JP3570071B2 - Emulsifier composition and emulsion - Google Patents

Description

【００２９】
【表２】

【００３０】
上述の表１、表２より、純度が８０モル％以上の脂肪酸乳酸エステル塩（脂肪酸の炭素数１４〜２２の範囲内）を、脂肪酸乳酸エステル塩およびショ糖脂肪酸エステル（脂肪酸の炭素数１４〜２２の範囲内）とのモル数の総和に対する脂肪酸乳酸エステル塩のモル分率が０．００８〜０．１５なる配合比としたとき著しく乳化安定性が向上し、好ましい乳化物が得られることが示された。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to an emulsifier composition which is safe, has no coloring or odor, is easy to disperse, and has an excellent emulsion stabilizing effect, and an emulsion using the same.
[0002]
[Prior art]
Emulsions are used in a wide range of technical fields such as foods, cosmetics, pharmaceuticals, building materials, paints, and the like. Emulsification is a method in which one of water and oil, which are not originally mixed, is made into fine droplets and the other is dispersed uniformly in a medium with a continuous phase. There is a strong need in the field. In particular, cosmetics and pharmaceuticals that may be used in contact with the mucous membranes and skin of the human body, and foods to be ingested orally, are required to have an emulsifier that is safe, less irritating, has high emulsifying ability, and is easy to use. I have.
[0003]
However, in reality, conventional emulsifiers do not always sufficiently satisfy such requirements. For example, nonionic surfactants such as glycerin fatty acid esters and polyoxyethylene alkylene ethers are highly safe and gentle on the human body, but may have insufficient emulsifying ability.On the other hand, fatty acid soaps, ether carboxylic acids and salts thereof Although ionic surfactants such as alkane sulfonates, dialkyl sulfosuccinic acids, higher alcohols, alkylamine acids and alkanolamine fatty acid derivatives have high emulsifying ability, they have problems in safety and gentleness to the human body.
[0004]
Under such circumstances, various attempts have been made to satisfy a wide range of safety, mildness, emulsifying ability and the like by blending a plurality of emulsifiers. For example, in JP-A-5-246821 and JP-A-7-25724, an emulsified composition having high water resistance of a coating film is obtained by combining an ionic surfactant represented by a sucrose fatty acid diester and a soap. are doing. JP-A-5-246821 provides an emulsion composition having a similarly high water resistance by combining a polyglycerin fatty acid ester and a fatty acid lactic acid ester salt.
[0005]
In addition, in fields other than emulsification, several attempts to improve the function by blending a plurality of emulsifiers have been reported. JP-A-62-65646, JP-A-6-225684, JP-A-6-181701 and JP-A-5-161446 disclose various food emulsifiers containing a sucrose fatty acid ester and a fatty acid lactic acid ester salt. And other substances in combination to improve the quality and process of flour foods. In Japanese Patent Application Laid-Open No. 7-173045, skin treatment properties are developed by combining a sucrose fatty acid ester and a fatty acid lactic acid ester salt.
However, these techniques are directed to a specific system, for example, a cosmetic having high water repellency and the like, and their use is limited to a specific field and lacks versatility. Further, in the prior art, the purity of the emulsifier and the compounding ratio were not examined at all, and there were cases where coloring and odor were present.
[0006]
That is, conventionally, a fatty acid lactic acid ester salt reacts a reactive derivative such as a fatty acid or a fatty acid chloride with lactic acid or a lactate to produce a fatty acid lactic acid ester, and reacts this with a basic substance. It was used for the purpose. This is presumably because no industrially applicable method for purifying the fatty acid lactate ester salt was known, and the effect of coexisting substances on the fatty acid lactate ester salt was not sufficiently elucidated. Actually, there is a problem that such a fatty acid lactate ester reaction mixture has insufficient emulsifying power as compared with a high-purity fatty acid lactate ester salt.
