JPH0430417B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention provides a silicone emulsion, particularly a silicone emulsion having excellent storage stability, water dispersibility and dilution stability.
It relates to a hygienically harmless silicone emulsion which can also be used as a food antifoaming agent. (Prior Art) A silicone emulsion for antifoaming is obtained by emulsifying a silicone oil compound in which finely divided inorganic fillers such as finely divided silica, titanium dioxide, aluminum oxide, etc. are dispersed in silicone oil. It is well known that defoaming emulsions for food use are hygienically harmless emulsified liquid or paste silicone oil compounds consisting of dimethylpolysiloxane with a viscosity of 100 cS or more and finely powdered silica. The extracted dimethylpolysiloxane has a viscosity of 100 to 1100 cS and a silica content of 3 to 15% by weight.
The use of silicone oil compounds is permitted. Furthermore, the emulsifier used to emulsify this silicone oil compound to create a defoaming emulsion for food must be hygienically safe even if ingested into the body, and must be approved for addition to food. Yes, these are limited to glycerin fatty acid esters, sorbitan fatty acid esters, sucrose fatty acid esters, and propylene glycol fatty acid esters, but it is extremely difficult to obtain stable emulsions from dimethyl silicone oil compounds when these are used alone. It is customary to use a combination of these and to stabilize the emulsion by adjusting the viscosity by using a large amount of emulsifier or adding various thickeners. That is, a mixture of sorbitan fatty acid ester and glycerin fatty acid ester is widely used as an emulsifier for silicone defoaming emulsion for food additives, but in the emulsion obtained from this mixture, all of these emulsifiers are lipophilic. Because of this, it has poor stability, causing separation during storage and increased viscosity, and poor water dispersibility and dilution stability, which significantly impairs its workability as an antifoaming agent. The method of using propylene glycol in combination with the combination of sorbitan fatty acid ester and glycerin fatty acid ester, which was proposed to solve the problem (see Japanese Patent Application Laid-open No. 51-2688), still has satisfactory storage stability and dispersibility. It does not give In addition, an emulsifier is used in which a sucrose fatty acid ester hybrid having a monoester content of 50 to 80% by weight and a di- and/or triester content of 50 to 20% by weight is added to a combination of sorbitan fatty acid ester and glycerin fatty acid ester. A method has also been proposed (see Japanese Patent Publication No. 58-7335), but this method aims to stabilize the system by making the sucrose fatty acid ester act as a hydrophilic protective colloid rather than as a hydrophilic emulsifier. If used in the same way as an emulsifier, it would not be able to demonstrate its performance, and there is a disadvantage in the process that it must be dispersed in water before being added.
Furthermore, this composition has the disadvantage that a satisfactory effect of defoaming of animal proteins and defoaming of vegetable proteins cannot be obtained. Regarding the production method of this type of defoaming emulsion, it is known that a lipophilic emulsifier and a hydrophilic emulsifier are used together, but an emulsifier containing a polyoxyethylene group in its molecule to impart hydrophilicity is used. This emulsion has the disadvantage that it is unsuitable for use as a food additive because it is not sanitary. (Structure of the Invention) The present invention relates to a silicone emulsion that solves the above-mentioned disadvantages.
