WO2023171660A1 - 化粧料用または医薬部外品用架橋重合体粒子 - Google Patents

化粧料用または医薬部外品用架橋重合体粒子 Download PDF

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Publication number
WO2023171660A1
WO2023171660A1 PCT/JP2023/008540 JP2023008540W WO2023171660A1 WO 2023171660 A1 WO2023171660 A1 WO 2023171660A1 JP 2023008540 W JP2023008540 W JP 2023008540W WO 2023171660 A1 WO2023171660 A1 WO 2023171660A1
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crosslinked polymer
mass
polymer particles
parts
quasi
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French (fr)
Japanese (ja)
Inventor
浩祐 藤田
達史 平内
繁 阪本
智嗣 松本
一平 秋岡
修輔 鎌田
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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Priority to JP2024506341A priority Critical patent/JP7802909B2/ja
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    • 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
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q1/00—Make-up preparations; Body powders; Preparations for removing make-up
    • 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
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • 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
    • C08F220/04—Acids; 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
    • 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
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide

Definitions

  • the present invention relates to crosslinked polymer particles for cosmetics or quasi-drugs.
  • thickeners are used in cosmetics or quasi-drugs to improve the feeling of use when applied to the skin.
  • carboxyvinyl polymers, xanthan gum, cellulose, guar gum, polyacrylic acid, etc. which have a thickening effect, are used, and by using these depending on the purpose and changing the blending amount and ingredients, it is possible to achieve a thickening effect similar to that of a lotion. It can be prepared from low viscosity cosmetics to solid gels such as Hair Tick.
  • carboxyvinyl polymer is widely used because it is inexpensive, has a high thickening effect, and gels in a small amount.
  • carboxyvinyl polymer is increased in order to obtain a thickening effect, it tends to feel sticky when applied to the skin.
  • Patent Document 1 describes that a viscous composition containing an alkyl-modified carboxyl group-containing water-soluble polymer and a modified polyalkylene oxide exhibits high viscosity even in a small amount. ing. Furthermore, in Patent Document 2, a water-soluble ethylenically unsaturated monomer is obtained by reverse-phase suspension polymerization in a petroleum-based hydrocarbon dispersion medium in the presence of a surfactant and a water-soluble radical polymerization initiator. A cosmetic containing a water-absorbing resin is described, and it is described that the cosmetic can be provided with excellent spreadability and texture upon application.
  • Cosmetics or quasi-drugs using thickeners are achieving both a thickening effect and improving stickiness on the skin, and in cosmetics using the polymer described in Patent Documents 1 or 2, It has been found that increasing the amount added in order to improve the thickening effect causes a problem in that the feeling when applied to the skin deteriorates.
  • the inventors have conducted studies in view of the above-mentioned problems, and have developed crosslinked polymer particles for cosmetics or quasi-drugs that contain (per 100 parts by mass of the crosslinked polymer)
  • the content of structural units derived from meth)acrylic acid (salt) is 20 parts by mass or more and 100 parts by mass or less
  • the volume average particle diameter of the crosslinked polymer particles is 8 ⁇ m or more and 20 ⁇ m or less
  • the half width is 3 ⁇ m or more and 20 ⁇ m.
  • the present invention has been completed based on the discovery that crosslinked polymer particles for cosmetics or quasi-drugs with a particle size of less than 100% can achieve both a thickening effect and a feeling of use when applied to the skin.
  • crosslinked polymer particles for cosmetics or quasi-drugs are provided that can achieve both a thickening effect and a good feeling when applied to the skin.
  • FIG. 2 is a graph showing the results of UV resistance evaluation of crosslinked polymer particles when a chelating agent is added.
  • FIG. 3 is a graph showing the results of stability evaluation of crosslinked polymer particles under a fluorescent lamp.
  • FIG. 2 is a graph showing the results of stability evaluation under fluorescent lamp of crosslinked polymer particles when a chelating agent is added.
  • the structural unit derived from (meth)acrylic acid (salt) in 100 parts by mass of the crosslinked polymer is 20 parts by mass or more and 100 parts by mass or less
  • the volume average particle diameter is Crosslinked polymer particles for cosmetics or quasi-drugs, which have a particle size of 8 ⁇ m or more and a width of 20 ⁇ m or less, and a half width of 3 ⁇ m or more and less than 20 ⁇ m.
  • ⁇ acid (salt) means “ ⁇ acid and/or its salt
  • (meth)acrylic means “acrylic and/or methacrylic.” That is, “(meth)acrylic acid (salt)” means “acrylic acid (salt) and/or methacrylic acid (salt).”
  • the term "resin” refers to a broader concept than polymer.
  • the resin may contain one or more kinds of polymers, and may further contain materials other than the polymers, such as additives, if necessary.
  • crosslinked polymer particles are intended to be particles containing a crosslinked polymer as a main component.
  • the crosslinked polymer particles may be composed of one or more types of crosslinked polymers.
  • the crosslinked polymer particles may further contain materials other than the crosslinked polymer, such as additives, if necessary.
  • the structural unit derived from (meth)acrylic acid (salt) may be formed by polymerizing (meth)acrylic acid (salt), or the structure may be formed by post-modification. You may let them.
  • the (meth)acrylic acid (salt) includes acrylic acid (salt) and methacrylic acid (salt), and acrylic acid (salt) is more preferable.
  • the (meth)acrylic acid according to an embodiment of the present disclosure is not particularly limited, and any known (meth)acrylic acid may be used.
  • the known (meth)acrylic acid can be obtained by, for example, collecting gaseous (meth)acrylic acid obtained by a catalytic gas phase oxidation method with a solvent such as water, and then purifying it by distillation, crystallization, etc. It will be done.
  • (Meth)acrylic acid may contain trace amounts of components such as polymerization inhibitors and impurities.
  • the content ratio of structural units derived from (meth)acrylic acid (salt) per 100 parts by mass of the crosslinked polymer according to an embodiment of the present disclosure is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and 50 parts by mass or more. It is more preferably 70 parts by mass or more, 90 parts by mass or more, and particularly preferably 100 parts by mass.
  • the above-mentioned (meth)acrylic acid neutralized with the following basic compound is used.
  • the "basic compound” specifically includes alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides, ammonia, organic amines, and the like.
  • a compound exhibiting strong basicity is preferably selected as the basic compound. That is, the basic compound used is more preferably a hydroxide of an alkali metal such as sodium, potassium, or lithium, and still more preferably sodium hydroxide.
  • the neutralization rate of (meth)acrylic acid in an embodiment of the present disclosure is preferably 10 mol% to 90 mol%, more preferably 40 mol% to 85 mol%, and It is preferably set appropriately within the range of 50 mol% to 80 mol%, particularly preferably 60 mol% to 75 mol%.
  • the neutralization rate is less than 10 mol%, the thickening property may decrease.
  • the neutralization rate exceeds 90 mol%, the pH of the crosslinked polymer particles may become excessively high.
  • the above neutralization rate is applied as the average neutralization rate of all monomers containing acid groups including (meth)acrylic acid.
  • the crosslinked polymer particles of the present disclosure may be crosslinked polymer particles having 20 parts by mass or more of structural units derived from (meth)acrylic acid (salt) in 100 parts by mass of the crosslinked polymer; (salt) may also contain a structural unit derived from a monomer other than the salt.
  • a monomer other than (meth)acrylic acid (salt) a water-soluble monofunctional unsaturated monomer other than (meth)acrylic acid (salt) is preferable, such as (meth)acrylic acid (salt).
  • Monofunctional unsaturated monomers having carboxyl groups other than those mentioned above can be suitably used.
  • the monofunctional unsaturated monomer means a compound having one ethylenically unsaturated group in one molecule.
  • the crosslinked polymer according to an embodiment of the present disclosure may include a structural unit derived from a monomer other than (meth)acrylic acid (salt).
  • monomers other than (meth)acrylic acid (salt) include (anhydrous) maleic acid, itaconic acid, cinnamic acid, vinylsulfonic acid, allyltoluenesulfonic acid, vinyltoluenesulfonic acid, styrenesulfonic acid, 2- Anionic unsaturated monomers such as (meth)acrylamido-2-methylpropanesulfonic acid, 2-(meth)acryloylethanesulfonic acid, 2-(meth)acryloylpropanesulfonic acid, 2-hydroxyethyl (meth)acryloylphosphate, etc.
  • mercaptan group-containing unsaturated monomers phenolic hydroxyl group-containing unsaturated monomers; amide groups such as (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, etc.
  • amide groups such as (meth)acrylamide, N-ethyl (meth)acrylamide, N,N-dimethyl (meth)acrylamide, etc.
