US20160250131A1 - Low-Stringiness Thickener and Cosmetic Material Admixed with Said Thickner - Google Patents

Low-Stringiness Thickener and Cosmetic Material Admixed with Said Thickner Download PDF

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US20160250131A1
US20160250131A1 US15/028,134 US201315028134A US2016250131A1 US 20160250131 A1 US20160250131 A1 US 20160250131A1 US 201315028134 A US201315028134 A US 201315028134A US 2016250131 A1 US2016250131 A1 US 2016250131A1
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molecular weight
weight
stringiness
million
salt
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Atsushi Sogabe
Ayano Matsuo
Shin-ichi Yusa
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Shiseido Co Ltd
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Shiseido Co Ltd
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Assigned to SHISEIDO COMPANY, LTD. reassignment SHISEIDO COMPANY, LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: SOGABE, ATSUSHI, YUSA, SHIN-ICHI, MATSUO, AYANO
Publication of US20160250131A1 publication Critical patent/US20160250131A1/en
Priority to US15/784,337 priority Critical patent/US11439582B2/en
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    • 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
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8147—Homopolymers or copolymers of acids; Metal or ammonium salts thereof, e.g. crotonic acid, (meth)acrylic acid; Compositions of derivatives of such polymers
    • 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
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8152—Homopolymers or copolymers of esters, e.g. (meth)acrylic acid esters; Compositions of derivatives of such polymers
    • 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
    • A61K8/8141—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • A61K8/8158—Homopolymers or copolymers of amides or imides, e.g. (meth) acrylamide; Compositions of derivatives of such polymers
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/04—Acids; Metal salts or ammonium salts thereof
    • C08F120/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F120/00—Homopolymers 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
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/52—Amides or imides
    • C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F120/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloyl morpholine
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/44—Preparation of metal salts or ammonium salts
    • 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
    • A61K2800/10—General cosmetic use
    • 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
    • A61K2800/48—Thickener, Thickening system

Definitions

  • the present invention relates to a less stringiness thickener suitable for cosmetics and a cosmetic admixed with the said thickeners.
  • various kinds of thickeners are blended in cosmetics for the realization of a viscosity suitable for use, the improvement in the feeling in use, and the stabilization of emulsion systems.
  • Many of them are water-soluble polymer compounds and classified, depending upon their origins, into natural polymers (xanthan gum, hyaluronic acid, etc.), semi-synthetic polymers in which functional groups are added to natural polymers by synthesis reactions, and synthetic polymers.
  • natural polymer compounds have issues such as supply stability and quality stability (lot-dependent viscosity variation, contamination by microorganisms, etc.); thus the demand for synthetic polymer compounds is becoming high in recent years.
  • the present invention was made in view of the above-described problems in conventional art, and aimed to provide a less stringiness thickener consisting of a compound in high demand as a thickener for cosmetics, i.e., polyacrylic acid or a salt thereof, or PAMPS or a salt thereof, where a stringiness property of the compound was reduced.
  • the present inventors have diligently studied the above-described problems. As a result, the present inventors have found that, in the polyacrylic acid or a salt thereof, or PAMPS or a salt thereof having the weight-average molecular weight of 500 thousand to 8 million, the stringiness property displayed by the compound can be significantly reduced by allowing the content of the compound having the molecular weight of 10 million or higher to be 10 mass % or less.
  • the present inventors have found that the cosmetics in which the sodium polyacrylate or sodium PAMPS, having a low stringiness property, of the present invention is blended, the stringy feeling, sliminess, and stickiness are hardly felt and the spreadability is excellent, thus leading to the completion of the present invention.
  • the present invention provides a less stringiness thickener consisting of a polymer having a weight-average molecular weight between 500 thousand and 8 million, wherein said polymer contains not more than 10% by mass of the same having the molecular weight of 10 million or higher, and said polymer is selected from the group consisting of polyacrylic acid, a salt of polyacrylic acid, PAMPS, and a salt of PAMPS.
