WO2016204258A1 - Polymère pour formation de gel et matériau adhésif dermatologique - Google Patents

Polymère pour formation de gel et matériau adhésif dermatologique Download PDF

Info

Publication number
WO2016204258A1
WO2016204258A1 PCT/JP2016/068029 JP2016068029W WO2016204258A1 WO 2016204258 A1 WO2016204258 A1 WO 2016204258A1 JP 2016068029 W JP2016068029 W JP 2016068029W WO 2016204258 A1 WO2016204258 A1 WO 2016204258A1
Authority
WO
WIPO (PCT)
Prior art keywords
monomer unit
skin
copolymer
formula
group
Prior art date
Application number
PCT/JP2016/068029
Other languages
English (en)
Japanese (ja)
Inventor
翼 菓子野
武久 岩間
柴田　雅史
Original Assignee
日産化学工業株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 日産化学工業株式会社 filed Critical 日産化学工業株式会社
Priority to JP2017524843A priority Critical patent/JPWO2016204258A1/ja
Publication of WO2016204258A1 publication Critical patent/WO2016204258A1/fr

Links

Images

Classifications

    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/32—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. carbomers, poly(meth)acrylates, or polyvinyl pyrrolidone
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
    • A61K8/81—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/08—Solutions
    • 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
    • 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

