KR20030022702A - Pearl gloss agent dispersions and method for producing the same - Google Patents

Abstract

PURPOSE: A dispersion agent, as a pearl gloss agent and a method for producing the same are provided, thereby cheaply and easily producing a dispersion agent, as a pearl gloss agent, having improved pearl gloss using small scale equipments. CONSTITUTION: A dispersion agent, as a pearl gloss agent, has two peaks when crystal particle size distribution is measured using the relative refraction rate to water of 1.08 by a laser diffraction particle size distribution measuring machine, wherein the particle diameter of one peak is 0.1 to 1 micrometer and the particle diameter of the other peak is 3 to 30 micrometer. A method for producing a dispersion, as a pearl gloss agent, comprises the steps of: mixing fatty acid glycol ester and a surfactant at the melting point or more of the fatty acid glycol ester; adding 0.5 to 35 weight times of a coolant into the mixture and mixing them; and cooling the mixture to the melting point or less of the fatty acid glycol ester.

Description

Pearl gloss agent dispersions and method for producing the same

The present invention relates to pearlescent gloss agent dispersions and pearlescent varnish dispersions which add value to shampoos, rinses, and other liquid detergents.

Background Art Conventionally, a technique of increasing product value by imparting pearlescent varnish to shampoo or the like has been widely performed. For example, Japanese Unexamined Patent Application Publication No. 47-804 discloses a technique in which fatty acid glycol esters and the like are added at the time of manufacture of a product, heated and melted above the melting point of the fatty acid glycol ester, and then cooled and recrystallized. However, this technique requires a large amount of water, a surfactant, and the like, and also has a problem that the cooling rate is slow, the production time is long, and the productivity decreases because the size of the apparatus is increased.

Japanese Patent Application Laid-Open No. 58-216728 discloses a technique in which a fatty acid glycol ester is dissolved in a specific solvent by heating and then indirectly cooled to obtain a pearl dispersion. However, this technique has a problem that the cooling time is long because it is indirectly cooled, the viscosity is increased in the vicinity of the heat transfer surface, the heat transfer is deteriorated, and the mixing is uneven.

In Japanese Patent Laid-Open No. 61-268797, Japanese Patent Laid-Open No. 63-132973, Japanese Patent Laid-Open No. 4-45843, and Japanese Patent Laid-Open No. 5-20386, a low concentration of fatty acid glycol ester dispersion is prepared as a nucleus. And the technique of aging at the crystal growth temperature is disclosed. However, these techniques require various process facilities such as a seed preparation step, a dissolution step, and a aging step, and strict temperature control is required, and thus there is a problem that the operation is complicated.

In the Japanese Patent Application Laid-Open No. 6-182173, a fatty acid precipitated inside a cylinder by scraping an aqueous solution containing a fatty acid glycol ester and a surfactant maintained at a melting point or higher into the inside, and feeding and cooling it to a cylindrical heat exchanger having wings and a jacket. A method for preparing a pearl dispersion is disclosed by scraping a glycol ester with an internal scraping blade and dispersing it in an aqueous solution. However, there is a problem in that the facility becomes large when trying to increase the throughput because it requires large power because it precipitates crystals on the inner wall surface and scrapes it.

This invention solves the said various conventional problems, and makes it a subject to achieve the following objectives.

That is, an object of the present invention is to provide a pearlescent varnish dispersion having an excellent pearlescent gloss, and a pearlescent varnish dispersion which can be produced inexpensively, efficiently, and easily in a small facility. .

The pearlescent varnish dispersion of the present invention has two peaks when the crystal particle size distribution is measured with a relative refractive index of 1.08 by a laser diffraction particle size distribution analyzer, and the particle diameters at the two peaks ( One is 0.1-1 micrometer, and the other is 3-30 micrometers.

In the method for producing a pearlescent varnish dispersion of the present invention, at least a fatty acid glycol ester and a surfactant-containing component are mixed at a temperature equal to or higher than the melting point of the fatty acid glycol ester, and a mixture of 0.5 to 35 times the mass ratio of the refrigerant is blended with the mixture. It cools to the temperature below melting | fusing point of the said fatty acid glycol ester.

Hereinafter, a method of preparing the pearlescent varnish dispersion and the pearlescent varnish dispersion of the present invention will be described.

