WO2006051746A1 - Microgel gonflant dans les solvants organiques et procede pour le preparer - Google Patents

Microgel gonflant dans les solvants organiques et procede pour le preparer Download PDF

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Publication number
WO2006051746A1
WO2006051746A1 PCT/JP2005/020341 JP2005020341W WO2006051746A1 WO 2006051746 A1 WO2006051746 A1 WO 2006051746A1 JP 2005020341 W JP2005020341 W JP 2005020341W WO 2006051746 A1 WO2006051746 A1 WO 2006051746A1
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Prior art keywords
carbon atoms
water
microgel
represents alkyl
chemical
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PCT/JP2005/020341
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English (en)
Japanese (ja)
Inventor
Yoshiko Hiwatari
Yuki Suzuki
Isamu Kaneda
Yumi Ueda
Yuko Nakanishi
Nobuyoshi Koga
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Shiseido Company, Ltd.
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Publication of WO2006051746A1 publication Critical patent/WO2006051746A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/0241—Containing particulates characterized by their shape and/or structure
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/02—Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04—Dispersions; Emulsions
    • A61K8/042—Gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B01J13/0065—Preparation of gels containing an organic phase
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
    • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
    • A61K2800/41—Particular ingredients further characterized by their size
    • A61K2800/412—Microsized, i.e. having sizes between 0.1 and 100 microns

Definitions

  • the present invention relates to a novel organic solvent swellable microgel and a method for producing the same.
  • the organic solvent swellable microgel of the present invention is a corona-core type polymer microgel having a hydrophobic core and hydrophilic corona force, and various chemical products, for example, cosmetics, etc. in which the polymer microgel is blended. It is useful as a blending component.
  • Microgels are expected to be applied in the pharmaceutical and cosmetic industries by applying their swelling and shrinkage functions.
  • Synthetic polymer microgels Non-patent Document 4
  • These are all applications of polymer electrolytes such as polyacrylic acid, and their water dispersibility is not acid-resistant nor salt-resistant.
  • acid resistance and salt resistance are very important performances in order to adapt under physiological conditions.
  • Non-patent Document 5 there have been several reports on the polymer fine particle polymerization method based on the so-called macromonomer method using a macromonomer containing a water-soluble polymer structure. This method can be said to be an excellent method in that it can produce fine polymer particles having a uniform particle size without controlling the stirring conditions of the polymerization system, which is a problem in mass production of heterogeneous polymerization (non-patent literature). Five).
  • Patent Document 1 JP 2001-114650 A
  • Patent Document 2 Japanese Patent Laid-Open No. 2002-327019
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-20314
  • Non-Patent Document 2 M.Q. Chen et al: J. Polym. Sci .: A: Polym. Chem., 38 1811-1817 (200 0)
  • Non-Patent Document 5 C. Wu, Macromolecules 27, 7099 (1944) [0011] [Invention c]
  • cloudy cosmetics such as cloudy lotion have a cosmetic effect, such as moisturizing, moisturizing, and fuller skin, than transparent lotion due to the appearance characteristic of cloudiness. It is attracting attention because of For example, it is the same reason that the Shirahone hot springs in Nagano Prefecture are popular because they feel the effects of hot springs due to cloudiness.
  • Patent Document 6 Japanese Patent Laid-Open No. 11 269055
  • polyhydric alcohols such as 1,3 butylene glycol, propylene glycol, polyethylene glycol, sorbitol, and xylitol are known as humectants other than glycerin (Patent Document 8).
  • polyhydric alcohols are less sticky than glycerin, but have a low moisturizing effect and rough skin improving effect.
  • glycerin when applied to the skin, there were problems to be solved, such as being repelled by sebum and becoming less familiar to the skin.
  • Non-Patent Document 6 New Cosmetic Science, Nanzan-do, p. 144
  • Patent Document 7 JP 2002-356416
  • Patent Document 8 JP-A-11 322575
  • Multi-layer cosmetics like powder Z water, powder Z oil, water Z oil, the appearance looks multilayer.
  • Cosmetics For example, in the case of water Z oil two-layer cosmetics, the upper layer is roughly divided into two types: oil alone or emulsified.
  • Multilayer cosmetics are useful for various cosmetics including multilayer skin lotions from the viewpoint of beauty of appearance and usability (Patent Documents 9 to 15).
  • Patent Document 9 JP-A-2005-281193
  • Patent Document 10 Japanese Patent Application Laid-Open No. 2004-203764
  • Patent Document 12 Japanese Unexamined Patent Application Publication No. 2002-234815
  • Patent Document 13 Japanese Patent Application Laid-Open No. 11 92356
  • Patent Document 14 Japanese Patent Application Laid-Open No. 11 71230
  • Patent Document 15 JP-A-10-182340
  • the present invention provides a novel polymer microgel and a method for producing the same.
  • the microgel of the present invention has a narrow particle size distribution and excellent organic solvent swellability.
  • the present invention provides a cosmetic obtained by means fundamentally different from conventional cloudy cosmetics, and is obtained by polymerizing a specific polyethylene oxide macromonomer, a hydrophobic monomer, and a crosslinkable monomer. As a result of discovering that the obtained copolymer is dispersed in water, surprisingly, a cosmetic having good white turbidity and excellent storage stability and usability can be obtained.
