WO2011162093A1 - Procédé de production de nanoparticules hydrophiles émulsifiantes - Google Patents

Procédé de production de nanoparticules hydrophiles émulsifiantes Download PDF

Info

Publication number
WO2011162093A1
WO2011162093A1 PCT/JP2011/063015 JP2011063015W WO2011162093A1 WO 2011162093 A1 WO2011162093 A1 WO 2011162093A1 JP 2011063015 W JP2011063015 W JP 2011063015W WO 2011162093 A1 WO2011162093 A1 WO 2011162093A1
Authority
WO
WIPO (PCT)
Prior art keywords
amphiphilic substance
hydrophilic nanoparticles
producing
water
hydrophilic
Prior art date
Application number
PCT/JP2011/063015
Other languages
English (en)
Japanese (ja)
Inventor
田嶋　和夫
今井　洋子
Original Assignee
学校法人神奈川大学
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 学校法人神奈川大学 filed Critical 学校法人神奈川大学
Priority to JP2011527914A priority Critical patent/JP5881042B2/ja
Publication of WO2011162093A1 publication Critical patent/WO2011162093A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/002—Inorganic compounds

Definitions

  • the present invention relates to a method for producing hydrophilic nanoparticles used for producing an emulsion, a method for producing an emulsion using the hydrophilic nanoparticles, a method using the hydrophilic nanoparticles, a method for producing an emulsifier, and an emulsifier preparation solution.
  • a method for producing hydrophilic nanoparticles used for producing an emulsion a method for producing an emulsion using the hydrophilic nanoparticles
  • a method using the hydrophilic nanoparticles a method for producing an emulsifier, and an emulsifier preparation solution.
  • a surfactant when emulsifying and dispersing a functional oil base or functional granule in water, a surfactant was selected according to the required HLB of the functional oil base and the properties of the granule surface, and emulsified and dispersed. .
  • the required HLB value of the surfactant used as an emulsifier needs to be properly used depending on whether an O / W type emulsion is made or a W / O type emulsion, and further, thermal stability and aging Since the stability is not sufficient, a wide variety of surfactants were mixed and used (see Non-Patent Documents 1 to 4, etc.).
  • physicochemical emulsification methods such as an HLB method, a phase inversion emulsification method, a phase inversion temperature emulsification method, and a gel emulsification method are generally performed. Since the basis of emulsion preparation is to reduce the interfacial energy at the oil / water interface and to stabilize the system thermodynamically, it is very cumbersome and labor intensive to select the most suitable emulsifier In addition, when many kinds of oils are mixed, stable emulsification is almost impossible.
  • Patent Document 1 discloses an emulsifier containing hydrophilic nanoparticles formed by an amphiphilic substance that spontaneously forms closed vesicles and having a particle size distribution of 200 nm to 800 nm.
  • Patent Document 1 since the emulsifier disclosed in Patent Document 1 has a high viscosity of the amphiphile and poor dispersibility in water, it is difficult to efficiently generate hydrophilic nanoparticles.
  • gelation, solidification, and the like make it difficult to obtain the emulsifying ability expected by the prepared hydrophilic nanoparticle dispersion.
  • the present invention has been made in view of the above circumstances, and provides a method for producing hydrophilic nanoparticles, a method for producing an emulsifier, and an emulsifier preparation solution capable of producing a wide range of amounts of hydrophilic nanoparticles.
  • Another object of the present invention is to provide a novel use of hydrophilic nanoparticles.
  • the present inventors have found that hydrophilic nanoparticles having an emulsifying action are precipitated by dissolving an amphiphilic substance in a good solvent and mixing the solution with water, thereby completing the present invention. .
  • the present invention provides the following.
  • a method for producing hydrophilic nanoparticles used in the production of an emulsion A liquid preparation step of dissolving an amphiphilic substance in a good solvent for the amphiphilic substance; A method of producing hydrophilic nanoparticles comprising: a precipitation step of precipitating the amphiphilic substance as hydrophilic nanoparticles having an emulsifying action by mixing the solution obtained in the liquid preparation step with water.
