DETERGENT COMPOSITION FOR TEXTILE PRODUCTS

Abstract

The present invention relates to a detergent composition for textile products containing the following component (A) and component (B): component (A): an internal olefin sulfonate having 15 or more and 24 or less carbon atoms and including an internal olefin sulfonate having 15 or more and 24 or less carbon atoms with the sulfonate group at position 5 or higher, and component (B): a nonionic surfactant having an HLB of more than 10.5 and 19 or less.

Claims

1. A detergent composition for textile products comprising the following component (A) and component (B): component (A): an internal olefin sulfonate having 15 or more and 24 or less carbon atoms and including an internal olefin sulfonate having 15 or more and 24 or less carbon atoms with the sulfonate group at position 5 or higher, and component (B): a nonionic surfactant having an HLB of more than 10.5 and 19 or less.

2. The detergent composition for textile products according to claim 1, wherein the component (B) is a nonionic surfactant containing a polyoxyethylene group and having an HLB of more than 10.5 and 19 or less.

3. The detergent composition for textile products according to claim 1, wherein the component (B) is a nonionic surfactant having an HLB of more than 10.5 and 19 or less and represented by the following general formula (b1):
R.sup.1(CO).sub.mO-(A.sup.1O).sub.nR.sup.2(b1) wherein R.sup.1 is an aliphatic hydrocarbon group having 9 or more and 18 or less carbon atoms, R.sup.2 is a hydrogen atom or a methyl group, CO is a carbonyl group, m is 0 or 1, A.sup.1O group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group, and n is an average number of added moles and is 6 or more and 50 or less.

4. The detergent composition for textile products according to claim 3, wherein in the general formula (b1), the A.sup.1O group is a group containing an ethyleneoxy group.

5. The detergent composition for textile products according to claim 1, wherein the component (A) is an internal olefin sulfonate having 15 or more and 24 or less carbon atoms and including 5% by mass or more and 60% by mass or less of an internal olefin sulfonate having 15 or more and 24 or less carbon atoms with the sulfonate group at position 5 or higher.

6. The detergent composition for textile products according to claim 1, wherein a mass ratio (B)/(A) of the component (B) to the component (A) is 0.05 or more and 9 or less.

7. The detergent composition for textile products according to claim 1, wherein the component (A) is one or more selected from the following component (a1) and component (a2), wherein a mass ratio (a2)/(a1) of the component (a2) to the component (a1) is 0 or more and 1 or less: component (a1): an internal olefin sulfonate having 15 or more and 16 or less carbon atoms and including an internal olefin sulfonate having 15 or more and 16 or less carbon atoms with the sulfonate group at position 5 or higher, and component (a2): an internal olefin sulfonate having 17 or more and 24 or less carbon atoms and including an internal olefin sulfonate having 17 or more and 24 or less carbon atoms with the sulfonate group at position 5 or higher.

8. The detergent composition for textile products according to claim 1, wherein a total of the content of the component (A) and the content of the component (B) in a11 surfactants in the detergent composition for textile products is 60% by mass or more and 100% by mass or less.

9. The detergent composition for textile products according to claim 1, further comprising water.

10. The detergent composition for textile products according to claim 1, wherein a total of the content of the component (A) and the content of the component (B) in the detergent composition for textile products is 4% by mass or more and 60% by mass or less.

11. A method for washing textile products with a detergent liquid comprising the following component (A) and component (B), and water, wherein a hardness of the detergent liquid is more than 0 dH: component (A): an internal olefin sulfonate having 15 or more and 24 or less carbon atoms and including an internal olefin sulfonate having 15 or more and 24 or less carbon atoms with the sulfonate group at position 5 or higher, component (B): a nonionic surfactant having an HLB of more than 10.5 and 19 or less.

12. The method for washing textile products according to claim 11, wherein the component (B) is a nonionic surfactant containing a polyoxyethylene group and having an HLB of more than 10.5 and 19 or less.

