Detergent composition for textile products

Abstract

The present invention provides a detergent composition for textile products, containing the following component (A) and component (B): component (A): an internal olefin sulfonate having 16 or more and 18 or less carbons; and component (B): an alkyl sulfate having 12 or more and 14 or less carbons.

Claims

1. A detergent composition for textile products, comprising the following component (A), component (B) and water: component (A): an internal olefin sulfonate having 16 or more and 18 or less carbons; and component (B): one or more anionic surfactants selected from an alkyl sulfate having 12 or more and 14 or less carbons and an alkane sulfonate having 12 or more and 14 or less carbons, wherein the component (A) is an internal olefin sulfonate having 16 or more and 18 or less carbons and, in the internal olefin sulfonate, a mass ratio of an internal olefin sulfonate having the sulfonate group at position 2 or higher and 4 or lower and having 16 or more and 18 or less carbons (IO-1S) to an internal olefin sulfonate having the sulfonate group at position 5 or higher and having 16 or more and 18 or less carbons (IO-2S), (IO-1S)/(IO-2S), is 0.75 or more and 5.5 or less; wherein a mass ratio of the content of the component (B) to the content of the component (A), (B)/(A), is 0.25 or more and 6 or less, and wherein the composition is used by diluting with water having a hardness of 4° dH or more in terms of German hardness and the total content of component A and the total content of component B is 1 mass % or more and 50 mass % or less.

2. The detergent composition for textile products according to claim 1, wherein the content of one or more anionic surfactants selected from an alkyl sulfate having 12 carbons and an alkane sulfonate having 12 carbons in the whole component (B) contained in the detergent composition for textile products is 50 mass % or more and 100 mass % or less.

3. The detergent composition for textile products according to claim 1, wherein the content of an internal olefin sulfonate having 16 carbons in the component (A) is 0 mass % or more and 80 mass % or less.

4. The detergent composition for textile products according to claim 1, wherein a proportion of the total amount of the component (A) and the component (B) in all surfactants contained in the detergent composition for textile products is 50 mass % or more and 100 mass % or less.

5. The detergent composition for textile products according to claim 1, wherein a proportion of the total amount of the component (A) and the component (B) in all anionic surfactants contained in the detergent composition for textile products is 50 mass % or more and 100 mass % or less.

6. A method for cleaning a textile product, comprising cleaning the textile product with a cleaning liquid in which the detergent composition for textile products according to claim 1 is diluted with water, and wherein the diluting water is water having a hardness of 4° dH or more in terms of German hardness.

7. The method for cleaning a textile product according to claim 6, wherein a total concentration of the component (A) and the component (B) in the cleaning liquid is 0.001 mass % or more and 0.1 mass % or less.

8. The method for cleaning a textile product according to claim 6, wherein a pH of the cleaning liquid at 20° C. is 5 or more and 10 or less.

9. The method for cleaning a textile product according to claim 6, wherein a hardness of water for diluting the composition is 1° dH or more and 20° dH or less in terms of German hardness.

10. A method for producing a detergent composition for textile products, comprising mixing the following component (A), component (B) and water: component (A): an internal olefin sulfonate having 16 or more and 18 or less carbons; and component (B): one or more anionic surfactants selected from an alkyl sulfate having 12 or more and 14 or less carbons and an alkane sulfonate having 12 or more and 14 or less carbons, wherein the component (A) is an internal olefin sulfonate having 16 or more and 18 or less carbons and, in the internal olefin sulfonate, a mass ratio of an internal olefin sulfonate having the sulfonate group at position 2 or higher and 4 or lower and having 16 or more and 18 or less carbons (IO-1S) to an internal olefin sulfonate having the sulfonate group at position 5 or higher and having 16 or more and 18 or less carbons (IO-2S), (IO-1S)/(IO-2S), is 0.75 or more and 5.5 or less; wherein a mass ratio of the content of the component (B) to the content of the component (A), (B)/(A), is 0.25 or more and 6 or less, and wherein the diluting water is water having a hardness of 4° dH or more in terms of German hardness and the total content of component A and the total content of component B is 1 mass % or more and 50 mass % or less.

