detergent composition before dilution can be achieved.

Examples

[0028] Hereinafter, the present invention will be described in detail with reference to examples, but the present invention is not limited by the following description.

[0029] ≪Measurement method and evaluation method≫ <pH measurement> [Measurement of pH (X) of liquid detergent composition] 50 mL of each liquid detergent composition was sampled into a glass bottle and allowed to stand in a thermostatic bath at 25°C for 30 minutes, and then the pH was measured using a glass electrode type pH meter (manufactured by Toa DKK Corporation, product name: GST-5721C). [Measurement of pH (Y) of dilution solution] 50 mL of the dilution solution of each liquid detergent composition diluted to a predetermined dilution concentration with water of 2°DH in advance was sampled into a glass bottle and allowed to stand in a thermostatic bath at 25°C for 30 minutes, and then the pH was measured using the above glass electrode type pH meter. The dilution concentration was the dilution concentration in the evaluation of the following cleaning performance.

[0030] <Evaluation of cleaning performance> The reflectance of 10 pieces of artificially soiled fabric (product name: Wet Artificially Soiled Fabric, manufactured by the Laundry Science Association, hereafter referred to as "soiled fabric") before washing was measured using a color difference meter (product name: SE-7700, manufactured by Nippon Denshoku Industries Co., Ltd.) (reflectance was calculated as R = Z / 100 based on Hunter whiteness Z; the same applies below). A Terg-O-Tometer (manufactured by USTesting) was used as a cleaning tester. Ten soiled fabrics and a charge fabric (knitted fabric cut into small pieces, thoroughly washed, rinsed, and dried) were weighed to a predetermined liquor ratio (30:1) and placed in a washing tank. The washing tank was then filled with the cleaning solution. Each liquid detergent composition was dissolved in 900 mL of 2°DH water at 25°C to the dilution concentration shown in the table (1167 to 2000 ppm by mass). After washing for 10 minutes at 120 rpm and 25°C, the soiled fabric was rinsed twice for 3 minutes with 900 mL of tap water at 25°C. After rinsing, drying, and washing, the reflectance of the soiled fabric was measured using a 460 nm filter, and the cleaning rate was calculated using the following formula. Cleaning rate (%) = (K / S of soiled cloth - K / S of cleaned cloth) / (K / S of soiled cloth - K / S of unsoiled cloth) × 100 (i) (In formula (i), K / S is (1-R / 100) 2 / (2R / 100), where the soiled cloth refers to the above artificially soiled cloth, the washed cloth refers to the soiled cloth after washing, and the unsoiled cloth refers to the original unsoiled white cloth (raw cloth), where K is the absorption coefficient, S is the scattering coefficient, and R is the absolute reflectance. Based on the obtained cleaning rate, cleaning performance was evaluated according to the following evaluation criteria. [Evaluation criteria] ◎: The average cleaning rate of 10 soiled cloths is 75% or more (passed). ○: The average cleaning rate of 10 soiled cloths is 70% or more but less than 75% (pass). ×: The average cleaning rate of 10 soiled cloths is less than 70% (failure).

[0031] <Evaluation of storage stability> 50 g of each liquid detergent composition was dissolved in 0.001% by mass of each of Blue No. 1 and Green No. 3 dyes, and the resulting composition was placed in a 50 mL glass bottle with a lid, sealed, and left to stand in a thermostatic bath at 50°C for 2 weeks. After that, the glass bottles were removed and allowed to air-cool at room temperature. After air-cooling, the appearance of each composition was visually evaluated according to the following evaluation criteria. [Evaluation criteria] ◎: No change in appearance from before storage (passed). ○: Slight discoloration is observed (pass). △: Discoloration is observed, but acceptable for practical use (pass). ×: Significant discoloration (failure).

[0032] <Evaluation of rinsing ability (foam suppression)> 1 g of each liquid detergent composition was diluted with 500 mL of 2°DH water to prepare a cleaning solution. 20 mL of the resulting cleaning solution was placed in an Epton tube (volume 100 mL, barrel diameter 25 mm), and the Epton tube was shaken by hand 20 times at 1 stroke / second. The height of the foam (the height from the boundary between the foam and the cleaning solution to the top surface of the foam) was read one minute after the end of shaking, and the rinsing performance was evaluated according to the following evaluation criteria. ◎: The bubble height is less than 50 mm. ×: The bubble height is 50 mm or more.

[0033] ≪Raw materials used≫ <Component (A)> A1: MGDA3Na, trisodium methylglycine diacetate, product name "Trilon M Powder", manufactured by BASF Japan, formula weight: 271.1. A2: EDTA4Na, tetrasodium ethylenediaminetetraacetic acid, product name "Trilon B Powder", manufactured by BASF Japan, formula weight: 380.2. A3: HIDS4Na, tetrasodium hydroxyiminodisuccinate, product name "HIDS", manufactured by Nippon Shokubai Co., Ltd., formula weight: 353.1. <Comparison component (A')> A'4: Trisodium citrate, trisodium citrate dihydrate, product name "trisodium citrate dihydrate", manufactured by Kanto Chemical Co., Ltd., formula weight: 258.1.