  • the amphiphilic substance is a derivative of polyoxyethylene hydrogenated castor oil represented by the following general formula, and the average added mole number (E) of ethylene oxide of the derivative is 3 to 100 (1 The manufacturing method of the hydrophilic nanoparticle as described in).
  • the hydrophilic nanoparticle according to (2) in which a surfactant of 0.1 to 0.33 mole fraction is further dissolved in the polyoxyethylene hydrogenated castor oil derivative. Production method.
  • the good solvent is methanol, ethanol, isopropanol, isobutanol, ter-butanol, sec-butanol, pentanol, methyl ethyl ketone, 1,3-propanediol, 2- (2-ethoxyethoxy) ethanol, 1,4
  • (1) The manufacturing method of the hydrophilic nanoparticle in any one.
  • a method for producing an emulsifier containing hydrophilic nanoparticles having an emulsifying action A liquid preparation step of dissolving an amphiphilic substance in a good solvent for the amphiphilic substance; A method for producing an emulsifier, comprising: a step of precipitating the amphiphilic substance as hydrophilic nanoparticles having an emulsifying action by mixing the solution obtained in the liquid preparation step with water.
  • hydrophilic nanoparticles having an emulsifying action are precipitated by mixing a solution in which an amphiphilic substance is dissolved in a good solvent with water. For this reason, by appropriately adjusting the amount of amphiphile dissolved in a good solvent, a desired amount of hydrophilic nanoparticles can be produced from a wide range, and hydrophilic nanoparticles can be produced.
  • the hydrophilic nanoparticle of this invention is used for manufacture of an emulsion,
  • the manufacturing method has a liquid preparation process and a precipitation process.
  • a liquid preparation process and a precipitation process.
  • the amphiphile is dissolved in a good solvent for the amphiphile.
  • the amphiphilic substance used in the present invention is not particularly limited, but is a polyoxyethylene hydrogenated castor oil derivative represented by the following general formula 1, or a dialkyl ammonium derivative, a trialkyl ammonium derivative represented by the general formula 2, Examples thereof include tetraalkylammonium derivatives, dialkenylammonium derivatives, trialkenylammonium derivatives, and derivatives of halogenated salts of tetraalkenylammonium derivatives.
  • E which is the average added mole number of ethylene oxide, is 3 to 100. If E is excessive, the type of good solvent that dissolves the amphiphilic substance is limited, and thus the degree of freedom in producing hydrophilic nanoparticles is narrowed.
  • the upper limit of E is preferably 50, more preferably 40, and the lower limit of E is preferably 5.
  • R 1 and R 2 are each independently an alkyl group or alkenyl group having 8 to 22 carbon atoms
  • R 3 and R 4 are each independently hydrogen or an alkyl group having 1 to 4 carbon atoms
  • X is F, Cl, Br or I.
  • the hydrophilic nanoparticles may be ionized in order to increase the adhesion force of the hydrophilic nanoparticles to the emulsification target.
  • alkyl or alkenyl trimethylammonium salt carbon chain length 12 to 22
  • hexadecyltrimethylammonium bromide Hexadecyltrimethylammonium Bromide: hereinafter referred to as CTAB
  • CTAB hexadecyltrimethylammonium bromide
  • a mixed vesicle of a polyoxyethylene hydrogenated castor oil derivative such as HCO-10 (when E is 10 in the general formula 1) and CTAB the molar fraction (Xs) of CTAB is less than 0.1.
  • Xs is preferably 0.1 or more and 0.33 or less.
  • phospholipids As the amphiphilic substance forming the hydrophilic nanoparticles, phospholipids, phospholipid derivatives, and the like may be employed.
  • phospholipid among the structures represented by the following general formula 3, DLPC (1,2-Dilauroyl-sn-glycero-3-phospho-rac-1-choline) having a carbon chain length of 12, DMPC (1,2-Dimyristol-sn-glycero-3-phospho-rac-1-choline), DPPC with a carbon chain length of 16 (1,2-Dipalmitoyyl-sn-glycero-3-phospho-rac-1-choline) Can be adopted.
  • DLPG (1,2-Diilauroyl-sn-glycero-3-phospho-rac-1-glycerol) Na salt or NH4 salt
  • DPPG 1,2-Dipalmitoyyl-sn-glycero-3 having a carbon chain length of 16 -Phospho-rac-1-glycerol
  • examples of phospholipids include other glycerophospholipids (lecithin, ethanolamine, serine, inositol, etc.) and sphingophospholipids. Natural substances such as egg yolk lecithin or soybean lecithin may be employed.
