JP2019209330A - Process for preparation of dispersion liquid - Google Patents

Abstract

To produce a dispersion liquid in which an oily component having a small average particle diameter is dispersed in an aqueous component.SOLUTION: There is provided a method for producing a dispersion liquid of particles having an average particle diameter of 10 μm or less. In this method for producing a dispersion liquid, an aqueous component and an oily component are made to join together. One or two or more of an aqueous component before joining, an oily component before joining, and a fluid after joining the aqueous component and the oily component are allowed to flow through pores under the condition that the segregation index (Xs) is 0.15 or less.SELECTED DRAWING: None

Description

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

  A method for producing a dispersion using a micromixer is known.

  Patent Document 1 discloses a method for producing a dispersion (emulsion) in which each of an aqueous component and an oily component is caused to flow into the pores of a micromixer and collide with them.

  In Patent Document 2, an aqueous component is made to flow, and an oily component containing melted ceramide and nonionic surfactant is made to flow, and the combined fluid is circulated through the pores of the micromixer to prepare an emulsion. Thereafter, a method for producing a ceramide fine particle dispersion in which the ceramide is solidified by cooling it is disclosed.

  Patent Document 3 discloses a dispersion (emulsion) in which an aqueous component is allowed to flow through a microchannel of a micromixer and an oily component is allowed to flow into the microchannel through an open area, thereby bringing the oily component into contact with and dispersing the aqueous component. A manufacturing method is disclosed.

  Patent Document 4 discloses a method for producing a dispersion liquid in which an oily component as a continuous phase liquid and an aqueous component as a dispersed phase liquid are joined in a micromixer, and then the joined fluid is circulated through an orifice. Has been.

JP 2008-142588 A JP 2008-037842 A Special table 2007-516067 gazette Japanese translation of PCT publication No. 2006-507921

  In dispersions used in the fields of cosmetics and pharmaceuticals, it is desired that fine particles are dispersed from the viewpoint of usability and the like.

  However, in the technique disclosed in Patent Document 1, since a surfactant is contained in the aqueous component, a nonionic ion of a specific HLB is used in order to participate in the formation of emulsified droplets with the surfactant contained in the aqueous component. Active surfactant is required. Therefore, the range of application of the obtained dispersion as a blending technique for cosmetics and pharmaceuticals is narrowed.

  In the technique disclosed in Patent Document 2, since the oil component contains ceramide which is a solid fat, the particles obtained after cooling are not emulsified droplets but solid dispersed particles.

  In the techniques disclosed in Patent Documents 3 to 4, since a water-soluble solvent is not used, it is difficult to obtain a fine emulsion liquid dispersion.

  An object of the present invention is to produce a dispersion in which fine particles are dispersed.

  The present invention includes a merging step for merging an aqueous component and an oily component, the aqueous component before merging in the merging step, the oily component before merging in the merging step, and the aqueous component in the merging step. An average particle having a pore circulation step of causing one or more of the fluids after having joined the oil component to circulate in the pores under a condition that the segregation index (Xs) is 0.15 or less. A method for producing a dispersion of particles having a diameter of 10 μm or less, wherein the oil component is one or more selected from the group consisting of oils and compounds represented by the following general formulas (I) to (III) And a surfactant and at least one of a surfactant precursor that forms a surfactant when combined with the aqueous component.

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. P1, p2, p3, q1, q2, q3, r1, r2, and r3 each represent an average added mole number. ≦ p1 + p2 + p3 ≦ 20, 0 ≦ q1 + q2 + q3 ≦ 10, and 0 ≦ r1 + r2 + r3 ≦ 10, and 1 ≦ p1 + p2 + p3 + q1 + q2 + q3 + r1 + r2 + r3 ≦ 40. EO, PO, and BO are added in a random or block form.

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. S, t, and u each represent an average number of added moles. 1 ≦ s ≦ 70, 0 ≦ t ≦ 70, and 0 ≦ u ≦ 10 and 1 ≦ s + t + u ≦ 100, EO, PO, and BO are added in a random or block form, and R ¹ is a hydrocarbon group having 2 to 5 carbon atoms. .)

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. V1, v2, w1, w2, x1, and x2 each represent an average added mole number. 1 ≦ v1 + v2 ≦ 10, 0 ≦ w1 + w2 ≦ 9, 0 ≦ x1 + x2 ≦ 9, and 1 ≦ v1 + v2 + w1 + w2 + x1 + x2 ≦ 10 EO, PO, and BO are added in a random or block form, R ² and R ³ are independent of each other. And a hydrocarbon group having 1 to 4 carbon atoms, and n is a number having 1 to 4 carbon atoms.)

  According to the present invention, an oil component, an oil agent, a water-soluble solvent having a specific structure, and at least one of a surfactant precursor that forms a surfactant when combined with a surfactant and an aqueous component. 1 or 2 or more of the aqueous component before joining and the oily component before joining, and the fluid after joining them, the segregation index (Xs) is 0.15 or less. By allowing the fine particles having an average particle diameter of 10 μm or less to be dispersed, it is possible to produce a dispersion in which the fine particles having a mean particle size of 10 μm or less are dispersed.

It is a figure which shows the structure of a dispersion liquid manufacturing system. It is a fragmentary longitudinal cross-sectional view of the principal part in the micro mixer of a 1st structure. It is the III-III sectional view in FIG. FIG. 5A is a partial longitudinal sectional view of a main part in a modified example of the micromixer having the first configuration, and FIG. 4B is a transverse sectional view of IVB-IVB in FIG. It is a longitudinal cross-sectional view of the micro mixer of a 2nd structure. It is a longitudinal cross-sectional view of the modification of the micro mixer of a 2nd structure. (A) Partial longitudinal cross-sectional view of the main part of the micro mixer of the third configuration, (b) a cross-sectional view of VIIB-VIIB in FIG. 7 (a), and (c) a cross-sectional view of VIIC-VIIC in FIG. 7 (a) FIG. FIG. 10 is a (a) partial longitudinal sectional view and (b) a VIIIB-VIIIB transverse sectional view in FIG.

  The method for producing a dispersion according to this embodiment includes a merging step in which an aqueous component and an oily component are merged, an aqueous component before merging in the merging step, an oily component before merging in the merging step, and an aqueous component in the merging step. A pore circulation step of circulating one or more of the fluids after the components and the oily component are merged into pores having a pore diameter of 0.1 mm or more and 3 mm or less. The oil component is combined with an oil agent, one or more water-soluble solvents selected from the group of compounds represented by the following general formulas (I) to (III), a surfactant and an aqueous component. And at least one of a surfactant precursor that forms a surfactant when it is heated.

  In addition, a surfactant precursor is neutralized by the component which comprises an anionic surfactant by neutralizing with the alkaline component in an aqueous component among the oil-based components, or the acid component in an aqueous component. Is a component that forms a cationic surfactant.

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. P1, p2, p3, q1, q2, q3, r1, r2, and r3 each represent an average added mole number. ≦ p1 + p2 + p3 ≦ 20, 0 ≦ q1 + q2 + q3 ≦ 10, and 0 ≦ r1 + r2 + r3 ≦ 10, and 1 ≦ p1 + p2 + p3 + q1 + q2 + q3 + r1 + r2 + r3 ≦ 40. EO, PO, and BO are added in a random or block form.

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. S, t, and u each represent an average number of added moles. 1 ≦ s ≦ 70, 0 ≦ t ≦ 70, and 0 ≦ u ≦ 10 and 1 ≦ s + t + u ≦ 100, EO, PO, and BO are added in a random or block form, and R ¹ is a hydrocarbon group having 2 to 5 carbon atoms. .)

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. V1, v2, w1, w2, x1, and x2 each represent an average added mole number. 1 ≦ v1 + v2 ≦ 10, 0 ≦ w1 + w2 ≦ 9, 0 ≦ x1 + x2 ≦ 9, and 1 ≦ v1 + v2 + w1 + w2 + x1 + x2 ≦ 10 EO, PO, and BO are added in a random or block form, R ² and R ³ are independent of each other. And a hydrocarbon group having 1 to 4 carbon atoms, and n is a number having 1 to 4 carbon atoms.)

  Generally, in a dispersion liquid used in the fields of cosmetics and pharmaceuticals, it is desired that fine particles are dispersed from the viewpoint of usability and the like. On the other hand, according to the method for producing a dispersion according to this embodiment, a surfactant is formed when an oil component is combined with a water-soluble solvent having a specific structure, a surfactant, and an aqueous component. At least one of the surfactant precursors is contained and one or two or more of the aqueous component before joining, the oily component before joining, and the fluid after joining them have a pore size of 0. 0. By flowing through pores of 1 mm or more and 3 mm or less, a dispersion in which fine particles are dispersed can be produced.

  This is because, in the method for producing a dispersion according to the present embodiment, the aqueous component before joining in the joining step, the oily component before joining in the joining step, and the fluid after joining the aqueous component and oily component in the joining step Since one or two or more pores are passed through pores having a pore diameter of 0.1 mm or more and 3 mm or less, the interface existing in the oil component due to the turbulent stirring effect at the time of joining or after joining the oily component and the aqueous component. It is effectively suppressed that the active agent diffuses into the aqueous component without contributing to dispersion, and as a result, the surfactant is efficiently supplied to the oil-water interface, and in addition, the specific component contained in the oily component It is thought that the water-soluble solvent having a structure significantly reduces the interfacial tension of oil water.

  In the conventional method for producing a dispersion using a homomixer or the like, the same effect cannot be obtained even if the oil component contains the same water-soluble solvent and surfactant. This is presumably because both the water-soluble solvent and the surfactant diffuse into the aqueous component before the oily component reaches the shear field.

  Details will be described below.

  The method for producing a dispersion according to this embodiment includes a merging step and a pore circulation step.

[Join step]
In the merging step, the liquid aqueous component and the liquid oily component are merged.

(Aqueous component)
The aqueous component is preferably composed only of water from the viewpoint of easy preparation, but other than that, for example, an aqueous solution in which a solute such as a salt is dissolved in water or a mixed solution of water and a water-soluble solvent is used. It may be. In that case, the content of water in the aqueous component is preferably 50% by mass or more, more preferably 70% by mass or more, still more preferably 90% by mass or more, and still more preferably from the viewpoint of obtaining a fine particle dispersion. It is 95 mass% or more, More preferably, it is 98 mass% or more. Examples of the water-soluble solvent include alcohols having 1 to 6 carbon atoms such as methanol, ethanol, glycerin, propylene glycol, dipropylene glycol, and 1,3-butylene glycol.

  The aqueous component may contain an alkali component or an acid component that neutralizes the surfactant precursor.

  Examples of the alkali component include alkali metal hydroxide, ammonia, alkanolamine, and the like, and these neutralize the surfactant precursor to form an anionic surfactant.

  Examples of the acid component include mineral acids such as phosphoric acid and hydrochloric acid, and organic acids such as carboxylic acids and amino acids, and these neutralize the surfactant precursor to form a cationic surfactant.

(Oil component)
The oil component contains an oil agent, a water-soluble solvent having a specific structure, and at least one of a surfactant and a surfactant precursor.

<Oil agent>
Oils include liquid oils that are liquid at 20 ° C. and solid fats that are solid at 20 ° C. The oil component may contain only liquid oil as an oil agent, may contain only solid fat, or may contain both of them. In addition, when using solid fat, it heats and melts an oil-based component to the temperature beyond melting | fusing point of solid fat.

  Examples of the liquid oil include liquid higher alcohols, liquid ester oils, liquid hydrocarbon oils, liquid silicone oils, liquid dialkyl ethers, liquid fats and oils, liquid functional oils, liquid fragrances, and the like. . Among these, from the viewpoint of obtaining a dispersion of fine particles, liquid higher alcohols, liquid ester oils, liquid hydrocarbon oils, and liquid silicone oils are preferable, liquid higher alcohols, liquid ester oils, And liquid hydrocarbon oils are more preferred, liquid higher alcohols and liquid ester oils are more preferred, and liquid higher alcohols are even more preferred. The liquid oil may be volatile or non-volatile.

