Method and apparatus for producing cleaning agent

TECHNICAL FIELD

The present invention relates to a new washing process and a washing apparatus suitable to washing clothes, tableware, medical equipments and washing hands, etc.

BACKGROUND OF THE INVENTION

Surfactant, such as chemicals and soup, has been heretofore been used for washing clothes, tableware, medical equipment, toilets, etc., however, there have been problems of causing chapping hands when washing, a safety issue on body by residual detergent on washing items, and residual harmful substances after a treatment of discharging water, etc.

Inventors of the present invention proposed a method of washing washing items while softening washing water containing at least one of carbonate ion or bicarbonate ion and alkali metal ion (refer to PCT/JP99/00242, WO99/37414). This directs attention to the fact that a composite generated at the time of softening a solution containing alkali metal ion and carbonate ion and/or bicarbonate ion realizes cleansing effect and adsorption effect, which shows detergency comparable to or more excellent than the conventional detergent such as surfactant and becomes human body-friendly and environment-friendly.

However, when trying to produce a solution containing alkali metal ion and carbonate ion and/or bicarbonate ion as an undiluted detergent it is necessary to use as its material a substance having a problem on handle ability such as sodium hydroxide, thus there has been a problem to carry out at home from producing detergent to washing.

DISCLOSURE OF INVENTION

The present invention has as an object thereof to provide a method of enabling to produce detergent only by substances superior in being handled and an apparatus therefor.

(1) According to a first aspect of the present invention, a method of producing detergent includes a step of electrolyzing a solution containing at least one of carbonate and bicarbonate of alkali metal.

Namely, as shown in

FIG. 1

, by making a solution of a substance containing at least one of carbonate and bicarbonate of alkali metal (see Step

1

to

2

in

FIG. 1

) and by electrolyzing the solution (see Step

3

in FIG.

1

), an undiluted detergent can be obtained (see Step

4

in FIG.

1

).

By electrolyzing a solution containing at least one of carbonate and bicarbonate of alkali metal, for example, a solution of substances superior in handle ability such as sodium carbonate, potassium carbonate, lithium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, as a solution to be electrolyzed, it is possible to obtain an undiluted detergent containing alkali metal ion and carbonate ion and/or bicarbonate ion, and by washing as softening the same, it shows detergency comparable to or better than the conventional detergent, such as surfactant, and becomes human body-friendly and environment-friendly. Accordingly, a series of procedures from producing detergency to washing can be realized at home.

As alkali metal carbonate according to the present invention, for example, sodium carbonate Na

2

CO

3

, potassium carbonate K

2

CO

3

, lithium carbonate Li

2

CO

3

, etc. can be listed, while as alkali metal bicarbonate, for example, potassium hydrogen carbonate KHCO

3

, sodium hydrogen carbonate NaHCO

3

, etc. can be listed.

Also, when making a solution of carbonate or bicarbonate of alkali metal, a variety of kinds of water may be used, such as tap water, well water, soft water, refined water, pure water, or mixed water of these, etc.

(2) Although, it is often the case that a pH, etc. of detergent to be used differ in accordance with a property of washing items, in the present invention, when producing detergent by electrolyzing a solution containing at least one of carbonate and bicarbonate of alkali metal, it is possible to adopt forms below in accordance with an aimed potential of hydrogen (pH=6 to 12) of the detergent.

As a first embodiment, cathode water or anode water obtained by electrolyzing by supplying the above solution to be electrolyzed at least to an anode chamber of an electrolyzing cell having a cathode chamber and an anode chamber separated by a diaphragm can be used as an undiluted detergent (see FIG.

4

A). The cathode water obtained by this form becomes an alkaline undiluted detergent having a high pH.

In this case, as a second embodiment, when cathode water obtained by electrolyzing by supplying the above solution to be electrolyzed to both of the anode chamber and the cathode chamber of the electrolyzing cell having a cathode chamber and an anode chamber separated by a diaphragm is used as an undiluted detergent, it is possible to obtain a highly concentrated undiluted detergent wherein rising of the pH is suppressed (see FIG.

4

B).

Also, as a third embodiment, cathode water or anode water obtained by electrolyzing by supplying the above solution to be electrolyzed at least to an anode chamber of an electrolyzing cell having a cathode chamber and an anode chamber separated by a diaphragm or mixture of the both water is further added and dissolved at least one of carbonate and bicarbonate of alkali metal after completing the electrolysis and thus obtained solution can be used as an undiluted detergent (see FIG.

4

C).

