Method for washing hard article

Abstract

The present invention provides a method for washing a hard article, the method including: the contact step of bringing a detergent liquid obtained by mixing (a) a potassium internal olefin sulfonate and (b) water having a hardness of 5° DH or more, into contact with the hard article, and the step of rinsing the hard article after the contact step with water having a hardness of 5° DH or more, wherein the detergent liquid at 30° C. or more is brought into contact with the hard article in at least a part of the contact step.

Claims

1. A method for washing a hard article, the method comprising: 1) bringing a detergent liquid comprising (a) a potassium internal olefin sulfonate and (b) water having a hardness of 5° DH or more, into contact with the hard article for a period of time, and 2) rinsing the hard article after said period of time with water having a hardness of 5° DH or more, wherein the detergent liquid has a temperature of 30° C. or more for at least a part of the period of time.

2. The method for washing a hard article according to claim 1, wherein bringing the detergent liquid into contact with the hard article comprises immersing the hard article in the detergent liquid at a temperature of 30° C.

3. The method for washing a hard article according to claim 1, wherein the hard article comprises at least one selected from the group consisting of plastic, metal, ceramics, lacquer, wood, and glass.

4. The method for washing a hard article according to claim 1, wherein the hard article comprises plastic.

5. The method for washing a hard article according to claim 1, wherein the hard article comprises glass.

6. The method for washing a hard article according to claim 1, wherein the potassium internal olefin sulfonate comprises a potassium internal olefin sulfonate having a sulfonic acid group at position 2 in an amount of 5% by mass to 20% by mass.

7. The method for washing a hard article according to claim 1, wherein: a content of a compound selected from a magnesium-containing inorganic compound and an alkylenediamine compound in the detergent liquid is 10% by mass or less; and the alkylene group of the alkylene diamine has 2 to 6 carbons.

8. The method for washing a hard article according to claim 1, wherein a content of a surfactant selected from a carbobetaine surfactant and an alkanolamide surfactant in the detergent liquid is 10% by mass or less.

9. The method for washing a hard article according to claim 1, wherein the detergent liquid has a temperature of 40° C. or more for at least a part of the period of time.

10. The method for washing a hard article according to claim 1, wherein rinsing is the hard article comprises rinsing with water having a hardness of 5° DH or more and 30° DH or less.

11. The method for washing a hard article according to claim 1, wherein the hard article is tableware.

12. The method for washing a hard article according to claim 1, wherein the potassium internal olefin sulfonate comprises a potassium internal olefin sulfonate having 16 to 18 carbons.

13. The method for washing a hard article according to claim 1, wherein the potassium internal olefin sulfonate comprises (i) a potassium internal olefin sulfonate having 16 carbons and (ii) a potassium internal olefin sulfonate having 18 carbons in a mass ratio, (i):(ii), of 0.1 or less.

14. The method for washing a hard article according to claim 1, wherein the detergent liquid comprises the potassium internal olefin sulfonate in an amount of 0.001% by mass to 30% by mass.

Description

EXAMPLES

Production Example 1 (Production of Internal Olefin Having 18 Carbons)

(1) A flask equipped with a stirring device was charged with 7000 g (25.9 mol) of 1-octadecanol (product name: Kalcol 8098, manufactured by Kao Corporation) and 700 g of γ-alumina (Strem Chemicals, Inc.) as a solid acid catalyst, and a reaction was performed at 280° C. under stirring while nitrogen was allowed to flow (7000 mL/min) in the reaction system. The reaction time was appropriately adjusted so as to produce internal olefins different in double bond distribution.

Production Example 2 (Production of Potassium Internal Olefin Sulfonate Having 18 Carbons)

(2) Each internal olefin produced in Production Example 1 was placed in a thin-film sulfonation reactor (inner diameter: 14 mmφ, length: 4 m), and a sulfonation reaction was performed using a sulfur trioxide gas having a concentration of SO.sub.3 of 2.8% by volume in a condition that cooling water at 20° C. was allowed to flow in an external jacket of the reactor. The reaction molar ratio of SO.sub.3/internal olefin was set to 1.09.