13. The method for washing textile products according to claim 11, wherein the component (B) is a nonionic surfactant having an HLB of more than 10.5 and 19 or less and represented by the following general formula (b1):
R.sup.1(CO).sub.mO-(A.sup.1O).sub.nR.sup.2(b1) wherein R.sup.1 is an aliphatic hydrocarbon group having 9 or more and 18 or less carbon atoms, R.sup.2 is a hydrogen atom or a methyl group, CO is a carbonyl group, m is 0 or 1, A.sup.1O group is one or more groups selected from an ethyleneoxy group and a propyleneoxy group, and n is an average number of added moles and is 6 or more and 50 or less.

14. The method for washing textile products according to claim 13, wherein in the general formula (b1), the A.sup.1O group is a group containing an ethyleneoxy group.

15. The method for washing textile products according to claim 11, wherein the component (A) is an internal olefin sulfonate having 15 or more and 24 or less carbon atoms and including 5% by mass or more and 60% by mass or less of an internal olefin sulfonate having 15 or more and 24 or less carbon atoms with the sulfonate group at position 5 or higher.

16. The method for washing textile products according to claim 11, wherein the content of the internal olefin sulfonate having 15 or more and 24 or less carbon atoms with the sulfonate group at position 2 or higher in the component (A) is 10% by mass or more and 60% by mass or less.

17. The method for washing textile products according to claim 11, wherein in the detergent liquid, a mass ratio (B)/(A) of the component (B) to the component (A) is 0.05 or more and 9 or less.

18. The method for washing textile products according to claim 11, wherein the component (A) is one or more selected from the following component (a1) and component (a2), and a mass ratio (a2)/(a1) of the component (a2) to the component (a1) in the detergent liquid is 0 or more and 1 or less: component (a1): an internal olefin sulfonate having 15 or more and 16 or less carbon atoms and including an internal olefin sulfonate having 15 or more and 16 or less carbon atoms with the sulfonate group at position 5 or higher, and component (a2): an internal olefin sulfonate having 17 or more and 24 or less carbon atoms and including an internal olefin sulfonate having 17 or more and 24 or less carbon atoms with the sulfonate group at position 5 or higher.

19. The method for washing textile products according to claim 11, wherein a total of the content of the component (A) and the content of the component (B) in a11 surfactants in the detergent liquid is 60% by mass or more and 100% by mass or less.

20. The method for washing textile products according to claim 11, wherein the hardness of the detergent liquid is, by German hardness, 0.5 dH or more and 20 dH or less.

21. The method for washing textile products according to claim 11, wherein the content of the component (A) in the detergent liquid is 0.005% by mass or more and 1.0% by mass or less, and the content of the component (B) in the detergent liquid is 0.001% by mass or more and 5.0% by mass or less.

22. A method for producing a detergent composition for textile products, comprising mixing the following component (A) and component (B): component (A): an internal olefin sulfonate having 15 or more and 24 or less carbon atoms and including an internal olefin sulfonate having 15 or more and 24 or less carbon atoms with the sulfonate group at position 5 or higher, and component (B): a nonionic surfactant having an HLB of more than 10.5 and 19 or less.

Description

EXAMPLES

<Components to be Blended>

[0194] In Examples and Comparative Examples, and Formulation Examples and Comparative Formulation Examples, the following components were used.

Synthesis of [Component (A)]

[0195] Internal olefins A to C which are raw materials of component (A) were synthesized as follows.

Synthesis of Internal Olefins a to C Having 16 Carbon Atoms (Production Examples a to C)

[0196] 7000 g (28.9 mol) of 1-hexadecanol (product name: KALCOL 6098, manufactured by Kao Corporation) and 700 g of -alumina (Strem Chemicals, Inc.) as a solid acid catalyst were introduced into a flask equipped with a stirring device, and allowed to react at 280 C. with stirring for a different reaction time for each of Production Examples A to C while circulating nitrogen (7000 mL/min) inside the flask. The resulting crude internal olefin was transferred to a distillation flask and subjected to distillation at 136 to 160 C./4.0 mmHg to obtain each of internal olefins A to C having 16 carbon atoms at an olefin purity of 100%. The double bond distribution of each of the obtained internal olefins is shown in Table 1.

