JP2012072000A - Method of manufacturing clay mineral dispersion liquid - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of manufacturing a clay mineral dispersion liquid whose viscosity is hardly reduced in the manufacturing process.SOLUTION: A method of manufacturing a clay mineral dispersion liquid containing: component (A): water swellable clay mineral; component (B): sugar alcohol; component (C): a water-soluble polymer compound; component (D): (poly)glycerol ester; and component (E): water includes: a clay dispersion process, in which the components (A) and (B) and part of component (E) are mixed and a clay dispersion liquid is obtained; a polymer dispersion process, in which the component (C) and the remaining part of the component(E) are mixed and a polymer dispersion liquid is obtained; a mixing process, in which the clay dispersion liquid and polymer dispersion liquid are mixed and a mixing liquid is obtained; and a dispersion liquid adjusting process, in which the mixing liquid and the component (D) are mixed.

Description

  The present invention relates to a method for producing a clay mineral dispersion.

Clay minerals such as smectite utilize physical properties such as thickening and thixotropy in aqueous dispersions.
For example, a bathing agent that makes the bath water cloudy by adding it to the bath water is mixed with powder for making the bath water cloudy or encapsulated oils and fats (white cloudy component), and maintaining the dispersed state of this cloudy component For example, clay minerals are blended.

 Conventionally, various inventions have been made in order to make the viscosity of clay mineral dispersions such as bathing agents moderate. For example, a liquid bath agent composition containing an inorganic pigment coated with sodium carboxymethylcellulose, a water-swellable clay mineral, and carboxymethylcellulose or alginic acid (salt) has been proposed (for example, Patent Document 1). According to the invention of Patent Document 1, freezing and restoring properties are improved while maintaining fluidity of the composition and dispersibility in bath water.

JP 2009-137849 A

However, in the conventional technology, the viscosity of the clay mineral dispersion decreases (decreases) during storage of the clay mineral dispersion prepared in the compounding tank or while it is transferred from the compounding tank and filled into a container for commercialization. There was a problem. In addition, since the viscosity of the clay mineral dispersion until commercialization is not constant, there is a problem that the viscosity of the product tends to vary.
In addition, simply increasing the amount of clay mineral, water-soluble polymer compound, etc. in the clay mineral dispersion to increase the viscosity will decrease the fluidity of the clay mineral dispersion or the dispersibility in hot water baths, etc. There was a problem.
Then, it aims at the manufacturing method of the clay mineral dispersion liquid which is hard to reduce in the manufacturing process.

 As a result of intensive studies, the present inventors previously prepared a clay dispersion in which a clay mineral is dispersed in water and a polymer dispersion in which a water-soluble polymer compound is dispersed in water, and then (poly) glycerin. It discovered that the viscosity reduction of a clay mineral dispersion liquid can be suppressed by mixing a ester and manufacturing a clay mineral dispersion liquid, It came to this invention.

That is, the method for producing a clay mineral dispersion of the present invention comprises (A) component: water-swellable clay mineral, (B) component: sugar alcohol, (C) component: water-soluble polymer compound, (D) A method for producing a clay mineral dispersion containing a component: (poly) glycerin ester and a component (E): water, comprising the component (A), the component (B), and the component (E). A clay dispersion step of mixing a part to obtain a clay dispersion, a polymer dispersion step of mixing the component (C) and the remainder of the component (E) to obtain a polymer dispersion, and the clay It comprises a mixing step of mixing a dispersion and the polymer dispersion to obtain a mixture, and a dispersion preparing step of mixing the mixture and component (D).
In the clay dispersion step, the component (A) and the component (B) are preferably mixed in a ratio (B) / (A) = 3 to 8 (mass ratio).

  ADVANTAGE OF THE INVENTION According to this invention, the clay mineral dispersion liquid which is hard to reduce in the manufacturing process can be provided.

It is a schematic diagram which shows an example of the batch type mixing apparatus used for the manufacturing method of the clay mineral dispersion liquid of this invention. It is a schematic diagram which shows an example of the continuous mixing apparatus used for the manufacturing method of the clay mineral dispersion liquid of this invention. It is a schematic diagram of the measuring apparatus used for the measurement of discharge flow volume. It is a schematic diagram of the measuring apparatus used for the measurement of discharge flow volume. It is a schematic diagram which shows the mixing apparatus used for the Example.

(Clay mineral dispersion)
The clay mineral dispersion of the present invention comprises (A) component: water-swellable clay mineral, (B) component: sugar alcohol, (C) component: water-soluble polymer compound, and (D) component: (poly). It contains glycerin ester and (E) component: water. The clay mineral dispersion of the present invention is used, for example, for liquid baths, body lotions, shampoos, treatments, etc. Among them, it is suitably used for liquid baths because of its excellent dispersibility in water.

 The viscosity of the clay mineral dispersion can be determined in consideration of applications and the like. For example, the viscosity of the liquid bath agent is preferably 400 to 2000 mPa · s, more preferably 800 to 1500 mPa · s. When it is less than 400 mPa · s, the component (A) is likely to settle during storage, or easily separated due to a temperature change. If it exceeds 2000 mPa · s, the fluidity is poor, and it becomes difficult to pour out the clay mineral dispersion from the container, or the dispersibility in water decreases.

<(A) component: water-swellable clay mineral>
The component (A) of the present invention is a water-swellable clay mineral. Since the clay mineral dispersion contains the component (A), the component (A) swollen with water forms a card house structure and exhibits an appropriate viscosity.

“Water swellability” means that the test method for bentonite specified in the 15th revised Japanese Pharmacopoeia is applied mutatis mutandis, and the swelling force expressed by the swelling volume (cm ³ ) of 2 g of clay mineral is 20 cm ³ / g or more. Say something. Clay minerals with a swelling power of less than 20 cm ³ / g are unlikely to form a card house structure and the viscosity of the clay mineral dispersion is insufficient.
The component (A) is preferably not cationized. This is because the non-cationized component (A) easily forms a card house structure with the components (B) to (D).

