JP3380606B2 - Emulsion manufacturing method - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a novel emulsion.

[0002]

2. Description of the Related Art Emulsion production methods are roughly classified into surface chemical methods and mechanical methods.

As the surface chemistry method, phase inversion emulsification method, H
The LB temperature emulsification method, the D phase emulsification method, the amino acid gel emulsification method and the like can be mentioned. The basis of this technique is an agglomeration method in which a dispersoid in which a molecule is dispersed is precipitated to grow it to a certain particle size and then stabilize it.

On the other hand, mechanical methods include a colloid mill, a homogenizer, an ultrasonic method and a high-pressure homogenizer. The basis of this technique is a dispersion method in which a large droplet mass is crushed by mechanical force and finely divided into emulsion particles.

Recently, a mechanical method using a microporous membrane has been disclosed (Japanese Patent Laid-Open No. 2-95433).
(Hereinafter referred to as SPG method). That is, the method for producing an emulsion is characterized in that a liquid as a dispersed phase is pressed into a liquid as a continuous phase through a microporous membrane having uniform pores. The emulsification method before that could finely prepare the emulsified droplets, but could not uniformly prepare them. However, by using the SPG method, it has become possible to prepare emulsion droplets uniformly and finely. Furthermore, since an emulsion can be prepared by a simple operation using a simple device, it is excellent in economical efficiency.

[0006]

However, in the conventional SPG method, depending on the combination of the surfactant and the oil, a hard gel is formed in the pores of the microporous membrane and the pores are clogged, resulting in a smooth emulsification. There was a drawback that it was not done.

[0007]

The present inventors have completed the present invention as a result of intensive studies in view of such circumstances. That is, the present invention provides a method for efficiently producing an emulsion by adding a polyhydric alcohol to a continuous phase, regardless of the compatibility of the surfactant and the oil component. Further, the present inventors have disclosed in Japanese Patent Application No. 4-302926 a method for producing an emulsion in which the surface of a microporous membrane is previously treated with a nonionic surfactant.
The present invention can also be applied to this manufacturing method. For example, a good emulsion can be prepared by using a microporous membrane body which is surface-treated by immersing it in an aqueous solution in which a nonionic surfactant and a polyhydric alcohol are dissolved.

The microporous membrane used in the present invention is
(1) The pore size distribution is as small as possible and penetrates. (2) Desired pore size (usually about 0.1 to 10 μm)
It can be adjusted to. (3) It has sufficient mechanical strength to prevent deformation or destruction when a liquid to be a dispersed phase is pressed into a liquid to be a continuous phase. (4) It has chemical durability with respect to the liquid forming the emulsion. (5) The wettability with respect to the liquid to be the continuous phase is higher than that to the liquid to be the dispersed phase. It has features such as. Microporous membranes having such characteristics include inorganic or organic ones, and are not particularly limited. For example, CaO disclosed in Japanese Patent Publication No. 62-25618.
_{-B 2 O 3 -SiO 2 -Al 2} O 3 based porous glass, Sho 61-40841 Patent Publication (U.S. Patent No. 4,857,87
No. 5)) disclosed in CaO—B ₂ O ₃ —SiO ₂ —
Al ₂ O ₃ -Na ₂ O-based porous glass and CaO-B ₂ O
_{3 -SiO 2 -Al 2 O 3 -Na} 2 which O-MgO-based porous glass and the like and the membrane-like body thereof. Further, in order to make the surface of these microporous membranes hydrophobic or hydrophilic, it is necessary to introduce a hydrophobic hydrocarbon group on the surface of the membrane with a silylating agent or to use a silane coupling agent. The surface of the membrane is modified with a hydrophilic functional group. In these porous glasses, it is important that the pore size can be controlled within a very narrow range. The body length of the microporous membrane is not particularly limited. The diameter is not particularly limited, but from the viewpoint of strength, it is preferably 30 mm or less, more preferably 10 to 20 mm. The thickness of the film body is not particularly limited, but it is preferably about 0.4 to 2 mm in consideration of strength and the like.

