JPH01281134A - Dissolution promoter for hardly-soluble surfactant - Google Patents

Abstract

PURPOSE:To increase dissolution property and dispersibility of a hardly-soluble surfactant by preparing a dissolution promoter, which contains a partially decomposed product of a grain protein as an effective component and whose weight- average molecular weight is 500-110000. CONSTITUTION:A partially decomposed product of 500-110000 in weight-average molecular weight is obtained by a partial decomposition treatment for a grain protein, which is a combination of alkali decomposition with one or more of decomposition treatments by acid, enzymatic reduction agent or oxidizing agent. A dissolution promoter is prepared by compounding this partially decomposed product as an effective component. Wheat gluten, corn gluten, soybean protein, etc., are preferable as the grain protein and a partially decomposed product, which is treated by a combination of an alkali decomposition with an acid decomposition, is preferred.

Description

[Detailed description of the invention] (b) Industrial application fields The present invention relates to a dissolution promoter for poorly soluble surfactants.

More specifically, the present invention relates to an agent for promoting the dissolution of poorly water-soluble surfactants such as polyhydric alcohol fatty acid ester surfactants and lecithin in water.

(b) Conventional technology Polyhydric alcohol fatty acid ester type surfactants such as sucrose fatty acid ester and glycerin fatty acid ester, lecithin, etc. have traditionally been used as surfactants with low toxicity in various applications including food. It is being

However, such polyhydric alcohol fatty acid ester type surfactants and lecithin usually have an HLB of less than 16 or equivalent, so when added to an aqueous medium, they are difficult to dissolve and have extremely high solubility and dispersibility. In many cases, this caused problems in handling.

For this reason, when dissolving these poorly soluble surfactants in water, it is possible to use a solubilizing agent such as a hydrophilic surfactant, but as mentioned above, polyhydric alcohol fatty acid ester type surfactants Since lecithin and lecithin are used in the food field, there are many restrictions on the solubilizers used in combination in terms of toxicity.

Therefore, conventionally, formulations have been prepared by mixing proviresin glycol (Japanese Patent Publication No. 50-30595) or by mixing saccharides (Japanese Patent Application Laid-open No. 54-95748).
li! Plans are still being made.

(c) Problems to be Solved by the Invention However, in the conventional methods described above, the effect of solubilizing the poorly soluble surfactant is not necessarily sufficient, and furthermore, formulation may be complicated.

The present invention was made under such circumstances, and it is an object of the present invention to provide a safe dissolution promoter that can be easily used in combination with the above-mentioned poorly soluble surfactant and can significantly improve the solubility and dispersibility of this surfactant. That is.

(d) Means and effect for solving the problem From the above viewpoint, the present inventors conducted intensive research and examination, and found that by avoiding the coexistence of partially decomposed products of grain proteins such as gluten when using the above-mentioned sparingly soluble surfactant. The inventors have discovered that the solubility and dispersibility of this surfactant are significantly improved, and have arrived at the present invention.

Thus, according to the present invention, there is provided a dissolution promoter for a sparingly soluble surfactant, which contains as an active ingredient a partially degraded product of grain protein having a weight average molecular weight in the range of 500 to 110,000. be done.

Typical poorly soluble surfactants to which this invention applies are the aforementioned polyhydric alcohol fatty acid ester type surfactants and lecithin, but there are also others with HLB7><16
The following so-called oil-soluble surfactants may be mentioned.

The grain protein partial decomposition product used in this invention is suitably one with a weight average molecular weight Mw of 500 to 110,000 as measured by gel filtration, and a weight average molecular weight of 500 to 50,000 in terms of dissolution promoting effect.
Preferably. In addition, if Mw is less than 500, the effect will be reduced because amino acids and their oligomers will be the main components, and if it exceeds 110,000, the properties will be similar to that of undecomposed substances, and the effect will be low, so it is not suitable. In addition, these molecular weights are 1600.6500° and 1.6000° as standard substances.
．． This is a value measured by a gel filtration method using sodium polystyrene sulfonate having a molecular weight of 65,000.88,000 and using Sephadex G-75 or G-100 manufactured by Pharmacia as a carrier.

Incidentally, in this invention, grain protein refers to protein contained in grains.
Wheat), corn, beans (eg, soybeans), etc. Among the proteins contained in such grains, wheat protein, for example, contains glutenin and gliadin as main components and is usually called wheat gluten. Moreover, 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 them from grains using conventional methods. For example, wheat protein (wheat gluten)
To obtain wheat flour, add a small amount of water and knead it until stiff, then knead it in a large amount of water, the starch will be suspended in the water and the gluten content will remain as a sticky mass. If this operation is repeated several times by changing the water, a grey-brown, viscous lump can be obtained. For the preparation of the partially decomposed product of this invention, such lumps can be used as they are, but their dried products may also be used, and further purified products, partially modified products, etc. may also be used. .

