JP4847762B2 - Cationic polymer adsorbing powder, thin film-coated powder and skin external preparation containing the same - Google Patents

Description

  The present invention relates to a cationic polymer adsorbed powder, a thin film-coated powder, and a skin external preparation containing the same, and more particularly to a cationic polymer serving as a polymerization initiator.

Techniques for coating thin films of different materials on solid surfaces such as metal oxides and resins are important techniques in various industrial fields.
As a technique for forming a thin film with a controlled film thickness on the surface of a solid substrate, a layer-by-layer method (electrostatic alternating lamination method) in which polycations and polyanions are alternately laminated is known. This method utilizes the phenomenon that polyions having opposite charges are irreversibly adsorbed on the surface of a solid substrate that is charged in a liquid. Since nanoscale thin films can be formed by extremely simple operations, various methods are available. Widely used in various fields.
JP 05-339387 A

However, in the above method, since the film thickness increase in a single operation is several nm, in order to construct a film having a thickness exceeding 100 nm, it is necessary to repeat the operation many times and it takes a long time. There were drawbacks.
The present invention has been made in view of the above-described conventional problems, and an object thereof is to construct a polymer thin film exceeding 100 nm in a short time by a simple operation.

As a result of intensive studies by the present inventors in view of the above problems, it is possible to easily obtain a polymer thin film exceeding 100 nm by using a cationic polymer in which a nitrogen atom of a polyamine compound is quaternized with a specific compound. I found it.
That is, the first subject of the present invention is a cationic polymer in which some or all of the nitrogen atoms of the polyamine compound are quaternized with a compound represented by the following general formula (I), and the ζ potential is negative. It is a cationic polymer adsorbing powder characterized by being adsorbed on the surface of a certain base powder.
(Chemical formula 1)
(Wherein X is a halogen atom, n is an integer of 1 to 20, and m is an integer of 1 to 20)

Further, after the polyamine compound is adsorbed on the surface of the base powder having a negative ζ potential, a part or all of the nitrogen atoms of the polyamine compound are quaternized with the compound represented by the general formula (I). It is a cationic polymer adsorbing powder characterized by having become.
The measurement method of ζ potential is as follows.
After the sample was dispersed and sonicated in 1M tris / HCl buffer having a pH of 7.5 manufactured by Wako Pure Chemical Industries, the supernatant liquid left for 18 hours was used for the measurement. The zeta potential was measured at 25 ° C. using an electrophoretic light scattering photometer LEZA-600 manufactured by Otsuka Electronics Co., Ltd. The measurement was performed three times, and the result was expressed as an average value.
The second subject of the present invention is a thin film-coated powder characterized in that monomer molecules are polymerized on the surface of the cationic polymer adsorbed powder to form a thin film.
The third subject of the present invention is a skin external preparation containing the cationic polymer adsorbing powder and a skin external preparation containing the thin film-coated powder.

  According to the present invention, by using a cationic polymer obtained by quaternizing a nitrogen atom of a polyamine compound with a specific compound as a polymerization initiator, a polymer thin film having a thickness of 100 nm or more can be obtained in a short time with a simple operation. .

[1] Cationic polymer The cationic polymer in the present invention is a cationic polymer in which some or all of the nitrogen atoms of the polyamine compound are quaternized with a compound represented by the following general formula (I).
(Chemical formula 2)
In the compound represented by the general formula (I) of the present invention, n is an integer of 1 to 20, preferably 4 to 14, particularly preferably 6 to 11. m is an integer of 1 to 20, preferably 2. X is a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a chlorine atom or a bromine atom, particularly preferably a bromine atom.

  The constituent monomer of the polyamine compound used in the present invention may be any of primary amine, secondary amine, and tertiary amine, or a mixture thereof. Further, it may be either a polyaromatic amine compound such as poly (4-vinylpyridine) in which the hydrocarbon group contains an aromatic group, or a polychain amine compound such as polyallylamine in which the hydrocarbon group is in a chain form. Preferred is a polypyridine compound containing pyridine or a derivative thereof as a constituent monomer, and particularly poly (4-vinylpyridine). Moreover, it is preferable that the molecular weight of a polyamine compound is 1000-100,000. Copolymers of amine compounds and other compounds are also included in the polyamine compounds used in the present invention.

Next, although the suitable manufacturing method of the cationic polymer of this invention is demonstrated, a manufacturing method is not limited to this.
(Production method)
Compound 3 was synthesized from Compound 1 and Compound 2 by Reaction A, and then an acid chloride reaction (Reaction B) was performed using phosphorus pentachloride to synthesize Compound 4. Further, Compound 5 was synthesized by an esterification reaction shown in Reaction C. And the compound 6 which is a cationic polymer was synthesize | combined by the quaternization reaction of the obtained compound 5 and a polyamine compound.

[2] Cationic polymer adsorbed powder The cationic polymer adsorbed powder in the present invention can be obtained by adsorbing a cationic polymer on a base powder.
Adsorption of the cationic polymer onto the base powder utilizes a phenomenon in which positively charged polyions are irreversibly adsorbed on the surface of a solid substrate that is negatively charged in the liquid. In general, since the surface of a solid is either positively or negatively charged in an aqueous solution, when the solid is immersed in an aqueous solution of polyion having the opposite charge for a certain period of time, electrostatic interaction between the solid and the polyion causes An adsorption phenomenon occurs and acts irreversibly on multiple points.

As the base powder, those having a negative ζ potential are preferable.
The powder placed in the medium is positively or negatively charged by adsorbing specific medium ions on the powder surface or transferring electrons to and from the medium. When an electric double layer composed of anions and cations is formed on the contact surface between the powder and the medium, a potential difference is generated between the double layers. This potential difference is referred to as ζ potential and is suitably used for evaluating the surface charge state of the object.
The method for measuring the ζ potential in the present invention is as follows.
After the sample was dispersed and sonicated in 1M tris / HCl buffer having a pH of 7.5 manufactured by Wako Pure Chemical Industries, the supernatant liquid left for 18 hours was used for the measurement. The zeta potential was measured at 25 ° C. using an electrophoretic light scattering photometer LEZA-600 manufactured by Otsuka Electronics Co., Ltd. The measurement was performed three times, and the result was expressed as an average value.

  In the present invention, the “base powder having a negative ζ potential” means silica, silicone resin, silicone rubber, silicone resin-coated silicone rubber, polyamide, polymethyl methacrylate, ethyl carbamate, mica, talc, sericite. Ζ potential of kaolin, titanium oxide, pearl mica, etc. (measured by electrophoresis at a temperature of 25 ° C. in 1M tris / HCl buffer of pH 7.5 manufactured by Wako Pure Chemical Industries) is negative. In addition to a certain powder, the ζ potential is originally near 0 or a positive value, and the surface is modified by the layer-by-layer method (electrostatic alternating lamination method) and measured by the same method as above. Also included are powders having a negative ζ potential.

Although the manufacturing method of the cationic polymer adsorption powder in this invention is demonstrated, it is not limited to these.
(Manufacturing method 1)
A cationic polymer having a polymerization initiator in the molecule in advance is synthesized as described above, and this is adsorbed on the surface of the base powder having a negative ζ potential.
(Manufacturing method 2)
After the polyamine compound is adsorbed on the surface of the base powder having a negative ζ potential, part or all of the nitrogen atoms of the polyamine compound are quaternized with the compound represented by the general formula (I). .

[3] Thin Film-Coated Powder The cationic polymer adsorbed powder of the present invention is in a state where polymerization initiators are scattered on the surface of the base powder. Therefore, when a polymer monomer solution is brought into contact with the powder surface and heat, light, etc. are applied, polymer polymerization starts on the powder surface to form a thin film, and the thin film-coated powder of the present invention is obtained. By adjusting the amount of monomer added in advance and the polymerization conditions, a polymer thin film having a thickness exceeding several tens of nanometers can be easily formed. If the cationic polymer is again adsorbed on the surface and polymerized with another monomer, a multilayer film composed of heterogeneous components in the Z-axis direction, that is, the film thickness direction of the thin film can be obtained.