The polyhydric alcohol used in the present invention is not particularly limited as long as it has two or more hydroxyl groups in the molecule. For example, propylene glycol and 1,3-
Butylene glycol, 1,4-butylene glycol, ethylene glycol, polyethylene glycol, polypropylene glycol, glycerin, dipropylene glycol, diglycerin, triglycerin, tetraglycerin, hexaglycerin, octaglycerin, nonaglycerin, decaglycerin, polyglycerin, glucose ,
There is a mixture of one or more of sorbitol, maltitol, sucrose, raffinose, trehanose and the like.

Among these, propylene glycol, 1,3
-Butylene glycol, 1,4-butylene glycol,
One or a mixture of two or more of ethylene glycol, glycerin and dipropylene glycol is preferable.

The surfactant used here is not particularly limited, but for example, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyglycerin fatty acid ester, polyoxyethylene. Sorbit fatty acid ester, polyethylene glycol fatty acid ester, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, and sucrose fatty acid Nonionic surfactants such as esters, anionic surfactants, cationic surfactants, and amphoteric surfactants can be mentioned.

Among these, polyoxyethylene (5 to 5
50) Lauryl ether, polyoxyethylene (5-5
0) Alkyl ether, polyoxyethylene (5-5
0) myristyl ether, polyoxyethylene (5-5
0) palmityl ether, polyoxyethylene (5-5
0) Stearyl ether, polyoxyethylene (5-5
0) Isostearyl ether, polyoxyethylene (5
~ 50) lauryl ether, polyoxyethylene (5 ~
100) hydrogenated castor oil, polyoxyethylene (5-2
0) sorbitan laurate, polyoxyethylene (5-
20) Sorbitan stearate, polyoxyethylene (5-20) sorbitan oleate, polyoxyethylene (5-20) sorbitan isostearate, sorbitan oleate, sorbitan isostearate, sorbitan laurate, polyoxyethylene (5-20) Glycerin stearate, polyoxyethylene (5-20) glycerin oleate, polyoxyethylene (5-20) glycerin isostearate, polyoxyethylene (5-2
0) Glycerin laurate, decaglyceryl tetraoleate, hexaglyceryl triisostearate, decaglyceryl monooleate, decaglyceryl monolaurate, decaglyceryl monostearate, hexaglyceryl triisostearate, hexaglyceryl triisostearate, tetra Triglycerin or higher polyglycerin fatty acid ester such as glyceryl diisostearate,
Polyoxyethylene polyoxypropylene block polymer, polyoxyethylene (5 to 20) sorbitolate, polyoxyethylene (5 to 20) sorbit sterate, polyoxyethylene (5 to 20) sorbit isosterate, polyoxyethylene (5 To 20) sorbitol laurate, polyoxyethylene (10 to 30) polyoxypropylene (0 to 10) decyl tetradecyl ether, polyoxyethylene (1 to 30) polyoxypropylene (0 to 10) cetyl ether polyethylene monooleate Particularly preferred is glycol or polyethylene glycol monolaurate.

The oil used in the present invention is not particularly limited to polar oils to non-polar oils, but examples thereof include hydrocarbon oils such as liquid paraffin, squalane, isoparaffin and branched light paraffin, isopropyl myristate, cetyl isooctano. And ester oils such as glyceryl trioctanoate and silicone oils such as decamethylpentasiloxane, dimethylpolysiloxane and methylphenylpolysiloxane.

The amount of the polyhydric alcohol used in the present invention is not particularly limited, but the surfactant / polyhydric alcohol weight ratio is preferably in the range of 1/3 to 1/500. More preferably, it is in the range of 1/6 to 1/100. If it is less than 1/3, the desired effect cannot be obtained, and 1/500
The above is uneconomical because the effect is not enhanced.

When surface treatment is applied to the microporous membrane,
For example, the weight ratio of surfactant / polyhydric alcohol is 1/10.
The surfactant / polyhydric alcohol is immersed in a solution having a surfactant / polyhydric alcohol concentration of 0.1 to 100% within the range of 00 to 1000/1 or circulated as a continuous phase to make the surfactant / polyhydric alcohol microporous membrane. Adsorb to the body. That is,
If a surface active agent / polyhydric alcohol is adsorbed on the microporous membrane body in a certain amount or more, the emulsification is efficiently performed. These adsorptions are characterized in that the film surface and the inside of the film are also wetted by the dispersed phase.