Pearlescent varnish dispersion

The pearlescent varnish dispersion of the present invention has two peaks when the crystal particle size distribution is measured with a relative refractive index of 1.08 by a laser diffraction particle size distribution analyzer, and one of the particle diameters at the two peaks. Is 0.1 to 1 m, and the other includes 5 to 30 m of pearlescent polish.

In the present invention, the above measurement has two peaks as described above. That is, the pearlescent polish particles (crystal of a pearlescent polish) of two types of particle diameters are contained. For this reason, light is shielded by the particle | grains (crystal) of a smaller particle diameter, and light is diffusely reflected, and the pearlescent varnish dispersion of this invention has the pearlescent gloss excellent compared with the pearlescent varnish dispersion which has only a single peak by the said measurement.

The particle diameter of one of the two peaks is preferably 0.2 to 0.8 m, more preferably 0.3 to 0.7 m.

When the particle diameter is outside the numerical range of 0.1 to 1 mu m, the diffuse reflection does not occur properly, so that excellent pearlescent luster is not obtained.

In the present invention, the "particle size at peak" refers to the "maximum frequency particle size", and in the particle size distribution obtained by the above measurement, the particle size at the intersection point of the tangent line drawn at the maximum inclination point on both sides of the peak. Means.

5-25 micrometers is preferable and, as for the other one of the particle size (maximum frequency particle diameter) in the said two peaks, 8-20 micrometers is more preferable.

If the particle diameter is less than 3μm, pearlescent luster is likely to fall, whereas if it is more than 30μm, the stability of the dispersion becomes poor.

<The composition of the pearlescent varnish dispersion>

As the composition of the pearlescent varnish dispersion of the present invention, it is particularly preferable to include a surfactant-containing component and the like in addition to the crystal of the fatty acid glycol ester.

Fatty acid glycol ester

Examples of the fatty acid glycol esters include diesters of ethylene glycol, stearic acid and palmitic acid, diesters of ethylene glycol, monostearic acid ethylene glycol and the like. Among these, in view of gloss and dispersibility after dispersion, a mixture of distearic acid ethylene glycol, stearic acid and palmitic acid and diester of ethylene glycol is preferable. These may be used independently and may use 2 or more types together.

As content of the said fatty acid glycol ester in the said pearlescent varnish dispersion, 0.4-40 mass% is preferable, and 0.75-30 mass% is more preferable.

If the content is less than 0.4% by mass, it may be too dilute to break down the composition balance in the product, whereas if it exceeds 40% by mass, dispersibility may be poor.

-Surfactants-

As said surfactant, anionic surfactant, a nonionic surfactant, an amphoteric surfactant, etc. are mentioned.

Examples of the anionic surfactants include polyoxyethylene alkyl ether sulfonates, α-olefin sulfonates, alkyl sulfonates, and higher fatty acid salts. As these counter ions, an alkali metal, alkaline earth metal, ammonium, etc. are mentioned. These may be used independently and may use 2 or more types together.

As said nonionic surfactant, palm oil fatty acid diethanol amide, palm oil fatty acid monoethanol amide, polyoxyethylene hardened castor oil, lauric acid diethanol amide, lauric acid monoethanol amide, polyoxyethylene alkyl ether, lauric acid Ethylene oxide adduct of mono ethanol amide, Ethylene oxide adduct of palm oil fatty acid monoethanol amide, Propylene oxide adduct of palm oil fatty acid mono isopropanol amide, Palm oil fatty acid mono isopropanol amide, Myristic acid diethanol amide, Stearic acid diethanol amide, Oleic acid Diethanol amide, myristic acid monoethanol amide, stearic acid mono ethanol amide, oleic acid mono ethanol amide, and the like. These may be used independently and may use 2 or more types together.

Examples of the amphoteric surfactant include alkyl amide propyl betaine, palm oil fatty acid amide propyl betaine, alkyl dimethyl carboxy methyl ammonium betaine, alkyl carboxy methyl imidazolium betaine, alkyl amide dimethyl dimethyl acetic acid betaine, alkyl dimethyl amino acetic acid Betaine and the like. These may be used independently and may use 2 or more types together.

Among these surfactants, alkyl amide propyl betaine and the like are preferable in view of dispersibility during cooling.

