JPH07119435B2 - Washing soap - Google Patents

Description

TECHNICAL FIELD The present invention relates to a cleaning agent. More specifically, food,
The present invention relates to a cleaning agent suitable as a cleaning agent for human bodies such as detergent for tableware and shampoo.

(B) Conventional technology For detergents such as food and tableware, various surfactants such as soap have been conventionally used, but in recent years, pollution problems, food hygiene problems, and high quality As the demands are highlighted, the following quality is required.

As well as food additives, there is no need to worry about toxicity, there is no skin disorder such as rough hands, good biodegradability, and excellent pesticide removal and bactericidal effects.

In addition, a similar quality is required for a cleaning agent for human body such as shampoo for its purpose.

In this regard, conventionally known safe and highly effective detergents include so-called polyhydric alcohol fatty acid esters such as polyethylene glycol fatty acid ester type surfactants, sucrose fatty acid ester type surfactants and sorbitan fatty acid ester type surfactants. Various types of type surfactants have been proposed, either alone or in combination (Japanese Patent Laid-Open Nos. 50-92908 and 50-1).
19812, 51-20907, 51-114406, 51-9280
No. 2, No. 49-67910, No. 49-90706, No. 51-72983,
50-109188, 51-30587, 50-39707, etc.).

(C) Problems to be Solved by the Invention However, although the polyhydric alcohol fatty acid ester type surfactant is recognized as a food additive, it is a chemical synthetic product per se, and therefore there is concern about toxicity. is there. Further, these surfactants are not always satisfactory in terms of cost and cleaning effect.

Furthermore, in detergents using these surfactants, a large amount of sequestering agent called a builder (for example, tripolyphosphoric acid) is usually used in order to prevent deterioration of washing ability due to metal ions in the target water. Although included, there was a pollution problem caused by the builder itself.

The present invention has been made under such circumstances, and in particular,
As described above, it is an object of the present invention to provide a new cleaning agent that is a safe and inexpensive cleaning agent that can substitute for the cleaning agent composed of a polyhydric alcohol fatty acid ester type surfactant that is widely used, and that has an excellent cleaning effect. .

(D) Means and Actions for Solving the Problems From the above viewpoints, the present inventors have conducted extensive research and study,
Partially decomposed products of grain proteins such as gluten have an excellent cleaning effect by themselves, and even in the presence of metal ions, they have found a surprising fact that they exhibit an excellent cleaning effect without using a builder, This invention was reached.

Thus, according to the present invention, there is provided a detergent comprising a decomposed product of a grain protein and having a weight-average molecular weight in the range of 500 to 110,000 as an active ingredient.

The cleaning agent of the present invention is suitable as a cleaning agent for the human body such as the above-mentioned food, dish detergent, shampoo, body shampoo, and can be used for other purposes, for example, as a laundry detergent. Especially when used as a food or dish detergent, it satisfies all of the above-mentioned requirements (1) to (4) and is extremely useful in that it can perform an excellent dry finish while preventing water spots that often occur in foods and the like. is there. Further, such excellent cleaning effect and dry finishing effect are excellent as compared with a cleaning agent using a polyhydric alcohol fatty acid ester type surfactant which has been widely used conventionally.

The grain protein partial hydrolyzate used in the present invention is preferably one having a weight average molecular weight Mw of 500 to 110,000 in the gel filtration method,
From the viewpoint of cleaning effect, those having 500 to 30,000 are preferable. Note that M
When w is less than 500, the effect is substantially reduced mainly by amino acids and oligomers thereof, and when it exceeds 110,000, the effect is close to that of undegraded one and the effect is low, which is not suitable. In addition,
These molecular weights are 1600,6500,16000,65 as standard substances.
Sephadex G-75 manufactured by Pharmacia Co., Ltd. using sodium polystyrene sulfonate having a molecular weight of 000,88,000.
Alternatively, it is a value measured by a gel filtration method using G-100 as a carrier.

