JPH0533272B2 - - Google Patents

Description

[Detailed description of the invention]

[Technical Field of the Invention] The present invention relates to a silicone emulsion composition that has excellent dispersibility in water, dilution stability, storage stability and heat stability, and is hygienically harmless. The present invention also relates to a stable silicone emulsion composition that has excellent defoaming ability and can be added particularly to foods. [Technical background of the invention and its problems] Silicone emulsion is obtained by blending an emulsifier with oily polyorganosiloxane, that is, silicone oil (generally polydimethylsiloxane), and emulsifying it using water as a medium. . At this time, it is known that the defoaming effect can be enhanced by dispersing inorganic fine powder in polyorganosiloxane. As food-grade silicone defoaming emulsions, liquid or paste mixtures consisting of polydimethylsiloxane with a viscosity of 100 cSt or higher and finely powdered silica are known to be hygienically harmless and are not subject to extraction under the Food Sanitation Law. It has been approved to use silicone antifoam emulsions in which the viscosity of polydimethylsiloxane is 100 to 1100 cSt and the silica content is 3 to 15% by weight, based on the siloxane. Examples of emulsifiers to be added to polyorganosiloxane include glycerin fatty acid ester, glycerin lactic acid fatty acid ester, glycerin citric acid fatty acid ester, glycerin tartaric acid fatty acid ester, glycerin succinic acid fatty acid ester, polyglycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, Nonionic surfactants such as propylene glycol fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid alcohol ether, polyoxyethylene alkyl phenyl ether; alkyl sulfone Anionic surfactants such as acid salts, alkylbenzene sulfonates, and polyoxyethylene alkyl phenyl ether sulfates; and cationic surfactants such as quaternary ammonium salts are known. Among these emulsifiers, those that are safe to ingest into the body and do not cause problems when added to food include glycerin fatty acid esters and their derivatives, polyglycerin fatty acid esters, sucrose fatty acid esters, sorbitan fatty acid esters, Limited to propylene glycol fatty acid esters. Note that in the present invention, glycerin fatty acid ester does not include derivatives and condensates thereof. However, it has been extremely difficult to emulsify a mixed system of polyorganosiloxane and finely powdered silica using these alone to obtain a stable oil-in-water emulsion. For this reason, the above-mentioned emulsifiers are generally used in a mixed system of two or more types, but
As an example of a combination of these, an emulsifier made by mixing sorbitan fatty acid ester and glycerin fatty acid ester is known. However, since both are lipophilic emulsifiers, the resulting emulsions do not have sufficient stability, often increasing viscosity during storage, causing phenomena such as solidification, and It has poor dispersibility and dilution stability, and for these reasons, workability is significantly hindered when used as an antifoaming agent. Furthermore, it is known to use the mixture together with a water-soluble emulsifier such as polyoxyethylene fatty acid ester or polyoxyethylene sorbitan fatty acid ester. However, although a stable oil-in-water emulsion can be obtained using this method, all of these water-soluble emulsifiers contain polyoxyethylene in their molecules, which has an unfavorable effect on food hygiene, making them difficult to use as food additives. It is not suitable as On the other hand, there are also known cases where silicone oil was emulsified using a combination of sucrose fatty acid ester and glycerin fatty acid ester, but this emulsified silicone oil even though it did not contain fine powdered silica, which is a factor that inhibits stability. It has not yet been able to provide sufficient stability. As a countermeasure to these problems, we have developed a product with excellent storage stability and dilution stability that contains finely powdered silica and emulsifiers such as sorbitan fatty acid ester, sucrose fatty acid ester, and glycerin fatty acid ester, which can be used as food additives. A silicone emulsion has been proposed (see Japanese Patent Publication No. 7335/1983). Although this silicone emulsion has improved storage stability compared to conventional emulsions for food additives, it is more susceptible to mechanical damage under harsh storage or use conditions, such as storage or use at high temperatures of 60°C or higher. When used under high shear conditions, the stability of the emulsified state is compared to that of a silicone emulsion containing finely powdered silica emulsified with a general industrial emulsifier.
It is still insufficient. [Object of the invention] The present invention solves the above problems, contains fine powder silica, uses only emulsifiers that can be used as food additives, and is excellent even under harsh conditions such as high temperatures. The object of the present invention is to provide a silicone emulsion composition having high emulsion stability. [Structure of the Invention] The present inventor has conducted a study on an emulsifier system that can be used as a food additive and can provide a silicone emulsion that has excellent emulsion stability similar to that for general industrial use. , to a mixture consisting of polydimethylsiloxane and finely powdered silica,