[4] External preparation for skin In the external preparation for skin of the present invention, the amount of the cationic polymer adsorbed powder or the thin film-coated powder can be appropriately changed according to the desired form.
In the external preparation for skin of the present invention, other components usually used in external preparations for skin such as cosmetics and pharmaceuticals, for example, powder components, liquid fats and oils, solid fats, waxes, hydrocarbons, as long as the effects of the present invention are not impaired. , Higher fatty acids, higher alcohols, esters, silicones, anionic surfactants, cationic surfactants, amphoteric surfactants, nonionic surfactants, humectants, water-soluble polymers, thickeners, film agents, UV absorbers , Sequestering agents, lower alcohols, polyhydric alcohols, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, skin nutrients, vitamins, antioxidants, antioxidant aids, fragrances, water, etc. Depending on the intended dosage form, it can be prepared by conventional methods. Specific ingredients that can be blended are listed below, and the skin external preparation of the present invention can be prepared by blending the above essential blending ingredients and any one or more of the following ingredients.

  Examples of the powder component include inorganic powders (for example, talc, kaolin, sericite, muscovite, phlogopite, synthetic mica, saucite, biotite, permiculite, magnesium carbonate, calcium carbonate, aluminum silicate, Barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (baked gypsum), calcium phosphate, fluorine apatite, hydroxyapatite, ceramic powder, metal Soap (for example, zinc myristate, calcium palmitate, aluminum stearate), boron nitride, etc .; organic powder (for example, polyamide resin powder (nylon powder), polyethylene powder, polymethyl methacrylate powder, polystyrene powder, Tylene and acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.); inorganic white pigment (eg, titanium dioxide, zinc oxide, etc.); inorganic red pigment (eg, iron oxide) (Bengara), iron titanate, etc.); inorganic brown pigments (eg, γ-iron oxide, etc.); inorganic yellow pigments (eg, yellow iron oxide, ocher, etc.); inorganic black pigments (eg, black iron oxide, Inorganic purple pigments (eg, mango violet, cobalt violet, etc.); Inorganic green pigments (eg, chromium oxide, chromium hydroxide, cobalt titanate, etc.); Inorganic blue pigments (eg, ultramarine blue) Pearl pigments (eg, titanium oxide coated mica, titanium oxide coated bismuth oxychloride, titanium oxide coated talc, colored titanium oxide) Coated mica, bismuth oxychloride, fish scale foil, etc.); metal powder pigments (eg, aluminum powder, copper powder, etc.); organic pigments such as zirconium, barium or aluminum lake (eg, red 201, red 202, red 204, Organic pigments such as Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203, Orange 204, Yellow 205, Yellow 401, and Blue 404, Red 3, Red 104, Red 106, Red 227, Red 230, Red 401, Red 505, Orange 205, Yellow 4, Yellow 5, Yellow 202, Yellow 203, Green 3 and Blue 1 Etc.); natural pigments (for example, chlorophyll, β-carotene, etc.) and the like.

Examples of liquid oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, southern castor oil, castor oil, linseed oil , Safflower oil, cottonseed oil, eno oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnagiri oil, Japanese kiri oil, jojoba oil, germ oil, triglycerin and the like.
Examples of the solid fat include cacao butter, palm oil, horse fat, hydrogenated palm oil, palm oil, beef tallow, sheep fat, hydrogenated beef tallow, palm kernel oil, pork fat, beef bone fat, owl kernel oil, hydrogenated oil, cattle Leg fats, moles, hydrogenated castor oil and the like.

Examples of waxes include beeswax, candelilla wax, cotton wax, carnauba wax, bayberry wax, ibota wax, whale wax, montan wax, nuka wax, lanolin, kapok wax, lanolin acetate, liquid lanolin, sugar cane wax, lanolin fatty acid isopropyl, hexyl laurate, and reduced lanolin. , Jojoballow, hard lanolin, shellac wax, POE lanolin alcohol ether, POE lanolin alcohol acetate, POE cholesterol ether, lanolin fatty acid polyethylene glycol, POE hydrogenated lanolin alcohol ether, and the like.
Examples of the hydrocarbon oil include liquid paraffin, ozokerite, squalane, pristane, paraffin, ceresin, squalene, petrolatum, microcrystalline wax, and the like.
Examples of higher fatty acids include lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, oleic acid, undecylenic acid, toluic acid, isostearic acid, linoleic acid, linolenic acid, eicosapentaenoic acid (EPA), docosahexaenoic acid ( DHA) and the like.

Examples of higher alcohols include linear alcohols (eg, lauryl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol, myristyl alcohol, oleyl alcohol, cetostearyl alcohol); branched chain alcohols (eg, monostearyl glycerin ether (batyl alcohol) ), 2-decyltetradecinol, lanolin alcohol, cholesterol, phytosterol, hexyl decanol, isostearyl alcohol, octyldodecanol and the like.
Synthetic ester oils include isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyl decyl dimethyloctanoate, cetyl lactate, myristyl lactate Lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, monoisostearate N-alkyl glycol, neopentyl glycol dicaprate, apple Acid diisostearyl, di-2-heptylundecanoic acid glycerin, tri-2-ethylhexanoic acid trimethylolpropane, triisostearic acid trimethylo Propane, tetra-2-ethylhexanoate pentaerythritol, glycerol tri-2-ethylhexanoate, glycerol trioctanoate, glycerol triisopalmitate, trimethylolpropane triisostearate, cetyl 2-ethylhexanoate, 2-ethylhexyl palmi Tate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, castor oil fatty acid methyl ester, oleyl oleate, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamic acid-2 -Octyldodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate Le, diisopropyl sebacate, 2-ethylhexyl succinate, and triethyl citrate.

  Examples of the silicone oil include linear polysiloxanes (for example, dimethylpolysiloxane, methylphenylpolysiloxane, diphenylpolysiloxane, etc.); cyclic polysiloxanes (for example, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexyl). And silicone resins that form a three-dimensional network structure, various modified polysiloxanes (amino-modified polysiloxane, polyether-modified polysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, etc.) It is done.

  Anionic surfactants include, for example, fatty acid soaps (eg, sodium laurate, sodium palmitate, etc.); higher alkyl sulfates (eg, sodium lauryl sulfate, potassium lauryl sulfate, etc.); alkyl ether sulfates (eg, POE-lauryl sulfate triethanolamine, POE-sodium lauryl sulfate, etc.); N-acyl sarcosine acids (eg, sodium lauroyl sarcosine, etc.); higher fatty acid amide sulfonates (eg, sodium N-myristoyl-N-methyl taurate, palm Oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc .; phosphate ester salt (POE-oleyl ether sodium phosphate, POE-stearyl ether phosphate, etc.); sulfosuccinate (eg, di-2-ethylhexyl sulfo) Sodium succinate, monolauroyl monoethanolamide sodium polyoxyethylene sulfosuccinate, sodium lauryl polypropylene glycol sulfosuccinate, etc.); alkyl benzene sulfonates (eg, sodium linear dodecyl benzene sulfonate, triethanol amine linear dodecyl benzene sulfonate, linear dodecyl) Higher fatty acid ester sulfates (eg, hydrogenated coconut oil fatty acid sodium glycerol sulfate); N-acyl glutamate (eg, monosodium N-lauroyl glutamate, disodium N-stearoyl glutamate, N-myristoyl) -L-glutamic acid monosodium, etc.); sulfated oil (eg funnel oil); POE-alkyl ether carboxylic acid; POE-alkyl allyl ether Α-olefin sulfonates; higher fatty acid ester sulfonates; secondary alcohol sulfates; higher fatty acid alkylolamide sulfates; 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-ethylhexylate); glycerin polyglycerin fatty acids (eg mono cottonseed oil fatty acid glycerin, monoerucic acid glycerin, sesquioleate glycerin, monostearin) Glycerin acid, α, α'-oleic acid pyroglutamate glycerin, monostearic acid glycerin malic acid, etc.); propylene glycol fatty acid esters (eg monostearies) Propylene glycolate, etc.); hardened castor oil derivative; glycerin alkyl ether, etc.