  • the present invention is obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formula (A-2), and a crosslinkable monomer of the following formula (A-3).
  • a copolymer comprising the monomers (1) to (A-3) in a mixture of water and ethanol under the following conditions (A—A), (A—B), (A—C):
  • A—A Polyethylene oxide macromonomer and hydrophobic monomer charge capacity
  • R represents alkyl having 1 to 3 carbon atoms, and n is a number from 20 to 200.
  • X is H or C
  • R represents an alkyl having from 3 to 8 carbon atoms, and R represents an alkyl having 4 to 8 carbon atoms.
  • R and R each independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2.
  • R represents alkyl having 1 to 3 carbon atoms, and n is a number from 20 to 200.
  • X is H or C
  • R represents alkyl having 1 to 3 carbon atoms, R represents alkyl having 4 to 8 carbon atoms
  • R and R each independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2.
  • the present invention provides a polyethylene oxide macromonomer represented by the following formula (1), a hydrophobic monomer represented by the following formulas (B-2) and (B-3), and a crosslinkable monomer represented by the following formula (B-4): A copolymer obtained by polymerization, wherein the particle size of the copolymer particles in water is d,
  • the particle size of the copolymer particles is d, and the swelling ratio (dZd) 3 is 1 or more.
  • An organic solvent swellable microgel is provided.
  • R represents alkyl having 1 to 3 carbon atoms, and n is a number from 20 to 200.
  • X is H or C
  • R represents alkyl having 1 to 3 carbon atoms
  • R. Represents alkyl having 1 to 3 carbon atoms, R represents alkyl having 4 to 8 carbon atoms
  • R may be the same as or different from R in formula (B-2).
  • R and R each independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2.
  • the present invention provides a polyethylene oxide macromonomer represented by the following formula (1) and the following formula (B 2) and the hydrophobic monomer of (B-3) and the crosslinkable monomer of the following formula (B-4) under the conditions of the following (BA), (BB), (BC)
  • the present invention provides a method for producing an organic solvent swellable microgel characterized by radical polymerization in a water-ethanol mixed solvent.
  • R represents alkyl having 1 to 3 carbon atoms, and n is a number from 20 to 200.
  • X is H or C
  • R represents alkyl having 1 to 3 carbon atoms.
  • R represents alkyl having 1 to 3 carbon atoms, R represents alkyl having 4 to 8 carbon atoms
  • R may be the same as or different from R in the formula (B-2).
  • R and R each independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2.
  • the present invention provides a cosmetic comprising the organic solvent swellable microgel described above.
  • the present invention provides a copolymer obtained by polymerizing a polyethylene oxide macromonomer of the following formula (1), a hydrophobic monomer of the following formula (C 2), and a crosslinkable monomer of the following formula (C 3).
  • the present invention provides a cosmetic characterized by containing a coalescence.
  • n is a number from 20 to 200.
  • X is H or C
  • R represents alkyl having 1 to 3 carbon atoms
  • R represents alkyl having 1 to 8 carbon atoms
  • R and R each independently represents alkyl having 1 to 3 carbon atoms, and m is a number from 0 to 2.
  • the present invention provides the monomers (1;) to (C-3) as water under the following conditions (C—A), (C—B), (C—C), and (C—D).
  • the present invention provides a cosmetic comprising a microgel comprising a copolymer obtained by radical polymerization in a mixed solvent of ethanol.
  • the (C A) hydrophobic monomer should have a composition in which one or more methacrylic acid derivatives having an alkyl having 1 to 8 carbon atoms are mixed.
  • the present invention provides the cosmetic described above, wherein the particle size of the microgel is 50 to 300 nm.
  • the present invention provides a cosmetic characterized in that the cosmetic described above contains a moisturizing agent.
  • the present invention provides the above cosmetic, wherein the humectant is a polyhydric alcohol.
  • the present invention provides a multilayer cosmetic comprising 5 to 40% by mass of a liquid oil in the cosmetic and satisfying the following condition (a) or (b).
  • the “surfactant content Z liquid oil content” is 0.8 or less by weight.
  • the present invention also provides the multilayer cosmetic described above, which further contains a thickener.
  • the microgel of the present invention is a core-corona type microgel in which a nonionic and water-soluble polyethylene oxide chain is grafted on the surface, and the core portion is a hydrophobic polymer crosslinked with a crosslinking monomer.
  • the present microgel can easily produce microgel particles with a narrow particle size distribution without controlling particularly strict stirring conditions. This makes mass production easy and is advantageous for industrial applications.
  • the microgel of the present invention is a water-dispersible force. Since the dispersion is stabilized with a nonionic polymer, acid resistance and salt resistance are expected. This feature is in the pharmaceutical or cosmetic industry It is considered to be an excellent material that satisfies the requirement of stable dispersion under physiological conditions required for application in Japan.
  • a notable characteristic of the microgel of the present invention is the ability to swell with a water-immiscible organic solvent. This swelling ability has very high solvent selectivity. In addition, the swelling efficiency shows surprising results, and the organic solvent swells up to about 400 times its own volume.
  • the selectivity of the swellable solvent can be expanded as compared with the case where the carbon number power is 3 to 3. Be expected.