Examples of such component (A) include natural products, purified natural products, modified natural swellability, synthesized products, and the like. Specifically, smectite group clay minerals such as natural or synthesized montmorillonite, beidellite, nontronite, saponite, sauconite, hectorite, and stevensite having the above-mentioned swelling power, vermiculite, and swellable synthetic fluoromica (Na type) Li-type synthetic mica), swellable mica, and the like can be used. Moreover, the high metal ion substitution clay mineral etc. which improved the swelling power by ion-exchanging the said clay mineral can be used. The component (A) used in the present invention contains exchangeable ions that hydrate and take in water molecules between layers, and has properties such as swelling, adsorptivity, binding, suspension, and thickening. However, it exhibits different properties from other clay minerals. The component (A) is preferably a smectite group or a bentonite mainly composed of a smectite group montmorillonite.
As component (A), Polagel (manufactured by American Colloid Co., Ltd.), Laponite (manufactured by Nippon Silica Industry Co., Ltd.), Bengel (manufactured by Toyshun Mining Co., Ltd.), Lucentite (manufactured by Corp Chemical Co., Ltd.), Kunipia (Kunimine Industry Co., Ltd.) Manufactured), Benclay (manufactured by Mizusawa Chemical Co., Ltd.), bee gum (manufactured by Vanderbilt), and the like, and those commercially available.
These can be used individually by 1 type or in combination of 2 or more types.

 The average particle size of the component (A) is preferably 1 to 5000 nm, more preferably 1 to 1000 nm, and still more preferably 1 to 700 nm. When the average particle size is more than 5000 nm, the surface area per unit mass of the clay mineral becomes small, and a large amount of the component (A) is required to obtain a desired viscosity. The average particle diameter of the component (A) is the median diameter measured by the dynamic light scattering method (the particle diameter at which the cumulative particle amount is 50% by volume). Measuring instrument: Shimadzu laser diffraction particle size distribution analyzer SALD -2200 measured value.

 The content of the component (A) in the clay mineral dispersion can be determined in consideration of the viscosity required for the clay mineral dispersion, and is preferably 0.05 to 3% by mass, more preferably 0.1 to 3% by mass. . If it is less than 0.05 mass%, the viscosity of the clay mineral dispersion becomes insufficient, or it becomes easy to separate during storage. If it exceeds 3% by mass, the viscosity of the clay mineral dispersion becomes too high, and the fluidity may decrease.

<(B) component: sugar alcohol>
The component (B) of the present invention is a sugar alcohol. By containing the component (B), the component (A) hardly swells and swells quickly.

 The component (B) is not particularly limited, and examples thereof include sorbit, glycerin, xylit, malt, lactit, propylene glycol, polyethylene glycol, etc. Among them, sorbit and xylit are preferable. This is because sorbit or xylit increases the dispersibility of the component (A) and hardly inhibits the swelling of the component (A).

 When the content of the component (B) in the clay mineral dispersion is too small, the component (A) is difficult to disperse, and when it is too large, the component (A) is difficult to swell. Therefore, the content of the component (B) in the clay mineral dispersion can be determined in consideration of the content of the component (A), the type of the component (B), etc., for example, sorbite or xylit as the component (B) Is preferably 0.15 to 24 mass%, more preferably 0.3 to 15 mass%. If it is in the said range, in the clay dispersion | distribution process mentioned later, (A) component can be disperse | distributed favorably and it can fully swell.

<(C) component: water-soluble polymer compound>
Component (C) of the present invention is a water-soluble polymer compound. A clay mineral dispersion liquid can exhibit moderate viscosity by containing (C) component.
“Water-soluble” means that the solubility in water (20 ° C.) is 0.1 g / 100 g or more of water. “Polymer” means a polymer having a weight average molecular weight of 1000 or more.
(C) The weight average molecular weight of component uses GPC-MALLS (gel permeation chromatography-multi-angle light scattering detector), 0.5 mol / L sodium perchlorate solution as a mobile phase, and the following method. It is a measured value. (A) About the sample solution diluted with the mobile phase so that the pure component density | concentration of the component may be about 1000 mass ppm, the wavelength of 633 nm is measured with a multi-angle scattering detector using a TSK-GELA column (made by Tosoh Corporation). To do. Polyethylene glycol with a known molecular weight is used as a standard product.

Examples of the component (C) include gums such as xanthan gum, tragacanth gum, karaya gum, gum arabic, and the like, synthetic polymers such as polyvinyl alcohol, sodium polyacrylate, carboxyvinyl polymer, polyvinylpyrrolidone, carboxymethylcellulose alkali metal salt, methylcellulose, Examples thereof include cellulose derivatives such as hydroxyethyl cellulose and sodium carboxymethyl hydroxyethyl cellulose. Among them, gums and cellulose derivatives are preferable. This is because gums and cellulose derivatives are less likely to produce mamako and are easy to handle.
These can be used individually by 1 type or in combination of 2 or more types.

 The weight average molecular weight of the component (C) is preferably 10,000 or more. This is because if the weight average molecular weight is 10,000 or more, an appropriate viscosity can be exhibited. Moreover, although the upper limit of the weight average molecular weight of (C) component is not specifically limited, For example, it shall be 10000000. This is because if it exceeds 10000000, the fluidity of the clay mineral dispersion is deteriorated.

 The content of the component (C) in the clay mineral dispersion can be determined in consideration of the use of the clay mineral dispersion, and is preferably 0.05 to 5% by mass, more preferably 0.1 to 2% by mass. preferable. If it is less than 0.05 mass%, the viscosity of the clay mineral dispersion becomes insufficient, or it becomes easy to separate during storage. If it exceeds 5% by mass, the viscosity of the clay mineral dispersion becomes too high, and the fluidity may decrease.

