JP5351398B2 - Method for producing water-based transparent composition containing micelle-silica composite capsule and method for producing emulsion-silica composite capsule-containing transparent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new method for preparing a new silica composite capsule with ease and to provide a composition comprising the silica composite capsule. <P>SOLUTION: The micelle-silica composite capsule, in which the periphery of the micelle is covered with silica, is easily prepared in aqueous solution by mixing a substance capable of forming micelle in water with a water-soluble silane derivative represented by following general formula (1). By mixing a surfactant, water, an oil, and a water-soluble silane derivative represented by following general formula (1), the emulsion-silica composite capsules can be easily obtained in which the emulsion particles as the inner phase are surrounded with the silica. Formula (1); Si-(OR<SP>1</SP>)<SB>4</SB>, (in the formula at least one of R<SP>1</SP>is a residue of a polyhydric alcohol and the rests are optionally an alkyl group). <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

The present invention relates to a method for producing a water-based transparent composition containing a micelle-silica composite capsule , a method for producing an emulsion-silica composite capsule- containing transparent composition , particularly a method for producing a silica composite capsule, and further comprising a silica composite capsule. It relates to the preparation of a composition.

  Conventionally, microcapsules having encapsulated substances inside capsules have been studied in various fields such as recording / display materials, drug delivery technology (DDS), cosmetics / fragrances, foods, and agricultural chemicals. As an example, an attempt has been made to improve the stability of a drug in a product, for example, by encapsulating the drug inside a capsule.

  As one of such microcapsules, silica microcapsules are known. Conventionally, as a method for producing silica microcapsules, although many reports have been made such as phase separation method, submerged drying method, spray drying method, interfacial polymerization method, in-situ polymerization method, etc., silica having an inclusion substance When trying to obtain a microcapsule, usually a separate treatment such as impregnation of a hollow silica microcapsule in a solution in which the encapsulated substance was previously dissolved was necessary.

On the other hand, by using a water-in-oil (W / O) emulsion in which an aqueous phase containing an inclusion substance is dispersed in advance, silica is polymerized at the water-oil interface. A method for preparing a silica composite microcapsule containing the same has been reported (for example, see Patent Document 1). However, in this method, since water-insoluble tetraalkoxysilane is used, the reaction system needs to be a water-in-oil type (W / O type), and the dosage form of the resulting preparation is limited. There was a drawback.
JP 2001-38193 A

  The present invention has been made in view of the above-mentioned problems of the prior art, and the object thereof is a novel silica composite capsule that can be easily prepared, a method for producing the same, and a composition containing the silica composite capsule Is to provide.

  In view of the problems of the prior art, as a result of intensive studies by the present inventors, by mixing a substance capable of forming micelles in water and a water-soluble silane derivative having a specific structure in an aqueous solution, It was found that a micelle-silica composite capsule was easily obtained, and the aqueous composition obtained thereby was transparent and the appearance of the composition was very excellent. Furthermore, by mixing a surfactant, water, oil, and a water-soluble silane derivative having a specific structure, an emulsion-silica composite capsule in which the periphery of the emulsion particles in the inner phase is coated with silica can be simplified. The present invention was also found and the present invention was completed.

That is, the method for producing an aqueous transparent composition containing a micelle-silica composite capsule according to the present invention comprises 0.1 to 30.0% by mass of a substance capable of forming micelles in water, and a water solution represented by the following general formula (1). 0.1-20.0% by mass of a functional silane derivative was mixed in an aqueous solution , and a micelle-silica composite capsule in which the outer periphery of the micelle made of the micelle-forming substance was coated with silica was dispersed in the aqueous phase. A water-based transparent composition is used.
Si- (OR ¹ ) ₄ (1)
(In the formula, ^{R 1} are both Ru polyhydric alcohol residue der.)

Moreover, the manufacturing method of the emulsion-silica composite capsule concerning this invention is 0.1-30.0 mass% of surfactant, water, oil, and the water-soluble silane derivative 0 shown by following General formula (1). 0.1-20.0% by mass, and the emulsion / silica composite capsule in which the outer periphery of the O / W or W / O emulsion particles is coated with silica is dispersed in the outer phase. It is what.
Si- (OR ¹ ) ₄ (1)
(In the formula, ^{R 1} are both Ru polyhydric alcohol residue der.)

  According to the present invention, by mixing a substance capable of forming micelles in water and a specific water-soluble silane derivative in an aqueous solution, a micelle-silica composite capsule can be easily obtained in an aqueous system. The obtained aqueous composition is transparent and the appearance of the composition is very excellent. Further, according to the present invention, an emulsion-silica composite in which the periphery of the emulsion particles in the inner phase is coated with silica by mixing a surfactant, water, oil, and a water-soluble silane derivative having a specific structure. Capsules are easily obtained.

A micelle-silica composite capsule according to the present invention is obtained by mixing a substance capable of forming a micelle in water and a water-soluble silane derivative represented by the following general formula (1) in an aqueous solution. It is what
Si- (OR ¹ ) ₄ (1)
(In the formula, at least one R ¹ may be a polyhydric alcohol residue, and the other may be an alkyl group.)