  Examples of liquid higher alcohols include saturated or unsaturated linear or branched liquid alcohols. The liquid higher alcohol is preferably a saturated alcohol from the viewpoint of obtaining a fine particle dispersion, and from the same viewpoint, a branched alcohol is preferable. The carbon number of the liquid higher alcohol is preferably 8 or more, more preferably 10 or more, still more preferably 12 or more, still more preferably 16 or more, and still more preferably 18 or more, from the viewpoint of obtaining a fine particle dispersion. From the same viewpoint, it is preferably 22 or less. Specific examples include 2-octyldodecan-1-ol.

  Examples of the liquid ester oil include liquid fatty acid glycerides such as liquid neopentyl glycol difatty acid ester, ethylene glycol difatty acid ester, fatty acid monoglyceride, fatty acid diglyceride, and fatty acid triglyceride. The liquid ester oil is preferably neopentyl glycol difatty acid ester from the viewpoint of obtaining a fine particle dispersion.

  From the viewpoint of obtaining a fine particle dispersion, the acyl group of the liquid ester oil is preferably linear or branched, and more preferably linear. From the same viewpoint, the carbon number of the acyl group of the liquid ester oil is preferably 6 or more, more preferably 8 or more, and from the same viewpoint, preferably 22 or less, more preferably 18 or less, and still more preferably 16 Hereinafter, it is more preferably 14 or less, and still more preferably 12 or less. A preferred liquid ester oil is neopentyl glycol dicaprate from the viewpoint of obtaining a dispersion of fine particles.

  Examples of the liquid hydrocarbon oil include liquid paraffin, squalene, squalane and the like. The liquid hydrocarbon oil is preferably a linear or branched hydrocarbon, more preferably a branched hydrocarbon, from the viewpoint of obtaining a fine particle dispersion, and a saturated or unsaturated hydrocarbon from the same viewpoint. Are preferred, and saturated hydrocarbons are more preferred. The carbon number of the liquid hydrocarbon oil is preferably 16 or more, more preferably 22 or more, still more preferably 28 or more from the viewpoint of obtaining a fine particle dispersion, and from the same viewpoint, preferably 50 or less. More preferably, it is 40 or less, More preferably, it is 32 or less. A preferred hydrocarbon oil is squalane from the viewpoint of obtaining a fine particle dispersion.

  Examples of the liquid silicone oil include dimethylpolysiloxane, methylpolysiloxane, methylphenylsiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, methylhydrogenpolysiloxane, silicone resin, amino-modified silicone, alkyl-modified silicone, Examples include polyether-modified silicone, glyceryl-modified silicone, and silicone wax. From the viewpoint of obtaining a fine particle dispersion, the liquid silicone oil is preferably one or more selected from these, and more preferably dimethylpolysiloxane.

  Examples of the liquid dialkyl ether include ethers having a saturated or unsaturated linear or branched alkyl group or alkenyl group (preferably 8 to 22 carbon atoms). Examples of liquid oils include vegetable oils such as soybean oil, coconut oil, palm kernel oil, linseed oil, cottonseed oil, rapeseed oil, tung oil, castor oil, and the like.

  Examples of the liquid functional oil include organic ceramides, organic ultraviolet absorbers such as 2-methoxyhexyl paramethoxycinnamate, and 1- (2-hydroxyethylamino) -3-isostearyloxy-2-propanol. Examples include liquid sphingolipids. Examples of liquid fragrances include those conventionally used.

  Examples of the solid fat include solid ceramide, solid paraffin, solid higher alcohol, petrolatum, solid silicone, hardened oil, solid fragrance, and the like. The solid fat is preferably a solid ceramide or a solid fragrance, and more preferably a solid ceramide, from the viewpoint of a remarkable effect of obtaining a fine particle dispersion.

  Examples of the solid ceramide include N- (2-hydroxy-3-hexadecyloxypropyl) -N-2-hydroxyethylhexadecanamide, which has good dispersion stability.

  Examples of the solid paraffin include paraffin wax, microcrystalline wax, ceresin, soft wax, and Japanese Pharmacopoeia paraffin described in JIS K 2235.

  Examples of solid higher alcohols include myristyl alcohol, cetyl alcohol, cetostearyl alcohol, stearyl alcohol, arachidyl alcohol, and behenyl alcohol. Examples of the solid silicone include alkyl-modified silicone, polymer silicone / alkyl co-modified acrylic resin, and the like.

  Examples of the hardened oil include hardened oil whose raw material oil is palm oil, palm oil, and beef tallow. Examples of solid fragrances include menthol and cedrol.

  The oil agent is preferably one or more selected from the group of liquid oil and solid fat listed above.

  It is preferable that an oil agent has 1 type, or 2 or more types of functional groups containing a hetero atom from a viewpoint of obtaining the dispersion liquid of a fine particle. Examples of such a functional group include an ester group, an amide group, a hydroxyl group, an ether group, and a carbonyl group. From the viewpoint of obtaining a fine particle dispersion, an ester group, an amide group, or a hydroxyl group is preferable.

  The content of the oil agent in the oil component is preferably 8% by mass or more, more preferably 10% by mass or more, still more preferably 15% by mass, and still more preferably 20% by mass or more, from the viewpoint of obtaining a fine particle dispersion. More preferably, it is 30% by mass or more, more preferably 40% by mass or more, and from the same viewpoint, it is preferably 95% by mass or less, more preferably 90% by mass or less, still more preferably 80% by mass or less. More preferably, it is 60 mass% or less, More preferably, it is 50 mass% or less.

  The content of the oil agent in the oil component when solid fat is used as the oil agent is preferably 30% by mass or less, more preferably 25% by mass or less from the viewpoint of obtaining a fine particle dispersion.

<Water-soluble solvent>
The oil component contains an oil agent and one or more water-soluble solvents selected from the group of compounds represented by the following general formulas (I) to (III).

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. P1, p2, p3, q1, q2, q3, r1, r2, and r3 each represent an average added mole number. ≦ p1 + p2 + p3 ≦ 20, 0 ≦ q1 + q2 + q3 ≦ 10, and 0 ≦ r1 + r2 + r3 ≦ 10, and 1 ≦ p1 + p2 + p3 + q1 + q2 + q3 + r1 + r2 + r3 ≦ 40. EO, PO, and BO are added in a random or block form.

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. S, t, and u each represent an average number of added moles. 1 ≦ s ≦ 70, 0 ≦ t ≦ 70, and 0 ≦ u ≦ 10 and 1 ≦ s + t + u ≦ 100, EO, PO, and BO are added in a random or block form, and R ¹ is a hydrocarbon group having 2 to 5 carbon atoms. .)

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. V1, v2, w1, w2, x1, and x2 each represent an average added mole number. 1 ≦ v1 + v2 ≦ 10, 0 ≦ w1 + w2 ≦ 9, 0 ≦ x1 + x2 ≦ 9, and 1 ≦ v1 + v2 + w1 + w2 + x1 + x2 ≦ 10 EO, PO, and BO are added in a random or block form, R ² and R ³ are independent of each other. And a hydrocarbon group having 1 to 4 carbon atoms, and n is a number having 1 to 4 carbon atoms.)

  In the water-soluble solvent represented by the general formula (I), p1 + p2 + p3 is 1 or more and 20 or less, but preferably 3 or more, more preferably 5 or more, and still more preferably from the viewpoint of obtaining a fine particle dispersion. From the same viewpoint, it is preferably 15 or less, more preferably 10 or less.

  q1 + q2 + q3 is 0 or more and 10 or less, preferably 1 or more, more preferably 3 or more, still more preferably 4 or more from the viewpoint of obtaining a dispersion of fine particles, and from the same viewpoint, preferably 8 or less, more preferably 6 or less.

  r1 + r2 + r3 is 0 or more and 10 or less, preferably 1 or more, more preferably 2 or more from the viewpoint of obtaining a fine particle dispersion, and preferably 6 or less, more preferably from the same viewpoint. 4 or less.

  p1 + p2 + p3 + q1 + q2 + q3 + r1 + r2 + r3 is 1 or more and 40 or less, preferably 5 or more, more preferably 10 or more, still more preferably 12 or more from the viewpoint of obtaining a fine particle dispersion, and from the same viewpoint, preferably 30 or less, more preferably 20 or less.

  EO, PO, and BO are added in a random or block form. From the viewpoint of obtaining a dispersion of fine particles, EO and PO are added in a random or block form, and BO is in a block form at the end. One or two or more water-soluble solvents selected from the group of compounds represented by the following general formula (IV) added to are preferred.

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. P1, p2, p3, q1, q2, q3, r1, r2, and r3 each represent an average added mole number. ≦ p1 + p2 + p3 ≦ 20, 1 ≦ q1 + q2 + q3 ≦ 10, and 1 ≦ r1 + r2 + r3 ≦ 10, and 3 ≦ p1 + p2 + p3 + q1 + q2 + q3 + r1 + r2 + r3 ≦ 40. EO and PO are added in a random or block form.

  In the water-soluble solvent represented by the general formula (IV), p1 + p2 + p3 is 1 or more and 20 or less, but preferably 3 or more, more preferably 5 or more, and still more preferably from the viewpoint of obtaining a fine particle dispersion. From the same viewpoint, it is preferably 15 or less, more preferably 10 or less.

  q1 + q2 + q3 is 1 or more and 10 or less, preferably 3 or more, more preferably 4 or more from the viewpoint of obtaining a fine particle dispersion, and from the same viewpoint, preferably 8 or less, more preferably 6 or less.

  r1 + r2 + r3 is 1 or more and 10 or less, preferably 2 or more from the viewpoint of obtaining a fine particle dispersion, and preferably 6 or less, more preferably 4 or less from the same viewpoint.

  p1 + p2 + p3 + q1 + q2 + q3 + r1 + r2 + r3 is 3 or more and 40 or less, but preferably 5 or more, more preferably 10 or more, still more preferably 12 or more from the viewpoint of obtaining a fine particle dispersion, and from the same viewpoint, preferably 30 or less, more preferably 20 or less.

  In the water-soluble solvent represented by the general formula (II), s is 1 or more and 70 or less, but preferably 2 or more, more preferably 5 or more, and still more preferably from the viewpoint of obtaining a fine particle dispersion. 10 or more, more preferably 15 or more, still more preferably 25 or more, still more preferably 28 or more, and from the same viewpoint, preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, More preferably, it is 32 or less.

  In the case of using solid fat as the oil agent, s is more preferably 10 or less, and further preferably 3 or less, from the viewpoint of obtaining a fine particle dispersion.

  t is from 0 to 70, but from the viewpoint of obtaining a fine particle dispersion, it is preferably 1 or more, more preferably 5 or more, still more preferably 10 or more, still more preferably 15 or more, and even more preferably 25. More preferably, it is 28 or more, and from the same viewpoint, it is preferably 50 or less, more preferably 40 or less, still more preferably 35 or less, and still more preferably 32 or less.

  From the viewpoint of obtaining a fine particle dispersion, t in the case of using solid fat as the oil is more preferably 10 or less, still more preferably 5 or less, and still more preferably 1 or less.

  u is 0 or more and 10 or less, but preferably 5 or less, more preferably 1 or less, and still more preferably 0, from the viewpoint of obtaining a dispersion of fine particles.

  Although s + t + u is 1 or more and 100 or less, it is preferably 2 or more from the viewpoint of obtaining a dispersion of fine particles, and from the same viewpoint, it is preferably 80 or less, more preferably 70 or less, and still more preferably. 64 or less.

  In the case of using solid fat as an oil agent, s + t + u is preferably 20 or less, more preferably 10 or less, and further preferably 3 or less, from the viewpoint of obtaining a fine particle dispersion.

  EO, PO, and BO are added in a random or block form.

The carbon number of R ¹ is 2 or more and 5 or less, but is preferably 4 or less from the viewpoint of obtaining a fine particle dispersion.

  In the water-soluble solvent represented by the general formula (III), v1 + v2 is 1 or more and 10 or less, but preferably 1 or more, more preferably 2 or more, and still more preferably from the viewpoint of obtaining a fine particle dispersion. From the same viewpoint, it is preferably 10 or less, more preferably 7 or even more preferably 5 or less.