For example, wheat gluten is commercially available as a dried product and can be easily obtained. Other commercially available corn gluten and soybean protein can be easily used. The protein may be either a crude product or a purified product, but it is preferable to use one containing 70% or more protein.

The grain protein partial decomposition product of this invention can be obtained by subjecting the above grain protein to a partial decomposition treatment.

In this partial decomposition process, the above grain proteins are treated with alkali,
This can be carried out by subjecting it to a decomposition treatment using an acid, an enzyme, a reducing agent, or an oxidizing agent.

The above decomposition treatment with alkali is suitably carried out by heating in a dilute aqueous alkali solution. Usually, an aqueous solution or aqueous dispersion of the substance to be decomposed is stirred at about 60 to 180°C for about 10 to 600 minutes in the presence of an alkaline agent such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, etc. It is appropriate to do so. Here, the aqueous solution or aqueous dispersion of the substance to be decomposed is 2 to 40
It is preferable to use % by weight, and the amount of alkaline agent used is preferably 0.1 to 6 g per 20 g of the substance to be decomposed.

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

Similarly, enzymatic decomposition treatment is suitably carried out in a dilute aqueous solution of an enzyme having protease activity;
A small amount of an enzyme such as pepsin, alkaline protease, papain, etc. is present in an aqueous solution or aqueous dispersion of the decomposition target, and the process is carried out at approximately 10 to 60°C for approximately 60 to 600 minutes under the optimal PL+ conditions for this enzyme. .

Here, the quantitative conditions are preferably the same as above except that the amount of the enzyme-using type is 0.02 to 5 g per 20 g of the substance to be decomposed.

Similarly, decomposition treatment using a reducing agent or oxidizing agent is suitably carried out in a dilute aqueous solution of the reducing agent or oxidizing agent, and sulfites, thiol compounds, and erythorbic acid are usually added to the aqueous solution or aqueous dispersion of the substance to be decomposed. , in the presence of a small amount of a reducing agent such as hydrazine or an oxidizing agent such as hydrogen peroxide or hypochlorite, at a temperature of 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 reducing agent or oxidizing agent used with respect to the decomposition object 209 is 0.1 to 5 g.

The above decomposition treatment may be carried out not only alone but also in combination of two or more kinds. In particular, according to the findings of the present inventors, the decomposition treatment with alkali (A) is an essential treatment, and the decomposition treatment (B) with one or more of acids, enzymes, oxidizing agents, and reducing agents is added to this. It has also been discovered that a decomposition product obtained by a combination of two or more decomposition processes is a new decomposition product different from conventional decomposition products, and is a suitable partial decomposition product for use in the present invention. . This novel grain protein partial decomposition product is characterized by the following physical properties.

(a) Weight average molecular weight (by gel filtration method) of 500~
It is in the range of 90,000.

(b) Ultraviolet absorption λmax is around 260 to 280 nlT+, and infrared absorption is 1400, 1630 and 3400
It is around cm-'.

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

(d) pH buffering property (IN-hydrochloric acid is 2 to 2 to lower 100 ml (p)l of 5 wt% aqueous solution of Honjima from 6 to 2.
253!12).

(e) Soluble in water and insoluble in methanol, ethanol, acetone, and ether.

(f) Appearance is pale yellow to reddish brown powder.

(g) Color develops due to xanthoprotein reaction and ninhydrin reaction.

(h) Strong surface tension lowering ability (main island is immersed in pure water at 25°C with 0.
By adding 1% by weight, the surface tension of pure water increases by 50%.
dyne/am (measured with a Dunui surface tension meter).

(i) Strong emulsifying ability (by using Honjima 19, a water-soybean oil mixture containing at least 30% by weight of soybean oil 10
Completely emulsify 0g (keep it uniformly emulsified for at least 10 minutes,
Preferably, this means holding for at least 1 hour).

Such partial decomposition products are particularly suitable for the above-mentioned surface tension lowering ability Ch)
It is distinguished from ordinary grain protein partial decomposition products in terms of emulsifying ability (i) and emulsifying ability (i).

Note that the order of the multistage decomposition processing is not particularly limited.