In the present invention, the grain protein means a protein contained in grain, and examples of grain include wheat (eg wheat), corn, beans (eg soybean) and the like. Among proteins contained in such grains, wheat protein, for example, contains glutenin and gliadin as main components, and is usually called wheat gluten. Further, corn protein contains zein as a main component and is usually called corn gluten. These are all known substances, and can be obtained by separating or extracting from grains by a conventional method. For example, when obtaining wheat protein (wheat gluten), a small amount of water is added to wheat flour and kneaded firmly, and then this is kneaded in a large amount of water, the starch is suspended in water, and the gluten-containing content becomes a sticky mass. Remain. If this operation is repeated several times while changing water, a grayish brown viscous mass can be obtained. For the preparation of the partially decomposed product of the present invention, such a lump can be used as it is, but a dried product thereof, a further purified product or a partially modified product may be used. . For example, wheat gluten is commercially available as a dried product and can be easily obtained. In addition, commercially available corn gluten and soybean protein can be easily used. Although such a protein may be a crude product or a purified product, it is preferable to use a protein containing 70% or more of the protein.

The grain protein partially decomposed product of the present invention can be obtained by subjecting the grain protein to a partial decomposition treatment. Here, the partial decomposition treatment can be carried out by subjecting the grain protein to a decomposition treatment using an alkali, an acid, an enzyme, a reducing agent or an oxidizing agent.

The decomposition treatment with alkali is suitably performed by heating in a dilute aqueous alkali solution. Usually, an aqueous solution or aqueous dispersion of a decomposition target is added in the presence of an alkali agent such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate or potassium carbonate at about 60 to 180 ° C. under about 1
It is suitable to stir for 0 to 600 minutes. The aqueous solution or aqueous dispersion of the decomposition target is preferably used in an amount of 2 to 40% by weight, and the amount of the alkaline agent used is preferably 0.1 to 6 g based on 20 g of the decomposition target.

On the other hand, the decomposition treatment with an acid is preferably performed by heating in a dilute aqueous acid solution. Usually, it is suitable to stir an aqueous solution or aqueous dispersion of the decomposition target in the presence of an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as acetic acid at about 60 to 120 ° C for about 10 to 600 minutes. There is. The quantitative conditions here are preferably the same as the above-mentioned conditions for the alkaline hydrolysis.

Similarly, the decomposition treatment with an enzyme is suitable to be carried out in a dilute aqueous solution of an enzyme having protease activity.
In an aqueous solution or aqueous dispersion of a substance to be decomposed in the presence of a small amount of an enzyme such as pepsin, alkaline protease, papain, etc., under the optimum pH conditions of this enzyme, under about 10 to 60 ° C, about 60 to 600.
Minutes. Here, the quantitative conditions are preferably the same as above except that the amount of enzyme used is 0.02 to 5 g per 20 g of the decomposition target.

Similarly, the decomposition treatment with a reducing agent or an oxidizing agent is preferably carried out in a dilute aqueous solution of a reducing agent or an oxidizing agent. Usually, an aqueous solution or an aqueous dispersion of an object to be decomposed contains a sulfite, a thiol compound, or erythorbic acid. , A reducing agent for hydrazinic acid or an oxidizing agent such as hydrogen peroxide or hypochlorite is present in a small amount at about 10 to 100 ° C. for 10 to 600 minutes. The quantitative conditions at this time are preferably the same as those described above except that the amount of the reducing agent or the oxidizing agent used relative to 20 g of the decomposition target is 0.1 to 5 g.

The decomposition treatment may be performed not only alone but also in combination of two or more kinds. In particular, the inventors of the present invention have found that the decomposition treatment (A) with an alkali is an essential treatment, and the decomposition treatment (B) of one or more of an acid, an enzyme, an oxidizing agent and a reducing agent is added to the treatment. It has also been found that the decomposed product obtained by the combined decomposition treatment of two or more steps is a novel decomposed product different from the conventional decomposed products and is one suitable partial decomposed product used in the present invention. . The novel grain protein partial hydrolyzate is characterized by the following physical properties.

(A) Weight average molecular weight (by gel filtration method) is 500 to 900
It is in the range of 00.

(B) The ultraviolet absorption λmax is around 260 to 280 nm, and the infrared absorption is around 1400, 1630 and 3400 cm ^-1 .

(C) The isoelectric point is in the range of 3.9 to 5.0.