Micelle-forming substance A substance capable of forming micelles in water (hereinafter simply referred to as a micelle-forming substance) is not particularly limited, but representative examples include anionic surfactants and cationic surfactants. And various surfactants such as amphoteric surfactants and nonionic surfactants.

Surfactant anionic surfactants include, for example, fatty acid soaps (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate); alkyl ether sulfates (Eg, POE-lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.); N-acyl sarcosine acid (eg, sodium lauroyl sarcosine, etc.); higher fatty acid amide sulfonate (eg, N-myristoyl-N-methyl taurine) Sodium, coconut oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc.); phosphate ester salts (POE-oleyl ether sodium phosphate, POE-stearyl ether phosphate, etc.); Acid salts (eg, sodium di-2-ethylhexyl sulfosuccinate, sodium monolauroyl monoethanolamide polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); alkyl benzene sulfonates (eg, sodium linear dodecyl benzene sulfonate, linear Dodecylbenzenesulfonic acid triethanolamine, linear dodecylbenzenesulfonic acid, etc.); higher fatty acid ester sulfates (for example, hydrogenated coconut oil fatty acid sodium glycerin sulfate, etc.); N-acyl glutamates (for example, monosodium N-lauroyl glutamate, Disodium N-stearoyl glutamate, monosodium N-myristoyl-L-glutamate, etc.); sulfated oil (eg funnel oil, etc.); OE-alkyl ether carboxylic acid; POE-alkyl allyl ether carboxylate; α-olefin sulfonate; higher fatty acid ester sulfonate; secondary alcohol sulfate ester salt; higher fatty acid alkylolamide sulfate ester; lauroyl monoethanolamide Sodium succinate; N-palmitoyl aspartate ditriethanolamine; sodium caseinate and the like.

  Examples of the cationic surfactant include alkyltrimethylammonium salts (eg, stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (eg, cetylpyridinium chloride, etc.); distearyldimethylammonium dialkyldimethylammonium chloride; Poly (N, N′-dimethyl-3,5-methylenepiperidinium chloride); alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkyl morpholinium salt; POE-alkylamine; Examples include alkylamine salts; polyamine fatty acid derivatives; amyl alcohol fatty acid derivatives; benzalkonium chloride; benzethonium chloride and the like.

  Examples of amphoteric surfactants include imidazoline-based amphoteric surfactants (eg, 2-undecyl-N, N, N- (hydroxyethylcarboxymethyl) -2-imidazoline sodium, 2-cocoyl-2-imidazolinium hydroxide). Side-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylaminoacetic acid betaine, alkylbetaine, amide betaine) , Sulfobetaine, etc.).

  Examples of the lipophilic nonionic surfactant include sorbitan fatty acid esters (for example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, Sorbitan trioleate, diglycerol sorbitan penta-2-ethylhexylate, diglycerol sorbitan tetra-2-ethylhexyl); glycerin polyglycerin fatty acids (for example, mono-cotton oil fatty acid glycerin, mono-erucic acid glycerin, sesquioleate glycerin, monostearin) Glycerin acid, α, α′-oleic acid pyroglutamate glycerin, monostearate glycerin malate, etc.); propylene glycol fatty acid esters (for example, And propylene glycol monostearate); hardened castor oil derivatives; glycerin alkyl ethers and the like.

  Examples of the hydrophilic nonionic surfactant include POE-sorbitan fatty acid esters (for example, POE-sorbitan monooleate, POE-sorbitan monostearate, POE-sorbitan monooleate, POE-sorbitan tetraoleate). POE sorbite fatty acid esters (eg, POE-sorbite monolaurate, POE-sorbite monooleate, POE-sorbite pentaoleate, POE-sorbite monostearate, etc.); POE-glycerin fatty acid esters (eg, POE- Glycerol monostearate, POE-glycerol monoisostearate, POE-monooleate such as POE-glycerol triisostearate, etc.); POE-fatty acid esters (eg POE-distearate, P E-monodiolate, ethylene glycol distearate, etc.); POE-alkyl ethers (for example, POE-lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldecyl ether, POE cholesteryl ether) , POE phytosterol ether, etc.); Pluronic type (for example, Pluronic etc.); POE • POP-alkyl ethers (for example, POE • POP-cetyl ether, POE • POP-2-decyltetradecyl ether, POE • POP-mono) Butyl ether, POE / POP-hydrogenated lanolin, POE / POP-glycerin ether, etc.); tetra-POE / tetra-POP-ethylenediamine condensates (eg Tetronic, etc.); POE- Castor oil hardened castor oil derivatives (eg POE-castor oil, POE-hardened castor oil, POE-hardened castor oil monoisostearate, POE-hardened castor oil triisostearate, POE-hardened castor oil monopyroglutamic acid monoisostearate Acid diesters, POE-hardened castor oil maleic acid, etc.); POE-beeswax lanolin derivatives (eg POE-sorbite beeswax etc.); alkanolamides (eg coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.) POE-propylene glycol fatty acid ester; POE-alkylamine; POE-fatty acid amide; sucrose fatty acid ester; alkylethoxydimethylamine oxide; trioleyl phosphoric acid and the like.