  • the present invention also provides a cosmetic raw material including a less stringiness thickener consisting of a polymer having a weight-average molecular weight between 500 thousand and 8 million,
  • said polymer contains not more than 10% by mass of the same having the molecular weight of 10 million or higher, and said polymer is selected from the group consisting of polyacrylic acid, a salt of polyacrylic acid, PAMPS, and a salt of PAMPS.
  • the present invention provides a cosmetic including a less stringiness thickener consisting of a polymer having a weight-average molecular weight between 500 thousand and 8 million,
  • said polymer contains not more than 10% by mass of the same having the molecular weight of 10 million or higher, and said polymer is selected from the group consisting of polyacrylic acid, a salt of polyacrylic acid, PAMPS, and a salt of PAMPS.
  • a less stringiness thickener consisting of polyacrylic acid or a salt thereof, or PAMPS or a salt thereof, which has a low stringiness property, generates almost no stringy feeling, sliminess, and stickiness, and is excellent in spreadability, can be obtained.
  • the cosmetics that are improved in the stringy feeling, sliminess, and stickiness and excellent in spreadability can be prepared by using this less stringiness thickener.
  • FIG. 1 A chart of gel permeation chromatography (GPC) analysis of the sodium polyacrylate in the present invention (Precision-synthesized sodium polyacrylate-2).
  • the polyacrylic acid or a salt thereof and PAMPS or a salt thereof usable in the present invention are those having the weight-average molecular weight of 300 thousand to 8 million, preferably 500 thousand to 8 million, and the content of the compound having the molecular weight of 10 million or higher being 10 mass % or less. This is because if the weight-average molecular weight is less than 300 thousand, the spreadability tends to be poor, and if the weight-average molecular weight exceeds 8 million, it becomes technically difficult to suppress the content of the compound having the molecular weight of 10 million or higher to be 10 mass % or less. As described later, if the content of the compound having the molecular weight of 10 million or higher exceeds 10 mass %, the stringiness property becomes severe, and a stringy feeling, sliminess, and the stickiness are likely generated; thus it is not desirable.
  • the synthetic polymer compound of the present invention if the content of the compound having the molecular weight that is three times or higher of the weight-average molecular weight is 10 mass % or less, the stringiness property tends to be further suppressed; thus it is desirable.
  • the molecular weight distribution (namely, weight-average molecular weight/number-average molecular weight) of the synthetic polymer compound of the present invention is preferably 2.0 or lower and more preferably 1.0 to 1.8. This is because if the molecular weight distribution exceeds 2.0, the stringiness property may become prominent.
  • alkali metal salts for example, sodium salt, potassium salt, magnesium salt, calcium salt, etc.
  • organic amine salts for example, monoethanolamine salt, diethanolamine salt, triethanolamine salt, triisopropanolamine salt, etc.
  • the salts of basic nitrogen-containing compounds such as 2-amino-2-methyl-1-propanol, 2-amino-2-methyl-1,3-propanediol, 2-amino-2-hydroxymethyl-1,3-propanediol, L-arginine, L-lysine, and L-alkyl taurine.
  • monovalent alkali metal salts and organic amine salts are preferable, more preferably a sodium salt, potassium salt and triethanolamine salt, and most preferably a sodium salt.
  • the polyacrylic acid salt or PAMPS salt indicates the compound obtained by neutralizing the polyacrylic acid or PAMPS with the above-described base (namely, the above-described alkali metals, organic amines, basic nitrogen-containing compounds, etc.) or the compound obtained by polymerizing the acrylic acid or 2-acrylamide-2-methylpropanesulfonic acid (hereinafter abbreviated as AMPS) whose acid section is beforehand neutralized with the above-described base.
  • the above-described base namely, the above-described alkali metals, organic amines, basic nitrogen-containing compounds, etc.
  • AMPS 2-acrylamide-2-methylpropanesulfonic acid
  • acrylic acid monomers such as methacrylic acid, alkyl acrylates, alkyl methacrylates, acrylic acid esters
  • acrylamide monomers such as acrylamide and dimethylacrylamide
  • vinyl monomers such as vinyl alcohol, vinylpyrrolidone, vinyl acetate, carboxyvinyl, and vinyl methyl ether
  • styrene, urethane, etc. are the constituent unit monomer
  • copolymers and/or salts thereof consisting of two kinds or more of the monomers selected from these monomers, acrylic acid, and AMPS.
