JP6274477B2 - Manufacturing method of emulsifier manufacturing material, emulsifying material, and manufacturing method of emulsifier - Google Patents

Description

  The present invention relates to a method for producing an emulsifier-producing material, an emulsifier-producing material, and a method for producing an emulsifier.

  Conventionally, when emulsifying and dispersing a functional oil base or functional granule in water, a surfactant was selected according to the required HLB of the functional oil base and the properties of the granule surface, and emulsified and dispersed. . In addition, the required HLB value of the surfactant used as an emulsifier needs to be properly used depending on whether an O / W type emulsion is made or a W / O type emulsion, and further, thermal stability and aging Since the stability is not sufficient, a wide variety of surfactants are mixed and used (see Non-Patent Documents 1 to 4).

  However, since the surfactant has low biodegradability and causes foaming, it is a serious problem such as environmental pollution. In addition, as a method for preparing an emulsified preparation of a functional oil base, physicochemical emulsification methods such as an HLB method, a phase inversion emulsification method, a phase inversion temperature emulsification method, and a gel emulsification method are generally performed. Since the basis of emulsion preparation is to reduce the interfacial energy at the oil / water interface and to stabilize the system thermodynamically, it is very cumbersome and labor intensive to select the most suitable emulsifier In addition, when many kinds of oils are mixed, stable emulsification is almost impossible.

  Therefore, Patent Document 1 discloses an emulsifier containing hydrophilic nanoparticles formed of an amphiphilic substance that spontaneously forms closed vesicles and having a particle size distribution of 200 nm to 800 nm. In Patent Document 1, an emulsifier is produced by adding an amphiphile to water and dispersing it by stirring for several minutes, and then dropping the dispersion into cold water.

Japanese Patent No. 3855203

“Emulsion Science” Edited by P.I. Sherman, Academic Press Inc. (1969) "Microemulsions-Theory and Practice" Edited by Leon M. et al. price, Academic Press Inc. (1977) "Emulsification / Solubilization Technology" Recommended, Engineering Book Publishing (1976) "Development Technology of Functional Surfactants" CM Publishing (1998)

  However, in the production method shown in Patent Document 1, the resulting hydrophilic nanoparticles have a large variation in diameter, and the emulsifying function of the emulsifier is sufficiently exhibited because the yield of hydrophilic nanoparticles having a small particle size is particularly low. Or the homogeneity of the emulsifier is insufficient.

  The present invention has been made in view of the above circumstances, and can produce an emulsifier-producing material that can suppress variation in the particle size of hydrophilic nanoparticles or can improve the yield of small-sized hydrophilic nanoparticles. It is an object to provide a method, a material for producing an emulsifier, and a method for producing an emulsifier.

  The present inventors stir a material containing a bilayer film of an amphiphile, and form hydrophilic nanoparticles of the bilayer film from the layer, thereby reducing variation in particle diameter, particularly small diameter. The present inventors have found that hydrophilic nanoparticles having a large ratio can be obtained, and have completed the present invention. Specifically, the present invention provides the following.

  (1) A method for producing an emulsifier-producing material, comprising a step of dispersing a bilayer film of an amphiphilic substance composed of amphiphilic molecules in water.

  (2) The production method according to (1), further comprising a step of heating water during and / or before the dispersion to promote the formation of the layered body.

  (3) The production method according to (1) or (2), wherein the amphiphilic substance is dispersed in water at a concentration of 0.1 to 20% by mass with respect to the material for producing an emulsifier.

  (4) The production method according to any one of (1) to (3), wherein the amphiphilic molecule is at least one selected from the group consisting of fatty acid esters, phospholipids, polyoxyethylene castor oil, and derivatives thereof. .

  (5) An emulsifier-producing material comprising a dispersion in which a bilayer film of amphiphilic molecules is dispersed in water.

  (6) The emulsifier-producing material according to (5), wherein the content of the amphiphilic molecule is 0.1 to 20% by mass with respect to the emulsifier-producing material.

  (7) The material for producing an emulsifier according to (5) or (6), wherein the amphiphilic molecule is at least one selected from the group consisting of fatty acid esters, phospholipids, polyoxyethylene castor oil, and derivatives thereof. .