TABLE-US-00001 TABLE 1 Internal olefin A B C Number of carbon atoms of hydrocarbon group 16 16 16 Distribution of double Position 1 1.8 0.5 0.4 bond in olefin as raw Position 2 40.7 30.1 15.3 material (% by mass) Position 3 29.3 25.5 13.8 Position 4 15.7 18.9 15.2 Position 5 7.3 11.0 18.4 Position 6 3.0 7.0 15.1 Position 7 1.1 3.5 10.9 Position 8 1.1 3.5 10.9 Position 9 0.0 0.0 0.0 Total 100.0 100.0 100.0 Total of positions 5 to 9 12.5 25.0 55.3

[0197] The double bond distribution of each of the internal olefins was measured by gas chromatography (hereinafter abbreviated as GC). Specifically, the internal olefin was reacted with dimethyl disulfide to form its dithiolated derivative, and then each component was subjected to separation by GC. The double bond distribution of internal olefin was determined from each of the resulting peak areas. For the olefins having 16 carbon atoms, the internal olefin having a double bond at position 7 and the internal olefin having a double bond at position 8 cannot be distinguished from each other in structure but distinguished when they are sulfonated, therefore, the value obtained by dividing the amount of the internal olefin having a double bond at position 7 by 2 is conveniently shown in each of the columns for positions 7 and 8.

[0198] The devices and the analysis conditions used for the measurement are as follows: a GC system: HP6890 (manufactured by Hewlett-Packard Company); a column: Ultra-Alloy-1 HT Capillary Column (30 m250 m0.15 m, manufactured by Frontier Laboratories, Ltd.); a detector (hydrogen flame ionization detector (FID)); injection temperature: 300 C.; detector temperature: 350 C.; and He flow rate: 4.6 mL/min.

Synthesis of Components (a-1) to (a-10)

[0199] Each of internal olefins A to C obtained in Examples A to C was subjected to sulfonation reaction by passing sulfur trioxide gas therethrough using a thin film-type sulfonation reactor equipped with an external jacket while passing cooling water at 20 C. through the external jacket. The molar ratio of SO.sub.3/the internal olefin during the sulfonation reaction was set at 1.09. The resulting sulfonated product was added to an alkaline aqueous solution which had been prepared using sodium hydroxide in an amount of 1.5 molar times the theoretical acid value, and the mixture was neutralized at 30 C. for 1 hour while being stirred. The neutralized product was hydrolyzed by being heated in an autoclave at 160 C. for 1 hour to obtain a crude product of a sodium internal olefin sulfonate having 16 carbon atoms. 300 g of the crude product was transferred to a separating funnel, 300 mL of ethanol was added thereto and petroleum ether in an amount of 300 mL per time was then added thereto to extract and remove oil-soluble impurities. At this time, inorganic compounds (mainly including sodium sulfate decahydrate) which precipitated at the oil/water interface by the addition of ethanol was also separated and removed from the aqueous phase by oil-water separation operation. This extraction and removal operation was carried out three times. The aqueous phase was evaporated to dryness to obtain each of the components (a-1), (a-4) and (a-10), as sodium internal olefin sulfonates having 16 carbon atoms. The internal olefin sulfonate obtained by using internal olefin A as a raw material is referred to as component (a-1), the internal olefin sulfonate obtained by using internal olefin B as a raw material is referred to as component (a-4), and the internal olefin sulfonate obtained by using internal olefin C as a raw material is referred to as component (a-10).

[0200] The distribution of the positions of the carbon through which each of sulfonate groups of components (a-1), (a-4) and (a-10) obtained are attached is shown in Table 2.