  • constituent unit is an acrylic acid monomer or acrylamide monomer
  • constituent unit is an acrylic acid monomer or acrylamide monomer
  • macro-monomers in which polyethylene glycol, silicone-based polymer compound, etc. are added to the above-described monomer, as the side chain, can also suitably be used as the constituent unit.
  • Specific compound examples include polyacrylamide, polydimethylacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, polyvinylmethyl ether, polyvinyl acetate, carboxyvinyl polymer, etc.; and (acrylic acid/alkyl acrylate) copolymer, (acrylic acid/alkyl methacrylate) copolymer, (alkyl acrylate/styrene) copolymer, polyacrylic acid ester copolymer, (dimethylacrylamide/2-acrylamido-2-methylpropanesulfonic acid) copolymer and salts thereof.
  • the synthetic polymer compound of the present invention can be synthesized by a publicly known living polymerization method.
  • living polymerization include living anionic polymerization, living cationic polymerization, living radical polymerization (precise radical polymerization, or controlled radical polymerization), etc.
  • Examples of living radical polymerization include (radical) polymerization that is mediated by nitroxide, or nitroxide-mediated (radical) polymerization (NLRP), atom transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, etc.
  • Examples of atom transfer radical polymerization (ATRP) include electron transfer generated activator ATRP, or activators generated by electron transfer ATRP (AGET ATRP), electron transfer regenerated activator ATRP, or activators regenerated by electron transfer ATRP (ARGET ATRP), initiators to continuously regenerate active species ATRP, or initiators for continuous activator regeneration ATRP (ICAR ATRP), and reverse ATRP (Reverse ATRP).
  • RAFT reversible addition-fragmentation chain transfer
  • living radical polymerization in which organic tellurium is the growing end or organic tellurium-mediated living radical polymerization (TERP), antimony-mediated living radical polymerization (SBRP), and bismuth-mediated living radical polymerization (BIRP) can be listed.
  • examples of other living radical polymerizations include iodine transfer radical polymerization (IRP), cobalt-mediated radical polymerization (CMRP), etc.
  • the direct polymerization of acrylic acid is preferable because of the simplicity of polymerization.
  • protected acrylic acid esters such as t-butyl acrylate, methoxymethyl acrylate, and methyl acrylate are used, and the desired polymer compound can be obtained by the succeeding deprotection.
  • the reversible addition-fragmentation chain transfer polymerization method (RAFT polymerization method) is preferable because the precision synthesis (namely, the synthesis of polymer compounds with narrow molecular weight distribution) is possible (PTL 4).
  • Preferable chain transfer agents are of dithio-type and trithio-type.
  • a polymerization initiator that has a similar chemical structure as that of the chain transfer agent is preferable, and an azo initiator is preferable.
  • the polymerization solvent is not limited in particular, and those having high solubility of monomers and polymers are suitably selected.
  • the polymerization time is preferably several hours to 50 hours.
  • the molecular weight of the polymer compound synthesized by the method of the present invention can be measured by publicly known methods, such as a light scattering method, an ultracentrifugal method, and a chromatographic method, for the weight-average molecular weight; and an osmometric method and a chromatographic method, for the number-average molecular weight.
  • the chromatographic method is preferable because the weight-average molecular weight, the number-average molecular weight, and the molecular weight distribution can easily be obtained with a small amount of sample; in particular, a gel permeation chromatographic method (hereinafter abbreviated as GPC) is preferable.
  • GPC gel permeation chromatographic method
  • the molecular weight distribution used in this application is the value determined by dividing the weight-average molecular weight obtained by GPC analysis by the number-average molecular weight.
  • Polyacrylic acid or a salt thereof, and PAMPS or a salt thereof of the present invention can be blended into various cosmetics as a less stringiness thickener or as a cosmetic raw material with low stringiness property.
  • the most preferable blending method is the substitution of the commercial polyacrylic acid or a salt thereof, or PAMPS or a salt thereof whose molecular weight is not suitably controlled.