In addition, the reaction mixture of the fatty acid lactic acid ester salt is often accompanied by coloring and caramel odor, and not only in an aqueous solution but also in a product using the same, undesirably affecting the appearance and odor was also a major problem. .
[0007]
[Problems to be solved by the invention]
Under such circumstances, the present invention is versatile, safe, gentle on the human body, free of coloring and odor, easy to disperse, has no unnecessary foaming at the time of homogenization, and is more emulsion stable. An object of the present invention is to provide an emulsifier composition having an excellent emulsifying effect and an emulsion using the same.
[0008]
[Means for Solving the Problems]
As a result of repeated studies to achieve the above object, the use of a fatty acid lactate ester salt and a sucrose fatty acid ester having a specific fatty acid chain length of a purity of 80 mol% or more in combination at a specific ratio provides high safety. An emulsifier composition that is not irritating to the human body and has excellent emulsification stability, has excellent dispersibility in oil or water, has no unnecessary or foaming at the time of homogenization, has no appearance of coloring or odor, and It led to the discovery of an emulsion.
[0009]
That is, the gist of the present invention is an emulsifier composition containing a fatty acid lactate ester salt having a purity of 80 mol% or more and a sucrose fatty acid ester, wherein the constituent fatty acids of the fatty acid lactate ester salt are fatty acids having 14 to 22 carbon atoms, The constituent fatty acids of the sucrose fatty acid ester are fatty acids having 14 to 22 carbon atoms, and the mole fraction of the fatty acid lactate ester salt relative to the total number of moles of the fatty acid lactate ester salt and the sucrose fatty acid ester is 0.008 to 0. 15, wherein the fatty acid lactic acid ester salt is obtained by reacting the fatty acid lactic acid ester with a basic substance at a molar ratio of 1 / 0.7 to 1 / 1.3. An emulsifier composition and an emulsion containing 0.01 to 60% by weight thereof.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
Hereinafter, the present invention will be described in detail.
As the fatty acid constituting the fatty acid lactic acid ester salt used in the present invention, a fatty acid having 14 to 22, preferably 14 to 18, and more preferably 16 to 18 carbon atoms is used. If the fatty acid chain length is shorter than this range, the affinity of the lipophilic portion with the oil is weak, so that the emulsion stability is deteriorated, and remarkable foaming may occur during emulsification, which is not preferable. Further, if the fatty acid chain length is longer than this range, the crystallinity of the emulsifier itself is too high, and the lipophilic portion is less likely to be compatible with the oil, and the emulsion stability is deteriorated as in the case where it is too short. Moreover, it is not preferable because it is difficult to obtain raw materials.
[0011]
If the number of carbon atoms is within the above range, the fatty acid may be saturated or unsaturated, and may be linear or branched. In the case of a branched chain, the length of the longest chain is preferably at least 8 carbon atoms, more preferably at least 10 carbon atoms. In some cases, a hydroxyl carboxylic acid having a hydroxyl group may be used. These fatty acids include myristic acid, palmitic acid, stearic acid, arachiic acid, behenic acid, tetradecenoic acid, hexadecenoic acid, octadecene acid (oleic acid, elaidic acid, etc.), octadecadienoic acid (linoleic acid, etc.), octadeca Trienoic acid (such as linolenic acid), eicosenoic acid, eicosatetraenoic acid (arachidonic acid), docosenoic acid (erucic acid), isostearic acid, hexyldecanoic acid, hexylundecanoic acid, octyldecanoic acid, hydroxytetradecanoic acid, hydroxyhexadecanoic acid, And hydroxyoctadecanoic acid.
[0012]
Among these, palmitic acid, stearic acid, etc. are particularly preferred because they have excellent emulsifying performance and are easily available. In the fatty acid lactic acid ester salt, these fatty acids may be a mixture of two or more kinds in an arbitrary ratio.
Lactic acid in the fatty acid lactic acid ester salt may be produced by either a fermentation method or a synthesis method, and D-form and L-form are not limited.