  (8) By stirring the emulsifier-producing material produced by any one of the production methods according to (1) to (4) or the emulsifier-producing material according to any one of (5) to (7), the layered body The manufacturing method of the emulsifier which has the process of forming the hydrophilic nanoparticle of the said bimolecular film from.

  (9) The production method according to (8), wherein the stirring is performed until an average particle size of particles present in the liquid becomes 20 nm to 800 nm.

  According to the present invention, a material containing a bilayer membrane of an amphiphilic substance is stirred, and hydrophilic nanoparticles of the bilayer membrane are formed from the lamellar body. A hydrophilic nanoparticle with a large ratio is obtained. Thereby, the dispersion | variation in the particle diameter of a hydrophilic nanoparticle can be suppressed, or the yield of the hydrophilic nanoparticle of a small particle diameter can be improved.

  Hereinafter, although embodiment of this invention is described, this does not limit this invention.

<Emulsifier production material and production method thereof>
The method for producing an emulsifier producing material according to the present invention includes a step of dispersing a layered body of a bilayer film of an amphiphilic substance composed of amphiphilic molecules in water. Such a method has been conventionally used as a method for producing an emulsifier, and the composition obtained is not only a layered body that is a bilayer lamellar liquid crystal, but also a bilayer hydrophilic nanoparticle formed from a layered body ( (Closed endoplasmic reticulum) may also be included in a small amount, but since the abundance of hydrophilic nanoparticles is not sufficient, the emulsifying function is not sufficiently exhibited.

  However, this method in the present invention is a method for producing an emulsifier-producing material, and the resulting emulsifier-producing material is stirred as described later. Thereby, the obtained emulsifier contains a large amount of bimolecular hydrophilic nanoparticles having a small diameter and exhibits a more excellent emulsifying function.

  Although it does not specifically limit as an amphipathic substance used by this invention, It is preferable that it is 1 or more types chosen from the group which consists of fatty acid ester, phospholipid, polyoxyethylene castor oil, and these derivatives.

  Examples of the fatty acid ester include glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, and propylene glycol fatty acid ester. Among these, glycerin fatty acid esters and sorbitan fatty acid esters are useful in the present invention in that it is difficult to produce hydrophilic nanoparticles by conventional methods.

  Examples of phospholipids include egg yolk lecithin and soybean lecithin, or DLPC (1,2-Dilauroyl-sn-glycero-3-phospho-rac-1-) having a carbon chain length of 12 in the structure represented by the following general formula 3. choline), DMPC (1,2-Dimyristol-sn-glycero-3-phospho-rac-1-choline) having a carbon chain length of 14, DPPC (1,2-Dipalmitoyyl-sn-glycero-3-choline) having a carbon chain length of 16 phospho-rac-1-choline) can be employed.

General formula 3

  In addition, among the structures represented by the following general formula 4, DLPG (1,2-Diilauroyl-sn-glycero-3-phospho-rac-1-glycerol) Na salt or NH4 salt, carbon chain of carbon chain length 12 Na or NH4 salt of DMPG having a length of 14 (1,2-Dimyristol-sn-glycero-3-phospho-rac-1-glycerol), DPPG having a carbon chain length of 16 (1,2-Dipalmitoyyl-sn-glycero-3) -Phospho-rac-1-glycerol) Na salt or NH4 salt may be employed.

Formula 4

  In addition, a polyoxyethylene castor oil derivative represented by the following general formula 1, or a dialkylammonium derivative, a trialkylammonium derivative, a tetraalkylammonium derivative, a dialkenylammonium derivative, a trialkenylammonium derivative represented by the general formula 2 Or a derivative of a halogen salt of a tetraalkenyl ammonium derivative.

General formula 1

  In the formula, E, which is the average added mole number of ethylene oxide, is 3 to 100. If E is excessive, the type of good solvent that dissolves the amphiphilic substance is limited, and thus the degree of freedom in producing hydrophilic nanoparticles is narrowed. The upper limit of E is preferably 50, more preferably 40, and the lower limit of E is preferably 5.

General formula 2

  In the formula, R 1 and R 2 are each independently an alkyl group or alkenyl group having 8 to 22 carbon atoms, R 3 and R 4 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms, and X is F, Cl, Br or I.