The content of the surfactant in the pearlescent varnish dispersion is preferably 3 to 70 mass%, more preferably 10 to 60 mass%.

If the content is less than 3% by mass, the gloss in the pearlescent varnish dispersion may drop, whereas if it exceeds 70% by mass, the raw material cost may increase, which may cause a rise in manufacturing cost.

Other Ingredients

The pearlescent varnish dispersion of the present invention may contain a reducing agent or the like as other components. Examples of the reducing agent include sodium benzoate, potassium chloride, polyethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, ethanol, and the like. These may be used independently and may use 2 or more types together.

<Method of producing a pearlescent varnish dispersion>

Although there is no restriction | limiting in particular as a method of manufacturing the pearlescent varnish dispersion of this invention, The manufacturing method of the pearlescent varnish dispersion of this invention mentioned later is especially preferable at the point of cost, efficiency, and a point which can be easily manufactured by a small scale facility.

Since the pearlescent varnish dispersion liquid of this invention demonstrated above has the outstanding pearlescent gloss, it is used especially suitably for various liquid detergents, such as a shampoo and a rinse.

[Method of producing a pearlescent varnish dispersion]

In the method for producing a pearlescent varnish dispersion of the present invention, by mixing at least a fatty acid glycol ester and a surfactant-containing component at a temperature equal to or higher than the melting point of the fatty acid glycol ester, by mixing a refrigerant having a mass ratio of 0.5 to 35 times with respect to the mixture liquid It cools to the temperature below melting | fusing point of the said fatty acid glycol ester.

In the method for producing a pearlescent varnish dispersion of the present invention, as described above, the fatty acid glycol ester and the surfactant-containing component are cooled by blending a mixed liquid and a refrigerant mixed at a temperature equal to or higher than the melting point of the fatty acid glycol ester. For this reason, in the manufacturing method of the pearlescent varnish dispersion liquid of this invention, since the fatty acid glycol ester melt | dissolved once at the temperature more than melting | fusing point is instantaneously cooled and crystallized by crystallization, it is efficient in a short time, and it is inexpensive in a small scale facility. A pearlescent varnish dispersion having an excellent pearly luster can be obtained.

-mix-

As content of the said fatty acid glycol ester in the liquid mixture of the said fatty acid glycol ester and surfactant containing component, 10-60 mass% is preferable, and 20-50 mass% is more preferable.

When the content exceeds 60% by mass, in the operation of direct cooling (in the present invention, refers to "mixing of the mixture and the refrigerant"), the dispersibility is poor, the viscosity is high, and the handling property is deteriorated. If less than 10% by mass, it is too thin to be added to the product in large amounts, so that the composition balance as the product can be broken.

In the mixed liquid of the fatty acid glycol ester and the surfactant-containing component, the mixing ratio of the surfactant to the fatty acid glycol ester is preferably 0.3 to 5 times by mass ratio, and more preferably 0.35 to 3 times.

If the compounding ratio is less than 0.3 times, the solubilization or emulsification of fatty acid glycol esters becomes insufficient when mixed and dissolved, and the crystallization when directly cooled and crystallized becomes poor, and the gloss may be degraded, whereas it exceeds 5 times. If this occurs, the raw material cost of pearlescent varnish dispersion itself may increase, which may lead to an increase in manufacturing cost.

When mixing and dissolving the mixed liquid of the said fatty acid glycol ester and surfactant containing component at the temperature more than melting | fusing point of the said fatty acid glycol ester, it mixes and melts by stirring in well-known Vessel, etc. equipped with the jacket, coil, etc. which are mentioned later, It is desirable to maintain the proper temperature.

-Cooling-

As the quantity of the refrigerant | coolant to mix | blend at the time of the said cooling, 0.5-30 times are preferable by mass ratio with respect to the said mixed liquid, and 0.5-20 times are more preferable.

If the amount of the coolant is less than 0.5 times, cooling is insufficient, and crystallization at the time of crystallization is poor and gloss falls, whereas if the amount of the refrigerant exceeds 35 times, the concentration of the pearlescent polish after crystallization is low, so that the gloss is degraded when commercialized.

As temperature of the said coolant, 5-50 degreeC is preferable and 10-45 degreeC is more preferable.