The method for obtaining a fatty acid lactic acid ester or a salt thereof having a purity of 80 mol% or more is not particularly limited, and any method may be used. An example is a method for purifying a reaction product by a known production method by some means.
The fatty acid lactic acid ester salt is usually obtained by reacting a fatty acid or a reactive derivative such as a fatty acid chloride, a fatty acid salt or a fatty acid ester with lactic acid or lactate. The reaction is usually performed at a temperature of 100 to 250 ° C. for 2 to 10 hours, and can be performed in the presence or absence of a solvent. In particular, when a fatty acid chloride is used in a basic solvent, the reaction can be performed at 10 to 90 ° C. for 1 to 3 hours.
[0013]
The reaction solution of fatty acid lactic acid ester or its salt produced by a known method includes, in addition to fatty acid lactic acid ester or its salt, unreacted fatty acid or its salt, lactic acid or its salt, polylactic acid or its salt, When a lactic acid ester or a salt thereof and a solvent are used, a solvent is further present. They are often colored or have a certain smell. At this time, the content of the desired fatty acid lactate ester or its salt in the reaction product excluding the solvent varies depending on the ratio of the fatty acid and the lactic acid subjected to the reaction, but the fatty acid lactate ester or its salt, the unreacted fatty acid Or about 30 to 70 mol% based on the total amount of the salt thereof, lactic acid or the salt thereof, polylactic acid or the salt thereof, and the fatty acid polylactic acid ester or the salt thereof. The fatty acid lactic acid ester salt having a purity of 80 mol% or more used in the present invention can be obtained by purifying the esterification reaction product by an ordinary purification technique.
Alternatively, a method may be adopted in which a fatty acid lactic acid ester having a purity of 80 mol% or more or a salt thereof is produced, and synthesis conditions are devised so that unreacted raw materials and the like do not remain at the same time.
[0014]
As a method for producing a fatty acid lactic acid ester having a purity of 80 mol% or more or a salt thereof, for example, as described in JP-A-8-34758, a reaction mixture is subjected to liquid-liquid extraction with an aqueous solvent and an organic solvent at a pH of 5.0 or less. Then, a method of generating an organic solvent phase rich in fatty acid lactate ester and an aqueous solvent phase rich in lactic acid and separating both phases, and then separating the fatty acid lactate ester of the organic solvent phase from coexisting fatty acids by crystallization Alternatively, an aqueous acid solution is added to the reaction mixture until the pH becomes lower than 3.0 to precipitate fatty acid lactic acid ester as an oily substance. The oily substance is separated and dissolved in an organic solvent to form a solution. Of lactic acid esters of fatty acids by crystallization. By this method, a fatty acid lactic acid ester having a purity of 80 mol% or more can be easily produced.
[0015]
To the thus obtained fatty acid lactic acid ester having a purity of 80 mol% or more, a basic substance is added in an aqueous solution or an alcoholic aqueous solution such as ethanol in a molar ratio (fatty acid lactic acid ester / basic substance) of 1 / 0.7 to 1/1 /. When added and reacted in 1.3, a fatty acid lactic acid ester salt having a purity of 80 mol% or more is obtained.
The molar ratio of the fatty acid lactic acid ester to the basic substance is more preferably 1 / 0.9 to 1 / 1.2, and by maintaining the molar ratio in this range, the surface activity can be kept good. . If the molar ratio of the basic substance is too large, the stability of the fatty acid lactic acid ester salt over time in the presence of water is reduced, and the emulsifying ability is reduced. It is considered that this is because the hydrolysis of the fatty acid lactic acid ester is promoted by the increase of the basic substance, the fatty acid lactic acid ester salt is reduced, and the ratio of soap and lactic acid is increased.
[0016]
Conversely, even when the molar ratio of the basic substance is too small, the surface activity of the fatty acid lactic acid ester salt decreases. In this case, although the hydrolysis rate of the fatty acid lactic acid ester is low, the emulsifying ability as an ionic surfactant is low due to a small amount of basic ions.