A silicone emulsion composition obtained by adding an emulsifier mixture consisting of a conventionally known emulsifier for silicone oil and a polyglycerin fatty acid ester represented by the above general formula, has the following properties: It was discovered that excellent emulsion stability can be imparted, and the present invention was completed. That is, the silicone emulsion composition of the present invention includes (A) a mixture of polydimethylsiloxane and finely powdered silica: (B) 100 parts by weight (1) Formula (In the formula, R ¹ , R ² and R ³ may be the same or different between the same symbols or between different symbols, and at least one of them represents a fatty acid residue having 8 or more carbon atoms. (2) Sorbitan fatty acid ester: 10 to 70% by weight (2) Sorbitan fatty acid ester: 10 to 70% by weight (2) Sorbitan fatty acid ester
(3) A mixture of sucrose fatty acid esters with a monoester content of 60-70% by weight and a di- and/or triester content of 40-30% by weight: 10-50% by weight, and (4) an emulsifier mixture consisting of 1 to 50 parts by weight of glycerin fatty acid ester: 0 to 50% by weight, and (C) water: 30 to 600 parts by weight. Polydimethylsiloxane, one of the components (A) used in the present invention, preferably has a viscosity of 50 to 10,000 cSt at 25°C, and more preferably 50 to 10,000 cSt.
1000cSt is preferable. If the viscosity is less than 50 cSt, the defoaming effect will be poor, and if it exceeds 10,000 cSt, the stability of the emulsion obtained will be poor, thereby causing problems in actual work. Further, as the finely powdered silica which is the other component in component (A), known silica powder used in the production of silicone emulsions can be used, but it usually has a surface area of 100 to 400 m ² /g and an average Particle size 3
Preferably, ~500 μm finely powdered silica is used. The amount added is 0.5 to 20%, preferably 2 to 15%, based on the weight of polydimethylsiloxane.
%, more preferably 3 to 8%. If it is less than 0.5%, the antifoaming effect will be reduced, and if it exceeds 20%, the dispersibility will be poor, making emulsification difficult, inhibiting the stability of the composition, and reducing the antifoaming effect. The polyglycerol fatty acid ester of component (1) in component (B) used in the present invention has the formula (wherein R ¹ , R ² and R ³ and n are as described above). Component (1) is a mixture of various polyglycerin fatty acid esters having different degrees of polymerization as substantially represented by the above formula. (1) The number of carbon atoms in the fatty acid residue contained in the ingredient is 8.
The number is preferably 12 to 20, particularly from the viewpoint of emulsification performance and ease of synthesis and handling.
Examples of such fatty acid residues include octanoic acid, capric acid, lauric acid, tridecanoic acid,
Residues of saturated fatty acids such as myristic acid, palmitic acid, stearic acid, isostearic acid or arachidic acid; residues of unsaturated fatty acids such as oleic acid, linoleic acid or linolenic acid; The above can be contained. When the number of carbon atoms in these fatty acid residues is less than 8, the emulsifying power is insufficient, and it is necessary that at least one of these fatty acid residues is contained in one molecule. The average of n in the formula is represented by a number from 0 to 20. This is because if n exceeds 20, synthesis and handling become difficult. Component (1) is often used as a highly hydrophilic emulsifier among the combinations of various emulsifiers that make up component (B), so from this point of view it is preferable that the average of n is 2 or more, and is preferably 3 to 8. Moreover, as component (1), one in which n is 3 to 8 and the number of fatty acid residues is 1 or 2, particularly 1 is preferable. This means that if component (1) has such a high degree of polymerization and low degree of esterification, a stable emulsifier adsorption layer can be formed in the composition in the emulsion state, and the temperature and dilution This is because it is effective in maintaining a stable emulsified state against changes in conditions such as magnification and mechanical shearing force. Examples of such component (1) include tetraglycerin monostearate, tetraglycerin monooleate, tetraglycerin dioleate,
Pentaglycerin monomyristate, pentaglycerin monostearate, pentaglycerin monoisostearate, pentaglycerin diisostearate, hexaglycerin monolaurate, hexaglycerin monomyristate, hexaglycerin monostearate, decaglycerin monolaurate, Or decaglycerin distearate, etc. can be mentioned. The blending ratio of component (1) in component (B) is 10 to 70
% by weight, preferably 20-50% by weight. If it is less than 10% by weight, emulsification performance is poor, resulting in increased viscosity and separation of components during storage. Moreover, if it exceeds 70% by weight, the emulsification performance will be poor and a drainage phenomenon will occur at the bottom. Examples of the sorbitan fatty acid ester which is component (2) in component (B) used in the present invention include those having 1 to 3 fatty acid residues having 12 or more carbon atoms in the molecule. Examples of such fatty acid residues include lauric acid, myristic acid,
