Method for washing clothing

Abstract

The present invention relates to a method for washing clothing, including washing clothing with a detergent liquid having a pH of 3.5 or more and 8.5 or less at 20 C. obtained by mixing the following component (A) and component (B), and water having a hardness: component (A): an internal olefin sulfonate having 15 or more and 24 or less carbon atoms; and component (B): protease.

Claims

1. A method for washing clothing, comprising washing clothing with a detergent liquid having a pH of 3.5 or more and 8.5 or less at 20 C. obtained by mixing the following component (A) and component (B), and water having a hardness: component (A): an internal olefin sulfonate including an internal olefin sulfonate having 15 or more and 24 or less carbon atoms with the sulfonate group at position 2 or higher and position 4 or lower (IO-1S) and an olefin having 15 or more and 24 or less carbon atoms with the sulfonate group at position 5 or higher (IO-2S); and component (B): protease.

2. The method for washing clothing according to claim 1, wherein a mass ratio of (IO-1S)/(IO-2S) is 0.50 or more and 6.5 or less.

3. The method for washing clothing according to claim 1, 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) 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 component (a2): an internal olefin sulfonate having 17 or more and 24 or less carbon atoms.

4. The method for washing clothing according to claim 1, wherein a content of an internal olefin sulfonate with the sulfonate group at position 2 in the component (A) is 10% by mass or more and 60% by mass or less.

5. The method for washing clothing according to claim 1, wherein a content of an internal olefin sulfonate with the sulfonate group at position 1 in the component (A) is 10% by mass or less and 0.01% by mass or more.

6. The method for washing clothing according to claim 1, wherein the component (B) is a subtilisin protease derived from Bacillus sp.

7. The method for washing clothing according to claim 1, wherein the hardness of water having a hardness is, by German hardness, 1 dH or more and 20 dH or less.

8. The method for washing clothing according to claim 1, wherein a content of the component (A) in the detergent liquid is 50 mg/kg or more and 4000 mg/kg or less.

9. The method for washing clothing according to claim 1, wherein a content of the component (B) in the detergent liquid is, as an amount of an enzyme protein, 0.1 mg/kg or more and 100 mg/kg or less.

10. The method for washing clothing according to claim 1, wherein the pH of the detergent liquid at 20 C. is 4.0 or more and 8.0 or less.

11. The method for washing clothing according to claim 1, wherein time to wash clothing is 1 minute or more and 12 hours or less.

12. The method for washing clothing according to claim 1, wherein clothing is washed by being soaked in the detergent liquid.

13. The method for washing clothing according to claim 12, wherein clothing is soaked in the detergent liquid, and thereafter the clothing is mixed with the detergent liquid and subjected to stirring-washing.

14. The method for washing clothing according to claim 1, wherein clothing after being washed is rinsed with water.

15. The method for washing clothing according to claim 1, wherein the detergent liquid further contains, as a component (C), a surfactant other than the component (A).

16. The method for washing clothing according to claim 15, wherein the component (C) is a nonionic surfactant having a hydroxy group or polyoxyalkylene group.

17. The method for washing clothing according to claim 16, wherein the component (C) is a nonionic surfactant containing a polyoxyethylene group and having an HLB of 8 or more and 20 or less.

18. The method for washing clothing according to claim 15, wherein the component (C) is a nonionic surfactant having an HLB of 8 or more and 20 or less and represented by the following general formula (C5-1):
R.sup.1(CO).sub.mO-(A.sup.1O)n-R.sup.2(C5-1) wherein R.sup.1 is an aliphatic hydrocarbon group having 9 or more and 16 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.

19. A method for enhancing a detergent activity of the following component (B), wherein, at the time of washing clothing with a detergent liquid having a pH of 3.5 or more and 8.5 or less at 20 C. obtained by mixing the component (B) and water having a hardness, the following component (A) is present in the detergent liquid: component (A): an internal olefin sulfonate having 15 or more and 24 or less carbon atoms with the sulfonate group at position 2 or higher and position 4 or lower and an olefin having 15 or more and 24 or less carbon atoms with the sulfonate group at position 5 or higher; and component (B): protease.

Description

EXAMPLES

Synthesis of Component (A)

(1) Synthesis of Internal Olefins A (Production Example A)

(1) Internal olefin A used as a raw material for component (A) was synthesized as follows.

(2) 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 passing nitrogen (7000 mL/min) in 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 having 16 carbon atoms at an olefin purity of 100%. The double bond distribution of each of the obtained internal olefins A is shown in Table 1.