  Examples of hydrophilic nonionic surfactants 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- POE-monooleate such as glycerol monostearate, POE-glycerol monoisostearate, POE-glycerol triisostearate); POE-fatty acid esters (eg POE-distearate, POE-monodiolate, ethylene glycol distearate, etc.) POE-alkyl ethers (eg POE- Lauryl ether, POE-oleyl ether, POE-stearyl ether, POE-behenyl ether, POE-2-octyldodecyl ether, POE-cholestanol ether, etc.); Pluronic type (eg, Pluronic, etc.); POE / POP-alkyl ether (For example, POE / POP-cetyl ether, POE / POP-2-decyltetradecyl ether, POE / POP-monobutyl 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 monoisostearic acid diester, POE-hardened castor oil maleic acid, etc.) POE-beeswax lanolin derivatives (eg POE-sorbite beeswax); 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; alkyl ethoxydimethylamine oxide; trioleyl phosphate and the like.

  Examples of the humectant include polyethylene glycol, propylene glycol, glycerin, 1,3-butylene glycol, xylitol, sorbitol, maltitol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate Sodium lactate, bile salt, dl-pyrrolidone carboxylate, alkylene oxide derivative, short-chain soluble collagen, diglycerin (EO) PO adduct, Izayoi rose extract, yarrow extract, merirot extract and the like.

  Examples of natural water-soluble polymers include plant-based polymers (for example, gum arabic, gum tragacanth, galactan, guar gum, carob gum, caraya gum, carrageenan, pectin, agar, quince seed (malmello), alge colloid (guckweed extract), starch (Rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (eg, xanthan gum, dextran, succinoglucan, bullulan, etc.); animal polymers (eg, collagen, casein, albumin, gelatin, etc.), etc. Is mentioned.

  Semi-synthetic water-soluble polymers include, for example, starch polymers (eg, carboxymethyl starch, methylhydroxypropyl starch, etc.); cellulose polymers (methylcellulose, ethylcellulose, methylhydroxypropylcellulose, hydroxyethylcellulose, sodium cellulose sulfate) Hydroxypropylcellulose, carboxymethylcellulose, sodium carboxymethylcellulose, crystalline cellulose, cellulose powder and the like); alginic acid polymers (for example, sodium alginate, propylene glycol alginate, etc.) and the like.

  Synthetic water-soluble polymers include, for example, vinyl polymers (eg, polyvinyl alcohol, polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl polymer); polyoxyethylene polymers (eg, polyethylene glycol 20,000, 40,000, 60,000). Polyoxyethylene polyoxypropylene copolymer, etc.); acrylic polymers (for example, sodium polyacrylate, polyethyl acrylate, polyacrylamide, etc.); polyethyleneimine; cationic polymers, and the like.

  Examples of the thickener include gum arabic, carrageenan, caraya gum, gum tragacanth, carob gum, quince seed (malmello), casein, dextrin, gelatin, sodium pectate, sodium alginate, methylcellulose, ethylcellulose, CMC, hydroxyethylcellulose, hydroxypropyl Cellulose, PVA, PVM, PVP, sodium polyacrylate, carboxyvinyl polymer, locust bean gum, guar gum, tamarind gum, cellulose dialkyldimethylammonium sulfate, xanthan gum, magnesium aluminum silicate, bentonite, hectorite, silicate A1Mg (vee gum), Examples thereof include laponite and silicic anhydride.

  Examples of UV absorbers include benzoic acid UV absorbers (eg, paraaminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N, N-dipropoxy PABA ethyl ester, N, N-diethoxy PABA ethyl ester. N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA butyl ester, N, N-dimethyl PABA ethyl ester, etc.); anthranilic acid-based UV absorbers (for example, homomenthyl-N-acetyl anthranilate, etc.); Salicylic acid ultraviolet absorbers (for example, amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isopropanol phenyl salicylate, etc.); cinnamic acid ultraviolet absorbers (for example, octylmethoxycinnamate, ethyl) -4-Isopropylcinname , Methyl-2,5-diisopropylcinnamate, ethyl-2,4-diisopropylcinnamate, methyl-2,4-diisopropylcinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p -Methoxycinnamate, octyl-p-methoxycinnamate (2-ethylhexyl-p-methoxycinnamate), 2-ethoxyethyl-p-methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β -Phenyl cinnamate, 2-ethylhexyl-α-cyano-β-phenyl cinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxy cinnamate, etc.); benzophenone UV absorbers (for example, 2,4-dihydroxybenzophenone) 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzo Phenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5- Sulfonate, 4-phenylbenzophenone, 2-ethylhexyl-4′-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone, etc.); 3- (4'-methylbenzylidene) -d, l-camphor, 3-benzylidene-d, l-camphor; 2-phenyl-5-methylbenzoxazole; 2,2'-hydroxy-5-methylphenylbenzotriazole; 2 -(2'-hydroxy-5'-t-octylphenyl) benzotriazole; 2- (2'-hydroxy-5'-methylphenylbenzotriazole; dibenzalazine; dianisoylmethane; 4-methoxy-4'-t-butyl Dibenzoylmethane; 5- (3,3-dimethyl-2-norbornylidene) -3-pentan-2-one, dimorpholino pyridazinone like.

  Examples of the sequestering agent include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, disodium edetate, trisodium edetate, tetrasodium edetate Sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetic acid, trisodium ethylenediaminehydroxyethyl triacetate and the like.

  Examples of the lower alcohol include ethanol, propanol, isopropanol, isobutyl alcohol, t-butyl alcohol and the like.

  Examples of the polyhydric alcohol include divalent alcohols (for example, ethylene glycol, propylene glycol, trimethylene glycol, 1,2-butylene glycol, 1,3-butylene glycol, tetramethylene glycol, 2,3-butylene glycol, Pentamethylene glycol, 2-butene-1,4-diol, hexylene glycol, octylene glycol, etc.); trivalent alcohol (eg, glycerin, trimethylolpropane, etc.); tetravalent alcohol (eg, 1,2,6) Pentaerythritol such as hexanetriol); pentahydric alcohol (eg, xylitol, etc.); hexavalent alcohol (eg, sorbitol, mannitol, etc.); polyhydric alcohol polymer (eg, diethylene glycol, dipropylene glycol, triethylene glycol, polypropylene Glycol, tetraethylene glycol, diglycerin, polyethylene glycol, triglycerin, tetraglycerin, polyglycerin, etc.); divalent alcohol alkyl ethers (for example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene) Glycol monophenyl ether, ethylene glycol monohexyl ether, ethylene glycol mono 2-methylhexyl ether, ethylene glycol isoamyl ether, ethylene glycol benzyl ether, ethylene glycol isopropyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, etc.) ; Dihydric alcohol alkyl ester Tellurium (for example, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol butyl ether, diethylene glycol methyl ethyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether , Propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol isopropyl ether, dipropylene glycol methyl ether, dipropylene glycol ethyl ether, dipropylene glycol butyl ether, etc.); divalent alcohol Ether esters (eg, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether acetate, ethylene glycol diazinate, ethylene glycol disuccinate, diethylene glycol monoethyl ether acetate, diethylene glycol) Monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monophenyl ether acetate, etc .; glycerin monoalkyl ether (for example, xyl alcohol, ceralkyl alcohol) Sugar alcohol (for example, sorbitol, maltitol, maltotriose, mannitol, sucrose, erythritol, glucose, fructose, amylolytic sugar, maltose, xylitolose, amylolytic sugar reducing alcohol, etc.); Solid; Tetrahydrofurfuryl alcohol; POE-Tetrahydrofurfuryl alcohol; POP-Butyl ether; POP / POE-Butyl ether; Tripolyoxypropylene glycerin ether; POP-glycerin ether; POP-glycerin ether phosphate; POP / POE-pentane erythritol Examples include ether and polyglycerin.

