KR20110046069A - A method for preparing a clear micro emulsion - Google Patents

Abstract

PURPOSE: A method for manufacturing transparent microemulsion is provided to ensure transparency and to excellent stability at high temperature. CONSTITUTION: A method for manufacturing transparent microemulsion comprises: a step of preparing a microemulsion from a mixture containing water, anionic surfactant, and organopolysiloxane; and a step of inputting at least a part of organopolysiloxane into an emulsifying device at high temperature. The emulsifying device is a mixer, homogenizer, or colloid mill. The anionic surfactant is sulfonic acid surfactant.

Description

A method for preparing a clear micro emulsion

The present invention relates to a process for preparing a transparent microemulsion, and more particularly to preparing a microemulsion from a mixture comprising water, anionic surfactant and organopolysiloxane using an emulsifier, wherein at least a portion of the organopolysiloxane The present invention relates to a method for producing a microemulsion, characterized in that it is added to the emulsifying apparatus at a temperature higher than room temperature (25 ° C.). When applied to the excellent lubricity, it is possible to prepare a micro emulsion excellent in high temperature stability.

Microemulsions generally refer to emulsions with particle sizes of microns or sub-microns, and are applied to a variety of cosmetic products, including hair care products, and are water continuous (O / W) or oil continuous (W / O). Can be. U.S. Patents 5,683,625 and 5,759,530 disclose methods for preparing water-continuous (O / W) microemulsions using non-mechanical methods.

As the microemulsion for cosmetics, silicone-based materials such as polysiloxane and the like are utilized, and are commonly used as softeners and / or lubricants in hair products such as transparent shampoos, herbal shampoos, hair nail polishes, transparent shower gels, and the like.

In such cosmetic microemulsion, transparency in the formulation is considered as an important problem, but many known silicone-based microemulsion preparation methods do not provide the emulsion with a level of transparency suitable for cosmetic use.

Meanwhile, as a method of preparing a silicone emulsion for improving transparency, for example, a method by polymerization of diorganopolysiloxane (US Pat. No. 5,523,081, US Pat. No. 4,733,677, etc.) has been introduced. The short duration of maintenance and low stability at high temperature has the disadvantage.

Therefore, there is a demand for a microemulsion production technology that is excellent in transparency and can provide excellent lubricity when applied to hair products.

The present invention is to solve the problems of the prior art as described above, excellent transparency than the conventional micro emulsion, in particular, when applied to hair products, such as cosmetics or shampoo, excellent lubricity, high temperature stability micro emulsion It is the technical problem to provide a method for producing the same.

In order to solve the above technical problem, in the preparation of a microemulsion from a mixture containing water, anionic surfactant and organopolysiloxane using an emulsifier, at least a part of the organopolysiloxane is at room temperature (25 It provides a method for producing a micro-emulsion, characterized in that it is put into the emulsifying apparatus at a temperature higher than (℃).

In one preferred embodiment of the invention, at least a portion of the organopolysiloxane is introduced into the emulsifying apparatus at 70-90 ° C.

In another preferred embodiment of the present invention, the amount of organopolysiloxane added to the emulsifying apparatus at a temperature above room temperature is 40-100% by weight of the total organopolysiloxane input.

In another preferred embodiment of the invention, 5 to 60% by weight of the total organopolysiloxane dose is added to the emulsifier at room temperature and 40 to 95% by weight is added to the emulsifier at temperatures above room temperature.

In another preferred embodiment of the present invention, the emulsifying apparatus is selected from the group consisting of a stirred mixer, a homogenizer and a colloid mill.

In another preferred embodiment of the invention, the anionic surfactant is a sulfonic acid based surfactant.

In another preferred embodiment of the invention, the organopolysiloxane is an alkyl group containing polysiloxane having a viscosity of 1 to 100 centipoise (cP).

In another preferred embodiment of the invention, after at least a portion of the organopolysiloxane is introduced into the emulsifying apparatus and mixed at a temperature above room temperature, the resulting mixture is cooled to room temperature and further neutralizer is added thereto.

In another preferred embodiment of the present invention, the neutralizing agent is added at a time point when the viscosity of the mixture is 40,000 to 100,000 cP after the temperature is cooled.

In another preferred embodiment of the invention, the neutralizing agent is an alkaline amine compound.

According to another aspect of the present invention, there is provided a hair product comprising a micro emulsion prepared by the above method.

The microemulsion prepared according to the present invention preferably has an average particle diameter of 100 nm or less, more preferably 1 nm to 60 nm, in particular, because of its excellent transparency, excellent storage stability at room temperature and high temperature, and excellent lubricity, Or it is very suitable for hair products.