  • unpleasant usability such as a stringy feeling, sliminess, stickiness, and poor spreadability, of the cosmetics containing the above-described commercial products, can be improved.
  • the synthetic polymer compound of the present invention has a low stringiness property, and the above-described unpleasant usability is not present; therefore, more material can be blended than the corresponding commercial product.
  • the polyacrylic acid or a salt thereof and PAMPS or a salt thereof of the present invention can be suitably blended as a substitute for the thickener of other compounds whose molecular weight is not controlled.
  • the polyacrylic acid or a salt thereof and PAMPS or a salt thereof of the present invention can be blended, as a guide, preferably 0.01 to 5.0 mass % with respect to the total cosmetic, and more preferably 0.05 to 2.5 mass %.
  • the polyacrylic acid or a salt thereof and PAMPS or a salt thereof of the present invention can be suitably blended in makeup cosmetics such as foundation, eyeshadow, eyeliner, mascara, eyebrow, lip liner, and pre-makeup; and skin care cosmetics such as cream, milky lotion, lotion, gel, pack, and mask.
  • makeup cosmetics such as foundation, eyeshadow, eyeliner, mascara, eyebrow, lip liner, and pre-makeup
  • skin care cosmetics such as cream, milky lotion, lotion, gel, pack, and mask.
  • the present invention is described below in more detail with reference to examples, however, the scope of the present invention is not limited thereto.
  • the weight average molecular weight and the number average molecular weight of a polymer compound are sometimes referred to as Mw and Mn, respectively.
  • RAFT polymerization method which is a living radical polymerization
  • six kinds of sodium polyacrylate with different weight-average molecular weights and four kinds of sodium PAMPS with different weight-average molecular weights were precision-synthesized.
  • Detailed procedures are shown below.
  • 4,4′-azobis-(4-cyanovaleric acid) V-501, manufactured by Wako Pure Chemical Industries, Ltd.
  • 4-cyanopentanoic acid dithiobenzoate (synthesized according to NPL 1, hereinafter abbreviated as CPD) was used as the chain transfer agent.
  • ⁇ -(methyltrithiocarbonate)-S-phenylacetic acid (synthesized according to NPL 2, normally abbreviated as MTPA) may also be used.
  • Acrylic acid (2504 mg), methylenebisacrylamide (38.4 ⁇ g), and V-501 (0.68 mg) were dissolved in ion-exchanged water (9 mL), a methanol solution (1 mL) in which CPD (0.68 mg) had been dissolved was added, and a polymerization reaction was carried out under an argon atmosphere at 60° C. for 24 hours. After the polymerization reaction, sodium hydroxide aqueous solution was added for neutralizing the pH completely, and then the mixture was dialyzed against purified water for 4 days. Precision-synthesized sodium polyacrylate-2 (1.71 g, yield: 68%) was collected by freeze-drying. As a result of GPC analysis, the weight-average molecular weight was 6.33 million, and the molecular weight distribution was 1.4.
  • Acrylic acid (2514 mg), methylenebisacrylamide (9.6 ⁇ g), and V-501 (0.17 mg) were dissolved in ion-exchanged water (9 mL), a methanol solution (1 mL) in which CPD (0.17 mg) had been dissolved was added, and a polymerization reaction was carried out under an argon atmosphere at 60° C. for 24 hours. After the polymerization reaction, sodium hydroxide aqueous solution was added for neutralizing the pH completely, and then the mixture was dialyzed against purified water for 4 days. Precision-synthesized sodium polyacrylate-3 (1.99 g, yield: 79%) was collected by freeze-drying. As a result of GPC analysis, the weight-average molecular weight was 3.26 million, and the molecular weight distribution was 1.7.
  • AMPS (2500 mg), the pH of which had been adjusted to 7.0 by sodium hydroxide, and V-501 (0.84 mg) were dissolved in ion-exchanged water (9 mL), a methanol solution (1 mL) in which CPD (0.17 mg) had been dissolved was added, and a polymerization reaction was carried out under an argon atmosphere at 60° C. for 24 hours, After the polymerization reaction, the mixture was dialyzed against purified water for 4 days. Precision-synthesized sodium PAMPS-1 was collected by freeze-drying. As a result of GPC analysis, the weight-average molecular weight was 4.03 million, and the molecular weight distribution was 1.4.