<(D) component: (poly) glycerin ester>
(D) component of this invention is (poly) glycerin ester. A clay mineral dispersion liquid becomes difficult to reduce viscosity by containing (D) component. Although the mechanism by which the viscosity reduction is suppressed is not clear, an association between the component (A) and the component (D) is formed, and this association forms a structure similar to the card house structure, and the component (D) Is considered to function as a binder between the components (A). Moreover, (D) component functions as an emulsifier for disperse | distributing an oil-based component in (E) component, when mix | blending an oil-based component in a clay mineral dispersion liquid among the arbitrary components mentioned later.

(Poly) glycerin ester is meant to include monomers and polymers of glycerin ester.
Examples of such component (D) include monoglycerides, monoglyceride derivatives such as acetic acid monoglyceride, citric acid monoglyceride, and succinic acid monoglyceride, and fatty acid polyglycerin esters, among which fatty acid polyglycerin esters are preferable.
Examples of fatty acid polyglycerin esters include diglyceryl monostearate, hexaglyceryl monostearate, decaglyceryl monostearate, diglyceryl distearate, hexaglyceryl distearate, decaglyceryl distearate, pentaglyceryl tristearate, tristearin Hexaglyceryl acid, decaglyceryl tristearate, hexaglyceryl tetrastearate, decaglyceryl tetrastearate, tetraglyceryl pentastearate, hexaglyceryl pentastearate, decaglyceryl pentastearate, pentaglyceryl hexastearate, hexastearate hexastearate Glyceryl, hexaglyceryl octastearate, decaglyceryl decastearate, monoisostearin Diglyceryl, hexaglyceryl monoisostearate, decaglyceryl monoisostearate, diglyceryl diisostearate, hexaglyceryl diisostearate, decaglyceryl diisostearate, pentaglyceryl triisostearate, hexaglyceryl triisostearate, decaglyceryl triisostearate, tetraisostearate Hexaglyceryl acid, decaglyceryl tetraisostearate, tetraglyceryl pentaisostearate, hexaglyceryl pentaisostearate, decaglyceryl pentaisostearate, pentaglyceryl hexaisostearate, hexaglyceryl hexaisostearate, hexaglyceryl octaisostearate, decaisostearate deca Glyceryl, monoolei Diglyceryl acid, glyceryl monomyristic acid heptabehenate decaglyceryl, pentaglyceryl trioleate, pentaglyceryl tribehenate, pentaglyceryl tetrabehenate, pentaglyceryl pentabehenate, triglyceryl dibehenate, triglyceryl tribehenate, triglyceryl tetrabehenate Examples thereof include glyceryl. Among them, those having 2 to 22 fatty acid carbon atoms are preferred, those having 16 to 18 fatty acid carbon atoms are more preferred, and glycerin OH of a (poly) glycerin ester that is a two-chain type that easily forms a structure (molecular assembly). Those having a fatty acid in which any two of the groups are hydrophobic groups are more preferred, and decaglyceryl distearate and polyglyceryl diisostearate are particularly preferred.

 The content of the component (D) in the clay mineral dispersion can be determined in consideration of the type of the component (D) and the amount of the oily component among the optional components described below. For example, 0.05 to 10% by mass Is preferable, and 0.1 to 2 mass% is more preferable. If it is within the above range, the aggregate with the component (A) can be formed satisfactorily, and the oil component can be appropriately dispersed and stabilized.

<(E) component: water>
The component (E) of the present invention is water. The component (E) is not particularly limited, and examples thereof include tap water, well water, purified water treated by distillation, ion exchange, filtration, or a combination thereof.
The compounding amount of the component (E) in the clay mineral dispersion can be determined in consideration of the compounding amount of the components (A) to (D), the use, and the like.

<Optional component>
In the clay mineral dispersion liquid, arbitrary components can be contained alone or in combination of two or more, as long as the effects of the present invention are not impaired. Optional ingredients include oil-based ingredients, anionic surfactants, cationic surfactants, surfactants such as zwitterionic surfactants, water-insoluble powders such as inorganic powders and organic powders, vitamins, amino acids , Anti-inflammatory agents, ultraviolet absorbers, cooling agents, antioxidants, colorants, fragrances, antiperspirants, bactericides, deodorants, preservatives, inclusion compound fragrances, dyes and the like.

The oil component can be determined in consideration of the use of the clay mineral dispersion, for example, vegetable oil such as rice germ oil, rice bran oil, olive oil, soybean oil, jojoba oil, eucalyptus oil, lemon oil, peppermint oil, jasmine oil, Essential oils such as cypress oil, mandarin oil, rose oil, thyme oil, menthol and peppermint oil, hydrocarbon oils such as squalane and liquid paraffin, methylphenylpolysiloxane, methylpolysiloxane, octamethylcyclotetrasiloxane, dimethylsiloxane methyl Examples thereof include silicones such as a siloxane copolymer, decamethylcyclopentasiloxane, myristyl silicone, tetradecamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, and hexanemethylcyclotrisiloxane.
The content of the oil component in the clay mineral dispersion can be determined in consideration of the use of the clay mineral dispersion.

(Production method)
The method for producing a clay mineral dispersion of the present invention comprises a clay dispersion step of mixing a component (A), a component (B), and a part of the component (E) to obtain a clay dispersion, E) The polymer dispersion step of mixing the remainder of the component to obtain a polymer dispersion, the mixing step of mixing the clay dispersion and the polymer dispersion to obtain a mixture, the mixture and the component (D) And a dispersion liquid preparation step of mixing.

<Clay dispersion process>
The clay dispersion step is a step of obtaining a clay dispersion by mixing the component (A), the component (B), and a part of the component (E). By providing this step, the component (A) has a sufficient amount of water permeated between the layers to saturate the swollen state and stabilize the viscosity of the clay mineral dispersion.

 In this step, the mixing ratio of the component (A) and the component (B) is such that the mass ratio ((B) / (A) ratio) represented by (B) component / (A) component is 3-8. Of these, 4 to 6 is more preferable. If it is less than 3, swelling of the component (A) may be insufficient, and if it exceeds 8, the component (A) is difficult to swell.