(D) pH buffering property (pH of 100 ml of a 5% by weight aqueous solution of this product is 6%
2 to 25 ml of 1N-hydrochloric acid is required to reduce the amount from 1 to 2).

(E) It is soluble in water and insoluble in methanol, ethanol, acetone and ether.

(F) Appearance is a light yellow to reddish brown powder.

(G) Color is developed by a xanthoprotein reaction and a ninhydrin reaction.

(H) Strong ability to reduce surface tension (By adding 0.1% by weight of this product to pure water at 25 ° C, the surface tension of pure water is reduced to 50 dyne / c
m or less (measured with Dunui's surface tensiometer)
Have.

(I) Strong emulsifying ability (100 g of a water-soybean oil mixture containing at least 30% by weight of soybean oil is completely emulsified by the use of 1 g of this product (a uniform emulsified state is maintained for at least 10 minutes, preferably 1 hour or more). Meaning).

Such a partially decomposed product has a surface tension reducing ability (h).
And the emulsifying ability (i) distinguishes it from a normal grain protein partial degradation product.

The order of the multistage decomposition process is not particularly limited.
That is, a raw material such as wheat gluten is first subjected to an alkali decomposition treatment (A), and then a decomposition treatment (B) (decomposition treatment other than alkali) using the above-mentioned acid, enzyme, reducing agent or oxidizing agent.
Alternatively, two or more kinds of the treatments may be applied, or the decomposition treatments may be performed in the reverse order. Alternatively, it can be obtained by first subjecting it to a decomposition treatment other than alkali (B), then subjecting it to alkali decomposition treatment (A), and then again subjecting it to a decomposition treatment other than alkali (B). In addition, a neutralization treatment may be appropriately performed between these treatments. Among these, the combination of the alkali decomposition treatment (A) and the acid decomposition treatment (B) is most preferable in terms of the cleaning effect.

The grain protein partially decomposed product-containing solution thus obtained can be used as it is as a detergent, but can also be used as a powder after drying. Further, for example, a purified product that has been desalted or decolorized by ultrafiltration or the like can also be used favorably. Furthermore, if necessary, it can be used by formulating it in combination with other various additives and organic solvents.

Examples of other additives include solubilizing agents, builders, preservatives, coloring agents, and aromatic agents. Here, as the dissolution aid, ethanol, propylene glycol,
Glycerin, saccharose, glucose, sorbitol, dextrin and the like can be mentioned. Examples of the organic builders include organic acids such as gluconic acid, citric acid, malic acid and tartaric acid, amino acids such as glycine, glutamic acid and alanine, and potassium or sodium salts thereof. Examples of the inorganic builders include alkali carbonate, alkali phosphate, alkali silicate, mirabilite, and salt.
Examples of antiseptics include ethanol, propionic acid, lactic acid, sorbic acid, dehydroacetic acid, and salt.

The formulation may be in the form of powder or liquid, but it is suitable to prepare it so that at least the cleaning action of the grain protein partial hydrolyzate is not hindered. Especially when used as a cleaning agent for food and tableware,
From the viewpoint of ease of use, it is usually desirable to use an aqueous solution-based formulation.

Further, in the cleaning agent of the present invention, in addition to the partial decomposition product, a surfactant may be contained in other cleaning active ingredients, for example, various anions including lecithin and the like,
In one preferred embodiment, nonionic and cationic surfactants can be used in combination, especially polyhydric alcohol fatty acid ester type surfactants or anionic surfactants represented by alkylbenzene sulfonic acid type salts. At this time, if the compounding ratio of the partially decomposed protein and the surfactant is 1: 6 to 6: 1 (weight ratio) (preferably 1: 4 to 4: 1), a synergistic cleaning effect can be obtained. More preferable.

(E) Examples The present invention will be described in more detail by the following examples and test examples.

Examples 1 to 7 (preparation of partially decomposed product of wheat gluten with alkali) 20 g of wheat gluten (reagent product) manufactured by Wako Pure Chemical Industries, Ltd.,
Add caustic soda to 100 g of 7 aqueous solutions each dissolved in the range of 0.2 to 4 g, mix well, and in a flask or autoclave at 80 ° C to 150 ° C for 30 to 360 minutes at each temperature and time. Each was heated and stirred. Inventive products Nos. 1 to 7 were obtained by neutralizing these with hydrochloric acid and making the total amount to 200 g with pure water.