  • AMPS (2510 mg), the pH of which had been adjusted to 7.0 by sodium hydroxide, and V-501 (0.70 mg) were dissolved in ion-exchanged water (9 mL), a methanol solution (1 mL) in which CPD (0.70 mg) had been dissolved was added, and a polymerization reaction was carried out under an argon atmosphere at 60° C. for 24 hours. After the polymerization reaction, the mixture was dialyzed against purified water for 4 days. Precision-synthesized sodium PAMPS-2 was collected by freeze-drying. As a result of GPC analysis, the weight-average molecular weight was 2.24 million, and the molecular weight distribution was 1.2.
  • AMPS (9.98 g), the pH of which had been adjusted to 6.0 by sodium hydroxide, and V-501 (0.001 g) were dissolved in ion-exchanged water (40 mL), a methanol solution (3.78 mL) in which CPD (0.027 g) had been dissolved was added, and a polymerization reaction was carried out under an argon atmosphere at 70° C. for 16 hours. After the polymerization reaction, the mixture was dialyzed against purified water for 2 days. Precision-synthesized sodium PAMPS-3 (8.5 g, yield: 85.1%) was collected by freeze-drying. As a result of GPC analysis, the weight-average molecular weight was 13 thousand, and the molecular weight distribution was 1.4.
  • AMPS (9,98 g), the pH of which had been adjusted to 6.0 by sodium hydroxide, and V-501 (0.01 g) were dissolved in ion-exchanged water (40 mL), a methanol solution (3.78 mL) in which CPD (0.27 g) had been dissolved was added, and a polymerization reaction was carried out under an argon atmosphere at 70° C. for 16 hours. After the polymerization reaction, the mixture was dialyzed against purified water for 2 days. Precision-synthesized sodium PAMPS-4 (9.2 g, yield: 92.9%) was collected by freeze-drying. As a result of GPC analysis, the weight-average molecular weight was 1.5 thousand, and the molecular weight distribution was 1.1.
  • the polyacrylic acid and PAMPS sodium which were precision-synthesized by the above-described methods, were filtered through a pre-filter (DISMIC-13HP PTFE filter, pore size 0.45 ⁇ m, manufactured by Advantec Co., Ltd.). Then, GPC analysis was carried out to measure the molecular weight of those compounds.
  • the elution peak obtained in the GPC analysis of the above-described precision-synthesized sodium polyacrylate-2 is shown in FIG. 1 .
  • the weight-average molecular weight is 6.33 ⁇ 10 6
  • the number-average molecular weight is 4.37 6 ⁇ 10 6 ; therefore, the molecular weight distribution (weight-average molecular weight/number-average molecular weight) is 1.4.
  • the precision-synthesized sodium polyacrylate-2 synthesized by the method of the present invention is seen to be a uniform molecular weight compound.
  • Region 1 compound whose molecular weight is three times or higher of the weight-average molecular weight
  • Region 2 compound whose molecular weight is three times or lower—two times or higher of the weight-average molecular weight
  • Region 3 compound whose molecular weight is two times or lower of the weight-average molecular weight—equal to the weight-average molecular weight or higher
  • Region 4 compound whose molecular weight is equal to the weight-average molecular weight or lower—one half of the weight-average molecular weight or higher
  • Region 5 compound whose molecular weight is one half or lower—one third or higher of the weight-average molecular weight
  • Region 6 compound whose molecular weight is one third or lower of the weight-average molecular weight.
  • the weight-average molecular weight for the commercially available polyacrylic acid or a salt thereof and PAMPS or a salt thereof for cosmetics can be known as the product information; however, the molecular weight distribution is often unknown. Therefore, the filtration was attempted for the above-described commercial product with the above-described prefilter (pore size: 0.45 ⁇ m). However, the filtration could not be carried out in all cases because of clogging; thus GPC analysis could not be carried out.
  • the filtration with a prefilter having a pore size of 0.45 ⁇ m is an operation that is normally carried out to remove macromolecules whose analysis is not possible by GPC.