  • the mass ratio of the emulsified oil component and the emulsifier is preferably 4 to 200 and mixed.
  • the good solvent used in the present invention has an ability to dissolve the amphiphilic substance to be used and is miscible with water.
  • a good amount of amphiphile can be dissolved in the good solvent, and the solution can be mixed in an amount corresponding to the water miscibility of the good solvent, so that a desired amount of hydrophilic nanoparticles can be produced.
  • the good solvent may be appropriately selected depending on the amphiphilic substance to be used.
  • the good solvent is not limited to the above, and may be benzyl alcohol, n-butanol or the like. These solvents are not excellent in water miscibility, but are excellent in the ability to dissolve amphiphiles, so that a solution that dissolves many amphiphiles at a high concentration can be formed. Thereby, since the quantity of the solution mixed with water can be suppressed to a small amount, the low mixing property with water is not likely to be a problem. Thus, the good solvent in the present invention may be appropriately selected in consideration of the balance between the solubility of the amphiphile and the miscibility with water.
  • the amphiphilic substance is precipitated as hydrophilic nanoparticles having an emulsifying action by mixing the solution obtained in the liquid preparation step with water.
  • the mixing of the solution and water may be performed through an external action such as stirring, or may be spontaneous by diffusion depending on the water mixing property of a good solvent.
  • the former is preferable from the viewpoint of efficiency.
  • Stirring may be performed simultaneously with the addition of the solution to water or with the solution of water, or after the addition.
  • the water may be ion-exchanged water, pure water, ultrapure water, or tap water, and may be appropriately selected according to the required purity.
  • the hydrophilic nanoparticles thus precipitated have an average particle diameter of about 20 nm to 800 nm when present at 0.1 to 20% by mass in the dispersion.
  • the hydrophilic nanoparticles having such a particle size distribution exhibit an excellent and stable emulsion forming action with an average particle diameter of about 8 to 500 nm by making the hydrophilic nanoparticles finer in the emulsion forming step at the time of use.
  • the average particle diameter in this specification refers to the average value based on the number frequency, and the measuring device is “FPAR (manufactured by Otsuka Electronics Co., Ltd.)”.
  • the present invention also provides a method for producing an emulsifier containing hydrophilic nanoparticles. This method has the same steps as the method for producing the hydrophilic nanoparticles described above.
  • the precipitated hydrophilic nanoparticles are dispersed in a mixed solvent of water and a good solvent. Such a dispersion may be appropriately treated according to the target of emulsification with hydrophilic nanoparticles, or may be used as an emulsifier without treatment.
  • an emulsion for example, a product used in a living body, specifically, an ingested product (for example, a food or drink, a preparation for oral administration), an external preparation, a cosmetic, an agricultural chemical, or the like (for example, a protein) affected by a good solvent
  • an ingested product for example, a food or drink, a preparation for oral administration
  • an external preparation for example, a cosmetic, an agricultural chemical, or the like (for example, a protein) affected by a good solvent
  • the content of the good solvent is low from the viewpoint of improving safety and reducing irritation. Then, you may perform the process (for example, fractional distillation, water dilution) which reduces content of a good solvent.
  • the treatment for reducing the content of the good solvent for example, fractional distillation, water dilution
  • the good solvent for example, fractional distillation, water dilution
  • the treatment for reducing the content of the good solvent is performed for a long time before emulsification. Desirably not.
  • an emulsion is used for the thing which is not used for a biological body, for example, a fuel, a coating material, etc., it is not necessary to perform the said process.