Definitions

  • the present invention relates to a gel-forming polymer, a gel-forming polymer mixture, a skin-adhesive material, and a skin-adhesive gel suitable as a base for external preparations for skin, such as cosmetics and external preparations for skin use used in the skin care field.
  • a base for example, there is a sheet-like base in which a layer of a composition containing a polymer or copolymer and a crosslinking agent is formed on a support, and more specifically, the polymer or copolymer Water-soluble sheet-like base using polyvinyl alcohol, polyacrylic acid or a salt thereof as a combination, a hydrophobic copolymer using a rubber-based copolymer or a silicone-based copolymer as a polymer or copolymer
  • a sheet-like base Generally, a skin external preparation using a water-soluble sheet base is called a poultice, and a skin external preparation using a hydrophobic sheet base is called a tape.
  • the external preparation for skin using the above sheet-like base also has disadvantages. That is, there are very fine irregularities on the skin surface, and it is difficult to say that the solidified sheet-like base is completely in contact with the skin surface, and there are always voids. Therefore, the adhesiveness of the base to the skin is weak, and the external preparation for skin may fall off during daily activities. In addition, moisture and the like in the base evaporate with time and cure to lose flexibility. If the patch or tape loses its flexibility, it will not be able to follow the movement of the body of the applicator, and the adhesion to the skin will be further reduced, making it easier to peel off, and active ingredients and moisture will not penetrate into the skin well. A phenomenon occurs.
  • Patent Documents 1 to 3 propose a base formulation that improves the adhesiveness and prevents moisture evaporation by devising the composition of the adhesive (polymer or copolymer).
  • the tape agent is a polymer or copolymer that becomes an adhesive, a cross-linking agent that cross-links the polymer or copolymer, and an active ingredient and moisture. It is obtained by spreading the mixture on the support, but at that time, the active ingredient and moisture are partially bonded to the crosslinking agent or polymer due to the chemical reaction with the crosslinking agent or polymer, so the tape agent is applied Even if affixed to the site, the active ingredient and water do not transfer to the skin, and the effect may not be sufficiently exhibited.
  • Patent Document 6 has developed a copolymer having a structure capable of directly crosslinking between copolymers without using a crosslinking agent composed of a low-molecular compound, and effective in that.
  • a combination of ingredients and moisture has been proposed to improve the transfer of active ingredients and moisture to the skin compared to existing sheet bases. No mention is made of the problem of adhesion and the problem of adhesiveness of the base material over time.
  • film forming agent in which a solution in which a polymer or a copolymer is dissolved is directly applied to an application site, and the solution is dried on the skin to form a film.
  • a film forming agent a film forming agent using a highly unique artificial synthetic copolymer in order to exhibit a specific function in addition to those actually used for a long time using polyvinyl pyrrolidone, polyvinyl alcohol, etc.
  • Patent Document 7 Nail polish applied to nails and the like
  • Patent Document 8 Antibacterial and antifouling
  • Patent Document 9 Protection from external stimuli such as ultraviolet rays
  • Patent Document 10 Hairdressing
  • Patent Document 11 Prevention of skin roughness due to drying
  • Patent Documents 12 and 13 General makeup such as eyeliner, mascara, facial cosmetics, etc.).
  • JP 2011-88890 A Japanese Patent Laid-Open No. 6-40893 JP 2013-216636 A JP-A-6-142178 JP-A-8-208459 JP 2009-149660 A JP-A-2005-350466 JP 2010-5161 A Japanese Patent Laid-Open No. 5-331019 Special table 2006-508937 JP 2003-12437 A JP 2006-507367 A Special table 2014-528420 gazette
  • the present invention has been made in view of the above circumstances, and the problem to be solved is a novel adhesive for skin that can form a hydrogel excellent in adhesion to the skin surface and adhesion to the skin. It is to provide a material and to provide a gel-forming polymer material for use in the adhesive material for skin.
  • the inventors have completed the present invention as a result of intensive studies from a completely new viewpoint in order to solve the above problems. That is, a liquid material (sol) containing moisture and polymer is applied to the skin to wet the skin crevice, and a part of the moisture in the liquid volatilizes or is absorbed into the skin to quickly gel. In the hypothesis that the resulting gel will adhere to the skin surface without forming a gap, and the adhesiveness will not easily decrease over time.
  • a liquid material (sol) containing moisture and polymer is applied to the skin to wet the skin crevice, and a part of the moisture in the liquid volatilizes or is absorbed into the skin to quickly gel.
  • the resulting gel will adhere to the skin surface without forming a gap, and the adhesiveness will not easily decrease over time.
  • a copolymer having a monomer unit containing a polyalkylene glycol skeleton having a specific degree of polymerization in the side chain and a monomer unit containing a branched alkyl group having a specific number of carbon atoms in the side chain is converted into an aqueous solvent. It has been found that the dispersion liquid dispersed in can be a material that quickly gels on the skin when applied to the above skin, and has completed the present invention.
  • a monomer unit (I) having a polyalkylene glycol skeleton having a polymerization degree of 2 to 100 in the side chain and a monomer unit (II) having a branched alkyl group having 3 to 30 carbon atoms in the side chain A gel-forming polymer comprising the copolymer (A).
  • the monomer unit (I) is a monomer unit represented by the following formula (1)
  • the monomer unit (II) is a monomer unit represented by the following formula (2)
  • R 1 represents a hydrogen atom or a methyl group
  • X 1 represents —O—, —CH 2 —O—, —CO—, —CO—O—, or —CO—NR 2 —
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms
  • A represents an alkylene group, 2 ⁇ n ⁇ 100 .
  • R 4 represents a hydrogen atom or a methyl group
  • X 2 represents —O—, —CH 2 —O—, —CO—, or —CO—O—
  • R 5 represents 3 carbon atoms
  • the copolymerization ratio a1 ((1) :( 2)) of the monomer unit represented by the formula (1) and the monomer unit represented by the formula (2) in the copolymer (A) is: 5.
  • the polymer according to [6], wherein the monomer unit (III) is a monomer unit represented by the following formula (3).
  • the monomer unit (I) is a monomer unit represented by the following formula (1)
  • the monomer unit (II) is a monomer unit represented by the following formula (2)
  • R 1 represents a hydrogen atom or a methyl group
  • X 1 represents —O—, —CH 2 —O—, —CO—, —CO—O—, or —CO—NR 2 —
  • R 2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms
  • R 3 represents a hydrogen atom or an alkyl group having 1 to 18 carbon atoms
  • A represents an alkylene group, 2 ⁇ n ⁇ 100 .
  • R 4 represents a hydrogen atom or a methyl group
  • X 2 represents —O—, —CH 2 —O—, —CO—, or —CO—O—
  • R 5 represents 3 carbon atoms
  • R 6 represents a hydrogen atom or a methyl group
  • X 3 represents —O—, —CH 2 —O—, —CO—, or —CO—O—
  • R 7 represents 3 carbon atoms
  • the branched alkyl group having 3 to 30 carbon atoms represented by R 5 in the formula (2) is any one of groups represented by the following formulas (4) to (6). Or a polymer mixture according to [11].