  • the present inventors have confirmed that 10 mass % solution of a linear water-soluble polymer compound with the weight-average molecular weight of about 10 million can be filtered with such a prefilter.
  • more than 10 mass % of macromolecules with the molecular weight of 10 million or higher are contained in the commercial sodium polyacrylate and sodium PAMPS used in this application.
  • the polymer compounds used in this analysis are as follows.
  • Test Example 1 Sodium salt of Carbopol 981 (manufactured by Lubrizol Advanced Materials Co., Ltd.), completely neutralized Test Example 2: Sodium salt of Synthalen L (manufactured by 3V Sigma), completely neutralized Test Example 3: Sodium salt of ARONVIS S (manufactured by Japan Pure Chemical), completely neutralized Test Example 4: Sodium salt of polyacrylic acid (306223, manufactured by Sigma-Aldrich Corporation), completely neutralized Test Example 5: Sodium salt of polyacrylic acid (306215, manufactured by Sigma-Aldrich Corporation), completely neutralized Test Example 6: Sodium salt of polyacrylic acid (manufactured by Wako Pure Chemical Industries, Ltd.), completely neutralized Test Example 7: A mixture of Test Example 1 and Test Example 14 in a ratio of 5:5 by weight Test Example 8: A mixture of Test Example 1 and Test Example 14 in a ratio of 1:9 by weight Test Example 11: Precision-synthesized sodium polyacrylate-1 Test Example 12: Precision-synthesized sodium polyacryl
  • Test Example 9 KELTROL (manufactured by CP Kelco Co.)
  • Test Example 10 NATROSOL 250HHR (manufactured by Hercules Inc.)
  • Test Example 17 Hostacerin AMPS (manufactured by Clariant) Test
  • Example 18 Precision-synthesized sodium PAMPS-1 Test
  • Example 19 Precision-synthesized sodium PAMPS-2 Test
  • Example 20 Precision-synthesized sodium PAMPS-3 Test
  • Example 21 Precision-synthesized sodium PAMPS-4
  • all the commercial sodium polyacrylates are considered to contain 10 mass % or more of macromolecules with the molecular weight of 10 million or higher.
  • the weight-average molecular weight is 1 million to 3 million
  • at least more than 10 mass % of the compound with the molecular weight that is three times or higher of the weight-average molecular weight is considered to be contained.
  • many of commercial polyacrylic acids and salts thereof, which are widely used as the thickener for cosmetics are collections of those with non-uniform molecular weights and containing a large amount of compounds having significantly larger molecular weights than the weight-average molecular weight.
  • the molecular weight distribution of precision-synthesized sodium polyacrylates (Test Examples 11 to 16) prepared in this application was 1.1 to 2.0 and it was narrow in the range of the weight-average molecular weight of 20 thousand to 7.3 million, and the content of macromolecules with molecular weights of 10 million or higher was 9.2 mass % or less.
  • the content of the compound with the molecular weight of three times or higher or one third or lower of the weight-average molecular weight were 5.1 mass % or less, or 14.3 mass % or less, respectively. From these, the sodium polyacrylate prepared by the method of the present invention is seen to be a collection of those with uniform molecular weights.
  • the molecular weight distribution of the precision-synthesized sodium PAMPS in this application was 1.1 to 1.4 and it was narrow in the range of the weight-average molecular weight of 15 thousand to 4.03 million.
  • the content of macromolecules with the molecular weight of 10 million or higher was 3.6 mass % or less
  • the content of the compound with the molecular weight that is three times or higher of the weight-average molecular weight was 7.7 mass % or less
  • the content of the compound with the molecular weight that is one third or lower of the weight-average molecular weight was 11.2 mass % or less (Table 3).
  • One mass % solution of each polymer compound was prepared and placed in a container at room temperature.
  • the container was set on a texture analyzer (TA.XT Plus, manufactured by Stable Micro Systems), a round disk with the diameter of about 1 cm was uniformly and lightly contacted on the surface of the above-described solution, and the stringiness behavior of the solution was observed by letting down the container at the velocity of 5 mm/sec. The distance that the container descended, until the cut of the stringiness solution, was measured as the “stringiness length”.