The peculiarity of the manufacturing process of the present invention is that, unlike the prior art, all or part of the organopolysiloxane is introduced into the emulsion system and mixed at a temperature higher than room temperature (25 ° C.) to ensure transparency. Hereinafter, the technical configuration of the present invention will be described in detail.

In the method for producing a microemulsion according to the present invention, the temperature of at least a room temperature at which a part of the organopolysiloxane is added is preferably 70 to 90 ° C, more preferably 75 to 85 ° C. If the temperature is less than 70 ℃ there may be a problem that the polymerization is not achieved sufficiently, if it exceeds 90 ℃ may adversely affect the final physical properties of the product.

In the microemulsion preparation method according to the present invention, the amount of organopolysiloxane added to the emulsifying apparatus at a temperature higher than room temperature is all or part of the total organopolysiloxane input amount, and preferably 40 to 100% by weight of the total input amount. More preferably, it is 45-100 weight%. If the amount of organopolysiloxane added at a temperature higher than room temperature is less than 40% by weight of the total amount, the emulsion particle size may not be uniform and stability may be deteriorated.

According to one preferred embodiment of the invention, a portion of the total organopolysiloxane input, such as 5 to 60% by weight, more preferably 5 to 50% by weight, is added at room temperature and the remainder, such as 40 to 95% by weight, more preferably 50 to 95% by weight is preferably added at a temperature higher than room temperature in terms of making the emulsion particle size more uniform and maintaining stability and transparency of the product continuously.

In the method of preparing a microemulsion according to the present invention, a conventional emulsifying apparatus may be used, and preferably, one selected from the group consisting of a stirred mixer, a homogenizer and a colloid mill may be used, but this is limited. It doesn't happen. In the case of using a stirring mixer, the stirring speed is preferably a high speed stirring, such as about 200 to 800 rpm, to enable the preparation of the microemulsion.

There is no particular limitation on the kind of anionic surfactant used in the microemulsion preparation method according to the present invention, and those commonly used in the preparation of the microemulsion can be used. Preferably sulfonic acid-based surfactant, more specifically, linear C6-C18 alkylbenzene sulfonic acid such as dodecylbenzene sulfonic acid, branched C6-C18 alkylbenzene sulfonic acid, ammonium C6-C18 alkyl sulfate, sodium C6-C18 alkyl sulfate, Surfactants, such as sodium C 6 -C 18 alkyl ether sulfate, are used alone or in combination.

In the method of preparing a microemulsion according to the present invention, the anionic surfactant is used in an amount of preferably 0.1 to 30% by weight, more preferably 0.5 to 20% by weight based on the total weight of the emulsion composition. If the anionic surfactant content is less than 0.1% by weight, the stability of the resulting emulsion may be insufficient, and if it exceeds 30% by weight, the transparency and stability of the emulsion may be lowered.

There is no particular limitation on the type of organopolysiloxane used in the microemulsion preparation method according to the present invention, and polysiloxanes having organic group-containing siloxane units commonly used in the preparation of the microemulsion can be used. Preferably alkyl group containing polysiloxane having a viscosity of 1 to 100 centipoise), such as poly C1 to C4 alkyl siloxane, poly C1 to C4 alkoxysiloxane, poly C1 to C4 alkyl vinyl siloxane, poly C1 to C4 alkyl hydroxysiloxane, etc. The same polysiloxanes are used alone or in combination.

In the method of preparing a micro emulsion according to the present invention, the organopolysiloxane is preferably used in an amount of 15 to 30% by weight, more preferably 20 to 25% by weight, based on the total weight of the emulsion composition. If the organopolysiloxane content is less than 15% by weight, there is a concern that application properties such as conditioning and combing of the hair may be degraded. If the organopolysiloxane content is more than 30% by weight, particle formation during polymerization may not be smooth and stability may be reduced.

According to one preferred embodiment of the invention, after at least a portion of the organopolysiloxane is introduced into the emulsifying apparatus at a temperature higher than room temperature and mixed, the resulting mixture is cooled to room temperature and further neutralizer is added thereto. When the neutralizing agent is added at the time when the viscosity of the mixture is 40,000 to 100,000 cP after the temperature is increased, it is preferable in terms of giving a suitable conditioning effect and shortening the process when applying the shampoo.

As the neutralizing agent, neutralizing agents commonly used in the preparation of microemulsions can be used. Preferably, an alkaline amine compound (eg, diethylamine, triethylamine, diethanolamine, triethanolamine, etc.) or a caustic soda may be used alone or in combination, but is not limited thereto.

In the method of preparing a microemulsion according to the present invention, the neutralizing agent is preferably used in an amount of 1 to 20% by weight, more preferably 5 to 15% by weight, based on the total weight of the emulsion composition. If the amount of neutralizing agent is less than 1% by weight, the stability of the emulsion is insufficient, and if it is more than 20% by weight, there is a fear of decreasing the transparency in the final shampoo formulation.