  Monosaccharides include, for example, tricarbon sugars (eg, D-glyceryl aldehyde, dihydroxyacetone, etc.); tetracarbon sugars (eg, D-erythrose, D-erythrulose, D-treose, erythritol, etc.); pentose sugars (eg, , L-arabinose, D-xylose, L-lyxose, D-arabinose, D-ribose, D-ribulose, D-xylulose, L-xylulose, etc .; hexose (eg, D-glucose, D-talose, D) -Bucicose, D-galactose, D-fructose, L-galactose, L-mannose, D-tagatose, etc.); pentose sugar (eg, aldheptose, heproose, etc.); octose sugar (eg, octulose, etc.); For example, 2-deoxy-D-ribose, 6-deoxy-L-galactose, 6-deoxy-L-mannose, etc .; amino sugar (eg, D-glucosamine, D-galactosamine, shea Acid, Aminouron acid, muramic acid); uronic acid (e.g., D- glucuronic acid, D- mannuronic acid, L- guluronic acid, D- galacturonic acid, L- iduronic acid) and the like.

  Examples of the oligosaccharides include sucrose, gnocyanose, umbelliferose, lactose, planteose, isoliquinoses, α, α-trehalose, raffinose, lycnose, umbilicin, stachyose verbus courses and the like.

  Examples of the polysaccharide include cellulose, quince seed, chondroitin sulfate, starch, galactan, dermatan sulfate, glycogen, gum arabic, heparan sulfate, hyaluronic acid, tragacanth gum, keratan sulfate, chondroitin, xanthan gum, mucoitin sulfate, guar gum, dextran, kerato sulfate. , Locust bean gum, succinoglucan, caronic acid and the like.

  Examples of amino acids include neutral amino acids (eg, threonine, cysteine, etc.); basic amino acids (eg, hydroxylysine, etc.) and the like. Examples of amino acid derivatives include acyl sarcosine sodium (lauroyl sarcosine sodium), acyl glutamate, acyl β-alanine sodium, glutathione, and pyrrolidone carboxylic acid.

Examples of organic amines include monoethanolamine, diethanolamine, triethanolamine, morpholine, triisopropanolamine, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and the like. Is mentioned.
Examples of the polymer emulsion include an acrylic resin emulsion, a polyethyl acrylate emulsion, an acrylic resin liquid, a polyacryl alkyl ester emulsion, a polyvinyl acetate resin emulsion, and a natural rubber latex.

Examples of the pH adjuster include buffers such as lactic acid-sodium lactate, citric acid-sodium citrate, and succinic acid-sodium succinate.
Examples of vitamins include vitamins A, B1, B2, B6, C, E and derivatives thereof, pantothenic acid and derivatives thereof, biotin and the like.
Examples of the antioxidant include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters and the like.

  Examples of the antioxidant assistant include phosphoric acid, citric acid, ascorbic acid, maleic acid, malonic acid, succinic acid, fumaric acid, kephalin, hexametaphosphate, phytic acid, and ethylenediaminetetraacetic acid.

  Other ingredients that can be blended include, for example, preservatives (ethyl paraben, butyl paraben, etc.); anti-inflammatory agents (eg, glycyrrhizic acid derivatives, glycyrrhetinic acid derivatives, salicylic acid derivatives, hinokitiol, zinc oxide, allantoin, etc.); Extract, placenta extract, saxifrage extract, arbutin, etc.); various extracts (eg, buckwheat, auren, shikon, peonies, assembly, birch, sage, loquat, carrot, aloe, mallow), iris, grape, yokuinin, loofah, lily , Saffron, nematode, ginger, hypericum, onionis, garlic, capsicum, chimney, red snapper, seaweed, etc.), activator (eg, royal jelly, photosensitizer, cholesterol derivative, etc.); blood circulation promoter (eg, nonyl acid wallenylamide, nicotine) Acid Gyl ester, nicotinic acid β-butoxyethyl ester, capsaicin, gingerone, cantalis tincture, ictamol, tannic acid, α-borneol, tocopherol nicotinate, inositol hexanicotinate, cyclandrate, cinnarizine, trazoline, acetylcholine, verapamil, cephalanthin , Γ-oryzanol, etc.); antiseborrheic agents (eg, sulfur, thianthol, etc.); anti-inflammatory agents (eg, tranexamic acid, thiotaurine, hypotaurine, etc.) and the like.

  Furthermore, edetate disodium, edetate trisodium, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, malic acid and other metal sequestering agents, caffeine, tannin, verapamil, tranexamic acid and its derivatives, licorice, Various herbal extracts such as Karin and Ichiyakusou, drugs such as tocopherol acetate, glycyrrhizic acid, glycyrrhizic acid and derivatives or salts thereof, whitening agents such as vitamin C, magnesium ascorbate phosphate, glucoside ascorbate, arbutin, kojic acid, Amino acids such as arginine and lysine and derivatives thereof, saccharides such as fructose, mannose, erythritol, trehalose and xylitol can also be appropriately blended.

The external preparation for skin of the present invention can be widely applied to cosmetics, pharmaceuticals, and quasi drugs applied to the outer skin. The dosage form is arbitrary, such as solution system, solubilization system, emulsification system, powder dispersion system, water-oil two-layer system, water-oil-powder three-layer system, gel, aerosol, mist, capsule, etc. It can be provided in the form. Further, the product form of the external preparation for skin of the present invention is also arbitrary, such as facial cosmetics such as lotion, milky lotion, cream, pack, etc .; foundation, funny, blusher, lipstick, eye shadow, eyeliner, mascara, sunscreen, etc. Makeup cosmetics; body cosmetics; aromatic cosmetics; skin cleansing agents such as make-up removers, facial cleansers, body shampoos; hair cosmetics such as hair rinses and shampoos; ointments; bath preparations; It can be applied in any form as long as it is used.
Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to these examples. Unless otherwise specified, the blending amount indicates mass%.

[Synthesis Example 1 of Cationic Polymer]
1.38 g of poly (4-vinylpyridine) (Mw = 7.0 × 10 ⁴ , Mn = 3.1 × 10 ⁴ , Mw / Mn = 2.3) and the compound represented by the above general formula (I) (m = 2, n = 11, X = Br) 5.03 g and 44 mL of N, N-dimethylformamide (DMF) as a reaction solvent were mixed, and the mixture was stirred at 25 ° C. for 2 weeks in the dark.
The reaction solution was added dropwise to ether for reprecipitation. The powder obtained by filtration was dissolved again in DMF, re-precipitated in the same manner using ether, filtered and dried under reduced pressure to obtain a yellow powder.

FT-IR measurement was performed to confirm cation introduction.
FIG. 1 shows the compound represented by the above general formula (I) (m = 2, n = 11, X = Br) and poly (4-vinylpyridine) FT-IR spectrum.
FIG. 2 shows an FT-IR spectrum of the product obtained in Synthesis Example 1.
1200cm ^-1, 1700cm ^-1, around 2350 cm ^-1 and 2800 cm ^-1, a peak characteristic to the compound represented by the general formula (I) was observed. Thereby, formation of the cation site | part by the quaternization reaction of poly (4-vinyl pyridine) was confirmed.

FIG. 3 shows ¹ H-NMR of the product obtained in Synthesis Example 1 in heavy DMSO.
Protons derived from the α-position and β-position of the pyridinium group were observed at 8.9 ppm and 7.7 ppm. This confirmed that poly (4-vinylpyridine) was quaternized.
From the integral ratio of the β-position proton of the non-quaternized pyridyl group appearing at 6.8 ppm and the α-position proton of the quaternized pyridinium group appearing at 8.9 ppm, the poly (4-vinylpyridine) It was confirmed that the quaternization reaction had progressed about 55% (hereinafter referred to as cation introduction rate 55%).

[Synthesis Example 2 of Cationic Polymer]
0.336 g of poly (4-vinylpyridine) (Mw = 7.0 × 10 ⁴ , Mn = 3.1 × 10 ⁴ , Mw / Mn = 2.3), compound represented by the above general formula (I) (m = 2, n = 6, X = Br) 1.00 g, and 7.06 mL of N, N-dimethylformamide (DMF) as a reaction solvent were mixed, and the mixture was stirred at 25 ° C. for 2 weeks in the dark.
The reaction solution was added dropwise to ether for reprecipitation. The powder obtained by filtration was dissolved again in DMF, reprecipitated with ether, filtered and dried under reduced pressure to obtain a yellow powder (yield 0.3 g, cation introduction rate 55%).