  • the microgel of the present invention is a core-corona type microgel in which a nonionic and water-soluble polyethylene oxide chain is grafted on the surface, and the core portion is a hydrophobic polymer crosslinked with a crosslinking monomer.
  • this microgel can easily produce microgel particles with a narrow particle size distribution without controlling particularly strict stirring conditions. This is easy for mass production and is advantageous for industrial applications.
  • the microgel of the present invention is a water-dispersible force. Since the dispersion is stabilized with a nonionic polymer, acid resistance and salt resistance are expected. This feature is considered to be an excellent material that satisfies the requirement of stable dispersion under physiological conditions required for applications in the pharmaceutical or cosmetic industry.
  • microgel of the present invention a notable characteristic of the microgel of the present invention is swelling ability with a water-immiscible organic solvent. This swelling ability has very high solvent selectivity. Its swelling efficiency shows surprising results, and it absorbs organic solvents up to 400 times its own volume and swells.
  • microgel of the present invention is particularly useful as a cosmetic raw material.
  • the cosmetic of the present invention is excellent in storage stability. In other words, the turbidity is stable even after long-term storage.
  • the cosmetics of the present invention are excellent in the feeling of use. In other words, there is a feeling of stickiness. In addition, there is an effect of suppressing shine when applied to the skin with which familiarity is early.
  • the multilayer cosmetic of the present invention is excellent in storage stability and can maintain its multilayer appearance even after long-term storage.
  • microgel having a particle diameter of 50 to 300 nm and a dispersion degree of less than 0.01 is obtained.
  • This microgel has the property of swelling in an organic solvent.
  • the particle diameter of so-called colloidal particles such as emulsified particles or polymer emulsions can be measured by a dynamic light scattering method or a photon correlation method.
  • This measurement method irradiates a sample dispersion prepared to a sufficiently dilute concentration with laser light and measures the scattered light intensity scattered from the sample particles, thereby obtaining the translational diffusion coefficient (average value) of the sample particles. It is a method of measuring.
  • the sample particles are constantly moving in Brownian motion in the dispersion. It is possible to analyze the movement speed of the particles by this Brownian motion, that is, the translational diffusion coefficient (average value) from the result of the temporal change of the scattered light intensity.
  • the hydrodynamic size of the sample particles can be calculated from the translational diffusion coefficient (average value) thus obtained according to the Stokes-Suinstein equation (Equation 1).
  • an organic solvent swellable microgel having a swelling ratio (dZd) 3 of 20 to 450 is obtained, where d is the particle size of the copolymer particles when stirring until swelling saturation occurs.
  • microgels are dispersed in water and benzene with the same volume as this mixed solvent is added and stirred for 5 hours, it is sufficient to swell and saturate.
  • the particle diameters d and d can be measured by the dynamic light scattering method. Measurement conditions are as follows
  • a stirring time of about 5 hours is sufficient. After stirring, perform a light centrifuge operation of about 1000 X g together with the sample tube. Lift up the organic solvent and disperse the microgel. Collect the water phase part with a careful syringe. The average particle size and the degree of dispersion of this sample collected are measured in the same manner using the above-mentioned commercially available dynamic light scattering measuring device.
  • a polymer microparticle polymerization method based on a macromonomer method using a macromonomer containing a water-soluble polymer structure is known.
  • the core portion is crosslinked with a crosslinkable monomer to form a microgel.
  • the manufacturing method is known.
  • the method for producing a microgel used in the present invention is a core in which an aqueous macromonomer and a hydrophobic monomer are ordered in a solvent as shown in FIG. 1, the particle diameter is almost constant, and the core part is crosslinked. It is thought that a corona-type polymer microgel is formed.
  • the microgel is useful as a cosmetic raw material.
  • the cosmetic of the present invention can be produced by blending the above microgel into the cosmetic. That is, microgels and cosmetic ingredients (for example, powder ingredients, liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils, higher fatty acids, higher alcohols, ester oils, silicone oils, ionic surfactants, cationic surfactants) , Amphoteric surfactants, nonionic surfactants, moisturizers, water-soluble polymers, thickeners, film agents, ultraviolet absorbers, sequestering agents, lower alcohols, polyhydric alcohols, sugars, amino acids, organic any Amin, polymer Emarujiyon, P H adjusting agents, skin nutrients, vitamins, antioxidants, oxidation preventing aid, perfume, suitably blended with water or the like), by a conventional method depending on the dosage form for the purpose Of cosmetics.
  • cosmetic ingredients for example, powder ingredients, liquid fats and oils, solid fats and oils, waxes, hydrocarbon oils,
  • the blending amount of the microgel is appropriately determined according to the cosmetic. It is desirable to blend in the range of 0.01 to 10% by mass.
  • the cloudy cosmetic means a cosmetic whose appearance can be recognized as visually cloudy.
  • the cloudiness with the L value of 1 to 90 is preferred. More preferably, the turbidity is 1 to 60. Within this range, the significance of the present invention is high. This is because it is very difficult to adjust the balance between the surfactant and the oil content of white cloudy cosmetics having an L value of 1 to 60, and it is difficult to produce a stable cloudy cosmetic.
  • a translucent lotion prepared by the microemulsion method or the like is also a cloudy cosmetic of the present invention, and its L value is around 90.