  • Containing unsaturated monomers unsaturated monomers containing amino groups such as N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, etc. Examples include mercury. Among them, (meth)acrylamide is preferably used. In one embodiment of the present disclosure, the content of the (meth)acrylamide-derived structural unit per 100 parts by mass of the crosslinked polymer is preferably 50 parts
  • the crosslinked polymer particles according to an embodiment of the present disclosure are crosslinked polymer particles having 20 parts by mass or more and 100 parts by mass or less of structural units derived from (meth)acrylic acid (salt) in 100 parts by mass of the crosslinked polymer.
  • the content of structural units derived from (meth)acrylic acid (salt) per 100 parts by mass of crosslinked polymer particles is 50 parts by mass or more and 100 parts by mass or less, and/or the content per 100 parts by mass of crosslinked polymer particles is
  • the content of structural units derived from (meth)acrylamide is 50 parts by mass or more and 80 parts by mass or less.
  • the crosslinked polymer according to an embodiment of the present disclosure may be crosslinked using a crosslinking agent. Furthermore, the crosslinked polymer particles according to an embodiment of the present disclosure need only have at least a crosslinked structure inside the crosslinked polymer that constitutes the crosslinked polymer particles, and The surface of the crosslinked polymer, in other words, the surface of the crosslinked polymer particles may have a crosslinked structure. From the viewpoint of water retention, the crosslinked polymer particles according to an embodiment of the present disclosure preferably have a crosslinked structure on the particle surface.
  • an internal crosslinking agent that crosslinks the inside of the resulting crosslinked polymer particles or a surface crosslinking agent that crosslinks the surface of the crosslinked polymer particles may be used depending on the purpose. I can do it.
  • a crosslinking agent either the inside or the particle surface may be crosslinked, or both the inside and the particle surface may be crosslinked.
  • ethylene glycol diethylene glycol, triethylene glycol, polyethylene glycol, glycerin, polyglycerin, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexane Diol, neopentyl alcohol, diethanolamine, tridiethanolamine, polypropylene glycol, polyvinyl alcohol, pentaerythritol, sorbitol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, 1,3-butanediol, 1,3-pentanediol, 1, Polyhydric alcohols such as 4-pentanediol, 2,4-pentanediol, 2,5-hexanediol, trimethylolpropane, sorbitol, sorbitan, glucose, mannitol, mannitan, sucrose,
  • the internal crosslinking agent compounds having two or more ethylenically unsaturated groups in one molecule are more preferable, and examples include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and propylene.
  • the crosslinked polymer is preferably crosslinked with a compound having two or more ethylenically unsaturated groups in one molecule.
  • the amount of the internal crosslinking agent used is preferably 0.0001% by mass to 10% by mass, more preferably 0.001% by mass to 1% by mass, and even more preferably 0.01% by mass, based on the entire monomer. It is appropriately set within the range of ⁇ 1% by mass. By controlling the amount of the internal crosslinking agent within the above range, a crosslinked polymer having desired thickening properties can be obtained. On the other hand, outside the above range, an increase in the water-soluble content due to a decrease in gel strength, a decrease in thickening property, and a decrease in handling properties after liquid absorption are observed, which is not preferable.
  • the crosslinking agent that can be used as the surface crosslinking agent according to an embodiment of the present disclosure is not particularly limited, and includes organic or inorganic surface crosslinking agents. Among these, organic surface crosslinking agents that react with carboxyl groups are preferred from the viewpoint of the physical properties of the resulting crosslinked polymer and the ease of handling the surface crosslinking agent.
  • Polyhydric alcohols polyvalent amine compounds such as diethanolamine, triethanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl Polyvalent glycidyl compounds such as ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, 2,4-tolylene diisocyanate, ethylene carbonate (1,3-dioxolan-2-one), propylene carbonate (4-methyl-1 , 3-dioxolan-2-one), 4,5-dimethyl-1,3-dioxolan-2-one, (poly, di, or mono) 2-oxazolidinone, epichlorohydrin, epibromohydrin, diglycol Examples include silicates, poly
  • One or more surface crosslinking agents are selected from these, taking reactivity etc. into consideration.
  • organic compound includes polyhydric alcohol compounds, epoxy compounds, polyvalent amine compounds, condensates of polyvalent amine compounds and haloepoxy compounds, oxazoline compounds, oxazolidinone compounds, alkylene carbonate compounds, and polyvalent glycidyl compounds. , oxetane compounds, vinyl ether compounds, cyclic urea compounds, and the like.
  • the amount of the surface crosslinking agent to be used (the total amount if more than one is used) is preferably 0.001 parts by mass to 10 parts by mass, more preferably 0.01 parts by mass to 100 parts by mass of the crosslinked polymer. It is appropriately set within the range of 5 parts by mass. By controlling the amount of the surface crosslinking agent within this range, an optimal crosslinked structure can be formed in the surface layer of the crosslinked polymer, and crosslinked polymer particles with good handling properties can be obtained.
  • the crosslinked polymer particles according to an embodiment of the present disclosure may contain additives for various purposes.
  • additives for various purposes.
  • organic or inorganic water-insoluble fine particles, water-soluble polymers, surfactants, polyhydric alcohols, and water-soluble polyvalent metal salts may be added to improve the handling properties of powders and the texture of gels. You can stay there.
  • a chelating agent, a reducing agent, an antioxidant, and a hydroxycarboxylic acid (salt) may be included.
  • it may contain UV absorbers, dyes, pigments, and fragrances.
  • the content of the additive in the crosslinked polymer particles according to an embodiment of the present disclosure (the total content when using multiple types together) is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably is 1% by mass or less.
  • the volume average particle diameter D10 of the crosslinked polymer particles according to an embodiment of the present disclosure is preferably 1 ⁇ m or more, more preferably 3 ⁇ m or more, from the viewpoint of feeling when applying the crosslinked polymer particle composition to the skin. , more preferably 6 ⁇ m or more, preferably 20 ⁇ m or less, more preferably 15 ⁇ m or less, even more preferably 10 ⁇ m or less. Furthermore, from the above viewpoint, the volume average particle diameter D10 of the crosslinked polymer particles according to an embodiment of the present disclosure is preferably 1 ⁇ m to 20 ⁇ m, more preferably 3 ⁇ m to 15 ⁇ m, and preferably 6 ⁇ m to 10 ⁇ m. It is even more preferable that there be.
  • the volume average particle diameter D50 of the crosslinked polymer particles according to an embodiment of the present disclosure is preferably 8 ⁇ m or more, more preferably 9 ⁇ m or more, from the viewpoint of feeling when applying the crosslinked polymer particle composition to the skin. , more preferably 10 ⁇ m or more, preferably 20 ⁇ m or less, more preferably 18 ⁇ m or less, even more preferably 15 ⁇ m or less. Furthermore, from the above viewpoint, the volume average particle diameter D50 of the crosslinked polymer particles according to an embodiment of the present disclosure is preferably 8 ⁇ m to 20 ⁇ m, more preferably 9 ⁇ m to 18 ⁇ m, and 10 ⁇ m to 15 ⁇ m. It is even more preferable that there be.
  • the volume average particle diameter D90 of the crosslinked polymer particles according to an embodiment of the present disclosure is preferably 9 ⁇ m or more, more preferably 10 ⁇ m or more, from the viewpoint of feeling when applying the crosslinked polymer particle composition to the skin. , more preferably 15 ⁇ m or more, preferably 50 ⁇ m or less, more preferably 40 ⁇ m or less, even more preferably 25 ⁇ m or less. Further, from the above viewpoint, the volume average particle diameter D90 of the crosslinked polymer particles according to an embodiment of the present disclosure is preferably 9 ⁇ m to 50 ⁇ m, more preferably 10 ⁇ m to 40 ⁇ m, and 15 ⁇ m to 25 ⁇ m. It is even more preferable that there be.
  • the volume average particle diameter "D10” means a particle diameter where the cumulative frequency of the volume average particle diameter is 10% by volume
  • the volume average particle diameter "D50” means a particle diameter where the cumulative frequency of the volume average particle diameter is 10% by volume.
  • the volume average particle diameter "D90” means a particle diameter of 50 volume %
  • the volume average particle diameter "D90” means a particle diameter where the cumulative frequency of the volume average particle diameter is 90 volume %.
  • the volume average particle diameter of the crosslinked polymer particles in the present disclosure can be measured using a known method, for example, the following method. Measured using a laser diffraction scattering particle size distribution analyzer LA-950 manufactured by HORIBA. Ethyl acetate is used as a circulating solvent during measurement, and the refractive index of the dispersion is 1.59 and the refractive index of the dispersion medium is 1.371. The median diameter ( ⁇ m) is calculated from the volume-based particle size distribution obtained by the measurement, and is defined as the volume average particle diameter.
