Liquid detergent composition for textile products comprising an internal olefin sulfonate/organic solvent mixture

Abstract

The present invention relates to a liquid detergent composition for textile products containing the following component (A) in an amount of 10% by mass or more and 60% by mass or less, the following component (B), and water: component (A): an internal olefin sulfonate having 14 or more and 16 or less carbon atoms, wherein the mass ratio of an internal olefin sulfonate having 14 or more and 16 or less carbon atoms with the sulfonate group at position 2 or higher and position 4 or lower (IO-1S) to an internal olefin sulfonate having 14 or more and 16 or less carbon atoms with the sulfonate group at position 5 or higher (IO-2S), (IO-1S)/(IO-2S), is 0.50 or more and 4.2 or less; and Component (B): an organic solvent having a hydroxy group.

Claims

1. A method for washing textile products, comprising washing the textile products with a detergent liquid containing a liquid detergent composition for textile products, and water; said liquid detergent composition for textile products comprising the following component (A) in an amount of 10% by mass or more and 60% by mass or less, the following component (B) in an amount of 4% by mass or more and 40% by mass or less, and water, wherein component A is: an internal olefin sulfonate having 14 or more and 16 or less carbon atoms, wherein a mass ratio of an internal olefin sulfonate having 14 or more and 16 or less carbon atoms with the sulfonate group at position 2 or higher and position 4 or lower (IO-1S) to an internal olefin sulfonate having 14 or more and 16 or less carbon atoms with the sulfonate group at position 5 or higher (IO-2S), (IO-1S)/(IO-2S), is 1.0 or more and 3.2 or less; and component B is: one or more selected from the following components (B3) and (B4): component (B3): an organic solvent having a hydrocarbon group with 1 or more and 8 or less carbon atoms, an ether group and a hydroxy group (provided that an aromatic group is excluded from the hydrocarbon group); component (B4): an organic solvent having an optionally partially substituted aromatic group, an ether group and a hydroxy group; and wherein C log P of the component (B) is −1.2 or more and 1.5 or less.

2. The method for washing textile products according to claim 1, wherein a percentage of the component (A) in all anionic surfactants contained in the liquid detergent composition for textile products is 50% by mass or more and 100% by mass or less.

3. The method for washing textile products according to claim 1, wherein a percentage of an internal olefin sulfonate having 15 or more and 16 or less carbon atoms contained in the component (A) in all anionic surfactants contained in the liquid detergent composition for textile products is 60% by mass or more and 100% by mass or less.

4. The method for washing textile products according to claim 1, wherein the organic solvent having a hydrocarbon group having 1 or more and 8 or less carbon atoms, an ether group and a hydroxy group which is the component (B3) (provided that an aromatic group is excluded from the hydrocarbon group) is a compound selected from the group consisting of diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, triethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 2-methyl glycerol ether, 1,3-dimethyl glycerol ether, 1-ethyl glycerol ether, 1,3-diethyl glycerol ether, triethyl glycerol ether, 1-pentyl glyceryl ether, and 2-pentyl glyceryl ether.

5. The method for washing textile products according to claim 1, wherein the organic solvent having an optionally partially substituted aromatic group, an ether group and a hydroxy group which is the component (B4) is a compound selected from the group consisting of 2-phenoxyethanol, diethylene glycol monophenyl ether, triethylene glycol monophenyl ether, 2-benzyloxy ethanol and diethylene glycol monobenzyl ether.

6. The method for washing textile products according to claim 1, wherein the content of water is 10% by mass or more and 80% by mass or less.

7. The method for washing textile products according to claim 1, further comprising, as a component (c5), a nonionic surfactant having a hydroxy group or polyoxyalkylene group.

8. The method for washing textile products according to claim 7, wherein the component (c5) is a nonionic surfactant which is a polyoxyethylene alkyl ether having an alkyl group with 10 or more and 18 or less carbon atoms and an average number of moles of added alkylene oxide of 3 or more and 60 or less, the alkylene oxide being ethylene oxide and/or propylene oxide.

9. The method for washing textile products according to claim 7, wherein the content of the component (c5) in the composition is 0.5% by mass or more and 40% by mass or less.

10. The method for washing textile products according to claim 1, further comprising a method for producing the liquid detergent composition for textile products, comprising mixing the component (A), the component (B), and water, wherein a percentage of the component (A) in all components to be mixed is 10% by mass or more and 60% by mass or less and a percentage of the component (B) in all components to be mixed is 4% by mass or more and 40% by mass or less.

11. The method for washing textile products according to claim 1, wherein the component (A) is the following component (A1): component (A1): an internal olefin sulfonate obtained from an internal olefin having 14 or more and 16 or less carbon atoms, wherein the mass ratio of an olefin having 14 or more and 16 or less carbon atoms with a double bond at position 1 or higher and position 3 or lower (IO-1) to an olefin having 14 or more and 16 or less carbon atoms with a double bond at position 5 or higher (IO-2), (IO-1)/(IO-2) is 0.60 or more and 5.0 or less.