(3) The resulting sulfonated product was added to an aqueous alkaline solution which had been prepared by adding potassium hydroxide so as to satisfy an acid value (AV) 1.2 times by mol higher than the theoretical acid value, and the resulting mixture was neutralized with stirring at 30° C. for 1 hour. The neutralized product was heated in an autoclave at 160° C. for 1 hour to thereby perform hydrolysis, thereby producing a crude product of a potassium internal olefin sulfonate having 18 carbons.

(4) 300 g of the resulting crude product was transferred to a separatory funnel. 300 mL of ethanol was added thereto, and then 300 mL of petroleum ether per operation was added thereto to remove oil-soluble impurities. At this time, a component such as a salt cake precipitated at the oil-water interface by addition of ethanol was also separated and removed from an aqueous phase by the oil-water separation operation, and the operation was performed three times. The aqueous phase was subjected to evaporation to dryness, thereby providing a potassium internal olefin sulfonate having 18 carbons. This compound is represented by “C18” and “K salt” in the Tables.

Production Example 3 (Production of Sodium Internal Olefin Sulfonate Having 18 Carbons)

(5) The internal olefin produced in Production Example 1 was placed in a thin-film sulfonation reactor (inner diameter: 14 mmφ, length: 4 m), and a sulfonation reaction was performed using a sulfur trioxide gas having a concentration of SO.sub.3 of 2.8% by volume in a condition that cooling water at 20° C. was allowed to flow in an external jacket of the reactor. The reaction molar ratio of SO.sub.3/internal olefin was set to 1.09.

(6) The resulting sulfonated product was added to an aqueous alkaline solution which had been prepared by adding sodium hydroxide so as to satisfy an acid value (AV) 1.2 times by mol higher than the theoretical acid value, and the resulting mixture was neutralized with stirring at 30° C. for 1 hour. The neutralized product was heated in an autoclave at 160° C. for 1 hour to thereby perform hydrolysis, thereby producing a crude product of a sodium internal olefin sulfonate having 18 carbons.

(7) 300 g of the resulting crude product was transferred to a separatory funnel. 300 mL of ethanol was added thereto, and then 300 mL of petroleum ether per operation was added thereto to remove oil-soluble impurities. At this time, a component such as a salt cake precipitated at the oil-water interface by addition of ethanol was also separated and removed from an aqueous phase by the oil-water separation operation, and the operation was performed three times. The aqueous phase was subjected to evaporation to dryness, thereby providing a sodium internal olefin sulfonate having 18 carbons. This compound is represented by “C18” and “Na salt” in the Tables.

Production Example 4 (Production of Internal Olefin Having 16 Carbons)

(8) A flask equipped with a stirring device was charged with 7000 g (28.9 mol) of 1-hexadecanol (product name: Kalcol 6098, manufactured by Kao Corporation) and 700 g of γ-alumina (Strem Chemicals, Inc.) as a solid acid catalyst, and a reaction was performed at 280° C. under stirring while nitrogen was allowed to flow (7000 mL/min) in the reaction system. The reaction time was appropriately adjusted so as to thereby produce internal olefins different in double bond distribution.

Production Example 5 (Production of Potassium Internal Olefin Sulfonate Having 16/18 Carbons)

(9) The internal olefin produced in Production Example 1 and the internal olefin produced in Production Example 3 were mixed at a mass ratio, internal olefin in Production Example 1/internal olefin in Production Example 3, of 80/20, thereby providing an internal olefin having 16/18 carbons. This olefin was placed in a thin-film sulfonation reactor (inner diameter: 14 mmφ, length: 4 m), and a sulfonation reaction was performed using a sulfur trioxide gas having a concentration of SO.sub.3 of 2.8% by volume in a condition that cooling water at 20° C. was allowed to flow in an external jacket of the reactor. The reaction molar ratio of SO.sub.3/internal olefin was set to 1.09.