[Adsorption of cationic polymer on substrate 1]
The cationic polymer obtained in Synthesis Example 1 was dissolved in ethanol and filtered through a 200 nm syringe filter to prepare a polymer solution having a concentration of 1 × 10 ⁻² mol / dm ³ .
A clean silicon wafer substrate was immersed in the above solution under 100 min ^-1 immersion. The substrate was taken out, washed with ethanol, and dried with nitrogen gas to adsorb the cationic polymer (FIG. 4A).

For the substrate before and after the treatment, the contact angle, ζ potential, and ultraviolet visible absorption spectrum were measured.
The substrate before the treatment showed a static contact angle with respect to water having an angle of 5 °, and a negative ζ potential of −70 ± 10 mV at pH 7.
On the other hand, the substrate after the treatment exhibited a static contact angle with respect to water having an angle of 60 ± 5 °, and a positive ζ potential of 40 ± 10 mV at pH 7. From the absorption spectrum, an absorption band derived from a pyridyl group and a pyridinium group was confirmed at 260 nm (FIG. 5).
From the above, it was confirmed that the cationic polymer was adsorbed on the treated substrate.

[Adsorption of cationic polymer on substrate 2]
The cationic polymer obtained in Synthesis Example 1 was dissolved in ethanol and filtered through a 200 nm syringe filter to prepare a polymer solution having a concentration of 1 × 10 ⁻² mol / dm ³ .
A clean silica substrate was immersed in the above solution under 100 min ^-1 immersion. The substrate was taken out and dried with nitrogen gas as it was to adsorb the cationic polymer (FIG. 4B).

[Relationship between concentration of cationic polymer solution and adsorption amount of cationic polymer]
The cationic polymer obtained in Synthesis Example 1 was dissolved in ethanol to prepare solutions of 10 ⁻¹ , 10 ⁻² , 10 ⁻³ , 10 ⁻⁴ mol / dm ³ .
Method 1 (casting method): Each concentration of solution was dropped onto a clean surface-oxidized silicon wafer substrate and allowed to dry naturally at room temperature (FIG. 4C).
Method 2 (dipping method): A clean surface-oxidized silicon wafer substrate was immersed in a solution of each concentration, immediately pulled up, and naturally dried at room temperature (FIG. 4D).

The measurement result of FT-IR is shown in FIG.
It was confirmed that the higher the concentration of the cationic polymer, the stronger the characteristic peaks (around 3400, 2900, 1750 cm ⁻¹ ) observed in the cationic polymer, and the more the cationic polymer adsorbed.
Further, it was confirmed that the amount of the cationic polymer adsorbed was larger when the cast method was used than when the dipping method was used.

[Polymerization of styrene on the substrate]
Next, styrene was polymerized on the substrate on which the cationic polymer was adsorbed.
Into the eggplant flask, 50 mL of styrene monomer distilled under reduced pressure, a substrate on which a cationic polymer was adsorbed (Example 3), and a clean substrate were added, and the mixture was added at 80 to 85 ° C. for 3 hours in a nitrogen atmosphere. Heated. The substrate was taken out and vacuum dried for 3 hours.
In order to confirm the polymerization reaction of styrene, FT-IR measurement was performed. FT-IR spectra of styrene and polystyrene are shown in FIG.
FIG. 8 shows an FT-IR spectrum of the substrate.
As a result, polystyrene (2924, 1600, 1492, 1028 cm ⁻¹ ) peaks were confirmed on the substrate on which the cationic polymer was adsorbed. That is, it was confirmed that the polymerization reaction of styrene proceeds on the substrate on which the cationic polymer was adsorbed. On the other hand, no polystyrene peak was observed on a clean substrate on which no cationic polymer was adsorbed.
When the film thickness of the polystyrene film was determined by stylus-type film thickness measurement, it was 700 ± 20 nm. Thus, a polymer thin film can be easily formed in a short time by using the cationic polymer of the present invention.

[Relationship between concentration of cationic polymer solution and film thickness of polystyrene film]
Polymerization of styrene was attempted on each substrate on which the cationic polymer was adsorbed.
In order to remove the stabilizer, 5 mL of styrene monomer distilled under reduced pressure was placed in an eggplant flask and degassed by bubbling nitrogen for 20 minutes. Thereafter, each substrate (Example 5) on which the cationic polymer was adsorbed and a clean substrate were placed and polymerized at 80 ° C. for 3 hours in an oil bath. After completion of the reaction, it was taken out and dried with nitrogen gas.
The measurement result of FT-IR is shown in FIG.
It was confirmed that the intensity of the characteristic peaks (2924, 1600, 1492, 1028 cm ⁻¹ ) observed in polystyrene was stronger as the adsorption amount of the cationic polymer was larger (the concentration of the cationic polymer solution was higher).
On the other hand, on the clean substrate, the styrene monomer peaks (3000, 1630, 1575, 1494 cm ⁻¹ ) were observed, but the polystyrene peaks were not observed (FIG. 10). That is, styrene polymerization did not proceed on the substrate on which the cationic polymer had not been adsorbed.

Table 1 shows the film thickness measurement results.
(Table 1)
Concentration of cationic polymer solution (mol / dm ³ )
10 ^-1 10 ^-2 10 ^-3 10 ^-4
Film thickness (nm) Method 1 (Cast method) 2170 ± 880 950 ± 115--
Method 2 (Dipping method) 105 ± 35 885 ± 245--
When the concentration of the cationic polymer solution was 10 ⁻¹ , 10 ⁻² mol / dm ³ , formation of a polystyrene film (polymerization of styrene) was confirmed. It was also confirmed that a thick polystyrene film was formed by the casting method rather than the dipping method.
From the above, it was confirmed that as the adsorption amount of the cationic polymer increases, a thick polystyrene film is formed, and in particular, when a cast method is used, a thick polystyrene film is formed.

[Preparation of cationic polymer adsorbed powder 1]
In this method, a cationic polymer having a polymerization initiator in the molecule is synthesized in advance and adsorbed on the surface of the base powder (FIG. 11A).
The cationic polymer obtained in Synthesis Example 1 was dissolved in a solvent (ethanol 10 mL + water 40 mL) and then filtered through a 200 nm syringe filter to obtain a polymer solution.
Porous silica (Sunsphere L51 ^TM manufactured by Dokai Chemical Co., Ltd.) or nonporous silica (Seahoster KEP50 ^TM manufactured by Nippon Shokubai Co., Ltd.) is immersed in the above polymer solution under 100 min ^-1 immersion, taken out, and then left as it is. Dry with gas.
(Table 2)
Cationic
Base powder (g) Polymer (g) Reaction conditions Reaction time C%
Test Example 1-1 Porous silica 0.5 0.05 Room temperature, shading overnight 2.6
Test Example 1-2 Porous silica 0.5 0.05 Refrigerated / light-shielded overnight 1.56
Test Example 1-3 Porous silica 0.5 0.05 Ice-cooled, light-shielded for 1 hour 2.3
Test Example 1-4 Nonporous silica 2.0 0.05 Ice-cooled / light-shielded for 1 hour 5.46
As shown in Table 2, the adsorption of the cationic polymer on the powder was confirmed by the increase in C%.
FIG. 12 shows the FT-IR spectrum measurement results of the powder of Test Example 1-1. A characteristic peak was confirmed in the cationic polymer.
FIG. 13 shows a comparison of the ζ potential. The base powder (porous silica) had a pH of −32 mV, but the powder of Test Example 1-1 had a voltage of −14 mV.
From the above, adsorption of the cationic polymer on the base powder was confirmed.