Furthermore, as a fourth embodiment, by electrolyzing by supplying the above solution to be electrolyzed at least to an anode chamber of an electrolyzing cell having a cathode chamber and an anode chamber separated by a diaphragm, and mixing the obtained cathode water or anode water after the electrolysis is completed, the thus obtained solution can be used as an undiluted detergent (see FIG.

4

D).

In this case, as a fifth embodiment, it is also possible to use as an undiluted detergent mixture of cathode water or anode water obtained by electrolyzing by supplying the solution to be electrolyzed to both of the anode chamber and the cathode chamber of the electrolyzing cell having a cathode chamber and an anode chamber separated by a diaphragm (see FIG.

4

E).

In the fourth and fifth embodiments, since the mixture of the anode water and the cathode water becomes an undiluted detergent, a production amount of the obtained undiluted detergent becomes doubled, or otherwise, the capacity of the electrolysis cell can be halved.

The cathode water in the first embodiment, the cathode water in the second embodiment, the cathode water in the third embodiment, the mixed water in the fourth embodiment and the mixed water in the fifth embodiment have a pH of 9.5 to 12.0 and can be used as an alkaline undiluted detergent.

On the other hand, the anode water in the first embodiment and the anode water in the third embodiment have a pH of 6 to 8 and can be used as a neutral undiluted detergent.

In a method of producing detergent of the present invention, the pH and electric conductivity can be easily adjusted by suitably setting the conditions of electrolysis.

(3) The above undiluted detergent can be used for washing as it is or diluted (see Step

5

to

6

in FIG.

1

. Hereinafter, also referred to as a diluted detergent A). An electric conductivity of the diluted detergent is 100 mS/m or more, preferably, 150 mS/m or more.

Also, a variety of washing aid agents for improving detergency, etc. can be added (see Step

9

in FIG.

1

).

Namely, the above alkaline detergent can be added fatty acid or soap, such as oleic acid or oleic acid potassium, at the time of or after being diluted by water, to be used as detergent.

Also, the above neutral detergent can be added a variety of washing aid agents to be used as detergent, such as antisoil redeposition (for example, carboxyl methyl cellulose), nonionic surfactant (for example, sugar fatty acid ester, polyoxyethylene sorbitan fatty acid ester), dispersing agents (for example, carboxyl methyl cellulose) and water softening agents (for example, EDTA, citric acid).

Auxiliary/aid agents used in the present invention are emulsifier (surfactant) used for food processing and gum/thickening agent as food additives, and by not using the conventional surfactant for washing, safer detergent can be provided. Furthermore, since the detergency is given to the electrolytic water obtained by electrolysis of a solution of alkali metal carbonate/bicarbonate, the surfactant can be made to be minimum thickness required for antisoil redeposition, and it becomes possible to reduce a burden on an environment by suppressing usage of organic substances.

(4) Note that the present invention may include a step of softening the detergent containing at least one of carbonate ion and bicarbonate ion and alkali metal ion, particularly the above undiluted detergent or the diluted detergent A (see Steps 7 to 8. Hereinafter, the obtained detergent will be also referred to as diluted detergent B).

In this case, it is preferable to adopt a means to make it contact solid carbonate composite which is water-insoluble or hard to be dissolved in water.

(5) Further, according to a second aspect of the present invention, an electrolysis cell wherein an anode chamber and a cathode chamber are separated by a diaphragm, a solution tank for making a solution by dissolving at least carbonate or bicarbonate of alkali metal in water, a detergent producing apparatus having a first supply means for supplying the solution in the solution tank at least to the anode chamber of the electrolysis cell and a mixing means for mixing anode water and cathode water respectively generated in the anode chamber and the cathode chamber to make mixed electrolytic water after completion of the electrolysis are provided.

In this case, preferably, the mixing means comprises a water tank for storing anode water and cathode water after completion of the electrolysis and a second-supply means for supplying the anode water and cathode water generated in said anode chamber and cathode chamber to said water tank.

Also, there is provided a detergent producing apparatus, comprising an electrolysis cell wherein an anode chamber and a cathode chamber separated by a diaphragm, a solution tank for making a solution by dissolving at least one of carbonate and bicarbonate of alkali metal in water, a first supply means for supplying the solution in said solution tank at least to the anode chamber of said electrolysis cell, a detergent tank for storing detergent discharged from said electrolysis cell, and a third supply means for supplying one of cathode water after completing the electrolysis generated in said cathode chamber and anode water after completing the electrolysis generated in said anode chamber to said detergent tank.

In this case, it is preferable to comprise a means for adding and dissolving at least one of carbonate and bicarbonate of alkali metal to at least one of anode water generated in said anode chamber and cathode water generated in said cathode chamber.