  • the copolymerization ratio a3 ((1) :( 2)) of the monomer unit represented by the formula (1) and the monomer unit represented by the formula (2) in the copolymer (A) is: 1:99 to 90:10 (molar ratio), and the copolymer ratio of the monomer unit represented by the formula (1) and the monomer unit represented by the formula (3) in the copolymer (B)
  • [14] (a) The polymer or polymer mixture according to any one of [1] to [13] above, A liquid composition comprising (b) water, and (c) an oil component, An adhesive material for skin that turns into a gel on the skin. [15] The adhesive material for skin according to [14], further comprising (d) an organic solvent. [16] The material according to [14] or [15] above, which is used as a base for an external preparation for skin. [17] The material according to [16] above, wherein the external preparation for skin is a cosmetic. [18] The material according to [16] above, wherein the external preparation for skin is an external preparation for skin. [19] A method for forming a skin adhesive gel, comprising bringing the skin adhesive material according to [14] or [15] into contact with the skin.
  • a gel-forming polymer or polymer mixture it is a liquid before application to the skin, but has excellent adhesion to the skin surface on the skin and good adhesion to the skin. It is possible to realize a pressure-sensitive adhesive material for skin that preferably changes to a gel (preferably a hydrogel having excellent adhesion to the skin surface, good adhesion to the skin, and no stickiness).
  • the adhesive material for skin obtained by the present invention is suitable as a base for external preparations for skin, and when used as a base for external preparations for skin, the base adheres to the skin and the skin is sufficiently hydrated. Since the moist state can be maintained, it is possible to obtain a skin external preparation excellent in the penetration of active ingredients and moisture into the skin.
  • FIG. 2 is a phase diagram of the composition prepared in Example 3.
  • FIG. 2 is a phase diagram of the composition prepared in Example 4.
  • FIG. 2 is a phase diagram of the composition prepared in Example 5.
  • FIG. 2 is a phase diagram of the composition prepared in Example 6.
  • FIG. 2 is a phase diagram of the composition prepared in Comparative Example 1.
  • the gel-forming polymer of the present invention comprises a monomer unit (I) having a polyalkylene glycol skeleton having a degree of polymerization of 2 to 100 in the side chain and a monomer having a branched alkyl group having 3 to 30 carbon atoms in the side chain. It consists of a copolymer (A) containing unit (II).
  • Copolymer (A) gels by coexisting with water. That is, the polyalkylene glycol skeletons having a degree of polymerization of 2 to 100 in the side chain of the monomer unit (I) are cross-linked via water molecules to form a gel and form a hydrogel.
  • the branched alkyl group having 3 to 30 carbon atoms in the side chain of the monomer unit (II) gives skin adhesiveness. Accordingly, a skin-adhesive hydrogel can be formed.
  • the monomer unit (I) is preferably a monomer unit represented by the following formula (1) (hereinafter also abbreviated as “monomer unit of formula (1)”).
  • R 1 represents a hydrogen atom or a methyl group
  • X 1 represents —O—, —CH 2 —O—, —CO—, —CO—O— or —CO—NR 2 —.
  • R 2 in —CO—NR 2 — represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
  • R 3 represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms, preferably a hydrogen atom, a methyl group, an ethyl group, a propyl group, or an isopropyl group, and more preferably a hydrogen atom or a methyl group.
  • A represents an alkylene group, and the alkylene group preferably has 1 to 5 carbon atoms, more preferably 2 to 3 carbon atoms.
  • n — represents a polyalkylene glycol skeleton, and the oxyalkylene group represented by A—O may be composed of one oxyalkylene group, for example, an ethylene oxide group and You may be comprised from multiple types of oxyalkylene groups, such as two types with a propylene oxide group.
  • the polymerization degree n of the polyalkylene glycol skeleton is 2 ⁇ n ⁇ 100, preferably 5 ⁇ n ⁇ 10000, more preferably 10 ⁇ n ⁇ 100, and particularly preferably 10 ⁇ n ⁇ 50. . If n is in such a preferable range, a sufficient effect can be easily obtained.
  • the monomer unit of the formula (1) is a unit derived from a (meth) acrylic monomer (wherein X 1 is —CO—O—), a unit derived from a (meth) allyl ether monomer (formula Wherein X 1 is —CH 2 —O—), a unit derived from a vinyl ether monomer (wherein X 1 is —O—), and a unit derived from a (meth) acrylamide monomer (wherein X 1 is preferably any one or more selected from —CO—NR 2 —), more preferably a unit derived from a (meth) acrylic monomer.
  • “(meth) acryl” means both “acryl” and “methacryl”.
  • R 1 is a methyl group
  • X 1 is —CO—O—
  • — (A—O) n — has a degree of polymerization of 10 to 100 polyethylene glycol residues, polyethylene glycol methacrylate, wherein R 3 is a hydrogen atom.
  • the monomer unit (II) having a branched alkyl group having 3 to 30 carbon atoms in the side chain is preferably a monomer unit represented by the following formula (2) (hereinafter referred to as “single unit of the formula (2) It is also abbreviated as “mer unit”).
  • R 4 represents a hydrogen atom or a methyl group
  • X 2 represents —O—, —CH 2 —O—, —CO—, or —CO—O—
  • R 5 represents a branched alkyl group having 3 to 30 carbon atoms.
  • Examples of the branched alkyl group having 3 to 30 carbon atoms represented by R 5 include isopropyl group, isobutyl group, sec-butyl group, t-butyl group, isohexyl group, isoheptyl group, isopentyl group, neopentyl group, t- Pentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group 1,1-dimethylbutyl group, 2,2-dimethylbutyl group, 3,3-dimethylbutyl group, 1,2-dimethylbutyl group, 2,3-dimethylbutyl group, 1,3-dimethylbutyl group, 1 -Ethylbutyl group, 2-ethylbutyl group, 1,1,2-trimethylpropyl group,
  • the monomer unit of the formula (2) is a unit derived from a (meth) acrylic monomer (wherein X 2 is —CO—O—), a unit derived from a (meth) allyl ether monomer (formula Wherein X 2 is —CH 2 —O—) and a unit derived from a vinyl ether monomer (wherein X 2 is —O—), and is preferably one or more of them, More preferably, it is a unit derived from a (meth) acrylic monomer.
  • R 4 is a hydrogen atom or a methyl group
  • X 2 is —CO—O—
  • R 5 is a branched alkyl of the formula (4) It is a (meth) acrylate monomer that is a group.
  • the copolymer (A) may be either a random copolymer or a block copolymer, but is preferably a random copolymer.
  • the copolymerization ratio a1 ((1) :( 2)) of the monomer unit of the formula (1) and the monomer unit of the formula (2) is 5:95 to 90 in terms of molar ratio. : 10 is preferable, 15:85 to 80:20 is more preferable, 20:80 to 70:30 is still more preferable, and 20:80 to 55:45 is particularly preferable.
  • the ratio of the monomer unit of formula (1) is too small, it is difficult to form a gel on the skin, and when it is too large, adhesion to the skin is difficult to obtain.
  • the copolymer (A) is a monomer unit having a linear alkyl group having 3 to 30 carbon atoms in the side chain ( It may be a copolymer further comprising III).
  • the monomer unit (III) is preferably a monomer unit represented by the following formula (3) (hereinafter also abbreviated as “monomer unit of formula (3)”).
  • R 6 represents a hydrogen atom or a methyl group
  • X 3 represents —O—, —CH 2 —O—, —CO—, or —CO—O—
  • R 7 represents 3 carbon atoms
  • the linear alkyl group having 3 to 30 carbon atoms represented by R 7 is, for example, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group.