  Although w1 + w2 is 0 or more and 9 or less, it is preferably 5 or less, more preferably 1 or less, and still more preferably 0 from the viewpoint of obtaining a fine particle dispersion.

  x1 + x2 is 0 or more and 9 or less, but preferably 5 or less, more preferably 1 or less, and still more preferably 0 from the viewpoint of obtaining a fine particle dispersion.

  v1 + v2 + w1 + w2 + x1 + x2 is 1 or more and 10 or less, but preferably 2 or more, more preferably 3 or more from the viewpoint of obtaining a fine particle dispersion, and from the same viewpoint, preferably 7 or less, more preferably 5 or less.

  EO, PO, and BO are added in a random or block form.

The carbon number of R ² and R ³ is 1 or more and 4 or less, preferably 2 or more from the viewpoint of obtaining a fine particle dispersion, and preferably 3 or less from the same viewpoint.

  n is 1 or more and 4 or less, but preferably 2 or more from the viewpoint of obtaining a fine particle dispersion, and preferably 3 or less from the same viewpoint.

  The water-soluble solvent is one or more selected from the group of compounds represented by the general formulas (I) to (III). From the viewpoint of obtaining a fine particle dispersion, the general formula (I) It is preferable that it is 1 type, or 2 or more types chosen from the group of the compound represented by thru | or (III).

  The content of the water-soluble solvent in the oil component is preferably 4% by mass or more, more preferably 10% by mass or more, still more preferably 20% by mass or more, and still more preferably 30%, from the viewpoint of obtaining a fine particle dispersion. In addition, from the same viewpoint, it is preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less, and still more preferably 70% by mass. It is at most mass%, more preferably at most 60 mass%, still more preferably at most 50 mass%.

  The mass ratio of the content of the water-soluble solvent to the content of the oil agent in the oil component (water-soluble solvent / oil agent) is preferably 0.1 or more, more preferably 0.2, from the viewpoint of obtaining a fine particle dispersion. Or more, more preferably 0.3 or more, still more preferably 0.5 or more, still more preferably 0.8 or more, and from the same viewpoint, it is preferably 9 or less, more preferably 8 or less, still more preferably Is 5 or less, more preferably 3.5 or less, even more preferably 2 or less, still more preferably 1.5 or less, and still more preferably 1.2 or less.

<Surfactant>
The oily component further contains at least one of a surfactant precursor that forms a surfactant when combined with the surfactant and the aqueous component. Therefore, the oil component may contain only the surfactant, may contain only the surfactant precursor, or may contain both of them.

  Surfactants include nonionic surfactants, anionic surfactants, and cationic surfactants.

  Nonionic surfactants include, for example, polyoxyethylene hydrogenated castor oil, polyoxyethylene castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene glycerin fatty acid ester, polyoxyethylene fatty acid and the like. Oxyethylene ether ester type nonionic surfactant; polyoxyethylene ether type nonionic surfactant such as polyoxyethylene alkyl ether and polyoxyethylene alkylphenyl ether; sorbitan fatty acid ester, sucrose fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid Polyhydric alcohol fatty acid ester type nonionic surfactants such as esters; Polyhydric alcohol alkyl ether type nonionic interfaces such as alkyl glycosides Sex agents; fatty acid mono alkanolamide, polyoxyethylene alkyl amines, nitrogen-containing type nonionic surfactants such as alkyl polyoxyethylene fatty acid amides.

  Among these, nonionic surfactants are polyoxyethylene ether ester type nonionic surfactants, polyoxyethylene ether ester type nonionic surfactants, polyoxyethylene ether type nonionic surfactants, from the viewpoint of obtaining a dispersion of fine particles. One or more selected from activators, polyhydric alcohol fatty acid ester type nonionic surfactants, polyhydric alcohol alkyl ether type nonionic surfactants and nitrogen-containing nonionic surfactants are preferred, and polyoxyethylene ether ester type 1 type or 2 or more types selected from nonionic surfactants are more preferable, 1 type or 2 or more types selected from polyoxyethylene hydrogenated castor oil and polyoxy fatty acid are still more preferable, 1 type selected from polyoxyethylene hydrogenated castor oil Or two or more types are even more preferred .

  From the viewpoint of obtaining a dispersion of fine particles, the average number of moles of polyethylene oxide added to polyethylene hardened castor oil is preferably 1 mole or more, more preferably 10 moles or more, and even more preferably 20 moles or more. Therefore, it is preferably 100 mol or less, more preferably 70 mol or less, still more preferably 50 mol or less, and still more preferably 30 mol or less.

  The HLB of the nonionic surfactant is preferably 7 or more, more preferably 8 or more, still more preferably 9 or more, still more preferably 10 or more, still more preferably 12 or more, from the viewpoint of obtaining a fine particle dispersion. From the same viewpoint, it is preferably 20 or less, more preferably 18 or less, still more preferably 16 or less, and still more preferably 15 or less. The HLB is obtained based on the calculation formula described in “Emulsification / Solubilization Technology” Engineering Book Co., Ltd. (Sho 59-5-20) p.8-12. More specifically, in the case of a polyhydric alcohol fatty acid ester type nonionic surfactant, the formula: [HLB] = 20 (1-S / A) (wherein S is the saponification value of the ester, and A is the acid of the fatty acid) (Indicative value).

  In the case of a polyoxyethylene ether ester type nonionic surfactant, based on the formula: [HLB] = (E + P) / 5 (wherein E represents an ethylene oxide content (mass%) and P represents an alcohol content (mass%)). Is required.

  In the case of polyoxyethylene alkyl ether, it is determined based on the formula: [HLB] = E / 5 (wherein E is the same as above). Here, the acid value and the saponification value can be determined according to JISK0070-1992.

  In the case of other nonionic surfactants, the formula: [HLB] = 7 + 11.71 log (Mw / Mo) (where Mw is the molecular weight of the hydrophilic group of the surfactant, Mo is the hydrophobic group of the surfactant) The molecular weight, log, is determined based on the base 10 logarithm).

When two types of surfactant A and surfactant B having different HLBs are used in combination as the nonionic surfactant, if each HLB is HLB _A and HLB _B , the HLB of the nonionic surfactant in which both are mixed is When the respective mass fractions (mass%) are W _A and W _B , based on the formula: [HLB] = [(W _A × HLB _A ) + (W _B × HLB _B )] ÷ (W _A + W _B ) Is required. Moreover, when using together 3 or more types of surfactant as a nonionic surfactant, HLB of the nonionic surfactant which mixed them can be calculated | required similarly to the above.

  Examples of the anionic surfactant include sulfate anion surfactants such as alkyl sulfate ester salts, alkenyl sulfate ester salts, polyoxyalkylene alkyl ether sulfate ester salts, and polyoxyalkylene alkenyl ether sulfate ester salts; , Sulfosuccinic acid alkyl ester salt, polyoxyalkylene sulfosuccinic acid alkyl ester salt, secondary alkyl sulfonate, α-olefin sulfonic acid, α-sulfo fatty acid ester salt, acyl isethionate, N-acyl-N-methyl taurate salt Sulfonic acid type anionic surfactants such as: fatty acid salts, ether carboxylates, alkenyl succinates, N-acyl amino acid salts and the like carboxylic acid type anionic surfactants; alkyl phosphate ester salts, polyoxya Examples thereof include phosphate anionic surfactants such as a ruxylene alkyl ether phosphate.

  Among these, from the viewpoint of obtaining a dispersion of fine particles, the anionic surfactant is preferably a carboxylic acid type anionic surfactant, more preferably a fatty acid salt or an alkyl ether carboxylate, and even more preferably a fatty acid salt.

  The number of carbon atoms of the fatty acid salt is preferably 8 or more, more preferably 12 or more, still more preferably 16 or more, and preferably 22 or less, more preferably 20 from the viewpoint of obtaining a fine particle dispersion. It is as follows.

  The alkyl chain of the fatty acid salt is preferably a straight chain from the viewpoint of obtaining a fine particle dispersion.

  Specific examples of fatty acid salts include salts of coconut oil fatty acid, oleic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid and the like.

  Of these, from the viewpoint of obtaining a fine particle dispersion, the fatty acid salt is preferably a sodium salt or potassium salt of coconut oil fatty acid, oleic acid, lauric acid, or myristic acid, and coconut oil fatty acid or sodium salt of oleic acid. Or a potassium salt is more preferable, a sodium salt or potassium salt of oleic acid is still more preferable, and potassium oleate is still more preferable.

  Examples of the cationic surfactant include a quaternary ammonium salt, a pyridinium salt, a tertiary amine, or a secondary having a hydrocarbon group having 12 to 28 carbon atoms which may be separated by an amide group, an ester group, or an ether group. Examples thereof include a mineral acid or an organic acid salt of an amine. Moreover, as a tertiary amine or a secondary amine, the compound represented by the following general formula (V) is mentioned from a viewpoint of obtaining the dispersion liquid of a fine particle.

(R ⁴ represents a linear or branched hydrocarbon group having 1 to 22 carbon atoms which may be substituted with a hydroxyl group, and R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are the same or Differently, it represents a hydrocarbon group having 1 to 22 carbon atoms which may be substituted with a hydrogen atom or a hydroxyl group, and X represents —O— or —CO—O— (wherein the carbonyl group is bonded to R ^4. Show))

Here, in the general formula (V), the carbon number of R ⁴ is preferably 8 or more, more preferably 12 or more, and still more preferably 18 or more, from the viewpoint of obtaining a fine particle dispersion. From this viewpoint, it is preferably 22 or less, more preferably 20 or less. R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are preferably hydrogen atoms from the viewpoint of availability of a cationic surfactant and a dispersion of fine particles. X is preferably —O— from the viewpoint of availability of a cationic surfactant and obtaining a dispersion of fine particles.

  Specifically, examples of the quaternary ammonium salt include mono long-chain alkyltrimethylammonium salts such as cetyltrimethylammonium salt, stearyltrimethylammonium salt, behenyltrimethylammonium salt, okdadecyloxypropyltrimethylammonium salt, and distearyldimethyl. Examples thereof include dilong chain alkyldimethylammonium salts such as ammonium salts and diisotetradecyldimethylammonium salts. Examples of the tertiary amine salt include stearyl dimethylamine, behenyl dimethylamine, octadecyloxypropyl dimethylamine, dimethylaminopropyl stearamide hydrochloride, mono-long-chain alkyldimethylamine salts such as citric acid or lactate, etc. Can be mentioned. Examples of the secondary amine salt include 1- (2-hydroxyethylamino) -3-isostearyloxy-2-propanol or 1- (2-hydroxyethylamino) -3- (12-hydroxystearyloxy) -2. -Amine salts such as propanol hydrochloride, glutamic acid, citric acid or lactate.

  Among these, the cationic surfactant is a compound having 12 to 28 carbon atoms which may be divided by an amide group, an ester group or an ether group from the viewpoint of obtaining a fine particle dispersion using an oil agent of liquid oil. A quaternary ammonium salt having a hydrocarbon group is preferred, a dilong chain alkyldimethylammonium salt is more preferred, and a dilong chain alkyldimethylammonium chloride is still more preferred.

  From the viewpoint of obtaining a fine particle dispersion, the number of carbon atoms of each alkyl group of the di-long-chain alkyldimethylammonium salt is preferably 8 or more, more preferably 12 or more, still more preferably 16 or more, and from the same viewpoint. , Preferably 22 or less, more preferably 20 or less.

  The carbon number of each alkyl group of the di-long-chain alkyldimethylammonium salt may be the same or different, but the same is preferable from the viewpoint of obtaining a fine particle dispersion.

  From the viewpoint of obtaining a fine particle dispersion using a solid fat oil agent, the cationic surfactant is a salt of 1- (2-hydroxyethylamino) -3-isostearyloxy-2-propanol, and 1- ( A salt of 2-hydroxyethylamino) -3- (12-hydroxystearyloxy) -2-propanol is preferred, and a salt of 1- (2-hydroxyethylamino) -3-isostearyloxy-2-propanol is more preferred.

Examples of the surfactant precursor that neutralizes to form an anionic surfactant include, for example, carboxylic acid, sulfonic acid, which forms the anionic surfactant with Na ⁺ or K ⁺ contained in the aqueous component as a counter ion, Phosphate ester etc. are mentioned. Among these, the surfactant precursor is preferably one that forms the preferred carboxylic acid type anionic surfactant from the viewpoint of obtaining a fine particle dispersion, and more preferably the preferred fatty acid salt. Or an alkyl ether carboxylate, and more preferably the above fatty acid salt.