In the method of preparing a microemulsion according to the present invention, water is preferably used as a medium, and water is preferably used in an amount of 40 to 70% by weight, more preferably 50 to 60% by weight, based on the total weight of the emulsion composition. If the amount of water used is less than 40% by weight, the size of the emulsion particles may not be formed small, and transparency may not be secured. If the amount of water is used, the stability of the emulsion may be insufficient.

In preparing the microemulsion according to the present invention, additives such as cryoprotectants may be further added as necessary. Applicable additives include PG (propylene glycol), PEG (polyethylene glycol), PPG (polypropylene glycol), glycerin, and the like as cryoprotectants, and glycerin is preferably used. These additives are mainly used for the purpose of further improving the high / low temperature stability of the product and making the appearance (transparency) with temperature unaffected. In addition, there is an effect that the viscosity of the product is lowered due to the presence of the additive. There is no particular limitation on the dosage of such additives, and is usually used in the range of 0.01 to 10% by weight of the total weight of the composition, but is not limited thereto.

In addition, in preparing the microemulsion according to the present invention, a silane-based catalyst may be added up to 0.01 to 0.5% by weight of the total weight of the emulsion to shorten the viscosity rise time of the emulsion and increase the viscosity.

The microemulsion prepared according to the present invention preferably has an average particle diameter of 100 nm or less, more preferably 1 nm to 60 nm, especially for hair because of its excellent transparency, excellent room temperature and high temperature storage stability, and excellent lubricity. It can be applied to the product very well. Accordingly, according to another aspect of the present invention, there is provided a hair product, such as a shampoo, rinse, hair conditioner, etc., comprising a micro emulsion prepared by the above method.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, these examples are not intended to limit the scope of the present invention.

Example 1

At room temperature, a mixture of 530 g of water (deionized water), 150 g of anionic surfactant (linear dodecylbenzenesulfonic acid) and 50 g of polydimethylsiloxane (viscosity: 2.5 centipoise) was added to a mixer and stirred at 200 to 400 rpm. Then, the resultant was heated up at 70-90 degreeC.

After the temperature increase was completed, 170 g of polydimethylsiloxane (viscosity: 2.5 centipoise) was uniformly pumped using a metering pump over 2 to 3 hours, and then introduced into the mixer bottom part. After the addition of the polydimethylsiloxane was completed, the temperature was maintained for 3 to 4 hours and then slowly cooled. In this case, it was confirmed that the particle size of the laser light scattering method (LLS, Photal ELS-Z, OTSUKA ELECTRONICS) has a particle size in the range of 30 ~ 50 nm.

After cooling below 40 ° C, stirring was maintained until the internal viscosity reached 40,000 ~ 100,000 cP. After confirming that the internal viscosity was reached, 80 g of 95% water-soluble triethanolamine was added to neutralize the emulsion and reacted. Was terminated. And 20 g of Glycerine (95%), a cryoprotectant, was added.

Batch 1 having a reaction capacity of 1 L was prepared as described above, and Batch 2 having a reaction capacity of 20 L and Batch 3 having a reaction capacity of 200 L were further prepared in the same manner using the same ratio of raw materials. Table 1 shows the measurement results of the basic physical properties of each of the prepared batch 1-3 emulsions.

As can be seen in Table 1 below, in the emulsion production method according to the present invention, even if the reaction capacity is increased, the resultant emulsion has little or no change in physical properties, thereby enabling scale-up of the process while satisfying all necessary criteria.

Example 2

At room temperature, a mixture of 360 g of water (deionized water), 90 g of anionic surfactant (linear dodecylbenzenesulfonic acid), and 220 g of polydimethylsiloxane (viscosity: 2.5 centipoise) was added to a mixer and stirred at 200 to 300 rpm. Pre-emulsions were made and stored in a dropping funnel.

The mixture of 170 g of water (deionized water) and 60 g of anionic surfactant (linear dodecylbenzenesulfonic acid) was heated to 78-82 ° C. with stirring, and the pre-emulsion stored in the dropping funnel was heated for 2-4 hours after the temperature was completed. It was dripped uniformly over. After the dropping was completed, the temperature was maintained for 2 to 3 hours, and then slowly cooled. In this case, it was confirmed that the particle size of the laser light scattering method (LLS, Photal ELS-Z, OTSUKA ELECTRONICS) has a particle size in the range of 30 ~ 50 nm.

After cooling below 40 ° C, stirring was maintained until the internal viscosity reached 40,000 ~ 100,000 cP. After confirming that the internal viscosity was reached, 80 g of 95% water-soluble triethanolamine was added to neutralize the emulsion and reacted. Was terminated. And 20 g of Glycerine (95%), a cryoprotectant, was added.

