JP2014205120A - Formulation using for reduction or increase of wettability, raw material for producing the same and method for reducing or increasing wettability - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide formulation and a method for realizing the reduction of wettability to the hydrophobic surface of O/w type emulsion or the increase of wettability to a hydrophilic surface.SOLUTION: Formulation includes the closed endoplasmic reticula of an amphipathic substance for spontaneously forming the closed endoplasmic reticula or a sugar polymer particle and is used for the reduction of wettability to the hydrophobic surface of O/w type emulsion or the increase of wettability to a hydrophilic surface. The closed endoplasmic reticulum or the sugar polymer particle has preferably an average particle diameter of 8 nm to 500 nm and is preferably used so as to interpose between the interfaces of an oil phase and an aqueous phase.

Description

  The present invention relates to a preparation used for reducing or increasing wettability, a raw material for production thereof, and a method for reducing or increasing wettability.

  The O / W type emulsion is obtained by dispersing oil in water by emulsification, and the emulsification is generally realized by a surfactant having a hydrophobic part and a hydrophilic part. Conventionally, O / W type emulsions are used in various fields including foods and drinks and pharmaceuticals. At that time, the O / W type emulsions are stored in containers or applied to the surfaces to be applied, and various materials such as plastic and glass are used. To touch.

  Conventional O / W type emulsions have the property that they are difficult to wet with respect to the surface of the hydrophilic solid and easily wet with respect to the surface of the hydrophobic solid. Specifically, as a result of the hydrophilic portion of the surfactant adsorbing to the hydrophilic solid, the hydrophobic portion is oriented on the droplet (water) side, so that the droplet is slippery (that is, difficult to wet). On the contrary, as a result of the hydrophobic portion of the surfactant adsorbing to the hydrophobic solid, the hydrophilic portion is oriented on the droplet (water) side, so that the droplet is difficult to slip (that is, easily wet).

  However, the wettability of the aforementioned O / W emulsion is unnatural, which is different from the wettability of water. For example, when food / beverage products and medicines of O / W type emulsion are accommodated in a container made of a hydrophobic material such as polypropylene, the O / W type emulsion is likely to get wet, so that the inclusions dissolved in the oil easily adhere to the container, etc. There can be disadvantages.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a preparation and a method for realizing reduction in wettability with respect to a hydrophobic surface or increase in wettability with respect to a hydrophilic surface of an O / W emulsion. And

  The inventors have found that closed vesicles of amphiphiles and sugar polymer particles achieve reduced wettability on hydrophobic surfaces or increased wettability on hydrophilic surfaces of O / W emulsions, The present invention has been completed. Specifically, the present invention provides the following.

  (1) Manufacture of a preparation composed of an amphiphilic substance or a sugar polymer that spontaneously forms a closed endoplasmic reticulum, and used for reducing wettability to a hydrophobic surface or increasing wettability to a hydrophilic surface of an O / W emulsion. Raw material.

  (2) It contains closed vesicles of amphiphiles that spontaneously form closed vesicles, or sugar polymer particles, and reduces wettability to hydrophobic surfaces or increases wettability to hydrophilic surfaces of O / W emulsions. Formulation used.

  (3) The preparation according to (2), wherein the closed endoplasmic reticulum or the sugar polymer particles have an average particle size of 8 nm to 500 nm.

  (4) The preparation according to (2) or (3), wherein the closed endoplasmic reticulum or the sugar polymer particles are used so as to intervene at an interface between an oil phase and an aqueous phase.

  (5) By including closed vesicles of amphiphiles that spontaneously form closed vesicles or sugar polymer particles as components of the O / W emulsion, the hydrophobic surface of the O / W emulsion is included. A method of reducing wettability or increasing wettability to a hydrophilic surface.

  (6) The method according to (5), wherein the closed endoplasmic reticulum or the sugar polymer particles have an average particle diameter of 8 nm to 500 nm.

  (7) The method according to (5) or (6), wherein the closed endoplasmic reticulum or the sugar polymer particles are interposed at an interface between an oil phase and an aqueous phase.

  According to the present invention, by using closed endoplasmic reticulum or sugar polymer particles, it is possible to reduce the wettability of the O / W emulsion to the hydrophobic surface or increase the wettability to the hydrophilic surface.

It is a schematic diagram which shows the state of O / W type | mold emulsion on a hydrophilic surface. It is a schematic diagram which shows the state of O / W type | mold emulsion on a hydrophobic surface.

  Hereinafter, although embodiment of this invention is described, this does not limit this invention.

  The preparation of the present invention contains closed vesicles of amphiphiles that spontaneously form closed vesicles, or sugar polymer particles, and reduces wettability to hydrophobic surfaces or wettability to hydrophilic surfaces of O / W emulsions. Used to increase sex.

