JPH10180085A - Production of emulsified liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase the affinity of an aq. phase for an oil phase and to efficiently obtain an emulsified liq. having a uniformly dispersed state of the oil phase by using an aq. soln. of a specified high molecular compd. having a prescribed concn. as the aq. phase at the time of the phase inversion of a liq. crystal structure into an oil-in-water emulsion. SOLUTION: When an oil-in-water emulsion type emulsified liq. such as a hair rinse is produced, an aq. phase for forming liq. crystals is added to an oil phase contg. a film forming component besides an oil component, the resultant liq. crystal structure is mixed with an aq. phase for forming an emulsion and the oil phase is made dispersoid by phase inversion. The aq. phase for forming an emulsion is an aq. soln. contg. a cellulose or carboxyvinyl polymer having hydrophobic groups by >=0.1wt.% of the total amt. of the aq. phase. The film forming component in the oil phase is one or more kinds of cationic surfactants, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an emulsified liquid capable of uniformly dispersing an oil phase in an aqueous phase when preparing an O / W emulsion type emulsified liquid.

[0002]

2. Description of the Related Art
O / W for hair rinse, softener, cream, lotion, etc.
As a suitable method for preparing an emulsified liquid of an oil-in-water (oil-in-water) emulsion type, for example, a liquid crystal structure composed of an oil phase and a part of an aqueous phase is formed in advance, and the remainder of the aqueous phase is added thereto and inverted. There is a method of forming an O / W emulsion by mixing the emulsions. According to this method, an O / W emulsion type emulsified liquid can be easily formed as compared with another method of simply mixing and emulsifying an oil phase and an aqueous phase. It is possible to obtain an emulsified liquid that can be produced, has a uniform dispersion state of the oil phase, and has excellent stability.

However, in the case of the above-mentioned method, the aqueous phase may be water in addition to water, such as a low-temperature stabilizer, organic salts, inorganic salts, etc. Is used, there is no affinity between the water phase and the oil phase, and it is difficult to disperse the oil phase in the water phase. Not only is it necessary, but there is also a limit to the uniformity of the dispersed state of the oil phase in the emulsified liquid. In order to obtain a uniform emulsified liquid by the above method, the liquid crystal structure must be
When inverting a W-type emulsion, it is necessary to raise the phase inversion temperature above the melting point of the oil phase to facilitate the dispersion of the oil phase in the aqueous phase, and it requires energy and time for heating and cooling. And it was.

The present invention has been made in view of the above circumstances, and facilitates the dispersion of an oil phase in an aqueous phase when a liquid crystal structure is converted into an O / W type emulsion, and a liquid phase in an emulsified liquid. It is an object of the present invention to provide a method for producing an emulsified liquid capable of producing an emulsified liquid having a more uniform dispersibility of an oil phase in the emulsion.

[0005]

Means for Solving the Problems and Embodiments of the Invention The present inventor has conducted intensive studies in order to solve the above problems, and as a result,
By using a polymer solution prepared by preparing a specific polymer compound into an aqueous solution having a predetermined concentration as an aqueous phase when the liquid crystal structure is converted into an O / W emulsion, the affinity between the aqueous phase and the oil phase is increased. It has been found that the oil phase can be easily dispersed in the aqueous phase, and an emulsified liquid in which the oil phase is dispersed uniformly can be obtained, and the present invention has been accomplished.

That is, according to the present invention, after an aqueous phase for forming a liquid crystal is added to an oil phase containing a film forming component to form a liquid crystal structure, an aqueous phase for forming an emulsion is added and mixed to the liquid crystal structure. A method for producing an O / W emulsion type emulsified liquid in which the oil phase is a dispersoid by phase inversion, wherein the aqueous phase for forming an emulsion comprises a cellulose polymer or a carboxyvinyl polymer having a hydrophobic group. Provided is a method for producing an emulsified liquid, which is an aqueous solution containing 0.1% by weight or more based on the whole aqueous phase for forming an emulsion. Here, when the aqueous phase for forming an emulsion is an aqueous solution containing 0.2% by weight or more of the cellulose polymer or carboxyvinyl polymer having a hydrophobic group with respect to the entire aqueous phase for forming an emulsion, the liquid crystal structure is phase-inverted. Even when the temperature at this time is lower than the melting point of the oil phase, a uniform emulsified liquid can be obtained. Here, the melting point of the oil phase means a temperature at which the entire oil phase prepared by mixing the respective oil phase components is melted as described later.