By using a high-purity fatty acid lactate ester salt neutralized at a predetermined molar ratio, the emulsifier composition containing the fatty acid lactate ester salt exhibits remarkably excellent performance. Examples of the basic substance include hydroxides or carbonates of alkali metals or alkaline earth metals, ammonia, alkanolamines such as ethanolamine, and lower alkali amines such as tributylamine. Among them, hydroxides and carbonates of calcium, potassium, sodium and the like are preferable because they are highly safe, mild and have excellent emulsifying power.
[0017]
In the sucrose fatty acid ester used together with the above fatty acid lactic acid ester salt, the fatty acid constituting the sucrose has 14 to 22, preferably 14 to 18, and more preferably 16 to 18 carbon atoms. If the fatty acid chain length is shorter than this range, the affinity of the lipophilic portion with the oil is weak, so that the emulsion stability is deteriorated, and remarkable foaming may occur during emulsification, which is not preferable. Further, if the fatty acid chain length is longer than this range, the crystallinity of the emulsifier itself is too high, and the lipophilic portion is less likely to be compatible with the oil, and the emulsion stability is deteriorated as in the case where it is too short. Moreover, it is not preferable because it is difficult to obtain raw materials.
[0018]
This fatty acid may be saturated or unsaturated. In some cases, a hydroxyl carboxylic acid having a hydroxyl group may be used. These fatty acids include myristic acid, palmitic acid, stearic acid, arachiic acid, behenic acid, tetradecenoic acid, hexadecenoic acid, octadecenoic acid (oleic acid, elaidic acid, etc.), octadecadienoic acid (linoleic acid, etc.), eicosenoic acid , Eicosatetraenoic acid (arachidonic acid), docosenoic acid (erucic acid), octadecatrienoic acid (linolenic acid and the like), and the like. Among these, palmitic acid, stearic acid, etc. are particularly preferred because they have excellent emulsifying performance and are easily available.
These fatty acids can be used as a mixture of two or more kinds in any ratio. Industrially, it is preferable to use a mixed fatty acid obtained from coconut oil, palm oil, tallow or the like as a raw material for production.
[0019]
The emulsifier composition of the present invention contains a fatty acid lactic acid ester salt and a sucrose fatty acid ester as essential components. When the same anionic surfactant is used other than the fatty acid lactic acid ester salt, the stability and safety of the emulsion are not sufficient, and the handleability may be poor.
Further, the fatty acid lactate ester salt and the sucrose fatty acid ester have a mole fraction of the fatty acid lactate ester salt of 0.008 to 0.15, preferably 0.01 to 0.15, more preferably 0 to the total of the moles of both. 0.03 to 0.1.
The fatty acid lactic acid ester salt and the sucrose fatty acid ester to be mixed may have the same or different fatty acid chain length.
[0020]
In addition, the emulsifier composition of the present invention may be added to the emulsifier composition of the present invention by selecting any one of the commonly used additive components within a range that does not impair the purpose of the present invention. Examples of such additional components include polyglycerin fatty acid ester, monoglyceride, organic acid monoglyceride, sorbitan fatty acid ester, lecithin, sodium polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, and polyoxyethylene. Sorbitan fatty acid ester, fatty acid alkanolamide, or highly safe surfactant such as carboxybetaine type, imidazolinium type, sulfobetaine type, amino acid type surfactant, and carrageenan, locust bean gum, guar gum, tamarind gum, Arabic Natural thickening stabilizers such as gum, xanthan gum, pectin, pullulan, casein, gelatin, albumin, casein, soy protein, gluten, etc. Cellulose, sodium casein, synthetic thickening stabilizer such as polyacrylic acid, more flavors, sweeteners, flavorings, colorants, humectants, disinfectants, enzymes, and the like anti-inflammatory agents.