11. A method for improving the resistance to hardness of a detergent composition for textile products, comprising using the following component (A) and the component (B) in combination: component (A): an internal olefin sulfonate having 16 or more and 18 or less carbons; and component (B): one or more anionic surfactants selected from an alkyl sulfate having 12 or more and 14 or less carbons and an alkane sulfonate having 12 or more and 14 or less carbons, wherein the component (A) is an internal olefin sulfonate having 16 or more and 18 or less carbons and, in the internal olefin sulfonate, a mass ratio of an internal olefin sulfonate having the sulfonate group at position 2 or higher and 4 or lower and having 16 or more and 18 or less carbons (IO-1S) to an internal olefin sulfonate having the sulfonate group at position 5 or higher and having 16 or more and 18 or less carbons (IO-2S), (IO-1S)/(IO-2S), is 0.75 or more and 5.5 or less; wherein a mass ratio of the content of the component (B) to the content of the component (A), (B)/(A), is 0.25 or more and 6 or less, and wherein the diluting water is water having a hardness of 4° dH or more in terms of German hardness and the total content of component A and the total content of component B is 1 mass % or more and 50 mass % or less.

Description

EXAMPLES

(1) [Preparation of Internal Olefin Sulfonate]

(2) Internal olefins as raw materials for component (A) or component (A′) [comparative compound of component (A)] are as follows.

(3) Internal Olefin A

(4) Internal olefin A is an internal olefin having 16 carbons and obtained by reference to the method described in JP-A 2014-76988, Production Example C. The double bond distribution (mass ratio) of internal olefin A is shown below.

(5) Double bond distribution of internal olefin A: 1-olefin/2-olefin/3-olefin/4-olefin/5-olefin/6-olefin/7-olefin/8-olefin=1.0/29.8/24.4/18.3/13.0/7.1/3.2/3.2

(6) Internal Olefin B

(7) Internal olefin B is an internal olefin having 18 carbons and obtained by reference to the method described in JP-A 2014-76988, Production Example. The double bond distribution (mass ratio) of internal olefin B is shown below.

(8) Double bond distribution of internal olefin B: 1-olefin/2-olefin/3-olefin/4-olefin/5-olefin/6-olefin/7-olefin/8-olefin/9-olefin=2.3/25.7/21.6/19.1/12.3/8.0/5.4/2.8/2.8

(9) Internal Olefin C

(10) Internal olefin C as a raw material for component (A′) is an internal olefin having 12 carbons and obtained by reference to the method described in JP-A 2014-167108, Production Example B. The double bond distribution (mass ratio) of internal olefin C is shown below.

(11) Double bond distribution of internal olefin C: 1-olefin/2-olefin/3-olefin/4-olefin/5-olefin/6-olefin=0.5/33.1/23.6/21.2/15.0/6.6

(12) Internal Olefin D

(13) Internal olefin D is an internal olefin having 16 carbons and obtained by reference to the method described in JP-A 2014-76988, Production Example A. The double bond distribution (mass ratio) of internal olefin D is shown below.

(14) Double bond distribution of internal olefin D: 1-olefin/2-olefin/3-olefin/4-olefin/5-olefin/6-olefin/7-olefin/8-olefin=0.4/15.3/13.8/15.2/18.4/15.1/10.9/10.9

(15) The double bond distribution of the internal olefin was measured by gas chromatography (hereinafter, abbreviated as GC). Specifically, dimethyl disulfide was reacted with the internal olefin to obtain a dithioated derivative, and each component was separated by GC. Accordingly, the double bond distribution of the internal olefin was determined from the peak area of each component. In the olefin having 18 carbons, the internal olefin having a double bond at position 8 and the internal olefin having a double bond at position 9 cannot be structurally discriminated, and can be discriminated when subjected to sulfonation. Thus, a value obtained by dividing the amount of internal olefins having a double bond at position 8 by 2 is shown in each of the fields of positions 8 and 9 for the sake of convenience. Similarly, in the olefin having 16 carbons, a value obtained by dividing the amount of internal olefins having a double bond at position 7 by 2 is shown in each of the fields of positions 7 and 8 for the sake of convenience.