  • the cosmetic of the present invention further includes a medicinal agent, a moisturizing component, an anti-inflammatory agent, a bactericidal agent, an antiseptic agent, an ultraviolet absorber, an antioxidant, an organic and inorganic agent that are usually used in cosmetics, pharmaceuticals, and the like. Powders, fragrances, pigments, etc. can be blended as necessary.
  • the copolymer used in the present invention is the same as the copolymer of Invention C.
  • the external preparation for skin of the present invention is produced by mixing and dispersing this copolymer in water (or an aqueous phase in which water-soluble cosmetic ingredients are dissolved) by a conventional method. That is, the external preparation for skin of the present invention is a cosmetic having excellent commercial value that can be produced by a very simple manufacturing process.
  • the microgel used in the present invention has a particle size of 250 ⁇ when dispersed in ion-exchanged water. It is desirable to use m or less. In the case of a particle size exceeding 250 nm, the stability viewpoint may be unfavorable as a cosmetic material during long-term storage under high-temperature conditions, or the feeling of use may be unfavorable.
  • the microgel used in the present invention can be confirmed to reduce the characteristic stickiness of the moisturizer only by adding 0.001% by mass in water, and functions as a usability improver by mixing. It is. With the conventional technology, it has been difficult to suppress the stickiness of the skin at the time of application and after drying while maintaining the moisturizing effect due to the high formulation of the moisturizing agent.
  • the blending amount of the moisturizer is preferably 0.1% by mass or more and less than 40% by mass with respect to the total amount of the external preparation for skin.
  • the humectant used in the present invention is preferably a polyhydric alcohol.
  • glycerin is preferable, and as humectants other than glycerin, polyethylene glycol, 1,3-butylene glycol, erythritol, dipropylene glycol, betaine, sonorebitole, xylitol, maltitol, mucopolysaccharide, hyaluronic acid, chondroitin sulfate, chitin , Chitosan and the like.
  • the external preparation for skin of the present invention comprises an oil, an oil-soluble drug that dissolves in the oil, and Z or fragrance. Even if it is used in cosmetics containing a cosmetic, it can provide an external preparation for skin with excellent moisturizing effect and usability. In this case as well, as described above, the moisturizing amount is based on the total amount of the external preparation for skin.
  • the oily component to be blended in the system may be any of a liquid oil, a solid oil, a semi-solid oil, or a substance hardly soluble in water. Among these, it is most preferable to blend a liquid polar oil.
  • the copolymer used in the present invention is the same as the copolymer of Invention C.
  • the multilayer cosmetic of the present invention is produced by mixing and dispersing this copolymer in water (or an aqueous phase in which water-soluble cosmetic ingredients are dissolved) by a conventional method. That is, the multilayer cosmetic of the present invention is a composition having an excellent commercial value that can be produced by an extremely simple manufacturing process.
  • the microgel used in the present invention is desirably blended in the range of usually 0.001 to 90% by mass based on the total amount of the multilayer cosmetic, and more preferably 0.01 to 50% by mass. It is difficult to obtain a stable multi-layered composition if the blending amount of the Miku Mouth gel is less than 0.001% by mass. There are cases.
  • microgel used in the present invention becomes cloudy only by adding 0.01 mass% to water.
  • a layer boundary with a clear layer boundary is obtained with a blending amount of 0.01% by mass, and functions as an excellent clouding agent.
  • it is difficult to clarify the layer boundary and there is no one in which the aqueous phase is cloudy.
  • the multilayer cosmetic of the present invention contains 540 mass% of a liquid oil.
  • the liquid oil is exemplified below. Even when oil-soluble chemicals and fragrances are dissolved in liquid oil, the layer boundary is clear. Layered cosmetics can be provided.
  • 5 to 40% by mass of the content of the liquid oil means the content including oil such as solid, semi-solid oil, oil-soluble drug, oil-soluble fragrance, etc. that dissolves in the liquid oil of the base. .
  • the liquid oil used in the present invention is not limited as long as it is a liquid oil at room temperature (15 ° C).
  • the multilayer cosmetic of the present invention having a clear layer boundary is substantially free of a surfactant.
  • a surfactant When a surfactant is added, an emulsification phenomenon may occur, and it may be difficult to form a clear boundary.
  • a stable and uniform emulsion composition is generated and can be separated even if left standing. In some cases, the multi-layered appearance does not occur.
  • Any surfactant that can be added in a weight composition with respect to the liquid oil with a blending amount of 0.8 or less is not limited.
  • the multilayer cosmetic of the present invention is blended with a thickener of a natural polymer or a synthetic polymer, the usability and the separation rate of the multilayer can be adjusted.
  • a thickener when such a thickener is blended, the boundary in an ordinary multilayer cosmetic becomes unclear, but in the present invention, a clear and beautiful multilayer cosmetic can be provided.
  • the amount of thickener is not limited, but is preferably 0.01 to LO mass% with respect to the total amount of the multilayer cosmetic.
  • the thickener that can be blended in the multilayer cosmetic of the present invention is not limited to either a natural water-soluble polymer or a semi-synthetic synthetic water-soluble polymer.
  • the multi-layer cosmetic of the present invention includes a medicinal agent, a moisturizing component, an anti-inflammatory agent, a bactericide, an antiseptic, an ultraviolet absorber, an antioxidant, an organic and inorganic powder, and a fragrance that are commonly used in cosmetics. , Pigments and the like can be blended as necessary.