  Further, in this step, the mixing ratio of the component (A) and the component (E) is a mass ratio ((A) / (E) ratio) represented by [(A) component / (E) component] × 100. Is preferably 0.05 to 5% by mass, and more preferably 0.5 to 4% by mass. If it is less than 0.05% by mass, the amount of component (E) used in the polymer dispersion step may be insufficient, and if it exceeds 5% by mass, component (A) may not be sufficiently swollen.

For the mixing in this step, a conventionally known mixing device can be used, and examples thereof include a batch mixing device such as a vessel equipped with a propeller blade, and a continuous mixing device such as an in-line mixer.
The mixing temperature in this step is not particularly limited and is, for example, 5 to 90 ° C. If the temperature is less than 5 ° C., mamaco is likely to be generated, and if it exceeds 90 ° C., the balance of the composition may change due to volatilization of moisture.
In addition, the mixing time is a time during which the component (A) is sufficiently dispersed and swollen in the component (E) in consideration of the capacity and volume of the mixing apparatus.

<Polymer dispersion process>
In the polymer dispersion step, the component (C) and the remainder of the component (E) are mixed to obtain a polymer dispersion. When the lumps of the component (C) occur during the production of the clay mineral dispersion, it is necessary to mix for a long time by applying a high shearing force in order to disperse the lumps. At this time, if the component (A) is present, the card house structure due to the component (A) is hardly formed, and the desired viscosity may not be obtained.

 In this step, the mixing ratio of the component (C) and the component (E) is 0.05 to 5 by mass ratio ((C) / (E) ratio) represented by the component (C) / (E) component. And is more preferably 0.5-4. If it is less than 0.05, the component (E) used in the clay dispersion step may be insufficient, and if it exceeds 5, the component (C) may be insufficiently swelled.

The mixing of this process can use the same mixing apparatus as the clay dispersion | distribution process.
The mixing temperature in this step can be determined in consideration of the type of component (C) and the like, for example, 5 to 90 ° C. If it is less than 5 ° C, the viscosity may increase or Mako may be easily formed. If it exceeds 90 ° C, the component (C) may be denatured or the balance of the composition may change due to volatilization of moisture. Because.
In addition, the mixing time is set to a time during which the component (C) is sufficiently dispersed in the component (E) in consideration of the capacity and volume of the mixing device.

 When blending water-soluble optional components (for example, water-soluble pigments, fragrances, surfactants, etc.) and oily components into the clay mineral dispersion, it can be added to the polymer dispersion obtained in this step. .

<Mixing process>
The mixing step is a step of obtaining a mixed liquid by mixing the clay dispersion obtained in the clay dispersion step and the polymer dispersion obtained in the polymer dispersion step. By this step, a mixed liquid in which the (A) component and the (C) component swollen with the (E) component are dispersed in the (E) component can be obtained.
The mixing of this process can use the same mixing apparatus as the clay dispersion | distribution process.
The mixing temperature in this step can be determined in consideration of the ability of the mixing apparatus and the like, for example, 5 to 90 ° C. If it is less than 5 ° C, the viscosity may increase or Mako may be easily formed. If it exceeds 90 ° C, the component (C) may be denatured or the balance of the composition may change due to volatilization of moisture. Because.
In addition, the mixing time is set to a time during which the component (C) is sufficiently dispersed in the component (E) in consideration of the capacity and volume of the mixing device.

<Dispersion preparation process>
In this step, the mixture obtained in the mixing step and the component (D) are mixed to obtain a clay mineral dispersion. By this step, the component (D) is dispersed in the mixed liquid, and a clay mineral dispersion liquid having an appropriate viscosity and not decreasing in storage / transfer is obtained.

For the mixing in this step, a conventionally known mixing apparatus can be used.
An example of a mixing apparatus used in this step will be described below with reference to the drawings. FIG. 1 is a schematic view of a batch type mixing apparatus 1 showing an example of a mixing apparatus. The batch-type mixing apparatus 1 includes a stirring tank 10, and a wall surface scraping blade provided with a substantially U-shaped scraper blade 31 that scrapes the inner surface 12 of the stirring tank 10 and a protruding blade 32 protruding in the center direction of the stirring tank 10. 30, an agitation shaft 22 extending in the vertical direction substantially at the center of the agitation tank 10, and an agitation blade 20 protruding from the agitation shaft 22 toward the inner surface 12.
In this batch-type mixing apparatus 1, the mixed liquid and the component (D) are supplied into the stirring tank 10, and the supplied raw material is the inner surface 12 by rotating the stirring blade 20 and the wall scraping blade 30. Mixing while receiving shearing force generated between the stirring blades 20.
Examples of such a batch type mixing apparatus include Ajihomo mixer (manufactured by NP Lab Co., Ltd.), Robomix homomixer (manufactured by Primics Co., Ltd.), Claremix (manufactured by M Technique Co., Ltd.), and the like.

Moreover, the continuous mixing apparatus 100 as shown in FIG. 2 can be used for this process. The continuous mixing apparatus 100 is roughly configured by a substantially cylindrical housing 110, a rotor 120 provided with a stirring blade 122, and a stator 130 that covers the rotor 120 with a space around its rotation axis.
In the continuous mixing apparatus 100, the fluid supplied by mixing the liquid mixture and the component (D) is supplied from the suction port 112 to the housing 110 while rotating the rotor 120. And the inner surface 132 of the stator 130 are mixed while receiving a shearing force and discharged from the discharge port 114 to the outside of the apparatus.
Examples of such a continuous mixing apparatus include milder (manufactured by Taiheiyo Kiko Co., Ltd.), line homomixer (manufactured by Primics Co., Ltd.) and the like.