(10) The resulting sulfonated product was added to an aqueous alkaline solution which had been prepared by adding potassium hydroxide so as to satisfy an acid value (AV) 1.2 times by mol higher than the theoretical acid value, and the resulting mixture was neutralized with stirring at 30° C. for 1 hour. The neutralized product was heated in an autoclave at 160° C. for 1 hour to thereby perform hydrolysis, thereby producing a crude product of a potassium internal olefin sulfonate having 16/18 carbons.

(11) 300 g of the resulting crude product was transferred to a separatory funnel. 300 mL of ethanol was added thereto, and then 300 mL of petroleum ether per operation was added thereto to remove oil-soluble impurities. At this time, a component such as a salt cake precipitated at the oil-water interface by addition of ethanol was also separated and removed from an aqueous phase by the oil-water separation operation, and the operation was performed three times. The aqueous phase was subjected to evaporation to dryness, thereby providing potassium internal olefin sulfonate having 16/18 carbons. The compound is represented by “C16/C18” and “K salt” in the Tables.

(12) (1) Preparation of Concentrated Composition for Detergent Liquid

(13) Each component (a) and ion exchange water, shown in Tables 1 to 3, were used to prepare a concentrated composition for a detergent liquid, the concentrated composition having a content of component (a) of 25% by mass. A compound not corresponding to component (a) was also shown as component (a) in Table 3.

(14) (2) Evaluation

(15) (2-1) Evaluation of Detergency

(16) The mass of a glass slide or a polypropylene plate (represented by “PP” in the Tables) was measured (tare mass). The glass slide or polypropylene plate was coated with 0.1 g of beef tallow, and the beef tallow was solidified to provide test piece (1). The mass (mass before washing) of test piece (1) was measured.

(17) One gram of the concentrated composition for a detergent liquid was diluted with 1000 mL of component (b), thereby preparing a detergent liquid.

(18) The detergent liquid and test piece (1) were set in a tester described in “Detergency Evaluation Method of Synthetic Detergent for Kitchen” in JIS K 3362 9.2, and subjected to washing with stirring at each washing temperature in Tables 1 to 3 for 3 minutes. After the washing, test piece (1) was rinsed with water having the hardness in Tables 1 to 3.

(19) After the rinsing, test piece (1) was dried, the mass thereof (mass after washing) was measured and compared with the mass before washing, the amount of beef tallow removed by washing was calculated, and the washing rate was determined by the following formula. The results were shown in Tables 1 to 3.
Washing rate (%)={(Mass before washing)−(Mass after washing)}/{(Mass before washing)−(Tare mass)}×100
(2-2) Evaluation of Rinsability

(20) One gram of the concentrated composition for a detergent liquid was diluted to 30-fold with water having a hardness in Tables 1 to 3, thereby preparing a detergent liquid.

(21) Thirty grams of the detergent liquid was absorbed in a sponge (Kikulon A manufactured by Kikulon Co., Ltd.) and foamed by crumpling ten times, and 3 g of such foam was added to a measuring cylinder (manufactured by ARROW, 2000 mL: bottom area: 50 cm.sup.2).

(22) Water having the hardness at the temperature in Tables 1 to 3 was continuously dropped from above of the measuring cylinder.

(23) The dropping was performed at a total rate of 20 mL/sec using a tool, which was a resin bottle having a bottom area of 7 cm.sup.2 and having 19 holes each having a diameter of 1 mm on the bottom.

(24) The state of foam immediately after the dropping was observed. The point of time when foam disappeared to allow the water surface to be seen from above of the measuring cylinder was defined as an endpoint, and the amount of water at the endpoint was recorded. The results were shown in Tables 1 to 3.