  Examples of the surfactant precursor that forms a cationic surfactant by neutralization include amine compounds that react with an acid component contained in an aqueous component to form the cationic surfactant. Among these, from the viewpoint of obtaining a dispersion of fine particles using an oil agent of liquid oil, those that form the preferred quaternary ammonium salts are preferred, and the preferred dilong-chain alkyldimethylammonium salts are formed. More preferred are those that form the di-long chain alkyldimethylammonium chloride. From the viewpoint of obtaining a dispersion of fine particles using an oil agent of solid fat, one that forms a salt of 1- (2-hydroxyethylamino) -3-isostearyloxy-2-propanol is preferable. More preferred are those that form glutamate of 2-hydroxyethylamino) -3-isostearyloxy-2-propanol.

  The surfactant may be one or more selected from the group of nonionic surfactants, anionic surfactants, and cationic surfactants listed above from the viewpoint of obtaining a dispersion of fine particles. preferable. Nonionic surfactants are preferred from the standpoint that dispersibility is less affected by pH, and anionic surfactants are preferred from the standpoint of dispersion stability. Affinity to the skin when used for application to the skin From this viewpoint, a cationic surfactant is preferable.

  The content of the surfactant and the surfactant precursor in the oil component is preferably 30% by mass or less, more preferably 20% by mass or less, from the viewpoint of obtaining a dispersion of fine particles with a small amount of surfactant. Preferably, it is 15% by mass or less, more preferably 12% by mass or less, still more preferably 10% by mass or less, and from the viewpoint of dispersing the oily component in the aqueous component, preferably 0.5% by mass or more, more Preferably it is 2 mass% or more, More preferably, it is 4 mass% or more, More preferably, it is 6 mass% or more, More preferably, it is 8 mass% or more.

  The aqueous component may contain a surfactant, but the content of the aqueous component is preferably 2% by mass or less, more preferably 1% by mass or less from the viewpoint of obtaining a fine particle dispersion. More preferably, it is 0.5 mass% or less, may be substantially 0 mass%, or may be 0.1 mass% or more.

<Self-emulsifying>
The oil component is preferably self-emulsifying with respect to the aqueous component from the viewpoint of obtaining a fine particle dispersion. Here, the presence or absence of self-emulsification can be determined as follows.

  First, 90 ml of the aqueous component and 10 ml of the oily component are weighed. Next, the oil component is introduced into the aqueous component at a rate of 10 ml / min using an injection needle (outer diameter: 1.58 mm, inner diameter: 0.25 mm). At this time, the tip of the injection needle is immersed in an aqueous component, and stirring is not performed. After the entire amount of the oily component has been charged, a volume-based average of particles in the dispersion by laser scattering / diffraction using a laser diffraction / scattering particle size distribution measuring device such as LA-910 (manufactured by Horiba Ltd.) Measure the dispersed particle size. When the measured average dispersed particle diameter is 0.25 mm or less of the inner diameter of the injection needle, it is determined that “there is self-emulsifying”, whereas when it is larger than 0.25 mm, “there is no self-emulsifying”. to decide.

(Merging of water component and oil component)
In the merging step, the flow rate of the aqueous component before the merging is preferably 0.1 L / h or more, more preferably 1 L / h or more, from the viewpoint of increasing the effect of turbulence and obtaining a fine particle dispersion. It is preferably 2 L / h or more, more preferably 2.5 L / h or more, and from the viewpoint of obtaining a fine particle dispersion by increasing the mixing property after merging, preferably 300 L / h or less, more Preferably it is 200 L / h or less, More preferably, it is 100 L / h or less, More preferably, it is 30 L / h or less, More preferably, it is 20 L / h or less, More preferably, it is 10 L / h or less, More preferably, it is 4 L / h or less More preferably, it is 3 L / h or less. The flow rate of the oily component before merging is preferably 0.01 L / h or more, more preferably 0.1 L / h or more, from the viewpoint of increasing the effect of turbulence and obtaining a fine particle dispersion. Preferably, it is 0.2 L / h or more, and from the viewpoint of improving the mixing property after merging and obtaining a dispersion of fine particles, it is preferably 150 L / h or less, more preferably 100 L / h or less, More preferably, it is 50 L / h or less, More preferably, it is 2 L / h or less, More preferably, it is 1 L / h or less, More preferably, it is 0.5 L / h or less, More preferably, it is 0.3 L / h or less.

  In the merging step, the flow rate ratio of the aqueous component to the oily component before merging (flow rate of the aqueous component / flow rate of the oily component) is preferably 1 or more, more preferably 2 or more, from the viewpoint of obtaining a fine particle dispersion. Yes, more preferably 5 or more, and from the viewpoint of increasing the content of the oil agent in the dispersion, it is preferably 200 or less, more preferably 100 or less, still more preferably 50 or less, even more preferably 25 or less, and even more. Preferably it is 15 or less. The mixing mass ratio of the aqueous component and the oil component is preferably 1 or more, more preferably 2 or more, still more preferably 5 or more, from the viewpoint of obtaining an O / W type dispersion having a small average particle diameter of the particles. Further, from the viewpoint of increasing the content of the oil agent in the dispersion, it is preferably 200 or less, more preferably 100 or less, still more preferably 50 or less, still more preferably 25 or less, and still more preferably 15 or less.

  In the merging step, the temperature of the aqueous component before merging is preferably 5 ° C or higher, more preferably 10 ° C or higher, still more preferably 15 ° C or higher, and preferably 95 ° C or lower, more preferably 90 ° C or lower, More preferably, it is 85 degrees C or less, More preferably, it is 60 degrees C or less, More preferably, it is 50 degrees C or less. The temperature of the oily component before joining is preferably 5 ° C or higher, more preferably 10 ° C or higher, preferably 95 ° C or lower, more preferably 90 ° C or lower, still more preferably 85 ° C or lower, and still more Preferably it is 50 degrees C or less. The temperature of the aqueous component before joining and the temperature of the oily component may be the same or different, but are preferably the same from the viewpoint of obtaining a fine particle dispersion.

  In the merging step, the viscosity of each of the aqueous component and the oily component before merging is preferably 0.1 mPa · s or more, more preferably at each temperature when merging them, from the viewpoint of satisfactory liquid feeding. 1 mPa · s or more, more preferably 5 mPa · s or more, and from the viewpoint of obtaining a dispersion of fine particles, preferably 1000 mPa · s or less, more preferably 500 mPa · s or less, and even more preferably 300 mPa · s or less. It is. The viscosity of the aqueous component and the viscosity of the oil component may be the same or different. The viscosity of the aqueous component and the oily component was measured using a Brookfield type (B type) rotational viscometer, rotor No. 3 is used as a standard (when the viscosity cannot be measured, the rotor is changed to No. 1, 2, or 4), and the measurement is performed under conditions of a rotation speed of 30 r / min and a measurement time of 1 minute.

  In the merging step, the mode of merging of the aqueous component and the oily component is not particularly limited.

  As a collision mode (angle) when the aqueous component and the oil component are merged, for example, a mode in which both are collided by frontal collision, a mode in which one is collided from a direction orthogonal to the other, a mode in which one is merged, and the other is the other And a mode in which one side collides with the other from the front side, and a mode in which one side collides with the other from the front side, and a mode in which one side is brought into contact with the other along the other side.

  In addition, as a mode (number, etc.) of the merging method when the aqueous component and the oily component are merged, for example, a mode in which both are collided from a plurality of directions respectively, and one is collided with the other from a plurality of directions. And a mode in which one side is caused to collide from the other circumference to be joined. In a mode in which both are caused to collide from a plurality of directions, the particles are preferably collided from two or more directions from the viewpoint of obtaining a dispersion of fine particles, and there is no particular upper limit. In view of the above, it is preferable to cause the collision from four or less directions. In an embodiment in which one side collides with the other from a plurality of directions, it is preferable that one collide with the other from two or more directions, and there is no particular upper limit. It is preferable to collide with the other from four or less directions.

  Of these, as the mode of collision when merging, from the viewpoint of obtaining a dispersion of fine particles, a mode in which the oily component collides with the aqueous component from an orthogonal direction or obliquely rearward is preferable. From the viewpoint of obtaining a dispersion of fine particles, an embodiment in which oily components collide and join together from the entire periphery of the aqueous component is preferable.

[Pore distribution step]
In the pore flow step, one or two of the aqueous component before joining in the joining step, the oily component before joining in the joining step, and the fluid after joining the aqueous component and oily component in the joining step The above is distributed to the pores. Here, “before joining” means immediately before joining.

  Accordingly, the first mode may be such that neither the aqueous component before joining nor the oily component before joining flows through the pores, but only the fluid after joining flows through the pores. The second aspect may be such that the oily component before joining is not passed through the pores, but the aqueous component before joining and the fluid after joining are passed through the pores, respectively. A third mode may be employed in which the aqueous component before merging is not circulated through the pores, but the oily component before merging and the fluid after merging are respectively circulated through the pores.

  Moreover, the 4th aspect which distribute | circulates the aqueous | water-based component before joining and the oil-based component before joining to each pore, and does not distribute | circulate the fluid after joining to a pore may be sufficient. A fifth mode may be employed in which only the aqueous component before joining flows through the pores, and neither the oily component before joining nor the fluid after joining flows through the pores. A sixth embodiment may be employed in which only the oily component before joining flows through the pores, and neither the aqueous component before joining nor the fluid after joining flows through the pores.

  Further, the seventh aspect may be one in which any of the aqueous component before joining, the oily component before joining, and the fluid after joining flows through the pores.

  Among these, from the viewpoint of obtaining a dispersion of fine particles, the first to third and seventh embodiments in which the fluid after the joining of the aqueous component and the oily component in the joining step is circulated through the pores are preferable.

  The cross-sectional shape of the pores is preferably circular from the viewpoint of obtaining a dispersion of fine particles, but semicircular, elliptical, semielliptical, square, rectangular, trapezoidal, parallelogram, star, It may be non-circular such as indefinite shape. The cross-sectional shape of the pores is preferably the same shape along the length direction.

  The direction in which the pores extend is preferably the same as the flow direction of the aqueous component and / or the flow direction of the oily component from the viewpoint of obtaining a dispersion of fine particles.

  The pore diameter is from 0.1 mm to 3 mm, but from the viewpoint of obtaining high productivity, it is preferably 0.2 mm or more, and from the viewpoint of obtaining a dispersion of fine particles due to the occurrence of turbulence. The thickness is preferably 1.0 mm or less, more preferably 0.50 mm or less, more preferably 0.45 mm or less, more preferably 0.30 mm or less, and still more preferably 0.25 mm or less. Here, the pore diameter is the diameter when the cross-sectional shape of the pore is circular, but the equivalent hydraulic diameter (4 × channel area / cross-section) when the cross-sectional shape of the pore is non-circular. Long).

  The length of the pores is preferably 0.05 mm or more, more preferably 0.1 mm or more, and still more preferably 0.3 mm or more from the viewpoint of increasing the pressure loss and improving the mixing properties of the aqueous component and the oil component. In addition, from the viewpoint of instantly mixing the aqueous component and the oily component after merging to obtain a fine particle dispersion, it is preferably 5 mm or less, more preferably 3 mm or less, more preferably 2 mm or less, and even more preferably 1 mm or less. More preferably, it is 0.8 mm or less.

Flow area of pores, in view of preventing to bring the fault to equipment caused excessive pressure loss, preferably 0.01 mm ² or more, more preferably 0.03 mm ² or more, the pressure loss From the viewpoint of increasing the mixing property of the aqueous component and the oil component, it is preferably 7 mm ² or less, more preferably 2 mm ² or less, still more preferably 1 mm ² or less, still more preferably 0.5 mm ² or less, and still more preferably 0. .15Mm ² or less, even more preferably 0.1 mm ² or less, even more preferably 0.05 mm ² or less.

  The ratio of the length of the pores to the pore diameter (length / pore diameter) is preferably 0.15 or more, more preferably 0.2 or more, and still more preferably from the viewpoint of obtaining a fine particle dispersion by the generation of turbulent flow. Is 0.5 or more, more preferably 1 or more, still more preferably 2 or more, and from the same viewpoint, it is preferably 40 or less, more preferably 20 or less, still more preferably 10 or less, and still more preferably 5 or less, more preferably 3 or less.