  • the half width of the volume average particle diameter of the crosslinked polymer particles according to an embodiment of the present disclosure is preferably 3 ⁇ m to 20 ⁇ m, and 5 ⁇ m to 19 ⁇ m from the viewpoint of feeling when applying the crosslinked polymer particle composition to the skin. is more preferable, 7 ⁇ m to 18 ⁇ m is even more preferable, and 8 ⁇ m to 16 ⁇ m is particularly preferable.
  • the half width of the volume average particle diameter of the crosslinked polymer according to an embodiment of the present disclosure is within the above range, a good feeling of use can be expected in terms of slimy feeling when applied to the skin and stickiness when dry. .
  • the half-width of the volume average particle diameter of the crosslinked polymer according to an embodiment of the present disclosure exceeds the above upper limit range, the feeling of use deteriorates, such as poor skin feel and increased squeaky feeling. There are concerns.
  • the half width of the volume average particle diameter of the crosslinked polymer particles of the present disclosure can be measured using a known method, for example, based on the particle size distribution graph obtained by measuring the volume average particle diameter.
  • Price range can be calculated. Specifically, the half value of the frequency is calculated from the value of the maximum frequency, the volume average particle diameter at the half value is calculated from the approximate curve formula between two points including the half value, and the volume average particle diameter of the two points calculated from the calculation is calculated. The difference can be taken as the half width.
  • the turbidity of the crosslinked polymer particles according to an embodiment of the present disclosure is preferably 50% or less, more preferably 25% or less, and even more preferably 10% or less.
  • the lower limit of the turbidity of the crosslinked polymer particles according to an embodiment of the present disclosure is not particularly limited, and may be, for example, 0.01% or more, 0.1% or more, or 1% or more, but preferably 0.01% or more, 0.1% or more, or 1% or more. %.
  • the turbidity of the crosslinked polymer particles in the present disclosure can be measured using a known method, for example, by the method below.
  • the turbidity of the crosslinked polymer particles can be measured using a haze meter NDH7000 manufactured by Nippon Denshoku Co., Ltd.
  • a 1% by mass dispersion of crosslinked polymer particles can be prepared using a HEIDON Three-One motor at 600 rpm for 30 minutes, and filled into a quartz cell with an optical path length of 10 mm to measure turbidity.
  • the measurement temperature can be 25°C.
  • the crosslinked polymer particles according to an embodiment of the present disclosure may be water-swellable crosslinked polymer particles.
  • the crosslinked polymer particles are said to have water-swellability when the non-pressure water absorption capacity of the following physiological saline (0.9 mass% sodium chloride aqueous solution) (sometimes referred to as "physiological saline water absorption capacity") is 5 g. /g or more.
  • the non-pressure water absorption capacity of the crosslinked polymer particles according to an embodiment of the present disclosure is preferably 10 (g/g) or more, more preferably 20 (g/g) or more, and 30 (g/g) or more. g/g) or more is more preferable.
  • the physiological saline water absorption capacity is 10 (g/g) or more, sufficient liquid can be absorbed to obtain a soft gel.
  • the physiological saline water absorption capacity of the crosslinked polymer particles according to an embodiment of the present disclosure is preferably 100 (g/g) or less, more preferably 60 (g/g) or less. Since the physiological saline water absorption capacity of the crosslinked polymer particles is 100 (g/g) or less, there is no excessive stickiness.
  • the non-pressure water absorption capacity of the crosslinked polymer particles according to an embodiment of the present disclosure is 10 (g/g) to 100 (g/g). It is preferably 20 (g/g) to 60 (g/g), more preferably 30 (g/g) to 60 (g/g).
  • the method for measuring the physiological saline water absorption capacity of crosslinked polymer particles is as follows. Note that measurements of various performances of the crosslinked polymer particles in the present disclosure were carried out in a room at a temperature of 25° C. and a relative humidity of 40 to 50% using a power source of AC 100 V and 60 Hz, unless otherwise specified.
  • the crosslinked polymer particles are dried at 80° C. for 3 hours in a vacuum dryer with a reduced pressure of 5 kPa.
  • a glass filter (diameter 120 mm, pore size JIS standard No. 0, height 5 mm) is placed in the center of a tray (SUS square shape, D20 cm x L 20 cm x H 10 mm), and 200 g of a 0.9 mass% sodium chloride aqueous solution is added.
  • a filter paper manufactured by ADVANTEC, No. 2, 110 mm
  • a cylindrical cylinder with a diameter of 6 cm manufactured by Machintek, C-207431-D
  • a 400 mesh stainless steel mesh pasted on one opening was placed. -2 with screen (400mesh)).
  • the physiological saline water absorption capacity (g/g) of the crosslinked polymer particles is calculated by the following formula.
  • WBC Cylinder mass (g)
  • WBS Silica mass (g) used for blank test
  • WBS1 Total cylinder mass (g) after 30 minutes of immersion in blank test
  • WSS1 Silica mass (g) used to prepare mixed sample for measurement
  • WSA1 Mass (g) of crosslinked polymer particles used to prepare mixed sample for measurement
  • WS Mass of measurement mixed sample used for measurement (g)
  • WSA Mass of crosslinked polymer
  • the crosslinked polymer particles according to an embodiment of the present disclosure have a non-pressure water absorption capacity of deionized water (sometimes referred to as "deionized water absorption capacity"), which will be described later, of 10 (g/g) or more. It is preferably at least 20 (g/g), more preferably at least 30 (g/g), even more preferably at least 30 (g/g). When the deionized water absorption capacity is 10 (g/g) or more, sufficient liquid can be absorbed to obtain a soft gel.
  • the upper limit of the deionized water absorption capacity of the crosslinked polymer particles according to an embodiment of the present disclosure is not particularly limited, but is, for example, 150 (g/g) or less, 100 (g/g) or less, or 50 (g/g) or less.
  • g) may be:
  • Examples of the method for measuring the deionized water absorption capacity of crosslinked polymer particles in the present disclosure include a method in which deionized water is used instead of the 0.9% by mass aqueous sodium chloride solution in the method for measuring the physiological saline water absorption capacity. I can do it.
  • the ratio of the water absorption capacity of deionized water to the water absorption capacity of physiological saline of the crosslinked polymer particles is preferably such that the water absorption capacity of deionized water is 1 time or more and 10 times or less, and 1 time or more and 8 times or less, relative to the physiological saline water absorption capacity. It is more preferably not more than 1 time, and even more preferably not less than 1 time and not more than 5 times.
  • the soluble content per 100% by mass of the crosslinked polymer particles is preferably 50% by mass or less, more preferably 40% by mass or less, and 30% by mass or less. It is more preferable that it is less than % by mass. By controlling the soluble content to 50% by mass or less, excessive stickiness is not caused.
  • the lower limit of the soluble content of the crosslinked polymer particles according to an embodiment of the present disclosure is not particularly limited, but may be, for example, 0.01% by mass or more, 0.1% by mass or more, or 1% by mass or more.
  • the method for measuring the soluble content of crosslinked polymer particles in the present disclosure is as follows.
  • the crosslinked polymer particles are dried at 80° C. for 3 hours in a vacuum dryer with a reduced pressure of 5 kPa.
  • the viscosity of a blend of crosslinked polymer particles according to an embodiment of the present disclosure with purified water at 1% by mass is determined from the viewpoint of thickening when used as a cosmetic or quasi-drug.
  • 5,000 mPa ⁇ s or more is preferable, 10,000 mPa ⁇ s or more is more preferable, 20,000 mPa ⁇ s or more is even more preferable, 50,000 mPa ⁇ s or less is preferable from the viewpoint of usability, and 30,000 mPa ⁇ s or less is preferable. More preferably, it is 25,000 mPa ⁇ s or less.
  • the crosslinked polymer particles according to an embodiment of the present disclosure are purified to a concentration of 1% by mass.
  • the viscosity of the formulation blended with water is preferably 5,000 mPa ⁇ s to 50,000 mPa ⁇ s, more preferably 10,000 mPa ⁇ s to 30,000 mPa ⁇ s, and 20,000 mPa ⁇ s. More preferably, it is 25,000 mPa ⁇ s.
  • the viscosity of a formulation containing the crosslinked polymer particles of the present disclosure can be measured using a known method, for example, using a B-type viscometer TVB-10 manufactured by Toki Sangyo Co., Ltd. with a rotor TM4 and a rotation speed of 6 rpm. It is also possible to perform the measurement under conditions of a measurement time of 60 seconds and a temperature of 25°C.
  • the crosslinked polymer particles according to an embodiment of the present disclosure contain silicon dioxide, since this can improve the feeling of use as a cosmetic.