[0021]
The present emulsifier composition can be used as an emulsifier for foods, cosmetics and the like. The form at this time is mainly affected by the melting points of the fatty acid lactate ester salt and sucrose fatty acid ester used, and is often in a solid form, but may be in a liquid form or a base form depending on the fatty acid species and additive components. .
Next, an emulsion using the present emulsifier composition will be described. The form of emulsification (oil-in-water type, multiple emulsification, microemulsion, etc.) is appropriately selected, but the emulsifier composition is particularly suitable for an oil-in-water type emulsion.
The aqueous component is not particularly limited, and includes water and various aqueous solutions. The aqueous component may be mixed with various water-soluble components, such as sugars, alcohols, salts such as sodium chloride and potassium carbonate, which are blended in ordinary foods, cosmetics, and the like.
[0022]
The oil component is not particularly limited, and includes animal and plant-derived fats and oils, mineral-derived fats and oils, and chemically synthesized products. Specifically, soybean oil, cottonseed oil, rapeseed oil, palm oil, coconut oil, sesame oil, castor oil, cocoa butter, safflower oil, olive oil, beef tallow, lard, fish oil, whale oil, butterfat, and hydrogenated products thereof Processing oils such as transesterified oils, waxes such as wood wax, beeswax and sheep wax, sterols such as lanolin and cholesterol, paraffins such as liquid paraffin, hydrocarbons such as petrolatum and squalane, palmitic acid, Examples include higher fatty acids such as stearic acid, higher aliphatic alcohols such as cetanol and stearyl alcohol, and esters such as diethyl phthalate, dibutyl phthalate and cholesterol isostearate. An antioxidant, an oil-soluble drug and the like can be further added to these oil components. Further, the oily components may be used alone or may be appropriately mixed.
[0023]
The content of fats and oils in the emulsion is not particularly limited, but is preferably 2 to 90% by weight.
A suitable use amount of the emulsifier composition is 0.01 to 60% by weight, preferably 0.01 to 20% by weight, more preferably 0.1 to 5% by weight based on the whole emulsion. If the amount used is smaller than this, sufficient stability cannot be obtained.On the other hand, even if it is used beyond this, not only the emulsification effect is not remarkably obtained, but also unnecessary thickening occurs, Is also disadvantageous.
The emulsification method is not particularly limited, but examples include the following methods. That is, the present emulsifier composition and water, an aqueous component obtained by heating and stirring at a temperature higher than the Kraft point of the emulsifier composition, and a method of homogenizing the oily component, or oil-soluble among the emulsifier composition A method of homogenizing an oily component obtained by heating and dissolving the component and water in which a predetermined amount of a basic substance is previously dissolved may be used.
[0024]
【The invention's effect】
The emulsifier composition of the present invention can provide an emulsion having high safety, no irritation to the human body, and excellent stability. In addition, it is highly dispersible in oil or water, and is excellent in convenience without unnecessary bubbling at the time of homogenization and no coloring or odor on products.
Further, the emulsion using the emulsifier composition of the present invention has high safety, is gentle, has excellent emulsion stability, and is suitably used for foods, cosmetics, and the like.
[0025]
【Example】
Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist.
<Examples 1 to 10, Comparative Examples 1 to 22>
An emulsifier containing a fatty acid lactic acid ester salt and a sucrose fatty acid ester was prepared, emulsified, and the results of evaluation were shown in Tables 1 and 2.
The high-purity potassium stearic acid lactate and the low-purity potassium stearic acid lactate in the table were produced by the following methods.
The production of low-purity potassium stearate lactate was carried out by reacting 170 g of stearic acid, 72 g of lactic acid (purity 90%), and 25 g of potassium carbonate at 200 ° C. for 5 hours in a nitrogen stream in accordance with a known example. The resulting low-purity potassium stearic acid lactate ester contains a total of 49 mol% of stearic acid lactate ester and stearic acid dilactic acid ester, 28 mol% of stearic acid, and lactic acid and a lactic acid polymer.