(6) According to a third aspect of the present invention, there is provided a washing machine comprising a detergent producing apparatus for producing detergent by electrolyzing a solution containing at least one of carbonate and bicarbonate of alkali metal; a detergent tank for storing said detergent; a washing tub for washing; a means for supplying diluting water of said detergent to said washing tub; and a means for supplying said detergent from said detergent tank to said washing tub.

In this case, it is preferable to further comprises a judgement means for judging an amount of washing items and/or an amount of washing water in said washing tub and a setting means for setting the amount of washing items and the amount of washing water; and a control means for outputting to said detergent supply means a control signal for supplying the washing tub an appropriate amount of detergent for washing based on an output signal from said judgement means or said setting means.

Furthermore, it is preferable to comprise a container for storing washing aid agents, a means for supplying washing aid agents from said container to said washing tub, and a control means for outputting to said supply means of washing aid agent a control signal for supplying an appropriate amount of the washing aid agents for washing to the washing tub.

(7) The above detergent producing apparatus or washing apparatus can be applied to a washing machine, dish washer, etc.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1

is a view of processes of an embodiment of a method of producing detergent of the present invention.

FIG. 2

is a view of a pH range of detergent obtained by a method of producing detergent of the present invention.

FIG. 3

is a schematic view of an embodiment of a washing apparatus of the present invention.

FIGS. 4A

to

4

E are views of respective use forms of an electrolysis cell of FIG.

3

.

BEST MODE FOR CARRYING OUT THE INVENTION

First, an embodiment of applying a detergent producing apparatus of the present invention to a washing machine will be explained.

FIG. 3

is a schematic view of an example of a washing machine WM wherein a detergent producing apparatus of the present invention is applied, and details of an electrolysis cell

11

shown in the same figure will be explained with reference to

FIGS. 4A

to

4

E.

The detergent producing apparatus

1

of the present embodiment comprises a solution tank

12

for storing-alkali metal sodium solution containing at least one of alkali metal carbonate and alkali metal bicarbonate (hereinafter, also referred to as a solution to be electrolyzed), an electrolysis cell

11

and a first supply system

13

for supplying the solution to be electrolyzed from the solution tank

12

to the electrolysis cell

11

.

The solution tank

12

is supplied a substance containing at least one of alkali metal carbonate and alkali metal bicarbonate (sodium hydrogen carbonate in this example) from a container

16

storing the same and tap water, etc. from a tap water source, etc. via a supply system

17

. An example below is for explaining a case of using sodium hydrogen carbonate.

As shown in

FIGS. 4A

to

4

E, the electrolysis cell

11

is formed an inlet

111

for being introduced a solution to be electrolyzed and an outlet

112

for taking out generated electrolytic water, and an electrolysis chamber

113

is formed between the inlet

111

and the outlet

112

.

Also, at the approximate center of the electrolysis chamber

113

is provided with a diaphragm

114

formed by a cation exchange film, and both electrolysis chambers

113

a

and

113

c

over the diaphragm

114

are respectively provided with a pair of electrode plates

115

a

and

115

c

facing to each other. Here, while not illustrated, the pair of electrode plates

115

a

and

115

c

are connected to a direct current power source, and one electrode plate

115

a

is to be applied the anode while the other electrode plate

115

c

is to be applied the cathode. Below, the electrolysis chamber

113

a

will be also referred to as an anode chamber, the electrolysis chamber

113

c

a cathode chamber, electrolytic water generated in the anode chamber an anode water, and electrolytic water generated in the cathode chamber a cathode water.

As the diaphragm

114

, a variety of ion exchange films, nonionic selective films, multi-porous films may be used. These films are provided for preventing anode water generated around the anode and cathode water generated around the cathode from being mixed. In the case of using a cation exchange film as in the present example, less hydroxide ion generated in the cathode chamber

113

c

transmits to the anode chamber

113

a

, so that it is preferable because it becomes easy to refrain the pH of the obtained undiluted detergent of anode water from becoming alkaline, and to heighten the pH of the cathode water to be obtained to produce a strong alkaline undiluted detergent of cathode water.

As the electrode plates

115

a

and

115

c

, it is preferable to be configured by materials not melted by electricity. Specifically, for example, platinum family metals, titanium, etc. have excellent corrosion resistance and preferably used. The distance between the electrode plates

115

a

and

115

c

is 1 mm to 6 mm, more preferably, 5 mm.