  • the monomer unit of the formula (3) is a unit derived from a (meth) acrylic monomer (wherein X 3 is —CO—O—), a unit derived from a (meth) allyl ether monomer (formula Wherein X 3 is —CH 2 —O—) and a unit derived from a vinyl ether monomer (wherein X 3 is —O—), and is preferably one or more of them, More preferably, it is a unit derived from a (meth) acrylic monomer.
  • the most preferred embodiment of the monomer unit of the formula (3) is a methacrylate type unit wherein R 6 is a methyl group, X 3 is —CO—O—, and R 7 is an n-octadecyl group. It is a mer.
  • the copolymer (A) when the copolymer (A) is a copolymer containing the monomer unit of the formula (3), the copolymer (A) may be either a random copolymer or a block copolymer. A random copolymer is preferred. Further, a copolymerization ratio a2 ((1) :( 2) :( 3)) of the monomer unit of the formula (1), the monomer unit of the formula (2), and the monomer unit of the formula (3) Is preferably 5 to 60:10 to 90: 5 to 50 (provided that the sum of the three numerical values is 100) in terms of molar ratio.
  • the proportion of the monomer unit of the formula (1) is too small, it is difficult to form a gel on the skin, and if the proportion of the monomer unit of the formula (3) is too small, the sticking suppression effect of the gel is sufficient. When it becomes difficult to obtain and is too large, the skin adhesiveness of the gel tends to decrease.
  • the weight average molecular weight (Mw) of the copolymer (A) is preferably 5000 to 200,000, more preferably 10,000 to 100,000.
  • Mw weight average molecular weight
  • adhesion to the skin and gelling ability tend to be difficult to be expressed.
  • weight average molecular weight (Mw) is greater than 200000, for example, when an organic solvent (diluent) described later is used, It tends to be difficult to mix with organic solvents. If the weight average molecular weight (Mw) is within such a preferable range, a sufficient effect is easily obtained.
  • the weight average molecular weight (Mw) in the present invention is measured by gel permeation chromatography (GPC) method (polystyrene conversion).
  • GPC gel permeation chromatography
  • the weight average molecular weight by the GPC method is manufactured by Tosoh Corporation, HLC-8320GPC Eco-SEC as a measuring device, Tosoh Corporation, SuperHZ as a column, tetrahydrofuran or the like as a mobile phase, It can be measured at a column temperature of 25 ° C. and calculated using a standard polystyrene calibration curve.
  • the gel-forming polymer of the present invention has a monomer unit (I) having a polyalkylene glycol skeleton having a polymerization degree of 2 to 100 in the side chain and a branched alkyl group having 3 to 30 carbon atoms in the side chain.
  • the copolymer (A) containing the monomer unit (II) is added to the monomer units of the formulas (1) and (2), and the monomer unit of the formula (3) is further copolymerized.
  • the gel-forming polymer of the present invention has a polymerization degree of 2 to 100 in the side chain.
  • a copolymer (A) containing a monomer unit (I) having a polyalkylene glycol skeleton and a monomer unit (II) having a branched alkyl group having 3 to 30 carbon atoms in the side chain, and polymerized in the side chain Has a polyalkylene glycol skeleton of 2 to 100 degrees
  • a mixture (polymer mixture) with a monomer unit (I) and a copolymer (B) containing a monomer unit (III) having a linear alkyl group having 3 to 30 carbon atoms in the side chain There may be.
  • the preferred embodiment of the copolymer (A) is the monomer unit of the above formula (1) and the above formula (3). It is a copolymer with monomer units.
  • the monomer unit (I) in the copolymer (B) is preferably a monomer unit of the above formula (1), and the monomer unit (III) is preferably the above-mentioned monomer unit (III). It is a monomer unit of formula (3).
  • the preferable aspect of the monomer unit of Formula (1) and the monomer unit of Formula (3) in this case follows that in the above-mentioned copolymer (A).
  • the copolymer (A) in the polymer mixture may be either a random copolymer or a block copolymer, but a random copolymer is preferred.
  • the copolymerization ratio a3 ((1) :( 2)) of the monomer unit of the formula (1) and the monomer unit of the formula (2) is 1:99 to 90 in terms of molar ratio. : 10 is preferable, and 5:95 to 80:20 is more preferable. If the proportion of the monomer unit of the formula (1) is too small, there is a possibility that a powdery precipitation of the copolymer occurs on the skin, and if it is too large, it tends to be difficult to suppress the stickiness of the gel. .
  • the copolymer (B) in the polymer mixture may be either a random copolymer or a block copolymer, but a random copolymer is preferred.
  • the copolymerization ratio b1 ((1) :( 3)) of the monomer unit of the formula (1) and the monomer unit of the formula (3) is 1:99 to 90 in terms of molar ratio. : 10 is preferable, 5:95 to 80:20 is more preferable, 10:90 to 80:20 is still more preferable, and 10:90 to 55:45 is particularly preferable.
  • the weight average molecular weight (Mw) of the copolymer (B) is preferably from 5,000 to 200,000, more preferably from 10,000 to 100,000. If the weight average molecular weight (Mw) is less than 5000, the sticking suppression effect is hardly exhibited, and if it is more than 200000, the stickiness may be increased. If the weight average molecular weight (Mw) is within such a preferable range, a sufficient effect is easily obtained. If it is out of the above range, it becomes difficult to obtain adhesion to the skin.
  • the mixing ratio ((A) :( B)) of the copolymer (A) and the copolymer (B) in the polymer mixture is determined depending on the copolymerization ratio a3 in the copolymer (A) and the copolymer (B).
  • the mass ratio is preferably 95: 5 to 10:90, more preferably 90:10 to 40:60, although it varies depending on the polymerization ratio b1. If the ratio of the copolymer (B) is too small, the sticking suppression effect tends to be hardly exhibited, and if too large, the adhesion to the skin tends not to be sufficiently exhibited.
  • Copolymer (A) and copolymer (B) are, for example, monomer units of formulas (1) and (2), monomer units of formulas (1) to (3), or formula (1) ) And (3) can be obtained by polymerizing a monomer mixture to be used in the monomer unit in an inert gas atmosphere such as nitrogen in the presence of a radical polymerization initiator.
  • the polymerization (reaction temperature) may be performed by heating or cooling to a temperature suitable for the polymerization initiator.
  • the polymerization method include solution polymerization, dispersion polymerization, precipitation polymerization, bulk polymerization, and the like. Among these, solution polymerization or precipitation polymerization is preferable.
  • the reaction by solution polymerization in an organic solvent from the viewpoint of molecular weight control.
  • the organic solvent include alcohols such as methanol, ethanol, n-propanol, and isopropanol; esters such as methyl acetate and ethyl acetate; ketones such as acetone and methyl ethyl ketone; aromatic hydrocarbons such as benzene and toluene; From the viewpoint of the safety of the polymer to the living body, alcohols are preferred.
  • the solvent can be used alone or in combination of two or more.
  • the content of the organic solvent in the entire polymerization reaction product is preferably 1 to 100 parts by weight, more preferably 5 to 50 parts by weight per 1 part by weight of the total amount of all monomers. It is.
  • the polymerization initiator may be a general one used for copolymerization of a monomer having a radical polymerizable double bond, and an azo polymerization initiator is preferably used.
  • the azo polymerization initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, 2,2′-azobis-2,4-dimethylvaleronitrile. 2,2′-azobis-4-methoxy-2,4-dimethylvaleronitrile, dimethyl 2,2′-azobisisobutyrate and the like. These can use 1 type (s) or 2 or more types.