12. The method for washing textile products according to claim 1, wherein the content of the component (A) in the detergent liquid is 0.005% by mass or more and 1% by mass or less.

13. The method for washing textile products according to claim 1, wherein the content of the component (B) in the detergent liquid is 0.001% by mass or more and 1% by mass or less.

Description

EXAMPLES

(1) [Preparation of Component (A)]

(1) Synthesis of Internal Olefins A to C (Production Examples A to C)

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

(3) 7000 g (28.9 mol) of 1-hexadecanol (product name: KALCOL 6098, manufactured by Kao Corporation) and 700 g (10% by mass of an alcohol as a raw material) of γ-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) through the system. 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.

(4) 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

(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.

(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 m×250 μm×0.15 μm, 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.

(2) Synthesis of (a-1), (a-4) and (a-10)

(7) Each of internal olefins A to C obtained from Production Examples A to C 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 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 (a-1), (a-4) and (a-10) respectively, which are 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 a component (a-1), the internal olefin sulfonate obtained by using internal olefin B as a raw material is referred to as a component (a-4), and the internal olefin sulfonate obtained by using internal olefin C as a raw material is referred to as a component (a-10).

(8) The percentage of the content of the internal olefin sulfonate having a sulfonic acid 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.

(9) 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®” (4.6×250 mm, particle size: 3 μm, 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 μL).

(3) Preparation of Component (A) Other than Described Above

(10) (a-1) and (a-4) were mixed to prepare (a-2) and (a-3). In addition, (a-4) and (a-10) were mixed to prepare (a-5) and (a-9).

(11) The bond distribution of sulfonic acid groups of internal olefin sulfonates of components (a-1) to (a-10) obtained is shown in Table 2.

(12) In addition, the double bond distribution of the internal olefins which are a raw material for components (a-1) to (a-10) obtained is shown in Table 3.

(13) TABLE-US-00002 TABLE 2 Component (A) or 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 16 16 16 16 16 16 16 16 16 16 as raw material Distribution Position 1 0.7 0.9 1.2 1.5 1.4 1.2 1.1 0.9 0.8 0.6 of (IO-1S) Position 2 32.1 30.2 27.2 24.1 22.3 20.4 18.6 16.8 14.9 13.1 sulfonate Position 3 24.2 23.1 21.6 19.9 18.4 17.1 15.6 14.3 12.9 11.5 group Position 4 25.8 25.5 25.0 24.6 23.5 22.4 21.3 20.2 19.1 18.0 (% by mass) (IO-2S) Positions 5 to 9 17.2 20.3 25.0 29.9 34.4 38.9 43.4 47.8 52.3 56.8 Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 (IO-1S) (% by mass) 82.1 78.8 73.8 68.6 64.2 59.9 55.5 51.3 46.9 25.2 (IO-1S)/(IO-2S) (mass ratio) 4.8 3.9 3.0 2.3 1.9 1.5 1.3 1.1 0.90 0.44

(14) TABLE-US-00003 TABLE 3 Component (A) or 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 16 16 16 16 16 16 16 16 16 16 as raw material Distribution of (IO-1) Position 1 1.8 1.4 1.0 0.5 0.5 0.4 0.4 0.4 0.4 0.4 double bond in Position 2 40.7 38.1 34.2 30.1 27.6 25.2 22.7 20.2 17.8 15.3 olefin as raw Position 3 29.3 28.3 27.0 25.5 23.6 21.7 19.6 17.7 15.6 13.8 material Position 4 15.7 16.5 17.6 18.9 18.3 17.7 17.1 16.5 15.8 15.2 (% by mass) (IO-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 [(IO-2)] (IO-1)/(IO-2) (mass ratio) of olefin as raw 5.7 43 3.1 2.2 1.7 1.4 1.1 0.85 0.67 0.53 material
<Components to be Blended>
[Component (A)]

(15) (a-2) to (a-9) in Table 3 were used.

(16) [Component (A′)] (Comparative Component of Component (A))

(17) (a-1) or (a-10) in Table 3 was used.

(18) [Component (B)]

(19) Component (b-1): phenoxyethanol (C log P=1.2)

(20) Component (b-2): diethylene glycol monobutyl ether (C log P=0.67)

(21) Component (b-3): propylene glycol (C log P=−1.1) [Component (C)]

(22) (C-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)

(23) [Water]

(24) Ion-Exchanged Water

(25) <Preparation of Liquid Detergent Composition for Textile Products>

(26) Liquid detergent compositions for textile products shown in Table 4 were prepared using the above-mentioned components to be blended, and were evaluated for the following items. The results are shown in Table 4.

(27) Specifically, the liquid detergent composition for textile products shown in Table 3 was as follows. A Teflon® stirrer piece having a length of 5 cm was placed in a 200 mL glass beaker and its mass was measured. Next, 80 g of ion-exchanged water at 20° C., component (A) or component (A′), component (B), and component (C) were introduced thereinto, and the beaker was sealed at its top side with Saran Wrap®.