[0201] The percentage of the content of the internal olefin sulfonate with the sulfonate group attached thereto of each component was measured by high performance liquid chromatography/mass spectrometer (HPLC-MS). Specifically, identification was carried out by separating the hydroxy form having the sulfonate group attached thereto by high performance liquid chromatography (HPLC) and subjecting it to mass spectrometer (MS). Each percentage was determined from the resulting HPLC-MS peak area. In the present specification, each percentage determined from the peak area was calculated as percentage by mass.

[0202] The devices and the analysis conditions used for the measurement are as follows: an HPLC device: LC-20ASXR (manufactured by Shimadzu Corporation); a column: ODS Hypersil (4.6250 mm, particle size: 3 m, manufactured by Thermo Fisher Scientific K.K.); sample preparation (1000 times diluted with methanol); eluent A (10 mM ammonium acetate-added water); eluent B (a 10 mM ammonium acetate-added methacrylonitrile/water=95/5 (v/v) solution); gradient (0 minute (A/B=60/40).fwdarw.15.1 to 20 minutes (30/70).fwdarw.20.1 to 30 minutes (60/40); an MS device LCMS-2020 (manufactured by Shimadzu Corporation); ESI detection (negative ion detection, m/z: 321.10 (component (A) having 16 carbon atoms); column temperature (40 C.); flow rate (0.5 mL/min); and injection volume (5 L).

TABLE-US-00002 TABLE 2 Component (A) (a-1) (a-4) (a-10) Number of carbon atoms of hydrocarbon group 16 16 16 Distribution of Position 1 0.7 1.5 0.6 sulfonate group Position 2 32.1 24.1 13.1 (% by mass) Position 3 24.2 19.9 11.5 Position 4 25.8 24.6 18 Positions 5 to 9 17.2 29.9 56.8 Total 100 100 100

[0203] Then, component (a-1) and component (a-4) were mixed to prepare component (a-2) and component (a-3). Component (a-4) and component (a-10) were also mixed to prepare components (a-5) to component (a-9).

[0204] The double bond distribution of the internal olefins obtained which are a raw material for components (a-1) to (a-10) obtained is shown in Table 3.

[0205] The distribution of the positions of the carbon through which each of sulfonate groups of components (a-1) to (a-10) obtained are attached is shown in Table 4.

TABLE-US-00003 TABLE 3 Component (A) (a-1) (a-2) (a-3) (a-4) (a-5) (a-6) (a-7) (a-8) (a-9) (a-10) Number of carbon atoms of olefin as raw material 16 16 16 16 16 16 16 16 16 16 Distribution of double Position 1 1.8 1.4 1.0 0.5 0.5 0.4 0.4 0.4 0.4 0.4 bond in olefin as raw Position 2 40.7 38.1 34.2 30.1 27.6 25.2 22.7 20.2 17.8 15.3 material Position 3 29.3 28.3 27.0 25.5 23.6 21.7 19.6 17.7 15.6 13.8 (% by mass) Position 4 15.7 16.5 17.6 18.9 18.3 17.7 17.1 16.5 15.8 15.2 Position 5 7.3 8.3 9.6 11.0 12.3 13.5 14.8 16.0 17.2 18.4 Position 6 3.0 4.0 5.4 7.0 8.3 9.7 11.0 12.4 13.8 15.1 Position 7 1.1 1.7 2.6 3.5 4.7 5.9 7.2 8.4 9.7 10.9 Position 8 1.1 1.7 2.6 3.5 4.7 5.9 7.2 8.4 9.7 10.9 Position 9 0 0 0 0.0 0 0 0 0 0 0 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 Total of positions 5 to 9 12.5 15.7 20.1 25.0 29.9 35 40.2 45.3 50.5 55.3