  The dispersion of the bilayer membrane into water can be performed by mixing the amphiphile and water and stirring for a short time (for example, 5 to 15 minutes) as necessary. However, when the temperature of the water as the dispersion medium is low, the layered body is not sufficiently formed, resulting in a deterioration in the yield of the obtained hydrophilic nanoparticles and a decrease in the production efficiency of the hydrophilic nanoparticles (that is, production). (Extended time) is a concern. Therefore, it is preferable that the method of the present invention further includes a step of heating water to promote formation of a layered body during and / or before dispersion in water. Thereby, since formation of a layered body is promoted by thermal energy, improvement in the yield of hydrophilic nanoparticles and improvement in production efficiency can be expected. The promotion of the formation of the layered body can be confirmed by measuring the particle size distribution before and after heating and changing the average particle size.

  If the heating of water is insufficient, the formation of the layered body is not sufficiently promoted. On the other hand, if it is excessive, there is a concern that the amphiphile may be denatured and the energy efficiency is lowered. Thus, the water temperature at the time of heating is not particularly limited, but the lower limit may be 40 ° C, preferably 50 ° C, and the upper limit may be 80 ° C, preferably 70 ° C.

  Moreover, you may perform the process of cooling a liquid after heating (for example, 5-10 degreeC), and heating further once to several times. Thereby, since the penetration | invasion of the water to the hydrophilic group which an amphiphilic substance has is promoted, the more excellent hydrophilic nanoparticle can be obtained.

  If the amount of the amphiphilic substance is too small, the production efficiency is deteriorated. On the other hand, if the amount is too large, it takes a long time to form the bilayer hydrophilic nanoparticles from the layered body. Therefore, the lower limit of the concentration of the amphiphilic substance relative to the emulsifier-producing material is preferably 0.1% by mass, and the upper limit is preferably 20% by mass. The allowable upper limit of the concentration of the amphiphile varies depending on the amphiphile used. For example, a derivative of polyoxyethylene castor oil is likely to form needle crystals at a high concentration, and is thus limited. Phospholipids do not have these problems and are almost unrestricted.

<Method for producing emulsifier>
The manufacturing method of the emulsifier of this invention has the process of forming the hydrophilic nanoparticle of a bilayer from a layered body by stirring the above-mentioned material for emulsifier manufacture. Thereby, the obtained emulsifier contains a large amount of bimolecular hydrophilic nanoparticles having a small diameter and exhibits a more excellent emulsifying function.

  Agitation in this step needs to be performed vigorously and sufficiently depending on the type and amount of the amphiphile used, unlike the agitation for dispersion in the production process of the above-mentioned emulsifier production material. In the exemplary stirring conditions, the lower limit of the water temperature is preferably 40 ° C, more preferably 50 ° C, and the upper limit is preferably 80 ° C, more preferably 70 ° C. The lower limit of the stirring speed is preferably 1200 rpm, more preferably 2000 rpm, and the upper limit is preferably 16000 rpm, more preferably 10,000 rpm. The lower limit of the time is preferably 30 minutes, more preferably 50 minutes, even more preferably 55 minutes, and the upper limit is preferably 90 minutes, more preferably 70 minutes, still more preferably 75 minutes. .

  In another aspect, the stirring is preferably performed until the average particle diameter of the particles present in the liquid is 20 nm to 800 nm as measured using a laser diffracted light scattering apparatus. Thereby, since the emulsifier contains a large amount of hydrophilic nanoparticles involved in emulsification, it can have an excellent emulsifying function. The stirring is more preferably performed until the average particle size becomes 20 nm to 600 nm.

In the emulsifier, the hydrophilic nanoparticles may be ionized in order to increase the adhesion force of the hydrophilic nanoparticles to the emulsification target. For cationization, alkyl or alkenyl trimethylammonium salt (carbon chain length 12 to 22), preferably hexadecyltrimethylammonium bromide (Hexadecyltrimethylammonium Bromide: hereinafter referred to as CTAB) is used as an ionic surfactant. ), for the anion of the alkyl sulfates (CnSO ₄ ^- M ⁺ carbon chain length 8 to 22, M: alkali metals, alkaline earth metals, ammonium salts, etc.), alkyl sulfonates (CnSO ₃ ^- M ⁺ Carbon chain length of 8 to 22, M: alkali metal, alkaline earth metal, ammonium salt, etc.) can be used.