Mention may be made of fatty acid residues such as palmitic acid, stearic acid or oleic acid. The blending ratio of component (2) in component (B) is 10 to 70
% by weight, preferably 20-50% by weight. If the blending ratio is less than 10% by weight, it will be difficult to emulsify the silicone oil, and if it exceeds 70% by weight, the stability of the emulsion obtained will deteriorate, resulting in layer separation of the emulsion or an increase in viscosity. It may also cause solidification. Examples of the sucrose fatty acid ester which is component (3) in component (B) used in the present invention include those having a fatty acid residue having 12 or more carbon atoms in the molecule. Such fatty acid residues include, for example, fatty acid residues such as lauric acid, myristic acid, palmitic acid, stearic acid or oleic acid. In addition, this (3) component is
From the viewpoint of defoaming effect and stability, the mixture contains 60 to 70% by weight of monoester and 40 to 30% by weight of di- and/or triester. The blending ratio of component (3) in component (B) is 10 to 50
% by weight, preferably 10-30% by weight. If the blending ratio exceeds 50% by weight, layer separation of the emulsion will occur, which is not preferable. Examples of the glycerin fatty acid ester that is component (4) in component (B) used in the present invention include those having 1 to 2 fatty acid residues having 12 or more carbon atoms in the molecule. Such fatty acid residues include residues of fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid or oleic acid. The proportion of component (4) in component (B) is 0 to 50% by weight, preferably 5 to 30% by weight. If the blending ratio exceeds 50% by weight, the stability of the resulting emulsion will deteriorate, resulting in layer separation of the emulsion, increased viscosity, and even solidification. Although component (4) in component (B) is not necessarily required,
By adding this, the heating stability of the resulting emulsion can be further improved. Component (B), which is an emulsifier mixture, can be obtained by mixing predetermined amounts of components (1) to (4) described above. The blending ratio of component (B) in the composition of the present invention is:
The amount is 1 to 50 parts by weight per 100 parts by weight of component (A).
If the blending ratio is less than 1 part by weight, a stable emulsion cannot be obtained, and if it exceeds 50 parts by weight, it may lead to increased viscosity and deterioration of dispersibility.
Moreover, a sufficient defoaming effect cannot be obtained. There is no need for any special water as component (c) used in the present invention, and the mixing ratio in the composition is 30 to 600 parts by weight, preferably 30 to 600 parts by weight, per 100 parts by weight of component (A).
60 to 250 parts by weight. If the blending ratio is outside the above range, the stability of the emulsion over time will deteriorate. In addition to components (A) to (c), natural or synthetic thickeners may be added to the composition of the present invention for the purpose of further increasing stability. Examples of natural thickening agents include locust bean gum, guar gum, starches, tamarind seed polysaccharides, and carrageenan. Examples of synthetic thickeners include sodium alginate, propylene glycol alginate, sodium cellulose glycolate, sodium starch glycolate, sodium polyacrylate and methylcellulose. The composition of the present invention includes, for example, a predetermined amount of component (A).
Add component (B), stir and mix while heating if necessary, then add component (c) at approximately the same temperature, continue stirring and mixing, and use a colloid mill or homogenizer as necessary. It can be produced by forming a uniform emulsion using an emulsifying device such as the following. [Examples of the Invention] Hereinafter, the present invention will be further explained in detail by presenting Examples and Comparative Examples. Examples 1 and 2 and Comparative Examples 1 and 2 6 parts of finely powdered silica was blended with 94 parts of polydimethylsiloxane having a viscosity of 350 cSt at 25°C and mixed in a kneader to prepare a uniform silicone oil paste. This was transferred to a mixing tank equipped with a stirrer and a heating and cooling jacket, and component (B) having the composition shown in Table 1 was mixed therein, and heated at 65 to 70°C while stirring.
The mixture was heated and mixed for 1 hour. Thereafter, the amount of component (c) shown in Table 1 heated to the same temperature was added, and stirring was continued while cooling to obtain a mixture. This is done with a mill spacing of 10 mils, an inlet temperature of 30-35℃, and an outlet temperature of 35-40℃.
A uniform emulsion composition was obtained by passing it through a colloid mill under the following conditions. In addition, sucrose stearate in Table 1 is as follows:
70% by weight of monoesters and 30% di- and triesters
A mixture of % by weight was used. Furthermore, all amounts of each component are expressed in parts by weight.