If the temperature is less than 5 ° C, cooling equipment such as a refrigerator is required at the time of temperature adjustment. On the other hand, if the temperature exceeds 50 ° C, the temperature of the dispersion after crystallization rises, so that the melting point of the fatty acid glycol ester or the melting point is exceeded. As a result, crystallization may not proceed properly, resulting in poor gloss of the pearlescent varnish dispersion.

In addition, the gloss of the pearlescent varnish dispersion includes a silky (white and smooth) gloss and a metallic (metallic sharpness) gloss. When the temperature of the coolant is lower than 40 ° C., the temperature at the time of dispersion is lowered and the crystal diameter is shifted to a smaller side, so that gloss of silk atmosphere appears. On the other hand, when the temperature of the coolant is 40 ° C or higher, the temperature at the time of dispersion increases, mild crystallization is performed, and the crystal diameter is shifted toward the larger side, so that the gloss of the metallic atmosphere appears.

There is no restriction | limiting in particular as said refrigerant | coolant, The liquid raw material generally used in water, a shampoo, rinse, body soap, etc. which are target products are mentioned. These refrigerant | coolants may be used independently and may use 2 or more types together.

There are no particular limitations on the mixing device to be used when mixing the mixed solution and the refrigerant and crystallizing the crystals by cooling. For example, a vessel having a stirrer having shear force, a line mixer having the stirrer inside, and the like are exemplified. Can be. As a stirrer provided with a shearing force, T.K. homodispa (made by Tokushu Kika Kogyo Co., Ltd.), the dispro wing (the stirring blade of Unexamined-Japanese-Patent No. 10-180071), a homomixer, etc. are mentioned, for example.

In the case of using the vessel, for example, the refrigerant is previously metered into the vessel, the stirrer is started, and a mixed liquid containing a fatty acid glycol ester and a surfactant-containing component maintained above the melting point of the fatty acid glycol ester is added, It is preferable to directly mix-disperse and cool and to crystallize.

When using the said line mixer, the mixed liquid containing a fatty acid glycol ester and surfactant containing component, and a refrigerant | coolant are transferred to the line mixer which started the stirrer beforehand by the quantitative pump, and it mixes continuously in the inside It is preferable to disperse | distribute and to cool, and to crystallize. In this system, mixing may be performed in one pass, or crystallization may be performed by continuously adding a mixed solution containing a fatty acid glycol ester and a surfactant-containing component to a loop in which a refrigerant is circulated.

In this invention, you may cool by adding the mixed liquid of a fatty acid glycol ester and surfactant containing component to a refrigerant | coolant, or you may cool by mixing-dispersing, adding the said refrigerant | coolant to the said mixed liquid.

In the former case, it is preferable to lower the temperature in an instant when the mixed liquid is in contact with the refrigerant and dispersed at the same time. As time required for temperature fall, less than 5 minutes are preferable, less than 1 minute are more preferable, and less than 30 second is the most preferable. Moreover, as temperature to drop, 5-50 degreeC is preferable, 10-50 degreeC is more preferable, and 20-50 degreeC is the most preferable. Although it cannot be said uniformly as addition completion time of a liquid mixture, although it depends on a manufacturing scale, within 1 hour is preferable from a liquid mixture addition, 30 minutes are more preferable, and 10 minutes are the most preferable.

In the latter case, the cooling rate depends on the time for adding the coolant. Therefore, if the production scale increases, the required amount of the coolant increases and the cooling rate is slowed. It is preferable to cool by. Moreover, it is more preferable to cool by adding a refrigerant for about 1 hour, and it is most preferable to cool by adding a refrigerant for about 30 minutes.

The peripheral speed of the tip of the stirrer is preferably 2 m / sec or more, more preferably 3 m / sec or more in terms of improving the dispersion state.

If the tip circumferential velocity is less than 2 m / sec, dispersion may be insufficient during cooling mixing, and the fatty acid glycol ester may be solidified without becoming fine crystals, resulting in agglomeration and deterioration of gloss.

In the pearlescent varnish dispersion liquid obtained by crystallization by the above-mentioned mixed dispersion, direct cooling, etc., when the viscosity immediately after crystallization is high, it is preferable to cool the temperature of a pearlescent varnish dispersion liquid to 48 degrees C or less, and to perform whole stirring. As a result, the network between the crystals is broken, the viscosity is sharply lowered, and the handling properties can be significantly improved. Moreover, once a viscosity falls, even if it is preserve | saved as it is, if storage conditions are 50 degrees C or less, it will aggregate and a viscosity will not rise.

