LIQUID DETERGENT COMPOSITION FOR TEXTILE PRODUCTS

Abstract

The present invention is a liquid detergent composition for textile products containing (a) a surfactant, (b) an alcohol with 10 or more and 16 or less carbons and (c) an antibacterial compound having an aromatic ring (excluding quaternary ammonium salts).

Claims

1: A liquid detergent composition for textile products, the composition comprising component (a): a surfactant, component (b): an alcohol with 10 or more and 16 or less carbons, and component (c): an antibacterial compound having an aromatic ring, which is not a quaternary ammonium salt.

2: The liquid detergent composition according to claim 1, wherein the component (a) is one or more surfactants selected from the group consisting of (a1) an anionic surfactant and (a2) a nonionic surfactant.

3: The liquid detergent composition according to claim 1, wherein the composition comprises component (a1), which is an anionic surfactant, and component (a2), which is a nonionic surfactant, as the component (a).

4: The liquid detergent composition according to claim 3, wherein a mass ratio of a content of the component (a1) to a total content of the components (a1) and (a2), (a1)/[(a1)+(a2)], is 0.05 or more and 0.95 or less.

5: The liquid detergent composition for textile products according to claim 1, wherein a mass ratio of a content of the component (a) to a content of the component (b), (b)/(a), is 0.010 or more and 0.1 or less.

6: The liquid detergent composition according to claim 1, wherein the composition comprises an internal olefin sulfonate salt with 10 or more and 18 or less carbons as the component (a).

7: The liquid detergent composition according to claim 1, wherein the composition comprises as the component (a) a nonionic surfactant represented by formula (1):
R.sup.1(CO).sub.mO-(AO).sub.n—R.sup.2  (1) wherein R.sup.1 is an aliphatic hydrocarbon group with 9 or more and 18 or less carbons; R.sup.2 is a hydrogen atom or a methyl group; CO is a carbonyl group; m is a number of 0 or 1; AO is one or more alkyleneoxy groups selected from the group consisting of an alkyleneoxy group with 2 carbons and an alkyleneoxy group with 3 carbons and includes at least an alkyleneoxy group with 2 carbons; when AO includes an ethyleneoxy group and a propyleneoxy group, the ethyleneoxy group and the propyleneoxy group are optionally bonded in blocks or bonded at random; and n represents an average number of added moles and is a number of 1 or more and 50 or less.

8: The liquid detergent composition according to claim 1, wherein the component (c) is a nonionic antibacterial compound having an aromatic ring.

9: The liquid detergent composition according to claim 1, wherein the component (c) is an antibacterial compound having a diphenyl ether backbone.

10: A method for washing a textile product, the method comprising washing the textile product with a detergent liquid obtained by mixing the liquid detergent composition according to claim 1 and water, and thereafter rinsing the textile product with water.

Description

EXAMPLES

[0125] The following are the components used in the examples and comparative examples.

<Formulation Component>

Component (a)

Component (a1)

[0126] (a1-1): Internal Olefin Sulfonate Potassium Salt with 16 Carbons

[0127] Using an internal olefin with 16 carbons and referring to methods described in production examples of JP-A 2014-76988, (a1-1) was obtained. In the resultant internal olefin sulfonate potassium salt of (a1-1), the mass ratio of olefin species (potassium olefin sulfonates)/hydroxy species (potassium hydroxy alkane sulfonates) is 17/83. Mass proportions in a distribution for the position of a sulfonic acid group of the hydroxy species in (a1-1) were as follows: position 1/position 2/position 3/position 4/position 5/positions 6-9=2.3%/23.6%/18.9%/17.5%/13.7%/11.2%/6.4%/6.4%/0% (100 mass % in total).

[0128] The mass proportions in the distribution for the position of a sulfonic acid group in the internal olefin sulfonate salt were measured by high-performance liquid chromatography/mass spectrometry (HPLC-MS).

[0129] Specifically, the hydroxy species in which a sulfonic acid group was bonded were separated by high-performance liquid chromatography (HPLC), and each of them was identified by mass spectrometry (MS). As a result, the proportion of each of them was determined from the HPLC-MS peak area thereof. Each proportion determined from the peak area was calculated as a mass proportion herein.