TABLE-US-00004 TABLE 4 Component (A) (a-1) (a-2) (a-3) (a-4) (a-5) (a-6) (a-7) (a-8) (a-9) (a-10) Number of carbon atoms of hydrocarbon group 16 16 16 16 16 16 16 16 16 16 Distribution of Position 1 0.7 0.9 1.2 1.5 1.4 1.2 1.1 0.9 0.8 0.6 sulfonate Position 2 32.1 30.2 27.2 24.1 22.3 20.4 18.6 16.8 14.9 13.1 group Position 3 24.2 23.1 21.6 19.9 18.4 17.1 15.6 14.3 12.9 11.5 (% by mass) Position 4 25.8 25.5 25 24.6 23.5 22.4 21.3 20.2 19.1 18 Positions 5 to 9 17.2 20.3 25 29.9 34.4 38.9 43.4 47.8 52.3 56.8 Total 100 100 100 100 100 100 100 100 100 100

[Component (B)]

[0206] (b-1): a polyoxyalkylene lauryl ether (a compound obtained by adding an average of 9 moles of an ethyleneoxy group per mole of lauryl alcohol, then adding an average of 2 moles of a propyleneoxy group per mole of lauryl alcohol and then adding an average of 9 moles of an ethyleneoxy group per mole of lauryl alcohol; HLB=14.5; a compound of the general formula (b1) wherein R.sup.1 is a lauryl group, m is 0, A.sup.1O is an ethyleneoxy group and a propyleneoxy group, n is 20, and R.sup.2 is a hydrogen atom)

[0207] (b-2): a polyoxyalkylene lauryl ether (the average number of moles of added oxyethylene group: 10 moles; HLB=14.0; a compound of the general formula (b1) wherein R.sup.1 is lauryl group, m is 0, A.sup.1O is an ethyleneoxy group, n is 10, and R.sup.2 is a hydrogen atom)

[0208] (b-3): a polyoxyethylene alkyl ether (the average number of moles of added oxyethylene group: 6 moles; HLB=12.1; a compound of the general formula (b1) wherein R.sup.1 is a mixed alkyl group of a lauryl group and a myristyl group, the ratio of the mass of the lauryl group to the mass of the myristyl group (lauryl group/myristyl group)=9/1, m is 0, A.sup.1O is an ethyleneoxy group, n is 6, and R.sup.2 is a hydrogen atom)

[0209] (b-4): a polyoxyethylene alkyl ether (the average number of moles of added oxyethylene group: 5 moles; HLB=10.7; a compound of the general formula (b1) wherein R.sup.1 is a mixed alkyl group of a lauryl group and a myristyl group, the ratio of the mass of the lauryl group to the mass of the myristyl group (lauryl group/myristyl group)=9/1, m is 0, A.sup.1O is an ethyleneoxy group, n is 5, and R.sup.2 is a hydrogen atom)

[Component (B)] (a Comparative Component of Component B)

[0210] (b-1): a polyoxyethylene lauryl ether (the average number of moles of added oxyethylene group: 3 moles; HLB=8.3; a compound of the general formula (b1) wherein R.sup.1 is a lauryl group, m is 0, A.sup.1O is an ethyleneoxy group, n is 3, and R.sup.2 is a hydrogen atom)

[Optional Component]

[Component (C)]

[0211] (c-1): a sodium alkylbenzene sulfonate (alkyl composition: C10/C11/C12/C13=11/29/34/26 (mass ratio); mass average number of carbon atoms=17.75)

[Water]

[0212] Ion-Exchanged Water

<Preparation of Detergent Compositions for Textile Products>

[0213] Detergent compositions for textile products shown in Tables 5 to 6 were prepared using the above-mentioned components to be blended, and were evaluated for the following items. The results are shown in Tables 5 to 6.