Further, to explain use forms the electrolysis cell

11

shown in

FIGS. 4A

to

4

E, in

FIG. 4A

, the anode chamber

113

a

is supplied a solution of sodium hydrogen carbonate from the solution tank

12

, while the cathode chamber

113

c

is supplied tap water, etc. Both of anode water generated in the anode chamber

113

a

and cathode water generated in the cathode chamber

113

c

may be used as undiluted detergent. According to this use form, little hydroxide ion generated in the cathode chamber

113

c

transmits to the anode chamber

113

a

, so it is possible to refrain the pH of the undiluted detergent of anode water from becoming alkaline, and it becomes easy to heighten the pH of cathode water to be obtained and to produce a strong alkaline undiluted detergent of cathode water.

On the other hand, in the use form shown in

FIG. 4B

, although sodium hydrogen carbonate solution is supplied to both the anode chamber

113

a

and the cathode chamber

113

c

from the solution tank

12

, only cathode water generated in the cathode chamber

113

c

is used as undiluted detergent. In this case, since a sodium hydrogen carbonate solution is supplied to the cathode chamber

113

c

, the undiluted detergent of cathode water to be obtained is suppressed not to rise the pH, so that weak alkaline undiluted detergent can be obtained and highly concentrated undiluted detergent can be generated.

Also, the use form shown in

FIG. 4C

is a modified example of the one shown in

FIG. 4A

, and the anode chamber

113

a

is supplied sodium hydrogen carbonate solution from the solution tank

12

while the cathode chamber

113

c

is supplied tap water, etc., and obtained anode water and cathode water are respectively further added with at least one of sodium carbonate and sodium hydrogen carbonate to become an undiluted detergent. According to this use form, it is possible to adjust the pH and concentration of the anode water and cathode water respectively obtained in the anode chamber

113

a

and the cathode chamber

113

c

after the electrolysis.

Furthermore, the use form shown in

FIG. 4D

is also a modified example of the one shown in

FIG. 4A

, wherein also the anode chamber

113

a

is supplied sodium hydrogen carbonate solution from the solution tank

12

while the cathode chamber

113

c

is supplied tap water, etc., but the obtained anode water and the cathode water are mixed to be an undiluted detergent. According to this use form, since all of the anode water and the cathode water are used, the production amount of the undiluted detergent to be obtained is doubled, or otherwise, the capacity of the electrolysis cell

11

may be halved.

Also, the use form shown in

FIG. 4E

is a modified example of the one shown in

FIG. 4D

, wherein both of the anode chamber

113

a

and the cathode chamber

113

c

are supplied sodium hydrogen carbonate solution from the solution tank

12

, and the obtained anode water and the cathode water are mixed to be an undiluted detergent. According to this use form, all of the anode water and the cathode water are used, so the production amount of the undiluted detergent to be obtained is doubled, or the capacity of the electrolysis cell

11

may be halved.

As explained above, according to the electrolysis

11

of the present invention, a variety of aimed undiluted detergent can be obtained by suitably changing the use form. The states are schematically shown in FIG.

2

.

Returning to

FIG. 3

, the first supply system

13

is provided with a pipe

131

for connecting a solution tank

12

to the inlet

111

of the electrolysis cell

11

and a pump

132

for sending by pressure the solution to be electrolyzed in the solution tank

12

to the electrolysis cell

11

.

Furthermore, the detergent producing apparatus

1

of the present embodiment comprises a detergent tank

15

for storing electrolytic water generated in the anode chamber

113

a

and/or the cathode chamber

113

c

of the electrolysis cell

11

, a second supply system

14

for supplying the electrolytic solution from the electrolysis cell

11

to the detergent tank

15

, and a diluting means

18

for diluting the undiluted detergent generated in the electrolysis cell

11

.

The second supply system

14

is comprised by a pipe

141

for connecting the outlet

112

of the electrolysis cell

11

to the detergent tank

15

and a pump

142

provided on the pipe

141

for sending by pressure the electrolytic solution generated in the electrolysis cell

11

to the detergent tank

15

.

Note that in the use form shown in

FIG. 4C

, when adding sodium hydrogen carbonate to the anode water or cathode water generated in the electrolysis cell

11

later on, it is sufficient to supply it from the container

16

shown in FIG.

3

.

Also, the diluting means

18

is comprised by a supply pipe

181

for supplying diluting water from a not shown tap water source to the detergent tank

15

and a pump

182

by which the undiluted detergent is diluted by a predetermined diluting rate to become diluted detergent A.

The above detergent producing apparatus

1

is provided to a washing machine body

2

having a washing tub

21

. It further comprises a third supply system

22

for supplying electrolytic water (diluted detergent A) stored in the detergent tank

15

to the washing tub

21

via a water softening filter

23

. The third supply system

22

is comprised by a pipe

221

for connecting the detergent tank

15

to the water softening filter

23

and a pump

222

provided on the pipe

221

for sending by pressure the diluted detergent A stored in the detergent tank

15

to the water softening filter

23

.