[0130] Note that the following were the devices and conditions used for measurement: HPLC device “LC-20ASXR” (manufactured by SHIMADZU CORPORATION); column “ODS Hypersil®” (4.6×250 mm, particle size: 3 μm, manufactured by Thermo Fisher Scientific K.K.); sample preparation (1000-fold dilution with methanol); eluent A (10 mM ammonium acetate-added water); eluent B (10 mM ammonium acetate-added methacrylonitrile/water=95/5 (v/v) solution); gradient (0 minutes (A/B=60/40)-15.1 to 20 minutes (30/70)-20.1 to 30 minutes (60/40)); MS device “LCMS-2020” (manufactured by SHIMADZU CORPORATION); ESI detection (anion detection, m/z: 321.10 (component (a) with 16 carbons)); column temperature (40° C.); flow rate (0.5 mL/min); and injection volume (5 μL).

[0131] The mass ratio of hydroxy species/olefin species of the internal olefin sulfonate salt was measured by HPLC-MS. Specifically, the hydroxy species and olefin species were separated by HPLC, and each of them was identified by MS. As a result, the proportion of each of them was determined from the HPLC-MS peak area thereof.

[0132] Note that the following were the devices and conditions used for measurement: HPLC device (product name: Agilent Technology 1100, manufactured by Agilent Technologies); column (product name: L-column ODS 4.6×150 mm, manufactured by Chemicals Evaluation and Research Institute, Japan); sample preparation (1000-fold dilution with methanol); eluent A (10 mM ammonium acetate-added water); eluent B (10 mM ammonium acetate-added methanol); gradient (0 minutes (A/B=30/70%).fwdarw.10 minutes (30/70%).fwdarw.55 minutes (0/100%).fwdarw.65 minutes (0/100%).fwdarw.66 minutes (30/70%).fwdarw.75 minutes (30/70%)); MS device (product name: Agilent Technology 1100MS SL (G1946D)); and MS detection (anion detection, m/z: 60-1600, UV 240 nm).

[0133] Further, a prescribed amount of α-olefin sulfonate salt having an aliphatic hydrocarbon group with 16 carbons was added to component (a1-1) as the external standard, and the peak area of the α-olefin sulfonate salt was compared with that of component (a1-1) to calculate the mass of component (a1-1). The number of moles of component (a1-1) was calculated from the molecular weight of component (a1-1). The molecular weight of component (a1-1) was calculated in terms of that of the acid form. The molecular weights of the olefin species and HAS species of the internal olefin sulfonate salt are 304.5 and 322.6, respectively.

(a1-2): lauryl benzenesulfonate

Component (a2)

[0134] (a2-1): polyoxyethylene lauryl ether (the average number of added moles of the oxyethylene group is 10 mol)
(a2-2): polyoxyethylene polyoxypropylene polyoxyethylene lauryl ether (the average numbers of added moles of the oxyethylene groups are 9 mol and 9 mol, and the average number of added moles of the oxypropylene group is 2 mol)
Component (b): 1-dodecanol (manufactured by Kao Corporation, KALCOL 2098)
Component (c): diclosan

(1) Method for Measuring pH

[0135] A composite electrode for pH measurement (manufactured by HORIBA, Ltd., glass slide-in sleeve type) is connected to a pH meter (pH/ion meter F-23 manufactured by HORIBA, Ltd.), and the power is turned on. A saturated potassium chloride aqueous solution (3.33 mol/L) is used as an internal solution of the pH electrode. Next, 100-mL beakers are filled respectively with a pH 4.01 standard solution (phthalate standard solution), a pH 6.86 standard solution (neutral phosphate standard solution) and a pH 9.18 standard solution (borate standard solution), and immersed in a constant temperature bath at 25° C. for 30 minutes. The electrode for pH measurement is immersed in the standard solutions adjusted to a constant temperature for 3 minutes such that a calibration operation is performed in the order of pH 6.86-pH 9.18-pH 4.01. A sample to be measured (liquid detergent composition for textile products) is adjusted to 25° C., the electrode of the pH meter is immersed in the sample, and the pH is measured 1 minute later.

(2) Preparation of Liquid Detergent Composition for Textile Products

[0136] The liquid detergent compositions for textile products shown in Tables 1 and 2 were each prepared in the following manner.

[0137] A Teflon® stirrer piece with a length of 5 cm was placed in a glass beaker with a capacity of 200 mL and the mass thereof was measured. Next, the glass beaker was charged with 20 g of ion exchange water and components (a1), (a2), (b) and (c), and while they were stirred at 100 r/min, monoethanolamine or hydrochloric acid was added to make the pH of the composition 8 and ion exchange water was added to make the total amount 100 g. After they were stirred at 100 r/min for 15 minutes, the resultant product was used as the liquid detergent composition for textile products.