[Table] The following tests were conducted using each of the compositions thus obtained. (1) Each composition was placed in a 250 ml glass bottle, the bottle was tightly capped, and the bottle was left standing in a constant temperature bath at 25°C and 45°C, and changes in the emulsion over time were observed. (2) In a 300ml beaker, 20g of each composition and 180g
of water, rotated at constant speed with a magnetic stirrer for 3 minutes, and left to stand for 10 minutes, and then observed the dispersion state (dispersibility). Then these beakers
After leaving it in a 100℃ water bath, remove it from the water bath,
The state was observed after cooling to room temperature (heating stability). Next, these samples were passed through a 50-mesh wire mesh, and the gel-like emulsion destruction material remaining in the wire mesh and beaker was weighed to measure the residual amount of the emulsion after heating (excess heating residual amount). (3) Check the emulsification state of the emulsion using an optical microscope.
The emulsion was observed under twice the magnification, and the average particle diameter of the emulsion was measured. The results of each of these tests are summarized in Table 2.

[Table] Considering the test results shown in Table 2, the composition of Comparative Example 2 is an emulsion emulsified with sorbitan monostearate and sucrose stearate, but this has a large particle size. Therefore, the state changes greatly due to dilution or heating, and the stability is poor. The composition of Comparative Example 1 was obtained by further adding glycerin monostearate to the composition of Comparative Example 2, and the particle size was reduced and the storage stability and dispersibility were improved to the extent that there were almost no problems in practical use. However, part of the emulsion was destroyed when a heat stability test was conducted, and an increase in viscosity was also observed during a storage stability test. Each of the compositions of Examples 1 and 2 showed good storage stability, dispersibility, and heating stability. In particular, the composition of Example 2, which used four types of emulsifiers, had a small particle size and was resistant to heating. There is little excess leftover,
The best results are obtained. From the above results, it is possible to obtain an aqueous emulsion from a mixture of polydimethylsiloxane and finely powdered silica by using a mixed system of polyglycerin fatty acid ester and sorbitan fatty acid ester, which are safe emulsifiers from a food hygiene perspective. It is possible to obtain an emulsion with superior heat stability than when using the system, and in addition to this, sucrose fatty acid ester or glycerin fatty acid ester,
It has become clear that even better stability is exhibited when both are preferably used in combination. Examples 3 to 6 4 parts of finely powdered silica was blended with 96 parts of polydimethylsiloxane having a viscosity of 1000 cSt at 25°C, heated and mixed at 140°C for 3 hours with stirring, and then cooled to prepare a silicone oil paste. Using this, components (B) and (c) having the composition shown in Table 3 were blended in the same manner as in Example 1 to obtain a uniform emulsion composition. In Table 3, sucrose palmitate and sucrose oleate are 60% by weight of monoester and 40% by weight of di- and triester, respectively.
A mixture of was used. Furthermore, all amounts of each component in Table 3 are expressed in parts by weight. Comparative Example 3 Monoester as sucrose palmitate ester
The emulsion composition shown in Table 3 was obtained in the same manner as in Example 6, except that a mixture of 50% by weight and 50% by weight of di- and triester was used.