The water softening filter

23

is provided in this example for softening the undiluted detergent (see Step

4

in

FIG. 1

) as it is obtained by the detergent producing apparatus

1

or diluted detergent A after diluting (see Step

6

in FIG.

1

).

In the water softening filter

23

, inside its casing is filled with solid hydroxide composite which is insoluble or hard to be dissolved in water, for example, calcium carbonate or calcium phosphate, and by making the above undiluted detergent and diluted detergent contact such carbonate composites, calcium ion and magnesium ion included in the undiluted detergent and diluted detergent are educed as calcium carbonate and magnesium carbonate, and thereby, the detergent can be made to be low in hardness. Note that the carbonate composite may be in a suitably granulated ball shape or pelletized form other than powder and a crushed shape, and may include filling agents and amount increasing agents other than carbonate composite. Also, the solid carbonate composite is sufficient if at least the surfaces thereof are carbonate composite, and may be a compound body wherein a suitable core body is covered with carbonate composite.

Returning back to

FIG. 3

, the washing tub

21

is provided with a fourth supply system

24

for supplying tap water, etc. for diluting the detergent, and the fourth supply system

24

is configured by a pipe

241

, a pump

242

and a not shown tap water supplying source.

Furthermore, the washing-machine WM of the present embodiment is provided with a washing aid agent tank

25

for storing a variety of washing aid agents, such as antisoil redeposition (for example, carboxyl methyl cellulose), nonionic surfactant (for example, sugar fatty acid ester, polyoxyethylene sorbitan fatty acid ester), dispersing agents (for example, carboxyl methyl cellulose) and water softening agents (for example, EDTA, citric acid), and a fifth supply system

26

for supplying the washing aid agents stored in the washing aid agent tank

25

to the washing tub

21

. The fifth supplying system

26

is configured by a pipe

261

and a pump

262

.

Furthermore, the washing machine WM of the present embodiment is provided as a control system with a judgement/setting means

27

for detecting and judging or manually setting an amount of washing items put in the washing tub

21

or an amount of washing water filled in the washing tub

21

and a control means

28

for controlling the operations of the pumps

222

and

262

based on the amounts of washing items or washing water input to the means

27

. As a result, detergent and washing aid agents in accordance with the washing load are supplied respectively from the detergent tank

15

and the washing aid agent tank

25

to the washing tub

21

.

Next, an example of washing process using the above washing machine WM will be explained.

First, an anode of a direct current power source of the detergent producing apparatus

1

is connected to the electrode plate

115

a

, while a cathode is connected to the electrode plate

115

c

, and a direct current voltage is applied to the both electrode plates

115

a

and

115

c

. Then, the pump

132

is operated to introduce sodium hydrogen carbonate solution as the solution to be electrolyzed from the solution tank

12

to the inlet

111

. As a result, electrolysis is carried out in both of the electrolysis chambers

113

a

and

131

c

, and after a certain period of time, electrolytic solution is discharged from the respective outlets

112

. These electrolytic waters are supplied to the detergent tank

15

by the pump

142

via the pipe

141

, mixed during the time and becomes an undiluted detergent of the present invention.

The undiluted detergent stored in the detergent tank

15

is diluted by the diluting means

18

, and then supplied to the water softening filter

23

, wherein it is softened, and supplied to the washing tub

21

of the washing machine WM.

At this time, amounts of detergent and washing aid agents to be supplied are controlled in accordance with the amount of washing items. Namely, when the judging means automatically detects or setting means

27

is manually input the amount of washing items (for example, the weight, volume, etc.) put in the washing tub

21

and the amount of tap water poured in the washing tub

21

, a signal is sent to the control means

28

and a signal of operation time, etc. in accordance with the washing load is sent therefrom to the pumps

222

and

262

. As a result, the washing tub

21

is supplied an appropriate amount of detergent and washing aid agents in accordance with the washing load.

A specific example of producing detergent by the present invention will be explained next.

Embodiment 1 (FIG.