  In the pore flow step, as a method of circulating the fluid after the merging of the aqueous component and the oily component in the merging step, the aqueous component and the oily component are once merged in the liquid reservoir, and they are mixed. However, from the viewpoint of obtaining a dispersion of fine particles, a joining portion of an aqueous component and an oily component is provided immediately before the pores or joined within the pores. It is preferable.

  In the pore circulation step, the flow rate when the fluid after the merging of the aqueous component and the oil component in the merging step is circulated through the pores is preferably 0 from the viewpoint of increasing the pressure loss and obtaining a fine particle dispersion. 1 L / h or more, more preferably 1 L / h or more, still more preferably 2.0 L / h or more, still more preferably 2.5 L / h or more, and from the viewpoint of obtaining a dispersion of fine particles, Preferably not more than 300 L / h, more preferably not more than 200 L / h, still more preferably not more than 100 L / h, still more preferably not more than 30 L / h, still more preferably not more than 15 L / h, still more preferably not more than 10 L / h, More preferably, it is 5 L / h or less, More preferably, it is 3.5 L / h or less.

In the pore circulation step, it is preferable to cause the aqueous component and the oily component to flow through the pores under turbulent flow conditions from the viewpoint of obtaining a dispersion of fine particles. The Reynolds number at this time is preferably 1000 or more, more preferably 2000 or more, from the viewpoint of increasing the stirring efficiency of the aqueous component and the oily component after pore circulation, and preferably 150,000 or less from the same viewpoint. More preferably, it is 100,000 or less. Here, the Reynolds number is a value of an average flow velocity u (m / s), a pore diameter d (m), a fluid viscosity μ (Pa · s), and a fluid density ρ (kg / m ³ ). Can be obtained by a general Reynolds number calculation formula (Reynolds number Re = duρ / μ) of the pipe flow.

  In the pore circulation step, from the viewpoint of obtaining a dispersion of fine particles, it is preferable that the fluid after the aqueous component and the oily component in the merging step are circulated through the pores and flowed out to the channel expanding portion. Thereby, particles can be miniaturized by generating turbulent flow due to both components. In particular, when the fluid after joining the aqueous component and the oil component is circulated through pores having a pore diameter of 0.1 mm or more and 3 mm or less, both components are agitated by turbulent flow in the channel expansion region after the pore circulation. Thus, the surfactant is more efficiently supplied from the oil component to the oil-water interface. As a result, a fine particle dispersion can be obtained with a small amount of surfactant.

  From the viewpoint of obtaining a fine particle dispersion, the cross-sectional shape of the flow channel in the flow channel expanding portion is preferably circular, but is semicircular, elliptical, semielliptical, square, rectangular, trapezoidal, parallelogram A non-circular shape such as a shape, a star shape, or an indefinite shape may be used. The cross-sectional shape of the flow channel enlarged portion is preferably the same shape along the length direction, but may include different shapes along the length direction.

  From the viewpoint of obtaining a fine particle dispersion, the flow channel expanding portion is preferably formed so as to expand in a cone shape from the pore to the portion having the maximum flow channel diameter. The cone expansion angle is preferably 90 ° or more, more preferably 100 ° or more, still more preferably 110 ° or more, and preferably 180 ° or less, more preferably 170 ° or less, still more preferably 150 ° or less, More preferably, it is 130 degrees or less.

  From the viewpoint of obtaining a fine particle dispersion, the maximum flow path diameter of the flow path enlarged portion is preferably 3 times or more, more preferably 5 times or more, and preferably 50 times or less, more preferably the pore diameter. Preferably it is 40 times or less, More preferably, it is 20 times or less, More preferably, it is 15 times or less. Here, the maximum flow path diameter of the flow path expanding portion is a diameter when the cross-sectional shape of the flow path is circular, but is an equivalent hydraulic diameter when the cross-sectional shape of the flow path is non-circular.

  In the pore flow step, the dispersion after flowing through the pores is cooled as necessary. As a result, when the oil agent is liquid oil, a dispersion liquid (emulsion) in which liquid particles are dispersed is obtained, and when the oil agent is solid fat, a dispersion liquid in which solid particles are dispersed is obtained.

  From the viewpoint of obtaining a fine particle dispersion, the average particle size of the particles in the produced dispersion is preferably 1/100 or less, more preferably 1/200 or less, and even more preferably 1/300 of the pore size. Or less, more preferably 1/500 or less, still more preferably 1/900 or less, still more preferably 1/3000 or less, still more preferably 1/5000 or less, still more preferably 1/7000 or less, and even more preferably. Is 1/8000 or less, and from the viewpoint of productivity, preferably 1/20000 or more, more preferably 1/15000 or more, still more preferably 1/11000 or more, still more preferably 1/10000 or more, more preferably Is 1/9000 or more, more preferably 1/8000 or more, still more preferably 1/6000 or more, and still more Mashiku is 1/3000 or higher, even more preferably 1/2000 or more, and even more preferably 1/1700 or more. Specifically, the average particle size of the particles in the dispersion is preferably 10 μm or less, more preferably 5 μm or less, still more preferably 3 μm or less, even more preferably 2 μm or less, and still more from the viewpoint of the stability of the dispersion. Preferably it is 1 micrometer or less, More preferably, it is 0.5 micrometer or less, More preferably, it is 0.3 micrometer or less, More preferably, it is 0.15 micrometer or less, More preferably, it is 0.1 micrometer or less, More preferably, it is 0.05 micrometer or less In addition, from the viewpoint of productivity, it is preferably 0.02 μm or more, more preferably 0.03 μm or more, still more preferably 0.04 μm or more, still more preferably 0.05 μm or more, still more preferably 0.07 μm or more. More preferably, it is 0.1 μm or more. Here, the average particle size of the particles in the dispersion is the median of particles measured by a laser scattering / diffraction method using a laser diffraction / scattering particle size distribution measuring device, for example, LA-910 (manufactured by Horiba, Ltd.). Is the diameter.

  The content of the oil in the produced dispersion is preferably 0.5% by mass or more, more preferably 0.6% by mass or more, more preferably 0.8% by mass from the viewpoint of increasing the content of the oil in the dispersion. % Or more, more preferably 1% by mass or more, further preferably 3% by mass or more, and preferably 20% by mass or less, more preferably 15% by mass or less, from the viewpoint of obtaining a fine particle dispersion. Preferably it is 10 mass% or less, More preferably, it is 8 mass% or less, More preferably, it is 5 mass% or less, More preferably, it is 2 mass% or less, More preferably, it is 1.5 mass% or less, More preferably, it is 1. 2% by mass or less.

  The content of the water-soluble solvent in the produced dispersion is preferably 0.5% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, from the viewpoint of obtaining a fine particle dispersion. More preferably, it is 2.5% by mass or more, still more preferably 3% by mass or more, and from the same viewpoint, it is preferably 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass. It is not more than mass%, more preferably not more than 8 mass%, still more preferably not more than 5 mass%, still more preferably not more than 4 mass%.

  The content of the surfactant in the produced dispersion is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and still more preferably 0.1% from the viewpoint of obtaining a fine particle dispersion. % By mass, more preferably 0.3% by mass or more, still more preferably 0.4% by mass or more, still more preferably 0.6% by mass or more, and from the same viewpoint with a small amount of surfactant. Preferably, it is 2 mass% or less, More preferably, it is 1.5 mass% or less, More preferably, it is 1 mass% or less.

  The content of water in the produced dispersion is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 90% by mass or more, from the viewpoint of containing an oil in the dispersion. From this viewpoint, it is preferably 99% by mass or less, more preferably 98% by mass or less, still more preferably 97% by mass or less, still more preferably 96% by mass or less, and still more preferably 92% by mass or less.

  From the viewpoint of obtaining a fine particle dispersion, the dispersion operation of the aqueous component and the oil component in the method for producing a dispersion according to the present embodiment has a segregation index (Segregation index (Xs)) determined by a method described later. It is preferably performed under the condition of 0.15 or less, more preferably 0.1 or less, still more preferably 0.05 or less, still more preferably 0.01 or less, and still more preferably 0.0003 or less. Although there is no particular lower limit, it is sufficient if it is 0.0001 or more, and may be 0.001 or more.

  Here, the segregation index (Xs) indicates the mixing and stirring effect of the aqueous component and the oil component in the method for producing a dispersion according to the present embodiment, and indicates that the smaller the value, the higher the mixing property. It is an index used academically for mixing performance evaluation of mixers and can be derived from the following formula (iv) using Villermaux / Dushman reaction. The details of this reaction system are described in P. Guichardon and L. Falk, Chemical Engineering Science 55 (2000) 4233-4243.

  Specifically, first, 0.171N sulfuric acid and borate buffer are prepared as two aqueous solutions that react by mixing. The composition of the borate buffer is 0.045 mol / L boric acid, 0.045 mol / L sodium hydroxide, 0.00313 mol / L potassium iodate, and 0.0156 mol / L potassium iodide. When these two liquids are mixed, the following neutralization reaction (A) and the oxidation-reduction reaction (B) in which iodine is generated proceed simultaneously. In addition, mixing of 2 liquid is implemented on the conditions from which an alkali becomes excess in the state after mixing.

  According to the above-described method for producing a dispersion according to the present embodiment, a surfactant is formed when an oily agent is combined with an oil agent, a water-soluble solvent having a specific structure, a surfactant and an aqueous component. 1 or 2 or more of the aqueous component before joining, the oily component before joining, and the fluid after joining them, containing at least one of the surfactant precursors to be joined. A dispersion liquid in which fine particles are dispersed can be produced by flowing through pores of 1 mm or more and 3 mm or less.

  FIG. 1 shows an example of a dispersion manufacturing system A that can be used in the method for manufacturing a dispersion according to the present embodiment.

  This dispersion manufacturing system A is composed of a micromixer 100 having a first configuration and an accompanying part such as a fluid supply system.

  2 and 3 show a micromixer 100 of a first configuration. In the micro mixer 100 having the first configuration, the first aspect, that is, the aqueous component before joining and the oily component before joining are not circulated through the pores, and only the fluid after joining is passed through the pores. A dispersion liquid is produced according to an embodiment in which the liquid is distributed.

  The micromixer 100 having the first configuration includes a fluid flow path portion 110, a fluid merging / contracting portion 120 continuously provided on the downstream side thereof, and a fluid outflow portion 130 continuously provided on the downstream side thereof. With.

  The fluid flow path unit 110 includes a small diameter pipe 111 and a large diameter pipe 112. The large-diameter pipe 112 accommodates the small-diameter pipe 111, which have a common length direction and are arranged coaxially. Thereby, in the fluid flow path part 110, the 1st flow path 111a is comprised inside the small diameter pipe | tube 111, and the 2nd flow path 112a is comprised inside the large diameter pipe | tube 112 and the small diameter pipe | tube 111 outside. In addition, the 1st flow path 111a in the small diameter pipe | tube 111 is connected to the aqueous component supply part 101 provided in the apparatus one end, and the 2nd flow path 112a in the large diameter pipe | tube 112 was provided in the apparatus side surface. It communicates with the oil component supply unit 102.

  The outer shape of the small-diameter tube 111 and the cross-sectional shape of the hole are not particularly limited. For example, the shape is circular, semicircular, elliptical, semielliptical, square, rectangular, trapezoidal, parallelogram, star, indefinite. Etc. The cross-sectional shape of the hole of the large-diameter tube 112 is not particularly limited, and is the same as that of the small-diameter tube 111, for example, a circle, a semicircle, an ellipse, a semi-elliptical, a square, a rectangle, a trapezoid, a parallelogram, It may be a star shape, an irregular shape, or the like. However, it is preferable that the cross-sectional shape of any of the outer shape and hole of the small diameter tube 111 and the hole of the large diameter tube 12 is circular. Further, it is preferable that the small-diameter pipe 111 and the large-diameter pipe 112 are provided so that the cross-sectional shape is symmetrical and coaxial. Therefore, as shown in FIG. 3, the small-diameter pipe 111 and the large-diameter pipe 112 have a circular cross-sectional shape of the first channel 111a and a donut-shaped cross-sectional shape of the second channel 112a. It is preferable that the configuration is provided.