(2) Synthesis of Internal Olefins B (Production Example B)

(3) By replacing 1-hexadecanol (KALCOL 6098) in Production Example A described above with 7000 g (28.9 mol) of 1-octadecanol (product name: KALCOL 8098, manufactured by Kao Corporation), an internal olefin B having 18 carbon atoms as a raw material for component (B) was obtained. The double bond distribution of internal olefin B obtained is shown in Table 1.

(4) TABLE-US-00001 TABLE 1 Internal olefin A B Number of carbon atoms of hydrocarbon group 16 18 Distribution of Position 1 1.8 0.9 double bond in olefin Position 2 40.7 25 as raw material Position 3 29.3 21.9 (% by mass) Position 4 15.7 19 Position 5 7.3 13.6 Position 6 3.0 8.6 Position 7 1.1 5.6 Position 8 1.1 2.7 Position 9 0.0 2.7 Total 100.0 100.0 Total of positions 5 to 9 12.5 33.2

(5) 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 the each of the columns for positions 7 and 8. Similarly, for the olefins having 18 carbon atoms, the internal olefin having a double bond at position 8 and the internal olefin having a double bond at position 9 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 8 by 2 is conveniently shown in the each of the columns for positions 8 and 9.

(6) 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.

(3) Production of Internal Olefin Sulfonates Having 16 Carbon Atoms

(7) The internal olefin A obtained in Production Example A was subjected to sulfonation reaction by passing sulfur trioxide 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 was then added thereto in an amount of 300 mL per one time 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 an aqueous phase by oil-water separation procedure. This extraction and removal procedure was carried out three times. The aqueous phase was evaporated to dryness to obtain (a-1) which is a sodium internal olefin sulfonate having 16 carbon atoms.

(8) (a-1) had the mass ratio of the olefin form/the hydroxy form of 8/92. The mass ratio of the olefin form/the hydroxy form was measured by HPLC-MS. Specifically, identification was carried out by separating the hydroxy form and the olefin form by HPLC and subjecting them to MS. Each percentage was determined from the resulting HPLC-MS peak areas.

(9) The devices and the analysis conditions used for the measurement are as follows: an HPLC device: Agilent Technology 1100 (manufactured by Agilent Technologies); a column: L-column ODS (4.6150 mm, manufactured by Chemicals Evaluation and Research Institute, Japan); sample preparation (1000 times diluted with methanol); eluent A (10 mM ammonium acetate-added water), eluent B (10 mM ammonium acetate-added methanol); gradient (0 min (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%); an MS device: Agilent Technology 1100MSSL (G1946D) (manufactured by Agilent Technologies); and MS detection (negative ion detection, m/z: 60-1600, UV 240 nm).

(4) Production of Internal Olefin Sulfonates Having 18 Carbon Atoms

(10) Internal olefin B 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 each sodium internal olefin sulfonate. 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 following sodium internal olefin sulfonates. The mass ratio of the olefin form (sodium olefin sulfonate)/the hydroxy form (sodium hydroxyalkane sulfonate) of each component is 17/83.

(11) 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 a sulfonic acid 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.

(12) 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: 349.15 (component (A) having 18 carbon atoms), 321.10 (component (A) having 16 carbon atoms); column temperature (40 C.); flow rate (0.5 mL/min); and injection volume (5 L).

(13) In addition, the distribution of the positions of the carbon through which each of sulfonate groups of (a-1) and (a-2) obtained is attached is shown in Table 2.

(14) TABLE-US-00002 TABLE 2 Component (A) (a-1) (a-2) Number of carbon atoms of hydrocarbon group 16 18 Distribution Position 1 0.7 1.4 of sulfonate (IO-1S) Position 2 32.1 22.1 group Position 3 24.2 17.3 (% by mass) Position 4 25.8 21.8 (IO-2S) Positions 5 to 9 17.2 37.4 Total 100.0 100 (IO-1S) (% by mass) 82.1 61.2 (IO-2S) (% by mass) 17.2 37.4 (IO-1S)/(IO-2S) mass ratio 4.8 1.6
<Components to be Blended>
[Component (A)]

(15) (a-1): a sodium internal olefin sulfonate obtained from internal olefin A. The mass ratio of the olefin form (sodium olefin sulfonate)/the hydroxy form (sodium hydroxyalkane sulfonate) in the sodium internal olefin sulfonate: 8/92