  When an O / W emulsion emulsified with a conventional surfactant is applied to a hydrophilic surface, the hydrophilic portion of the surfactant is adsorbed to the hydrophilic surface as shown in FIG. As a result, the hydrophobic portion is oriented on the droplet (water) side, so that the droplet is slippery (that is, difficult to wet). On the other hand, when the O / W emulsion is emulsified with closed vesicles or sugar polymer particles, as shown in FIG. 1B, the hydrophilic outer side of the closed vesicles or sugar polymer particles is Since it is attached to the hydrophilic surface and also faces the droplet (water) side, the droplet is difficult to slip (that is, easily wet). Therefore, the preparation of the present invention can be used for increasing the wettability of the O / W emulsion to the hydrophilic surface.

  The hydrophilic surface is not particularly limited, and examples thereof include hydrophilic plastics such as glass and acrylate, metals, plastics subjected to hydrophilic surface treatment, and the like. Increase in wettability to these surfaces is not particularly limited, but printing of O / W emulsion paints on these surfaces, spray coating, rust preventives, antifungal agents, agricultural chemicals, cutting on these surfaces It is advantageous that oil can be easily developed. The use of closed endoplasmic reticulum or sugar polymer particles in these applications, or the use of increased wettability or parameter changes correlated therewith in advertising, etc., falls within the practice of the present invention.

  When an O / W emulsion emulsified with a conventional surfactant is applied to a hydrophobic surface, the hydrophobic portion of the surfactant is adsorbed to the hydrophobic surface as shown in FIG. As a result, the hydrophilic portion is oriented on the droplet (water) side, so that the droplet is difficult to slip (that is, easily wet). On the other hand, when the O / W emulsion is emulsified with closed vesicles or sugar polymer particles, as shown in FIG. 2 (B), the hydrophilic outer side of the closed vesicles or sugar polymer particles is Although it may adhere to the hydrophobic surface over time due to Van der Waals attraction, it is difficult to wet because the surface tension of the droplet does not decrease. Therefore, the preparation of the present invention can be used for reducing the wettability of the O / W emulsion to the hydrophobic surface.

  The hydrophobic surface is not particularly limited, and examples thereof include hydrophobic plastics such as polyolefins such as polypropylene, and polyesters such as polyethylene terephthalate, hydrophobic surface-treated plastics, metals, and the like. By reducing wettability to these surfaces, there is no particular limitation. However, since the adhesion of components in the oil to these surfaces is suppressed, it is possible to make O / W emulsion foods and drinks, pharmaceuticals, and cosmetics hydrophobic. It is suitable when accommodated in a container having a conductive surface. The use of closed endoplasmic reticulum or sugar polymer particles in these applications, or the use of reduced wettability or parameter changes correlated therewith in advertising, etc., falls within the practice of the present invention.

  A closed vesicle of an amphiphile that spontaneously forms a closed vesicle has a two-layer structure in which the hydrophobic portions of the amphiphile face each other and the hydrophilic portions face outward. In addition, the sugar polymer particles have a structure in which a plurality of sugar polymer molecules are intertwined in water with the hydrophobic portion facing inward and the hydrophilic portion facing outward. Since both are common in that they are fine particles having a hydrophilic surface, they have the same effect on the surface wettability described above. Details of these characteristics are disclosed in Japanese Patent No. 3855203.

  The closed endoplasmic reticulum or sugar polymer particles used in the present invention are not particularly limited, but have an average particle size of 8 nm to 500 nm. The closed endoplasmic reticulum and sugar polymer particles having such a fine size sufficiently surround oil droplets and are easy to emulsify, and also have excellent adhesion performance to hydrophilic surfaces and sufficiently increase wettability. Cheap. In addition, an average particle diameter is computed from the particle size distribution obtained using the particle size distribution measuring apparatus FPAR (made by Otsuka Electronics Co., Ltd.).

  Closed endoplasmic reticulum or sugar polymer particles are used so as to intervene at the interface between the oil phase and the water phase of the O / W emulsion. Closed endoplasmic reticulum or sugar polymer particles intervene at the interface between the water phase and the oil phase, and constitute an emulsified state via van der Waals attraction. Therefore, regardless of the composition and conditions of the oil phase and the water phase, An emulsified state can be configured. Moreover, the excessive closed endoplasmic reticulum or sugar polymer particle which does not intervene in an oil phase and a water phase adheres to a hydrophilic surface, and increases the wettability of an O / W type | mold emulsion. In addition, it can confirm with a transmission electron microscope that a closed endoplasmic reticulum or a sugar polymer particle intervenes in the interface of an oil phase and a water phase.