  Further, in the micelle-silica composite capsule of the present invention, a nonionic surfactant can be suitably used as the micelle-forming substance, and among them, a nonionic surfactant having a hydrophilic group having a branched chain can be used. It can be particularly preferably used. Specific examples of the hydrophilic group having a branched chain include a polyoxypropylene group. When using a nonionic surfactant having a branched hydrophilic group, for example, compared to using a nonionic surfactant having only a linear hydrophilic group such as a polyoxyethylene group. It is difficult to cause solidification of the bulk phase and it is possible to react with a larger amount of the water-soluble silane derivative.

  In the micelle-silica composite capsule of the present invention, the micelle-forming substance needs to be used in such a concentration that micelles are formed in an aqueous solution and the micelles can be dispersed transparently. The concentration at which micelles start to be formed is called a critical micelle concentration (CMC), and is a specific value corresponding to the type of various micelle-forming substances. For example, there have been many reports on the critical micelle concentration (CMC) in any surfactant, and most surfactants can be obtained as needed. is there.

  Moreover, in the micelle-silica composite capsule of the present invention, it may be in the state of a micelle swelling solution in which any water-insoluble component is solubilized in the micelle. For example, when the micelle-forming substance is a surfactant, it can be a micelle swelling solution in which oil is solubilized in the surfactant micelle. In such a case, a micelle in which oil is encapsulated in the micelle- Obtained as a silica composite capsule. Moreover, as this capsule inclusion component, it can select suitably and mix | blend according to the objective, such as a chemical | medical agent and a coating material.

  For example, when any insoluble component is solubilized in a surfactant, the micellar swelling solution generally depends on whether the solubilizing system is thermodynamically stable (one-phase system) or unstable (two-phase system). And emulsion. And in this invention, it is also possible to form an emulsion-silica composite capsule as an emulsion formed with surfactant similarly to the said micelle-silica composite capsule.

The emulsion-silica composite capsule, that is, the emulsion-silica composite capsule according to the present invention is obtained by mixing a surfactant, water, oil, and a water-soluble silane derivative represented by the above general formula (1). Is.

  Moreover, what was enumerated above can be used as surfactant used for the emulsion-silica composite capsule concerning this invention. As the surfactant, a nonionic surfactant can be preferably used, and among them, a nonionic surfactant having a hydrophilic group having a branched chain can be particularly preferably used.

  Moreover, the oil component used for the emulsion-silica composite capsule concerning this invention is not specifically limited, The oil component used in general cosmetics can be used. For example, silicone oil, synthetic, natural ester oil, or hydrocarbons can be used. These oils may be used alone or in combination of two or more.

  In the emulsion-silica composite capsule of the present invention, the surfactant, water, and oil are used in concentrations capable of forming an emulsion. The form of the emulsion may be either an O / W emulsion in which an oil phase is emulsified and dispersed in an outer aqueous phase, or a W / O emulsion in which an aqueous phase is emulsified and dispersed in an outer oil phase. More preferably, it is an emulsion. In the case of an O / W emulsion, an emulsion-silica composite capsule in which the outer periphery of an emulsion particle containing an oil component is coated with silica is obtained. On the other hand, in the case of a W / O emulsion, an emulsion particle containing an aqueous component inside An emulsion-silica composite capsule whose inner periphery is coated with silica is obtained. In these emulsions, an aqueous or oily drug or paint can be appropriately blended as a capsule inclusion component.

  In the production method of the present invention, the preferred concentration of the micelle-forming substance (surfactant) varies depending on the type of micelle-forming substance (surfactant), but is 0.1 to 30 in the total amount of the composition. It is preferably used in the range of 0.0 mass%. In order to preferentially advance the polymerization of silica around micelles (emulsions) and prepare silica composite capsules, a certain number of micelles (emulsion particles) are dispersed in an aqueous solution at a certain interval. Need to be. For this reason, when it is less than 0.1% by mass, the number of micelles (emulsion particles) in the aqueous solution is too small, and an excessive water-soluble silane derivative may be polymerized in the bulk phase and solidify the entire system. On the other hand, if it exceeds 30.0% by mass, micelles (emulsions) are too close to each other and are connected in the course of silica polymerization to form a network, resulting in solidification of the entire system.

Water-soluble silane derivative The water-soluble silane derivative is represented by the general formula (1). In the water-soluble silane derivative represented by the general formula (1), at least one R ¹ may be a polyhydric alcohol residue, and the other may be an alkyl group. The polyhydric alcohol residue is shown as a form in which one hydroxyl group in the polyhydric alcohol is removed. The water-soluble silane derivative can usually be prepared by a substitution reaction between tetraalkoxysilane and a polyhydric alcohol, and the polyhydric alcohol residue of R ¹ varies depending on the type of polyhydric alcohol used. When ethylene glycol is used as the polyhydric alcohol, R ¹ becomes —CH ₂ —CH ₂ —OH. Note that at least one of R ¹ may be a substituted polyhydric alcohol residue, and the other may be an unsubstituted alkyl group.