That is, raw materials such as wheat gluten are first subjected to alkaline decomposition treatment (A), and then decomposition treatment using the above-mentioned acid, enzyme, reducing agent, or oxidizing agent (B) (decomposition treatment other than alkali)
Alternatively, it may be subjected to two or more types of treatment, or the decomposition treatment may be performed in the reverse order. In addition, after first being subjected to decomposition treatment other than alkali (B), alkaline decomposition treatment (A
) and then again subjected to a decomposition treatment (B) using a substance other than an alkali. In addition, neutralization treatment may be performed as appropriate between each of these treatments. Among these, alkaline decomposition treatment (A) and acid decomposition treatment (B)
A combination of these is most desirable in terms of the dissolution promoting effect.

The grain protein partial decomposition product-containing solution obtained in this way can be used as a solubility promoter as it is, but it can also be used as a powder after drying. In addition, purified products that have been subjected to desalination treatment or decolorization treatment, such as by ultrafiltration, can also be used satisfactorily.

Further, for example, it can be used in the form of a formulation mixed with a powder of a poorly soluble surfactant. In any case, when a poorly soluble surfactant is dissolved in an aqueous medium, the effect of dissolving the poorly soluble surfactant in a shorter time is achieved, and the partially decomposed product itself is quickly dissolved in an aqueous medium. It is dissolved in the medium.

The amount of partially decomposed products used here varies depending on the conditions, but
Usually, 1 to 10 parts by weight per 100 parts by weight of poorly soluble surfactant.
It is suitable to use 00 parts by weight together. If the amount is less than 1 part by weight, the dissolution promoting effect will be insufficient, and even if more than 1000 parts by weight is used, no further dissolution promoting effect will usually be obtained. However, since the partially decomposed product itself has surface activity, it can be used in excess depending on the purpose.

(Margin below) (e) Examples This invention is further illustrated by the following Examples and Test Examples.

will be explained in detail.

Examples 1 to 7 (Preparation of partial decomposition product of wheat gluten with alkali) 20 g of wheat gluten (reagent) manufactured by Wako Tsumugi Kogyo Co., Ltd. was dissolved separately in 0.2 to 4 g of caustic soda.
Add to 100g of aqueous solution of
Each mixture was heated and stirred separately at a temperature and time within a range of 60 minutes. These were neutralized with hydrochloric acid, and the total amount was 200 g with pure water to obtain invention products Nos. 1 to 7.

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

Examples 8 to 10 (Preparation of partially decomposed products of wheat gluten with acid) Three flasks containing 100 g of an aqueous hydrochloric acid solution corresponding to tg, 2 g, and 4 g in terms of hydrogen chloride were each given a 20g of wheat gluten (reagent) was added, and the mixture was heated and stirred at 100°C for 60 minutes. After that, it was neutralized with caustic soda and made into a total amount of 200g with pure water, and the invention No.
I got a score of 8-10.

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

Example 11 (Preparation of enzymatic partial decomposition product of wheat gluten) Example! 20g of wheat gluten used in 0. This was added to a flask containing 150 g of IN-hydrochloric acid solution to obtain an aqueous solution with a pH of 15, and 0.2 g of pepsin was added thereto and reacted at 37° C. for 90 minutes. Thereafter, the mixture was neutralized with caustic soda and added with pure water to a total amount of 200 g to obtain invention product No. 11. The average molecular weight was 60,000.

Example 12 (Preparation of partially decomposed product of wheat gluten using a reducing agent), 20 g of the wheat gluten used in Example 1 was added to 100 g of an aqueous solution in which 4 g of sodium sulfite was dissolved, and the mixture was heated at 30°C for 6 hours.
After stirring for 0 minutes, the total amount was adjusted to 200g with pure water and the invention product No.
I got 12. The average molecular weight was 79,000.

Examples 13 to 22 (Preparation of decomposition product by partial decomposition of wheat gluten with acid and subsequent partial decomposition with alkali) 10% aqueous solution of partial decomposition product of wheat gluten with acid under the same conditions as in Examples 8 to IO. Prepare 100 g of each into 8 flasks or autoclaves, add 0.5 to 2 g of caustic soda to each, and add 100 g of each to 8 flasks or autoclaves.
The mixture was heated and stirred at 00 or 150°C for 60 or 360 minutes. After that, neutralize with hydrochloric acid and rinse with pure water! Invention products Nos. 13 to 20 were obtained at 200 g. Invention product No. 21 was obtained in the same manner as above except that sodium carbonate was used instead of caustic soda. The conditions for partial decomposition with an acid are: 0.5 g of hydrochloric acid added, i'M degree 80°C, time 60 minutes, and the conditions of partial decomposition with an alkali: 0.5 g of caustic soda added.
Invention product N was prepared in the same manner as above at a temperature of 80°C and a time of 30 minutes.
o, 22 was obtained.