  • the product type of the multilayer cosmetic of the present invention is not limited.
  • the most preferred product is multi-layered lotion, but it can also be applied to cosmetics such as liquid hair cosmetics and liquid baths.
  • Polyethylene oxide macromonomer polyethyleneglycololemethinoreethenore methacrylate; Nippon Oil & Fats Bremer PME-4000
  • C4MA n-butyl methacrylate
  • C8MA 2-ethylhexyl methacrylate
  • C12MA dodecyl methacrylate
  • EGDM ethylene glycol dimethacrylate
  • a polymerization initiator 2,2, azobis (2-methylpropionamidine dihydrochloride) (manufactured by Aldrich) was used.
  • water ion exchange water was used.
  • Other organic solvents used are as follows. Ethyl alcohol (Aldrich), benzene (Aldrich) and hexane (Aldrich).
  • the polymerization of the microgel was carried out by the following method.
  • PME-4000 219.5 mg
  • C4MA n-butyl methacrylate
  • C4MA n-butyl methacrylate
  • the completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred for 8 hours in an oil bath at 65 to 70 ° C while stirring with a magnetic stirrer. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water.
  • the sample obtained here is PMG 1.
  • the polymerization of the microgel was carried out by the following method.
  • 2,2′azobis (2-methylpropionamidine dihydrochloride) is added at a ratio of 1 mol% with respect to the total amount of monomers and further dissolved.
  • the completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred for 8 hours in an oil bath at 65 to 70 ° C while stirring with a magnetic stirrer. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water.
  • the sample obtained here is PMG2.
  • the polymerization of the microgel was carried out by the following method.
  • PME-4000 136.
  • lmg dodecylmetatalylate (C12MA) 863.9 mg
  • Dissolve 1.2 mg of ethylene glycol dimetatalylate After sufficient dissolution, add 2,2′azobis (2-methylpropionamidine dihydrochloride) at a ratio of 1 mol% with respect to the total amount of monomer and further dissolve.
  • the completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred for 8 hours in an oil bath at 65 to 70 ° C while stirring with a magnetic stirrer. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water.
  • the sample obtained here is PMG3.
  • the polymerization of the microgel was carried out by the following method.
  • 2,2'azobis (2-methylpropionamidine dihydrochloride) at a rate of lmol% with respect to the total amount of monomer and further dissolve.
  • the completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred for 8 hours at 65 to 70 ° C in an oil bath while stirring with a magnetic stirrer. After the polymerization, the polymerization solution is returned to room temperature, Dialyze for 5 days to remove residual monomer and simultaneously replace the dispersion with water.
  • the sample obtained here is PMG4.
  • Sample numbers PMG1 and PMG2 are the microgels of the present invention.
  • PMG3 and PMG4 both have an alkyl chain length (R) of the hydrophobic monomer of formula (A-2)
  • Comparative Example A-1 uses dodecylmetatalylate, which is a hydrophobic monomer with a large number of R carbon atoms.
  • the Comparative Example A-2 (PMG4) uses methylmetatalate, which has R carbon atoms
  • PMG3 was transparent in the polymerization solution at the end of polymerization and did not take the form of a microgel. Due to the high content of ethanol, the polymer appears to be dissolved in ethanol. Further, when the alcohol content of the mixed solvent was decreased, the hydrophobic monomer was not sufficiently dissolved, and the reaction solution before the polymerization reaction became cloudy.
  • Crosslinking rate (%) is mass% of EGDM with respect to the total mass of PME4000 and hydrophobic monomer.
  • the microgel particle size was measured using a zeta plus manufactured by Ichibun Co., Ltd. in Brook. Prepare a measurement sample by adjusting the microgel concentration of the microgel dispersion to approximately 0.1%, remove dust with a 0.45 micrometer filter, and then determine the scattering intensity at 25 ° C at a scattering angle of 90 °.
  • the average particle size and the degree of dispersion were calculated using analysis software installed in the measuring device.
  • the particle size is analyzed by cumulant analysis, and the degree of dispersion is obtained by cumulant analysis. This is a numerical value obtained by standardizing the value of the second-order cumulant.
  • This degree of dispersion is a commonly used parameter and can be automatically prayed by using a commercially available dynamic light scattering measurement device.
  • the viscosity of the solvent necessary for the particle size analysis the viscosity of pure water at 25 ° C., that is, a value of 0.89 mPas was used.
  • the measurement was performed 10 times for each sample and the average value was taken.
  • the degree of swelling with an organic solvent was measured by the following method. RA-PE408 and MCX! /, which are oils commonly used in cosmetics, used artificial sebum.
  • Samples of PMG1, 2, and 4 had a particle size of about 50 to 150 nm, the dispersities were both less than 0.05, and the particle size distribution was relatively narrow.
  • a mixed solution obtained by dissolving (9) to (12) and (20) to (22) in (26) was added to a solution obtained by melting and mixing other components to obtain an emulsion.
  • a liquid obtained by melting and mixing (1), (2) and (7) was stirred and mixed with other components at a high temperature, and cooled to obtain a conditioner.