  As the amphipathic substance, egg yolk lecithin, soybean lecithin, rapeseed lecithin, lysolecithin or fractionated lecithin obtained from these may be employed as phospholipids.

  A fatty acid ester may be adopted as the amphiphilic substance. As the fatty acid ester, it is preferable to use those suitable for food use such as glycerin fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, and propylene glycol fatty acid ester. The fatty acid ester may be used in combination with the phospholipid. Fatty acid esters and phospholipids may be used in combination. As fatty acid ester used together with phospholipid, sucrose fatty acid ester is preferable.

  The sugar polymer is a polymer having a glucoside structure such as cellulose and starch. For example, those produced by microorganisms with some sugars among monosaccharides such as ribose, xylose, rhamnose, fucose, glucose, mannose, glucuronic acid, gluconic acid, xanthan gum, gum arabic, guar gum, caraya gum, carrageenan , Pectin, fucoidan, quinseed gum, tranto gum, locust bean gum, galactomannan, curdlan, gellan gum, fucogel, casein, gelatin, starch, collagen and other natural polymers, methylcellulose, ethylcellulose, methylhydroxypropylcellulose, carboxymethylcellulose, Hydroxymethylcellulose, hydroxypropylcellulose, sodium carboxymethylcellulose, propylene glycol alginate, cell Examples include semi-synthetic polymers such as glucose crystals, starch / sodium acrylate graft polymers, hydrophobized hydroxypropylmethylcellulose, and synthetic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, carboxyvinyl polymer, polyacrylate, and polyethylene oxide. It is done.

  In the present invention, the amount of the amphiphilic substance or sugar polymer is not particularly limited, but is 0.01% by mass to 10% by mass with respect to the fat and oil component from the viewpoint of sufficiently surrounding and emulsifying the oil droplets. Is more preferable, and it is 0.01 mass% or more and 2.5 mass% or less. In order to increase the wettability with respect to the hydrophilic surface, it is preferable that an excess amphiphilic substance or sugar polymer exceeding the amount used for emulsification is included, and specifically, 1.5% by mass with respect to the fat and oil component. It is preferable that it is above, and more preferably 2.0% by mass or more. In addition, the amount of the amphiphilic substance or the sugar polymer with respect to the fat and oil component is measured by any appropriate method of GC-MS, LC-MS, or TLC depending on the type.

  The closed endoplasmic reticulum and the sugar polymer may be used singly or in combination, and may be appropriately selected according to the use of the O / W emulsion. For example, when applied to the human body (particularly internal use) such as foods and drinks, pharmaceuticals, and cosmetics, a sugar polymer that is a natural molecule is generally desired from the viewpoint of safety.

  In the O / W type emulsion, the ratio of water and oil may be appropriately selected as long as the emulsification is not impaired. In addition, since closed vesicles or sugar polymer particles have extremely excellent emulsifying performance, water: oil may be 5% by mass: 95% by mass to 95% by mass: 5% by mass.

  Other water-soluble components and oil and fat components may be appropriately selected according to the use of the O / W emulsion. In the case of foods and drinks, water-soluble and oil-soluble seasonings may be included, in the case of pharmaceuticals, water-soluble and oil-soluble active ingredients may be included, and in the case of cosmetics, water-soluble and oil-soluble flavors may be included. .

  O / W emulsions may or may not contain conventional surfactants, but emulsification can be achieved with closed vesicles or sugar polymer particles, whereas surfactants are hydrophilic and hydrophobic. Since it is adsorbed on any surface of the material to change the wettability, the wettability change by the closed endoplasmic reticulum or the sugar polymer particles is masked. For this reason, the amount of the surfactant in the O / W emulsion is preferably 10% by mass or less, more preferably 5% by mass or less, 2% by mass or less, and 1% by mass or less, and most preferably zero. It is.

  The method for producing an O / W emulsion using the present invention is a process of mixing an aqueous dispersion in which closed vesicles or sugar polymer particles are dispersed with an oil component, and emulsifying the aqueous phase and the oil phase with each other. Have Since the mixing ratio and mixing conditions of the water phase and the oil phase are conventionally known, they are omitted.

  Specifically, closed vesicles or sugar polymer particles are formed by adding an amphiphile or sugar polymer to water and heating to disperse the particles. The dispersion prepared in this manner and the fat and oil component are stirred and mixed with a homomixer or the like to form an O / W type emulsion. Detailed conditions are as disclosed in Japanese Patent No. 3855203, WO2011 / 162094, and the like.

  Since the O / W emulsion containing the preparation according to the present invention has the wettability changed as described above, the product (for example, food / beverage products, pharmaceuticals, cosmetics) contained in a container having a hydrophobic surface, hydrophilicity It is useful as a product (for example, paints, rust preventives, antifungal agents, agricultural chemicals, cutting oils) applied to the surface.