[0214] Specifically, the method for preparing the detergent compositions for fibers shown in Tables 5 to 6 was as follows. A Teflon stirrer piece having a length of 5 cm was placed in a 200 mL glass beaker and its weight was measured. Next, 80 g of ion-exchanged water at 20 C., either component (A) or component (C) and either component (B) or component (B) were introduced thereinto, and the beaker was sealed at its top side with Saran Wrap. The beaker containing the contents was placed in a water bath at 60 C. placed on a magnetic stirrer, and the contents were stirred at 100 r/min for 30 minutes at a water temperature range in the water bath of 602 C. Next, the water in the water bath was replaced with tap water at 5 C. and cooled until the temperature of the composition in the beaker was 20 C. Next, Saran Wrap was removed, ion-exchanged water was added so that the weight of the contents was 100 g, and the contents were stirred again at 100 r/min for 30 seconds to obtain each of the detergent compositions for textile products shown in Tables 5 to 6.

[0215] In Formulation Examples 1 to 6 and Comparative Formulation Example 1 in Table 6, the detergent compositions for textile products were compositions prepared by setting the total of the content of component (A) and the content of component (B) in detergent composition for textile products as 10% by mass, and changing the mass ratios between component (A) and component (B). In each Formulation Example, the composition was a composition prepared by using one of (a-1) to (a-10) as component (A). As component (B), (b-1) was used in Formulation Examples 1 to 3, (b-2) was used in Formulation Example 4, (b-3) was used in Formulation Example 5, and (b-4) was used in Formulation Example 6, respectively.

<Evaluation Method>

[Preparation of Textile Products for Evaluation]

(1) Preparation of Textile Products for Evaluation of Adsorption Percentage of Surfactants

[0216] 1.7 kg of knitted cotton (un-mercerized knitted cotton (not mercerized one), cotton 100%, manufactured by Shikisensha Co., Ltd.) was washed cumulatively twice with a standard course of a fully automatic washing machine (NA-F702 P manufactured by Matsushita Electric Industrial Co., Ltd.) (4.7 g of Emulgen 108 (manufactured by Kao Corporation) at washing; water amount: 47 L; washing for 9 minutes, rinsing twice and spin-drying for 3 minutes) followed by cumulatively washing three times with water only (water amount: 47 L; washing for 9 minutes, rinsing twice and spin-drying for 3 minutes), and dried under an environment of 23 C. and 45% RH for 24 hours. It was then cut into 6 cm6 cm in size.

(2) Preparation of Textile Products for Evaluation of Washing Percentage

Preparation of the Model Artificially Sebum-Stained Cloth

[0217] A model artificially sebum-stained cloth was prepared by applying a model artificially sebum-staining liquid of the following composition to a cloth (Cotton 2003 (manufactured by Tanigashira Shoten)). The application of the model artificially sebum-staining liquid to the cloth was carried out by printing the artificially staining liquid on the cloth using a gravure roll coater. The process for preparing the model artificially sebum-staining liquid by applying the model artificially sebum-staining liquid to the cloth was carried out with a cell capacity of the gravure roll of 58 cm.sup.3/m.sup.2, a coating speed of 1.0 m/min, a drying temperature of 100 C. and a drying time of 1 minute. The cloth was then cut into 6 cm6 cm in size. [0218] The composition of the model artificially sebum-staining liquid: lauric acid: 0.4% by mass, myristic acid: 3.1% by mass, pentadecanoic acid: 2.3% by mass, palmitic acid: 6.2% by mass, heptadecanoic acid: 0.4% by mass, stearic acid: 1.6% by mass, oleic acid: 7.8% by mass, triolein: 13.0% by mass, n-hexadecyl palmitate: 2.2% by mass, squalene: 6.5% by mass, egg white lecithin liquid crystal product: 1.9% by mass, Kanuma red clay: 8.1% by mass, carbon black: 0.01% by mass and water: balance (total 100% by mass).