  • the hydrophilic nanoparticles and the emulsifier produced by the method described above can be used for emulsification of various oily substances.
  • an emulsion in which an oil phase containing an oily substance and an aqueous phase are dispersed is produced by mixing the oily substance with or without adding a substance that is distributed to the aqueous phase as appropriate to the emulsifier. it can.
  • an oily substance means the substance which contains only oil or oil as a main component. A detailed use procedure is described in Japanese Patent No. 3855203.
  • the hydrophilic nanoparticles and the emulsifier can form an emulsified dispersion having excellent thermal stability and stability over time with respect to the interface between the functional oil base and water or the functional granules and water.
  • the emulsifying dispersant of the present invention can be used for stable emulsification in a wide temperature range over a long period of time.
  • the hydrophilic nanoparticles and the emulsifier of the present invention include light oil, heavy oil A, heavy oil C, tar, biodiesel fuel, recycled heavy oil, waste cooking oil, cosmetic oil, cooking oil, industrial oil (for example, silicon oil, kerosene) and the like. Can be used to emulsify water in various oils.
  • hydrophilic nanoparticles and the emulsifier of the present invention can be used to produce an emulsion under conditions that are difficult to emulsify with a surfactant.
  • Such conditions include strongly acidic (for example, pH 4 or less) and strongly basic (for example, pH 12 or more), high salt concentration (for example, 0.1 mol / L or more) conditions, natural product oils (vegetable oil, mineral oil)
  • Examples include emulsification and emulsification of an oil agent having a high melting point (for example, 50 ° C. or higher) (oil agent that is liquid at high temperature and solidifies after emulsification).
  • HCO-100, water and ethanol or isopropyl alcohol were mixed at a ratio of 7: 1.5: 1.5 (mass ratio).
  • the mixture was a uniform liquid regardless of whether ethanol or isopropyl alcohol was used. Accordingly, it was confirmed that a large amount of amphiphilic substance that gels when a solvent containing only water can be dissolved by using a good solvent.
  • Example 1 Polyoxyethylene hydrogenated castor oil derivative 10 mL of a solution obtained by mixing HCO-10, water, and ethanol in a ratio of 7: 1.5: 1.5 (mass ratio) was added to 25 ° C. water. Added to 1 L and mixed by stirring at 500 rpm for 5 minutes.
  • a particle size distribution analyzer FPAR manufactured by Otsuka Electronics Co., Ltd.
  • the peak indicating the presence of hydrophilic nanoparticles was also around 400 nm and also at several ⁇ m. Was confirmed.
  • Example 1 The dispersions of Example 1 and Comparative Example were emulsified with A-heavy oil at the respective mass ratios shown in Tables 3 and 4 by stirring at 8000 rpm for about 5 minutes using a homomixer at room temperature, and the emulsified state was evaluated. did.
  • the evaluation criteria are as follows. ⁇ : No phase separation, ⁇ : Separation by specific gravity difference (coacervation), ⁇ : Separation 1: O / W emulsion, 2: W / O emulsion, 3: W / O emulsion and separated water phase
  • the dispersion of Comparative Example could not emulsify 80% by mass or more of A heavy oil, and the emulsion stability of 60 to 70% by mass of A heavy oil was insufficient.
  • the dispersion liquid of Example 1 A heavy oil of any amount, at least 95% by mass or less, was stably and satisfactorily emulsified.
  • Example 2 Phospholipid A chloroform solution of hydrogenated lecithin shown in Table 2 was mixed with water in the same procedure as in Example 1. About the obtained mixture, when the particle size distribution was measured like Example 1, the peak which shows presence of a hydrophilic nanoparticle was confirmed by 100 nm vicinity.
  • the obtained dispersion was stirred and emulsified in the same manner as in Example 1 with each oil within the range shown in Table 5, and the emulsified state was evaluated.
  • the evaluation criteria are as described above.
  • Example 5 As shown in Table 5, the dispersion liquid of Example 2 stably emulsified various oils over a wide range of mixing ratios.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Preparation (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Colloid Chemistry (AREA)
  • Polyethers (AREA)