As the emulsifying apparatus in the present invention, for example, the one disclosed in FIG. 3 of JP-A-2-95433 can be used as it is.

The emulsion obtained by the method of the present invention is extremely useful for producing cosmetics, foods, pharmaceuticals and the like.

[0018]

EXAMPLES In order to further understand the present invention, examples will be described in more detail. The present invention is not limited to this. In the examples,% means% by weight
Is.

Example 1 Polyoxyethylene (9) lauryl ether / 1,3-
A 5% aqueous solution of butylene glycol in a weight ratio of 1/6 was used as a continuous phase, and liquid paraffin was used as a dispersed phase to press-fit into a microporous membrane to perform SPG emulsification. As a result, the emulsion had a particle size of 1.0 μm and was stable. An O / W type emulsion composition was prepared. The microporous membrane used has a length of 10c
m, diameter 0.6 mm, film thickness 0.6 mm, average pore diameter 0.
The one having a thickness of 3 μm was used.

Example 2 Polyoxyethylene (9) lauryl ether / 1,3-
The same microporous membrane body as that used in Example-1 was immersed in a 5% aqueous solution having a butyleneglycol weight ratio of 1/6 for 1 hour for surface treatment. The surface-treated microporous membrane was subjected to SPG emulsification using the same continuous phase and dispersed phase as in Example-1. As a result, the particle size of the emulsion was 1.0.
A stable O / W type emulsion composition having a thickness of μm was obtained.

Example 3 A 10% aqueous solution having a polyoxyethylene (3) oleyl ether / polyoxyethylene (20) oleyl ether / glycerin weight ratio of 1/1/30 was used as a continuous phase, and methylphenylpolysiloxane was used. Was dispersed in the microporous membrane body under pressure to carry out SPG emulsification. As a result, an O / W type emulsion composition having an emulsion particle size of 2.8 μm was obtained.

The microporous membrane used in the present invention is CaO-
It was a B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ —Na ₂ O based porous glass, and had a length of 1 m, a diameter of 15 mm, a film thickness of 2 mm, and an average pore diameter of 0.8 μm.

Example 4 Polyoxyethylene (3) oleyl ether / polyoxyethylene (20) oleyl ether / glycerin weight ratio of 1/2/45 was used as a continuous phase with a 10% aqueous solution (surface treatment liquid). The surface treatment was performed by circulating it using a pump for 1 hour. The surface treatment liquid was prepared as a 2.0% aqueous solution to form a continuous phase, and methylphenylpolysiloxane was used as a dispersed phase into the microporous membrane body under pressure to perform SPG emulsification.
As a result, the emulsion particle size is 2.8 μm and stable O /
A W type emulsion composition was obtained.

Example 5 Sorbitan monolaurate / polyoxyethylene (2
0) A 10% aqueous solution of sorbitan monolaurate / ethylene glycol in a weight ratio of 1/1/200 was used as a continuous phase, and isopropyl myristate was used as a dispersed phase in a microporous membrane body under pressure to perform SPG emulsification. As a result, a stable O / W type emulsion composition having an emulsion particle size of 2.3 μm was obtained.

The microporous membrane is made of CaO-B ₂ O ₃ -SiO.
_{Using 2-} Al ₂ O ₃ based porous glass, the length is 50 cm, the diameter is 8 mm, the film thickness is 1.5 mm, and the average pore diameter is 0.8 μm.

Example 6 Sorbitan monolaurate / polyoxyethylene (2
0) Prepare a 10% acetone solution with a sorbitan monolaurate / ethylene glycol weight ratio of 1/1/200. This is immersed in the same microporous membrane body as used in Example-5 for 0.5 hours. After drying it, a 10% aqueous solution having a sorbitan monolaurate / polyoxyethylene (20) sorbitan monolaurate / ethylene glycol weight ratio of 1/1/20 was used as the continuous phase, and the dispersed phase was isopropyl. SPG emulsification was performed by press-fitting using Millistate. As a result, the particle size is 2.3.
A stable O / W type emulsion composition having a thickness of μm was obtained.