[Washing Test]

(1) Washing Test 1

[0219] Washing procedure was carried out by using Terg-0-Tometer (manufactured by Ueshima Seisakusho Co., Ltd.). The water to be used for washing was obtained by adding calcium chloride and magnesium chloride to ion-exchanged water at a mass ratio of 8:2 and adjusting the hardness to 4 dH. The detergent liquid was obtained by mixing each detergent composition for textile products shown in Tables 5 or 6 with the water for washing so that the total amount of component (A), component (B), component (C) and component (B) in the detergent composition for textile products is at a concentration of 167 mg/kg in the detergent liquid. 0.6 L of the detergent liquid and five cut pieces of each of the above-mentioned textile products for evaluation of adsorption percentage of surfactants were introduced into a 1 liter-stainless steel beaker. The bath ratio was adjusted to 15 with respect to each of the above-mentioned textile products for evaluation of adsorption percentage. The temperature of the detergent liquid was 20 C. Each of the textile products for evaluation was washed at 85 rpm with Terg-O-Tometer for 10 minutes. After washing, it was spin-dried and dried in an environment of 23 C. and 45% RH for 24 hours.

(2) Washing Test 2

[0220] Washing procedure was carried out by using Terg-O-Tometer (manufactured by Ueshima Seisakusho Co., Ltd.). The water to be used for washing was obtained by adding calcium chloride and magnesium chloride to ion-exchanged water at a mass ratio of 8:2 and adjusting the hardness to 4 dH. The detergent liquid was obtained by mixing each detergent composition for textile products shown in Tables 5 or 6 with the water for washing so that the total amount of component (A), component (B), component (C) and component (B) in the detergent composition for textile products is at a concentration of 167 mg/kg in the detergent liquid. 0.6 L of the detergent liquid and five cut pieces of each of the above-mentioned textile products for evaluation of washing percentage were introduced into a 1 liter-stainless steel beaker. The bath ratio was adjusted to 15 with respect to each of the above-mentioned textile products for evaluation of adsorption percentage of surfactants, and the temperature of the detergent liquid was 20 C. Each of the textile products for evaluation was washed at 85 rpm with Terg-O-Tometer for 10 minutes. After washing, it was spin-dried and was dried with an iron press machine.

[Quantification of Amount of Surfactants Adsorbed to Textile Products]

[0221] Two cut pieces were taken out of the cut pieces of each of the textile products for evaluation of adsorption percentage of surfactants after the washing test 1, and the cut pieces were weighed while being sealed in a No. 7 screw tube. 40 mL of a methanol/chloroform solution (methanol:chloroform=1:1 (by volume)) was added thereto, and subjected to ultrasonication for 50 minutes with an ultrasonic washing machine. The extract was diluted 20 times to prepare a solution to be measured. Next, each of component (A), component (B) and component (C) was diluted with a methanol/chloroform solution (methanol:chloroform=1:1 (by volume)) to prepare 0.1 g/mL, 0.5 g/mL, 1 g/mL and 5 g/mL solutions for preparing a calibration curve. The amount of the surfactant in the solution to be measured was quantified by a liquid chromatograph/mass spectrometer (hereinafter abbreviated as LCMS device), and the amount of the active agent adsorbed to textile product from the solution for preparing calibration curve was determined. [0222] LCMS device: LCMS-2020, manufactured by Shimadzu Corporation [0223] Eluent A: a 10 mmol/L aqueous solution of ammonium acetate in distilled water

[0224] Eluent B: a 10 mmol/L methanolic solution of ammonium acetate [0225] Gradient condition: eluent A/B=1:1 (0 minutes).fwdarw.eluent B (2 to 5 minutes).fwdarw.eluent A/eluent B=1/1 (5.1 minutes to 8 minutes), flow rate: 0.6 mL/min, sample injection volume: 5 l, column temperature: 40 C.

[0226] The adsorption percentage of the surfactant to textile products was determined by the following formula. The results are shown in Table 5.