(28) The beaker containing the contents was placed in a water bath at 60° C. placed on a magnetic stirrer, and stirred at 100 r/min for 30 minutes at a water temperature range in the water bath of 60±2° 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 stirred again at 100 r/min for 30 seconds to obtain each of the liquid detergent composition for textile products shown in Table 4.

(29) <Evaluation of Appearance>

(30) 30 g of the liquid detergent composition for textile products listed in Table 4 was placed in a No. 6 glass standard bottle, and the bottle was sealed with a cap. By placing this in a thermostatic bath at −5° C. and allowed to stand for 4 days, the standard bottle containing the liquid detergent composition for textile products was placed in an environment at −5° C. After 4 days passed, the appearance of the liquid detergent composition for textile products in the standard bottle at −5° C. was visually observed and evaluated according to the following criteria. The results are shown in Table 4.

(31) A: It has the same appearance as that of the liquid detergent composition for textile products before placed in an environment of −5° C.

(32) B: It has a slightly more turbid appearance than the liquid detergent composition for textile products before placed in an environment of −5° C., but the turbidity is within the allowable range. “Slightly turbid” means that the characters of the newspaper placed behind the standard bottle, when seen through the standard bottle from the front of the standard bottle, can be discriminated.

(33) C: This means that solid matter precipitates in the liquid detergent composition for textile products before placed in an environment of −5° C., it has a turbid appearance and the characters of the newspaper placed behind the standard bottle, when seen through the standard bottle from the front of the standard bottle, cannot be discriminated; or the liquid detergent composition for textile products in the standard bottle is not uniform and separates into two or more layers.

(34) <Evaluation of Detergent Property>

(35) [Preparation of Model Artificially Sebum-Stained Cloth]

(36) 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-stained cloth 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 used was Cotton 2003 (manufactured by Tanigashira Shoten).

(37) * 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).

(38) [Washing Test]

(39) The 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 at the mass ratio of 8:2 to ion-exchanged water to adjust the hardness of water to 4° dH. A detergent liquid was obtained by mixing each of the detergent composition for textile products listed in Table 4 with the water for washing so that the total amount of component (A), component (B) and optionally component (C) in a detergent composition for textile products is 167 mg/kg in the detergent liquid. 0.6 L of the detergent liquid and five cut pieces of the above-mentioned model artificially sebum-stained cloth were introduced into a 1 liter-stainless steel beaker. The bath ratio was 15, and the temperature of the detergent liquid was 20° C. Cut pieces of the model artificially sebum-stained cloth to be evaluated were washed at 85 rpm with Terg-O-Tometer for 10 minutes. After washing, they were spin-dried and dried with an iron press machine.

(40) [Method for Evaluating Washing Percentage]

(41) The washing percentage was measured by the following method, and the average value of washing percentages of the five cut pieces was determined. Based on each washing percentage (average value) for the washing time of 10 minutes, the relative value of washability was obtained by the following equation. The results are shown in Table 4.

(42) 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 equation. The values in the Table 4 are average values of the washing percentages for 5 cut pieces.
Washing percentage (%)=100×[(reflectance after washing−reflectance before washing)/(reflectance of original cloth−reflectance before washing)]

(43) TABLE-US-00004 TABLE 4 Example 1 2 3 4 5 6 Detergent Content (A) (a-2) 27 composition (% by mass) (a-3) 27 for (a-4) 27 textile (a-5) 27 products (a-6) 27 (a-7) 27 (a-8) (a-9) (A′) (a-1) (a-10) (B) (b-1) 9 9 9 9 9 9 (b-2) (b-3) (C) (c-1) 15 15 15 15 15 15 Ion-exchanged water Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 (IO-1)(IO-2)(mass ratio).sup.(1) 4.3 3.1 2.2 1.7 1.4 1.1 (IO-1S)(IO-2S)(mass ratio).sup.(2) 3.9 3.0 2.3 1.9 1.5 1.3 Evaluation Appearance B A A A A A results Washing Percentage (%) 30 30 30 30 29 28 Comparative Example Example 7 8 9 10 1 2 Detergent Content (A) (a-2) composition (% by mass) (a-3) for (a-4) textile (a-5) products (a-6) 23 (a-7) 23 (a-8) 27 (a-9) 27 (A′) (a-1) 27 (a-10) 27 (B) (b-1) 9 9 9 9 (b-2) 10 10 (b-3) 8 8 (C) (c-1) 15 15 23 23 15 15 Ion-exchanged water Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 (IO-1)(IO-2)(mass ratio).sup.(1) 0.85 0.67 1.4 1.1 5.7 0.55 (IO-1S)(IO-2S)(mass ratio).sup.(2) 1.1 0.9 1.5 1.3 4.8 0.44 Evaluation Appearance A B A A C.sup.(3) C.sup.(4) results Washing Percentage (%) 28 28 29 28 31 23

(44) (1) Mass ratio of (IO-1)/(IO-2) in an olefin as a raw material

(45) (2) Mass ratio of (IO-1S)/(IO-2S) in an internal olefin sulfonate

(46) (3) In Comparative Example 1, solid matter generated.

(47) (4) In Comparative Example 2, separation occurred.