4

A)

A saturated solution of sodium hydrogen carbonate prepared by dissolving and diluting 100 g of sodium hydrogen carbonate in 1 litter of tap water (municipal tap water in Fujisawa city, pH 7.2, EC 15.5 mS/m, water temperature 24.5° C.) was supplied to the anode chamber

113

a

of the batch type electrolysis cell

11

(a capacity of the anode chamber and the cathode chamber are both 0.5 litter) shown in

FIG. 4A

, and the above tap water was supplied to the cathode chamber

113

c

shown in the same figure. Then, electrolysis was carried out by applying a direct current voltage so that a constant current of 20A flows to both the electrode plates

115

a

and

115

c

, and pH and electric conductivity EC of an undiluted solution of cathode water obtained at every five minutes and a diluted solution by diluting the same to be thirty times (30 litters) were measured. Measurement of the diluted water was made after mixing for one minute. The result will be shown in Table 1.

Note that a pH was measured by using a pH meter (trade name of D-13, manufactured by Horiba Ltd.), an EC was measured by using an EC meter (trade name of CM-14P, manufactured by TOA Corporation). The mark * of EC in the table indicates it exceeded the measurable limit (1999 mS/m or less).

Both of the undiluted detergent and diluted detergent A obtained in the present embodiment become alkaline having a pH of 10.5 or more, and those which had a long electrolysis time became detergent having strong alkaline and the EC value of 100 mS/m or more, so that it becomes preferable to be used as detergent for non fibrous washing items, such as tableware.

TABLE 1

undiluted

electrolytic solution

diluting water

pH

EC (mS/m)

pH

EC (mS/m)

before electrolysis

7.23

15.5

—

—

after 3 min.

12.64

2000 or more *

10.53

47.1

after 5 min.

12.88

2000 or more *

10.92

59.6

after 10 min.

13.05

2000 or more *

11.34

87.2

after 15 min.

13.20

2000 or more *

11.79

133.0

after 20 min.

13.35

2000 or more *

12.26

180.3

Embodiment 2 (FIG.

4

B)

A solution prepared by dissolving and diluting 36 g of sodium hydrogen carbonate in 1 litter of tap water (municipal tap water in Fujisawa city, pH 7.3, EC 17.9 mS/m, water temperature 20.2° C.) was supplied to the cathode chamber

113

c

of the batch type electrolysis cell

11

(a capacity of the anode chamber and the cathode chamber are both 1 litter) shown in

FIG. 4B

, and saturated solution of sodium hydrogen carbonate was supplied to the anode chamber

113

a

. Then, electrolysis was carried out by applying a direct current voltage so that a constant current of 15A flows to both of the electrode plates

115

a

and

115

c

, and a pH and electric conductivity EC of an undiluted solution of cathode water obtained at every ten minutes and a diluted solution by diluting the same to be thirty times (30 litters) were measured. Measurement of the diluted water was made after mixing for one minute. The result will be shown in Table 2.

Both of the undiluted detergent and diluted detergent A obtained in the present embodiment become weak alkaline of a pH of 9.0 to 10.5, and the EC value of 100 mS/m or more, so that it becomes preferable to be used as detergent for fibrous washing items, such as cotton, hemp, rayon, polynosic, polyester, nylon and acryl.

TABLE 2

undiluted

electrolytic solution

diluting water

pH

EC (mS/m)

pH

EC (mS/m)

before electrolysis

8.02

2000 or more *

8.20

120.3

after 10 min.

9.36

2000 or more *

9.52

140.3

after 20 min.

9.65

2000 or more *

9.94

168.0

after 30 min.

9.98

2000 or more *

10.23

196.9

after 36 min.

10.20

2000 or more *

10.44

204.0

Embodiment 3 (FIG.

4

E)

A solution prepared by dissolving and diluting 36 g of sodium hydrogen carbonate in 2 litters of tap water (municipal tap water in Fujisawa city, pH 7.3, EC 18.5 mS/m, water temperature 20.6° C.) was divided to be 1 litter and respectively supplied to the anode chamber

113

a

and the cathode chamber

113

c

of the batch type electrolysis cell

11

(a capacity of the anode chamber and the cathode chamber are both 1 litter) shown in FIG.

4

E. Then, electrolysis was carried out by applying a direct current voltage so that a constant current of 15A flows to both the electrode plates

115

a

and

115

c

, and a pH and electric conductivity EC of mixture of an undiluted solution of anode water and cathode water obtained at every ten minutes and a diluted solution by diluting the same to be thirty times (30 litters) were measured. Measurement of the diluted water was made after mixing for one minute. The result will be shown in Table 3.

Both of the undiluted detergent and diluted detergent A obtained in the present embodiment became weak alkaline of a pH of 8.5 to 10.5, and the EC value of 100 mS/m or more, so that it becomes preferable to be used as detergent for fibrous washing items, such as cotton, hemp, rayon, polynosic, polyester, nylon and acryl.

TABLE 3

undiluted

electrolytic solution

diluting water

pH

EC (ms/m)

pH

EC (ms/m)

before electrolysis

8.06

1460

8.13

121.3

after 5 min.

