JPH0218124B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing an antifoaming agent for a protein-containing aqueous solution, and in particular, an antifoaming agent that can effectively eliminate foam generated when heating an aqueous protein solution extracted from soybeans, defatted soybeans, other vegetable protein-containing substances, etc. The present invention relates to a method for producing the agent. Traditionally, degraded oils such as aged tempura oil and recovered highly oxidized oils have been used as antifoaming agents to suppress the foaming that occurs when aqueous protein solutions such as bean juice are heated during tofu production. , or heat-polymerized animal and vegetable oils and fats, and processed oils with hydroxyl groups added thereto, mixed with calcium carbonate, etc. have been used. However, these fats and oils have problems in terms of toxicity due to the production of peroxides and carbonyl compounds, and are not completely satisfactory in terms of taste and odor. In addition, various silicone defoaming agents have been used in recent years, but in addition to being expensive, the amount used is equivalent to a kilogram of silicone resin.
There is a usage limit of 0.05g or less per bottle, and there are inherent problems such as certain limitations on the expression of antifoaming effects. Here, the present inventors used natural, undegraded oils and fats as a base, there are no food hygiene problems, and the addition of a small amount has an excellent antifoaming effect.
With the aim of obtaining an inexpensive antifoaming agent for food products, as a result of various studies, we focused on phospholipid (lecithin), which is a natural food additive and has useful properties, and completed the present invention. That's what I came to do. By the way, phospholipids (lecithin) are the only natural emulsifier, and in addition to emulsifying effects, they also have antioxidant effects,
It is known that it not only has water retention and dispersion effects, but also has foaming and antifoaming effects, which are seemingly contradictory effects, and antifoaming agents have already been developed using such phospholipids as a component. Although it has been disclosed in Japanese Patent Publication No. 51-22914, its effects have not yet been fully satisfactory. Therefore, as a result of repeated research in order to more effectively express the effects of phospholipids, the present inventors have adopted a manufacturing method based on new knowledge that is completely different from conventional thinking. They succeeded in obtaining an antifoaming agent that not only has an increased antifoaming effect but also has excellent durability, can be used in a small amount, and is free from food hygiene issues. That is, the present invention comprises: (a) 1 to 40% by weight of phospholipids; (b) 15 to 70% by weight of animal or vegetable oil or a mixture thereof with a natural wax substance; (c) calcium carbonate;
10-80 of calcium compounds such as calcium hydroxide
When producing an antifoaming agent by blending the phospholipid with the alkaline earth metal salt or hydroxide in a proportion of 1 to 30% by weight with respect to the phospholipid, the above formulation component ( It is characterized in that it is added to a) or a mixture of (a) and (b), heated and mixed, and then the remaining ingredients are further added and blended. As described above, in the present invention, the antifoaming agent is composed of a phospholipid as a compounding component (a), or a combination of such phospholipid and a predetermined animal or vegetable oil or a natural wax as a compounding component (b). After adding and blending a predetermined amount of alkaline earth metal salt or hydroxide to a mixture of substances (hereinafter referred to as oils and fats), the remaining ingredients are added. However, on the contrary, such phospholipids (compounding component a), oils and fats (compounding component b), calcium compounds (compounding component c)
When the above-mentioned alkaline earth metal salt or hydroxide is added and blended in the form of an aqueous solution after mixing all of the above, when the heating temperature for the mixed product is low and the stirring time is short, On the other hand, good effects cannot be obtained, such as the antifoaming effect becoming uneven and problems with sustainability.