Abstract

La présente invention concerne un procédé de production de particules hydrophiles qui permet la production de particules hydrophiles dans une gamme étendue de quantités, un procédé de production d'un émulsifiant et une solution d'élaboration d'un émulsifiant. Le procédé selon l'invention de production de particules hydrophiles employées pour produire une émulsion implique : une étape d'élaboration d'une solution pour dissoudre une substance amphiphile dans un bon solvant de la substance amphiphile ; et une étape de précipitation pour mélanger la solution élaborée dans ladite étape d'élaboration d'une solution avec de l'eau, et ainsi précipiter la substance amphiphile sous forme de particules hydrophiles présentant un effet émulsifiant.
PCT/JP2011/063015 2010-06-23 2011-06-07 Procédé de production de nanoparticules hydrophiles émulsifiantes WO2011162093A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2011527914A JP5881042B2 (ja) 2010-06-23 2011-06-07 乳化物製造用親水性ナノ粒子の製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010142968 2010-06-23
JP2010-142968 2010-06-23

Publications (1)

Publication Number Publication Date
WO2011162093A1 true WO2011162093A1 (fr) 2011-12-29

Family

ID=45371289

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/063015 WO2011162093A1 (fr) 2010-06-23 2011-06-07 Procédé de production de nanoparticules hydrophiles émulsifiantes

Country Status (2)

Country Link
JP (1) JP5881042B2 (fr)
WO (1) WO2011162093A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10186827B2 (en) 2014-07-11 2019-01-22 Trumpf Lasersystems For Semiconductor Manufacturing Gmbh Amplifying pulsed laser radiation for EUV radiation production
US10638589B2 (en) 2015-11-27 2020-04-28 Trumpf Lasersystems For Semiconductor Manufacturing Gmbh Amplifying laser pulses having different wavelengths for EUV radiation generation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63116737A (ja) * 1986-07-15 1988-05-21 シラグ・リミテツド 一様な二重層化されたリポソームの製造法
JP2002536316A (ja) * 1999-02-08 2002-10-29 アルザ・コーポレーション リポソームサイズを調節する方法
JP2004130300A (ja) * 2002-08-12 2004-04-30 Univ Kanagawa 混合ベシクル、これを用いたエマルション、及びこれらの調製方法
JP2006239666A (ja) * 2004-04-05 2006-09-14 Univ Kanagawa 乳化分散剤及びこれを用いた乳化分散方法並びに乳化物
WO2010064678A1 (fr) * 2008-12-03 2010-06-10 株式会社 資生堂 Produit cosmétique de type huile-dans-eau

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2708440C (fr) * 2004-04-05 2013-05-14 Kanagawa University Agents dispersants d'emulsification, methode d'emulsification et de dispersion utilisant lesdits agents dispersants d'emulsification, emulsions connexes et combustibles emulsionnes
KR20080014996A (ko) * 2005-05-09 2008-02-15 후지필름 가부시키가이샤 유기 입자의 제조 방법
JP2007061688A (ja) * 2005-08-29 2007-03-15 Mitsubishi Chemicals Corp 有機化合物微粒子の調製条件の探索方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63116737A (ja) * 1986-07-15 1988-05-21 シラグ・リミテツド 一様な二重層化されたリポソームの製造法
JP2002536316A (ja) * 1999-02-08 2002-10-29 アルザ・コーポレーション リポソームサイズを調節する方法
JP2004130300A (ja) * 2002-08-12 2004-04-30 Univ Kanagawa 混合ベシクル、これを用いたエマルション、及びこれらの調製方法
JP2006239666A (ja) * 2004-04-05 2006-09-14 Univ Kanagawa 乳化分散剤及びこれを用いた乳化分散方法並びに乳化物
WO2010064678A1 (fr) * 2008-12-03 2010-06-10 株式会社 資生堂 Produit cosmétique de type huile-dans-eau