  • the content of silicon dioxide with respect to 100 parts by mass of the crosslinked polymer particles according to an embodiment of the present disclosure is preferably 0.5 parts by mass or less, and 0.3 parts by mass or less from the viewpoint of providing excellent usability as a cosmetic. It is more preferably 0.1 parts by mass or less.
  • the lower limit of the content of silicon dioxide with respect to 100 parts by mass of the crosslinked polymer particles is not particularly limited, but for example, 0.0001 parts by mass or more, 0. It may be .001 parts by mass or more, or 0.01 parts by mass or more.
  • Step of producing a monomer aqueous solution This step is a step of producing a monomer aqueous solution (hereinafter referred to as "monomer aqueous solution").
  • monomer aqueous solution a monomer aqueous solution
  • an internal crosslinking agent and other substances described below may be added to the monomer aqueous solution as necessary.
  • monomer slurry liquids can also be used as long as the water absorption performance of the crosslinked polymer particles obtained as the final product does not deteriorate. .
  • a monomer composition containing (meth)acrylic acid and/or (meth)acrylate is used as a monomer from the viewpoint of physical properties and productivity of a crosslinked polymer.
  • the (meth)acrylic acid and/or (meth)acrylate of the present disclosure are as described above. That is, the monomer composition according to an embodiment of the present disclosure is a composition containing 20 parts by mass or more and 100 parts by mass or less of (meth)acrylic acid (salt) in 100 parts by weight of the monomer composition.
  • the "(meth)acrylic acid” is not particularly limited, and any known (meth)acrylic acid may be used.
  • the known (meth)acrylic acid can be obtained by, for example, collecting gaseous (meth)acrylic acid obtained by a catalytic gas phase oxidation method with a solvent such as water, and then purifying it by distillation, crystallization, etc. It will be done.
  • (Meth)acrylic acid may contain trace amounts of components such as polymerization inhibitors and impurities.
  • the above-mentioned (meth)acrylic acid is neutralized with the following basic compound, but the (meth)acrylate is a commercially available (meth)acrylic acid. It may be an acid salt (for example, sodium (meth)acrylate), or it may be one obtained by neutralizing (meth)acrylic acid in a crosslinked polymer production plant.
  • an acid salt for example, sodium (meth)acrylate
  • the "basic compound” specifically includes alkali metal carbonates, alkali metal hydrogen carbonates, alkali metal hydroxides, ammonia, organic amines, and the like.
  • a compound exhibiting strong basicity is preferably selected as the basic compound. That is, the basic compound used is more preferably a hydroxide of an alkali metal such as sodium, potassium, or lithium, and still more preferably sodium hydroxide.
  • the basic compound is preferably in the form of an aqueous solution from the viewpoint of ease of handling.
  • any one of these (1) to (3) can be selected or used in combination as the timing for neutralization.
  • these neutralizations may be carried out in a continuous mode or in a batch mode and are not particularly limited, but from the viewpoint of production efficiency of the crosslinked polymer, it is preferable to carry out in a continuous mode.
  • the neutralization rate of (meth)acrylic acid in one embodiment of the present disclosure is as described above.
  • the range of the neutralization rate is applied to any of the above-mentioned neutralizations before, during, and after the polymerization.
  • various forms of crosslinked polymers in the manufacturing process of crosslinked polymers including crosslinked polymers as final products (e.g., hydrogel-like crosslinked polymers after polymerization, dry polymers after drying, and crosslinked polymers before surface crosslinking)
  • the above neutralization rate is similarly applied to crosslinked polymer particles, crosslinked polymer particles after surface crosslinking, etc.).
  • neutralization conditions such as a neutralization device, neutralization temperature, and residence time
  • the conditions described in International Publication No. 2009/123197 and the like are applied to one embodiment of the present disclosure.
  • monomers other than the above-mentioned acrylic acid (salt) may be used in combination with acrylic acid (salt) as necessary. I can do it.
  • the monomer composition may be a mixture of (meth)acrylic acid (salt) and other monomers.
  • the compounds and compositions used as the other monomers are as described above.
  • the compound and composition used as the internal crosslinking agent used in the method for producing crosslinked polymer particles according to an embodiment of the present disclosure are as described above.
  • a method is preferably employed in which the internal crosslinking agent is added in advance during the preparation of the monomer aqueous solution, and the crosslinking reaction (crosslinking polymerization) is carried out simultaneously with the polymerization reaction.
  • this method is not limited to this method, and a method in which polymerization is performed without adding an internal crosslinking agent and crosslinking is performed by adding an internal crosslinking agent during or after the polymerization may also be adopted. good.
  • these methods can also be used together.
  • the following substances are added at one or more locations during the preparation of the monomer aqueous solution, during the polymerization process, and after the polymerization process. It can be added with.
  • the substance is not particularly limited, but includes, for example, hydrophilic polymers such as starch, starch derivatives, cellulose, cellulose derivatives, polyvinyl alcohol, polyacrylic acid (salt), and crosslinked polyacrylic acid (salt).
  • the substance may be a compound such as a carbonate, an azo compound, a foaming agent such as a bubble, a surfactant, or a chain transfer agent. These substances may be added alone or in combination of two or more.
  • the amount of the hydrophilic polymer added is preferably 50% by mass or less, more preferably 20% by mass or less, even more preferably 10% by mass or less, based on the entire monomer (including other monomers). It is particularly preferably set within a range of 5% by mass or less (the lower limit is 0% by mass). Further, the amount of the compound added is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass, based on the entire monomer (including other monomers). It is appropriately set within the following range (the lower limit is 0% by mass).
  • a graft polymer or a crosslinked polymer composition for example, a starch-acrylic acid polymer, a PVA-acrylic acid polymer, etc.
  • these polymers and crosslinked polymer compositions are also included in the crosslinked polymer of one embodiment of the present disclosure.
  • a monomer aqueous solution is prepared by appropriately selecting each of the above-mentioned components according to the purpose and mixing a predetermined amount of each component that satisfies the above-mentioned range.
  • the monomer containing acrylic acid (salt) is preferably used as an aqueous solution, or dissolved in a mixed solvent of water and a hydrophilic solvent, and more preferably as an aqueous solution.
  • the concentration of the monomer components in the monomer aqueous solution is not particularly limited, but from the viewpoint of physical properties of the crosslinked polymer, it is preferably 10% by mass to 80% by mass, more preferably 20% to 75% by mass, More preferably, it is appropriately set within the range of 30% by mass to 70% by mass.
  • the above-mentioned "monomer component concentration" is a value calculated from the following formula 1.
  • the mass of the monomer aqueous solution includes the graft component, crosslinked polymer, and hydrophobicity in reversed phase suspension polymerization. The mass of organic solvent is not included.
  • Polymerization initiator examples include thermal decomposition type polymerization initiators, photodecomposition type polymerization initiators, and redox type polymerization initiators combined with reducing agents that promote the decomposition of these polymerization initiators.
  • thermal decomposition type polymerization initiators examples include thermal decomposition type polymerization initiators, photodecomposition type polymerization initiators, and redox type polymerization initiators combined with reducing agents that promote the decomposition of these polymerization initiators.
  • the polymerization initiator described in US Pat. No. 7,265,190 and the like can be used.
  • One or more types of polymerization initiators are selected from these in consideration of the polymerization form and the like.
  • the polymerization initiator is preferably a peroxide or an azo compound, more preferably a peroxide, and still more preferably a persulfate.
  • the amount of the polymerization initiator used is preferably 0.001 part by mass to 1 part by mass, more preferably 0.001 part by mass, based on 100 parts by mass of the entire monomer (including other monomers). It is appropriately set within the range of ⁇ 0.5 parts by mass. Further, the amount of the reducing agent to be used is preferably set appropriately within the range of 0.0001 part by mass to 0.02 part by mass based on the entire monomer (including other monomers). By controlling the amounts of the polymerization initiator and reducing agent within these ranges, a crosslinked polymer having desired performance can be obtained.
  • the polymerization reaction of an embodiment of the present disclosure may be initiated by irradiation with active energy rays such as radiation, electron beams, and ultraviolet rays.
  • active energy rays such as radiation, electron beams, and ultraviolet rays.
  • the irradiation with the active energy rays and the polymerization initiator may be used in combination.
  • the polymerization form of the aqueous monomer solution applied in the polymerization process according to an embodiment of the present disclosure is not particularly limited, but includes, for example, aqueous solution polymerization, reversed-phase suspension polymerization, spray polymerization, droplet polymerization, bulk polymerization, and precipitation polymerization. etc.
  • aqueous solution polymerization or reverse phase suspension polymerization more preferably aqueous solution polymerization, and even more preferably continuous aqueous solution polymerization are selected in consideration of polymerization controllability, water absorption performance of the crosslinked polymer, etc.