Table 1 shows the decomposition conditions and the average molecular weight of the decomposed product (measured as Mw by the gel filtration method).

Examples 8 to 12 (Preparation of partially decomposed product of wheat gluten with acid) Five flasks or autoclaves containing 100 g of hydrochloric acid aqueous solution corresponding to 1 to 8 g in terms of hydrogen chloride were manufactured by Wako Pure Chemical Industries, Ltd., respectively. Add 20g of wheat gluten (reagent product), 1
The mixture was heated and stirred at 00 or 120 ° C. for 60 minutes. After that, it was neutralized with caustic soda and the total amount was 200 g with pure water.
Got

Table 2 shows the decomposition conditions and the average molecular weight of the decomposed products.

Example 13 (Preparation of partially decomposed product of wheat gluten by enzyme) 20 g of wheat gluten used in Example 1 was added with 150 g of 0.1N hydrochloric acid solution.
Was added to the flask containing to obtain an aqueous solution of pH 1.5.
0.2 g of pepsin was added and reacted at 37 ° C for 90 minutes. After that, it was neutralized with caustic soda and the total amount was 200 g with pure water.
I got o.13. The average molecular weight was 60,000.

Examples 14 to 22 (partial decomposition of wheat gluten by acid and subsequent preparation of decomposed product by partial decomposition with alkali) A 10% aqueous solution of the partial decomposition product of wheat gluten with acid was prepared under the same conditions as in Examples 8 to 12. 100 g of each of them was put into a flask or 9 autoclaves, and caustic soda was added thereto in an amount within the range of 0.5 to 2 g, and the mixture was heated and stirred at 100 or 150 ° C. for 60 or 360 minutes. Then, the mixture was neutralized with hydrochloric acid and the total amount was 200 g with pure water to obtain invention products Nos. 14 to 22.

Table 3 shows the decomposition conditions and the average molecular weight of the decomposition products.

Examples 23 to 26 (Preparation of Degradation Products by Partial Decomposition of Corn Corn Gluten and Soybean Protein by Acid and Subsequent Partial Decomposition by Alkali) Using corn gluten manufactured by Nippon Food Kako Co., Ltd. as a raw material and under the same conditions as Examples 16 and 20. Inventive products Nos. 23 and 24 were obtained by sequentially carrying out partial decomposition with acid and alkali. The average molecular weights were 11800 and 2700, respectively.

Further, using soybean protein obtained by defatting commercially available yuba with acetone as a raw material, partial decomposition was sequentially carried out using an acid and an alkali under the same conditions as in Examples 16 and 20 to obtain invention products No. 25 and 26.

The average molecular weights were 12000 and 3000, respectively.

Examples 27 and 28 (Partial decomposition of wheat gluten with alkali and subsequent preparation of decomposed product by partial decomposition with acid) Obtained by partial decomposition of wheat gluten with alkali under the same conditions as in Examples 3 and 4. A 10% aqueous solution of the partially decomposed product was prepared, 100 g of each was placed in two flasks, and hydrochloric acid corresponding to 2 g and 4 g in terms of hydrogen chloride was separately added thereto, and the mixture was heated and stirred at 100 ° C. for 60 minutes. After that, the product was neutralized with caustic soda and the total amount was 200 g with pure water to obtain invention products 27 and 28.

Table 4 shows the decomposition conditions and the average molecular weight of the decomposition products.

Example 29 (Preparation of partially decomposed product of wheat gluten with an enzyme and then carried out partially decomposed product with an alkali) A 10% aqueous solution of the partially decomposed product of wheat gluten with an enzyme was prepared under the same conditions as in Example 13. , 100g of caustic soda
1 g was added and the mixture was heated and stirred in the flask for 60 minutes. After that, the product was neutralized with hydrochloric acid and the total amount was 200 g with pure water to obtain Inventive Product No. 29.

The average molecular weight was 29,000.