Examples of the R ¹ polyhydric alcohol residue in the general formula (1) include an ethylene glycol residue, a diethylene glycol residue, a triethylene glycol residue, a tetraethylene glycol residue, a polyethylene glycol residue, and a propylene glycol residue. , Dipropylene glycol residue, polypropylene glycol residue, butylene glycol residue, hexylene glycol residue, glycerin residue, diglycerin residue, polyglycerin residue, neopentyl glycol residue, trimethylolpropane residue, penta An erythritol residue, a maltitol residue, etc. are mentioned. Among these, it is preferable that R ¹ is any one of an ethylene glycol residue, a propylene glycol residue, a butylene glycol residue, and a glycerin residue.

More specifically, examples of the water-soluble silane derivative used in the present invention include Si— (O—CH ₂ —CH ₂ —OH) ₄ and Si— (O—CH ₂ —CH ₂ —CH ₂ —OH) _4. , Si— (O—CH ₂ —CH ₂ —CHOH—CH ₃ ) ₄ , Si— (O—CH ₂ —CHOH—CH ₂ —OH) _{4 and the} like.

  The water-soluble silane derivative used in the present invention can be prepared, for example, by reacting a tetraalkoxysilane and a polyhydric alcohol in the presence of a solid catalyst.

  The tetraalkoxysilane is not particularly limited as long as four alkoxy groups are bonded to a silicon atom. Examples of the tetraalkoxysilane used for the production of the water-soluble silicate monomer include tetramethoxysilane, tetraethoxysilane, tetraisopropoxysilane, tetrapropoxysilane, and tetrabutoxysilane. Of these, tetraethoxysilane is most preferable from the viewpoint of availability and safety of reaction by-products.

  As an alternative compound of tetraalkoxysilane, mono, di, or trihalogenated alkoxysilane such as monochlorotriethoxysilane, dichlorodimethoxysilane, monobromotriethoxysilane, or the like, or tetrahalogenated silane such as tetrachlorosilane or the like may be used. However, since these compounds produce strong acids such as hydrogen chloride and hydrogen bromide in the reaction with polyhydric alcohols, corrosion of the reactor occurs, and separation and removal after the reaction are difficult. Therefore, it is hard to say that it is practical.

  The polyhydric alcohol is not particularly limited as long as it is a compound having two or more hydroxyl groups in the molecule. Examples of the polyhydric alcohol used in the production of the water-soluble silicate monomer include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexylene glycol, and glycerin. , Diglycerin, polyglycerin, neopentyl glycol, trimethylolpropane, pentaerythritol, maltitol and the like. Among these, it is preferable to use any of ethylene glycol, propylene glycol, butylene glycol, and glycerin.

  The solid catalyst is a solid catalyst that is insoluble in the raw material components, reaction solvent, and reaction product to be used, and has an acid site and / or a base site having activity for a substituent exchange reaction on a silicon atom. What is necessary is just solid. Examples of the solid catalyst used in the present invention include an ion exchange resin and various inorganic solid acid / base catalysts.

  Examples of the ion exchange resin used as the solid catalyst include acidic cation exchange resins and basic anion exchange resins. Examples of the resin that forms the base of these ion exchange resins include styrene-based, acrylic-based, and methacrylic-based resins, and functional groups that exhibit catalytic activity include sulfonic acid, acrylic acid, methacrylic acid, quaternary ammonium, And secondary amines. The substrate structure of the ion exchange resin can be selected from a gel type, a porous type, a bipolar type, and the like according to the purpose.

  Examples of acidic cation exchange resins include Amberlite IRC76, FPC3500, IRC748, IRB120B Na, IR124 Na, 200CT Na (above, manufactured by Rohm and Haas), Diaion SK1B, PK208 (above, manufactured by Mitsubishi Chemical Corporation), Dow EX monosphere 650C, Marathon C, HCR-S, Marathon MSC (above, manufactured by Dow Chemical Co., Ltd.) and the like. Examples of the basic anion exchange resin include Amberlite IRA400J CL, IRA402BL CL, IRA410J CL, IRA411 CL, IRA458RF CL, IRA900J CL, IRA910CT CL, IRA67, IRA96SB (above, manufactured by Rohm and Haas), Dia Ion SA10A, SAF11AL, SAF12A, PAF308L (manufactured by Mitsubishi Chemical Corporation), Dow EX monosphere 550A, marathon A, marathon A2, marathon MSA (manufactured by Dow Chemical Co., Ltd.) and the like.