  • Continuous aqueous solution polymerization specifically includes continuous belt polymerization as described in US Pat. No. 4,893,999 and continuous kneader polymerization as described in US Pat. No. 6,987,151. Through these continuous aqueous solution polymerizations, crosslinked polymers can be produced with high productivity.
  • Each of the above polymerization forms can be carried out under an air atmosphere, but from the viewpoint of preventing discoloration of the resulting crosslinked polymer, it is preferably carried out under an inert gas atmosphere such as nitrogen or argon (for example, under an atmosphere of an inert gas such as nitrogen or argon (for example, under an oxygen concentration of 1% by volume or less). ).
  • an inert gas atmosphere such as nitrogen or argon
  • dissolved oxygen in the monomer aqueous solution is also preferably sufficiently replaced with an inert gas (for example, the amount of dissolved oxygen is less than 1 mg/l).
  • the polymerization step according to an embodiment of the present disclosure can be said to be a step of polymerizing a monomer composition containing 20 parts by mass or more and 100 parts by mass or less of (meth)acrylic acid (salt) per 100 parts by mass of all monomers. .
  • This step is a step of gel grinding the hydrogel obtained in the polymerization step to obtain particulate hydrogel (hereinafter referred to as "particulate hydrogel”).
  • gel grinding refers to turning a hydrogel into particles using a gel grinder such as a kneader, meat chopper, or cutter mill.
  • a gel grinder such as a kneader, meat chopper, or cutter mill.
  • the polymerization step and gel crushing step are performed simultaneously. Furthermore, when a particulate hydrogel is obtained during the polymerization process, such as in reverse-phase suspension polymerization or droplet polymerization, the gel crushing step may not be carried out.
  • the hydrogel obtained in the polymerization step is subjected to the next drying step in the form of particles as they are or in the form of particles obtained by gel crushing.
  • the mass average particle diameter (D50) of the particulate hydrogel International Publication No. 2011/126079 Paragraph [0255] (d) is measured according to the weight average particle diameter (D50) and the logarithmic standard deviation ( ⁇ ) of the particle size distribution. from the viewpoint of drying efficiency, is preferably set within the range of 0.1 mm to 50 mm, more preferably 0.1 mm to 10 mm, still more preferably 0.2 mm to 5 mm.
  • the particulate hydrogel obtained in the polymerization step or the particulate hydrogel obtained in the gel crushing step is dried to a desired solid content range to obtain a dry polymer. It is a process.
  • the desired range of solids content is preferably 80% by mass or more, more preferably 85% to 99% by mass, even more preferably 90% to 98% by mass, particularly preferably 92% to 97% by mass. is set appropriately.
  • “solid content” is a value calculated from drying loss (mass change when 1 g of sample is dried at 180° C. for 3 hours), and is calculated from the following (Equation 2).
  • Solid content (mass%) (mass of sample (1 g) - loss on drying) / (mass of sample (1 g)) x 100...
  • the drying method in an embodiment of the present disclosure is not particularly limited, but includes, for example, heating drying, hot air drying, reduced pressure drying, fluidized bed drying, infrared drying, microwave drying, drum dryer drying, and co-existence with a hydrophobic organic solvent. Examples include drying by boiling dehydration and high-humidity drying using high-temperature steam. Among these, from the viewpoint of drying efficiency, preferably hot air drying, more preferably band drying in which hot air drying is performed on a ventilation belt, is selected.
  • the drying temperature in this step is not particularly limited, but from the viewpoint of drying efficiency and color tone of the crosslinked polymer, it is preferably set appropriately within the range of 120°C to 250°C, more preferably 150°C to 200°C. Further, the drying time is appropriately set within a range of preferably 10 minutes to 120 minutes, more preferably 20 minutes to 90 minutes, and even more preferably 30 minutes to 60 minutes. By setting the drying temperature and drying time within this range, it is possible to change the polymer chains inside the crosslinked polymer and reduce damage, resulting in a crosslinked polymer with high physical properties that suppresses the increase in soluble content. A union is obtained.
  • the physiological saline water absorption capacity and soluble content of the crosslinked polymer can be set within a desired range.
  • the drying temperature is usually specified by the temperature of the heat medium (for example, in the case of hot air drying, it is specified by the temperature of the hot air), but in the case of drying such as microwave drying that cannot be specified by the temperature of the heat medium. is defined by the temperature of the particulate hydrogel. Further, the drying temperature may be constant or may be changed as appropriate during drying.
  • the drying conditions other than the drying temperature and drying time may be appropriately set depending on the water content of the particulate hydrogel, the amount of the particulate hydrogel supplied to the drying process, the target solid content, etc.
  • band drying the conditions described in, for example, International Publication No. 2006/100300 are applied to one embodiment of the present disclosure.
  • the dry polymer obtained in the drying step is pulverized (pulverization step) and adjusted to have a particle size within a desired range (classification step) to obtain a desired particle size.
  • This is a step of obtaining crosslinked polymer particles. Note that this pulverization step differs from the gel pulverization step (iii) above in that the dry polymer to be pulverized undergoes a drying step.
  • crosslinked polymer particles that have undergone a drying step before surface crosslinking are sometimes referred to as "crosslinked polymer powder before surface crosslinking" or "crosslinked polymer powder A.”
  • the pulverizer used in this step may be either a continuous type or a batch type, and specific examples include a roll mill, a vibration mill, a ball mill, a hammer mill, a pin mill, a flash mill, a jet mill, and the like.
  • the ball mill is not limited to a type using only spherical mills, but has a broad concept that includes rod mills and compound mills.
  • Preferred pulverizers are those in which the material to be pulverized floating or falling in the air is broken by impact and the parts of the pulverizer do not come into contact with each other; specific examples include pin mills, flash mills, and jet mills. It will be done.
  • the three preferred types of pulverizers mentioned above cause a small temperature rise of the material to be pulverized during pulverization, which suppresses deterioration of the crosslinked polymer particles, and causes almost no wear or damage to the pulverizer itself, which improves the quality of the product after pulverization. It has the advantage of less contamination by foreign matter.
  • jet mills include fluidized bed jet mills, collision plate jet mills, rotary mechanical mills, etc., and preferred are fluidized bed jet mills, particularly pneumatic jet mills.
  • the crushing pressure when using an air jet mill is, for example, 0.01 MPa or more, preferably 0.05 MPa or more, more preferably 0.1 MPa or more, and, for example, 3 MPa or less, preferably 1 MPa or less, more preferably 0. .7 MPa or less.
  • the crosslinked polymer particles according to an embodiment of the present disclosure have a very fine particle size, they are preferably pulverized in multiple stages. That is, it is first coarsely crushed (first crushing step) and then finely crushed (second and subsequent crushing steps).
  • multi-stage pulverization is performed using a combination of multiple types of pulverizers.
  • the combination of crushers varies depending on the particle size before crushing and the target particle size, but the first stage crusher is preferably a roll mill, a vibration mill, a hammer mill, or a pin mill.
  • a jet mill or a ball mill more preferably a jet mill, is preferably used in the final pulverization step.
  • the final stage of pulverization may be referred to as fine pulverization.
  • the temperature of the inner wall of the grinding chamber in each grinding step is preferably 30 to 150°C, more preferably 35 to 120°C, and particularly preferably 40 to 100°C. .
  • the relative humidity in the grinding chamber is preferably 70% RH or less, more preferably 50% RH or less, and even more preferably 30% RH or less.
  • the dew point of the gas is preferably 0°C or lower, more preferably -5 to -80°C, and particularly preferably -10 to -50°C.
  • Other operating conditions may be appropriately set in consideration of the particle size of the material to be crushed, the throughput, the size of the crusher, etc.
  • the equipment (classifier) used in the classification step is not particularly limited, and examples include a sieve classifier and an air classifier. Furthermore, a material having a crushing function, for example, a turbo screener (manufactured by Matsubo Co., Ltd.) can also be used, and in this case, the crushing process and the classification process are performed at the same time.
  • the classification step may be performed simultaneously with the pulverization step, before the pulverization step for the purpose of removing coarse particles that are difficult to crush, and/or after the pulverization step for the purpose of removing particles larger than the desired particle size of the crosslinked polymer of the present disclosure. It can be carried out. Furthermore, when the pulverization is performed in multiple stages, it can also be carried out between the pulverization steps. Large particles removed during the classification process are preferably ground again to reduce losses.
  • the thus obtained irregularly shaped crushed crosslinked polymer particles have the above-mentioned particle size.
  • the particle size can be appropriately adjusted not only in this step (pulverization step, classification step) but also in the polymerization step (particularly in the case of reverse phase suspension polymerization or droplet polymerization).
  • This step is performed for the purpose of improving the water absorption rate and liquid dispersibility of the crosslinked polymer particles after drying and pulverization.