Example 30 (Preparation of Decomposition Product by Partial Decomposition of Wheat Gluten with Reducing Agent and Subsequent Partial Decomposition with Alkali) 20 g of wheat gluten used in Example 1 was added to 100 g of an aqueous solution containing 4 g of sodium sulfite, and the mixture was heated to 30 ° C. After stirring for 60 minutes, a total amount of 200 g was prepared with pure water to prepare a 10% aqueous solution of a partially decomposed product of wheat gluten with a reducing agent, 2 g of caustic soda was added to 100 g of the solution, and the mixture was heated and stirred at 100 ° C. for 60 minutes in a flask. After that, the product was neutralized with hydrochloric acid and the total amount was 200 g with pure water to obtain Inventive Product No. 30. The average molecular weight was 15200.

Example 31 (Preparation of Degradation Product of Wheat Gluten with Partial Decomposition of Alkali and Partial Decomposition with Enzyme Performed Next (Reverse Order from Example 29)) Partial Decomposition Product of Wheat Gluten with Alkali under the Same Conditions as in Example 3 A 10% aqueous solution of 1 is prepared, and 100 g of the solution is added with hydrochloric acid as a reagent to obtain an aqueous solution having a pH of 1.5.
Pepsin was added and reacted at 37 ° C. for 90 minutes. afterwards,
Inventive product No. 31 was obtained by neutralizing with caustic soda and making the total amount to 200 g with pure water. The average molecular weight was 24500.

Example 32 (Preparation of Decomposition Product of Partial Decomposition of Wheat Gluten with Alkali and Subsequent Partial Decomposition with Oxidizing Agent) A 10% aqueous solution of partial decomposition product of wheat gluten with alkali was prepared under the same conditions as in Example 3. Hydrogen peroxide solution equivalent to 1.0 g in terms of H ₂ O ₂ was added to 100 g of the mixture, and the mixture was heated with stirring at 40 ° C. for 60 minutes. Then, the remaining H ₂ O ₂ and an equivalent amount of sodium thiosulfate (for masking hydrogen peroxide) were added, and the total amount was 200 g with pure water to obtain the invention product No. 32. Average molecular weight is 2
It was 3000.

Example 33 A corn gluten produced by Nippon Shokuhin Kako Co., Ltd. was used as a raw material, and partial decomposition was carried out using an alkali under the same conditions as in Example 3 to obtain Inventive Product No. 33. The average molecular weight was 25600.

The following tests were performed on the above-mentioned invention products.

Comparative Example 1 The wheat gluten used in the examples was used as a comparative product No. 1 without being decomposed.

Comparative Example 2 A fatty acid ester such as sho (DK Ester F-160; manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) was used as a comparative product No. 2 as it was.

Comparative Example 3 Palmitic acid monoglyceride (Sunsoft No. 3 8001;
Taiyo Kagaku Co., Ltd. was used as it was as a comparative product No. 3.

Test Example 1 (cleaning test for dirt adhering to foods, etc.)
(Based on JIS K-3370) 1. Test method and conditions (i) Preparation of model soil pieces 200 g of mixed fat and oil of beef tallow and soybean oil (1: 1), monoolein
Chloroform 600 with 2.5g, oil red (Sudan III) 1g
Dissolve in ml to prepare a dirty bath.

Approximately 55 mm in a dirty bath as a set of 6 slide glasses
After soaking it for 1-2 seconds, slowly remove it.

Air-dry the slide glass with stains for 90 minutes and then perform a cleaning test.

(The above operation was carried out in a constant temperature and humidity room at a temperature of 25 ° C and a humidity of 40%.) (Ii) Cleaning test method 6 slide glasses with dirt and stains were set on the rinatsu improved cleaning power tester and the inspection was performed. Add water and sample (detergent) and wash for 3 minutes. After that, the sample was rinsed with only the test water for 1 minute, air-dried and then the detergency was determined. The properties of test water and each condition are as follows.

・ Test water: 59.0mg / of calcium chloride (dihydrate) in distilled water
, Dissolved magnesium chloride (hexahydrate) 27.2mg / ・ Water amount …… 700ml ・ Water temperature …… 30 ± 1 ℃ (both cleaning and rinsing) ・ Rotation speed …… 250 ± 10rpm (iii) Judgment of cleaning power Method Dissolve stains on air-dried glass slides with ethyl acetate to make the total volume 100 ml. Then, the absorbance of the cleaning solution is measured at a wavelength of 500 nm, and the cleaning rate is calculated by the following formula.