The operating conditions of the mixing apparatus in this step are not particularly limited, and the shear rate and the like are adjusted so that the component (D) can be sufficiently swollen with the component (E).
Shear rate in this step is preferably 1000～10000Sec ^-1, more preferably 2000～8000Sec ^-1, more preferably 3000~6000sec ^-1. If the shear rate is less than 1000 sec ⁻¹ , component (D) may not be sufficiently dispersed. When the shear rate is more than 10,000 sec ⁻¹ , for example, when an oil component is blended, the component (D) may be arranged on the surface of the emulsified particles, and an association with the component (A) may not be formed.

The shear rate is calculated as v / D (sec ⁻¹ ), where v (m / s) is the tip speed of the stirring blade of the mixing device and D (m) is the clearance between the tip and the inner surface of the mixing device. Is the value to be
For example, the shear rate in the batch mixing apparatus 1 shown in FIG. 1 can be calculated from the tip speed of the tip 24 of the stirring blade 20 and the clearance (D1 in FIG. 1) between the tip 24 and the inner surface 12 of the stirring tank 10. .
Further, the shear rate in the continuous mixing apparatus 100 shown in FIG. 2 can be calculated from the speed of the tip 124 of the stirring blade 120 and the clearance between the tip 124 and the inner surface 132 of the stator 130 (D2 in FIG. 2).
The shear rate can be adjusted by adjusting the rotational speed of the stirring blade of the mixing device or the clearance between the stirring blade and the inner surface.

 Moreover, 1-9 are preferable and, as for the frequency | count of circulation in this process, 3-5 are more preferable. If the number of circulations is less than 1, the dispersion of the component (D) may be insufficient. There is a risk that it will not be.

  The number of circulations indicates the number of times the contents are sheared by the stirring blades. The number of circulations is defined by the following (I) when a batch type mixing apparatus is used.

(I) When this step is performed with a batch type mixing apparatus, a value obtained by the following equation (i).
Number of circulations = Nqd × r × d ³ × θ ÷ V (i)
(In the formula (i), Nqd: discharge flow coefficient, r: rotation speed of the stirring blade (rpm), d: diameter of the stirring blade (m), θ: stirring time (min), V: volume of the content liquid (m ³ ))

  In (I) above, the discharge flow coefficient Nqd is a constant determined by the type of the stirring blade, and can be calculated by the following equation (a) based on the discharge flow Qd.

Nqd = Qd / NR ³ (A)
(In formula (a), Qd: discharge flow rate (m ³ / min), N: number of revolutions of stirring blade (rpm), R: inner diameter of stirring tank (m))

Qd is “the particle is discharged from the blade tip, carried to the flow of the discharge flow from the blade and sucked again into the blade tip” or “from the discharge flow from the blade to the flow induced by the discharge flow from the blade. It can be defined as “a flow that is returned to the flow of the discharge flow from the blade and sucked into the blade after repeating the circulation without returning to the blade”.
Here, Qd can be measured by a known method according to the shearing speed of the stirring blade (Reference 1: Tadamasa Sato, Atsushi Taniyama, “Discharge circulation flow rate in stirring tank”, Japan Society for Chemical Engineering, Chemical Engineering, No. 1 29, No. 3, 1965, Reference 2: edited by 70th Anniversary Business Special Committee, “Theory and Practice of Emulsification / Dispersion”, Special Machine Industries Co., Ltd., April 17, 1997).
For example, the Qd of a stirring blade having a shear rate of less than 5500 sec ⁻¹ , such as a propeller blade, a paddle blade, a turbine blade, a dislop blade, and a disper blade, can be measured using the measuring device 200 shown in FIG.
As shown in FIG. 3, the measuring apparatus 200 includes a stirring tank 202, a stirring blade 230 provided in the stirring tank 202, and a mirror 240. The mirror 240 is provided below the stirring tank 202 at an angle α with respect to the bottom surface 214 of the stirring tank 202. The agitation tank 202 includes a substantially cylindrical water tank 210, and two baffle plates 220 provided on the inner peripheral surface of the water tank 210 from the opening 212 to the bottom surface 214 at equal intervals. The material is such that at least the inside of the water tank 210 can be visually recognized by the mirror 240, such as glass or transparent resin. The stirring blade 230 is connected to a stirring shaft 232, and the stirring shaft 232 is connected to power not shown.

In the measuring apparatus 200, each constituent member satisfies the following conditions.
d / R = 0.25-0.5, C / R = 0.1-0.8, W / R = 0.1, α = 45 °
(D is the diameter (m) of the stirring blade, C is the mounting height (m) of the stirring blade, W is the width (m) of the baffle plate, R is the inner diameter (m) of the stirring vessel, and α is the bottom of the stirring vessel Mirror angle (°)

Next, a method for measuring Qd of a stirring blade having a shear rate of less than 5500 sec ⁻¹ will be described. The content liquid 260 in which particles 262 dispersed within the stirred tank 202 was charged, when stirring the liquid contents 260 in the stirring blade 230, the number of times mq the particle 262 passes through the stirring blade 230 during the measurement time _{T A,} arrows Count visually through mirror 240 in direction F. And it can obtain | require from the counted frequency mq by the following (A) formula (refer p.153-158 of the reference literature 1). The particles 262 used for the measurement are spherical polypropylene particles (spherical 3 mm, specific gravity 1.1 g / cm ³ ), and the number thereof is ten. Contents liquid 25 ° C., the measurement time _{T A} is 10 to 15 minutes.

Qd = mqV _{/ T} A ··· (i)
(In the formula (I), mq the passage number, V is the volume ^(m 3 of liquid content 260), _{T A} represents the measurement time (min).)