(a) General formula (Here, R is a hydrogen atom or a fatty acid residue, at least one fatty acid residue having 12 to 18 carbon atoms, n = 3 to 12, and the number of R groups is 7 to 16), and esterification (b) 10 to 70% by weight of polyglycerol fatty acid esters with a ratio of 50% or less; (b) 10 to 70% by weight of monoglycerol esters of fatty acids having 12 to 18 carbon atoms; (c) sorbitan esters of fatty acids having 12 to 18 carbon atoms; 10~70
1 to 80 parts by weight of an emulsifier consisting of % by weight,
It is characterized by being emulsified in water. That is, the present inventors conducted various studies on silicone emulsion, which is considered to be an antifoaming agent for foods that has good storage stability, dilution stability, and water dispersibility, and found that it consists of dimethylpolysiloxane and finely powdered silica. As an emulsifier for emulsifying a known silicone oil compound, when the three types described above, (a) polyglycerin fatty acid ester, (b) fatty acid monoglycerin ester, and (c) fatty acid sorbitan ester, are used in combination, (a) The polyglycerin ester shown has a degree of esterification of 50% or less of the total number of hydroxyl groups in the polyglycerin, and has a large number (n+4/2 or more) of hydroxyl groups in the molecule, making it hydrophilic, and when used in combination with a lipophilic emulsifier. Because the emulsifying effect is further enhanced, a stable emulsion with extremely low viscosity can be obtained even with a small amount of emulsifier, and even if this product is stored for 2 to 3 months, no increase in viscosity is observed, and there is no separation or other state change. In addition, we discovered that this emulsion has excellent water dispersibility and dilution stability, and that this emulsion is hygienically harmless even when added to food, and furthermore, it requires only a small amount of emulsifier. Antifoaming silicone emulsions for food use, which have superior foam suppression and foam breaking properties compared to conventional products, can be produced industrially and advantageously, especially for animal and vegetable proteins, which have the most foaming problems in the food industry. The present invention was completed by conducting research on the types of emulsifier components to be used and how to combine them. The silicone oil compound as component (a) forming the emulsion of the present invention is a paste-like compound obtained by adding finely powdered silica to dimethylpolysiloxane oil and appropriately heat-treating the mixture.
This may be any known material conventionally used in the production of silicone defoaming emulsions. If the viscosity of this dimethylpolysiloxane is lower than 100 cS, the antifoaming effect will decrease, and if it is higher than 10,000 cS, the workability will deteriorate and the stability of the emulsion will also deteriorate. It is said to be in the range of ~1000cS. In addition, this fine powder silica may have a specific surface area of 100 to 400 m ² /g and a particle size of 5 to 500 mμ, which is commonly used, and the blending amount is 0.5 parts by weight per 100 parts by weight of dimethylpolysiloxane. If the amount is less than 50 parts by weight, the defoaming effect will decrease, and if it is more than 50 parts by weight, the dispersibility will deteriorate and emulsification will become difficult. On the other hand, the emulsifier used to emulsify this dimethyl silicone oil compound is said to be a mixture of (a), (b), and (c) described above, but the polyglycerin fatty acid ester as component (a) is generally formula R is a hydrogen atom or a fatty acid residue, and at least one is a fatty acid residue of a fatty acid having 12 to 18 carbon atoms selected from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, etc. However, in terms of emulsifying power, antifoaming property, and stability, the degree of condensation n is 3 to 12, and it is an esterified product of 1 mol of polyglycerin and 1 to 7 mol of the above fatty acids, In addition, the degree of esterification of fatty acids is 50% of the total number of hydroxyl groups in polyglycerin.
The following are required. Polyglycerin ester as a hydrophilic emulsifier produces an emulsion that is extremely stable and has good dispersibility when used in combination with other lipophilic emulsifiers, and is therefore presumed to fully exhibit the defoaming performance of silicone oil compounds. Therefore, in order to satisfy this condition, if the condensation degree n of polyglycerin is less than 3, it will not be able to impart sufficient hydrophilicity and the emulsifying power will be insufficient, and if n is 12 or more, the viscosity will become high and it will be difficult to handle. However, the degree of esterification of fatty acids is limited by the total number of hydroxyl groups in polyglycerin.
If it exceeds 50%, the number of hydrophilic groups increases and the HLB becomes low, and the polyglycerol fatty acid ester's intended function as a hydrophilic emulsifier is not fully demonstrated, resulting in poor emulsion stability and quenching. Foam performance also deteriorates. Specific examples of such emulsifiers include pentaglyceryl monostearate, pentaglyceryl dilaurate, pentaglyceryl monooleate, hexaglyceryl dipalmitate, octaglyceryl tristearate, octaglycerine tetralaurate, and decaglyceryl monooleate. , decaglycerin distearate, decaglycerin pentaoleate, undecaglycerin penstearate, tridecaglycerin pentalaurate, tetradecaglycerin pentalaurate, etc., which account for the total emulsifier amount of this polyglycerin fatty acid ester. If the proportion is less than 10% by weight, its performance as a hydrophilic emulsifier will not be fully demonstrated, and if it is more than 70% by weight, it will be difficult to emulsify the emulsion, and its stability will deteriorate, causing layer separation.