  • Titanium oxide appropriate amount
  • Polyethylene oxide macromonomer polyethyleneglycololemethinoreethenore methacrylate; Nippon Oil & Fats Bremer PME-4000
  • methyl methacrylate abbreviated as C1MA; manufactured by Aldrich
  • n-butyl methacrylate abbreviated as C4MA; Aldrich
  • 2-ethyl hexamethyl methacrylate abbreviated as C8MA; manufactured by Aldrich
  • EGDM ethylene glycol dimethacrylate
  • the polymerization of the microgel was carried out by the following method.
  • 2,2′azobis (2-methylpropionamidine dihydrochloride) is added at a ratio of 1 mol% with respect to the total amount of monomers and further dissolved.
  • the completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred in a magnetic stirrer and kept in an oil bath at 65 to 70 ° C for 8 hours for polymerization. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water.
  • the sample obtained here is PMG1.
  • the polymerization of the microgel was carried out by the following method.
  • 2, 2'azobis (2-methylpropionamidine) Dihydrochloride is added at a rate of 1 mol% with respect to the total monomer amount and further dissolved.
  • the completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred in a magnetic stirrer and kept in an oil bath at 65 to 70 ° C for 8 hours for polymerization. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water.
  • the sample obtained here is PMG2.
  • the polymerization of the microgel was carried out by the following method.
  • a 200 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube is mixed with water.
  • 2,2′azobis (2-methylpropionamidine dihydrochloride) is added at a ratio of 1 mol% with respect to the total amount of monomers and further dissolved.
  • the completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred in a magnetic stirrer and kept in an oil bath at 65 to 70 ° C for 8 hours for polymerization. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water.
  • the sample obtained here is PMG3.
  • the polymerization of the microgel was carried out by the following method.
  • 2,2′azobis (2-methylpropionamidine dihydrochloride) is added at a ratio of 1 mol% with respect to the total amount of monomers and further dissolved.
  • the polymerization of the microgel was carried out by the following method.
  • 280 mg of PME-4000 and 853.2.2 mg of methyl metatalylate (C IMA) Dissolve 2. mg of ethylene glycol dimetatalylate.
  • C IMA methyl metatalylate
  • the completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred for 8 hours at 65 to 70 ° C in an oil bath while stirring with a magnetic stirrer.
  • the polymerization solution After completion of the polymerization, the polymerization solution is returned to room temperature, and the polymerization solution is dialyzed against water for 5 days to remove residual monomers, and at the same time, the dispersion is replaced with water.
  • the sample obtained here is PMG5.
  • Sample numbers PMG1, 2, 3, and 4 are the microgels of the present invention.
  • PMG5 is a comparative example in which only the hydrophobic monomer of formula (B-2) is used without using the hydrophobic monomer of formula (B-3). Each sample had a cloudy color at the end of the reaction.
  • crosslinking ratio (%) is the mass 0/0 of EGD M to the total mass of PME4000 and hydrophobic monomers.
  • the microgel particle size was measured using a zeta plus manufactured by Ichibun Co., Ltd. in Brook. Prepare a measurement sample by adjusting the microgel concentration of the microgel dispersion to about 0.1%. After removing dust with a micrometer filter, the scattering intensity at 25 ° C was measured at a scattering angle of 90 °, and the average particle size and degree of dispersion were calculated with the analysis software installed in the measuring device.
  • the particle size is analyzed by the cumulant analysis method, and the degree of dispersion is a numerical value obtained by standardizing the value of the secondary cumulant obtained by the cumulant analysis. This degree of dispersion is a commonly used parameter and can be automatically prayed by using a commercially available dynamic light scattering measurement device.
  • the viscosity of the solvent necessary for the particle size analysis the viscosity of pure water at 25 ° C., that is, a value of 0.89 mPas was used.
  • the measurement was performed 10 times for each sample and the average value was taken.
  • the degree of swelling with an organic solvent was measured by the following method.
  • polymethacrylalkyl forms a core portion.
  • the solvent used was benzene, which is a good solvent, and hexane, which is a poor solvent, for polymethacrylic methyl.
  • RA-PE408, MCX or artificial sebum which is a common oil used in cosmetics, was used.
  • the sample particle size was about 50-150 nm. Although the degree of dispersion of the microgel of the present invention was higher than that of PMG5, monodisperse particles having a degree of dispersion of less than 0.10 were obtained.
  • the PMG1-5 samples were measured for swelling degree by RA-PE408, MCX and artificial sebum. The results are shown in “Table B-3”.
  • PMG5 does not swell at all for polar oils such as RA-PE408 and MCX and human sebum, which are widely used as cosmetic raw materials, and a monomer having several alkyl chain lengths is mixed with a hydrophobic monomer As a result, it swelled with respect to these oils. This is because the length of the alkyl chain in the core part of the mouth-opening gel becomes bulky, and the glass transition temperature decreases, so the range of solvents that can be swollen with high flexibility is widened. It is done.