[Polymerization of acrylamide]
Next, acrylamide polymerization was attempted using the cationic polymer adsorbed powder.
When 0.1 g of the powder of Test Example 1-1 was reacted with 1.0 g of acrylamide and 2.0 g of water, polymerization of acrylamide started on the surface of the powder at 69 ° C. and quickly solidified.

Using the powder of Test Example 1-4, the relationship between the ratio of the cationic polymer adsorbed powder and the acrylamide monomer / water ratio was examined. The results are shown in FIG.
It was found that the polymerization state changed depending on the concentration of the cationic polymer adsorbed powder and the concentration of the monomer.

[Preparation of Cationic Polymer Adsorbed Powder 2-1]
Next, another method for producing the cationic polymer adsorbed powder in the present invention will be described. This method is a method in which the polyamine compound is adsorbed on the base powder, and then the nitrogen atom of the polyamine compound is quaternized (FIG. 11B).
(1) Adsorption of polyamine compound on base powder 1 g of poly (4-vinylpyridine) (Mw = 6.0 × 10 ⁴ ) was dissolved in 39 g of an aqueous solution containing 50% by mass of ethanol, and sericite (average particle size of 5 μm) was obtained. ) 1 g was added and stirred at room temperature for 1 day. Centrifugation (5000 rpm, 15 minutes) and washing with ethanol three times. Dry with nitrogen gas.
(2) Quaternization of nitrogen atom of polyamine compound 10 g of N, N-dimethylformamide (DMF) was added 0.2468 g of the compound represented by the above general formula (I) (m = 2, n = 6, X = Br). Added and dissolved. (1) was added and stirred at room temperature in the dark for 2 weeks. The mixture was centrifuged (5000 rpm, 15 minutes), washed twice with DMF, and then washed 3-5 times with diethyl ether. Drying was performed with nitrogen gas (cation introduction rate: 15.4%).

[Polymerization of acrylamide]
Next, acrylamide polymerization was attempted using the cationic polymer-adsorbed sericite.
Nitrogen bubbling was performed on 3 g of 33% by mass acrylamide aqueous solution, and 0.1 g of the cationic polymer-adsorbed sericite was added. The mixture was stirred and refluxed (80 ° C.) under a nitrogen atmosphere. Polymerization rapidly occurred in the form of a gel at around 65 ° C.
On the other hand, when the base powder (sericite) to which the cationic polymer was not adsorbed was added and reacted, polymerization did not occur.
From the above, it was confirmed that the cationic polymer could be immobilized on the base powder.

[Preparation of Cationic Polymer Adsorbed Powder 2-2]
First, 50 g of spherical silica (KEP50: average particle diameter of 500 nm) serving as a base powder was baked in an electric furnace at 550 ° C. for 6 hours, allowed to cool to room temperature, and the remaining organic substances were removed.
C% Average particle diameter Isoelectric point Specific surface area
Before firing 5.46% 500 nm --- 45.14m ² / g
After baking −0.0075% 500 nm 3.76 147.45m ² / g
Organic substances could be removed without being affected by sintering.

(1) Adsorption of polyamine compound on base powder A water / ethanol solution containing 2.5% by mass of poly (4-vinylpyridine) (Mw = 6.0 × 10 ⁴ ) was prepared as shown in Table 3, and calcined as described above. 1 g of spherical silica was added and stirred at room temperature for 1 day. Centrifugation (5000 rpm, 15 minutes) and washing with ethanol three times. Dry with nitrogen gas.
(Table 3)
Test example
2-1 2-2 2-3 2-4 2-5
Ethanol 39.0g 26.0g 19.5g 13.0g 9.75g
Water --- 13.0g 19.5g 26.0g 29.25g
Poly (4-vinylpyridine) 1.0g 1.0g 1.0g 1.0g 1.0g
Solubility of poly (4-vinylpyridine) ○ ○ ○ ○ ×
C% 1.87% 1.96% 1.99% 2.03% ---
Average particle size 880nm --- --- 880nm ---
Isoelectric point +5 to 6 --- --- +5 to 6 ---
The isoelectric point shifted in the positive direction (3.76 → 5-6), suggesting the adsorption of polyamine compounds.
Moreover, it is thought that the average particle diameter is increasing because the aggregated particles are partially formed.

(2) Quaternization of nitrogen atoms of polyamine compounds
The compound represented by the general formula (I) (m = 2, n = 11, X = Br) was added to 10 g of N, N-dimethylformamide (DMF) and dissolved. The polyamine compound-adsorbed silica (1) was added and stirred for 5 days or 14 days in the dark at room temperature. Centrifugation (5000 rpm, 15 minutes) was performed, followed by washing twice with DMF and then washing three times with diethyl ether. Dry with nitrogen gas.
(Table 4)
Test example
3-1 3-2 3-3 3-4
DMF 10g 10g 10g 10g
Compound represented by formula (I) 0.3394g 0.3684g 0.3394g 0.3684g
Test Example 2-1 0.8g --- 0.8g ---
Test Example 2-4 --- 0.8g --- 0.8g
Agitation days 5 days 5 days 14 days 14 days C% 2.44% 2.19% 2.83% 2.79%
Cation introduction rate (%) 11.84% 3.07% 16.59% 14.61%
* Compound represented by formula (I) / poly (4-vinylpyridine) = 5 (molar ratio)
The progress of the quaternization reaction on the base powder was confirmed by increasing C%. In addition, no change in isoelectric point was observed.
Further, from the change in the FT-IR spectrum shown in FIG. 15, the adsorption of the polyamine compound to the base powder and the progress of the quaternization reaction were confirmed.

[Polymerization of acrylamide]
Next, acrylamide polymerization was attempted using the cationic polymer adsorbed powder.
An aqueous solution containing 50% by mass of acrylamide was bubbled with nitrogen for 10 minutes, and the powder of Test Example 3-3 was added and ultrasonically dispersed for 1 minute. The mixture was stirred and refluxed (80 ° C.) under a nitrogen atmosphere. Centrifugation and water washing were performed 3 times, and it was made to dry at 60 degreeC for 1 day.
C% was 3.65%. An increase in C% (2.83% → 3.65%) confirmed the polymerization on the base powder.
Further, as shown in FIG. 16, the particle size of the powder was increased by about 40 nm before and after the polymerization of acrylamide, so that the polymerization of acrylamide on the powder surface was confirmed.

[Preparation of Cationic Polymer Adsorbed Powder 2-3]
Surface modification of base powder (PSS / PDDA / synthetic fluorine phlogopite laminated powder)
1 mass of negatively charged synthetic fluorine phlogopite with an average particle size of 30 μm (topy industry), polydiallyldimethylammonium chloride (PDDA) (Aldrich MW: <200000), a cationic polymer electrolyte PDDA was adsorbed on fluorine phlogopite by immersing it in an aqueous solution containing 1% (after washing with PDDA, it was thoroughly washed with water).
Furthermore, by immersing PSS on the powder surface by immersing it in an aqueous solution containing 1% by mass of sodium polystyrenesulfonate (PSS) (Aldrich MW: 70000), which is an anionic polymer electrolyte, and further washing with water. PSS / PDDA / synthetic fluorine phlogopite laminated powder was prepared.

(1) Adsorption of polyamine compound on base powder 1 g of poly (4-vinylpyridine) (Mw = 6.0 × 10 ⁴ ) is dissolved in 39 g of 50% ethanol solution, and the above PSS / PDDA / synthetic fluorophlogopite laminated powder 1 g of body was added and stirred at room temperature for 1 day. Centrifugation (5000 rpm, 15 minutes) and washing with ethanol three times. Dry with nitrogen gas.
(2) Quaternization of nitrogen atom of polyamine compound 10 g of N, N-dimethylformamide (DMF) was added 0.2468 g of the compound represented by the above general formula (I) (m = 2, n = 11, X = Br). Added and dissolved. (1) was added and stirred at room temperature in the dark for 2 weeks. The mixture was centrifuged (5000 rpm, 15 minutes), washed twice with DMF, and then washed 3-5 times with diethyl ether. Dry with nitrogen gas.