Also, for example, T.W. K. Homomixer MARK type II (manufactured by Primix Co., Ltd.), Ultra Tarrax (manufactured by IKA), Sherflow, Silverson mixer (manufactured by Silverson Co., Ltd.), PVT-1-20 type (manufactured by Mizuho Industrial Co., Ltd.), shear rate 5500 sec ⁻ The Qd of ^one or more stirring blades can be measured using a measuring apparatus 300 shown in FIG.
As shown in FIG. 4, the measuring apparatus 300 includes a stirring tank 301 and a stirring unit 304 provided in the stirring tank 301. The stirring unit 304 includes a stirring blade 302 that is a turbine blade, and a baffle plate. And a stator 303 that serves as The stirring blade 302 is connected to a stirring shaft 307, and the stirring shaft 307 is connected to power not shown. The agitation tank 301 is composed of a water tank 305 and a commutation plate 306 provided above the agitation unit 304, and the water tank 305 is made of a material such as glass or transparent resin that can visually recognize at least the inside of the water tank 305.
In the measuring apparatus 300, each component satisfies the following conditions.
d / R = 0.2-0.3, z / Z = 0.5-0.7, l / L = 0.5-0.7
(D is the diameter (m) of the stirring blade, R is the inner diameter (m) of the stirring vessel, z / Z is the mounting position of the stirring blade (m / m), and 1 / L is the mounting position of the commutation plate (m / m ).)

Next, a method for measuring Qd of a stirring blade having a shear rate of 5500 sec ⁻¹ or more will be described. The content liquid 260 in which the particles 262 are dispersed is put into the stirring tank 301, and the content liquid 260 is stirred with the stirring blade 302. At this time, the content liquid 260 is such that the water surface is above the commutation plate 306. When the agitation is performed, the particles 262 once circulate after entering the stator 303 and then return to the stator 303 again to be one circulation. The time for one circulation is measured 1000 times, and a circulation time distribution is created from the measured values for 1000 times. The distribution is created by plotting the horizontal axis as time t [sec] and the vertical axis as g (t) = [number of times in a certain time zone / total number of times]. Based on this circulation time distribution, Qd can be obtained by the following equation (c) (see pages 13 to 15 of Reference 2).

Qd = V / T _B (U)
In the formula (c), V represents the volume of the liquid content 260 ^(m 3), _{T B} is the mixing time (min).
Incidentally, _{T B} is the following (d) below, can be obtained.

T _B = T ₁ + T ₂ ( _D )
In the formula (d), _{T 1,} when the t-axis corresponding to the top peak of g (t) distribution was _{t 1,} representing the average mixing time to t = 0 to t _1. T ₂ represents an average of time from t = t _{1 to} ∞, where t ₁ corresponding to the g (t) distribution top peak is t ₁ . t = g in 0 to t ₁ period _{(t), t = t 1} g in to ¶ (t), based on the plot of g (t) axis can be calculated as an approximation equation.

Nqd of both the stirring blade having a shear rate of less than 5500 sec ⁻¹ and the stirring blade having a shear rate of 5500 sec ⁻¹ or more varies depending on the number of rotations, that is, the stirring Reynolds number. Regarding the relationship of the stirring Reynolds number to Nqd, Nqd also takes a large value as the stirring Reynolds number increases. In the turbulent flow region where the stirring Reynolds number is large, Nqd becomes a constant value. Therefore, when the stirring Reynolds number is increased, it is confirmed that the value of Nqd is within 10%, and the value is used as Nqd of the stirring blade.

  For example, in the batch mixing device 1, the diameter d of the stirring blade 20 is a circular diameter (d1 in FIG. 1) drawn by the tip 24 of the stirring blade 20.

  In addition, the number of circulations is the same as that of this process. K. When performing with a continuous mixing apparatus such as a pipeline homomixer type M (manufactured by PRIMIX Co., Ltd.), it is defined by (II) below.

(II) A value obtained by the following equation (ii).
Number of circulations = Nqd × r × d ³ ÷ F (ii)
[In formula (ii), Nqd: discharge flow coefficient, r: rotation speed of stirring blade (rpm), d: diameter of stirring blade (m), F: flow rate of fluid supplied to mixing device (m ³ / min ]]
In (II) above, Nqd is the same as in (I).

  For example, in the continuous mixing apparatus 100, the diameter d of the stirring blade 122 is a diameter of a circle drawn by the tip 124 of the stirring blade 122 (d2 in FIG. 2).

The mixing temperature in this process is not specifically limited, For example, 40-80 degreeC is preferable and 50-70 degreeC is more preferable. This is because if it is lower than 40 ° C., the water-soluble optional component may not be sufficiently dissolved, and if it exceeds 80 ° C., the water-soluble optional component may be modified or decomposed.
Further, the mixing time is set to a time during which the component (D) can be sufficiently dispersed in consideration of the capacity and volume of the mixing device.

 In addition, when using the component which does not have fluidity | liquidity at room temperature (25 degreeC), such as a distearic acid decaglycel and diisostearic acid polyglyceryl, as a (D) component, it is preferable to add, after previously warming and melt | dissolving more than melting | fusing point.

When a water-soluble optional component is blended in the clay mineral dispersion, the water-soluble optional component can be dissolved in the mixed solution in advance (dissolution operation).
As the mixing apparatus used for the melting operation, a conventionally known mixing apparatus can be used, and examples thereof include a batch type mixing apparatus such as a vessel and a kneader provided with propeller blades, and a continuous mixing apparatus such as an inline mixer. Moreover, you may use the same thing as the mixing apparatus used at the swelling process mentioned above.

The mixing temperature in this operation can be determined according to the kind of water-soluble arbitrary component, etc., for example, 40-80 degreeC is preferable and 50-70 degreeC is more preferable. If the temperature is lower than 40 ° C., the water-soluble optional component may not be sufficiently dissolved, and if it exceeds 80 ° C., the water-soluble optional component may be denatured.
The mixing time is set to a time during which the water-soluble optional component is sufficiently dissolved in the component (E) in consideration of the capacity and volume of the mixing device.

  Moreover, when mix | blending an oil-based component with a clay mineral dispersion liquid, it can mix | blend in this process. The oily component is dispersed in the mixed solution by being charged into the mixing apparatus together with the component (D) and mixed.