  The present invention includes a closed vesicle of an amphiphile that spontaneously forms a closed vesicle, or a sugar polymer particle as a component of the O / W emulsion, thereby allowing the O / W emulsion to have a hydrophobic surface. Also included are methods of reducing wettability or increasing wettability to hydrophilic surfaces. The closed endoplasmic reticulum or sugar polymer particles preferably have an average particle size of 8 nm to 500 nm. The closed vesicles or sugar polymer particles are preferably interposed at the interface between the oil phase and the water phase.

  The O / W type emulsions of Examples and Comparative Examples were prepared using squalane as an oil agent and the oil phase concentration was 30.0% by mass with respect to the O / W type emulsion.

<Example>
Distearyl decaglycerin is added to water in an amount of 1.0% by mass, heated to 80 ° C. with stirring, further stirred at 80 ° C. for 30 minutes, and then allowed to stand at room temperature overnight. A liquid (particle dispersion) in which distearyl decaglycerin particles were dispersed was prepared. An O / W emulsion was prepared by adding and mixing the oil agent described above.

(Comparative Example 1)
SDS as a surfactant was dissolved in water in an amount of 3.0% by mass. An O / W emulsion was prepared by adding and mixing the oil agent described above.

(Comparative Example 2)
Surfactant C ₁₂ (EO) ₈ was dissolved in water in an amount of 3.0% by mass. An O / W emulsion was prepared by adding and mixing the oil agent described above.

[Evaluation]
Polyethylene terephthalate (PET), polypropylene (PP), acrylate (AL), and glass for preparation (GL) were used as the surface to which the O / W emulsion was applied. Using a contact angle measuring device “FACE, Drop Master 100” (manufactured by Kyowa Interface Science Co., Ltd.), droplets were formed with an Auto dispenser AD-31 and landed on each surface. FAMAS was used as the analysis software, the shape of the droplet was imaged with a CCD camera, and the contact angle was determined at ± 1.0 ° by the θ / 2 method. Specifically, a series of measurements were performed at a titration start time of 0.5 seconds, a measurement interval of 1.0 seconds, a measurement count of 121 times, and a measurement time of 120.5 seconds, and this was repeated 5 to 10 times to obtain a contact angle. The average value of was obtained.

  Then, in any measurement system, the contact angle became almost steady after 40 to 60 seconds from the landing. For this reason, this time-dependent change in the steady state was interpolated at time 0 seconds to obtain a measured value. The results are shown in Table 1.

Further, the gas-liquid interfacial tension was measured by the Whilhelmy method using a surface tension meter “CBVP-A3” (manufactured by Kyowa Interface Science Co., Ltd.), and a value at which no change with time was confirmed was obtained. The measurement accuracy is ± 0.5 mNm- ¹ . The results are shown in Table 2.

  Based on the contact angle shown in Table 1 and the surface tension shown in Table 2, the wetting energy for each surface of each droplet was calculated. The results are shown in Table 3.

  As shown in Table 3, the O / W type emulsions of the examples had lower wetting energy and were hard to get wet with respect to the surfaces of hydrophobic plastics such as PET and PP, compared with the comparative examples, whereas AL The surface of a hydrophilic material such as glass or a hydrophilic material such as glass had high wetting energy and was easy to wet.

Claims (7)

  A raw material for producing a preparation, which is composed of an amphiphilic substance or a sugar polymer that spontaneously forms closed vesicles and is used to reduce wettability to a hydrophobic surface or increase wettability to a hydrophilic surface of an O / W emulsion.   A formulation containing closed vesicles of amphiphiles that spontaneously form closed vesicles, or sugar polymer particles, and used for reducing wettability to hydrophobic surfaces or increasing wettability to hydrophilic surfaces of O / W emulsions .   The preparation according to claim 2, wherein the closed endoplasmic reticulum or the sugar polymer particles have an average particle diameter of 8 nm to 500 nm.   The preparation according to claim 2 or 3, wherein the closed endoplasmic reticulum or the sugar polymer particles are used so as to intervene at an interface between an oil phase and an aqueous phase.   By including closed vesicles of amphiphiles that spontaneously form closed vesicles or sugar polymer particles as components of the O / W emulsion, the wettability of the O / W emulsion to the hydrophobic surface is improved. A method of reducing or increasing wettability to a hydrophilic surface.   The method according to claim 5, wherein the closed endoplasmic reticulum or the sugar polymer particles have an average particle diameter of 8 nm to 500 nm.   The method according to claim 5 or 6, wherein the closed endoplasmic reticulum or the sugar polymer particles are interposed at an interface between an oil phase and an aqueous phase.

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