  • This stringiness length is the indicator of the stringiness property of polymer compounds, and “the larger the value, the stronger the stringiness property” (PTL 5). In this application, when the stringiness length was 10 mm or less, the stringiness property was judged to be low.
  • compositions 1 and 2 were prepared, and the actual application tests were carried out by three expert panelists. They were asked to apply the composition I on the right face and the composition 2 on the left face and asked to evaluate the below-described usabilities, according to the criteria below, of the composition 1 by comparing with the composition 2.
  • Composition 1 A composition containing a polymer compound
  • composition 2 A composition containing no polymer compound
  • the stringiness property of all the precision-synthesized sodium polyacrylates of the present invention is low (stringiness length: 10 mm or less). Even when the composition containing 0.1 mass % thereof is applied on the skin, the stringy feeling and sliminess were hardly felt (Test Examples 11 to 16). As described above, the stringiness property of polymer compounds is dependent on viscosity; thus the stringiness property is generally considered to increase with the increase in the weight-average molecular weight.
  • the precision-synthesized sodium polyacrylate-4 (Test Example 14) hardly contains the compound with the weight-average molecular weight of 10 million or higher, and it is a compound with very uniform molecular weights.
  • the commercial polyacrylic acid-1 (Test Example 1) with the weight-average molecular weight of 10 million or higher was added in equal masses.
  • a high-stringiness compound that displays a stringiness length that is close to the average of those of Test Example 14 and Test Example 1 (stringiness length: 12 mm) was obtained (Test Example 7). This mixture generated a stringy feeling, sliminess, and also stickiness.
  • the stringiness property, stringy feeling, sliminess, and stickiness are considered to be suppressible, for the polyacrylic acid and a salt thereof with the weight-average molecular weight of 8 million or less, by suppressing the content of macromolecules with molecular weights of 10 million or higher to be 10 mass % or less.
  • the stringiness property is low, a stringy feeling, sliminess, and stickiness are hardly observed, and the spreadability is also excellent if the content of the macromolecule with the molecular weight of 10 million or higher is 10 mass % or less.
  • the polyacrylic acid or a salt thereof and PAMPS or a salt thereof of the present invention can be suitably used in cosmetics as the cosmetic raw material and preferably as the less-stringiness thickener, where the stringiness property is low and a stringy feeling, sliminess, and stickiness are not present.
  • Blending Component quantity (% by mass) (1) Precision-synthesized sodium polyacrylate-2 0.1 (2) Glycerin 1.0 (3) Dipropylene glycol 12.0 (4) Ethanol 8.0 (5) POE (10) methyl glucoside 3.0 (6) POE (24) POP (13) decyltetradecyl ether 0.5 (7) Citric acid 0.02 (8) Sodium citrate 0.08 (9) Hydroxypropyl- ⁇ -cyclodextrin 0.5 (10) Thiotaurine 0.1 (11) Adenosine triphosphate disodium salt 0.1 (12) Sodium hyaluronate 0.01 (13) EDTA trisodium salt 0.01 (14) Paraben q.s. (15) Fragrance q.s. (16) Purified water balance
  • Components (6) and (15) were dissolved in component (4), and the resulting mixture is referred to as A.
  • Component (14) was dissolved in component (3), and the resulting mixture is referred to as B.
  • the mixture A and B were dissolved in component (16) in which the remaining components had been dissolved, to obtain a lotion.
  • Blending Component quantity (% by mass) (1) Precision-synthesized sodium 0.1 PAMPS-2 (2) Glycerin 6.0 (3) Dipropylene glycol 7.0 (4) 1,3-Butylene glycol 7.0 (5) Polyethylene glycol (molecular weight: app 5.0 1500) (6) POE (10) methyl glucoside 2.0 (7) Triethylhexanoin 0.3 (8) PEG-60 hydrogenated castor oil 0.5 (9) Diisostearate polyglyceryl-2 0.4 (10) Tranexamic acid 1.0 (11) Citric acid q.s. (12) Phenoxyethanol q.s. (13) Sodium metaphosphate q.s. (14) Fragrance q.s. (15) Purified water balance
  • Components (8), (9), and (14) were dissolved in component (7), and the resulting mixture is referred to as A.