(Table 5)
C%
Synthetic fluorine phlogopite 0%
PDDA / synthetic fluorine phlogopite 0.40%
PSS / PDDA / Synthetic fluorine phlogopite 0.78%
(1) After adsorption of poly (4 vinylpyridine) 2.2%
(2) 3.1% after quaternization reaction
As shown in Table 5, formation of a cationic polymer on the base powder was confirmed.

[Polymerization of acrylamide]
Next, polymerization of acrylamide was attempted using the powder.
Nitrogen bubbling was performed on 3 g of 33 mass% acrylamide aqueous solution, and 0.1 g of the cationic polymer adsorbed powder was added. The mixture was stirred and refluxed (80 ° C.) under a nitrogen atmosphere. Polymerization rapidly occurred in the form of a gel at around 65 ° C.
On the other hand, when the base powder (PSS / PDDA / synthetic fluorine phlogopite laminated powder) on which the cationic polymer was not adsorbed was added and reacted, polymerization did not occur.
From the above, it was confirmed that the cationic polymer could be immobilized on the base powder.
In the present invention, the base powder has a negative ζ potential (measured by electrophoresis at a temperature of 25 ° C. in a 1M Tris / HCl buffer solution, pH 7.5, manufactured by Wako Pure Chemical Industries, Ltd.). It is preferable to use a material having a ζ potential close to 0, such as zinc oxide or barium sulfate, or a positive value, by performing negative charge enhancement with a polymer electrolyte by the layer-by-layer method, It was confirmed that it can be used.

[Preparation of cationic polymer adsorbed powder 3]
In this method, a cationic polymer having a polymerization initiator in the molecule is synthesized in advance and adsorbed on the surface of the base powder (FIG. 11A).
The cationic polymer obtained in Synthesis Example 1 was dissolved in ethanol as a solvent, adjusted to 10 ⁻² mol / L, and then filtered through a 200 nm syringe filter to obtain a polymer solution.
Nonporous silica (Seahoster KEP30 ^™ manufactured by Nippon Shokubai Co., Ltd.) was shaken in the polymer solution for 24 hours, and then centrifuged at a rotational speed of 2000 rpm, and the precipitate was taken out. Thereafter, the obtained precipitate was washed with deionized water three times and then centrifuged, and the precipitate was taken out and dried with nitrogen gas to obtain a cationic polymer-adsorbed nonporous silica.
(Table 6)
Cationic
Base powder (g) Polymer solution (ml) Reaction conditions ζ potential (mV) C%
Test Example 4-1 Nonporous silica --- --- --- --43.48 4.29
Test Example 4-2 Nonporous silica 0.35 35 Room temperature / light-shielding +37.38 7.30
As shown in Table 6, C% increased after adsorption of the cationic polymer, confirming adsorption of the cationic polymer on the powder. Furthermore, from the ζ potential measurement, it was −43.48 mV before adsorption, but changed to +37.38 mV after adsorption.
From the above, adsorption of the cationic polymer on the base powder was confirmed.

[Polymerization of styrene monomer]
Next, polymerization of a styrene monomer was attempted using the above cationic polymer adsorbed powder (Test Example 4-2).
10 g of styrene monomer was degassed by bubbling with argon gas for 45 minutes, the powder (0.05 g) of Test Example 4-2 was added, and after bubbling with argon gas again for 5 minutes, argon gas was added. Stirring and refluxing (60 ° C., 16 hours) were performed under an atmosphere. The obtained residue was washed with chloroform and filtered to obtain a solid. This series of washing and filtration steps was performed five times. Then, the obtained solid is dispersed again in chloroform, ethanol is gradually added at a rate of 1 ml to 1 ml of the obtained dispersion, the obtained dispersion is cast on a sample stage, and dried with nitrogen gas. (Temperature 25 ° C.) and TEM observation was performed. The obtained TEM observation image is shown in FIG. From FIG. 17, it was confirmed that a 100 nm polystyrene film was coated on the nonporous silica substrate.

[Both-use foundation]
(Prescription) (mass%)
(1) Silicone-treated talc To 100
(2) Silicone-treated sericite 20
(3) Silicone-treated mica 10
(4) Silicone-treated titanium oxide 10
(5) Silicone-treated Bengala 0.8
(6) Silicone-treated yellow iron oxide 3
(7) Silicone-treated black iron oxide 0.2
(8) Surface acrylamide polymerized powder (powder obtained in Example 10) 10
(9) Liquid paraffin 4
(10) Vaseline 4
(11) Sorbitan sesquiisostearate 0.8
(12) Preservative appropriate amount (13) Antioxidant appropriate amount (14) Fragrance appropriate amount (Manufacturing method)
Manufactured in the usual manner. That is, the above components were mixed with a Henschel mixer, pulverized twice with a pulverizer, filled into a container (resin middle dish), and dry press molded by a known method.

[Both-use foundation]
(Prescription) (mass%)
(1) Silicone-treated talc To 100
(2) Silicone-treated sericite 20
(3) Silicone-treated mica 10
(4) Silicone-treated titanium oxide 10
(5) Silicone-treated Bengala 0.8
(6) Silicone-treated yellow iron oxide 3
(7) Silicone-treated black iron oxide 0.2
(8) Surface acrylamide polymerized powder (powder obtained in Example 11) 10
(9) Liquid paraffin 4
(10) Vaseline 4
(11) Sorbitan sesquiisostearate 0.8
(12) Preservative appropriate amount (13) Antioxidant appropriate amount (14) Fragrance appropriate amount (Manufacturing method)
Manufactured in the usual manner. That is, the above components were mixed with a Henschel mixer, pulverized twice with a pulverizer, filled into a container (resin middle dish), and dry press molded by a known method.

[Funny]
(Prescription) (mass%)
(1) Mica 10
(2) Talc to100
(3) Zinc oxide 5
(4) Fine particle titanium oxide 3
(5) Surface polystyrene polymerized powder (powder obtained in Example 12) 15
(6) Fluorophlogopite 10
(7) Vaseline 1
(8) Squalane 2
(9) Ester oil 1
(10) Preservative appropriate amount (11) Antioxidant appropriate amount (12) Fragrance appropriate amount (Manufacturing method)
Manufactured in the usual manner. That is, the above components were mixed with a Henschel mixer, pulverized twice with a pulverizer, filled into a container (resin middle dish), and dry press molded by a known method.

[Funny]
(Prescription) (mass%)
(1) Mica 10
(2) Talc to100
(3) Zinc oxide 5
(4) Fine particle titanium oxide 3
(5) Surface acrylamide polymerized powder (powder obtained in Example 10) 10
(6) Vaseline 1
(7) Squalane 2
(8) Ester oil 1
(9) Preservative appropriate amount (10) Antioxidant appropriate amount (11) Fragrance proper amount (Manufacturing method)
Manufactured in the usual manner. That is, the powder component and the oil phase component in the formulation were mixed with a Henschel mixer, pulverized twice with a pulverizer, then filled into a container (resin middle dish), and dry press molded by a known method.

[Pre-Math Closure]
(Prescription) (mass%)
Oil phase part (1) Decamethylcyclopentasiloxane To100
(2) Polyether-modified silicone 3
(3) Surface acrylamide polymerized powder (powder obtained in Example 11) 10
(4) Trimethylsiloxysilicic acid 2
Water phase (5) 1.3-butylene glycol 5
(6) Dynamite glycerin 2
(7) Preservative 0.5
(8) Purified water 30
(Manufacturing method)
Add the water phase part to the oil phase part heated to 70 ° C, fully emulsify with an emulsifier, cool with stirring, and when it becomes 35 ° C or less, pour it into a container and let it cool down. Got lotion.

[Eye Shadow]
(Prescription) (mass%)
(1) Talc Residual (2) Sericite 7
(3) Mica 15
(4) Spherical PMMA powder 3
(5) Surface acrylamide polymerized powder (powder obtained in Example 11) 10
(6) Barium sulfate 4
(7) Black iron oxide 5
(8) Squalane 2
(9) Dimethylpolysiloxane 2
(10) Sorbitan monooleate 0.5
(11) Preservative appropriate amount
(12) Appropriate perfume (production method)
Manufactured in the usual manner. That is, the above components were mixed with a Henschel mixer, pulverized twice with a pulverizer, filled into a container (resin middle dish), and dry press molded by a known method.