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

Examples 23 to 26 (Preparation of decomposed products by partial decomposition of corn gluten and soybean protein with acid and then partial decomposition with alkali) Using corn gluten manufactured by Nihon Shokuhin Kako Co., Ltd. as the raw material, the same conditions as in Examples 18 and 13. Partial decomposition was performed sequentially using acid and alkali to obtain invention product No. 23.24. The average molecular weights were 11,800 and 27,100, respectively.

In addition, an example using soybean protein obtained by defatting commercially available Yuba with acetone! Partial decomposition was performed sequentially using acid and alkali under the same conditions as No. 8 and No. 13, and Invention No. 25.2 was obtained.
I got 6.

The average molecular weights were 12,000 and 29,000, respectively.

Examples 27 and 28 (Preparation of decomposition product by partial decomposition of wheat gluten with alkali and subsequent partial decomposition with acid) Obtained by partial decomposition of wheat gluten with alkali under the same conditions as Examples 5 and 6. 10% of the partially decomposed product
An aqueous solution was prepared, and 100 g of each solution was placed in two flasks, and 0.5 g of hydrogen chloride and hydrochloric acid equivalent to Ig were added to each flask, and the mixture was heated and stirred at 100° C. for 60 minutes.

After that, neutralize with caustic soda and add pure water to a total ffi of 20.
0 g to obtain 27.28 of the invention product.

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

Example 29 (Preparation of enzymatic partial decomposition product of wheat gluten and subsequent alkali partial decomposition product) A 10% aqueous solution of enzymatic partial decomposition product of wheat gluten was prepared under the same conditions as in Example 11. Ig of caustic soda was added to 100 g of the mixture, and the mixture was heated and stirred in a flask for 60 minutes.

Thereafter, the mixture was neutralized with hydrochloric acid and purified with pure water to give a total ff of 1200 g to obtain Invention Product No. 29.

The average molecular weight was 29,000.

Example 30 (Preparation of a decomposed product by partial decomposition of wheat gluten with a reducing agent and subsequent partial decomposition with an alkali) A 10% aqueous solution of a partially decomposed product of wheat gluten with a reducing agent was prepared under the same conditions as in Example 12. , 1 g of caustic soda was added to 100 g of the mixture, and the mixture was heated and stirred at 100° C. for 60 minutes in a flask. Thereafter, the mixture was neutralized with hydrochloric acid and the total amount was adjusted to 200 g with pure water to obtain the invention product NoJO. Average molecular weight is 39
It was 500.

Example 31 (Preparation of a decomposition product by partial decomposition of wheat gluten with an alkali and subsequent partial decomposition with an enzyme (reverse order from Example 29)) A partial decomposition product of wheat gluten with an alkali under the same conditions as Example 5. A 10% aqueous solution was prepared, and the reagent hydrochloric acid was added to 100 g to obtain an aqueous solution with a pH of 1.5. This was reacted in a flask at 37° C. for 90 minutes with the addition of 0.1 g of pepsin. After that, it was neutralized with caustic soda and made into a total f3200 g with pure water.
I got 31. The average molecular weight was 245'00.

Example 32 (Preparation of decomposed product by partial decomposition of wheat gluten with alkali and subsequent partial decomposition with oxidizing agent) A 10% aqueous solution of wheat gluten partially decomposed with alkali was prepared under the same conditions as in Example 5, H to that 100g
Hydrogen peroxide solution equivalent to 0.5 g in terms of t02 was added, and the mixture was heated and stirred at 40° C. for 60 minutes. Thereafter, an amount of sodium thiosulfate (for masking hydrogen peroxide) equivalent to the remaining H2O was added, and the total amount was adjusted to 200 g with pure water to obtain Invention Product No. 32. The average molecular weight was 37,000.

Example 33 Using corn gluten manufactured by Nihon Shokuhin Kako Co., Ltd. as a raw material, partial decomposition was carried out using an alkali under the same conditions as in Example 5 to obtain Invention Product No. 33.

The average molecular weight was 25,600.

Example 34 Under the same conditions as in Example 8, 50 g of a pure aqueous solution in which 2 g of sodium sulfite (reducing agent) was dissolved was added to a long 10% aqueous solution of a partially decomposed product of wheat gluten with an acid, and the mixture was stirred at 30° C. for 60 minutes. Thereafter, the total ff was adjusted to 1200 g with pure water to obtain invention product No. 34. The average molecular weight was 53,000.