[0026]
High purity potassium stearic acid lactate was obtained by the following method. To 20 g of the reaction product obtained by the above method, 50 ml of 1N hydrochloric acid was added to neutralize the solution to pH 3.0 or less, 45 ml of hexane was added thereto, and the mixture was shaken well, followed by layer separation into a hexane phase and an aqueous phase. 40 ml of hexane was further added to the hexane phase, and the mixture was allowed to stand at room temperature overnight to precipitate crystals, filtered, and again precipitated in hexane under the same conditions to obtain stearic acid lactate having a purity of 80 mol% or more. Obtained. This high-purity stearic acid lactate was neutralized with an equivalent amount of potassium hydroxide to obtain potassium stearate lactate having a purity of 80 mol% or more.
The sucrose fatty acid ester is a mixture of 70% by weight of stearic acid and 30% by weight of palmitic acid, wherein the total of monoester and diester is 67% by weight, and 88% of the total with the diester was used.
The evaluation of the emulsifier composition and the emulsion was performed as follows.
[0027]
1. The color of the emulsifier composition; the appearance of the emulsifier composition was observed under natural light.
；: Colorless わ ず か; slight coloring x; brown coloring Odor of the emulsifier composition: At 25 ° C., the odor of the emulsifier composition was evaluated.
；: No odor △; slight caramel odor x; strong caramel odor Water dispersibility of emulsifier composition: At 25 ° C., the emulsifier composition was added to water (2.9% by weight), and the state of stirring was observed.
；: Disperse promptly △; Difficult to disperse ×; Difficult to disperse Emulsion appearance of emulsion: The appearance of the emulsion immediately after production was observed.
；: Uniform emulsion without unnecessary foaming.
X: A state in which remarkable foaming occurs and overflows from the emulsification container or cannot be called a uniform emulsion.
5. Emulsion stability: After production, the amount of water released (ml) of the emulsion stored at 25 ° C. for 24 hours was measured.
<Production method of oil-in-water emulsion>
The emulsifier composition was dispersed in water at 25 ° C, soybean oil or liquid paraffin was added, and the temperature was raised to 60 to 80 ° C and stirred. The aqueous phase and the oil phase were emulsified at 70 ° C. and 10,000 rpm for 5 minutes using an ACE homomixer manufactured by Nippon Seiki Co., Ltd., and then rapidly cooled with ice water.
[0028]
[Table 1]

[0029]
[Table 2]

[0030]
From the above Tables 1 and 2, the fatty acid lactic acid ester salt having a purity of 80 mol% or more (within the range of 14 to 22 carbon atoms of the fatty acid) was used for the fatty acid lactic acid ester salt and the sucrose fatty acid ester (the fatty acid having 14 to 22 carbon atoms). When the molar ratio of the fatty acid lactic acid ester salt is 0.008 to 0.15 with respect to the total number of moles (within the range of 22), the emulsification stability is remarkably improved, and a preferable emulsion can be obtained. Indicated.

Claims (4)

An emulsifier composition comprising a fatty acid lactate ester salt having a purity of 80 mol% or more and a sucrose fatty acid ester, wherein the fatty acid constituting the fatty acid lactate ester salt is a fatty acid having 14 to 22 carbon atoms, and The fatty acid is a fatty acid having 14 to 22 carbon atoms, and the mole fraction of the fatty acid lactate ester salt relative to the total number of moles of the fatty acid lactate ester salt and the sucrose fatty acid ester is 0.008 to 0.15. Emulsifier composition. The emulsifier composition according to claim 1, wherein the fatty acid lactic acid ester salt is obtained by reacting the fatty acid lactic acid ester with a basic substance at a molar ratio of 1 / 0.7 to 1 / 1.3. An emulsion containing 0.01 to 60% by weight of the emulsifier composition according to claim 1 or 2. The emulsion according to claim 3, wherein the weight ratio of water / oil is 10/90 to 98/2, and the emulsion type is an oil-in-water type.