According to the manufacturing method of the pearlescent varnish dispersion liquid of this invention demonstrated above, the pearlescent varnish dispersion liquid which has the outstanding pearlescent gloss can be manufactured cheaply, efficiently, and with a small scale facility easily. In particular, it is suitable for the preparation of the pearlescent varnish dispersion of the present invention.

(Example 1)

Preparation of Pearlescent Varnish Dispersion

After mixing and dissolving the composition of the mixed liquid (EG-DS solution) in Example 1 of Table 1 at 80 degreeC, and preparing a mixed liquid, it adds to the purified water (refrigerant: 24 degreeC) of the same mass as the said mixed liquid, and circumferential speed 2m It disperse | distributed and cooled by the dispro wing | blade (/ stirring blade of Unexamined-Japanese-Patent No. 10-180071) of / sec, and cooled (direct cooling). The time required when the mixed liquid was added to purified water (refrigerant) was 30 seconds, and after dispersion, a pearlescent varnish dispersion having a liquid temperature of 50 ° C was obtained. Table 1 shows the concentration of EG-DS (ethylene stearic acid ethylene glycol: manufactured by Gold Schmidt) in the obtained pearlescent varnish dispersion and the time required for producing the pearlescent varnish dispersion.

Measurement of particle size distribution

The particle size distribution of the obtained pearlescent varnish was measured using a laser diffraction particle size distribution analyzer (LA-920; manufactured by Horiba Seisakushosha) and measuring the particle size distribution of the crystal with a relative refractive index of 1.08 as water. Had two peaks. Table 1 shows particle diameters (maximum frequency particle diameters) at the two peaks.

Observation and Evaluation of the Dispersion State

About the obtained pearlescent varnish dispersion, the dispersion state was visually observed and evaluated by the following evaluation criteria. The results are shown in Table 1.

<Evaluation Criteria>

Good dispersibility of crystals

Poor dispersibility of crystals

Pearl tone evaluation

The pearl tone was evaluated by visually observing the obtained pearlescent varnish dispersion. The white silky smooth and fine pearlescent luster was evaluated as "silk atmosphere," and the metallic sharp pearly luster was evaluated as "metallic atmosphere." The results are shown in Table 1.

―Evaluation of gloss

The obtained pearlescent varnish dispersion was blended into a product (shampoo) so that the fatty acid glycol ester concentration was 1.5% by mass, placed in a glass container of 200 m1, and the gloss was visually observed and evaluated by the following evaluation criteria. The results are shown in Table 1.

<Evaluation Criteria>

Excellent gloss

· Glossy but poor quality · △

· No gloss ·· ×

(Example 2)

Preparation of Pearlescent Varnish Dispersion

About the composition in Example 2 of Table 1, after preparing a liquid mixture like Example 1, it added to the purified water (refrigerant: 28 degreeC) of the same mass as the said liquid mixture, and carried out similarly to Example 1, and the temperature of a liquid A pearlescent varnish dispersion of 53 ° C. was obtained. Table 1 shows the concentration of EG-DS (ethylene stearate ethylene glycol) in the obtained pearlescent varnish dispersion and the time required for preparing the pearlescent varnish dispersion.

Particle size distribution measurement, dispersion / observation and evaluation, pearl tone evaluation, gloss evaluation

Each evaluation was performed like Example 1 about the obtained pearlescent varnish dispersion liquid. The results are shown in Table 1.

(Comparative Example 1)

After mixing and dissolving the composition in the comparative example 1 of Table 1 at 80 degreeC, and preparing a liquid mixture, it cools (indirect cooling) to 30 degreeC from the average descent rate of 0.3 degree-C / min under low-speed stirring, and is a pearlescent varnish of liquid temperature of 30 degreeC. A dispersion was obtained. About the obtained pearlescent varnish dispersion, each measurement and evaluation were performed like Example 1-2. The results are shown in Table 1. In addition, in "particle size distribution measurement," the particle size distribution of the obtained crystal had a single peak. In addition, in "evaluation of glossiness", glossiness was inferior to Examples 1-2, and 1.3 times of compounding was required in order to obtain equivalent glossiness.