(Oil stick)
(Prescription) (mass%)
(1) Carnavalou 1
(2) Candelilla wax 2
(3) Ceresin 10
(4) Squalane Residual (5) Triisooctanoic acid glycerin 9
(6) Glycerin diisostearate 13
(7) Dimethylpolysiloxane 5
(Viscosity: 90,000 mPa · s at 25 ° C)
(8) Dimethylpolysiloxane 5
(Viscosity: 1,000 mPa · s at 25 ° C)
(9) Silicone resin 8
(10) Hydroxypropyl-β-cyclodextrin 1
(11) Macadamia nut oil fatty acid cholesteryl 3.5
(12) Synthetic sodium magnesium silicate 0.5
(13) Hydrophobic silica 0.5
(14) Purified water 2
(15) Spherical silicone resin powder-coated mica 3
(16) Surface acrylamide polymerized powder (powder obtained in Example 10) 5
(17) Barium sulfate 3
(18) Coloring agent appropriate amount (19) Preservative appropriate amount (20) Fragrance appropriate amount (Manufacturing method)
Disperse 12-13 in 11 heated to 60 ° C., add 10 and 14 uniformly dissolved therein, and stir well. This was added to 1 to 9 that had been separately heated and dissolved, and stirred sufficiently. Further, 15 to 20 was added and dispersed and stirred, and then filled into a container to obtain an oily stick.

〔cream〕
(Prescription) (mass%)
Oil phase
(1) Decamethylcyclopentasiloxane 10.5
(2) Dimethylpolysiloxane (6CS / 25 ° C) 4.0
(3) Stearyl alcohol 1.5
(4) Vaseline 5.0
(5) Squalane 1.0
(6) Vitamin E acetate 0.01
(7) Surface acrylamide polymerized powder (powder obtained in Example 10) 5.0
(8) Polyether-modified silicone 2.0
Water phase
(9) Preservative 0.2
(10) 1,3-butylene glycol 17.0
(11) Residue of purified water (Production method)
Add the water phase part to the oil phase part heated to 70 ° C, fully emulsify with an emulsifier, cool with stirring, and when it reaches 35 ° C or less, pour it into a container and let it cool down. Obtained.

[Sunscreen lotion]
(Prescription) (mass%)
Oil phase part (1) Dimethylpolysiloxane (6CS / 25 ° C) 5.0
(2) Dimethylpolysiloxane (1.5 CS / 25 ° C.) 13.0
(3) Phenyl-modified methylphenyl polysiloxane 3.0
(4) Surface acrylamide polymerized powder (powder obtained in Example 10) 5.0
(5) Polyether-modified silicone 2.0
Aqueous part (6) Sodium chloride 9.0
(7) Fragrance 0.2
(8) Preservative 0.2
(9) Ethanol 5.0
(10) Purified water residue (production method)
Add the water phase to the oil phase heated to 70 ° C, fully emulsify with an emulsifier, cool with stirring, pour into a container at 35 ° C or lower, allow to cool, and make the desired sunscreen Got lotion.

[Liquid emulsification foundation]
(Prescription) (mass%)
Oil phase part (1) Decamethylcyclopentasiloxane Residue (2) Trimethylsiloxysilicic acid 3.0
(3) Dimethylpolysiloxane 5.0
(4) Dimethylpolysiloxane polyoxyalkylene copolymer 2.5
(5) Sorbitan sesquiisostearate 2.0
Powder part (6) Silicone-treated talc 5.0
(7) Silicone-treated titanium dioxide 5.0
(8) Surface acrylamide polymerized powder (powder obtained in Example 10) 5.5
(9) Silicone-treated nylon powder 4.0
(10) Silicone-treated colored pigment 2.0
Aqueous part (11) 1,3-butylene glycol 3.0
(12) Ethanol 13.0
(13) Purified water 10.0
(Manufacturing method)
The oil phase part was heated and stirred at 70 ° C., and then the powder part was added and stirred and dispersed at 70 ° C. with a homomixer. After cooling to room temperature and adding the aqueous phase, the mixture was emulsified with a homomixer to prepare a liquid foundation.

It is a figure which shows the FT-IR spectrum of the compound represented with general formula (I), and poly (4-vinyl pyridine). 4 is a diagram showing an FT-IR spectrum of the cationic polymer obtained in Synthesis Example 1. FIG. 1 is a diagram showing ¹ H-NMR of the cationic polymer obtained in Synthesis Example 1 in heavy DMSO. FIG. It is the figure which showed the adsorption | suction method of the cationic polymer on a board | substrate. It is a figure which shows the ultraviolet visible absorption spectrum of the board | substrate which adsorb | sucked the cationic polymer. It is a figure which shows FT-IR at the time of making it adsorb | suck on a board | substrate using the cationic polymer of each density | concentration. It is a figure which shows the FT-IR spectrum of styrene and polystyrene. It is a figure which shows FT-IR at the time of polymerizing styrene on a cationic polymer adsorption substrate. It is a figure which shows FT-IR at the time of polymerizing styrene on the cationic polymer adsorption board | substrate manufactured using the cationic polymer of each density | concentration. It is a figure which shows FT-IR at the time of trying polymerization of styrene on a clean board | substrate. It is the figure which showed the manufacturing method of the cationic polymer adsorption powder of this invention. It is a figure which shows the FT-IR spectrum of a base powder and a cationic polymer adsorption powder. It is a figure which shows the zeta potential of a base powder and a cationic polymer adsorption powder. It is a figure which shows the polymerization conditions and states of an acrylic monomer. It is a figure which shows the FT-IR spectrum in Example 10 of this invention. It is the transmission electron microscope image which observed the powder before and behind acrylamide polymerization in Example 10 of this invention. It is the transmission electron microscope image which observed the powder after styrene polymerization in Example 17 of this invention.

Claims (5)

A cationic powder in which a part or all of nitrogen atoms of a polyamine compound having a molecular weight of 1,000 to 1,000,000 is quaternized with a compound represented by the following general formula (I): a base powder having a negative ζ potential Cationic polymer adsorbent powder characterized by being adsorbed on the body surface.
(Chemical formula 1)
(Wherein X is a halogen atom, n is an integer of 1 to 20, and m is an integer of 1 to 20)
The measurement method of ζ potential is as follows.
After the sample was dispersed and sonicated in 1M tris / HCl buffer solution of pH 7.5 manufactured by Wako Pure Chemical Industries, the supernatant liquid left for 18 hours was used for measurement. The zeta potential was measured at 25 ° C. using an electrophoretic light scattering photometer LEZ-600 manufactured by Otsuka Electronics Co., Ltd. The measurement was performed three times, and the result was expressed as an average value. Based powder surface is ζ potential negative, after the molecular weight was adsorbed polyamine compound is 1,000 to 1,000,000, some or all of the nitrogen atoms of the polyamine compound, the table the following general formula (I) Cationic polymer adsorbed powder, characterized in that it is quaternized with a compound obtained.
(Chemical formula 2)
(Wherein X is a halogen atom, n is an integer of 1 to 20, and m is an integer of 1 to 20)
The measurement method of ζ potential is as follows.
After the sample was dispersed and sonicated in 1M tris / HCl buffer solution of pH 7.5 manufactured by Wako Pure Chemical Industries, the supernatant liquid left for 18 hours was used for measurement. The zeta potential was measured at 25 ° C. using an electrophoretic light scattering photometer LEZ-600 manufactured by Otsuka Electronics Co., Ltd. The measurement was performed three times, and the result was expressed as an average value.   A thin film-coated powder, wherein a monomer film is polymerized on the surface of the cationic polymer-adsorbed powder according to claim 1 or 2 to form a thin film.   A skin external preparation comprising the cationic polymer adsorbed powder according to claim 1. A skin external preparation comprising the thin film-coated powder according to claim 3.