(3) PREPARATION OF TEXTILE PRODUCT FOR WASHING RATE Evaluation

(3-1) Preparation of Textile Product for Diclosan Adsorption Rate Evaluation

[0138] 1.7 kg of cotton fabric (cotton 2003 (manufactured by Tanigashira Shoten)) was washed in the standard course of a fully automatic washing machine (manufactured by Panasonic Corporation, NA-F702P) (adding 4.7 g of EMULGEN 108 (manufactured by Kao Corporation) when washing and using water in an amount of 47 L, washed for 9 minutes, rinsed twice, and dewatered for 3 minutes) twice in a cumulative manner, thereafter washed with water alone (using water in an amount of 47 L, washed for 9 minutes, rinsed twice, and dewatered for 3 minutes) three times in a cumulative manner, and dried for 24 hours under an environment at 23° C. and 45% RH. After that, the fabric was cut into pieces with a size of 6 cm×6 cm.

(3-2) Preparation of Textile Product for Washing Rate Evaluation

[0139] Preparation of Model Artificial Sebum-Soiled Fabric

[0140] A model artificial sebum soiling liquid of the composition below was adhered to fabric (cotton 2003 (manufactured by Tanigashira Shoten)) to prepare model artificial sebum-soiled fabric. The adhesion of the model artificial sebum soiling liquid to the fabric was carried out by printing the artificial soiling liquid on the fabric with a gravure roll coater. The step of adhering the model artificial sebum soiling liquid to the fabric to prepare the model artificial sebum-soiled fabric was carried out under the following conditions: cell capacity of the gravure roll 58 cm.sup.3/m.sup.2; coating rate 1.0 m/min; drying temperature 100° C.; and drying time 1 min. After that, the fabric was cut into pieces with a size of 6 cm×6 cm. [0141] Composition of model artificial sebum soiling liquid: lauric acid 0.4 mass %; myristic acid 3.1 mass %; pentadecanoic acid 2.3 mass %; palmitic acid 6.2 mass %; heptadecanoic acid 0.4 mass %; stearic acid 1.6 mass %; oleic acid 7.8 mass %; triolein 13.0 mass %; n-hexadecyl palmitate 2.2 mass %; squalene 6.5 mass %; egg white lecithin liquid crystal 1.9 mass %; Kanuma red-clay 8.1 mass %; carbon black 0.01 mass %; and water of the balance (100 mass % in total)

(4) Washing Test

(4-1) Washing Test 1

[0142] Using a tergotometer (manufactured by Ueshima Seisakusho Co., Ltd.), a washing operation was performed. Water used for washing was washing water obtained by adding calcium chloride and magnesium chloride to ion exchange water in proportions of 8:2 by mass ratio and adjusting the hardness to 4° dH. Each of the liquid detergent compositions for textile products listed in Tables 1 and 2 was mixed with the washing water such that the total amount of components (a1) and (a2) in the composition was 150 mg/kg in terms of the concentration in the detergent liquid to obtain the detergent liquid. 0.6 L of the detergent liquid and four pieces of the above textile product for diclosan adsorption rate evaluation were placed in a 1-liter stainless beaker for washing tests. The bath ratio was adjusted to 20 with the above textile product for adsorption rate evaluation. The temperature of the detergent liquid was 20° C. The fibers for evaluation were washed in the tergotometer at 85 rpm for 10 minutes. After washing, dewatering was carried out, and all the fibers dewatered were placed in 0.6 L of the washing water to carry out rinsing in the tergotometer at 85 rpm for 3 minutes. After rinsed, they were dewatered again and thereafter dried under an environment at 23° C. and 45% RH for 24 hours.

(4-2) Washing Test 2

[0143] Using a tergotometer (manufactured by Ueshima Seisakusho Co., Ltd.), a washing operation was performed. Water used for washing was washing water obtained by adding calcium chloride and magnesium chloride to ion exchange water in proportions of 8:2 by mass ratio and adjusting the hardness to 4° dH. Each of the liquid detergent compositions for textile products listed in Tables 1 and 2 was mixed with the washing water such that the total amount of components (a1) and (a2) in the composition was 150 mg/kg in terms of the concentration in the detergent liquid to obtain the detergent liquid. 0.6 L of the detergent liquid and five pieces of the above textile product for washing rate evaluation were placed in a 1-liter stainless beaker for washing tests. The bath ratio was adjusted to 20 with the above textile product for diclosan adsorption rate evaluation. The temperature of the detergent liquid was 20° C. The fibers for evaluation were washed in the tergotometer at 85 rpm for 10 minutes. After washed, they were dewatered and dried with an ironing press machine.