  • the amount of the polymerization initiator is preferably 1 to 100 mol%, more preferably 3 to 50 mol%, based on the total amount of monomers.
  • the polymerization reaction product containing the copolymer (copolymer (A) or copolymer (B)) produced by the polymerization reaction is appropriately dried, filtered, etc., and the copolymer is collected.
  • the solvent is concentrated (volatilized) by drying under reduced pressure, and the copolymer is collected.
  • [Skin adhesive material] (A) The gel-forming polymer or polymer mixture of the present invention, that is, the copolymer (copolymer (A) or copolymer (A) and copolymer (B) obtained as described above) For example, (b) water, (c) oily components, etc. are added to prepare a liquid composition of an emulsion (O / W emulsion). Such a liquid composition becomes the adhesive material for skin of the present invention.
  • the copolymer (copolymer (A) or a mixture of the copolymer (A) and the copolymer (B)) obtained as described above has a high viscosity and is an emulsion (O / W When it is difficult to form an emulsion, it is preferable to prepare a liquid composition by further adding (d) an organic solvent as a copolymer diluent.
  • the water is preferably ultrapure water, pure water, purified water or tap water, more preferably pure water or purified water.
  • perfume containing a fragrance, or fruit juice water that is naturally derived water can be used, and there is no particular limitation.
  • the oily component is not particularly limited, and includes hydrocarbon oils, higher fatty acids, higher alcohols, synthetic ester oils, liquid oils, silicone oils and the like that are usually used in cosmetics, skin external medicines, and the like. 1 type (s) or 2 or more types can be used.
  • hydrocarbon oil examples include isododecane, isohexadecane, isoparaffin, paraffin, liquid paraffin, squalane, squalene, and ceresin.
  • higher fatty acid examples 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.
  • higher alcohols examples 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.
  • 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 isoste
  • Synthetic ester oils include, for example, isopropyl myristate, cetyl octanoate, cetyl 2-ethylhexanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, dimethyloctane Hexyldecyl acid, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexanoate, dipentaerythritol fatty acid ester, N-alkyl monoisostearate Glycol, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptyl
  • liquid oils examples include linseed oil, camellia oil, macadamia nut oil, corn oil, mink oil, olive oil, avocado oil, sasanqua oil, castor oil, safflower oil, jojoba oil, sunflower oil, almond oil, rapeseed oil, sesame oil. , Soybean oil, peanut oil, triglycerin, glycerin trioctanoate, glycerin triisopalmitate and the like.
  • silicone oil examples include chain silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane, and cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
  • chain silicones such as dimethylpolysiloxane, methylphenylpolysiloxane, and methylhydrogenpolysiloxane
  • cyclic silicones such as octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, and dodecamethylcyclohexasiloxane.
  • the organic solvent may be a gel-forming polymer or polymer mixture (that is, a copolymer (A) or a mixture of a copolymer (A) and a copolymer (B)).
  • a gel-forming polymer or polymer mixture that is, a copolymer (A) or a mixture of a copolymer (A) and a copolymer (B)
  • alcohol solvents, ether solvents, ketone solvents and the like are suitable, and polar solvents (for example, ethyl acetate, tetrahydrofuran and the like) can also be used.
  • Examples of the alcohol solvent include lower monohydric alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol, propylene glycol, glycerin, 1,3- Examples include polyhydric alcohols such as butanediol.
  • Examples of ether solvents include diethyl ether, tetrahydrofuran, dioxane, ethyl cellosolve, butyl cellosolve, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, and the like.
  • ketone solvent examples include acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone, and cyclohexanone.
  • the organic solvent is preferably an alcohol solvent, and more preferably ethanol.
  • the organic solvent can use 1 type (s) or 2 or more types.
  • an organic solvent add the organic solvent to the gel-forming polymer or polymer mixture (that is, the copolymer (A) or the mixture of the copolymer (A) and the copolymer (B)) and mix.
  • (b) water and (c) oily components are added to prepare a liquid composition of emulsion (O / W emulsion).
  • the skin adhesive gel can be formed by bringing the adhesive material for skin of the present invention into contact with the skin. That is, when the adhesive material for skin of the present invention is applied to the skin, water partially volatilizes or penetrates into the skin, and the overall composition ratio changes, so that the monomer unit (I) of the copolymer is changed.
  • the polyalkylene glycol skeletons in the side chains are cross-linked through water to gel and stay on the skin.
  • the branched alkyl group in the side chain of the monomer unit (II) in the copolymer exhibits affinity with the skin and imparts skin adhesiveness.
  • the copolymer has a monomer unit (III)
  • the linear alkyl group in the side chain of the monomer unit (III) suppresses the stickiness of the hydrogel. Is obtained.
  • a hydrogel that is liquid before application to the skin but has excellent adhesion to the skin surface on the skin and good adhesion to the skin (preferably the skin surface). It is possible to realize an adhesive material for skin that is excellent in adhesiveness to the skin, has good persistence of adhesion to the skin, and changes to a sticky hydrogel).
  • the adhesive material for skin (liquid composition) of the present invention can be appropriately mixed with additives in addition to the water, the oil component and the organic solvent.
  • additives include other polymers, alcohol solvents, surfactants, preservatives, and the like, which can be freely blended.
  • the blending composition of the adhesive material for skin (liquid composition) of the present invention is not particularly limited, but preferred specific examples include the following blending compositions.
  • Gel-forming polymer or polymer mixture 2 to 40% by mass (preferably 5 to 20% by mass), Water: 20 to 95% by mass (preferably 30 to 90% by mass), Oil component: 1 to 60% by mass (preferably 2 to 50% by mass), Organic solvent: 2 to 40% by mass (preferably 5 to 20% by mass), Additive: 0-50% by mass (preferably 0-10% by mass)
  • the adhesive material for skin of the present invention is suitable as a base for external preparations for skin, such as cosmetics and external preparations for skin.
  • bases for cosmetics include basic cosmetics such as moisturizing sheets, whitening sheets, wrinkle-stretching sheets, exfoliating sheets, body moisturizing sheets, body whitening agents, and sunburn treatments.
  • additives include polyhydric alcohols such as glycerin, propylene glycol, dipropylene glycol, and 1,3-butanediol; lower alcohols such as ethanol and propanol; sorbitol, xylitol, Sugars such as mannitol; preservatives such as paraben, phenoxyethanol, chlorhexidine gluconate; antioxidants such as tocopherol and its derivatives, butylhydroxytoluene, pyrosulfite; ultraviolet absorbers such as paraaminobenzoic acid derivatives and benzophenone derivatives; polyethylene glycol Moisturizers such as hyaluronic acid; vitamin C derivatives such as vitamin C and ascorbic acid-2-glucoside; whitening agents such as arbutin and kojic acid; exfoliating agents such as urea, lactic acid and citric acid; Anti-inflammatory agents such as humic acid, allantoin and glycy