  It is preferable that the cross-sectional shapes of both the outer shape and the hole of the small-diameter tube 111 are the same along the length direction except for a tube end portion 111b described later. The cross-sectional shape of the hole of the large diameter tube 112 is also preferably the same shape along the length direction except for the portion corresponding to the tube end portion 111b of the small diameter tube 111.

If any of the cross-sectional shape of the outer shape and the hole of the small diameter tube 111 is also circular, the outer diameter D _1, from the viewpoint of obtaining a dispersion of fine particles, preferably 1.6mm or more, more preferably 2mm or more In addition, from the same viewpoint, it is preferably 25 mm or less, more preferably 15 mm or less, and further preferably 4 mm or less. From the viewpoint of obtaining a fine particle dispersion, the inner diameter D ₂ of the small-diameter tube 111, that is, the channel diameter of the first channel 111a is preferably 0.8 mm or more, more preferably 1 mm or more. From the viewpoint, it is preferably 20 mm or less, more preferably 10 mm or less, and still more preferably 3 mm or less. If the cross sectional shape of the hole of the large diameter tube 112 is circular, the inner diameter D _3, from the viewpoint of obtaining a dispersion of fine particles, preferably 1.8mm or more, more preferably 4mm or more, From the same viewpoint, it is preferably 50 mm or less, more preferably 20 mm or less, and still more preferably 6 mm or less. Further, the gap Δ of the second flow path 112a between the small diameter tube 111 and the large diameter tube 112 is preferably 0.1 mm or more, more preferably 0.3 mm or more, from the viewpoint of obtaining a fine particle dispersion. Preferably, it is 0.5 mm or more, more preferably 0.7 mm or more, and from the same viewpoint, it is preferably 12.5 mm or less, more preferably 6 mm or less, and further preferably 1 mm or less.

  As shown in FIG. 2, the pipe end portion 111b on the downstream side of the small-diameter pipe 111 preferably has a tapered outer periphery, and a steeple with a transverse cross-sectional shape in the thickness direction sharpened on the inner peripheral side. More preferably, it is formed in a shape.

  It is preferable that the gap δ which is a part of the second flow path 112a formed between the inner wall of the large diameter pipe 112 and the pipe end portion 111b of the small diameter pipe 111 is uniform in the fluid flow direction. The gap δ is preferably 0.02 mm or more, more preferably 0.05 mm or more, still more preferably 0.1 mm or more, and still more preferably 0.2 mm or more, from the viewpoint of obtaining a fine particle dispersion. From the same viewpoint, it is preferably 12.5 mm or less, more preferably 6 mm or less, still more preferably 1 mm or less, and still more preferably 0.3 mm or less.

  A fluid confluence region 121 is formed in the fluid confluence portion 120 in front of the tube end of the small-diameter tube 111, and pores 122 are continuously drilled in the fluid confluence region 121. In the fluid merging area 121, the aqueous component flowing through the first flow path 111a and the oily component flowing through the second flow path 112a merge, and in the pore 122, the aqueous component and oily immediately after merging in the fluid merging area 121 are combined. The ingredients circulate.

The fluid confluence region 121 is not particularly limited, but is formed in a tapered cone shape converged toward the pores 122 as shown in FIG. 2 from the viewpoint of obtaining a fine particle dispersion. Preferably it is. The cone convergence angle θ ₁ is preferably 90 ° or more, and more preferably 100 ° or more, still more preferably 110 ° or more, and preferably 180 ° or less, from the viewpoint of obtaining a fine particle dispersion. Preferably it is 170 degrees or less, More preferably, it is 130 degrees or less. The cone convergence angle θ ₁ is preferably the same as the cone expansion angle θ ₂ of the flow path expansion unit 131 described later. The distance L from the pipe end of the small diameter pipe 111 of the fluid confluence region 121, that is, the end of the fluid flow path portion 110 to the pore 122 is preferably 0.02 mm or more from the viewpoint of obtaining a fine particle dispersion. Preferably it is 0.2 mm or more, More preferably, it is 0.3 mm or more, Preferably it is 20 mm or less, More preferably, it is 3 mm or less, More preferably, it is 1 mm or less.

  The cross-sectional shape of the pores 122, the extending direction, the pore diameter d, the length l, the channel area s, and the ratio of the length l to the pore diameter d (length l / pore diameter d) are as described above.

  In the fluid outflow portion 130, a flow path expanding portion 131 is configured in front of the pore 122. The fluid that has flowed through the pores 122 flows out to the flow channel enlargement portion 131. In addition, the flow path expansion unit 131 communicates with the dispersion liquid recovery unit 103 provided at the other end of the apparatus.

The cross-sectional shape and shape of the flow path of the fluid outflow portion 130, the cone expansion angle θ ₂ , and the maximum flow path diameter D ₄ of the flow path expansion portion 131 are as described above.

  Each of the micromixers 100 may be composed of a plurality of members formed of metal, ceramics, resin, and the like, and a fluid flow path unit 110, a fluid confluence / confluence unit 120, and a combination of these members, The fluid outflow portion 130 may be configured.

  In the micro mixer 100 having the first configuration, the single small diameter tube 111 is accommodated in the large diameter tube 112. However, the present invention is not particularly limited to this, and FIGS. ), A configuration in which a plurality of small-diameter pipes 111 are accommodated in a large-diameter pipe 112 may be employed.

  In the micromixer 100, as shown in FIG. 1, an aqueous component supply pipe 42a extending from the aqueous component storage tank 41a is connected to an aqueous component supply unit 101 communicating with the first flow path 111a. The aqueous component supply pipe 42a is provided with a first pump 43a for circulating the aqueous component, a first flow meter 44a for detecting the flow rate of the aqueous component, and a first filter 45a for removing contaminants of the aqueous component in order from the upstream side. A first pressure gauge 46a that detects the pressure of the aqueous component is attached to a portion between the first flow meter 44a and the first filter 45a. Each of the first pump 43a, the first flow meter 44a, and the first pressure gauge 46a is electrically connected to the flow controller 47.

  An oil component supply pipe 42b extending from the oil component storage tank 41b is connected to the oil component supply portion 102 communicating with the second flow path 112a. In the oil component supply pipe 42b, a second pump 43b for circulating the oil component, a second flow meter 44b for detecting the flow rate of the oil component, and a second filter 45b for removing contaminants of the oil component are sequentially provided from the upstream side. A second pressure gauge 46b that detects the pressure of the oil component is attached to a portion between the second flow meter 44b and the second filter 45b. Each of the second pump 43b, the second flow meter 44b, and the second pressure gauge 46b is electrically connected to the flow controller 47.

  The flow rate controller 47 is configured to be capable of inputting the set flow rate and set pressure of the aqueous component and incorporates an arithmetic element, and includes the set flow rate information of the aqueous component, the flow rate information detected by the first flow meter 44a, and The first pump 43a is operated and controlled based on the pressure information detected by the first pressure gauge 46a. Similarly, the flow controller 47 is also configured to be able to input the set flow rate and set pressure of the oil component, and the set flow information of the oil component, the flow information detected by the second flow meter 44b, and the second pressure gauge 46b. The second pump 43b is controlled to operate based on the pressure information detected in step (b).

  A dispersion recovery pipe 48 extends from the dispersion recovery part 103 communicating with the flow path expanding part 131 and is connected to the dispersion recovery tank 49.

  Next, the operation of this dispersion manufacturing system A will be described.

  When the dispersion manufacturing system A is in operation, the first pump 43a causes the aqueous component to be a continuous phase to pass from the aqueous component storage tank 41a through the aqueous component supply pipe 42a, through the first flow meter 44a and the first filter 45a in this order. Then, the fluid is continuously supplied to the first channel 111a of the small-diameter pipe 111 of the fluid channel unit 110. The first flow meter 44 a sends the detected water phase flow rate information to the flow rate controller 47. Further, the first pressure gauge 46 a sends the detected pressure information of the first pressure gauge 46 a to the flow controller 47.

  The second pump 43b passes the oil component that becomes the dispersed phase from the oil component storage tank 41b through the oil component supply pipe 42b, the second flow meter 44b and the second filter 45b in this order, and the large diameter of the fluid flow path unit 110. It supplies continuously to the 2nd flow path 112a between the pipe | tube 112 and the small diameter pipe | tube 111. FIG. The second flow meter 44 b sends the detected oil phase flow rate information to the flow rate controller 47. Further, the second pressure gauge 46 b sends the detected pressure information of the second pressure gauge 46 b to the flow rate controller 47.

  The flow controller 47 sets the aqueous component set flow rate based on the set flow rate information and set pressure information of the aqueous component, and the flow rate information detected by the first flow meter 44a and the pressure information detected by the first pressure meter 46a. And the first pump 43a is controlled to maintain the set pressure. At the same time, the flow rate controller 47 sets the oil component based on the set flow information and set pressure information of the oil component, and the flow information detected by the second flow meter 44b and the pressure information detected by the second pressure meter 46b. The second pump 43b is operated and controlled so that the set flow rate and the set pressure are maintained.

  In the micromixer 100, in the fluid flow path section 110, the aqueous component flows through the first flow path 111a and the oil component flows through the second flow path 112a. At this time, the pressure of the aqueous component is, for example, 0.01 MPa or more and 5 MPa or less. The pressure of the oil component is, for example, 0.01 MPa or more and 5 MPa or less. The flow rate of the aqueous component is set to, for example, 0.05 m / s or more and 2 m / s or less by setting the flow rate and pressure of the aqueous component, and the flow rate of the oily component is set to 0, for example, by setting the flow rate and pressure of the oil component. .05 m / s to 2 m / s.

  In the fluid merging / contracting part 120, the aqueous component and the oily component that have flowed out from the fluid flow path part 110 merge in the fluid merging area 121 in a manner in which the oily component collides with the aqueous component obliquely from behind and from the entire circumference. To do. At this time, in the fluid confluence / confluence section 120, the flow rate of the fluid including the aqueous component and the oil component is, for example, 0.05 m / s or more and 2 m / s or less. This flow rate can be controlled by the respective flow rate settings and pressure settings of the aqueous and oily components.

  The aqueous component and oily component that merged in the fluid merge region 121 are mixed in the process of flowing through the pores 122. At this time, the flow conditions of the aqueous component and the oil component to be merged in the fluid merge region 121 can be controlled by the respective flow rate setting and pressure setting of the aqueous component and the oil component.

  In the fluid outflow portion 130, the fluid containing the aqueous component and the oily component flowing through the pores 122 flows out in the flow path expanding portion 131, and the average particle diameter of the particles is increased by convective mixing between the aqueous component and the oily component. A dispersion having 1/10 or less the pore diameter of the pores 122 is produced.

  The produced dispersion liquid is collected in the dispersion liquid collection tank 49 via the dispersion liquid collection pipe 48 from the dispersion liquid collection part 103 communicated with the flow path enlargement part 131. At this time, the pressure loss before and after the micromixer 100 is preferably 0.01 MPa or more, more preferably 0.1 MPa or more from the viewpoint of obtaining a dispersion of fine particles, and preferably from the viewpoint of productivity. Is 5 MPa or less, more preferably 3 MPa or less, still more preferably 1 MPa or less, and even more preferably 0.7 MPa or less. This pressure loss can be controlled by the flow rate setting and pressure setting of the aqueous component and the oil component, respectively.

  FIG. 5 shows a micromixer 200 having a second configuration. In the micromixer 200 having the second configuration, the dispersion is produced by the seventh aspect, that is, the aspect in which the aqueous component before merging, the oily component before merging, and the fluid after merging are circulated through the pores, respectively. .

  The micromixer 200 of the second configuration includes a straight tube portion 210 in which one tube end is an aqueous component supply unit 201 and the other tube end is an oily component supply unit 202, and a central portion of the straight tube portion 210. It is constituted by a T-shaped tube that is branched and extends in an orthogonal direction and is composed of a branch tube portion 220 whose end is a dispersion liquid recovery unit 203. The second configuration of the micro mixer 200 using a T-shaped tube has a simple device configuration and easy maintenance by disassembly and cleaning.