【table】

[Table] Using each of the compositions thus obtained, the same tests as in Example 1 were conducted. However, test (1)
The test was carried out in a constant temperature bath at 50°C. The results are shown in Table 4. From the results shown in Table 4, the composition of Comparative Example 3 using a sucrose fatty acid ester outside the range specified by the present invention had a relatively large emulsion particle size;
It can be seen that the heating stability is poor.

[Table] [Effects of the Invention] The composition of the present invention is not only hygienically harmless when added to foods, but also has excellent dispersibility in water and dilution stability. That is, even when the emulsion composition of the present invention is diluted 10 to 20 times with water, it remains stable as a homogeneous emulsion and does not cause separation. Furthermore, this diluted emulsion composition does not cause the emulsion to separate when heated or when mechanical shearing force is applied.
It cannot be destroyed. Furthermore, even when the composition of the present invention is stored for 6 to 12 months, no increase in viscosity is observed, and no separation or other changes in state are observed. The composition of the present invention is widely used as a general industrial antifoaming agent, but is particularly useful as a food additive antifoaming agent.

Claims (1)

[Claims] 1 (A) A mixture consisting of polydimethylsiloxane and finely powdered silica: 100 parts by weight (B) (1) Formula (In the formula, R ¹ , R ² and R ³ may be the same or different between the same symbols or between different symbols, and at least one of them represents a fatty acid residue having 8 or more carbon atoms. , all other than the fatty acid residues represent hydrogen atoms, and n represents a number from 0 to 20 on average):
10-70% by weight, (2) Sorbitan fatty acid ester:
(3) A sucrose fatty acid ester whose monoester content is 60 to 70% by weight and di- and/or
Or a mixture with a triester content of 40-30% by weight: 10-50% by weight, and (4) an emulsifier mixture consisting of 0-50% by weight of glycerin fatty acid ester: 1-50 parts by weight, and (C) water: 30-50% by weight. A silicone emulsion composition comprising 600 parts by weight. 2. The composition according to claim 1, wherein component (1) in component (B) is a polyglycerin fatty acid monoester. 3 The number of carbon atoms in the fatty acid residue of component (1) in component (B) is 12 or more
20. The composition according to claim 1, wherein the composition is 4. The composition according to claim 1, wherein n of component (1) in component (B) is 3 to 8. 5. The composition according to claim 1, wherein the proportion of component (1) in component (B) is 20 to 50% by weight. 6. The composition according to claim 1, wherein the proportion of component (2) in component (B) is 20 to 50% by weight. 7. The composition according to claim 1, wherein the proportion of component (3) in component (B) is 10 to 30% by weight. 8. The composition according to claim 1, wherein the proportion of component (4) in component (B) is 5 to 30% by weight.