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10186827B2 (en) 2014-07-11 2019-01-22 Trumpf Lasersystems For Semiconductor Manufacturing Gmbh Amplifying pulsed laser radiation for EUV radiation production
US10638589B2 (en) 2015-11-27 2020-04-28 Trumpf Lasersystems For Semiconductor Manufacturing Gmbh Amplifying laser pulses having different wavelengths for EUV radiation generation

Also Published As

Publication number Publication date
JP5881042B2 (ja) 2016-03-09
JPWO2011162093A1 (ja) 2013-08-19

Similar Documents

Publication Publication Date Title
JP3855203B2 (ja) 乳化分散剤及びこれを用いた乳化分散方法並びに乳化物
US9366387B2 (en) Process of preparing improved heavy and extra heavy crude oil emulsions by use of biosurfactants in water and product thereof
EP1754532B1 (fr) Dispersants emulsifiants, procede d'emulsification et de dispersion a l'aide de ceux-ci, emulsions, et combustibles a base d'emulsion
CN1324112C (zh) 官能化立方液晶相物质及其制备和使用方法
Silva et al. Size, Charge, and Stability of Fully Serine‐Based Catanionic Vesicles: Towards Versatile Biocompatible Nanocarriers
CN103788402B (zh) 一种碳量子点/锂皂石乳液稳定体系及制备石蜡乳液的方法
JPS5858392B2 (ja) 安定化した鉱油中水滴エマルシヨン
JP2010104946A (ja) 逆ベシクルを用いて形成された油中水（ｗ／ｏ）型エマルション
CN108159414B (zh) 动物疫苗用油包水佐剂及其制备方法和用途
TW201929835A (zh) 脂質微粒子分散物
US7001580B2 (en) Emulsions including surface-modified organic molecules
JP2007077178A (ja) シリコーン型エマルション及びその製造方法
CN112108075A (zh) 一种Pickering乳化剂及其制备方法与应用
JP5881042B2 (ja) 乳化物製造用親水性ナノ粒子の製造方法
JP2007161683A (ja) 乳化液体の製造方法
JP2007074909A (ja) 可食性エマルション及びその製造方法
JP3202984B2 (ja) 親油性乳化剤を用いて成るｏ／ｗエマルション
CA2803770C (fr) Procede de production d'une matiere produisant un emulsifiant, procede de production d'un emulsifiant, emulsifiant pour composition a administration orale et composition a adminis tration orale
TWI510457B (zh) 脂肪醯胺之水性分散液
JP6274477B2 (ja) 乳化剤製造用材料の製造方法、乳化剤製造用材料、及び乳化剤の製造方法
JP5409991B2 (ja) 乳化分散剤及びその製造方法
RU2006139072A (ru) Эмульгирующие диспергирующие средства, способ эмульгирования и диспергирования с использованием эмульгирующих диспергирующих средств, эмульсии и эмульсионные топлива
JPH10298149A (ja) 高濃度第４級アンモニウム塩分散液及びその調製方法
CN104667772B (zh) 一种耐温耐盐油包水纳米乳液及其制备方法
CN109929634B (zh) 一种可快速破乳的柴油乳状液及其制备方法

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2011527914

Country of ref document: JP

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11797979

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11797979

Country of ref document: EP

Kind code of ref document: A1