(16) Apparatuses used for measurement, and analysis conditions are as follows. GC apparatus: “HP6890” (manufactured by Hewlett-Packard Company), Column: “Ultra-Alloy-1HT Capillary Column” (30 m×250 μm×0.15 μm, Frontier Laboratories Ltd.), Detector: (hydrogen flame ionization detector (FID)), Injection temperature: 300° C., Detector temperature: 350° C., He flow rate: 4.6 mL/min

(17) (3) Synthesis of Sulfonates (a-1), (a-2) and (a′-1)

(18) Using internal olefins A to C, the following sodium internal olefin sulfonates were obtained by reference to the method described in JP-A 2014-76988, Production Example.

(19) Here, an internal olefin sulfonate obtained with internal olefin A as a raw material was defined as (a-1), an internal olefin sulfonate obtained with internal olefin B as a raw material was defined as (a-2), an internal olefin sulfonate obtained with internal olefin C as a raw material was defined as (a′-1), and an internal olefin sulfonate obtained with internal olefin D as a raw material was defined as (a-3).

(20) Details of the sodium internal olefin sulfonates are described below.

(21) (a-1): Sodium Internal Olefin Sulfonate Obtained from Internal Olefin A

(22) The mass ratio of hydroxy form (sodium hydroxyalkane sulfonate)/olefin form (sodium olefin sulfonate) in (a-1) is 83/17. The position-distribution-mass ratio of the sulfonate groups of the HAS forms in (a-1) is as follows: position 1/position 2/position 3/position 4/position 5/positions 6 to 9=1.6/31.5/25.1/24.7/10.3/6.8. The ratio (IO-1S)/(IO-2S) is 4.8.

(23) (a-2): Sodium Internal Olefin Sulfonate Obtained from Internal Olefin B

(24) The mass ratio of hydroxy form (sodium hydroxyalkane sulfonate)/olefin form (sodium olefin sulfonate) in (a-2) is 84/16. The position-distribution-mass ratio of the sulfonate groups of the HAS forms in (a-2) is as follows: position 1/position 2/position 3/position 4/position 5/positions 6 to 9=1.5/22.1/17.2/21.8/13.5/23.9. The ratio (IO-1S)/(IO-2S) is 1.6.

(25) (a-3): Sodium Internal Olefin Sulfonate Obtained from Internal Olefin D

(26) The mass ratio of hydroxy form (sodium hydroxyalkane sulfonate)/olefin form (sodium olefin sulfonate) in (a-3) is 86/14. The position-distribution-mass ratio of the sulfonate groups of the HAS forms in (a-3) is as follows: position 1/position 2/position 3/position 4/position 5/positions 6 to 9=0.6/13.1/11.5/17.9/17.1/39.8. The ratio (IO-1S)/(IO-2S) is 0.74.

(27) (a′-1): Sodium Internal Olefin Sulfonate Obtained from Internal Olefin C

(28) The mass ratio of hydroxy form (sodium hydroxyalkane sulfonate)/olefin form (sodium olefin sulfonate) in (a′-1) is 92/8.

(29) The position distribution of the sulfonate groups of the HAS forms contained in each internal olefin sulfonate was measured by a liquid chromatography mass spectrometer (hereinafter, abbreviated as LC-MS). The internal olefin sulfonate having a double bond at position 6 or higher was not definitely fractionated because peaks overlapped. Apparatuses used for measurement, and analysis conditions are as follows.

(30) [Measuring Instruments]

(31) LC apparatus: “LC-20ASXR” (manufactured by Shimadzu Corporation)

(32) LC-MS apparatus: “LCMS-2020” (manufactured by Shimadzu Corporation)

(33) Column: ODS Hypersil (length: 250 mm, inner diameter: 4.6 mm, particle diameter: 3 μm, manufactured by Thermo Fisher Scientific)

(34) Detector: ESI (−), m/z=349.15 (C18), 321.10 (C16), 293.05 (C14)

(35) [Solvents]

(36) Solvent A: 10 mM aqueous ammonium acetate

(37) Solvent B: acetonitrile/water=95/5 solution with 10 mM ammonium acetate added

(38) [Elution Conditions]

(39) Gradient: solvent A 60%-solvent B 40% (0-15 min).fwdarw.solvent A 30%-solvent B 70% (15.1-20 min).fwdarw.solvent A 60%-solvent B 40% (20.1-30 min)

(40) Flow rate: 0.5 ml/min

(41) Column temperature: 40° C.