(5) Quantification of Adsorption Amount of Diclosan to Textile Product (Evaluation of Antibacterial Properties)

[0144] As an indicator for antibacterial properties, the adsorption amount of the antibacterial agent to the textile product was used. The larger the adsorption amount of the antibacterial agents is, the higher antibacterial properties are and the better the antibacterial properties of the textile product after washing are maintained.

[0145] Two pieces were taken out from the above textile product for diclosan adsorption rate evaluation subjected to washing test 1, and the mass of the fabric pieces was measured while they were sealed in a screw tube bottle No. 7. 20 mL of methanol was added thereto and ultrasonic treatment was performed in an ultrasonic cleaner at 25° C. for 30 minutes to obtain a solution for measurement. Next, component (c) (diclosan) was diluted with methanol to prepare calibration-curve solutions of 0.01 μg/mL, 0.05 μg/mL, 0.1 μg/mL, 0.5 μg/mL and 1.0 μg/mL. The amount of diclosan in the solution for measurement was quantified by a liquid chromatograph mass spectrometer (hereinafter abbreviated as LCMS device), and the diclosan adsorption amount to the textile product was determined from the calibration-curve solutions. [0146] LCMS device: LCMS2020 manufactured by SHIMADZU CORPORATION [0147] Eluent A: an aqueous solution of 10 mmol/L ammonium acetate in distilled water [0148] Eluent B: a methanol solution of 10 mmol/L ammonium acetate [0149] Gradient conditions: eluent A/B=1:1 (0 minutes)-eluent B (2 to 5 minutes)-eluent A/eluent B=1:1 (5.1-8 minutes), flow rate: 0.6 mL/min, sample injection volume 5 μl, column temperature 40° C.

[0150] The diclosan adsorption rate to the textile product was determined by the formula below. The results are shown in Tables 1 and 2.

Diclosan adsorption rate=100×{(total mass of diclosan adsorbed to two pieces of textile product used to measure adsorption amount)×(total mass of textile product used in washing test 1)/(mass of two pieces of textile product used to measure adsorption amount)}/(total mass of diclosan used to prepare detergent liquid)

(6) Method for Evaluating Washing Rate

[0151] The washing rate of the above textile product for evaluation obtained in washing test 2 was measured by the method below, and the average value of five pieces was determined. The results are shown in Tables 1 and 2.

[0152] The reflectance at 550 nm of the original fabric before soiling and before and after washing was measured with a colorimeter (manufactured by NIPPON DENSHOKU INDUSTRIES CO., LTD., Z-300A) to determine the washing rate (%) by the following formula. Note that the values in Tables 1 and 2 are average values of the washing rates of five pieces.

Washing rate (%)=100×[(reflectance after washing-reflectance before washing)/(reflectance of original fabric-reflectance before washing)]

(7) Foaming Test

[0153] Water used for the foaming test was foaming test water obtained by adding calcium chloride and magnesium chloride to ion exchange water in proportions of 8:2 by mass ratio and adjusting the hardness to 4° dH. Each of the liquid detergent compositions for textile products listed in Tables 1 and 2 was mixed with the foaming test water such that the total amount of components (a1) and (a2) in the composition was 600 mg/kg in terms of the concentration in the detergent liquid to obtain a foaming test liquid. 50 g of the foaming test liquid was put into a screw tube bottle No. 8. The screw tube bottle containing the foaming test liquid was shaken vertically in a reciprocating manner at 300 rpm for 5 minutes in a shaker (Yamato Scientific Co., Ltd., model number: SA300). After shaken, the screw tube bottle was removed from the shaker and left to stand for 30 minutes, and then, the height from the water surface of the foaming test liquid to the surface of the foam was measured and defined as foam height. Foam with a foam height of 3.5 cm or more was taken as “Good,” and that with a foam height of less than 3.5 cm was taken as “Poor.”