  • This step is a step of further providing a portion with a high crosslink density on the surface layer of the dried crosslinked polymer particles, and includes, for example, a mixing step and a heat treatment step.
  • the surface crosslinking step radical crosslinking and/or monomer polymerization in the surface layer of the crosslinked polymer particles, crosslinking reaction between the surface layer of the crosslinked polymer particles and the surface crosslinking agent, etc. are performed, resulting in surface crosslinking. Polymer particles are obtained.
  • this step is also a step performed for the purpose of improving the handleability of the dried crosslinked polymer particles during pulverization, and the crosslinked polymer particles before being pulverized to the particle size of the final product, e.g. It may also be carried out on milled intermediates.
  • the surface crosslinked layer of this step does not need to remain on the surface of the crosslinked polymer particles of the final product.
  • (vi-1) Mixing step This step is a step in which a surface crosslinking agent is mixed with the dried and pulverized crosslinked polymer particles to obtain a humidified mixture.
  • the surface crosslinking agent is preferably added to the crosslinked polymer particles as an aqueous solution (surface crosslinking agent solution).
  • the amount of surface crosslinking agent solution used is preferably 0.1 parts by mass to 20 parts by mass, more preferably 0.3 parts by mass to 15 parts by mass, and even more preferably is appropriately set within the range of 0.5 parts by mass to 10 parts by mass. By controlling the amount of water used within this range, the handling of the surface crosslinking agent solution is improved, and the surface crosslinking agent can be evenly mixed with the crosslinked polymer particles.
  • (vi-2) Heat treatment step This step is a step in which the humidified mixture obtained in the mixing step is heat-treated to obtain surface-crosslinked crosslinked polymer particles.
  • the method of heating the humidified mixture is not particularly limited, and the humidified mixture may be heated in a stationary state, or may be heated using a mixing means such as stirring. From the viewpoint of uniformly heating the entire humidified mixture, it is preferable to heat the mixture with stirring.
  • the equipment used in this step includes a mortar mixer, paddle dryer, multi-fin processor, tower dryer, and the like.
  • the heating temperature in this step may be set depending on the type and amount of the surface crosslinking agent used, the absorption performance of the target crosslinked polymer particles, etc., and is not particularly limited, but the heating medium temperature is preferably 70°C. It may be set as appropriate within the range of ⁇ 250°C, more preferably 90°C ⁇ 210°C. Furthermore, the heating time is not particularly limited, but may be appropriately set within the range of 1 minute to 2 hours.
  • additives other than the above-mentioned additives may be added in order to add various functions to the crosslinked polymer particles.
  • Other additives include polyvalent metal salt compounds, ⁇ -hydroxycarboxylic acid compounds, surfactants, compounds with phosphorus atoms, oxidizing agents, organic reducing agents, water-insoluble inorganic particles, metal soaps, etc. organic powders, pulp and thermoplastic fibers, deodorants, antibacterial agents, bactericidal ingredients, fragrances, foaming agents, pigments, dyes, plasticizers, adhesives, fertilizers, salts, cationic polymers, polyethylene glycol and polyethylene imine, etc.
  • hydrophilic polymers examples include hydrophilic polymers, hydrophobic molecules such as paraffin, thermoplastic resins such as polyethylene and polypropylene, and thermosetting resins such as polyester resin and urea resin.
  • thermoplastic resins such as polyethylene and polypropylene
  • thermosetting resins such as polyester resin and urea resin.
  • surfactant the compound disclosed in International Publication No. 2005/075070 is preferably applied.
  • the amount of the additive to be used is not particularly limited as it is appropriately determined depending on the application, but it is preferably 3 parts by mass or less, more preferably 1 part by mass, based on 100 parts by mass of the crosslinked polymer particles. Parts by mass or less. Further, the additive can also be added to the crosslinked polymer particles in a step (another additive addition step) that is separate from the above step.
  • a humidification process in addition to the above-mentioned processes, a humidification process, a granulation process, a granulation process, a fine powder removal process, a fine powder reuse process, etc. may be provided as necessary. can. Moreover, it may further include one or more types of processes such as a transportation process, a storage process, a packaging process, and a storage process.
  • the "particle sizing step” includes a fine powder removal step after the surface crosslinking step and a step of classifying and pulverizing when the crosslinked polymer aggregates and exceeds a desired size.
  • the humidification step is a step of adding water to the crosslinked polymer particles to increase the water content, which may improve handling properties.
  • the water added may be liquid water or steam, or may be an aqueous solution or a fine particle dispersion.
  • the crosslinked polymer particles according to an embodiment of the present disclosure can be expected to have an excellent feel when used as a cosmetic or a quasi-drug. That is, in an embodiment of the present disclosure, a cosmetic or quasi-drug (sometimes simply referred to as a "cosmetic or quasi-drug") using the crosslinked polymer particles according to an embodiment of the present disclosure is provided. provide. Cosmetics or quasi-drugs using crosslinked polymer particles can also be said to be cosmetics or quasi-drugs containing crosslinked polymer particles.
  • the cosmetic or quasi-drug product it is preferable to use it as a skin cosmetic or a quasi-drug for the skin.
  • Cosmetics for the skin and quasi-drugs for the skin may be in any form such as liquid, gel, cream, semi-solid, solid, stick, or powder, and may include emulsions, creams, lotions, It can be used as skin cosmetics such as beauty serums, packs, face washes, and makeup cosmetics, and quasi-drugs for skin.
  • Cosmetics according to an embodiment of the present disclosure include skin cosmetics, external skin preparations, hair cosmetics, external hair preparations, and the like.
  • the content of crosslinked polymer particles in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is preferably 0.5 parts by mass or more from the viewpoint of obtaining a thickening effect, and 1.0 parts by mass. The above is more preferable, and 2.0 parts by mass or more is even more preferable.
  • the upper limit of the content of crosslinked polymer particles in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is not particularly limited, but is, for example, 20.0 parts by mass or less, 10.0 parts by mass or less, Alternatively, it may be 5.0 parts by mass or less.
  • the cosmetic or quasi-drug according to an embodiment of the present disclosure may contain compounds other than the crosslinked polymer particles according to an embodiment of the present disclosure.
  • compounds other than crosslinked polymer particles include thickeners, powder components, pH adjusters, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and oil agents. , humectants, water-soluble polymers, antioxidants, ultraviolet absorbers, chelating agents, preservatives, antibacterial agents, colorants, fragrances, and the like.
  • Thickeners include, for example, dextrin, sodium pectate, sodium alagate, PVM (methyl vinyl ether), locust bean gum, tamarind gum, dialkyldimethylammonium cellulose sulfate, magnesium aluminum silicate, bentonite. , hectorite, AlMg silicate (vegum), laponite, silicic anhydride, and the like.
  • the content of the thickener contained in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and 0.001 parts by mass or more, more preferably 0.005 parts by mass or more.
  • the amount is more preferably 0.05 parts by mass or more, preferably 3 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less.
  • the content of the thickener contained in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is preferably 0.001 parts by mass to 3 parts by mass, and preferably 0.005 parts by mass to 3 parts by mass. It is more preferably 1 part by weight, and even more preferably 0.05 part to 0.5 part by weight.
  • Examples of the powder component according to an embodiment of the present disclosure include inorganic powders (e.g., talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, rhodotite, biotite, permiculite, Magnesium carbonate, calcium carbonate, aluminum silicate, barium silicate, calcium silicate, magnesium silicate, strontium silicate, metal tungstate, magnesium, silica, zeolite, barium sulfate, calcined calcium sulfate (calcined gypsum), calcium phosphate, Fluorapatite, hydroxyapatite, ceramic powder, metal soap (e.g.
  • inorganic powders e.g., talc, kaolin, mica, sericite, muscovite, phlogopite, synthetic mica, rhodotite, biotite, permiculite
  • organic powder e.g. polyamide resin powder (nylon powder), polyethylene powder, polymethacrylic acid methyl powder, polystyrene powder, styrene and acrylic acid copolymer resin powder, benzoguanamine resin powder, polytetrafluoroethylene powder, cellulose powder, etc.
  • Inorganic white pigments e.g.
  • Inorganic red pigments e.g., iron oxide (red iron oxide), iron titanate, etc.
  • inorganic brown pigments e.g., ⁇ -iron oxide, etc.
  • inorganic yellow pigments e.g., yellow iron oxide, ocher, etc.
  • inorganic black pigments e.g., black iron oxide, lower titanium oxide, etc.
  • Inorganic purple pigments e.g., mango violet, cobalt violet, etc.
  • Inorganic green pigments e.g., chromium oxide, chromium hydroxide, cobalt titanate, etc.
  • Inorganic Blue pigments e.g. ultramarine, navy blue, etc.
  • Pearl pigments e.g.