  • the adhesive material for skin of the present invention is used as a base for external preparations for skin, for example, a wound / burn protection sheet containing an osmotic pressure adjusting agent such as salt, a heat-treatment sheet containing ethanol or menthol, an antihistamine Anti-pruritic agent with antibacterial and antibiotics, anti-inflammatory agent with anti-inflammatory agent, anti-inflammatory agent with anti-fungal agent, and anthesis drug It is suitable as.
  • Example 1 Synthesis of Copolymer 1 1.15 g (5.0 mmol) of dimethyl 2,2′-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd.) purified by recrystallization from methanol in a 500 mL round bottom flask.
  • ethanol is concentrated by drying under reduced pressure to form a monomer unit (x) having a polyethylene glycol skeleton in the side chain and a monomer unit (y) having a branched alkyl group of the formula (4) in the side chain.
  • a copolymer 1 having a content ratio (x: y) of 2: 8 in molar ratio was obtained.
  • the weight average molecular weight (Mw) 37681
  • the number average molecular weight (Mn) 14775
  • the polydispersity (Mw / Mn) 2.554.
  • Example 2 Synthesis of Copolymer 2 1.15 g (5.0 mmol) of dimethyl 2,2′-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd.) purified by recrystallization from methanol in a 500 mL round bottom flask.
  • Reference Example 1 Synthesis of Copolymer 3 1.15 g (5.0 mmol) of dimethyl 2,2′-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd.) purified by recrystallization from methanol in a 500 mL round bottom flask. ), 30.4 g (80 mmol) of stearyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd., alcohol residue consisting of n-octadecyl) purified by removing the polymerization inhibitor in advance with hexane, reprecipitated with hexane and polymerized.
  • dimethyl 2,2′-azobisisobutyrate manufactured by Wako Pure Chemical Industries, Ltd.
  • 30.4 g (80 mmol) of stearyl methacrylate manufactured by Tokyo Kasei Kogyo Co., Ltd., alcohol residue consisting of n-octadecyl
  • Reference Example 2 Synthesis of copolymer 4 1.15 g (5.0 mmol) of dimethyl 2,2′-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd.) purified by recrystallization from methanol in a 500 mL round bottom flask. ), 17.0 g (50 mmol) of stearyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd., methallylic acid ester whose alcohol residue is n-octadecyl) purified by removing the polymerization inhibitor in advance with hexane, reprecipitated with hexane, and polymerized.
  • dimethyl 2,2′-azobisisobutyrate manufactured by Wako Pure Chemical Industries, Ltd.
  • stearyl methacrylate manufactured by Tokyo Chemical Industry Co., Ltd., methallylic acid ester whose alcohol residue is n-octadecyl
  • the weight average molecular weight (Mw) was 78423
  • the number average molecular weight (Mn) was 38802
  • the polydispersity (Mw / Mn) was 2.016.
  • the white turbid solution was emulsified, the dispersion did not fall even when the test tube was turned upside down, the gel state, and the oily component discharged from the emulsion was judged as phase separation, and a phase diagram (Fig. 1) was created. .
  • the white turbid solution was emulsified, the dispersion did not fall even when the test tube was inverted, the gel state, and the oily component discharged from the emulsion was judged as phase separation, and a phase diagram (Fig. 2) was created. .
  • the white turbid solution was emulsified, the dispersion did not fall even when the test tube was inverted, the gel state, and the oily component discharged from the emulsion was judged as phase separation, and a phase diagram (Fig. 3) was created. .
  • the white turbid solution was emulsified, the dispersion did not fall even when the test tube was inverted, the gel state, and the oily component discharged from the emulsion was judged as phase separation, and a phase diagram (Fig. 4) was created. .
  • compositions containing the copolymers prepared in Examples 3 to 6 were the same component and were in an oil-in-water emulsified state, an oil-in-water gel state, and phase separation. It can be seen that there are three states. This is because it is liquid in the emulsified state, and spreads and adheres to the skin surface corresponding to the unevenness of the skin surface. When the composition changes due to partial evaporation of moisture or penetration into the skin, the gel state (hydrogel ).
  • Comparative Example 1 Synthesis of Copolymer 5 1.15 g (5.0 mmol) of dimethyl 2,2′-azobisisobutyrate (manufactured by Wako Pure Chemical Industries, Ltd.) purified by recrystallization from methanol in a 500 mL round bottom flask. ), 9.5 g (95 mmol) of methyl methacrylate (manufactured by Tokyo Kasei Kogyo Co., Ltd.), which was reprecipitated with hexane and purified by removing the polymerization inhibitor in advance, was reprecipitated with hexane, and purified by removing the polymerization inhibitor in advance.
  • copolymer 5 and the same amount of ethanol were added to a test tube, heated to 60 ° C. with a hot stirrer, and stirred manually for 10 minutes with a spatula to make uniform. Further, neopentyl glycol dicaprate was added as an oil component with stirring, and purified water was further added, followed by manual stirring for 30 minutes to prepare a sample. Copolymer 5 and ethanol, an oil component, and purified water were mixed at various ratios, and the shape of the obtained dispersion was visually confirmed.
  • the white turbid solution was emulsified, the dispersion did not fall even when the test tube was inverted, the gel state, and the oily component discharged from the emulsion was judged as phase separation, and a phase diagram (Fig. 5) was created. .
  • the copolymer 5 of Comparative Example 1 is a copolymer comprising 5 mol% of monomer units having a polyethylene glycol skeleton in the side chain and 95 mol% of monomer units having a methyl group in the side chain.
  • O / W type oil-in-water type
  • O / W type oil-in-water type
  • the side chain of the copolymer has an appropriate polyethylene glycol skeleton together with a branched alkyl group. It has been shown.
  • the formulation 1 containing the copolymer 1 having a high content of monomer units having a branched alkyl group in the side chain was evaluated as having the most stickiness. From the comparison between Formulation 3 in which copolymer 3 containing a monomer unit having a linear alkyl group in the side chain is added to Formulation 1 and Formulation 2 and Formulation 4, the side chain has a linear alkyl group. When a copolymer containing monomer units was blended, stickiness was suppressed.
  • Copolymer 1 containing a monomer unit having a polyethylene glycol skeleton in the side chain and a copolymer unit 1 having a monomer unit having a branched alkyl group in the side chain and a monomer unit having a linear alkyl group in the side chain It was confirmed that when the coalescence 3 was blended, the peeling stress was reduced. From this, it was recognized that the copolymer having a linear alkyl group in the side chain suppresses stickiness.
  • a dispersion of a copolymer containing a monomer unit having a polyalkylene glycol skeleton in the side chain and a monomer unit having a branched alkyl group in the side chain changes from liquid to gel on the skin, It is a material that adheres. Further, by copolymerizing such a copolymer with a monomer having a linear alkyl group in the side chain, or combining a copolymer containing a monomer unit having a linear alkyl group in the side chain. Can suppress stickiness on the skin.
  • These copolymers are useful as a new base for solving the problems of existing bases, as a base for skin external preparations such as cosmetics and external medicines appropriately blended with moisturizing agents and active ingredients.