<Cooling process>
In the method for producing a clay mineral dispersion of the present invention, it is preferable to provide a cooling step before the dispersion preparation step. In this cooling step, the mixed liquid obtained in the mixing step is cooled to an arbitrary temperature.
The cooling method is not particularly limited, and examples thereof include a method of cooling with stirring, a method of standing at room temperature, and a method of flowing through a heat exchanger. Among them, a method of cooling with stirring (stirring cooling) Method) is preferred. By using the stirring cooling method, the viscosity reduction of the clay mineral dispersion can be suppressed.
The stirring method in the stirring cooling method is not particularly limited. For example, the mixing device used in the dispersion preparation step is used, and stirring is preferably performed at a tip speed of the stirring blade of 5 to 25 m / s, more preferably 6 to 14 m / s. To do.
The cooling rate is preferably from 0.01 to 5 ° C / min, more preferably from 0.1 to 3 ° C / min. If it is in this range, it can cool efficiently, suppressing the viscosity reduction of a clay mineral dispersion.

  Alternatively, in the method for producing a clay mineral dispersion of the present invention, a cooling step may be provided after the dispersion preparation step. In this cooling step, the clay mineral dispersion obtained in the dispersion preparation step is cooled to an arbitrary temperature. However, it is preferable to provide a cooling process in the front | former stage of a dispersion liquid preparation process from a viewpoint of maintaining the swelling state of (A) component and (C) component.

 The clay mineral dispersion obtained in this way is used as it is or mixed with optional components such as fragrances and pigments to form liquid bathing agents, body lotions and the like.

As described above, a clay dispersion and a polymer dispersion are prepared in advance, and the viscosity of the clay mineral dispersion can be prevented by dispersing the component (D) in the mixture. The mechanism that can prevent the clay mineral dispersion from thinning is not clear, but in the clay dispersion step, the component (A) is sufficiently swollen with the component (B) and the component (E). The swelling degree of the component (A) is not easily changed. In addition, in the polymer dispersion step, the component (C) is dispersed in the component (E) and swells sufficiently, so that the degree of swelling of the component (C) is unlikely to fluctuate in the subsequent steps.
Since the dispersion preparation step is performed using the mixed liquid of the clay dispersion and the polymer dispersion in such a state, the swelling state of the component (A) and the component (C) is ensured, and the clay mineral dispersion The viscosity of is maintained. Furthermore, since the dispersed component (D) functions as a binder between the components (A), the card house-like structure formed by the association of the component (A) and the component (D) is destroyed during transportation and storage. This is thought to be as strong as possible.

EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated in detail, this invention is not limited by the following description.
(Raw material)
The raw materials used in each example and each comparative example are shown below.
<(A) component>
Bentonite: Kunipia-G (trade name), manufactured by Kunimine Industry Co., Ltd. Saponite: Smecton SA (product name), manufactured by Kunimine Industry Co., Ltd.

<(B) component>
・ Sorbit: Sorbit liquid (70%), NOSORB 70/02 SB (trade name), pure 70% by mass, manufactured by Rocket Japan Co., Ltd. ・ Xyrit: manufactured by Chuo Kasei Co., Ltd. <(B ′) component: (B) component Comparison product>
-Dipropylene glycol: Dipropylene glycol DPG-FC (trade name), manufactured by Asahi Glass Co., Ltd.-Cross-linked sodium polyacrylate: Rheodic 250H (trade name), manufactured by Nippon Pure Chemical Co., Ltd.

<(C) component>
・ Carboxymethylcellulose sodium (CMC-Na): Cellogen F-815A (trade name), manufactured by Daiichi Kogyo Seiyaku Co., Ltd. ・ Xanthan gum: Echo gum T (trade name), manufactured by Dainippon Sumitomo Pharma Co., Ltd.

<(D) component>
・ Destearic acid decaglycel: DECAGLYN 2-ISV (trade name), manufactured by Nikko Chemicals Co., Ltd.

<Common ingredients>
Common components having the composition shown in Table 1 were used. The composition ratio (mass%) of the common component in Table 1 is the content in the clay mineral dispersion.

(Evaluation methods)
<Evaluation of viscosity reduction>
The viscosity of the clay mineral dispersion immediately after production was measured, and the measurement result was designated as measured value A. After production, a hose (40A (inner diameter 40 mm) 4 m) is connected to a pump (MASTER FLEX, MODEL: 7523-00, supply capacity: 49 L / min (0.65 m / s), manufactured by Barnant Company), and clay mineral dispersion (25 ° C.) The entire amount was transferred in an environment of 25 ° C. The viscosity of the clay mineral dispersion after the transfer was measured, and the measurement result was measured value B. From the measured values A and B, the following (1) The viscosity reduction rate was calculated by the formula, and the viscosity reduction rate was classified into the following criteria.

 Thickness reduction (%) = [(measured value A−measured value B) / measured value A] × 100 (1)

<< Criteria >>
A: Thickening rate is less than 17% B: Thickening rate is 17% or more and less than 30% Δ: Viscosity reduction rate is 30% or more and less than 40% X: Viscosity reduction rate is 40% or more

The viscosity of the clay mineral dispersion was measured under the following measurement conditions using a BL type rotary viscometer manufactured by Tokyo Keiki Co., Ltd.
Rotor: No. 3, rotation speed: 60 rpm, measurement temperature: 25 ° C. (temperature of clay mineral dispersion), measurement time: after 60 seconds