Now, the present invention will be described in further detail. In the method for producing an emulsified liquid according to the present invention, an oil phase containing a film-forming component, an aqueous phase for forming a liquid crystal, a cellulose polymer having a hydrophobic group or a carboxyvinyl polymer are contained. An O / W emulsion is formed using the emulsion-forming aqueous phase.

The oil phase of the present invention comprises various oily components according to the type and purpose of the emulsified liquid. Examples of such oily components include clothing finishes, cosmetics, pharmaceuticals, and detergents. Hydrophobic oils used in products in various fields can be used, but they usually change the texture of clothing, provide moisturizing effects to the skin, nourish hair, provide antibacterial and sterilizing effects, etc. Those having a function are preferably used. Specifically, for example, synthetic oils such as silicone oil, cyclic silicone, and modified silicone, mineral oils such as liquid paraffin, liquid isoparaffin, and paraffin wax; vegetable oils such as jojoba oil, olive oil, olive squalane, castor oil, carnauba wax, and lanolin ,
Animal oils such as squalane and mink oil; and fatty acids and fatty acid esters such as hexyl laurate, isopropyl palmitate, oleic acid, and stearic acid. Further specific functions include triclosan, hinokitiol, triclocarban, and isopropylmethylphenol. Oil-soluble antibacterial agents such as butylparaben, propylparaben, benzoic acid, salicylic acid, and sorbic acid; oil-soluble antioxidants such as dibutylhydroxytoluene, butylhydroxyanisole, and tocopherol; linalool And oil-soluble flavors such as citronellol, geraniol, and geranyl acetate, and other oil-soluble UV absorbers, insect repellents, moisturizers, and the like. These may be used alone or in appropriate combinations of two or more. This Can.

The amount of the oily component can be appropriately selected depending on the kind, purpose and use of the emulsified liquid, but is usually 0.5 to 20% by weight of the whole emulsified liquid, particularly 1%.
It is desirably about 15% by weight. If the amount of the oil component is too small, the effect of the oil component may not be sufficiently obtained, and if the amount of the oil component is too large, formation of the liquid crystal structure and the emulsion may be difficult.

[0010] The oil phase of the present invention contains a film-forming component in addition to the above-mentioned oily component.
A quaternary ammonium salt, a tertiary amine salt, an imidazoline salt, an imidazolinium salt represented by the following general formula (1):
One or more selected from cationic surfactants such as amino acid-based cationic surfactants, or a mixture of the above cationic surfactant and a higher alcohol represented by the following general formula (2) is preferably used, Of these, quaternary ammonium salts are particularly preferred.

[0011]

Embedded image (Where R ¹ is an alkyl group or alkenyl group having 10 to 24 carbon atoms, R ² is an alkyl group having 1 to 3 carbon atoms, an alkyl group or alkenyl group having 10 to 24 carbon atoms,
¹ and R ² may each be unsubstituted;
It is divided by a functional group such as CONH- or -COO-
It may be substituted with a functional group such as H. R ³ has 1 carbon atom
And R ⁴ is an alkyl group having 1 to 3 carbon atoms or a benzyl group, and X is a halogen atom or a monoalkyl sulfate group. R ⁵ —OH (2) (wherein, R ⁵ is an alkyl group having 12 to 22 carbon atoms)