It needs to be 10-70% by weight. The monoglycerin fatty acid ester as component (b) constituting this emulsifier contains fatty acid residues of fatty acids with 12 to 18 carbon atoms selected from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, etc. in its molecule. These include glycerin monostearate, glycerin monolaurate, glycerin monopalmitate, glycerin dioleate, glycerin dilaurate,
Examples include glycerin tristearate.
Note that if the proportion of this glycerin fatty acid ester in the total amount of emulsifier is less than 100% by weight, its performance as a lipophilic emulsifier will not be fully demonstrated, and if it is more than 70% by weight, the lipophilicity will be too strong and silicone oil Since it becomes difficult to emulsify the compound and the stability of the emulsion deteriorates, resulting in layer separation and increased viscosity, it is necessary to keep the amount in the range of 10 to 17% by weight. In addition, the sorbitan fatty acid ester, which is the component (c) of this emulsifier, has fatty acid residues of fatty acids with 12 to 18 carbon atoms selected from lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, etc. in its molecule. These include sorbitan monostearate, sorbitan monolaurate,
Examples include sorbitan monopalmitate, sorbitan monooleate, sorbitan dipalmitate, sorbitan dilaurate, and sorbitan tristearate. If the proportion of this sorbitan fatty acid ester in the total amount of emulsifier is less than 10% by weight, its performance as a lipophilic emulsifier will not be fully exhibited, making it difficult to emulsify the silicone oil compound. If this happens, the stability of the emulsion may deteriorate and layer separation may occur, or the viscosity may increase and solidify.
It should be in the range of ~70% by weight. The emulsion of the present invention is obtained by emulsifying the dimethyl silicone oil compound as component (a) in water using a mixture of a predetermined amount of the three emulsifiers (a), (b), and (c) described above. However, this amount of emulsifier is
If the amount is less than 1 part by weight per 100 parts by weight, it will be difficult to emulsify and a stable emulsion will not be obtained. If it is more than 80 parts by weight, the emulsion will be stabilized, but the viscosity will become high and the antifoaming effect will not be sufficient. Therefore, it is necessary to set the amount in the range of 1 to 80 parts by weight. This emulsification is carried out by adding a predetermined amount of an emulsifier composition containing the emulsifiers (a), (b), and (c) mentioned above to the dimethylpolysiloxane compound, adding water to the dimethylpolysiloxane compound, and emulsifying it using a homomixer, colloid mill, etc. This may be carried out using a dispersing machine, and water may be further added to the homogeneous mixture obtained thereby to form an emulsion having the desired concentration. In order to improve the stability of the emulsion, protective colloids such as starch, polysaccharides, sucrose, natural cellulose, cyclodextrin, guar gum, and locust bee gum, sodium cellulose glycolate, sodium alginate, and alginic acid are added to the emulsification process to improve the stability of the emulsion. propylene glycol ester,
It is optional to add synthetic thickeners such as sucrose fatty acid ester, sodium starch glycolate, sodium polyacrylate, and methylcellulose. Next, examples of the present invention will be given, and all parts in the examples indicate parts by weight. Example 1 (Preparation of sample) A silicone oil compound was prepared by mixing 8 parts of finely powdered silica Nipsil-LP (trade name, manufactured by Nippon Silica Co., Ltd.) with 92 parts of dimethylpolysiloxane having a viscosity of 1000 cS at 25°C. Various emulsifiers shown in Table 1 were added thereto in the proportions shown in Table 1, and after uniformly dispersing with a homomixer, water was gradually added to emulsify to prepare samples A to H. Samples A to E show examples according to the present invention, and samples F to H show comparative examples. In the table, as the emulsifier (a) component, hexaglyceryl monostearate, octaglyceryl monostearate, The esterification rates of decaglyceryl monostearate are 12.5%, 10.0%, and 8.3%, respectively, and the sucrose fatty acid ester is stearic acid with an ester composition of 50% by weight monoester and 50% by weight ditriester. It is a fatty acid ester consisting of palmitic acid and palmitic acid. (Separation stability test of emulsion) 100 g of each of the above samples A to H was put into a glass bottle with a stopper, the bottle