(Examples 1-9, Comparative Examples 1-4)
According to the composition of Tables 2-3, 16 kg of the clay mineral dispersion liquid of each example was manufactured in the following procedures. In addition, the composition in a table | surface is pure conversion.
The components (A), (B) and (E) described in the column of the clay dispersion step are heated to 70 ° C. in a 10 L beaker, and the propeller stirring blade (600 rpm, tip speed of the propeller stirring blade: 1. 4 m / s) and stirred for 30 minutes to obtain a clay dispersion. The components (B), (C) and (E) described in the column of the polymer dispersion step are heated to 70 ° C. in a 2 L beaker, and a propeller stirring blade (600 rpm, tip speed of the propeller stirring blade: 1) (4 m / s) for 30 minutes to obtain a polymer dispersion.
In a mixing device (PVT-1-20 type, manufactured by Mizuho Kogyo Co., Ltd.) similar to the mixing device 400 shown in FIG. It was. In mixing, wall scraping blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, central blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, stirring blade: rotational speed 7600 rpm, tip speed = The mixing apparatus was operated for 0.5 minutes at 19 m / s. Thereafter, the stirring blade was stopped, and the mixing device was cleaned with a wall scraping blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, central blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, 4.5. Drove for a minute. Further, stirring with the wall scraping blade and the central blade was continued, and the mixed solution was cooled to 40 ° C. (mixing step).
The cooled mixture, the component (D) shown in the column for preparing the dispersion in the table (however, heated and dissolved in advance at 60 ° C.) and the component (B) are mixed to obtain a clay mineral dispersion. It was. In mixing, wall scraping blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, central blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, stirring blade: rotational speed 4000 rpm, tip speed = The mixing apparatus was operated for 4 minutes (mixing time) at 10 m / s. Thereafter, the stirring blade was stopped, and the mixing device was operated for 16 minutes at a wall scraping blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, central blade: rotational speed = 53 rpm, tip speed = 0.86 m / s. did. Further, stirring with the wall scraping blade and the central blade was continued, and the clay mineral dispersion was cooled to 40 ° C. (dispersion preparation step).

The mixing apparatus 400 in FIG. 5 is roughly configured by a stirring tank 410, a wall scraping blade 430, a central blade 420, a stirring unit 440 that is a homogenizer, and a jacket unit 450. The wall scraping blade 430 is provided with a plurality of substantially U-shaped anchor blades 431, a scraping plate 433 for scraping the inner surface of the stirring tank 410, and the anchor blade 431 to the center of the stirring tank 410. The central blade 420 is protruded from the stirring shaft 422 extending in the vertical direction at the approximate center of the stirring tank 410 toward the inner surface of the stirring tank 410. Is. The stirring unit 440 is provided at the lower end of the stirring shaft 422 and is schematically configured by a stirring blade 444 that is a turbine blade and a stator 442 that covers the stirring blade 444 so as to be spaced around the rotation shaft. The jacket portion 450 is provided on the outer surface of the stirring vessel 410, and adjusts the inside of the stirring vessel 410 to an arbitrary temperature by passing a heat medium therethrough.
The mixing device 400 causes the mixture in the stirring vessel 410 to flow by the rotation of the wall scraping blade 430 and the central blade 420, and applies a shearing force to the mixture by the stirring unit 440.
In the drawing, the symbol D3 represents the clearance between the tip of the stirring blade 444 and the inner surface of the stator 442, and the symbol d3 represents the diameter of the stirring blade 444.
In addition, the mixing apparatus (PVT-1-20 type, manufactured by Mizuho Kogyo Co., Ltd.) used in this example has D3 = 0.5 mm, d3 = 44 mm, and discharge flow coefficient (Nqd) = 0.1 in FIG. It is.

(Examples 10 to 11)
According to the composition of Table 3, a clay mineral dispersion was obtained in the same manner as in Example 1 except that the tip speed of the stirring blade and the operation time of the stirring blade were changed to the conditions shown in Table 3.

(Comparative Examples 5-6)
According to the composition of Table 4, the component (E) was added to a mixing apparatus (TK Ajihomomixer SL type (20 L)) and heated to 70 ° C. Next, the raw materials excluding the common components were put into the mixing apparatus, and the wall scraping blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, central blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, Stirring blade: The mixing apparatus was operated for 0.5 minutes at a rotational speed of 7600 rpm and a tip speed of 19 m / s to obtain a mixed solution. Thereafter, the stirring blade was stopped, and the mixing device was cleaned with a wall scraping blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, central blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, 4.5. Drove for a minute. Further, stirring with the wall scraping blade and the central blade was continued, and the mixed solution was cooled to 40 ° C.
Next, common components were added to the mixed solution, wall scraping blade: rotation speed = 53 rpm, tip speed = 0.86 m / s, central blade: rotation speed = 53 rpm, tip speed = 0.86 m / s, stirring blade: rotation The mixing apparatus was operated for 4 minutes (mixing time) at several 4000 rpm and tip speed = 10 m / s to obtain a clay mineral dispersion. Thereafter, the stirring blade was stopped, and the mixing apparatus was operated at a wall scraping blade: rotational speed = 53 rpm, tip speed = 0.86 m / s, central blade: rotational speed = 53 rpm, tip speed = 0.86 m / s. Further, stirring with the wall scraping blade and the central blade was continued, and the clay mineral dispersion was cooled to 40 ° C.

As shown in Tables 2 to 3, in each of Examples 1 to 11 to which the present invention was applied, the viscosity reduction evaluation was “◯” or “「 ”.
On the other hand, the comparative examples 5-6 which did not provide the clay dispersion | distribution process and the polymer dispersion | distribution process all were "(triangle | delta)" or "x".
From these results, it was found that by applying the present invention, it is possible to obtain a clay mineral dispersion liquid that is not easily reduced in viscosity during transfer.

Claims (2)

(A) component: water-swellable clay mineral, (B) component: sugar alcohol, (C) component: water-soluble polymer compound, (D) component: (poly) glycerin ester, and (E) component: A method for producing a clay mineral dispersion containing water,
A clay dispersion step of mixing the component (A), the component (B), and a part of the component (E) to obtain a clay dispersion;
A polymer dispersion step of mixing the component (C) and the remainder of the component (E) to obtain a polymer dispersion;
A mixing step of mixing the clay dispersion and the polymer dispersion to obtain a mixture;
The manufacturing method of the clay mineral dispersion characterized by having the dispersion liquid preparation process which mixes the said liquid mixture and (D) component. The said clay dispersion | distribution process mixes the said (A) component and the said (B) component by (B) component / (A) component = 3-8 (mass ratio). A method for producing a clay mineral dispersion.

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