Specific examples of the film forming component include quaternary ammonium salts of the formula (1): stearyltrimethylammonium chloride, distearyldimethylammonium chloride, dodecyltrimethylammonium chloride, ditallowalkyldimethylammonium bromide, dioleyldimethyl Amino acid-based cationic surfactants such as ammonium chloride, oleyltrimethylammonium chloride, behenyltrimethylammonium chloride and the like include coconut oil fatty acid L-arginineethyl-DL-pyrrolidonecarboxylic acid, 4-guanidinobutyllauramide acetic acid and the like, and tertiary. Examples of the amine salt include distearylmethylamine hydrochloride, dioleylmethylamine hydrochloride, distearylmethylamine sulfate and the like. For grade amine salts, alkyl chains, -COO -, - CONH- a functional group may be split such. Examples of imidazoline salts include 1-octadecanoylaminoethyl-2-heptadecylimidazoline hydrochloride, 1-octadecenoylaminoethyl-2-heptadecenyl imidazoline hydrochloride, and the like. Tallowamidoethyl-2-tallowalkylimidazolinium methyl sulfate, methyl-1
Cetostearyl as a higher alcohol of the formula (2) such as hexadecanoylamidoethyl-2-pentadecylimidazolinium chloride, ethyl-1-octadecenoylamidoethyl-2-heptadecenylimidazolinium ethyl sulfate Alcohol, dodecyl alcohol,
Cetyl alcohol, stearyl alcohol, behenyl alcohol and the like are exemplified.

The amount of the film-forming component is preferably 1 to 30% by weight, particularly 2 to 20% by weight, based on the whole emulsified liquid. If the amount is too small, it may be difficult to form a liquid crystal structure or an emulsion. On the other hand, if the amount is too large, the aging stability of the viscosity may be poor. The mixing ratio of the oily component with the oily component is desirably 50% by weight or less, particularly more than 0% by weight and 20% by weight or less of the film-forming component. If the compounding ratio of the oily component is too large. Vesicles composed of a film-forming component containing an oily component may be broken.

In the oil phase of the present invention, in addition to the above oily components and film-forming components, organic solvents such as polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin, and lower alcohols such as ethanol and isopropyl alcohol; Additives such as various emulsifiers such as alkyl ethers, sorbitan fatty acid esters, and polyoxyethylene sorbitan fatty acid esters can be blended in usual amounts.

Next, the aqueous phase of the present invention is obtained by inverting a liquid crystal forming aqueous phase composed of the same components as in the prior art and a liquid crystal structure to form an O 2.
/ Emulsion-forming aqueous phase comprising an aqueous solution of a specific polymer compound used in forming a / W emulsion. Examples of the aqueous phase component for forming liquid crystals and emulsions include emulsifiers, dispersion stabilizers, low-temperature stabilizers, inorganic salts, dyes, and various other water-soluble active ingredients, in addition to water. Specifically, nonionic surfactants such as polyoxyethylene nonylphenyl ether, polyoxyethylene octyl phenyl ether, glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene alkyl ether, and fatty acid polyethylene glycol as emulsifiers, As pigments such as polyacrylic acid and carboxymethylcellulose as dispersion stabilizers, ethylene glycol, propylene glycol and glycerin as low temperature stabilizers, and hydrochlorides such as sodium chloride and calcium chloride as inorganic salts and sulfates such as sodium sulfate and the like. Acid Red 138,
Acid Blue 9, Acid Yellow 141, Reactive Blue, and other various water-soluble active ingredients include antibacterial agents such as isothiazolone and antioxidants such as hydroxyethanediphosphonic acid.

In the present invention, specific polymer compounds used as an aqueous phase component for forming an emulsion when forming an O / W emulsion are a cellulose polymer having a hydrophobic group and a carboxyvinyl polymer, Examples of the polymer include hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, methylcellulose and the like, and these can be used alone or in an appropriate combination of two or more. here,
The degree of polymerization of the polymer compound can be appropriately selected depending on the concentration in the aqueous phase and the like. For example, when the viscosity of a 1% by weight solution is 0.5 to 10 Pa · s (25 ° C.), particularly 1
What becomes 6 Pa.s (25 degreeC) is preferable. Also,
The weight average molecular weight is 200 to 5000, particularly 400 to 40
00 is preferred.