(Comparative Example 2)

After mixing and dissolving the composition in the comparative example 2 of Table 1 at 80 degreeC, and preparing a liquid mixture, crystallization is performed by indirect cooling (cooling rate: 0.2-0.3 degreeC / min), and the dispersion liquid of the liquid temperature of 30 degreeC is prepared. Got it. Simultaneously with crystallization start, the viscosity of the liquid was increased to obtain a dispersion liquid having poor fluidity. About the obtained dispersion liquid, each measurement and evaluation are performed like Example 1-2. The results are shown in Table 1. In addition, in "particle size distribution measurement," the particle size distribution of the obtained crystal had a single peak. In addition, in "evaluation of glossiness", the aggregated mass was confirmed in the product, and glossiness was also inferior.

However, in Table 1, EG-DS (ethylene stearate ethylene glycol) shown by * 1 is TEGIN Gl100 (Gold Schmidt Co., Ltd. product).

(Examples 3 to 7)

Preparation of Pearlescent Varnish Dispersion

After mixing and dissolving the composition of the mixed liquid (EG-DS solution) in Examples 3-7 of Table 2 at the temperature of Table 2, and preparing a mixed liquid, the purified water and ethanol mixed solution of the same mass as the said mixed liquid (refrigerant) It added to the temperature of Table 2, disperse-mixed and cooled (direct cooling) with the dispro blade (stirrer of Unexamined-Japanese-Patent No. 10-180071) of 2 m / sec. The time required when the mixed liquid was added to purified water (refrigerant) was 30 seconds, and after dispersion, a pearlescent varnish dispersion of the liquid temperatures shown in Table 2 was obtained. In the obtained pearlescent varnish dispersion, the concentration of EG-DS (ethylene stearate: manufactured by Gold Schmidt), the time required for producing the pearlescent varnish dispersion, and the obtained pearlescent varnish dispersion were evaluated in the same manner as in Example 1. It was done. The results are shown in Table 2.

However, in Table 2, EG-DS (ethylene stearate ethylene glycol) indicated by * 1 is TEGIN Gl100 (Gold Schmidt).

Example 8-Example Using Shampoo Composition as Refrigerant

The mixture liquid (EG-DS solution) which is a composition shown in Table 3 is made into the refrigerant | coolant with the shampoo composition (component composition shown in Table 4) of 17 times that of the said mixture liquid at the circumferential speed of 8 m / sec by the line mixer provided with the dispro | swing blade. Cool by dispersion mixing. After dispersion mixing, EG-DS was crystallized and finished as a pearlescent luster shampoo. In the obtained pearlescent gloss shampoo, the concentration of EG-DS (ethylene stearate: manufactured by Gold Schmidt), the time required for preparing the pearlescent varnish dispersion, and the obtained pearlescent varnish dispersion were evaluated in the same manner as in Example 1. It was. The results are shown in Table 3.

(Examples 9-16)

In Examples 1 to 8, the compounding order and blending time of each mixed liquid and refrigerant were changed. That is, the pearlescent varnish dispersion liquid was obtained like Example 1-8 except having added each refrigerant | coolant for 30 minutes to each liquid mixture. When each evaluation was performed like Example 1 about the obtained pearlescent varnish dispersion, the favorable result similar to Examples 1-8 was obtained.

According to the present invention, pearlescent varnish dispersions having excellent pearlescent luster can be produced inexpensively, efficiently and easily in small-scale facilities.

Claims (2)

When a crystal diffraction particle size distribution was measured using a laser diffraction particle size distribution analyzer with a relative refractive index of 1.08, one of two peaks, and one of the particle diameters (maximum frequency particle diameters) at the two peaks, A pearlescent varnish dispersion, characterized in that from 0.1 to 1 µm and the other is from 3 to 30 µm. At least the fatty acid glycol ester and the surfactant-containing component are mixed at a temperature equal to or higher than the melting point of the fatty acid glycol ester, and the refrigerant is blended at a mass ratio of 0.5 to 35 times by mass to the temperature below the melting point of the fatty acid glycol ester. A method for producing a pearlescent varnish dispersion, characterized by cooling.