Example 3

A mixture of 530 g of water (deionized water) and 150 g of anionic surfactant (linear dodecylbenzenesulfonic acid) was stirred at 200-400 rpm with a mixer while warming to 78-82 ° C.

After the completion of the temperature increase, a mixture of 220 g of polydimethylsiloxane (viscosity: 2.5 centipoise) was added dropwise evenly over 2 to 4 hours, and the temperature was maintained for 2 to 3 hours after the dropping of the polydimethylsiloxane was completed. Cool slowly. In this case, it was confirmed that the particle size of the laser light scattering method (LLS, Photal ELS-Z, OTSUKA ELECTRONICS) has a particle size in the range of 30 ~ 50 nm.

After cooling to below 40 ℃, the stirring was continued until the internal viscosity reached 40,000 ~ 100,000 cP, and after confirming that the internal viscosity was reached, neutralized the emulsion by adding 80 g of 99% water-soluble triethanolamine. The reaction was terminated. And 20 g of Glycerine (95%), a cryoprotectant, was added.

Comparative Example 1

At room temperature, a mixture of 530 g of water (deionized water), 150 g of anionic surfactant (linear dodecylbenzenesulfonic acid) and 220 g of polydimethylsiloxane (viscosity: 2.5 centipoise) is placed in a mixer at room temperature at 200-400 rpm. Stirred.

Stirring was maintained until the internal viscosity reached 40,000 to 100,000 cP, and the internal viscosity was reached. Then, 80 g of 95% water-soluble triethanolamine was added to neutralize the emulsion, and the reaction was terminated. And 20 g of Glycerine (95%), a cryoprotectant, was added.

Comparative Example 2

At room temperature, a mixture of 530 g of water (deionized water), 150 g of anionic surfactant (linear dodecylbenzenesulfonic acid) and 220 g of polydimethylsiloxane (viscosity: 2.5 centipoise) was added to a mixer and stirred at 200 to 400 rpm. Then, the resultant was heated up at 70-90 degreeC.

The temperature was maintained for 5 to 6 hours and then slowly cooled. After cooling below 40 ° C, stirring was maintained until the internal viscosity reached 40,000 ~ 100,000 cP. After confirming that the internal viscosity was reached, 80 g of 95% water-soluble triethanolamine was added to neutralize the emulsion and reacted. Was terminated. And 20g of Glycerin (95%) was added as a cryoprotectant.

For the emulsions prepared in Examples 1 to 3 and Comparative Examples 1 and 2, the appearance, particle size, room temperature stability, and transparency were measured or evaluated, and the results are shown in Table 2 below.

As can be seen in Table 2, Comparative Examples 1 and 2 failed to form small and uniform particles during the process, and the stock appearance and transparency of AES dilution decreased.

In addition, the emulsion prepared in Examples 1 to 3 and Comparative Examples 1 to 2 was subjected to a high temperature stability test over 7 days in a 50 ℃ constant temperature oven. During the test period, the appearance of the emulsion was compared and observed on a daily basis, and the results are shown in Table 3 below.

Claims (11)

In preparing a microemulsion from a mixture comprising water, anionic surfactant and organopolysiloxane using an emulsifying device, at least a portion of the organopolysiloxane is introduced into the emulsifying device at a temperature higher than room temperature. Method for producing a micro emulsion. The method of claim 1, wherein at least a portion of the organopolysiloxane is introduced into the emulsifying apparatus at 70 to 90 ° C. The method of claim 1, wherein the amount of organopolysiloxane added to the emulsifier at a temperature higher than room temperature is 40 to 100% by weight of the total amount of organopolysiloxane. The microemulsion according to claim 1, wherein 5 to 60% by weight of the total organopolysiloxane input is added to the emulsifier at room temperature, and 40 to 95% by weight is input to the emulsifier at a temperature higher than room temperature. Manufacturing method. The method of claim 1, wherein the emulsifying apparatus is selected from the group consisting of a stirred mixer, a homogenizer and a colloid mill. The method of claim 1, wherein the anionic surfactant is a sulfonic acid surfactant. The method of claim 1, wherein the organopolysiloxane is an alkyl group-containing polysiloxane having a viscosity of 1 to 100 centipoise. 2. The microemulsion of claim 1, wherein after at least a portion of the organopolysiloxane is introduced into the emulsifying apparatus and mixed at a temperature higher than room temperature, the resulting mixture is cooled to room temperature and further neutralizer is added thereto. Manufacturing method. The method of claim 8, wherein the neutralizing agent is added at a point in time at which the viscosity of the mixture is 40,000 to 100,000 cP after cooling. The method of claim 8, wherein the neutralizing agent is an alkaline amine compound. A hair product comprising a micro emulsion prepared by the method of any one of claims 1 to 10.