  • HEDTA3 Sodium 0.1 Microgel (PMG1) 0.1
  • Decamethylcyclopentasiloxane 20 Ethanol 5 Isostearyl alcohol 2 Dipropylene glycol 3 Isostearic acid 2 Tri 2-Ethylhexanoic acid glyceryl 5 2-Ethylhexanoic acid cetyl 2 Dextrin fatty acid ester-coated fine particle acid-titanium (40) Chloride Sodium 2 edetic acid 3 sodium proper amount ubinal T-150 (manufactured by BASF) 1 4-tert-butyl-4'-methoxydibenzoylmethane 1 paramethoxycinnamic acid 2-ethylhexyl 7.5 carboxymethylcellulose Na 0.4 microgel (PMG4) 0.1 ethino Resenorelose 1 Spherical acrylic resin powder 5 Purified water Residue Fragrance Appropriate amount
  • 1,3-Butyleneglycolanol 10 Posiethyleneglycolole 1500 1 Polyoxyethylene methyl darcoside 1 Microgenole (PMG4) 0.05 Polyethylene glycol diisostearate 5 Dipotassium glycyrrhizinate 0.1 Cora 'de' cabaro extract 0.1 Tride acid tri Na 0.01 Hydroxypropylmethylcellulose 0.8 Carboxybule polymer potassium 0.35 Noroxybenzoate Suitable amount Purified water Residual
  • Example B 12 facial cleansing foam
  • Dimethylolene polysiloxane 2 Decamethylcyclopentasiloxane 5 Ethanol 3 Be Reinoreconolele 0.1 Notinorenoreconolele 0.1 Dipropylene glycol 5 1,3-Butyleneglycol / Le 3 Posiethylene gucco / re 1500 4 Plant squalene 0.1 Polyoxyethylene glyceryl isostearate 0.3 Titanium oxide 'Bengara-coated mica 0.3 Mica titanium 0.3 Potassium hydroxide 0.2 Hexametaphosphate 0.05 Tocopherol acetate 0.1 Noroxybenzoic acid ester Suitable amount Lithium cobalt titanate Suitable amount Porous spherical cellulose powder 0.5 Microgel (PMG2 ) 0.2 Canolepoxy bis / repolymer 0.2 Acrylic acid 'alkyl methacrylate copolymer 0.2 Purified water Residual
  • Titanium oxide Appropriate amount Plate-like barium sulfate Appropriate amount Kaolin 8
  • the polymerization of the microgel was carried out by the following method.
  • a 200 mL three-necked flask equipped with a reflux tube and a nitrogen inlet tube is mixed with water.
  • PME—4000 methyl metatalylate
  • nBMA butyl metatalylate
  • EHMA 2-ethylhexylmetatalylate
  • E GDMA ethylene glycol dimetatalylate
  • 2,2′azobis (2-methylpropionamidine dihydrochloride) is added at a ratio of 1 mol% with respect to the total amount of monomers and further dissolved.
  • the completely homogenized polymerization solution is purged with nitrogen for 20 minutes to remove dissolved oxygen, and then stirred in a magnetic stirrer and kept in an oil bath at 65 to 70 ° C for 8 hours for polymerization. After completion of the polymerization, the polymerization solution is returned to room temperature, and then the polymerization solution is dialyzed against water for 5 days to remove the residual monomer, and at the same time, the dispersion is replaced with water.
  • the amount of monomer used (g) is shown in “Table C-1”.
  • Production example 1 1 114.5 0.082
  • the white turbidity was evaluated based on the straightness (brightness) obtained by measuring the microgel-containing lotion with a Macbeth color difference meter.
  • microgel compounded lotion water was stored in a thermostatic bath, and the L value after one month was measured.
  • the following cloudy lotion (moisturizing lotion) was prepared by the following production method.
  • the lotion of Comparative Example c 1 is a transparent lotion without blending the polymer of Production Example.
  • Example 1 Example 2
  • Example 3 Example 4
  • Example 5 Example 6 Manufacturing Example 1 0.1-----Manufacturing Example 2-0. 1---Manufacturing Example 3--0. 1--- Production Example 4 ⁇ ⁇ ⁇ 0.1.
  • the cloudy lotion of each example is particularly It is a lotion that improves the stickiness derived from the surfactants of conventional cloudy lotions, and that also has a feeling of richness, quick familiarity, and shine control.
  • the present invention can provide an excellent cloudy cosmetic, not only for cosmetic raw material oils but also for cosmetics containing an oil-soluble drug and Z or a fragrance.
  • copolymer used in the present invention is the same as that of invention C.
  • Skin conductance was measured before and 120 minutes after application using the forearm of 10 panelists, and the moisturizing effect was evaluated from the rate of change. In addition, it is possible to examine the effect of the stratum corneum on the water absorption and water retention capacity by the skin conductance increase rate. .
  • Evaluation criteria of "Evaluation (1) Test by conductance measurement” are as follows. ⁇ ⁇ ⁇ ⁇ Panel 10 conductance increase average force 0% or more

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Abstract

L’invention concerne un microgel gonflant dans les solvants organiques, lequel est constitué d’un copolymère obtenu par polymérisation radicalaire, dans un solvant mixte eau/éthanol, d’un macromonomère spécifique de l’oxyde de polyéthylène avec un monomère hydrophobe spécifique et un monomère de réticulation spécifique, à la condition que : (A) le taux de charge de macromonomère d’oxyde de polyéthylène par rapport au monomère hydrophobe soit de 1/10 à 1/250 en mole, (B) la charge de monomère de réticulation varie de 0,1 à 1,5 % en poids, par rapport au poids du monomère hydrophobe, et (C) le rapport eau/éthanol du solvant mixte varie de (90 à 30)/(10 à 70) en volume, à 20 °C. L’invention a pour but de produire un nouveau microgel gonflant dans les solvants organiques, un procédé pour le préparer et des cosmétiques contenant le copolymère constituant le microgel.