(25) TABLE-US-00001 TABLE 1 Comparative Comparative Example Example Example Example 1-1 1-2 1-3 1-4 1-1 2-1 2-2 2-1 Component (a) Number of C18 C18 C18 C18 C18 C18 C18 C18 carbons Salt K salt K salt K salt K salt K salt K salt K salt K salt Percentage of 16.77 16.77 16.77 16.77 16.77 16.77 16.77 16.77 sulfonic acid at position 2 (% by mass) Component (b) Hardness (° DH) 15 15 15 15 15 10 10 10 Hardness of water .sup.(Note 1) (° DH) 15 15 15 15 15 10 10 10 Temperature .sup.(Note 2) (° C.) 60 50 40 30 25 50 40 25 Washing rate (glass) (%) 82.0 83.8 51.2 47.5 11.2 77.0 48.0 10.9 Washing rate (PP) (%) 65.0 63.5 45.6 33.1 5.4 59.4 30.7 2.5 Rinsability (mL) 350 400 500 500 750 500 725 800 Example Comparative Example Comparative Example 3-1 3-2 3-3 3-1 3-2 3-3 4-1 4-2 4-3 Component (a) Number of C18 C18 C18 C18 C18 C18 C18 C18 C18 carbons Salt K salt K salt K salt K salt K salt K salt K salt K salt K salt Percentage of 16.77 16.77 16.77 16.77 16.77 16.77 16.77 16.77 16.77 sulfonic acid at position 2 (% by mass) Component (b) Hardness (° DH) 5 5 5 3 3 3 0 0 0 Hardness of water .sup.(Note 1) (° DH) 5 5 5 3 3 3 0 0 0 Temperature .sup.(Note 2) (° C.) 50 40 30 50 40 30 50 40 25 Washing rate (glass) (%) 69.6 46.3 38.3 59.4 36.4 28.1 75.6 44.1 2.4 Washing rate (PP) (%) 59.1 30.3 23.1 30.5 22.8 19.1 29.0 28.9 1.8 Rinsability (mL) 550 575 575 800 950 1000 1150 1150 1250

(26) TABLE-US-00002 TABLE 2 Comparative Example Example Example Example Example 4-1 4-2 5-1 1-2 2-1 4-1 Component (a) Number of carbons C18 C18 C16/C18 C18 C18 C18 Salt K K K K K K Percentage of 16.77 4.98 16.77 16.77 16.77 16.77 sulfonic acid at position 2 (% by mass) Component (b) Hardness (° DH) 20 15 15 15 10 0 Hardness of water .sup.(Note 1) (° DH) 20 15 15 15 10 0 Temperature .sup.(Note 2) (° C.) 50 50 50 50 50 50 Washing rate (glass) (%) 84 65 75 83.8 77 75.6 Washing rate (PP) (%) 64 44.1 50 63.5 59.4 29 Rinsability (mL) 400 400 600 400 500 1150

(27) TABLE-US-00003 TABLE 3 Example Comparative Example 1-2 1-3 1-4 5-1 5-2 5-3 Component (a) Number of carbons C18 C18 C18 C18 C18 C18 Salt K salt K salt K salt Na salt Na salt Na salt Percentage of 16.77 16.77 16.77 16.77 16.77 16.77 sulfonic acid at position 2 (% by mass) Component (b) Hardness(° DH) 15 15 15 15 15 15 Hardness of water .sup.(Note 1) (° DH) 15 15 15 15 15 15 Temperature .sup.(Note 2) (° C.) 50 40 30 50 40 30 Washing rate (glass) (%) 83.8 51.2 47.5 60.3 44.1 40.3 Washing rate (PP) (%) 63.5 45.6 33.1 22.1 19.3 16.5 Rinsability (mL) 400 500 500 500 550 600
(Note 1) Hardness of water: hardness of water used in preparation of detergent liquid and evaluation of rinsability
(Note 2) Temperature: temperature of water used in evaluation of temperature or rinsability in washing

(28) In the Tables, C18 means that the number of carbons in component (a) is 18.

(29) In the Tables, the “Percentage of sulfonic acid at position 2” of component (a) means the ratio of IOS-K or IOS-Na having the sulfonic acid group at position 2 in component (a).

(30) In the Tables, water having a hardness not corresponding to the hardness of component (b) is also shown in the column of component (b), for convenience.

(31) Tables 2 and 3 again present Examples and Comparative Examples presented in a part of Table 1.