[0027]

The emulsion production method of the present invention provides an efficient and stable emulsion production method regardless of the compatibility of the surfactant and the oil component. next,
The effects of the present invention will be clarified by experiments.

Experiment-1 (Test method) 1,3-butylene glycol was used as a continuous phase, and various surfactant aqueous solutions were used, and SPG emulsification was carried out using methylphenylpolysiloxane as a dispersed phase.
The emulsion after the time was evaluated. The evaluation method was carried out by quantifying the amount of oil in the emulsion by gas chromatography. Table 1 shows the composition of the polyhydric alcohol, the surfactant and the water and the evaluation of the emulsified state.

The microporous membrane is made of CaO-B ₂ O ₃ -SiO.
_{A 2-} Al ₂ O ₃ based porous glass having a length of 5 cm, a diameter of 15 mm, a film thickness of 0.5 mm and an average pore diameter of 0.3 μm was used. Moreover, the measurement conditions of the gas chromatography are Hitachi 663 type, column; 1 m Silicon SE-3.
0,150 → 250 °, 5 ° C./min. Margin below

[0030]

(Test Results) From the results shown in Table 1, it can be seen that the emulsification was smoothly carried out by adding 1,3-butylene glycol to any of the surfactants.

Experiment-2 (Test method) Polyoxyethylene (9) lauryl ether and an aqueous solution of various polyhydric alcohols were used as a continuous phase, and liquid paraffin was used as a dispersed phase to carry out SPG emulsification to prepare an emulsion after 1 hour. evaluated. The evaluation method is the same as Experiment-1. Table 2 shows the composition and emulsified state of the polyhydric alcohol, the surfactant and the water.

The microporous membrane used in this experiment was CaO-
A B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ based porous glass having a length of 10 cm, a diameter of 10 mm, a film thickness of 1.0 mm and an average pore diameter of 0.5 μm was used.

(Test Results) From the results shown in Table 2, it can be seen that the emulsification was carried out smoothly when the polyhydric alcohol was blended. Margin below

[0035] Margin below

Experiment-3 (Test Method) The surface treatment solution was a mixed surfactant and a mixed polyhydric alcohol. Various 5.0 as continuous phase
% Mixed system surfactant aqueous solution, and SPG emulsification was performed using isopropyl myristate as a dispersed phase. . The dispersion phase was pressed into the continuous phase, and the emulsion was evaluated 1 hour later. The evaluation method was the same as in Experiment-1.

The microporous membrane used in this experiment is CaO-
B ₂ O ₃ —SiO ₂ —Al ₂ O ₃ —Na ₂ O based porous glass was used, and the length was 50 cm, the film thickness was 1.5 mm, and the average pore diameter was 0.
The one with 2 μm was used.

(Test Results) From the results shown in Table 3, it can be seen that the emulsification is carried out smoothly even in the mixed polyhydric alcohol. Margin below

[0039]

─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-4-118044 (JP, A) JP-A-3-169331 (JP, A) Patent 3155972 (JP, B2) (58) Fields investigated (Int. Cl. ⁷ , DB name) B01J 13/00 B01F 3 / 08,17 / 38

Claims (2)

(57) [Claims] 1. A method for producing an oil-in-water emulsion by press-fitting a liquid to be a dispersed phase into a liquid to be a continuous phase through a microporous membrane body, wherein a surfactant and a surfactant are used.
And a polyhydric alcohol having two or more hydroxyl groups in the molecule, which is a method for producing an oil- in- water emulsion. 2. A process for producing an oil-in-water emulsion by press-fitting a liquid to be a dispersed phase into a liquid to be a continuous phase through a microporous membrane body, wherein a surfactant and a molecule are previously prepared. polyhydric alcohols having 2 or more hydroxyl groups in a solution containing a polyhydric alcohol microporous membrane body immersion and / or by circulating as a continuous phase in the surfactant and the molecule having two or more hydroxyl groups within A method for producing an oil- in- water emulsion, which comprises subjecting a microporous membrane to a surface treatment.