The amount of the polymer compound is 0.1% by weight or more, preferably 0.1 to 2% by weight, based on the whole aqueous phase for forming an emulsion. When the amount of the polymer compound is too small (when the concentration in the aqueous phase for forming an emulsion is too low), the affinity between the oil phase and the aqueous phase becomes weak, and the phase is inverted in an aqueous phase containing no polymer compound. Only the same degree of uniformity can be obtained. Here, assuming that the blending amount of the polymer compound is 0.2% by weight or more based on the whole aqueous phase for forming an emulsion, the temperature at which the liquid crystal structure is phase-inverted as described later is set to be equal to or lower than the melting point of the oil phase. It can be carried out. For the same reason, it is desirable that the amount of the polymer compound to be added to the whole emulsified liquid is 0.2 to 2% by weight.

The aqueous phase for forming an emulsion contains, in addition to the above-mentioned polymer compound, a water-soluble component such as an emulsifier, a low-temperature stabilizer, an inorganic salt, a dye, etc. in an amount not to impair the effects of the present invention. It can be appropriately compounded according to the use and purpose. After the emulsion is formed, the emulsion may be appropriately diluted using the liquid crystal or the aqueous phase for forming an emulsion according to the use of the emulsified liquid or the like, or the above-mentioned polymer compound may be appropriately added and used.

The mixing ratio of the whole aqueous phase and the whole oil phase in the emulsified liquid of the present invention is appropriately selected depending on the composition of the oil phase, the use and purpose of the emulsified liquid, and the like. = 1: 2 to 1:20, and the mixing ratio of the aqueous phase for forming the liquid crystal is such that the liquid crystal structure immediately before the vesicle is formed from the viewpoint of the vesicle formation ratio of the liquid crystal structure forming and film forming components. Is preferred, and is usually in oil phase:
The amount of the liquid crystal forming aqueous phase = 1: 0.5 to 1: 2, and the amount of the liquid crystal forming aqueous phase: emulsion forming aqueous phase = 1: 1 to 1:40 with respect to the emulsion forming aqueous phase. Is preferred. The mixing ratio of the aqueous phase for forming an emulsion to the entire oil phase is appropriately selected depending on the concentration of the polymer compound, the stability of the emulsified liquid, the composition of the oil phase, and the like. It is preferred that the amount is such that the forming aqueous phase = 1: 1 to 1:20. The emulsified liquid of the present invention can be appropriately diluted with water or the like after the emulsion is formed as described above. In this case, the amount of water or the like to be added depends on the amount of the entire oil phase and the entire aqueous phase. It can be determined in consideration of the mixing ratio.

In the production method of the present invention, the above-mentioned oil component, film-forming component and other oil phase components are mixed to prepare an oil phase, and the above-mentioned aqueous phase for forming a liquid crystal is added to the oil phase to form a liquid crystal structure. An O / W (oil-in-water) emulsion type emulsified liquid is produced by forming a liquid crystal body, then adding and mixing the above-mentioned emulsion forming aqueous phase to the liquid crystal structure and inverting the phase.

In this case, the temperature for forming the liquid crystal structure is equal to or higher than the phase transition temperature (T _c ) of the film forming component. If the liquid crystal structure formation temperature is lower than _Tc , the liquid crystal structure formation and the mixing of the liquid crystal structure with components other than the film-forming component in the oil phase become insufficient, and the vesicle conversion rate of the film-forming component decreases. I will. The temperature difference between the liquid crystal structure forming temperature and _Tc can be appropriately selected in consideration of other forming conditions in forming the liquid crystal structure. It is desirable that the temperature is higher than _c by 5 to 20 ° C, particularly about 10 to 15 ° C.

When the oil phase and the aqueous phase for forming a liquid crystal are mixed, the order in which they are added is not particularly limited, and they may all be added simultaneously. The apparatus for forming the liquid crystal structure by mixing them is not particularly limited, and a conventionally used stirring device can be used, but the viscosity of the system increases as the liquid crystal structure is formed. In view of the fact that, it is desirable to be able to mix the high-viscosity material as a whole, such as a kneader, paddle mixer, screw mixer, spiral mixer, Nauter mixer, double helical ribbon mixer, continuous kneader, etc. Can be mentioned.

In the production method of the present invention, a liquid crystal structure is formed by the above-described kneading step. Whether or not the liquid crystal structure is formed in this step depends on whether the liquid crystal structure has been formed. Is 10 to 100 Pa.
s, it can be confirmed using this change in viscosity.