The expected antifoaming effect is achieved by such a mixed product,
It can only be obtained by heating and mixing at a temperature of 140°C for over an hour. However, phospholipids are sensitive to temperature and rapidly become colored at temperatures above 90°C, especially above 100°C, so heating and mixing operations at high temperatures such as those described above are not recommended. If the antifoam composition is employed, the antifoam composition will take on a blackish-brown hue, which may color the product to which the antifoam agent is added or cause brown spots in such product. This leads to the contamination of the product, leading to a decrease in product value. Furthermore, excessively colored products of phospholipids are based on the polymerization of phospholipids, but there are still many unknowns about the food hygiene problems of such colored products, and they are undesirable. Furthermore, it is not a good idea from the viewpoint of oxidation of the oil and fat that is the composition, and furthermore, it is not possible to always obtain constant properties in terms of the uniformity of the antifoaming effect of the product and the sustainability of the antifoaming effect. It is. However, in the present invention, as mentioned above, a predetermined alkaline earth metal salt or hydroxide is added to the compounded component (a) or the mixture of (a) and (b) in advance in an aqueous solution or the like. The antifoaming effect of the antifoaming agent obtained therefrom can be effectively enhanced by adding the antifoaming agent in the form of an antifoaming agent and stirring and mixing it at a relatively low stirrable temperature, usually 60°C or higher. In addition, we were able to achieve excellent effects such as improving the durability and minimizing the amount of coloring. The mechanism of the excellent action and effect of the present invention has not yet been fully elucidated and is still in the realm of speculation; however,
It is likely that in the presence of water, phospholipids easily dimerize with divalent metal cations (alkaline earth metal ions), and as a result, the molecular weight of the phospholipids themselves increases, increasing their antifoaming effect. It is also speculated that some kind of synergistic effect may be induced in the antifoaming effect with fats and oils and calcium compounds. This can be accomplished by simply mixing the same compositions, or by adding an aqueous solution of a divalent alkaline earth metal salt to a mixture of phospholipids, oils, and calcium compounds, as shown in the Examples below. This can be fully accepted, even though the anti-foaming effect and duration of anti-foaming are inferior to those of the present invention when heating and mixing are performed. However, it goes without saying that the present invention is not restricted in any way by such speculation regarding the mechanism of action of the present invention. By the way, the phospholipid that is the compounded component (a) used in the present invention is usually soybean phospholipid, which is a normal viscous paste containing about 30 to 40% soybean oil. However, there is no problem in using various other phospholipids derived from animal and vegetable oils, such as egg yolk phospholipids and rapeseed phospholipids. It is also possible to use powdered phospholipids. Such phospholipids are used in an amount of 1 to 40% by weight based on the total solid content of the antifoam composition. It should be noted that if the amount of phospholipid used is less than 1% by weight, the desired antifoaming effect cannot be sufficiently exhibited, and on the other hand, the upper limit is set at about 40% by weight from the point of view of economic efficiency, etc. Become. In particular, when producing the desired antifoam composition in solid form, the amount of phospholipid used is desirably 30% by weight or less. In addition, the animal and vegetable oils used as the compounding component (b) in the present invention may be any edible natural fats and oils, but the antifoam composition according to the present invention is preferably used as a solid substance. In general, solid fats such as beef tallow, coconut oil, and palm oil, and their hydrogenated oils; liquid fats such as soybean oil, corn oil, and cottonseed oil, and hydrogenated oils that are solid at room temperature. In particular, in order to impart hardness to the target antifoam composition at room temperature, in other words to effectively solidify it, it is desirable that the melting point is 35°C or higher, preferably
It is desirable to use solid fats and oils that have a temperature of 50°C. Of course, these animal and vegetable oils and fats may be used alone or in combination. It is also possible to use a natural wax substance with a high melting point, such as beeswax or rice wax, mixed with the animal or vegetable oil or fat. When manufacturing a solid product, there is no problem in adding fats and oils that are liquid at room temperature as long as the solidity can be maintained. These oils and fats are used to give products an antifoaming effect and, if necessary, to make them solid at room temperature, and their compositions vary depending on the ratio of phospholipids to calcium compounds. ,
It is used in an amount of 15 to 70% by weight based on the total solid content of the antifoam composition. Furthermore, the calcium compound that is the compounding component (c) in the present invention includes calcium carbonate, calcium sulfate, calcium hydroxide, calcium chloride, etc., and these may be used alone or in a mixture. The proportion will be from 10 to 80% by weight based on the total solids content of the antifoam composition. In addition, if the amount of the calcium compound used is less than 10% by weight, there is a problem in that it is insufficient to impart hardness to the antifoaming agent composition and the antifoaming agent composition is suitably used as a solid substance. In addition, there is a problem in terms of antifoaming effect, and the amount used is 80%.