(42) Injection amount: 5 μl

(43) <Formulation Component>

(44) [Component (A)]

(45) (a-1): sodium internal olefin sulfonate obtained from internal olefin A

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

(47) (a-3): sodium internal olefin sulfonate obtained from internal olefin D

(48) [Component (A′)]

(49) (a′-1): sodium internal olefin sulfonate obtained from internal olefin C

(50) [Component (B)]

(51) (b-1): sodium lauryl sulfate

(52) (b-2): sodium myristyl sulfate

(53) (b-3): sodium 1-dodecane sulfonate

(54) [Component (B′)]

(55) (b′-1): sodium decyl sulfate

Example 1 and Comparative Example 1

(56) <Preparation of Liquid Detergent Compositions for Textile Products>

(57) Liquid detergent compositions for textile products as shown in Table 1 were prepared using the above formulation components and ion-exchanged water, and evaluation was performed for the following items. The results are shown in Table 1.

(58) Specifically, the liquid detergent compositions for textile products as shown in Table 1 were prepared in the following manner. A 5 cm-long Teflon (registered trademark) stirrer piece was put in a glass beaker with a capacity of 200 mL, and the mass of the beaker was measured. Next, 80 g of ion-exchanged water at 20° C., component (A) or component (A′), and component (B) or component (B′) were put in the beaker, and the beaker was sealed on the upper side with Saran Wrap (registered trademark).

(59) The beaker with the contents was placed in a water bath installed in a magnetic stirrer and kept at 60° C., and the contents were stirred at 100 r/min for 30 minutes within a temperature range of 60±2° C. in terms of a temperature of water in the water bath. Next, the water in the water bath was replaced by tap water at 5° C., and the beaker was cooled to 20° C. in terms of a temperature of the composition in the beaker. Next, Saran Wrap (registered trademark) was removed, ion-exchanged water was added so that the contents had a mass of 100 g, and stirring was performed again at 100 r/min for 30 minutes to obtain each of the liquid detergent compositions for textile products as shown in Table 1. In Comparative Examples in Table 1, the mass ratio of (B)/(A) is shown with component (A′) and component (B′) used in place, respectively, of component (A) and component (B). The pH (20° C.) of each of the liquid detergent compositions for textile products as shown in Table 1 was measured by the pH measurement method described herein, and the results showed that all the compositions had a pH of 7.0.

(60) <Method for Evaluation of Cleaning Properties (Evaluation (I))>

(61) (1) Preparation of Model Artificially Sebum-Stained Cloth

(62) A model artificially sebum-stained cloth was prepared by applying a model artificially sebum-staining liquid of the following composition to a cloth. 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 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. Cotton 2003 (manufactured by Tanigashira Shoten K.K.) was used as the cloth. *The composition of the model artificially sebum-staining 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 %, trioleic acid: 13.0 mass %, n-hexadecyl palmitate: 2.2 mass %, squalene: 6.5 mass %, egg white lecithin liquid crystal substance: 1.9 mass %, Kanuma reddish soil: 8.1 mass %, carbon black: 0.01 mass %, and water: balance (total: 100 mass %).