The inorganic solid acid / base catalyst used as the solid catalyst is not particularly limited. Examples of the inorganic solid acid catalyst include single metal oxides such as Al ₂ O ₃ , SiO ₂ , ZrO ₂ , TiO ₂ , ZnO, MgO, Cr ₂ O ₃ , SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO _2. , SiO ₂ —ZrO ₂ , TiO ₂ —ZrO ₂ , ZnO—Al ₂ O ₃ , Cr ₂ O ₃ —Al ₂ O 3, SiO ₂ —MgO, ZnO—SiO _{2 and} other complex metal oxides, NiSO ₄ , FeSO _4, etc. of the metal sulfates, metal phosphates such as _{FePO 4, H 2 SO 4 /} SiO 2 or the like immobilized sulfuric _acid, H ₂ PO 4 / SiO ₂ or the like immobilized phosphoric _acid, H ₃ BO ₃ / SiO ₂ immobilization boric acid etc., activated clay, zeolite, kaolin, natural mineral or layered compounds such as montmorillonite, AlPO ₄ - synthetic zeolites such as _{zeolite, H 3 PW 12 O 40 ·} 5H 2 , Such heteropoly acids such as _H 3 _PW 12 _{O 40} and the like. Examples of the inorganic solid base catalyst include single metal oxides such as Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O, MgO, CaO, SrO, BaO, La ₂ O ₃ , ZrO ₃ , and ThO ₃ . , Na ₂ CO ₃ , K ₂ CO ₃ , KHCO ₃ , KNaCO ₃ , CaCO ₃ , SrCO ₃ , BaCO ₃ , (NH ₄ ) ₂ CO ₃ , Na ₂ WO ₄ .2H ₂ O, metal salt such as KCN, Na -Al ₂ O _3, K-SiO alkali metal supported metal oxide such as _2, Na-alkali metal-loaded zeolite such as _{mordenite, SiO 2 -MgO, SiO 2 -CaO} , SiO 2 -SrO, SiO 2 -ZnO, SiO _{2 -Al 2 O 3, SiO 2} -ThO 2, SiO 2 -TiO 2, SiO 2 -ZrO 2, SiO 2 -MoO 3, SiO 2 -WO, Al 2 O ₃ —MgO, Al ₂ O ₃ —ThO ₂ , Al ₂ O ₃ —TiO ₂ , Al ₂ O ₃ —ZrO ₂ , ZrO ₂ —ZnO, ZrO ₂ —TiO ₂ , TiO ₂ —MgO, ZrO ₂ —SnO ₂ And composite metal oxides.

  The solid catalyst can be easily separated from the product by a treatment such as filtration or decantation after completion of the reaction.

  In the production of the water-soluble silane derivative, a solvent may not be used during the reaction, but various solvents may be used as necessary. The solvent used in the reaction is not particularly limited, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, esters such as ethyl acetate, methyl acetate, acetone, methyl ethyl ketone, cellosolve, diethyl ether and dioxane, ethers, and the like. , Ketone solvents, polar solvents such as acetonitrile, dimethylformamide and dimethyl sulfoxide, and halogen solvents such as chloroform and dichloromethane. Here, in order to suppress the hydrolysis and condensation reaction of the tetraalkoxysilane used as a raw material, the solvent is preferably dehydrated in advance. Among these, it is preferable to use acetonitrile, toluene, or the like that can accelerate the reaction by forming an azeotrope with an alcohol such as ethanol that is by-produced during the reaction and removing it from the system.

  In the production method of the present invention, the concentration of the water-soluble silane derivative is not particularly limited, but it is preferably used in the range of 0.1 to 20.0% by mass in the total amount of the composition. If it is less than 0.1% by mass, it may not be sufficient to coat the periphery of the micelle (emulsion) with silica, and if it exceeds 20.0% by mass, polymerization of silica occurs in the bulk phase, and the system The whole may be solidified.

  In the method for producing a micelle-silica composite capsule of the present invention, a micelle-silica composite capsule in which the outer periphery of a micelle made of a micelle-forming substance is coated with silica is obtained as an aqueous transparent composition dispersed in an aqueous phase. The particle size of the micelle-silica composite capsule obtained by the production method of the present invention is about 4 to 20 nm, although it varies depending on the type of micelle-forming substance. Further, the micelle-silica composite capsule according to the present invention may be used as it is as the obtained aqueous transparent composition, or may be separately used by performing a filtration operation or the like to take out only the micelle-silica composite capsule. I do not care.

  Similarly, in the method for producing the emulsion-silica composite capsule of the present invention, the emulsion / silica composite capsule in which the periphery of the O / W or W / O emulsion particles is coated with silica is emulsified and dispersed in the outer phase. Obtained as an emulsion composition. The particle size of the emulsion-silica composite capsule obtained by the production method of the present invention is not particularly limited, but is usually about 0.1 to 50 μm. In addition, the emulsion-silica composite capsule according to the present invention may be used as it is as an emulsion composition, or may be separately used by performing a filtration operation or the like and taking out only the emulsion-silica composite capsule.

  In the production method of the present invention, in the aqueous solution, in addition to the micelle-forming substance (surfactant) and the water-soluble silane derivative, which are essential components, a range that does not impair the effects of the present invention, that is, the silica composite of the present invention. Other components may be blended as long as capsules can be formed. For example, when the water-based transparent composition or emulsion composition obtained by the production method of the present invention is used as it is as a cosmetic or pharmaceutical product, it is usually used as a base component or additive component for cosmetics or pharmaceutical products. Moisturizer, gelling agent, water-soluble polymer, sugar, UV absorber, amino acids, vitamins, drugs, plant extracts, organic acids, organic amines, sequestering agents, antioxidants, antibacterial agents, preservatives , Fresheners, fragrances, emollients, pigments and the like may be blended. In addition, whitening agents, anti-wrinkle agents, anti-aging agents, anti-inflammatory agents, hair growth agents, hair growth promoters, proteolytic enzymes and other medicinal ingredients used for the purpose of imparting functionality to cosmetics, etc. Steroids, anti-inflammatory agents including non-steroidal agents, immunosuppressive agents, analgesic / antiinflammatory agents, antibacterial agents, antifungal agents, antiviral agents, antitumor agents, anti-ulcer / decubitus agents, wound dressings, circulation improving agents , Antidiarrheal agents, local anesthetics, sickness agents, nicotine agents, female hormone agents, and the like. Moreover, you may mix | blend the said various component in the water-based transparent composition or emulsion composition previously prepared with the manufacturing method of this invention, and may use it as cosmetics, a pharmaceutical, etc.