If it exceeds % by weight, the proportions of other components will be low, resulting in problems such as insufficient antifoaming effect and poor sustainability of the effect. In the present invention, when mixing such ingredients (a), (b), and (c), for such ingredients (a), or such ingredients (a) and ingredients, A predetermined divalent alkaline earth metal salt or its hydroxide is added and blended into the mixture of (b) in the presence of water, but such alkaline earth metal salt or its water Oxide refers to divalent metal salts or hydroxides commonly used as food additives, such as calcium carbonate, magnesium carbonate, calcium hydroxide, calcium chloride, magnesium chloride, calcium sulfate, and magnesium sulfate. One type or a mixture of several types may be used. By the way, these alkaline earth metal salts or hydroxides have a content of 1 to
It is used in a proportion of 30% by weight. If the amount used is less than 1% by weight, the antifoaming effect of phospholipids cannot be sufficiently improved, and if it exceeds 30% by weight, no increase in the antifoaming effect can be expected. However, depending on the type of alkaline earth metal salt or hydroxide, problems such as a decrease in antifoaming effect may occur. Further, the desirable amount of such alkaline earth metal salts or hydroxides to be added varies depending on the type of each metal salt or hydroxide; for example, in the case of calcium chloride, it is 2 to 8% by weight based on the phospholipid. However, in the case of magnesium sulfate, 4 to 10
The respective weight percentages were those showing the most desirable defoaming effect. Note that it is also possible to replace a part of the alkaline earth metal salt or hydroxide with a monovalent alkali metal salt or hydroxide, but if only the monovalent metal salt or hydroxide is used alone, The antifoaming effect cannot be improved compared to that of phospholipids without any additives, and therefore the addition of a divalent alkaline earth metal salt or its hydroxide according to the present invention is necessary. In addition, in order to add and blend a predetermined amount of such an alkaline earth metal salt or hydroxide into compounding component (a) or a mixture of (a) and (b) in the presence of water, generally an alkaline earth metal A method in which a salt or hydroxide is added in the form of an aqueous solution and mixed is preferably adopted, but instead of this, it is possible to add the phospholipid as the compounded component (a) or a mixture containing the phospholipid in advance. It is also possible to adopt a method in which a predetermined amount of water is added to the mixture, and then a solid alkaline earth metal salt or hydroxide is added and mixed.
When adding this alkaline earth metal salt or its hydroxide in the form of an aqueous solution, a saturated aqueous solution is generally used, but there is no problem in using a dilute aqueous solution or a supersaturated aqueous solution. do not have. Then, the compounding component (a) or (a) to which a predetermined amount of such alkaline earth metal salt or its hydroxide is added.
and (b), in order to mix them uniformly and maximize the effect of the addition of the alkaline earth metal salt or hydroxide.
Stirring is carried out under heated flow, but the heating at that time is sufficient at a temperature that allows stirring (usually 60°C or higher), and there is no need to heat the mixture to a temperature of 100°C or higher. Therefore, relatively low stirring temperatures can be employed. In addition, in the present invention, a temperature of 60°C to 80°C is generally suitably adopted as the stirring temperature, and after being heated to such a temperature to become a fluid state, the stirring temperature is about 5 minutes to 30 minutes. By stirring, each component is uniformly mixed. The composition of such an alkaline earth metal salt or hydroxide and component (a) or a mixture of (a) and (b) is subjected to vacuum drying or other operations as necessary. After dehydration is performed to obtain a composition with a predetermined moisture content, the remaining ingredients are combined, namely ingredients (b) and (c) (alkaline earth metal salt or its hydroxide in the first step). (a) is the only component to which the alkaline earth metal salt or its hydroxide is blended), or component (c) (the component (a) to which the alkaline earth metal salt or its hydroxide is blended)
and (b)) is added;
The desired antifoam composition is obtained by uniformly blending the components according to conventional methods. This antifoaming agent composition is further heated and mixed as necessary to form a powder, granule, flake, or other solid material that is easy to handle. In addition, the antifoaming agent composition according to the present invention includes:
In addition, various additives such as food emulsifiers such as glycerin fatty acid ester, propylene glycol fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester can be added as long as there is no problem. The antifoaming agent composition according to the present invention thus obtained does not pose any problems in terms of food hygiene, has excellent uniformity of antifoaming effect, especially long lasting antifoaming, and is suitable for use in soybean soup, soybean It can be suitably used as an antifoaming agent when aqueous solutions of proteins, peanuts, other vegetable proteins, milk proteins, etc. are heated. Hereinafter, some examples of the present invention will be shown to clarify the present invention more specifically, but it goes without saying that the present invention should not be interpreted in any way limited by the description of these examples. It's a good place. Note that all parts and percentages in the examples are expressed on a weight basis. Further, the defoaming effect test in each example was conducted as follows. That is,
First, raw soybeans were soaked in water at 4°C for 15 hours, then ground, and diluted with water to an amount 10 times the amount of raw soybeans to obtain an aqueous bean juice solution. Then the diameter
Put 200g of the 10-fold diluted solution (bean juice aqueous solution) into a 11.2cm 2-volume beaker, and add 0.5g to the raw soybean.