  Such an emulsifier of the present invention is different from an emulsifier produced from a granule containing a conjugate of polycondensation polymer particles having a hydroxyl group (for example, starch granule; see JP-A-2006-239666). This is advantageous in that a process is unnecessary. The emulsifier of the present invention is also advantageous in that it can be emulsified more variously because it is less denatured than an emulsifier produced from granules containing a conjugate of polycondensation polymer particles having a hydroxyl group.

  Specifically, an emulsion in which an oil phase containing an oily substance and an aqueous phase are dispersed is produced by mixing the oily substance with or without adding a substance that is distributed to the aqueous phase as appropriate to the emulsifier. it can. In addition, an oily substance means the substance which contains only oil or oil as a main component. A detailed use procedure is described in Japanese Patent No. 3855203.

  Further, the emulsifier of the present invention can form an emulsified dispersion system having excellent thermal stability and stability over time with respect to the interface between the functional oil base and water or the functional granules and water. For this reason, the emulsifying dispersant of the present invention can be used for stable emulsification in a wide temperature range over a long period of time. In addition, it is possible to emulsify and disperse oily substances using one type of emulsifying dispersant regardless of the required HLB value of the oil to be emulsified or the surface state of the functional granules. Can be used. For this reason, it can also be used to emulsify a mixture of various types of oil. Therefore, the hydrophilic nanoparticles and the emulsifier of the present invention include light oil, heavy oil A, heavy oil C, tar, biodiesel fuel, recycled heavy oil, waste cooking oil, cosmetic oil, silicone oil, fluorine oil, vegetable oil, animal oil. It can be used for emulsification of water in various oils such as beef tallow and fish oil and lubricating oils.

<Example>
Glycerine stearate was added to water in an amount of 1.0% by mass, and the dispersion was heated to 80 ° C. and stirred at a speed of 500 rpm for 1 hour. When the particle size distribution of the liquid after stirring was measured with a dynamic light scattering photometer “FPAR-1000” (manufactured by Otsuka Electronics Co., Ltd.), a peak indicating the presence of hydrophilic nanoparticles was confirmed around 180 nm.

(Evaluation)
The dispersions of the examples were emulsified with A-heavy oil at various mass ratios by stirring at 8000 rpm for about 5 minutes using a homomixer at room temperature. Table 1 shows the range of conditions under which the emulsified state was observed and phase separation was not observed.

  As shown in Table 1, it was found that the emulsifiers of Examples emulsify various oils stably over a wide range of mixing ratios and have an excellent emulsifying function.

Claims (2)

A step of dispersing, in water, a layered body that is a lamellar liquid crystal of a bilayer film of an amphiphilic substance composed of one or more amphiphilic molecules selected from the group consisting of fatty acid esters and derivatives thereof;
Agitating the emulsifier-producing material to form hydrophilic nanoparticles of the bilayer membrane from the layered body, and
The dispersion is performed by stirring at 40 ° C. or more for 5 to 15 minutes,
The formation is carried out by stirring at 40 ° C. or higher for 30 minutes or longer until the average particle size of the particles present in the liquid reaches 20 nm to 600 nm (excluding 200 nm to 800 nm in a concentration range of 5 to 20 wt%). Method (however, the amphiphile is dissolved in a volatile solvent, the solvent is evaporated to form a film of the amphiphile on the wall of the container, and the mixture with the aqueous phase added to the container is mechanically stirred. Excluding methods having steps) . A step of dispersing, in water, a layered body that is a lamellar liquid crystal of a bilayer film of an amphiphilic substance composed of one or more amphiphilic molecules selected from the group consisting of fatty acid esters and derivatives thereof;
Agitating the emulsifier-producing material to form hydrophilic nanoparticles of the bilayer membrane from the layered body, and
The dispersion is performed by stirring at 40 ° C. or higher (excluding 60 ° C. or lower) for 5 to 15 minutes,
The method for producing an emulsifier is carried out until the average particle size of the particles existing in the liquid reaches 20 nm to 600 nm by stirring at 40 ° C. or higher (excluding 60 ° C. or lower) for 30 minutes or longer. The method includes the steps of dissolving the amphiphile, evaporating the solvent to form a film of the amphiphile on the wall of the container, and mechanically stirring the mixture with the aqueous phase added to the container. ).