  Moreover, in the water-based transparent composition or emulsion composition concerning this invention, the polyhydric alcohol produced | generated in the hydrolysis and dehydration condensation process of a water-soluble silane derivative is contained. As the polyhydric alcohol, depending on the type of water-soluble silane derivative used, for example, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, Examples include hexylene glycol, glycerin, diglycerin, polyglycerin, neopentyl glycol, trimethylolpropane, pentaerythritol, and maltitol. These polyhydric alcohols are widely used in cosmetics, pharmaceuticals, etc., for example, as moisturizer components, etc., and the water-based transparent composition or emulsion composition according to the present invention contains special components. Without blending separately, it has various effects such as moisture retention derived from the polyhydric alcohol produced in the silica polymerization process.

  In the aqueous transparent composition according to the present invention, “transparent” means that light is transmitted to such an extent that the back side can be recognized when the composition is observed from a certain direction. The water-based transparent composition according to the present invention does not need to be completely colorless, and may be transparent in a state excluding colorants such as dyes and pigments. More specifically, when a cell having an optical path length of 10 mm is filled and the transmittance of light having a wavelength of 550 nm is measured with a spectrophotometer, the transmittance is at least 5% or more.

  Water-based transparent composition according to the present invention The usage of the water-based transparent composition or emulsion composition is not particularly limited. For example, cosmetics such as a facial cleanser, foundation foundation, cosmetic liquid, milky lotion, cream, make-up, etc. It can be applied to various products in addition to a preparation, a cataplasm, a transdermal drug-containing preparation, and the like.

Hereinafter, the present invention will be described in more detail with reference to specific examples, but the present invention is not limited to these examples.
First, a method for producing a water-soluble silane derivative used in the present invention will be described.

Synthesis Example 1: 20.8 g (0.1 mol) of an ethylene glycol-substituted silane derivative tetraethoxysilane and 24.9 g (0.4 mol) of ethylene glycol were added to 150 ml of acetonitrile, and a strongly acidic ion as a solid catalyst. After adding 1.8 g of exchange resin (DowEX 50W-X8: manufactured by Dow Chemical Co., Ltd.), the mixture was stirred at room temperature. Initially, the reaction solution separated into two layers was uniformly dissolved after about one hour. Then, after stirring for 5 days, the solid catalyst was separated by filtration, and ethanol and acetonitrile were distilled off under reduced pressure to obtain 39 g of a transparent viscous liquid. As a result of ¹ H-NMR analysis, it was confirmed that the product was the target ethylene glycol-substituted product (tetra (2-hydroxyethoxy) silane) (yield: 72.5%).

Synthesis Example 2: 60.1 g (0.28 mol) of glycerin-substituted silane derivative tetraethoxysilane and 106.33 g (1.16 mol) of glycerin were mixed, and a strongly acidic ion exchange resin (as a solid catalyst without solvent) ( 1.1 g of DowEX 50W-X8 (manufactured by Dow Chemical Co., Ltd.) was added, and the mixture was stirred at 85 ° C. After about 3 hours, the mixture became a more clear solution. The reaction was further continued for 5 hours and 30 minutes, and then the resulting solution was allowed to stand overnight. The solid catalyst was separated by filtration under reduced pressure, and then washed with a small amount of ethanol. Further, ethanol was distilled off from this solution to obtain 112 g of a transparent viscous liquid. The product was slightly exothermic when mixed with the same amount of water at room temperature to form a uniform and transparent gel (yield: 97%).

  The present inventors prepared a polyhydric alcohol-substituted water-soluble silane derivative according to the above synthesis example, mixed various surfactants and the water-soluble silane derivative in an aqueous solution, and examined the resulting composition. Was done. The contents of the test are as follows. The results are shown in FIGS.

<contents of the test>
Using various surfactants and polyhydric alcohol-substituted silane derivatives in the combinations shown in the following (1) to (6), changing the respective concentrations and stirring and mixing in an aqueous solution, the state of the composition after 4 days Was observed visually.
(1) Surfactant: Polyoxyethylene (60 mol) hydrogenated castor oil (Nikkor HCO-60: manufactured by Nikko Chemicals)
Water-soluble silane derivative: ethylene glycol substituted silane derivative (2) Surfactant: polyoxyethylene (24 mol) polyoxypropylene (13 mol) 2-decyltetradecyl ether (Essafe 1324 (D): manufactured by NOF Corporation)
Water-soluble silane derivative: Glycerin substituted silane derivative

(3) Surfactant: Polyoxyethylene (20 mol) cetyl ether (Emalex 120: manufactured by Nippon Emulsion Co., Ltd.)
Water-soluble silane derivative: Glycerin substituted silane derivative (4) Surfactant: Polyoxyethylene (2 mol) sodium lauryl ether carboxylate (AKYPO PLM45NV: manufactured by Nikko Chemicals)
Water-soluble silane derivative: Glycerin substituted silane derivative

(5) Surfactant: Stearyl trimethyl ammonium chloride (Katinal TC-25AQ: manufactured by Toho Chemical Industries)
Water-soluble silane derivative: Glycerin substituted silane derivative (6) Surfactant: Polyoxyethylene (12 mol) modified dimethylpolysiloxane * 1 (SH3773M: manufactured by Dow Corning Silicone, HLB = 8)
Water-soluble silane derivative: Glycerin-substituted silane derivative * 1: A pendant-type polyoxyalkylene-modified silicone in which the side chain methyl group of a linear dimethylpolysiloxane is substituted with a polyoxyethylene (12 mol) group, accounting for the total molecular weight The molecular weight of ethylene oxide is 40%.