In addition, among the above invention products, the properties of the two-stage decomposition products of invention products Nos. 13 to 32 are shown in Table 5.

In the table, W on the raw material side means wheat gluten, C means corn gluten, and B means soybean protein. Note that a blank column means not measured or tested.

The following tests were conducted on the above invented product. In addition, the following comparative products Comparative product No. 1... Sucrose fatty acid ester (trade name 2 DK Ester F manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Comparative product N
o, 2... Tests were also conducted on soybean lecithin (trade name: Hounen Lecithin AY, manufactured by Hounen Oil Co., Ltd.).

Test Example Sucrose fatty acid ester [Product name manufactured by Daiichi Kogyo Seiyaku Co., Ltd.: DK Ester F-+60 (1ILB15), DK
Ester F-1'lO()ILBII)] or soybean lecithin [trade name: Hounen Lecithin AY, manufactured by Hounen Oil Co., Ltd.] 209 and a predetermined amount of the sample (powder product) are dispersed in 200 g of water or A pharmaceutical product was prepared by dissolving and spray drying.

However, the sucrose fatty acid ester was first added to a small amount of water and mixed and moistened, and then a necessary amount of water was added and heated to 60 to 80°C to dissolve or disperse it. Lecithin was dispersed in a predetermined amount of water.

In addition, a pharmaceutical product was prepared by mixing and stirring palmitic acid monoglyceride [manufactured by Taiyo Kagaku Co., Ltd.: Sunsoft No. 8001] 20y (powder product) and a predetermined amount of the test sample (powder product) in a V-type mixer. did.

Add 10 g of each formulation to a beaker containing 70°C warm water 2009, and use a magnetic stirrer to
An observation test for the solubility of the formulation was performed by stirring gently at i. The results are shown in Tables 6 to 8.

(Leaving space below) Table-6 Table-7 Table-8 Evaluation (01 Dispersed and dissolved uniformly within 1 minute ○ Dispersed and dissolved uniformly △, Slightly “clumps” occur ×・ Many “clumps” occur It is clear from this table As can be seen, the invented product has the effect of rapidly dissolving silosaccharide fatty acid ester, palmitic acid monoglyceride, and lecithin.

(F) Effects of the Invention According to the solubility promoter of the present invention, it is possible to significantly promote the dissolution and dispersion of poorly soluble surfactants such as polyhydric alcohol fatty acid ester type surfactants and lecithin in aqueous media. can.

Since the partial decomposition product of grain protein, which is an active ingredient, is food or food-like, it is very advantageous in that it is non-toxic, has improved safety as a food additive, and is inexpensive.

Therefore, the solubility promoter of the present invention is particularly useful as a solubility promoter for poorly soluble surfactants in foods.

Claims (1)

[Scope of Claims] 1. A decomposition product of grain protein with a weight average molecular weight of 5.
A dissolution promoter for a sparingly soluble surfactant, which contains a partially decomposed product having a molecular weight of 0.00 to 110,000 as an active ingredient. 2. The solubility promoter according to claim 1, wherein the grain protein is wheat gluten, corn gluten, or soybean protein. 3. Claim 1, wherein the partially decomposed product is obtained by subjecting grain protein to a decomposition treatment using one or a combination of two or more of decomposition treatments using an alkali, an acid, an enzyme, a reducing agent, or an oxidizing agent. Dissolution promoter as described. 4. The partial decomposition product is obtained by subjecting grain protein to partial decomposition treatment using one or a combination of two or more of decomposition treatment with an alkali (A) and decomposition treatment with an acid, an enzyme, a reducing agent, or an oxidizing agent (B). The solubility promoter according to claim 1, which is obtained by. 5. The solubility promoter according to claim 1, wherein the partial decomposition product is obtained by subjecting grain protein to a partial decomposition treatment using a combination of alkali decomposition treatment and acid decomposition treatment. 6. The solubility promoter according to claim 1, which has a weight average molecular weight of 500 to 50,000. 7. The solubility promoter according to claim 1, wherein the poorly soluble surfactant is a surfactant having an HLB of 16 or less. 8. The dissolution promoter according to claim 7, wherein the poorly soluble surfactant is a polyhydric alcohol fatty acid ester type surfactant or lecithin. 9. 1 to 10 parts by weight of poorly soluble surfactant
The solubility promoter according to claim 1, which is used in an amount of 0.00 parts by weight.