(16) (a-2): a sodium internal olefin sulfonate obtained from internal olefin B

(17) The mass ratio of the olefin form (sodium olefin sulfonate)/the hydroxy form (sodium hydroxyalkane sulfonate) in the sodium internal olefin sulfonate: 17/83

(18) [Component (A): Comparative Compound of Component (A)]

(19) (a-1): a sodium alkylbenzene sulfonate (Neopelex G-15, manufactured by Kao Corporation)

(20) [Component (B)]

(21) Component (b-1): a protease formulation (manufactured by Kao Corporation)

(22) Component (b-2): Savinase 16L enzyme preparation (manufactured by Novozymes A/S)

(23) [Component (C)]

(24) (c-1): a polyoxyethylene lauryl ether (average number of moles of added oxyethylene group: 40 mol)

(25) [Water]

(26) Water obtained by adjusting the hardness of ion-exchanged water to 10 dH by using calcium chloride and magnesium chloride at the mass ratio of 8/2 (calcium chloride/magnesium chloride).

(27) [Washing Test 1]

(28) The water having a hardness of 10 dH (the mass ratio of the hardness components is calcium chloride:magnesium chloride=8:2) was adjusted to pH 7.5 (20 C.) with 10 mM Tris-hydrochloric acid. To this water were added component (A) or component (A) and optionally component (C) at a ratio shown in Table 3 so that the total of the final concentrations in the detergent liquid was 2500 mg/kg. Component (B) was added thereto so that the protein concentration was 2.4 mg/kg or 6 mg/kg, to prepare a detergent liquid. The protein concentration in the enzyme preparation was measured by Protein Assay Rapid Kit WAKO (manufactured by Wako Pure Chemical Industries, Ltd.). The pH of the detergent liquid was measured according to the method for measuring pH described above.

(29) Cut pieces of artificially stained cloth CFT AS-10 (milk/peanut oil/pigment stained, manufactured by CFT Company) obtained by cutting it into 1 cm1 cm square was placed and soaked in 5 mL of the detergent liquid prepared above at 25 C. for 30 minutes. The bath ratio was 90. Thereafter, cut pieces were rinsed with tap water and air dried. The brightness was measured by using a color difference meter (MINOLTA, CM3500d), and the washing percentage was calculated from a change in the brightness before and after washing according to the following equation.

(30) In addition, cut pieces were washed with water adjusted to pH 9 with 10 mM Tris-hydrochloric acid and the washing percentage was calculated in the similar manner.

(31) The results are shown in table 3.
Washing percentage (%)=(L2L1)/(L0L1)100
wherein:
L0: a brightness of the raw cloth of the stained cloth,
L1: a brightness of the stained cloth before washing, and
L2: a brightness of the stained cloth after washing.

(32) TABLE-US-00003 TABLE 3 Comparative Comparative Comparative Example Example Example Example Example Example Example 1-1 1-1 1-2 1-2 1-3 1-3 1-4 Composiiton of (A) (a-1) 2500 2000 2000 1500 detergent liquid (a-2) 1000 (mg/kg) (A) (a-1) 2500 2000 2000 (B) (b-1) 2.4 2.4 2.4 2.4 2.4 (b-2) 6 6 (C) (c-1) 500 500 500 500 Water (hardness: 10 dH) Balance Balance Balance Balance Balance Balance Balance Evaluation Washing percentage at 37.7 39.4 35.7 35.5 38.2 38.5 36.8 results pH 9: X (%) Washing percentage at 31.5 27.1 29.4 23.1 31.5 26.1 30.0 pH 7.5: Y (%) (Washing percentage Y/washing 84 69 82 65 82 68 82 percentage X) 100 (%)

(33) The results of Table 3 show that when comparing the detergency of the detergent liquid having a pH of 9 with the detergency of the detergent liquid having a pH of 7.5, the washing method using protease in combination with component (A) of the present invention is lower in the degree of decrease in the washing percentage due to a decrease in pH than the washing method using protease in combination with an alkylbenzene sulfonate which is a common sulfonate, and can keep the detergency better than the latter method. It is also shown that the washing method using protease in combination with component (A) of the present invention is higher in the detergency than the washing method using protease in combination with an alkylbenzene sulfonate which is a common sulfonate.