  • Components (12) was dissolved in a mixture of components (3) and (4), and the resulting mixture is referred to as B.
  • Components (2), (5), (6), (10), (11), and (13) were dissolved in component (15), and the resulting mixture was stirred with a homomixer while the mixture A, B, and component (1) were added thereto. The resulting mixture was mixed and emulsified to obtain a serum.
  • Blending Component quantity (% by mass) (1) Precision-synthesized sodium polyacrylate-3 1.0 (2) Hydrogenated polydecene 1.0 (3) Dimethyl polysiloxane (6cs) 1.0 (4) Decamethylcyclopentasiloxane 2.0 (5) Behenyl alcohol 0.2 (6) Batyl alcohol 0.1 (7) Glycerin 7.0 (8) 1,3-Butylene glycol 8.0 (9) Ethyl hexane acid cetyl 2.0 (10) Polysorbate 60 0.1 (11) PEG-60 hydrogenated castor oil 0.1 (12) Citric acid q.s. (13) Sodium citrate q.s. (14) Potassium hydroxide q.s. (15) Sodium metaphosphate q.s. (16) Ascorbyl glucoside 2.0 (17) Phenoxyethanol q.s. (18) Disodium edetate q.s. (19) Iron oxide q.s. (20) Purified water balance
  • Components (2)-(6), (9)-(11) were heating dissolved to form A.
  • Component (17) was dissolved in component (8), and the resulting mixture is referred to as B.
  • Components (12)-(15), (18)-(19) were dissolved in component (20), and the resulting mixture was heated and stirred with a homomixer while the mixture A and. B were added thereto.
  • component (1) was added and mixed to be emulsified. After that, the resulting mixture was cooled and then component (16) was added thereto to obtain a milk.
  • Blending Component quantity (% by mass) (1) Precision-synthesized sodium polyacrylate-3 1.0 (2) Hydrogenated polydecene 1.0 (3) Dimethicone 1.0 (4) Cyclomethicone 2.0 (5) Behenyl alcohol 0.2 (6) Batyl alcohol 0.1 (7) Glycerin 7.0 (8) 1,3-Butylene glycol 8.0 (9) Ethyl hexane acid cetyl 2.0 (10) Polysorbate 60 0.1 (11) PEG-60 hydrogenated castor oil 0.1 (12) Citric acid q.s. (13) Sodium citrate q.s. (14) Potassium hydroxide q.s. (15) Sodium metaphosphate q.s. (16) Ascorbyl glucoside 2.0 (17) Phenoxyethanol q.s. (18) Disodium edetate q.s. (19) Iron oxide q.s. (20) Purified water balance
  • Components (2)-(6), (9)-(11) were heating dissolved to form A.
  • Component (17) was dissolved in component (8), and the resulting mixture is referred to as B.
  • Components (7), (12)-(15), (18)-(19) were dissolved in component (20), and the resulting mixture was heated and stirred with a homomixer while the mixture A and B were added thereto.
  • component (1) was further added and mixed to be emulsified. After that, the resulting mixture was cooled and then component (16) was added thereto to obtain a milk.

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WO2022047151A1 (en) * 2020-08-28 2022-03-03 The Regents Of The University Of Colorado, A Body Corporate Ultraviolet-absorptive nanoparticles and microparticles for intradermal use

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JP6634496B2 (ja) * 2018-10-30 2020-01-22 株式会社 資生堂 低曳糸性増粘剤、及び該増粘剤を配合した化粧料
JP7478725B2 (ja) 2019-04-24 2024-05-07 株式会社 資生堂 超低曳糸性感触調整剤及び化粧料
KR20210000456A (ko) 2019-06-25 2021-01-05 (주)씨엔엔티 나노셀룰로오스 기반의 화장료용 천연증점제 제조 방법 및 이에 의해 제조된 나노셀룰로오스 기반의 화장료용 천연증점제
WO2021182367A1 (ja) * 2020-03-09 2021-09-16 株式会社 資生堂 洗浄料
WO2021215211A1 (ja) * 2020-04-24 2021-10-28 株式会社 資生堂 化粧料
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