% of each antifoam composition was added, heated under constant conditions, and the lowest and highest foam heights and the duration at the lowest foam height for 3 minutes from the start of boiling were measured. This measurement was carried out five times on different days and times for the same antifoaming agent, and the average thereof was taken as the performance of the antifoaming agent. Example 1 Using paste-like soybean phospholipid as the phospholipid, 14.1 parts of it was heated to around 60°C, 0.9 parts of magnesium sulfate was added as a saturated aqueous solution, and after stirring and mixing for 30 minutes, It was dehydrated by vacuum drying method. Next, 45.0 parts of hardened beef tallow oil with a melting point of 60°C and 40.0 parts of calcium carbonate are added to the obtained mixture, and the mixture is mixed until the whole is homogeneous, then cooled and solidified, and the solidified product is pulverized. A powdered antifoam composition A was obtained. Comparative Example 1 15.0 parts of pasty soybean phospholipid, 45.0 parts of hardened beef tallow oil with a melting point of 60°C, and 40.0 parts of calcium carbonate were added in sequence, heated and mixed at a temperature of 60 to 70°C, and then cooled and solidified. The obtained solidified product was pulverized to obtain antifoam composition B. Comparative Example 2 14.1 parts of pasty soybean phospholipids were heated to around 60°C, and 0.9 parts of magnesium sulfate was added thereto in powder form, followed by stirring and mixing for 30 minutes. Next, 45.0 parts of hardened beef tallow oil with a melting point of 60°C and 40.0 parts of calcium carbonate were added thereto,
After mixing until the whole was homogeneous, the mixture was cooled and solidified, and the resulting solidified product was pulverized to obtain an antifoaming agent composition C. Comparative Example 3 14.1 parts of pasty soybean phospholipid, 45.0 parts of hardened beef tallow oil with a melting point of 60°C, and 40.0 parts of calcium carbonate were heated and mixed at a temperature of 60°C to 70°C, and then 0.9 parts of magnesium sulfate was added to the mixture. Add as a saturated aqueous solution and stir for 1 hour at a temperature of 60-70°C.
After mixing, the mixture was dehydrated and solidified by cooling. Then, antifoam composition D was obtained by pulverizing this solidified product. -Defoaming test- The results of the defoaming test performed using the defoaming agent compositions A to D obtained in Example 1 and Comparative Examples 1 to 3 above are shown in Figure 1. . FIG. 1 also shows the results when no antifoam composition was added. As is clear from the results shown in FIG. 1, compared to the case where antifoam composition A of Example 1 was used, antifoam compositions B to D of Comparative Examples 1 to 3 were However, the defoamer composition A in Example 1 according to the present invention is not only inferior in the highest foam height, but also shows a significant difference in the duration of the lowest foam height, and the antifoam composition A according to the present invention has excellent practical effects. This has been shown. Example 2 Soybean phospholipids as compounded ingredient (a) and compounded ingredients in various compounding ratios shown in Tables 1 and 2 below
An antifoam composition was produced in the same manner as in Example 1 using hardened beef tallow oil as (b), calcium carbonate as the compounded component (c), and calcium chloride or magnesium sulfate as the alkaline earth metal salt. The defoaming effect was tested using the same method as above, and the results are shown in Tables 1 and 2 below.
It is also shown in the table. As is clear from the results in Tables 1 and 2, when the antifoaming effect of each antifoaming agent composition is compared between components added in similar amounts, the lowest and highest foam heights and the lowest foam height The composition according to the invention, i.e. Nos. 1 to 11,
It is shown that the results are superior to those of Nos. 12 to 17 for comparison.

【table】

【table】 [Brief explanation of drawings]

FIG. 1 is a graph showing the antifoam test results of the antifoam compositions obtained in Example 1 and Comparative Examples 1 to 3.

Claims (1)

[Scope of Claims] 1 (a) 1 to 40% by weight of phospholipids; (b) 15 to 70% by weight of animal or vegetable oil or a mixture thereof with a natural wax substance; (c) calcium carbonate, calcium hydroxide. When producing an antifoaming agent by blending 10 to 80% by weight of a calcium compound such as A defoaming agent for a protein-containing aqueous solution, characterized in that the antifoaming agent is added to the above-mentioned compounding component (a) or a mixture of (a) and (b) in the presence of , and after heating and mixing, the remaining compounding components are further added and blended. Method of manufacturing the agent. 2. The manufacturing method according to claim 1, wherein the phospholipid is used in a proportion of 30% by weight or less, and the antifoaming agent is in solid form. 3. The manufacturing method according to claim 1 or 2, wherein the animal and vegetable oil has a high melting point of 35°C or higher. 4. The production method according to any one of claims 1 to 3, wherein the alkaline earth metal salt is calcium chloride or magnesium sulfate. 5. The method according to any one of claims 1 to 4, wherein the alkaline earth metal salt or hydroxide is added in the form of an aqueous solution.