(63) (2) Measurement of Cleaning Ratio

(64) Five model artificially sebum-stained cloths (6 cm×6 cm) prepared as described above were cleaned at 85 rpm for 10 minutes with a tergotometer (Ueshima, MS-8212). The cloths were each cleaned under the following conditions: water was injected so that the concentration of the liquid detergent composition for textile products as shown in Table 1 was 0.033 mass % (the water was prepared using ion-exchanged water, calcium chloride and magnesium chloride with the Ca/Mg ratio set to 8/2 (mass ratio) so that the German hardness was 3.5° dH, and the temperature of the water was adjusted to 20° C.), and cleaning was performed at a water temperature of 20° C. The pH of the cleaning liquid was measured in accordance with the method for measuring the pH of the detergent composition for textile products according to the present invention, and the results showed that the pH (20° C.) was 7.0. After cleaning, the cloth was rinsed with city water (20° C.) for 3 minutes. Thereafter, the stained cloth after rinsing was subjected to water removal treatment for 1 minute using a twin-tub washing machine, and then left standing at 20° C. and 43% RH for 12 hours to be dried. The cleaning properties were evaluated based on the cleaning ratio. The cleaning ratio (%) was measured by the following method, and an average for the five cloths was determined. The results are shown in Table 1. The reflectivity at 550 nm of unstained original cloths and cloths before and after cleaning were measured by a color-difference meter (Z-300A manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.).
Cleaning ratio (%)=100×[(reflectivity after cleaning−reflectivity before cleaning)/(reflectivity of original cloth−reflectivity before cleaning)]

(65) A cleaning ratio is compared against the cleaning ratio of Comparative Example 1-1, and when the value of the cleaning ratio is greater than that of Comparative Example 1-1, it can be determined that excellent detergency is exhibited. The liquid detergent compositions for textile products as described in Examples all had a cleaning ratio greater than that of the liquid detergent composition for textile products in Comparative Example 1-1. The greater the value of the cleaning ratio, the better.

(66) TABLE-US-00001 TABLE 1 Examples 1-1 1-2 1-3 1-4 1-5 1-6 1-7 1-8 1-9 1-10 Liquid Formulation (A) (a-1) 8 6 4 2 6 8 6 detergent compositions (a-2) 6 4 2 compositions for (mass %) (a-3) textile products (A′) (a′-1) (B) (b-1) 2 4 6 8 4 6 8 (b-2) 4 (b-3) 2 3 (B′) (b′-1) Ion-exchanged water Balance Balance Balance Balance Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 100 100 100 100 (B)/(A) (mass ratio) 0.25 0.67 1.5 4.0 0.67 1.5 4.0 0.67 0.25 0.67 Cleaning ratio (%) 29 30 30 29 27 28 29 27 29 30 [Evaluation (I)] Examples Comparative Examples 1-11 1-12 1-13 1-14 1-15 1-16 1-1 1-2 1-3 Liquid Formulation (A) (a-1) 4 2 4.5 6 6 10 detergent compositions (a-2) 10 compositions for (mass %) (a-3) 1.5 6 textile products (A′) (a′-1) (B) (b-1) 4 4 3.5 2.5 10 (b-2) 0.5 1.5 (b-3) 6 8 (B′) (b′-1) Ion-exchanged water Balance Balance Balance Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 100 100 100 (B)/(A) (mass ratio) 1.5 4.0 0.67 0.67 0.67 0.67 0 0 — Cleaning ratio (%) 28 27 29 27 30 28 25 (Reference) 23 25 [Evaluation (I)] Comparative Examples 1-4 1-5 1-6 1-7 1-8 1-9 1-10 1-11 Liquid Formulation (A) (a-1) 6 4 6 4 detergent compositions (a-2) compositions for (mass %) (a-3) textile products (A′) (a′-1) 4 4 6 6 (B) (b-1) 6 2.5 6.25 (b-2) 1.5 3.75 (b-3) 10 (B′) (b′-1) 4 6 Ion-exchanged water Balance Balance Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 100 100 (B)/(A) (mass ratio) 1.5 0 0 0.67 1.5 — 0.67 — Cleaning ratio (%) 18 22 19 22 19 23 16 22 [Evaluation (I)] *The ratio of (IO-1S)/(IO-2S) in component (A) in Example 1-13 is 2.6

Example 2 and Comparative Example 2

(67) For liquid detergent compositions for textile products in Example 2, the cleaning ratio was evaluated in the same manner as in Example 1 except that the hardness of water used for cleaning was changed as shown in Table 2. The results are shown in Table 2.