2. Test results (i) As a result of performing the above-mentioned cleaning test on the invention products Nos. 1 to 33 prepared by the respective examples, the cleaning rate is the addition concentration.
At 0.25 g / all, 60% or more and no additive (cleaning rate 29
%) Was good. The test results of the representative examples are shown in Table 5 together with the comparative examples.

(Ii) Table 6 shows the results of the combined use of Inventive Product No. 17 and sucrose fatty acid ester (known detergent).

(Iii) 176mg / of calcium chloride (dihydrate) in distilled water
Table 7 shows the results obtained by dissolving 81.6 mg / magnesium chloride (hexahydrate) as test water and using the above-mentioned invention product No. 17 or sodium dodecylbenzenesulfonate alone or in combination.

In the table, W in the raw material column means wheat gluten, C means corn gluten, and B means soy protein.

Thus, when high hardness water is used as the test water, the cleaning rate of sodium dodecylbenzenesulfonate, which is an anionic surfactant, decreases.

It can be seen that, when this invention product No. 17 is used in combination with this sodium dodecylbenzenesulfonate, a remarkable synergistic effect is exhibited.

Test example 2 (Dry finish effect) Automatic washing machine (MRK-NEWAMATIC JET WAS manufactured by Mitamura Riken Kogyo)
HER LABO-200), and put 36 glass transparent cups (those soaked in commercial milk and left at room temperature for 30 minutes) in a rack and use a commercial alkaline detergent solution of 0.15% at 60 ° C to Washed for minutes. After that, rinsing water at 85 ° C. in which a predetermined amount of a rinsing aid having the following composition was dissolved was sprayed for 15 seconds for rinsing.

Then, the cup was immediately taken out, and the wet state of the cup surface, the drying time and the finished state after drying were examined.

Composition of rinse aid The results are shown in Table 8.

<Evaluation of wet state> ○: Wet sufficiently Δ: Effective but insufficient ×: No effect <Evaluation of finished state> ○: No water spot is observed Δ: Water spot is observed However, it can withstand use x: Not withstand Test Example 3 (Effects of removing pesticides from foods) A) Method for preparing washed samples Apple apple skins are cut into approximately the same thickness and the same size, washed thoroughly with diluted hydrochloric acid water, and then washed with water. Repeat. This is dried to make clean apple skin. Then As As ₂ O ₃ and D ・ D ・
Accurately attach each T to the skin by 10 ppm.

B) Washing Make a 0.5% aqueous solution of the test substance and wash the apple skin made in A) at room temperature. After giving the same shaking for about 5 minutes, the apple skin was taken out and transferred to the washing solution.
Analyze T.

C) Method for measuring As removal rate A comparison was made with the coloring of As contained in the washing water after washing with respect to the standard color coloring according to the arsenic test method commented on by the Food Additives Standard.

D) D / D / T removal rate measurement method Compare the turbidity of washing with the standard turbidity by the chloride additive test method of the Food Additives Standard.

E) Evaluation of test results ◎ Good removal effect (removal rate 80% or more) ○ Effective effect (removal rate 50 to 80) △ Weak effect (removal rate 20 to 50) × Almost the same as water washing None (removal rate 20% or less) (F) Effect of the Invention The cleaning agent of the present invention has a useful property that it has an excellent cleaning effect and, even when it is not used in combination with a builder, the cleaning effect is not significantly reduced in high hardness water.

Since the partially decomposed product of grain protein as an active ingredient is a food or a food-like product, it is extremely advantageous in that it is not toxic, has improved safety as a food additive, and is inexpensive.

Therefore, the cleaning agent of the present invention is extremely useful as a food, a detergent for food and a cleaning agent for human body, and can be expected to be used as a cleaning agent for clothes.

Claims (1)

[Claims] 1. A decomposed product of a grain protein, wherein a partially decomposed product having a weight average molecular weight of 500 to 110,000 and a polyhydric alcohol fatty acid ester type surfactant or an anionic surfactant are used in a weight ratio of 1: 6. Detergent containing ~ 6: 1.