  • Metals Powder pigments e.g. aluminum powder, copper powder, etc.
  • organic pigments such as zirconium, barium or aluminum lake
  • Examples of the pH adjuster according to an embodiment of the present disclosure include mixtures of hydroxycarboxylic acids and alkali metal salts thereof such as lactic acid-sodium lactate, citric acid-sodium citrate; dicarboxylic acids such as succinic acid-sodium succinate; Mixtures of acids and their alkali metal salts; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia (which may be aqueous ammonia), citric acid, tartaric acid, lactic acid, phosphoric acid, neutral amino acids (eg, threonine, cysteine, etc.), sodium acylsarcosine (sodium lauroylsarcosine), acylglutamate, sodium acyl- ⁇ -alanine, glutathione, pyrrolidone carboxylic acid, and the like.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, ammonia (which may be aqueous ammoni
  • a cosmetic or quasi-drug containing crosslinked polymer particles according to an embodiment of the present disclosure has excellent dispersibility of an inorganic white pigment, and preferably also excellent dispersibility of titanium dioxide.
  • Cosmetics or quasi-drugs containing crosslinked polymer particles according to an embodiment of the present disclosure contain an inorganic white pigment because they can provide formulations (especially sun care formulations) that are highly stable and have an excellent feel when used. It is preferable.
  • the mass ratio of crosslinked polymer particles to inorganic white pigment in the cosmetic or quasi-drug according to an embodiment of the present disclosure is 1/3 to 1/3. 30, 1/5 to 1/20, and 1/8 to 1/15.
  • the mass of the crosslinked polymer particles means the mass of the dried crosslinked polymer particles.
  • the dried crosslinked polymer particles are dried in a hot air dryer at a temperature of 150°C or more and 200°C or less for a certain period of time (for example, about 30 minutes or more and 90 minutes or less) as described in the examples. It can be obtained by drying the particles.
  • the content of the pH adjuster contained in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and 0.001 parts by mass or more.
  • the amount is more preferably 0.01 parts by mass or more, preferably 3 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less.
  • the content of the pH adjuster contained in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is preferably 0.001 parts by mass to 3 parts by mass, and preferably 0.005 parts by mass to 3 parts by mass. It is more preferably 1 part by mass, and even more preferably 0.01 part to 0.5 part by mass.
  • nonionic surfactant examples include POE sorbitan fatty acid esters (for example, POE sorbitan monooleate, POE sorbitan monostearate, POE sorbitan monooleate, POE sorbitan tetraoleate, etc.) ; POE sorbitol fatty acid esters (e.g., POE sorbitol monolaurate, POE sorbitol monooleate, POE sorbitolpentaoleate, POE sorbitol monostearate, etc.); POE glycerol fatty acid esters (e.g., POE glycerol monostearate, POE POE monooleate such as glycerin monoisostearate, POE glycerin triisostearate, etc.); POE fatty acid esters (for example, POE distearate, POE monodioleate, POE monostea
  • POE castor oil, POE hydrogenated castor oil, or derivatives thereof e.g. POE castor oil, POE hydrogenated castor oil, POE hydrogenated castor oil monoisostearate, POE hydrogenated castor oil) castor oil triisostearate, POE hydrogenated castor oil monopyroglutamic acid monoisostearate diester, POE hydrogenated castor oil maleic acid, etc.
  • POE beeswax or POE lanolin derivatives e.g. POE sorbit beeswax, etc.
  • alkanolamide e.g.
  • coconut oil fatty acid diethanolamide, lauric acid monoethanolamide, fatty acid isopropanolamide, etc.
  • POE propylene glycol fatty acid ester POE alkylamine; POE fatty acid amide; sucrose fatty acid ester; alkyl ethoxydimethylamine oxide; trioleyl phosphoric acid, sorbitan fatty acid esters (For example, sorbitan monooleate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan sesquioleate, sorbitan trioleate, diglycerol pent-2-ethylhexylate, sorbitan, tetra- diglycerol sorbitan 2-ethylhexylate, etc.); glycerin fatty acids (e.g., glycerin monocottonseed oil fatty acid, glycerin monoerucate, gly
  • POE is a polyethylene glycol residue (if two hydroxyl groups are bonded, it will be a polyoxyethylene unit. If one hydroxyl group is bonded, it will be a polyoxyethylene unit with a hydroxyl group at the end) ), and the above “POP” represents a polypropylene glycol residue (if two hydroxyl groups are bonded, it is a polyoxypropylene unit. If one hydroxyl group is bonded, it is a polyoxypropylene unit with a hydroxyl group at the end) ).
  • POE/POP means POE or POP.
  • anionic surfactant examples include fatty acid soaps (e.g., sodium laurate, sodium palmitate, etc.); higher alkyl sulfate salts (e.g., sodium lauryl sulfate, potassium lauryl sulfate, etc.) ; Alkyl ether sulfate salts (e.g., POE triethanolamine lauryl sulfate, POE sodium lauryl sulfate, etc.); N-acyl sarcosinate (e.g., sodium lauroyl sarcosine, etc.); Higher fatty acid amide sulfonates (e.g., N-myristoyl- N-methyl taurate sodium, coconut oil fatty acid methyl tauride sodium, lauryl methyl tauride sodium, etc.); phosphate ester salts (POE sodium oleyl ether phosphate, POE stearyl ether phosphate, etc.); s
  • alkylbenzene sulfonates e.g., sodium linear dodecylbenzenesulfonate, triethanolamine linear dodecylbenzenesulfonate) , linear dodecylbenzenesulfonic acid, etc.
  • Higher fatty acid ester sulfate ester salts e.g., hydrogenated coconut oil fatty acid sodium glycerol sulfate, etc.
  • N-acylglutamates e.g., monosodium N-lauroylglutamate, disodium N-stearoylglutamate, monosodium N-myristoyl-L-glutamate, etc.
  • sulfated oil e.g.
  • Examples of the cationic surfactant according to an embodiment of the present disclosure include alkyltrimethylammonium salts (e.g., stearyltrimethylammonium chloride, lauryltrimethylammonium chloride, etc.); alkylpyridinium salts (e.g., cetylpyridinium chloride, etc.); Distearyldimethyammonium dialkyldimethylammonium salt; poly(N,N'-dimethyl-3,5-methylenepiperidinium) chloride; alkyl quaternary ammonium salt; alkyldimethylbenzylammonium salt; alkylisoquinolinium salt; dialkyl moly Examples include honium salt; POE alkylamine; alkylamine salt; polyamine fatty acid derivative; amyl alcohol fatty acid derivative; benzalkonium chloride; benzethonium chloride; and the like.
  • alkyltrimethylammonium salts e.g., stearyl
  • amphoteric surfactant examples include imidazoline-based amphoteric surfactants (for example, 2-undecyl-N,N,N-(hydroxyethylcarboxymethyl)-2-imidazoline sodium, 2- cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.); betaine surfactants (for example, 2-heptadecyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine, lauryldimethylamino (betaine acetate, alkylbetaine, amidobetaine, sulfobetaine, etc.);
  • the content of surfactant (if multiple types of surfactants are included, the total amount thereof) contained in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is 0.0001 parts by mass.
  • the above is preferred, more preferably 0.0005 parts by mass or more, even more preferably 0.001 parts by mass or more, preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less.
  • the content of the surfactant contained in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is preferably 0.0001 parts by mass to 3 parts by mass, and preferably 0.0005 parts by mass to 3 parts by mass. It is more preferably 1 part by weight, and even more preferably 0.001 part to 0.5 part by weight.
  • oil agent examples include, but are not limited to, fatty acids, fats and oils, ester oils, silicone oils, hydrocarbon oils, etc. These components may be used alone. , two or more types can be used in appropriate combination.
  • fatty acids examples include lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid, undecylenic acid, lanolic acid, and isostearic acid.
  • Examples of the fats and oils according to an embodiment of the present disclosure include coconut oil, palm oil, hydrogenated palm oil, avocado oil, sesame oil, olive oil, kukui nut oil, grape particle oil, safflower oil, almond oil, corn oil, and cottonseed oil. , sunflower seed oil, grape seed oil, hazelnut oil, macadamia nut oil, meadowfoam oil, rosehip oil, and the like.
  • ester oil examples include ethyl oleate, isopropyl myristate, isopropyl palmitate, myristyl myristate, cetyl palmitate, oleyl oleate, octyldodecyl myristate, octyldodecyl oleate, and isostearin.
  • Examples include pentaerythritol acid, isocetyl octoate, isostearyl octoate, isocetyl isostearate, octyldodecyl isostearate, octyldodecyl dimethyloctanoate, and the like.
  • silicone oil examples include methylpolysiloxane, highly polymerized methylpolysiloxane, methylphenylpolysiloxane, octamethyltrisiloxane, decamethyltetrasiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.