Landscapes

  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • General Health & Medical Sciences (AREA)
  • Public Health (AREA)
  • Veterinary Medicine (AREA)
  • Chemical & Material Sciences (AREA)
  • Epidemiology (AREA)
  • Medicinal Chemistry (AREA)
  • Pharmacology & Pharmacy (AREA)
  • Birds (AREA)
  • Dermatology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Cosmetics (AREA)
  • Medicinal Preparation (AREA)
  • Materials For Medical Uses (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne un matériau adhésif dermatologique qui est une composition liquide comprenant (a) un copolymère qui comprend des motifs de monomères (I) ayant un squelette de polyalkylène glycol ayant un degré de polymérisation de 2 à 100 dans une chaîne latérale et des motifs de monomères (II) comportant un groupe alkyle ramifié en C3-30 dans une chaîne latérale, (b) de l'eau, et (c) un composant huileux, et des changements dans un gel sur la peau. Un hydrogel ayant d'excellentes adhérence hermétique à la surface de la peau sur la peau et adhérence à la peau peut être formé par application de ce matériau adhésif dermatologique sur la peau.
PCT/JP2016/068029 2015-06-19 2016-06-17 Polymère pour formation de gel et matériau adhésif dermatologique WO2016204258A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2017524843A JPWO2016204258A1 (ja) 2015-06-19 2016-06-17 ゲル形成用ポリマー及び皮膚用粘着性材料

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015-124280 2015-06-19
JP2015124280 2015-06-19

Publications (1)

Publication Number Publication Date
WO2016204258A1 true WO2016204258A1 (fr) 2016-12-22

Family

ID=57546770

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/068029 WO2016204258A1 (fr) 2015-06-19 2016-06-17 Polymère pour formation de gel et matériau adhésif dermatologique

Country Status (2)

Country Link
JP (1) JPWO2016204258A1 (fr)
WO (1) WO2016204258A1 (fr)