In the production method of the present invention, the aqueous phase for emulsion formation is added to the liquid crystal structure, mixed and phase-inverted to obtain a desired emulsified liquid. By using an aqueous solution having the polymer compound concentration of 0.2% by weight or more as the aqueous phase, even if the temperature at the time of phase inversion is equal to or lower than the melting point of the oil phase,
An affinity between the oil phase and the water phase can be obtained to such an extent that the oil phase is sufficiently dispersed in the water phase. Therefore, when using an aqueous solution having a concentration of the polymer compound of 0.2% by weight or more, it is possible to invert the phase below the melting point of the oil phase, thereby greatly reducing the operation of heating and cooling. can do. A specific phase inversion temperature can be appropriately selected in consideration of a liquid crystal structure forming temperature, a preparation temperature of an aqueous phase for forming an emulsion, and the like, and is usually preferably from room temperature to a melting point of an oil phase. When the temperature of the phase inversion is equal to or lower than the room temperature, conversely, a cooling facility for cooling to the room temperature or lower is required.

As an apparatus used in the emulsion forming step, an apparatus used for ordinary emulsification and dispersion can be used. In this case, the order of adding the liquid crystal structure and the aqueous phase for forming an emulsion is not particularly limited, and they may be added simultaneously, for example.

As described above, the emulsified liquid obtained by the production method of the present invention, after the formation of the emulsion,
Various components can be further added as long as the effects of the present invention are not impaired.

The above-mentioned emulsified liquid is prepared by using O /
It is excellent in dispersion stability of the oil phase in a W-type emulsion type emulsified liquid, such as hair rinse, cream,
It is suitably used as a fiber finish such as an emulsion, a liquid detergent, and a softener.

[0028]

According to the present invention, when a liquid crystal structure composed of an oil phase and an aqueous phase is formed in advance, and this is converted into an O / W emulsion, the oil phase and the aqueous phase for forming an emulsion are combined. Since the affinity is high, it is easy to obtain an emulsified liquid in which the dispersibility of the oil phase is uniform and the stability is good. Further, an aqueous phase containing 0.2% by weight or more of the above polymer compound is used as an aqueous phase for forming an emulsion. Then, the operation of heating and cooling when producing the emulsified liquid can be greatly reduced, so that it is possible to save energy and shorten the production time.

[0029]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, comparative examples, and experimental examples, but the present invention is not limited to the following examples. In the following examples, “parts” means “parts by weight” and “%” means “% by weight”.

[Examples 1 to 5 and Comparative Examples 1 to 3] <Production of Rinse> First, an aqueous phase for emulsion formation (phase inversion) was prepared by mixing the components shown in Table 1, and this was mixed at about 70 ° C.
Held. On the other hand, the following components were mixed and dissolved at about 70 ° C. to obtain an oil phase.

Behenyltrimethylammonium chloride 12.5 parts stearyl alcohol 20.0 parts cetyl palmitate 5.0 parts sorbitan monolaurate 5.0 parts sorbitan monostearate 5.0 parts propylene glycol 50.3 parts methyl paraben 1.8 parts in the oil-soluble flavors 4.0 parts benzoic acid 1.0 part total 104.6 parts examples 1-5 and Comparative examples 1 and 2, the addition of purified water 115.0 parts of about 70 ° C. to the oil phase, The liquid crystal structure was formed by mixing. In Comparative Example 3, an aqueous phase in which 1.3 parts of hydroxyethyl cellulose was dissolved in 115.0 parts of purified water in advance and kept at about 70 ° C. was added to the oil phase to form a liquid crystal structure. Formed.

Each of the liquid crystal structures was added to the previously prepared aqueous phase for forming an emulsion, mixed, and phase-inverted into an O / W emulsion. Then, the post-added components shown in Table 1 were further added. Then, the components of each Example and Comparative Example were prepared so as to have the same amount to obtain an emulsified liquid.