[0034] <(B) component> B1: Sulfuric acid (3mol / L sulfuric acid), product name "3mol / L sulfuric acid (6N)", manufactured by Junsei Chemical Co., Ltd., formula weight: 98.08, valence: 2. B2: Hydrochloric acid (1 mol / L hydrochloric acid), product name "1 mol / L hydrochloric acid (1N)", manufactured by Kanto Chemical Co., Ltd., formula weight: 36.46, valence: 1. B3: Citric acid (anhydrous citric acid), product name "anhydrous citric acid", manufactured by Junsei Chemical Co., Ltd. Formula weight: 192.1, valence: 3. B4: Lactic acid, product name "DL-lactic acid", manufactured by Kanto Chemical Co., Ltd., formula weight: 90.1, valence: 2.

[0035] <(C) component> C1: Semi-polar surfactant, amine oxide (lauryl dimethylamine oxide), product name "Cadenax (registered trademark) DM12D-W", manufactured by Lion Specialty Chemicals. <(D) component> D1: Blue No. 1, product name "Food Blue No. 1", manufactured by Daiwa Chemical Industry Co., Ltd. D2: Green No. 3, Fast Green FCF, product name "Green No. 3", manufactured by Kishi Chemicals Co., Ltd. <Water> Water: Ion-exchanged water.

[0036] (Examples 1 to 18, Comparative Examples 1 to 5) According to the compositions (unit: mass %) shown in Tables 1 to 4, components (A) to (D) were added to water and mixed to prepare the liquid detergent compositions of each example. The blend amounts in the table are pure values ​​unless otherwise specified. Components without a blend amount listed in the table are not blended. The "balance" water content refers to the remainder added so that the total blend amount (mass %) of all blended components contained in the liquid composition becomes 100 mass %. The liquid detergent compositions of each example were evaluated for cleaning performance, storage stability and foam suppression (rinsing properties), and the results are shown in the table.

[0037] [Table 1]

[0038] [Table 2]

[0039] [Table 3]

[0040] [Table 4]

[0041] As shown in Tables 1 to 3, the liquid detergent compositions of Examples 1 to 16 had good cleaning performance and good storage stability. In addition, because they did not contain a surfactant, they had excellent foam suppression (rinsing properties). As shown in Table 3, the liquid detergent compositions of Examples 17 and 18 had good cleaning performance and good storage stability. In addition, because the surfactant content was small, they had excellent foam suppression (rinsing properties).

[0042] As shown in Table 4, Comparative Example 1, which contained a small amount of component (A), had poor cleaning performance. Comparative Example 2, in which component (A') was used instead of component (A), had poor cleaning performance. Comparative Example 3, in which the ratio (Z) exceeded 0.8, had poor cleaning performance. Comparative Example 4, which did not contain component (B), had poor storage stability. Comparative Example 5, in which the content of component (C) exceeded 3 mass %, exhibited poor foam suppression (rinsing performance).

Claims

1. 5 to 50% by mass of a salt of an aminocarboxylic acid-based chelating agent (A), and Contains 0.2 to 5 mass% of an acid (B), The surfactant (C) is not contained or is contained in an amount of 3 mass% or less, A liquid detergent composition for fabric products, wherein the ratio (Z) calculated by the following formula (1) is 0.5 to 0.8: Ratio (Z) = {valence of component (B) × molar concentration of component (B)} / molar concentration of component (A) (1)

2. 2. The liquid detergent composition for fabric products according to claim 1, wherein the salt (A) of the aminocarboxylic acid chelating agent comprises one or more selected from the group consisting of methylglycine diacetate, ethylenediaminetetraacetate, and hydroxyiminodisuccinate.

3. 2. The liquid detergent composition for textiles according to claim 1, wherein the pH of the liquid detergent composition for textiles at 25°C is X and the pH of a diluted solution obtained by diluting 1.8 g of the liquid detergent composition for textiles with 1000 mL of 2° DH water at 25°C is Y, and the value of Y-X is 0.4 or more.

4. A method for cleaning textile products using a cleaning liquid obtained by diluting the liquid detergent composition for textile products according to any one of claims 1 to 3 with water, comprising: The content of the liquid detergent composition for textile products relative to the total mass of the cleaning liquid is 500 to 5000 ppm, The method for cleaning textile products, wherein the pH of the cleaning liquid at 25°C is higher than the pH of the liquid detergent composition for textile products at 25°C before dilution, and the difference therebetween is 0.4 or more.

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