  The straight tube portion 210 has a narrow central portion of the flow path, and among the central portion, the aqueous component supply section 201 side is the first flow path 211a, and the oil component supply section 202 side is the second flow path 212a. Each is composed. Accordingly, the aqueous component supply pipe 42 a is connected to the aqueous component supply unit 201, and the oily component supply pipe 42 b is connected to the oily component supply unit 202.

  The branch pipe portion 220 is formed with pores 222 extending along the pipe axis and communicating with the straight pipe portion 210. The central portion of the straight tube portion 210, that is, the inside of the branch portion to the branch tube portion 220 is configured as a fluid merging region 221 that continues to the pores 222. Each of the first channel 211a and the second channel 212a preferably has a channel cross-sectional area, that is, a hole area that is the same or approximately the same as that of the pores 222, and can suppress pressure loss to a low level. It is preferable that the flow path length, that is, the hole length is the same as or similar to that of the pore 222. The branch pipe portion 220 is configured with a flow channel expanding portion 231 having a flow channel cross-sectional area that is continuous with the pores 222. The dispersion liquid collection pipe 48 is connected to the dispersion liquid collection part 203 of the branch pipe part 220.

  The micromixer 200 of the second configuration causes the first liquid of the aqueous component and the second liquid of the oily component to collide with each other and join each other, and each of the first liquid and the second liquid toward the fluid merge area 221. The flow direction and the extending direction of the pores 222 are different from each other.

  The micromixer 200 having the second configuration shown in FIG. 5 has a configuration in which the flow path in the central portion of the straight tube portion 210 is narrowed, but is not particularly limited thereto, as shown in FIG. In addition, there may be a configuration in which there is no portion where the flow path is narrowed and there is a uniform flow path from the aqueous component supply unit 201 to the oily component supply unit 202. In the micromixer 200 having the second configuration of the modified example shown in FIG. 6, the first aspect, that is, the aqueous component before merging and the oily component before merging are not circulated through the pores. A dispersion liquid is manufactured by the mode which distribute | circulates only the subsequent fluid to a pore.

  The micromixer 200 having the second configuration shown in FIG. 5 has a configuration in which the pores 222 are formed in the branch tube portion 220. However, the present invention is not limited to this, and the micromixer 200 is continuous with the branch tube portion. The structure which connected separately the member in which the pore was formed may be sufficient.

  FIGS. 7A to 7C show a micromixer 300 having a third configuration.

  The micro mixer 300 of the third configuration is provided continuously on the fluid flow path portion 310 provided on the piping path, the fluid confluence / confluence portion 320 provided continuously on the liquid outflow side thereof, and on the liquid outflow side thereof. The fluid outflow portion 330 is provided.

  The fluid flow path section 310 includes a small diameter pipe 311 and a large diameter pipe 312. The large-diameter pipe 312 accommodates a small-diameter pipe 311, which have a common length direction and are arranged coaxially. Thereby, in the fluid flow path section 310, the first flow path 311a is configured inside the small diameter pipe 311 and the second flow path 312a is configured inside the large diameter pipe 312 and outside the small diameter pipe 311. The tube end of the small diameter tube 311 is configured as an aqueous component supply unit (not shown), and the tube end of the large diameter tube 312 exposed to the outside of the fluid flow channel unit 310 is configured as an oily component supply unit (not shown). ing. Accordingly, the aqueous component supply pipe 42a is connected to the aqueous component supply section, and the oil component supply pipe 42b is connected to the oil component supply section. Such a micromixer 300 having a fluid flow path portion 310 having a double-pipe structure has a simple device configuration and is easy to maintain by disassembly and cleaning.

  The fluid converging / contracting part 320 forms an internal region continuously with the liquid outflow end of the fluid flow path part 310. This internal region is configured as a fluid confluence region 321 where the first liquid and the second liquid that have flowed out of the fluid flow path section 310 are in contact with each other. The fluid confluence / condensation unit 320 is formed with pores 322 continuously provided in the fluid confluence region 321. The pores 322 are formed to extend in the same direction as the direction in which the first flow path 311a and the second flow path 312a extend.

  The fluid outflow part 330 is configured by a cylindrical dispersion liquid recovery part 303 provided continuously to the pores 322. The dispersion liquid recovery unit 303 includes a flow channel enlargement unit 331 having a flow channel cross-sectional area continuously extending from the pores 322. Note that the dispersion liquid collection pipe 48 is connected to the dispersion liquid collection unit 303.

  The third configuration of the micromixer 300 has the same configuration in which the flow directions of the first liquid and the second liquid toward the fluid confluence region 221 and the direction in which the pores 322 extend are the same.

  By the way, the first liquid and the second liquid that have flowed out of the fluid flow path section 310 and contacted with each other in the fluid merge area 321 are finally mixed by the pores 322. At this time, in order to obtain a faster mixing performance, it is preferable that the mixed state in the fluid confluence region 321 is a structure in which fine segments of each liquid are configured. Therefore, it is preferable that the number of the first flow paths 311a is larger, and there are a plurality of small-diameter pipes 311 as shown in FIGS. 8A and 8B than in the case where there is one small-diameter pipe 311. In some cases, faster mixing characteristics can be obtained. In addition, when there are three or more channels 311a and 311b as described above, a third liquid different from the first liquid and the second liquid can be circulated through one of the channels 311a and 311b.

  In the micromixer 300 having the third configuration, the first liquid of the oil component is circulated through the first flow path 311a and the second liquid of the aqueous component is circulated through the second flow path 312a. it can.

(Manufacture of emulsion)
1. Experimental devices In Examples 1 to 23 and Comparative Examples 1 to 7, the one in which the micromixer 100 having the first configuration shown in FIGS. 2 and 3 is applied to the dispersion manufacturing system A shown in FIG. 1 in the above embodiment is used. It was.

In Examples 1 to 17 and Comparative Examples 1 to 7, the configuration of the micromixer 100 is such that the outer diameter D _{1 of} the small diameter tube 111 is 3 mm, the inner diameter D ₂ of the small diameter tube 111 is ₂ mm, and the inner diameter D _{3 of the} large diameter tube 112 is: 4.71 mm, gap Δ between the small-diameter pipe 111 and the large-diameter pipe 112: 0.855 mm, gap δ between the small-diameter pipe 111 and the large-diameter pipe 112: 0.25 mm, from the end of the fluid flow path section 110 to the pore 122 Distance L: 0.68 mm, cone convergence angle θ ₁ of fluid confluence region 121: 120 °, pore diameter d of pore 122: 0.22 mm, length of pore 122: 0.55 mm, flow of pore 122 Road area s: 0.038 mm ² , length l of pore 122 / pore diameter d of pore 122: 2.5, cone enlargement angle θ _{2 of} flow passage enlargement portion 131: 120 °, maximum of flow passage enlargement portion 131 Channel diameter D ₄ : 2 mm, and maximum channel diameter D ₄ / pore 12 No. 2 pore diameter d: 9.1.

In Examples 18 to 23, the same micromixer 100 as in Example 1 except that the pore diameter d of the pores 122 was 0.40 mm and the maximum flow path diameter D ₄ / the pore diameter d of the pores 122 was 5.0. Was used.

2. Compounds used in Examples 1 to 23 and Comparative Examples 1 to 7 (1) Oil agent / Neopentyl glycol dicaprate “Estemol N-01” (Nisshin Oillio Group, IOB = 0.25)
・ Squalane “Nikkor Squalane” (Nikko Chemicals, IOB = 0)
・ Higher alcohol “Calcoal 200GD” (Kao Corporation, IOB = 0.29)
・ Dimethylpolysiloxane “Silicone KF-96-50CS” (Shin-Etsu Chemical Co., Ltd., IOB = 0)
N- (2-hydroxy-3-hexadecyloxypropyl) -N-2-hydroxyethylhexadecanamide “Sofcare Ceramide SLE” (manufactured by Kao Corporation, IOB = 0.33)

(2) Water-soluble solvent / polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether “Wilbride S-753” (manufactured by NOF Corporation, general formula (IV), p1 + p2 + p3 = 8, q1 + q2 + q3 = 5, r1 + r2 + r3 = 3, EO and PO are added randomly)
Polyoxyethylene polyoxypropylene alkyl ether “Unilube 50MB-11” (manufactured by NOF Corporation, in general formula (II), s = 9, t = 10, u = 0, EO and PO are randomly added, R ¹ is n-butyl group)
・ Polyoxyethylene polyoxypropylene alkyl ether “Unilube 50MB-26” (manufactured by NOF Corporation, the same as Unilube 50MB-11 except that s = 17 and t = 17 in the general formula (II))
・ Polyoxyethylene polyoxypropylene alkyl ether “Unilube 50MB-72” (manufactured by NOF Corporation, the same as Unilube 50MB-11 except that s = 30 and t = 30 in General Formula (II))
・ Polyoxyethylene polyoxypropylene alkyl ether “Unilube 50MB-168” (manufactured by NOF Corporation, the same as Unilube 50MB-11 except that s = 37 and t = 38 in general formula (II))
-Bisethoxydiglycol succinate “High Aquastar DCS” (manufactured by Higher Alcohol Industry Co., Ltd., general formula (III), v1 + v2 = 2, w1 + w2 = 0, and x1 + x2 = 0, n = 2, R ² and R ³ Ethyl group)
・ Diethylene glycol monoethyl ether “Seafosol DG-S” (manufactured by Nippon Shokubai Co., Ltd.)
・ Ethanol “Ethanol grade 1” (Wako Pure Chemical Industries, Ltd.)
・ Glycerin “Concentrated Glycerin for Cosmetics” (Kao Corporation)
Polyoxypropylene alkyl ether “Unilube MB-7” (manufactured by NOF Corporation, in general formula (II), s = 0, t = 12, u = 0, R ¹ is n-butyl group)
・ Polyoxypropylene alkyl ether “Unilube MB-19” (manufactured by NOF Corporation, same as Uniluve MB-7 except that t = 24 in general formula (II))
・ Polyoxypropylene alkyl ether “Unilube MB-700” (manufactured by NOF Corporation, same as Uniluve MB-7 except that t = 52 in the general formula (II))

(3) Surfactant and Surfactant Precursor / Polyoxyethylene hydrogenated castor oil 1 “Emanon CH-60” (manufactured by Kao Corporation, saponification value = 44 KOH mg / g, EO average added mole number = 60, HLB = 13 .8)
Polyoxyethylene hydrogenated castor oil 2 “Emanon CH-25” (manufactured by Kao Corporation, saponification value = 75 KOH mg / g, EO average added mole number = 25, HLB = 10.7)
・ Dipolyhydroxystearic acid PEG-30 “cis roll DPHS” (manufactured by Croda Japan, HLB = 5.0)
・ Oleic acid "LUNAC O-LL-V" (manufactured by Kao)
・ Distearyldimethylammonium chloride “Varisoft TA-100” (Evonik)
1- (2-hydroxyethylamino) -3-isostearyloxy-2-propanol (manufactured by Kao Corporation)

3. Calculation of Segregation Index (Xs) For Examples 1-4, 8, and 10-23, and Comparative Examples 1-5, the segregation index (Xs) was calculated as follows. A borate buffer solution substituting for the aqueous component and 0.171N sulfuric acid substituting for the oily component were prepared. The composition of the borate buffer was 0.045 mol / L boric acid, 0.045 mol / L sodium hydroxide, 0.00313 mol / L potassium iodate, and 0.0156 mol / L potassium iodide. These two liquids were mixed under the same conditions as in the examples or comparative examples, and the absorbance of the solution 1 minute after mixing with respect to light having a wavelength of 353 nm was measured using a spectrophotometer UVmini-1240 (manufactured by Shimadzu Corporation). . And the segregation index (Xs) was computed from the measurement result of the light absorbency according to the above-mentioned formula (iv).

4). Method for measuring average particle size of particles in emulsion Using laser diffraction / scattering type particle size distribution measuring apparatus “LA-910” (manufactured by Horiba Ltd.), water as a solvent, and setting the relative refractive index to 1.20. The median diameter of the oil component measured by the laser scattering / diffraction method was taken as the average particle diameter of the particles in the emulsion.