  As shown in FIGS. 1 to 6, when various surfactants and a polyhydric alcohol-substituted water-soluble silane derivative are mixed in an aqueous solution, the micelle-silica composite capsule is dispersed in the aqueous phase in a specific concentration range. It was revealed that a transparent or translucent aqueous composition was obtained. This is thought to be because a very fine micelle-silica composite capsule is formed because the polymerization reaction of silica by hydrolysis / dehydration condensation of a water-soluble silane derivative proceeds preferentially in the outer periphery of the micelle. . Further, any type of surface activity of nonionic surfactants (1) to (3), anionic surfactant (4), cationic surfactant (5), or silicone surfactant (6). Even in the case of the agent, it was confirmed that a transparent aqueous composition was obtained although the concentration ranges were different.

  In addition, the present inventors examined the change in the particle size of the micelle-silica composite capsule with respect to the amount of the water-soluble silane derivative added using a particle size distribution measuring apparatus by laser diffraction / scattering method. In addition, POE (24 mol) POP (13 mol) 2-decyltetradecyl ether was used as a surfactant, and a glycerin-substituted silane derivative was used as a water-soluble silane derivative, and the surfactant concentrations were 5% by mass and 15% by mass, respectively. A test was conducted. The results are shown in FIG.

  As shown in FIG. 7, when the addition amount of the water-soluble silane derivative is changed, the particle size of the particles existing in the composition is increased stepwise with the increase of the water-soluble silane derivative. Was confirmed. From this, it is recognized that the micelle-silica composite capsule in which the micelle is coated with silica is formed by the polymerization of silica in the outer periphery of the micelle formed in the aqueous solution.

  Subsequently, the present inventors investigated the change in the particle size of the micelle-silica composite capsule in the same manner as in the above test using different types of surfactants under the same concentration conditions. As the surfactant, POE (24 mol) POP (13 mol) 2-decyltetradecyl ether and POE (20 mol) cetyl ether, a glycerin-substituted silane derivative as the water-soluble silane derivative, and a surfactant concentration of 5 The test was conducted under the condition of mass%. The results are shown in FIG.

  As shown in FIG. 8, when POE (24 mol) POP (13 mol) 2-decyltetradecyl ether was used, compared to the case where POE (20 mol) cetyl ether of the same concentration was used, It was difficult to cause gelation of the bulk phase and it was possible to react with about 4 times the amount of water-soluble silane derivative. In addition, since the micelle in aqueous solution is formed with a hydrophilic group outside, the above results are deeply related to the structure of the hydrophilic group of the surfactant. That is, POE (20 mol) POP (13 mol) 2-decyltetradecyl ether has a polyoxypropylene group having a branched chain as a hydrophilic group. By having this branched chain hydrophilic group, more micelles are obtained. It is considered that the polymerization of silica in the outer periphery is likely to proceed.

  As described above, it has been clarified that a micelle-silica composite capsule can be easily obtained in an aqueous system by mixing a surfactant and a water-soluble silane derivative in an aqueous solution. Moreover, as a result of conducting the same test using various surfactants and water-soluble silane derivatives, the particle size of the obtained micelle-silica composite capsules was about 4 to 20 nm.

  Subsequently, the present inventors tried to prepare a silica composite capsule by mixing a water-soluble silane derivative in the same manner as in the above test in an emulsion state in which a surfactant, an oil component, and water were mixed. The contents of the test are as follows.

<contents of the test>
Polyoxyethylene (8 mol) glyceryl monoisostearate (Emalex GWIS-108: manufactured by Nippon Emulsion Co., Ltd.) 3% by mass, glycerin-substituted silane derivative 10% by mass, decamethylcyclopentasiloxane (Execol D-5: manufactured by Shin-Etsu Chemical Co., Ltd.) ) 5% by mass, cetyl 2-ethylhexanoate (Nikkor CIO: Nikko Chemicals) 5% by mass, ethanol (reagent special grade: Wako Pure Chemical Industries) 11% by mass, water 66% by homomixer (Made by Kogyo Co., Ltd.) with stirring and mixing (9000 rpm, 90 seconds) to obtain a cloudy O / W emulsion composition.

  In the O / W emulsion composition obtained above, the polymerization of silica proceeds in the outer periphery of the O / W emulsion particles emulsified and dispersed in the outer aqueous phase, as in the case of the micelle-silica composite capsule described above. Thus, it is considered that an emulsion-silica composite capsule in which the O / W emulsion particles are coated with silica is formed.