TABLE-US-00001 TABLE 1 Example 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 Liquid Formulation (a) (a1) (a1-1) 36 27 18 13.5 36 27 18 13.5 detergent amount (a2) (a2-1) 9 18 27 31.5 0 0 0 0 composition (mass %) (a2-2) 0 0 0 0 9 18 27 31.5 for textile (b) 1-dodecanol 1 1 1 1 1 1 1 1 products (c) Diclosan 0.045 0.045 0.045 0.045 0.045 0.045 0.045 0.045 Ion exchange Bal- Bal- Bal- Bal- Bal- Bal- Bal- Bal- water ance ance ance ance ance ance ance ance Total 100 100 100 100 100 100 100 100 (a1)/[(a1) + (a2)] (mass ratio) 0.80 0.60 0.40 0.30 0.80 0.60 0.40 0.30 (b)/(a) (mass ratio) 0.022 0.022 0.022 0.022 0.022 0.022 0.022 0.022 Diclosan adsorption rate [%] 23.9 22.7 21.9 20.1 27.8 26.1 26.7 25.8 Washing rate [%] 34.0 35.9 38.5 38.3 35.1 36.1 36.8 37.5 Foaming Good Good Good Good Good Good Good Good Example Comparative example 1-9 1-10 1-11 1-12 1-1 1-2 1-3 Liquid Formulation (a) (a1) (a1-1) 9 9 45 0 36 36 0 detergent amount (a2) (a2-1) 36 0 0 45 9 0 0 composition (mass %) (a2-2) 0 36 0 0 0 9 0 for textile (b) 1-dodecanol 1 1 1 1 0 0 1 products (c) Diclosan 0.045 0.045 0.045 0.045 0.045 0.045 0.045 Ion exchange Bal- Bal- Bal- Bal- Bal- Bal- Bal- water ance ance ance ance ance ance ance Total 100 100 100 100 100 100 100 (a1)/[(a1) + (a2)] (mass ratio) 0.2 0.2 1.0 0.0 0.8 0.8 — (b)/(a) (mass ratio) 0.022 0.022 0.022 0.022 0.000 0.000 — Diclosan adsorption rate [%] 13.5 14.8 28.9 13.2 22.8 28.0 17.0 Washing rate [%] 39.1 39.5 22.5 42.6 33.0 34.5 1.0 Foaming Good Good Good Good Poor Poor Poor

TABLE-US-00002 TABLE 2 Example 2-1 2-2 2-3 2-4 2-5 2-6 2-7 2-8 Liquid Formulation (a) (a1) (a1-2) 36 27 18 13.5 36 27 18 13.5 detergent amount (a2) (a2-1) 9 18 27 31.5 0 0 0 0 composition (mass %) (a2-2) 0 0 0 0 9 18 27 31.5 for textile (b) 1-dodecanol 1 1 1 1 1 1 1 1 products (c) Diclosan 0.045 0.045 0.045 0.045 0.045 0.045 0.045 0.045 Ion exchange Bal- Bal- Bal- Bal- Bal- Bal- Bal- Bal- water ance ance ance ance ance ance ance ance Total 100 100 100 100 100 100 100 100 (a1)/[(a1) + (a2)] (mass ratio) 0.80 0.60 0.40 0.30 0.80 0.60 0.40 0.30 (b)/(a) (mass ratio) 0.022 0.022 0.022 0.022 0.022 0.022 0.022 0.022 Diclosan adsorption rate [%] 18.3 17.0 15.7 15.2 18.7 17.9 17.0 16.8 Washing rate [%] 28.8 33.7 37.4 37.8 30.9 32.7 33.1 36.7 Foaming Good Good Good Good Good Good Good Good Comparative Example example 2-9 2-10 2-11 2-12 2-13 2-1 Liquid Formulation (a) (a1) (a1-2) 9 9 45 27 27 13.5 detergent amount (a2) (a2-1) 36 0 0 18 18 31.5 composition (mass %) (a2-2) 0 36 0 0 0 0 for textile (b) 1-dodecanol 1 1 1 1.5 3 0 products (c) Diclosan 0.045 0.045 0.045 0.045 0.045 0.045 Ion exchange Bal- Bal- Bal- Bal- Bal- Bal- water ance ance ance ance ance ance Total 100 100 100 100 100 100 (a1)/[(a1) + (a2)] (mass ratio) 0.2 0.2 1.0 0.6 0.6 0.3 (b)/(a) (mass ratio) 0.022 0.022 0.022 0.033 0.067 0.000 Diclosan adsorption rate [%] 14.5 14.2 19.5 17.1 17.4 14.0 Washing rate [%] 40.1 37.6 20.4 33.5 32.5 38.0 Foaming Good Good Good Good Good Poor