8.72

1455

8.84

119.3

after 15 min.

9.56

1492

9.68

120.9

after 25 min.

10.21

1531

10.25

126.7

Embodiment 4 (FIG.

4

E)

A solution prepared by dissolving and diluting 72 g of sodium hydrogen carbonate in 1 litter of tap water (municipal tap water in Fujisawa city, pH 7.2, EC 15.5 mS/m, water temperature 24.5° C.) was divided to be 0.5 litter and respectively supplied to the anode chamber

113

a

and the cathode chamber

113

c

of the batch type electrolysis cell

11

(a capacity of the anode chamber and the cathode chamber are both 1 litter) shown in FIG.

4

. Then, electrolysis was carried out by applying a direct current voltage so that a constant current of 20A flows to both the electrode plates

115

a

and

115

c

, and a pH and electric conductivity EC of an undiluted solution of anode water obtained at every ten minutes and a diluted solution by diluting the same to be thirty times (30 litters) were measured. Measurement of the diluted water was made after mixing for one minute. The result will be shown in Table 4.

Both of the undiluted detergent and diluted detergent A obtained in the present embodiment became neutral of a pH of 7.0 to 8.0, and the EC value of 100 mS/m or more, so that it becomes preferable to be used as detergent for fibrous washing items, such as silk, wool, cupra, acetate.

TABLE 4

undiluted

electrolytic solution

diluting water

pH

EC (ms/m)

pH

EC (ms/m)

before electrolysis

8.02

—

—

—

after 20 min.

7.70

2000 or more *

7.82

164.5

after 30 min.

7.70

2000 or more *

7.85

133.6

Next, an embodiment of comparing detergency on a various kinds of stains will be explained by using the detergent produced by using the method of producing detergent of the present invention and commercially available detergent.

Embodiment 5 (weak alkaline detergent)

In the same way as in the Embodiment 3, a solution prepared by dissolving and diluting 22.5 of sodium hydrogen carbonate in 0.5 litter of tap water (municipal tap water in Fujisawa city, pH 7.2, EC 15.5 mS/m, water temperature 24.5° C.) was supplied to the anode chamber

113

a

and the cathode chamber

113

c

of the batch type electrolysis cell

11

(a capacity of the anode chamber and the cathode chamber are both 0.5 litter) shown in FIG.

4

E. Then, electrolysis was carried out by applying a direct current voltage so that a constant current of 20A flows to both the electrode plates

115

a

and

115

c

for 17 minutes. Thus obtained anode water and cathode water were mixed and 1 litter of mixed water was obtained.

A washing tub of a domestic washing machine of double-tub type (trade name of ES-25E, 2.5 kg type, manufactured by Sharp Corp.) was filled with 30 litters of tap water and put in 1000 cc of the above mixed water detergent (diluting rate=30 times). The diluted detergent had a pH of 10.2, EC value of 164.5 mS/m, and a water temperature of 25° C.

A standard stained fabric with “dirt on a collar”, and “mixed stain of china ink and olive oil”, “blood”, “cacao butter (animal and vegetable oil)”, “red wine”, and “mixed stain of blood, milk and china ink” being allowed to adhere to cotton fabric samples, respectively (EMPA101, 111, 112, 114, 115 and 116), were washed with the washing machine for 12 minutes, spin-dried and dried by a drier.

The detergency ratio of the respective stained fabrics before and after washing is shown in Table 5. Note that the “detergency ratio ” was calculated by the formula below.

Detergency ratio %=(whiteness index of stained fabric after washing−whiteness index of stained fabric before washing)÷(whiteness index of unstained fabric−whiteness index of stained fabric before washing)×100

Here, the “whiteness index” is an average of ten points on two sides of the artificially stained fabric measured by a whiteness index measure (trade name of CR-14, Whiteness Index Color Reader, manufactured by Minolta Co.,Ltd.).

COMPARATIVE EXAMPLE 1

As an comparative example of the embodiment 5, the same stained fabrics as in the Embodiment 5 were washed by using a commercially available synthetic detergent for washing (Attack (registered trademark), Kao Corporation) and a whiteness index and the detergency ratio were calculated. The results are shown in Table 5.