Adsorption percentage of total surfactants=100{(total weight of surfactants adsorbed to two cut pieces of textile product used for measurement of adsorption amount)(total weight of textile product used in washing test 1)/(weight of two pieces of textile product used in measurement of adsorption amount)}/(total weight of surfactants used for preparation of detergent liquid)

[Evaluation Method of Washing Percentage]

[0227] The washing percentage of the textile product to be evaluated obtained in the washing test 2 was measured by the following method, and the average value of 5 cut pieces was determined. The results are shown in table 6.

[0228] The reflectance at 550 nm of each of the original cloth before staining and the clothes before and after washing was measured with a differential colorimeter (Z-300A, manufactured by Nippon Denshoku Industries Co., Ltd.), and the washing percentage (%) was determined by the following formula (the values in Table 6 are average values of the washing percentages for 5 cut pieces).

Washing percentage(%)=100[(reflectance after washingreflectance before washing)/(reflectance of original clothreflectance before washing)]

TABLE-US-00005 TABLE 5 Example Comparative Example 1 2 3 1 2 3 4 5 Detergent composition Content Component (a-1) 5 10 for textile products (% by mass) (A) (a-4) 5 10 5 (a-10) 5 10 Component (b-1) 5 5 5 5 (B) Component (b-1) 5 (B) Component (c-1) 5 (C) Ion-exchanged water Balance Balance Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 100 100 (B)/(A) (mass ratio) 1 1 1 Evaluation Adsorption percentgage 28.8 25.6 24.3 39.7 36.3 32.8 40.3 48.7 results of surfactant (%)

DISCUSSION

[0229] Table 5 shows that when comparing Comparative Example 4 with Examples, the amount of the surfactant adsorbed to the textile product after washing was reduced more by using component (A) of the present invention as anionic surfactant than by using the alkylbenzene sulfonate which is a detergent component generally used. It is also shown that the amount of the surfactant adsorbed to the textile product after washing was reduced by using component (A) and component (B) in combination. It is further shown that even if component (A) of the present invention was used, the adsorption percentage was not reduced when using surfactants other than component (B) of the present invention.

TABLE-US-00006 TABLE 6 Component (B)/(A) (B) used (mass ratio) Washing percentage (%) Formulation (b-1) 0.11 31 30 31 32 31 32 30 30 28 25 Example 1 Formulation (b-1) 0.25 31 33 32 33 31 32 32 31 31 32 Example 2 Formulation (b-1) 0.43 33 34 33 35 33 34 32 34 34 35 Example 3 Formulation (b-2) 0.25 32 33 32 32 31 32 Example 4 Formulation (b-3) 0.25 31 32 31 31 31 31 Example 5 Formulation (b-4) 0.25 31 32 32 30 29 26 Example 6 Comparative None 0 31 32 31 31 29 31 28 27 25 24 Formulation Example 1 Component used as component (A) (a-1) (a-2) (a-3) (a-4) (a-5) (a-6) (a-7) (a-8) (a-9) (a-10) Content of olefin having double bond at 12.5 15.7 20.1 25.0 29.9 35 40.2 45.3 50.5 55.3 positions 5 to 9, in olefin as raw material of component (A) (% by mass) Content of internal olefin sulfonate having 17.2 20.3 25 29.9 34.4 38.9 43.4 47.8 52.3 56.8 sulfonate group at positions 5 to 9, in component (A) (% by mass)

DISCUSSION

[0230] Table 6 shows that if component (A) was used alone as in Comparative Formulation Example 1, the detergent property changed when the content of the olefin having a double bond at position 5 or higher in the olefin as a raw material for component (A) changed. However, from Formulation Examples 1 to 6 in which component (A) and component (B) were used in combination, it is shown that the washing percentage did not change over a wider range of the content of the olefin having a double bond at position 5 or higher in the olefin as a raw material for component (A). Further, it is shown that as the content ratio of component (B) increased, the washing percentage did not change over a still wider range of the content of the olefin having a double bond at position 5 or higher in the olefin as a raw material for component (A).