PCT/JP2005/020341 2004-11-09 2005-11-07 Microgel gonflant dans les solvants organiques et procede pour le preparer WO2006051746A1 (fr)

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WO2008040786A1 (fr) * 2006-10-05 2008-04-10 Basf Se Polymères en peigne et leur utilisation pour la préparation de formulations de substance active ou à effet
JP2009242326A (ja) * 2008-03-31 2009-10-22 Shiseido Co Ltd 美白液状化粧料
CN102415955A (zh) * 2010-09-27 2012-04-18 株式会社芳珂 乳化组合物
WO2013094298A1 (fr) * 2011-12-22 2013-06-27 株式会社資生堂 Émulsifiant à microgel de type cœur-couronne, et composition d'émulsion huile-dans-eau
FR2996133A1 (fr) * 2012-10-02 2014-04-04 Oreal Nouvelles utilisations cosmetiques de polymeres dispersants en association avec au moins un actif
WO2016025568A1 (fr) * 2014-08-15 2016-02-18 Dow Global Technologies Llc Dispersion d'éthylcellulose et de poudre
JP2016172703A (ja) * 2015-03-17 2016-09-29 積水化成品工業株式会社 化粧料
RU2645110C1 (ru) * 2014-08-06 2018-02-15 Шисейдо Компани, Лтд. Исходный материал для косметических средств
WO2019182127A1 (fr) * 2018-03-23 2019-09-26 株式会社 資生堂 Matière première pour produit cosmétique mettant en oeuvre des particules polymères de type coeur-couronne ainsi que produit cosmétique en émulsion de type huile dans l'eau
WO2019182125A1 (fr) * 2018-03-23 2019-09-26 株式会社 資生堂 Matière première pour produit cosmétique mettant en oeuvre des particules polymères de type coeur-couronne ainsi que produit cosmétique en émulsion de type huile dans l'eau
WO2019182124A1 (fr) * 2018-03-23 2019-09-26 株式会社 資生堂 Matière première pour produit cosmétique mettant en oeuvre des particules polymères de type coeur-couronne ainsi que produit cosmétique en émulsion de type huile dans l'eau
WO2019182126A1 (fr) * 2018-03-23 2019-09-26 株式会社 資生堂 Particules polymères de type coeur-couronne

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JP2006160725A (ja) * 2004-11-09 2006-06-22 Shiseido Co Ltd 化粧料
US9522970B2 (en) 2006-10-05 2016-12-20 Basf Se Comb polymers and use thereof for the production of active or effective ingredient formulations
WO2008040786A1 (fr) * 2006-10-05 2008-04-10 Basf Se Polymères en peigne et leur utilisation pour la préparation de formulations de substance active ou à effet
JP2009242326A (ja) * 2008-03-31 2009-10-22 Shiseido Co Ltd 美白液状化粧料
CN102415955A (zh) * 2010-09-27 2012-04-18 株式会社芳珂 乳化组合物
WO2013094298A1 (fr) * 2011-12-22 2013-06-27 株式会社資生堂 Émulsifiant à microgel de type cœur-couronne, et composition d'émulsion huile-dans-eau
CN104159662A (zh) * 2011-12-22 2014-11-19 株式会社资生堂 冠-核型微凝胶乳化剂和水包油型乳化组合物
CN104159662B (zh) * 2011-12-22 2016-05-11 株式会社资生堂 冠-核型微凝胶乳化剂和水包油型乳化组合物
TWI558416B (zh) * 2011-12-22 2016-11-21 Shiseido Co Ltd A core-corona type microgel emulsifier and a water-based emulsified composition
JP2013147486A (ja) * 2011-12-22 2013-08-01 Shiseido Co Ltd コロナ−コア型ミクロゲル乳化剤及び水中油型乳化組成物
US9539554B2 (en) 2011-12-22 2017-01-10 Shiseido Company, Ltd. Method of making oil-in-water emulsified composition using corona-core microgel emulsifying agent
US9539553B2 (en) 2011-12-22 2017-01-10 Shiseido Company, Ltd. Corona-core microgel emulsifying agent and oil-in-water emulsified composition
RU2607088C1 (ru) * 2011-12-22 2017-01-10 Шисейдо Компани, Лтд. Микрогелевый эмульгатор типа "ядро-оболочка" и эмульсионная композиция типа "масло в воде"
FR2996133A1 (fr) * 2012-10-02 2014-04-04 Oreal Nouvelles utilisations cosmetiques de polymeres dispersants en association avec au moins un actif
RU2645110C1 (ru) * 2014-08-06 2018-02-15 Шисейдо Компани, Лтд. Исходный материал для косметических средств
WO2016025568A1 (fr) * 2014-08-15 2016-02-18 Dow Global Technologies Llc Dispersion d'éthylcellulose et de poudre
JP2016172703A (ja) * 2015-03-17 2016-09-29 積水化成品工業株式会社 化粧料
WO2019182125A1 (fr) * 2018-03-23 2019-09-26 株式会社 資生堂 Matière première pour produit cosmétique mettant en oeuvre des particules polymères de type coeur-couronne ainsi que produit cosmétique en émulsion de type huile dans l'eau
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