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5785318A (en) * 1980-11-14 1982-05-28 Nitto Electric Ind Co Ltd Hydrophilic medical material
JPH07187999A (ja) * 1993-12-24 1995-07-25 Hisamitsu Pharmaceut Co Inc 粘着剤、それを用いる医療用貼付製剤及びその製造方法
JPH08509019A (ja) * 1993-04-14 1996-09-24 ミネソタ マイニング アンド マニュファクチャリング カンパニー 架橋吸収性感圧接着剤及び外傷包帯
JPH09227329A (ja) * 1996-02-16 1997-09-02 M & M Kenkyusho:Kk 香粧品基剤および外用香粧品
JP2000008013A (ja) * 1998-06-19 2000-01-11 Nichiban Co Ltd 感圧接着剤組成物
JP2002371257A (ja) * 2001-06-14 2002-12-26 Nichiban Co Ltd 湿潤面接着性粘着剤
JP2004534111A (ja) * 2001-04-23 2004-11-11 ウィスコンシン アルムニ リサーチ ファウンデイション 二機能性改変ハイドロゲル
JP2006037109A (ja) * 2004-07-29 2006-02-09 L'oreal Sa 選択のモノマーを含む高級分枝状コポリマー、それを含む組成物、および化粧方法
JP2006036911A (ja) * 2004-07-27 2006-02-09 Sekisui Chem Co Ltd 粘着テープ
JP2007506838A (ja) * 2003-09-26 2007-03-22 スリーエム イノベイティブ プロパティズ カンパニー 反応性を有する親水性オリゴマー
JP2007217348A (ja) * 2006-02-17 2007-08-30 Shiseido Co Ltd 増粘剤並びにこれを含有する化粧料及び洗浄料
JP2010180205A (ja) * 2009-01-08 2010-08-19 Kose Corp 凹凸補正用組成物、並びに該凹凸補正用組成物を含有する皮膚化粧料、及び皮膚外用剤
JP2015013842A (ja) * 2013-07-08 2015-01-22 花王株式会社 毛髪化粧料

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5785318A (en) * 1980-11-14 1982-05-28 Nitto Electric Ind Co Ltd Hydrophilic medical material
JPH08509019A (ja) * 1993-04-14 1996-09-24 ミネソタ マイニング アンド マニュファクチャリング カンパニー 架橋吸収性感圧接着剤及び外傷包帯
JPH07187999A (ja) * 1993-12-24 1995-07-25 Hisamitsu Pharmaceut Co Inc 粘着剤、それを用いる医療用貼付製剤及びその製造方法
JPH09227329A (ja) * 1996-02-16 1997-09-02 M & M Kenkyusho:Kk 香粧品基剤および外用香粧品
JP2000008013A (ja) * 1998-06-19 2000-01-11 Nichiban Co Ltd 感圧接着剤組成物
JP2004534111A (ja) * 2001-04-23 2004-11-11 ウィスコンシン アルムニ リサーチ ファウンデイション 二機能性改変ハイドロゲル
JP2002371257A (ja) * 2001-06-14 2002-12-26 Nichiban Co Ltd 湿潤面接着性粘着剤
JP2007506838A (ja) * 2003-09-26 2007-03-22 スリーエム イノベイティブ プロパティズ カンパニー 反応性を有する親水性オリゴマー
JP2006036911A (ja) * 2004-07-27 2006-02-09 Sekisui Chem Co Ltd 粘着テープ
JP2006037109A (ja) * 2004-07-29 2006-02-09 L'oreal Sa 選択のモノマーを含む高級分枝状コポリマー、それを含む組成物、および化粧方法
JP2007217348A (ja) * 2006-02-17 2007-08-30 Shiseido Co Ltd 増粘剤並びにこれを含有する化粧料及び洗浄料
JP2010180205A (ja) * 2009-01-08 2010-08-19 Kose Corp 凹凸補正用組成物、並びに該凹凸補正用組成物を含有する皮膚化粧料、及び皮膚外用剤
JP2015013842A (ja) * 2013-07-08 2015-01-22 花王株式会社 毛髪化粧料

Also Published As

Publication number Publication date
JPWO2016204258A1 (ja) 2018-04-05

Similar Documents

Publication Publication Date Title
EP2670383B1 (fr) Amidons modifiés destinés à être utilisés dans des applications de soins personnels
KR100922527B1 (ko) 코폴리머, 비-휘발성 오일 및 광택성 오일을 포함한 화장조성물
CN101507691B (zh) 水包油型乳化白浊皮肤化妆品
TWI524903B (zh) Esterification reaction products and cosmetics
BRPI0702106B1 (pt) Polímero seqüenciado, composição cosmética, processo cosmético de maquilagem ou de cuidado das matérias queratínicas, uso de um polímero e processo de preparação de um polímero
WO2007096400A1 (fr) Compositions cosmétiques comprenant un copolymère poly(alpha-oléfine-anhydride maléique) fonctionnalisé
TW200900090A (en) Skin cosmetic
JP3947102B2 (ja) 特定のプロ接着性物質を含むロングラスティング化粧品組成物
JP2011213676A (ja) 水中油型乳化組成物
JP2003535883A (ja) ポリマーで構造が与えられた液体脂肪相を含む固形エマルション
TWI516278B (zh) 油中水型乳化化妝料
WO2012012857A2 (fr) Émulsion de type huile dans l'eau sans tensioactif, procédé pour la préparation de celle-ci et ses utilisations
JP2004131475A (ja) デキストリンエステルでゲル化された組成物
TW200536890A (en) Ues of acrylates copolymer as waterproofing agent in personal care applications
JP6368064B1 (ja) 新規複合体および油中水型乳化組成物
JP2011195511A (ja) 水中油型乳化皮膚外用組成物
JP2006282517A (ja) ゲル組成物及びそれを含有する化粧料
TWI661840B (zh) 嶄新錯合物及乳化組合物
WO2016204258A1 (fr) Polymère pour formation de gel et matériau adhésif dermatologique
JPH1053625A (ja) アクリル酸系ポリマー及びこれを配合した乳化組成物
US10172780B2 (en) Acrylic polymer of maleic anhydride and use thereof in cosmetics
WO2021223652A1 (fr) Produit cosmétique et procédé de maquillage
JP2010195739A (ja) 水中油型乳化組成物および該組成物を含有する皮膚外用剤又は化粧料
JP6469286B1 (ja) 新規複合体および乳化組成物
JP2004059526A (ja) 油中水型乳化化粧料

Legal Events

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

Ref document number: 16811732

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2017524843

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16811732

Country of ref document: EP

Kind code of ref document: A1