(68) TABLE-US-00002 TABLE 2 Comparative Examples Example 2-1 2-2 2-3 2-4 2-1 Liquid Formulation (A) (a-1) 8 6 4 2 10 detergent components (B) (b-1) 2 4 6 8 compositions (mass %) Ion-exchanged water Balance Balance Balance Balance Balance for textile Total 100 100 100 100 100 products (B)/(A) (mass ratio) 0.25 0.67 1.5 4.0 0 Evaluation Hardness of 0° dH Cleaning ratio 1 (%) 25 25 25 23 23 results water used for 8° dH Cleaning ratio 2 (%) 27 27 27 27 22 cleaning Ratio of cleaning ratio 2/cleaning ratio 1 1.1 1.1 1.1 1.2 0.96

(69) The liquid detergent compositions for textile products in Examples using component (A) and component (B) in combination are found to be superior in detergency to Comparative Example under a condition in which cleaning water has high hardness. In Examples, the detergency can be maintained without being reduced even when the hardness of cleaning water increases.

Example 3 and Comparative Example 3

(70) Liquid detergent compositions for textile products as shown in Table 3 were obtained in the same manner as in Example 1. In Comparative Examples in Table 3, the mass ratio of (B)/(A) is shown with component (A′) and component (B′) used in place, respectively, of component (A) and component (B). The pH of each of the liquid detergent compositions for textile products as shown in Table 3 was measured by the pH measurement method described herein, and the results showed that all the compositions had a pH of 7.0.

(71) For the liquid detergent compositions for textile products in Table 3, the cleaning ratio was measured in the same manner as in “Measurement of cleaning ratio” in Evaluation (I) in Example 1 except that the concentration of the liquid detergent composition for textile products, which was used for cleaning, was 0.02 mass %, and the hardness of water used for cleaning was 7° dH (evaluation in these Examples is defined as Evaluation (II)). The pH of each of the cleaning liquids was measured in accordance with the method for measuring the pH of the detergent compositions for textile products according to the present invention, and the results showed that the pH (20° C.) was 7.0. The results are shown in Table 3.

(72) A cleaning ratio is compared against the cleaning ratio of Comparative Example 3-1, and when the value of the cleaning ratio is greater than that of Comparative Example 3-1, it can be determined that excellent detergency is exhibited. The liquid detergent compositions for textile products as described in Examples all had a cleaning ratio greater than that of the liquid detergent composition for textile products in Comparative Example 3-1. The greater the value of the cleaning ratio, the better.

(73) TABLE-US-00003 TABLE 3 Examples 3-1 3-2 3-3 3-4 3-5 3-6 3-7 3-8 3-9 Liquid Formulation (A) (a-1) 18 15 15 12.5 9.5 15 15 detergent compositions (a-2) 15 compositions for (mass %) (a-3) 2.5 5.5 15 textile products (A′) (a′-1) 1.5 (B) (b-1) 2 5 5 5 5 2.5 5 (b-2) 5 2.5 (B′) (b′-1) Ion-exchanged water Balance Balance Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 100 100 100 (B)/(A) (mass ratio) 0.11 0.33 0.33 0.33 0.33 0.33 0.33 0.33 0.33 Cleaning ratio (%) 33 39 31 30 38 34 32 30 37 [Evaluation (II)] Examples Comparative Examples 3-10 3-1 3-2 3-3 3-4 3-5 3-6 3-7 Liquid Formulation (A) (a-1) 15 20 12 15 detergent compositions (a-2) 20 compositions for (mass %) (a-3) textile products (A′) (a′-1) 5 8 8 15 (B) (b-1) 5 12 2.5 10 (b-2) 2.5 10 (B′) (b′-1) 5 Ion-exchanged water Balance Balance Balance Balance Balance Balance Balance Balance Total 100 100 100 100 100 100 100 100 (B)/(A) (mass ratio) 0.33 0 0 1.5 0 0.33 0.33 — Cleaning ratio (%) 35 27 (Reference) 25 19 23 24 12 15 [Evaluation (II)] *The ratio of (IO-1S)/(IO-2S) in component (A) in Example 3-5 is 3.2. *The ratio of (IO-1S)/(IO-2S) in component (A) in Example 3-6 is 2.1.