TABLE 5

detergency ratio

kind of stained fabric

comparative

stained fabric

stain

embodiment 5

example 1

standard stained

dirt on collar

49.7

44.5

fabric

EMPA101

china ink and olive oil

11.2

8.3

EMPA111

blood

81.1

44.7

EMPA112

cacao

19.6

11.7

EMPA114

red wine

13.8

19.9

EMPA116

mixed stain of blood,

15.2

13.6

milk and china ink

From the result, it was confirmed that the weak alkaline detergent (mixed electrolytic water) obtained by the present invention had detergency comparable to or better than the commercially available synthetic detergent. Especially, it is remarkably improved as to blood stain. Note that the detergent of the fifth embodiment had no problems at all concerning safety and treatment of discharging water after washing.

Embodiment 6 (neutral detergent)

A solution prepared by dissolving and diluting 36 g of sodium hydrogen carbonate in 1 litter of tap water (municipal tap water in Fujisawa city, pH 7.2, EC 15.5 mS/m, water temperature 24.5° C.) was supplied to the anode chamber

113

a

and the cathode chamber

113

c

of the batch type electrolysis cell

11

(a capacity of the anode chamber and the cathode chamber are both 1 litter) shown in

FIG. 4C

, and electrolysis was carried out by applying a direct current voltage so that a constant current of 15A flows to both the electrode plates

115

a

and

115

c

for 36 minutes. When measuring a pH and EC value of thus obtained anode water, pH=7.06 and EC=971 mS/m.

The anode water was further added with 52 g of sodium hydrogen carbonate and additionally added with 3 g of cane sugar fatty acid ester and 2 g of carboxyl methyl cellulose.

A washing tub of a domestic automatic washing machine (trade name of AW-C60VP, 6 kg type, manufactured by Toshiba Corporation) was filled with 31 litters of tap water and put in 1000 cc of the above detergent (diluting rate =31 times). The diluted detergent had a pH of 8.0, EC value of 175.5 mS/m, and a water temperature of 20.1° C.

A standard stained fabric with “dirt on collar”, and “mixed stain of china ink and olive oil”, “blood”, “cacao butter (animal and vegetable oil)”, “red wine”, and “mixed stain of blood, milk and china ink” being allowed to adhere to cotton fabric samples, respectively (EMPA101, 111, 112, 114, 115 and 116), were washed by setting the water current switch to pressing washing course for 3 minutes (soaked for 5 minutes before washing), rinsed for two times, spin-dried for 4 minutes and dried by a drier.

The detergency ratio of the respective stained fabrics before and after washing is shown in Table 6. note that the “detergency ratio” and “whiteness” were measured and calculated in the same way as in the fifth embodiment.

COMPARATIVE EXAMPLE 2

As a comparative example of Embodiment 6, the same stained fabric as in the Embodiment 6 was washed by using a commercially available neutral detergent for washing (Acron, Lion Corporation) and the detergency ratio was calculated. The results are shown in Table 6.

TABLE 6

detergency ratio

kind of stained fabric

comparative

stained fabric

stain

embodiment 6

example 2

standard stained

dirt on collar

13.8

12.5

fabric

EMPA101

china ink and olive oil

5.3

4.5

EMPA111

blood

52.5

34.9

EMPA112

cacao

3.9

6.0

EMPA114

red wine

24.3

19.7

EMPA116

mixed stain of blood,

10.2

8.3

milk and china ink

From the result, it was confirmed that the neutral detergent obtained by the present invention had detergency comparable to or better than the commercially available neutral detergent. Especially, it is remarkably improved as to blood stain. Note that the detergent of the sixth embodiment had no problems at all concerning safety and treatment of discharging water after washing.

Number	Date	Country	Kind
10-282767	Oct 1998	JP
11-211811	Jul 1999	JP

Number	Name	Date	Kind
3339737	Kiscellus et al.	Sep 1967	A
3937042	Loeb	Feb 1976	A
3985669	Krummel et al.	Oct 1976	A
4472287	Ramachandran et al.	Sep 1984	A
4530774	Davies et al.	Jul 1985	A
4605509	Corkill et al.	Aug 1986	A
4793942	Lokkesmoe et al.	Dec 1988	A
4911856	Lokkesmoe et al.	Mar 1990	A
5443751	Mazzola	Aug 1995	A
6461446	Satoh et al.	Oct 2002	B1
6596092	Satoh et al.	Jul 2003	B1

Number	Date	Country
0503589	Sep 1992	EP
63205196	Aug 1988	JP
08112573	Jul 1996	JP
9937414	Jul 1999	WO
00 20549	Apr 2000	WO

Method and apparatus for producing cleaning agent

Information

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Date Filed

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Agents

CPC

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Priority Claims (2)

PCT Information

US Referenced Citations (11)

Foreign Referenced Citations (5)

Non-Patent Literature Citations (2)

Entry
Machine translation of the above Japanese patent.*
English Language Abstract of WO 00/20549.