5. Operation and Result <Example 1>
Ion-exchanged water was prepared as an aqueous component and charged into the aqueous component storage tank 41a to normal temperature (20 ° C.). In addition, as an oil component, 45.5% by mass of neopentyl glycol dicaprate of liquid oil as an oil agent, 45.5% by mass of polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether as a water-soluble solvent, and HLB A uniform solution containing 9.0% by mass of polyoxyethylene hydrogenated castor oil 1 which is a 13.8 nonionic surfactant was prepared and charged in the oil component storage tank 41b to normal temperature (20 ° C.). The oily component used in Example 1 was liquid at room temperature (20 ° C.) and had self-emulsifying properties with respect to ion-exchanged water as an aqueous component.

  The dispersion production system A is operated, and the flow rate of the aqueous component is set to 2 so that the mixed mass ratio of the aqueous component / oil component becomes 91.2 / 8.8 (= 10.4) at room temperature (20 ° C.). The flow rate of .74 L / h and the oil component was 0.26 L / h, and they were mixed with the micromixer 100 to obtain an emulsion. At this time, the flow rate ratio of the aqueous component to the oil component (the flow rate of the aqueous component / the flow rate of the oil component) was 10.5. The flow rate of the fluid after the joining of the aqueous component and the oil component flowing through the pores 122 was 3.0 L / h. The pressure loss before and after the micromixer 100 was 0.4 MPa.

  In the obtained emulsion, the content of neopentyl glycol dicaprate is 4.00% by mass, the content of polyoxybutylene polyoxyethylene polyoxypropylene glyceryl ether is 4.00% by mass, polyoxyethylene hydrogenated castor oil 1 Was 0.80% by mass, and the content of ion-exchanged water was 91.20% by mass. The results are shown in Table 1.

Moreover, the segregation index (Xs) in the emulsification operation of Example 1 was 1.9 × 10 ⁻³ . In addition, [I ₃ ⁻ ] 1 minute after mixing was 3.98 × 10 ⁻⁶ mol / L as a value obtained from the absorbance with respect to light having a wavelength of 353 nm. [H ⁺ ] ₀ and [I ₂ ] were 0.171 mol / L and 3.16 × 10 ⁻⁷ mol / L, respectively, and _after V _mixing / V _{sulfuric acid water} was 11.4. It was 5.71 × 10 ⁻⁴ . Also, _[IO ³ _{-] 0} and _[H 2 _BO ³ _-] Because ₀ was respectively 0.00313mol / L and 0.045mol / _{L, Y ST} was 0.294. This is the same for Examples 2 to 4, 8, and 10 to 23, and Comparative Examples 1 to 5.

<Examples 2 to 7>
The emulsion was prepared in the same manner as in Example 1 except that the water-soluble solvent in the aqueous component in the oil component was changed to the compounds shown in Table 1, and that the merging step and the pore flow step were performed at 40 ° C. Obtained. The results are shown in Table 1. The oily components used in Examples 2 to 7 were liquid at 40 ° C. and had self-emulsifying properties with respect to ion-exchanged water as an aqueous component.

<Comparative Examples 1-5>
An emulsion was obtained in the same manner as in Example 1 except that the water-soluble solvent in the oil component was changed to the compounds shown in Table 2. The results are shown in Table 2.

  In the obtained emulsion, the content of neopentyl glycol dicaprate is 4.00% by mass, the content of polypropylene oxide alkyl ether is 4.00% by mass, and the content of polyethylene oxide hydrogenated castor oil 1 is 0.80% by mass. %, And the content of ion-exchanged water was 91.20% by mass.

<Examples 8 to 10>
An emulsion was obtained in the same manner as in Example 1 except that the oil agent in the oil component was changed to the compounds shown in Table 3. The results are shown in Table 3. The oily components used in Examples 8 to 10 were liquid at ordinary temperature (20 ° C.) and had self-emulsifying properties with respect to ion-exchanged water as an aqueous component.

<Comparative Examples 6 and 7>
Emulsions were obtained in the same manner as in Example 1 or 2 except that no water-soluble solvent was used. The results are shown in Table 4.

<Comparative Examples 8 and 9>
After mixing 729.6 g of the aqueous component and 70.4 g of the oily component (mixing mass ratio of the aqueous component / oily component 729.6 / 70.4 (= 10.4)), the homomixer “TK Homomixer MARKII2. 5 "(manufactured by Primics) was used in the same manner as in Example 1 or 2, except that an emulsion was prepared by mixing for 1 minute at a rotation speed of 8000 r / min. The results are shown in Table 5.

Moreover, the segregation index (Xs) in the emulsification operation of Comparative Examples 8 and 9 was 2.3 × 10 ⁻¹ . In addition, [I ₃ ⁻ ] 1 minute after mixing was 2.68 × 10 ⁻⁴ mol / L as a value obtained from the absorbance with respect to light having a wavelength of 353 nm. [H ⁺ ] ₀ and [I ₂ ] were 0.171 mol / L and 2.13 × 10 ⁻⁵ mol / L, respectively, and _after V _mixing / V _{sulfuric acid water} was 20, Y was 6. It was 76 × 10 ⁻² . Also, _[IO ³ _{-] 0} and _[H 2 _BO ³ _-] Since ₀ was respectively 0.00313mol / L and 0.045mol / _{L, Y ST} was 0.294.

<Examples 11 to 13>
The emulsion was prepared in the same manner as in Example 1 except that the content of the polyoxyethylene hydrogenated castor oil 1 as the nonionic surfactant in the oil component, the flow rate of the aqueous component, and the flow rate of the oil component were changed as shown in Table 6. Got. The results are shown in Table 6. The oily components used in Examples 11 to 13 were liquid at normal temperature (20 ° C.), and had self-emulsifying properties with respect to ion-exchanged water as an aqueous component.

<Examples 14 to 17>
An emulsion was obtained in the same manner as in Example 1 except that the surfactant in the oil component was changed to the compounds in Table 7. The results are shown in Table 7. In Example 15, as an aqueous component, a 1M potassium hydroxide aqueous solution “1M KOH” (manufactured by Kishida Chemical Co., Ltd.), which is a neutralizing agent, is 2.54% by mass and ion-exchanged water is 97.46% by mass uniformly. The solution was used. The oily components used in Examples 14 to 17 were liquid at normal temperature (20 ° C.) and had self-emulsifying properties with respect to ion-exchanged water as an aqueous component.

<Examples 18 to 23>
Examples except that the oily component, the aqueous component, and their contents, the flow rate of the oily component and the flow rate of the aqueous component were changed as shown in Table 8, and the merging step and the pore flow step were performed at 80 ° C. 1 was carried out to obtain an emulsion. The results are shown in Table 8. The oily components used in Examples 18 to 23 were liquid at 80 ° C. and had self-emulsifying properties with respect to the aqueous components.

(Consideration of results)
In Examples 1 to 23 in which oil components containing a water agent, a water-soluble solvent having a specific structure, and a surfactant or a surfactant precursor were dispersed in an aqueous component using a micromixer, the obtained emulsion The average particle diameter of the particles was 2.2 μm or less.

  On the other hand, in Comparative Examples 1 to 5 in which the water-soluble solvent does not have a specific structure, Comparative Examples 6 and 7 not containing the water-soluble solvent, and Comparative Examples 8 and 9 dispersed by a homomixer, the obtained emulsification The average particle size of the particles in the product was 3.0 μm or more.

  The present invention is useful for a method for producing a dispersion.

A Dispersion production system 100, 200, 300 Micromixer 101, 201 Aqueous component supply unit 102, 202 Oil component supply unit 103, 203, 303 Dispersion recovery unit 110, 310 Fluid flow path unit 111, 311 Small diameter tubes 111a, 211a , 311a 1st flow path 111b Pipe end portions 112, 312 Large diameter pipes 112a, 212a, 312a 2nd flow path 120, 320 Fluid confluence / condensation part 121, 221, 321 Fluid confluence area 122, 222, 322 330 Fluid outflow part 131,231,331 Channel expansion part 210 Straight pipe part 220 Branch pipe part 41a Aqueous component storage tank 41b Oily component storage tank 42a Aqueous component supply pipe 42b Oily component supply pipe 43a First pump 43b Second pump 44a First Flow meter 44b Second flow meter 45a First filter 45b Second fill 46a First pressure gauge 46b Second pressure gauge 47 Flow rate controller 48 Dispersion recovery pipe 49 Dispersion recovery tank

Claims (9)

A merging step for merging the aqueous component and the oily component;
One or two of the aqueous component before joining at the joining step, the oily component before joining at the joining step, and the fluid after joining the aqueous component and the oily component at the joining step A method for producing a dispersion of particles having an average particle diameter of 10 μm or less, having a pore flow step of passing through the pores under conditions where the segregation index (Xs) is 0.15 or less,
The oil component is combined with an oil agent, one or more water-soluble solvents selected from the group of compounds represented by the following general formulas (I) to (III), a surfactant, and the aqueous component. A method for producing a dispersion containing at least one of a surfactant precursor that forms a surfactant when heated.

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. P1, p2, p3, q1, q2, q3, r1, r2, and r3 each represent an average added mole number. ≦ p1 + p2 + p3 ≦ 20, 0 ≦ q1 + q2 + q3 ≦ 10, and 0 ≦ r1 + r2 + r3 ≦ 10, and 1 ≦ p1 + p2 + p3 + q1 + q2 + q3 + r1 + r2 + r3 ≦ 40. EO, PO, and BO are added in a random or block form.

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. S, t, and u each represent an average number of added moles. 1 ≦ s ≦ 70, 0 ≦ t ≦ 70, and 0 ≦ u ≦ 10 and 1 ≦ s + t + u ≦ 100, EO, PO, and BO are added in a random or block form, and R ¹ is a hydrocarbon group having 2 to 5 carbon atoms. .)

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. V1, v2, w1, w2, x1, and x2 each represent an average added mole number. 1 ≦ v1 + v2 ≦ 10, 0 ≦ w1 + w2 ≦ 9, 0 ≦ x1 + x2 ≦ 9, and 1 ≦ v1 + v2 + w1 + w2 + x1 + x2 ≦ 10 EO, PO, and BO are added in a random or block form, R ² and R ³ are independent of each other. And a hydrocarbon group having 1 to 4 carbon atoms, and n is a number having 1 to 4 carbon atoms.) The said oil-based component is a manufacturing method of the dispersion liquid of Claim 1 containing the 1 type, or 2 or more types of water-soluble solvent chosen from the group of the compound represented by the following general formula (IV).

(EO represents an ethylene oxide group, PO represents a propylene oxide group, and BO represents a butylene oxide group. P1, p2, p3, q1, q2, q3, r1, r2, and r3 each represent an average added mole number. ≦ p1 + p2 + p3 ≦ 20, 1 ≦ q1 + q2 + q3 ≦ 10, and 1 ≦ r1 + r2 + r3 ≦ 10, and 3 ≦ p1 + p2 + p3 + q1 + q2 + q3 + r1 + r2 + r3 ≦ 40. EO and PO are added in a random or block form.   The manufacturing method of the dispersion liquid of Claim 1 or 2 whose content of the said surfactant in the said oil-based component and the said surfactant precursor is 10 mass% or less.   The dispersion liquid production according to any one of claims 1 to 3, wherein in the pore circulation step, the fluid after the aqueous component and the oily component are merged at least in the merging step is circulated through the pores. Method.   In the pore circulation step, after the fluid that has joined the aqueous component and the oily component in the merging step is circulated through the pores, the maximum flow path diameter is at least three times the pore diameter of the pores. The method for producing a dispersion according to claim 4, wherein the dispersion is caused to flow out to a flow path enlarged portion that is 50 times or less.   In the pore circulation step, the flow rate when the fluid after the aqueous component and the oily component are merged at least in the merging step is circulated through the pores is 0.1 L / h or more and 300 L / h or less. The method for producing a dispersion according to claim 4 or 5.   The dispersion according to any one of claims 1 to 6, wherein the surfactant is one or more selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant. Production method.   The dispersion according to any one of claims 1 to 7, wherein in the merging step, a flow ratio of the aqueous component to the oil component before merging (the flow rate of the aqueous component / the flow rate of the oil component) is 1 or more and 200 or less. Liquid manufacturing method.   The method for producing a dispersion according to any one of claims 1 to 8, wherein in the merging step, the oily component is merged with the aqueous component from the entire circumference thereof.

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