(34) [Washing Test 2]

(35) The water having a hardness of 10 dH (the mass ratio of the hardness components is calcium chloride:magnesium chloride=8:2) was adjusted to pH 7.5 (20 C.) with 10 mM Tris-hydrochloric acid. To this water was added component (A) or component (A) so that the final concentration was 250, 500, 1000, 2000 or 4000 mg/kg. (a-1) was used as component (A), and (a-1) was used as component (A). A detergent liquid was prepared by adding thereto the Savinase 16L enzyme preparation (Novozymes A/S) of (b-2) so that the protein concentration is 6 mg/kg. The protein concentration in the enzyme preparation was measured by Protein Assay Rapid Kit WAKO (manufactured by Wako Pure Chemical Industries, Ltd.). The pH of the detergent liquid was measured according to the method for measuring pH described above.

(36) Cut pieces of artificially stained cloth CFT AS-10 (milk/peanut oil/pigment stained, manufactured by CFT Company) obtained by cutting into 1 cm1 cm square was placed and soaked in 5 mL of the detergent liquid prepared above at 25 C. for 30 minutes. The bath ratio was 90. Thereafter, cut pieces were rinsed with tap water and air dried. Thereafter, the washing percentage was calculated in the same manner as in Washing Test 1. The results are shown in Table 4.

(37) TABLE-US-00004 TABLE 4 Test Example 2-1 2-2 2-3 2-4 2-5 Compositon of Component (A) or component (A) 250 500 1000 2000 4000 detergent liquid (B) (b-2) 6 6 6 6 6 (mg/kg) Water (hardness: 10 dH) Balance Balance Balance Balance Balance pH of detergent liquid (20 C.) 7.5 7.5 7.5 7.5 7.5 Evaluation Washing Component (A):(a-1) 13.5 16.8 19.0 24.4 29.7 results percentage (1) [Example] Washing (Component (A):(a-1) 10.1 9.9 10.4 16.2 26.0 percentage (2) [Comparative Example] Washing percentage (1)/washing 1.3 1.7 1.8 1.5 1.1 percentage (2) ratio

(38) The results of Table 4 show that even when the concentration of component (A) in the detergent liquid varies, the washing method using protease in combination with component (A) of the present invention is higher in the detergency than the washing method using protease in combination with an alkylbenzene sulfonate which is a common sulfonate.

(39) [Washing Test 3]

(40) The water having a hardness of 10 dH (the mass ratio of the hardness components of calcium chloride to magnesium chloride is calcium chloride: magnesium chloride=8:2) was adjusted to pH 7.0, 7.5, 8.0, 8.5, or 9.0 with 10 mM Tris-hydrochloric acid. To each water was added component (A) or component (A) so that the final concentration was 1000 mg/kg. (a-1) was used as component (A), and (a-1) was used as component (A). A detergent liquid was prepared by adding Component (B) thereto so that the protein concentration was 6 mg/kg. The protein concentration in the enzyme preparation was measured by Protein Assay Rapid Kit WAKO (manufactured by Wako Pure Chemical Industries, Ltd.). The pH of the detergent liquid in Table 5 is pH of the detergent liquid containing component (A) or component (A) and component (B).

(41) Cut pieces of artificially stained cloth CFT AS-10 (milk/peanut oil/pigment stained, manufactured by CFT Company) obtained by cutting into 1 cm1 cm square was placed and soaked in 5 mL of the detergent liquid prepared above at 25 C. for 30 minutes. The bath ratio was 90. Thereafter, cut pieces were rinsed with tap water and air dried. Thereafter, the washing percentage was calculated in the same manner as in Washing Test 1. The results are shown in Table 5.

(42) TABLE-US-00005 TABLE 5 Test Example 3-1 3-2 3-3 3-4 Composition of Component (A) or component (A) 1000 1000 1000 1000 detergent liquid (B) (b-2) 6 6 6 6 (mg/kg) Water (hardness: 10 dH) Balance Balance Balance Balance pH of detergent liquid (20 C.) 7.0 7.5 8.0 8.5 Evaluation results Washing Component (A):(a-1) 15 20 28 30 percentage (3) [Example] Washing Component (A):(a-1) 6.3 11 20 26 percentage (4) [Comparative Example] Washing percentage (3)/washing 2.4 1.8 1.4 1.2 percentage (4) ratio

(43) The results of Table 5 show that even when the pH of the detergent liquid varies, the washing method using protease in combination with component (A) of the present invention is higher in the detergency than the washing method using protease in combination with an alkylbenzene sulfonate which is a common sulfonate.