was tightly stoppered, and the emulsion was left standing in a constant temperature bath at 40°C to observe the change over time of the emulsion. The results are shown in Table 1. (Dispersibility test in water) When 10 g of each sample was dropped into 90 g of water and the dispersion state was observed, the results were as shown in Table 1. (Defoaming test using anionic foaming liquid) After weighing 100ml of a 0.2% aqueous solution of sodium oleate into a measuring cylinder with an internal volume of 1000ml, 0.2ml of each of the above samples was added to it, and then passed through a glass ball filter. When air was continuously introduced at a rate of 1/min to examine the change over time in the amount of foaming, the results shown in Table 2 were obtained. (Defoaming test using animal protein) After weighing 200 g of a foaming liquid consisting of 66 g of whole eggs, 6 g of soybean oil, and 128 g of water into a measuring cylinder with an internal volume of 1000 ml, 250 ppm of each of the above samples was added to it, and then When air was introduced continuously at a rate of 1/min through a glass ball filter and the change in foaming amount over time was examined, the third
The results shown in the table were obtained. (Defoaming test using animal protein) After weighing 200 g of a foaming liquid consisting of 66 g of whole eggs, 6 g of soybean oil, and 128 g of water into a graduated cylinder with an internal volume of 1000 ml, 500 ppm of each of the above samples was added to it, and then this was stirred at high speed with a hand mixer for 10 minutes, left to stand for 5 minutes, placed in a defoamer, degassed under reduced pressure at -200 mmHg, and examined the change in foam height over time. The results shown in the table were obtained.

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[Table] Example 2 A silicone oil compound was prepared by mixing 90 parts of dimethylpolysiloxane with a viscosity of 500 cS at 25°C with 10 parts of the finely powdered silica used in Example 1, and added to the mixture shown in Table 5. After adding various emulsifiers in proportions and uniformly dispersing them with a homomixer,
Water was gradually added to emulsify and samples I to P were prepared. Note that samples I to M show examples according to the present invention, and samples N to P show comparative examples.
The degrees of esterification of decaglycerin monooleate, decaglycerin dioleate, decaglycerin trioleate, and decaglycerin tetraoleate as components of emulsifier (a) in the table are respectively
8.3%, 16.7%, 25.0%, and 33.3%, and the sucrose fatty acid ester is the same as that used in Example 1. Next, the viscosity of these samples I to P at 12 rpm was measured using a BM type rotational viscometer and the change over time was investigated. When the dispersibility and defoaming properties in water were examined, the results shown in Tables 6 and 7 were obtained.

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Claims (1)

[Claims] 1 (a) Silicone oil compound consisting of dimethylpolysiloxane and finely powdered silica
100 parts by weight (b) (a) General formula (R is a hydrogen atom or a fatty acid residue,
At least one fatty acid residue has 12 to 18 carbon atoms, n = 3 to 12, and the number of R groups is 7 to 16)
Polyglycerin fatty acid ester with an esterification rate of 50% or less 10-70% by weight (b) Monoglycerin ester of fatty acid with 12-18 carbon atoms 10-70% by weight (c) Polyglycerin fatty acid ester with 12-18 carbon atoms 1. A silicone emulsion comprising 1 to 80 parts by weight of an emulsifier consisting of 10 to 70% by weight of a sorbitan ester of a fatty acid, and emulsified in water. 2. Claim 1, wherein the fine powder silica has a specific surface area of 100 to 400 m ² /g and a particle size of 5 to 500 mμ.
Silicone emulsion as described in Section. 3. The silicone emulsion according to claim 1, wherein the polyglycerin fatty acid ester is polyglycerin palmitate, polyglycerin laurate, polyglycerin oleate, or polyglycerin stearate. 4. A patent claim in which the polyglycerin fatty acid ester is an esterified product of 1 mole of polyglycerin and 1 to 7 moles of a fatty acid having 12 to 18 carbon atoms, and the degree of esterification is 50% or less of the total hydroxyl groups of the polyglycerin. A silicone emulsion according to scope 1. 5 The monoglycerin ester is monoglycerin palmitate, monoglycerin laurate, monoglycerin oleate,
The silicone emulsion according to claim 1, which is a monoglycerol stearate. 6. The silicone emulsion according to claim 1, wherein the sorbitan ester is sorbitan palmitate, sorbitan oleate, or sorbitan stearate.