With respect to each of the obtained emulsified liquids, the uniformity of emulsification was evaluated by the following method. The results are also shown in Table 1, and FIG. 1 is a graph showing the correlation between the concentration of hydroxyethyl cellulose (HEC) in the aqueous phase for forming an emulsion and the maximum diameter / average diameter of the oil droplets. [Evaluation of Emulsification Uniformity] From a micrograph (magnification:
400 times), the oil droplet diameter was observed, and the ratio between the maximum oil droplet diameter and the average oil droplet diameter was used as an index of uniformity.

[0034]

[Table 1]

According to Table 1 and the graph shown in FIG. 1, in the production method of the present invention, when a liquid crystal structure composed of an oil phase and an aqueous phase formed in advance is converted into an O / W emulsion, the liquid crystal structure is inverted. When an aqueous solution of hydroxyethyl cellulose having a concentration of 0.1% by weight or more is used as the aqueous phase for the phase, a uniform emulsified liquid can be produced. On the other hand, when the concentration of hydroxyethyl cellulose is too low (Comparative Example 1), When hydroxyethyl cellulose is not used (Comparative Example 2),
It is recognized that a uniform emulsified liquid cannot be obtained under the same conditions as in the production method of the present invention. In addition, when an aqueous solution of hydroxyethylcellulose was added when forming the liquid crystal structure (Comparative Example 3), it was recognized that it did not contribute to uniform emulsification.

Incidentally, cellulose polymers having a hydrophobic group other than hydroxyethylcellulose and carboxyvinyl polymers also show the same tendency.

[Experimental Examples 1 to 6] In the above Examples, the aqueous phase for emulsion formation (phase inversion) was the component shown in Table 2,
An emulsified liquid was obtained in the same manner as in the above example, except that the temperature during phase inversion of the liquid crystal structure was set to the temperature shown in Table 2. The melting point of the oil phase is about 50 ° C.

With respect to each of the obtained emulsified liquids, the uniformity of emulsification was evaluated by the above method. The results are shown in Table 2, and a graph showing the correlation between the concentration of hydroxyethyl cellulose (HEC) in the aqueous phase for forming an emulsion and the maximum diameter / average diameter of the oil droplets is shown in FIG.

[0039]

[Table 2]

According to Table 2 and the graph shown in FIG. 2, when a liquid crystal structure composed of an oil phase and an aqueous phase formed in advance is phase-inverted into an O / W emulsion, the concentration as an aqueous phase for phase inversion is determined. It is recognized that by using an aqueous solution of hydroxyethyl cellulose of 0.2% by weight or more, a uniform emulsified liquid can be produced even at a low temperature below the melting point of the oil phase.

[Brief description of the drawings]

FIG. 1 is a graph showing the relationship between the concentration of a polymer compound (hydroxyethyl cellulose) in an aqueous phase for forming an emulsion and the uniformity of emulsification of an emulsified liquid in an example of the present invention.

FIG. 2 is a graph showing the relationship between the concentration of a polymer compound (hydroxyethyl cellulose) in an aqueous phase for forming an emulsion and the uniformity of emulsification of an emulsified liquid obtained by low-temperature emulsification in an experimental example of the present invention.

Claims (2)

[Claims] 1. An aqueous phase for forming a liquid crystal is added to an oil phase containing a film-forming component to form a liquid crystal structure, and then an aqueous phase for forming an emulsion is added to and mixed with the liquid crystal structure to cause phase inversion. A method of producing an O / W emulsion type emulsified liquid using the oil phase as a dispersoid, wherein the aqueous phase for forming an emulsion comprises a cellulose polymer or a carboxyvinyl polymer having a hydrophobic group and the aqueous phase for forming an emulsion. A method for producing an emulsified liquid, which is an aqueous solution containing 0.1% by weight or more based on the whole. 2. The aqueous phase for forming an emulsion contains a cellulose polymer or a carboxyvinyl polymer having a hydrophobic group in an amount of 0.2 to the whole aqueous phase for forming an emulsion.
2. The method for producing an emulsified liquid according to claim 1, wherein the aqueous solution contains not less than% by weight, and the temperature at which the liquid crystal structure is phase-inverted is equal to or lower than the melting point of the oil phase.