Hereinafter, the present invention will be described in more detail with reference to other examples of the aqueous transparent composition and the emulsion composition according to the present invention, but the present invention is not limited thereto.
Example 2-1 Lotion (mass%)
Water 88.045
Glycerin 2
1,3-butylene glycol 2
Citric acid 0.02
Na citrate 0.08
EDTA3Na · 2H ₂ O 0.05
Methylparaben 0.15
Fragrance 0.005
Vitamin E acetate 0.05
Ascorbic acid glucoside 2
POE (60 mol) hydrogenated castor oil 1.6
Ethylene glycol substituted water-soluble silane derivatives 4

Example 2-2 Lotion (mass%)
Water 88.045
Glycerin 2
1,3-butylene glycol 2
Citric acid 0.02
Na citrate 0.08
EDTA3Na · 2H ₂ O 0.05
Methylparaben 0.15
Fragrance 0.005
Vitamin E acetate 0.05
Ascorbic acid glucoside 2
POE (24 mol) POP (13 mol)
2-decyltetradecyl ether 5
Glycerin-substituted water-soluble silane derivative 5

  The lotion obtained in Examples 2-1 and 2-2 was transparent, and the micelle-silica composite capsule particles were dispersed in the aqueous phase.

Example 2-3 Latex (mass%)
Water 74.75
POE (20) stearyl ether 2
Decamethylcyclopentasiloxane 5
Dimethylsiloxane (6cs) 7
Squalane 5
Glyceryl tri-2-ethylhexanoate 3
Citric acid 0.01
Sodium citrate 0.09
Methylparaben 0.15
Ethylene glycol substituted water-soluble silane derivatives 3

Example 2-4 Latex (mass%)
Water 71.25
POE (20) stearyl ether 2
Decamethylcyclopentasiloxane 5
Dimethylsiloxane (6cs) 7
Squalane 5
Glyceryl tri-2-ethylhexanoate 3
Octyl methoxycinnamate 3
t-Butylmethoxydibenzoylmethane 0.5
Citric acid 0.01
Sodium citrate 0.09
Methylparaben 0.15
Glycerin-substituted water-soluble silane derivative 3

  The emulsions obtained in Examples 2-3 and 2-4 were all O / W emulsions, and emulsion-silica composite capsule particles were emulsified and dispersed in the outer aqueous phase.

It is the figure which put together the result of having observed the state of the composition obtained by changing each density | concentration variously about polyoxyethylene hydrogenated castor oil / ethylene glycol substituted silane derivative aqueous solution. The results of observing the state of the composition obtained by changing various concentrations of polyoxyethylene (24 mol) polyoxypropylene (13 mol) 2-decyltetradecyl ether / glycerin-substituted silane derivative aqueous solution are summarized. FIG. It is the figure which put together the result of having observed the state of the composition obtained by changing each density | concentration variously about polyoxyethylene (20 mol) cetyl ether / glycerol substituted silane derivative aqueous solution. It is the figure which put together the result of having observed the state of the composition obtained by changing each density | concentration variously about polyoxyethylene (2 mol) sodium lauryl ether carboxylate / glycerol substituted silane derivative aqueous solution. It is the figure which put together the result of having observed the state of the composition obtained by changing each density | concentration variously about stearyl trimethyl ammonium chloride / glycerol substituted silane derivative aqueous solution. It is the figure which put together the result of having observed the state of the composition obtained by changing each density | concentration variously about polyoxyethylene (12 mol) modified dimethylpolysiloxane / glycerol substituted silane derivative aqueous solution. Mice for POE (24 mol) POP (13 mol) 2-decyltetradecyl ether and glycerin-substituted silane derivative with respect to the addition amount of water-soluble silane derivative under the conditions of surfactant concentrations of 5 mass% and 15 mass% It is the figure which put together the result investigated about the change of the particle size of a silica composite capsule. Addition of water-soluble silane derivative using POE (24 mol) POP (13 mol) 2-decyltetradecyl ether or POE (20 mol) cetyl ether and glycerin substituted silane derivative under the condition of surfactant concentration of 5% by mass It is the figure which put together the result investigated about the change of the particle size of the micelle-silica composite capsule with respect to quantity.

Claims (2)

0.1 to 30.0% by mass of a substance capable of forming micelles in water and 0.1 to 20.0% by mass of a water-soluble silane derivative represented by the following general formula (1) are mixed in an aqueous solution , A micelle-silica composite capsule containing a micelle-silica composite capsule in which a micelle-silica composite capsule whose outer periphery is coated with silica is dispersed in an aqueous phase. A method for producing an aqueous transparent composition .
Si- (OR ¹ ) ₄ (1)
(In the formula, ^{R 1} are both Ru polyhydric alcohol residue der.) Surfactant 0.1-30.0 mass% , water, oil, and water-soluble silane derivative 0.1-20.0 mass% shown by following General formula (1) are mixed , and O / W An emulsion-silica composite capsule- containing transparent composition , characterized in that an emulsion-silica composite capsule in which the outer periphery of W / O emulsion particles is coated with silica is dispersed in the external phase Manufacturing method.
Si- (OR ¹ ) ₄ (1)
(In the formula, ^{R 1} are both Ru polyhydric alcohol residue der.)

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