  • examples include siloxane, dodecamethylcyclohexasiloxane, methylcyclopolysiloxane, alcohol-modified silicone, alkyl-modified silicone, amino-modified silicone, and epoxy-modified silicone.
  • hydrocarbon oil examples include liquid paraffin, olive squalane, rice squalane, squalane, pristane, white petrolatum, paraffin wax, ozokerite, ceresin, and microcrystalline wax.
  • humectant examples include glycerin, 1,3-butylene glycol, chondroitin sulfate, hyaluronic acid, mucoitin sulfate, caronic acid, atelocollagen, cholesteryl-12-hydroxystearate, sodium lactate, and bile.
  • examples include acid salts, dl-pyrrolidone carboxylic acid salts, short-chain soluble collagen, diglycerin (EO) PO adducts, Izayoirara extract, Yarrow extract, Melilot extract, and the like.
  • water-soluble polymers examples include plant-based polymers (e.g., gum arabic, gum tragacanth, galactan, guar gum, carob gum, gum karaya, carrageenan, pectin, agar, quince seed (quince), algae Colloids (cassow extract), starches (rice, corn, potato, wheat), glycyrrhizic acid); microbial polymers (e.g. xanthan gum, dextran, succinoglucan, bullulan, etc.); animal polymers (e.g.
  • collagen, casein, starch-based polymers e.g., carboxymethyl starch, methylhydroxypropyl starch, etc.
  • cellulose-based polymers methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxyethyl cellulose, sodium cellulose sulfate, hydroxypropyl cellulose, carboxy Methyl cellulose, sodium carboxymethyl cellulose, crystalline cellulose, cellulose powder, etc.
  • Alginate polymers e.g. sodium alginate, alginate propylene glycol ester, etc.
  • Vinyl polymers e.g.
  • polyvinyl alcohol polyvinyl methyl ether, polyvinyl pyrrolidone, carboxyvinyl) polymers (carbomer, etc.); polyoxyethylene polymers (e.g., polyethylene glycol 20,000, 40,000, 60,000, etc.); acrylic polymers (e.g., sodium polyacrylate, polyethyl acrylate, polyacrylamide) etc.); polyethyleneimine; cationic polymer; and the like.
  • the content of water-soluble polymer contained in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is preferably 0.001 parts by mass or more, more preferably 0.005 parts by mass or more, and 0.001 parts by mass or more, more preferably 0.005 parts by mass or more. It is more preferably .05 parts by mass or more, preferably 3 parts by mass or less, more preferably 1 part by mass or less, and even more preferably 0.5 parts by mass or less.
  • the content of water-soluble polymer contained in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is preferably 0.001 parts by mass to 3 parts by mass, and 0.005 parts by mass. It is more preferably 1 part by mass, and even more preferably 0.05 part by mass to 0.5 part by mass.
  • antioxidants examples include tocopherols, dibutylhydroxytoluene, butylhydroxyanisole, gallic acid esters, and the like.
  • UV absorber examples include benzoic acid-based ultraviolet absorbers (for example, para-aminobenzoic acid (hereinafter abbreviated as PABA), PABA monoglycerin ester, N,N-dipropoxy PABA ethyl ester, N,N-diethoxy PABA ethyl ester, N,N-dimethyl PABA ethyl ester, N,N-dimethyl PABA butyl ester, N,N-dimethyl PABA ethyl ester, etc.); anthranilic acid-based UV absorbers (e.g., homomenthyl-N -acetylanthranilate, etc.); salicylic acid-based UV absorbers (e.g., amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate, benzyl salicylate, p-isoprop
  • PABA para-amino
  • Examples of the chelating agent according to an embodiment of the present disclosure include 1-hydroxyethane-1,1-diphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid tetrasodium salt, edetate disodium, and edetate trisodium salt.
  • Examples include sodium, tetrasodium edetate, sodium citrate, sodium polyphosphate, sodium metaphosphate, gluconic acid, phosphoric acid, citric acid, ascorbic acid, succinic acid, edetate, trisodium ethylenediamine hydroxyethyl triacetate, and the like.
  • Examples of the preservative and antibacterial agent according to an embodiment of the present disclosure include parabens such as ethylparaben, isopropylparaben, butylparaben, and benzylparaben, and their sodium salts, benzoic acid, benzoates, and hydrochloric acid.
  • parabens such as ethylparaben, isopropylparaben, butylparaben, and benzylparaben, and their sodium salts, benzoic acid, benzoates, and hydrochloric acid.
  • the content of the preservative and/or antibacterial agent contained in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is preferably 0.001 part by mass or more, more preferably 0.01 part by mass or more. It is preferably 0.05 parts by mass or more, more preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less.
  • the content of the preservative and/or antibacterial agent contained in 100 parts by mass of the cosmetic or quasi-drug according to an embodiment of the present disclosure is preferably 0.001 parts by mass to 5 parts by mass, and 0.001 parts by mass to 5 parts by mass. The amount is more preferably from 0.001 parts by weight to 3 parts by weight, and even more preferably from 0.05 parts by weight to 1 part by weight.
  • the fragrance according to an embodiment of the present disclosure includes, for example, terpenes/terpenoids such as citral, menthol, camphor, salvinorin A, cannabinoids, hinokitiol, limonene, farnesol, and vitamin A; aromatic alcohols such as phenoxyethanol, eugenol, and gingerol. esters such as butyrate and propionate; lactones such as ⁇ -nonalactone and ⁇ -undecalactone; and aldehydes having 6 to 20 carbon atoms.
  • terpenes/terpenoids such as citral, menthol, camphor, salvinorin A, cannabinoids, hinokitiol, limonene, farnesol, and vitamin A
  • aromatic alcohols such as phenoxyethanol, eugenol, and gingerol. esters such as butyrate and propionate
  • lactones such as ⁇ -nonalactone and ⁇ -undecalact
  • One embodiment of the present disclosure may include the following aspects.
  • Crosslinked polymer particles for cosmetics or quasi-drugs wherein the crosslinked polymer particles have a content of structural units derived from (meth)acrylic acid (salt) per 100 parts by mass of the crosslinked polymer. is 20 parts by mass or more and 100 parts by mass or less, the volume average particle diameter D50 of the crosslinked polymer particles is 8 ⁇ m or more and 20 ⁇ m or less, and the half width of the volume average particle diameter is 3 ⁇ m or more and less than 20 ⁇ m, for cosmetics or medicine.
  • Crosslinked polymer particles for external products wherein the crosslinked polymer particles have a content of structural units derived from (meth)acrylic acid (salt) per 100 parts by mass of the crosslinked polymer. is 20 parts by mass or more and 100 parts by mass or less, the volume average particle diameter D50 of the crosslinked polymer particles is 8 ⁇ m or more and 20 ⁇ m or less, and the half width of the volume average particle diameter is 3 ⁇ m or more and less than 20 ⁇ m, for cosmetics or medicine
  • a method for producing crosslinked polymer particles for cosmetics or quasi-drugs wherein the crosslinked polymer contains 20 parts by mass or more of (meth)acrylic acid (salt) per 100 parts by mass of total monomers. 100 mass or less, the volume average particle diameter of the crosslinked polymer is 8 ⁇ m or more and 20 ⁇ m or less, and the half width of the volume average particle diameter is 3 ⁇ m or more and less than 20 ⁇ m.
  • Method for producing coalesced particles is
  • a reaction solution was prepared by dissolving 4.79 g of polyethylene glycol diacrylate (average number of added moles of ethylene oxide: 9) as an internal crosslinking agent in 5,500 g of a 33% by weight aqueous solution of sodium acrylate with a neutralization rate of 75 mol%. Next, this reaction solution was degassed for 30 minutes under a nitrogen gas atmosphere (dissolved oxygen in the reaction solution was expelled by blowing nitrogen gas into this reaction solution for 30 minutes).
  • the above reaction liquid was supplied to a reactor formed by attaching a lid to a jacketed stainless steel double-arm kneader having an internal volume of 10 L and having two sigma type blades, and the system was heated while keeping the reaction liquid at 25°C. Replaced with nitrogen gas. Subsequently, while stirring the reaction solution, 2.4 g of ammonium persulfate and 0.12 g of L-ascorbic acid were added as polymerization initiators, and polymerization started approximately 1 minute later. Then, polymerization was carried out at 25 to 90°C, and 40 minutes after the start of polymerization, the reaction was completed and the hydrogel crosslinked polymer was taken out.
  • hydrogel crosslinked polymer was subdivided into pieces having a diameter of about 5 mm.
  • This finely divided hydrogel-like crosslinked polymer (particulate hydrogel) was spread on a 50-mesh (opening size: 300 ⁇ m) wire gauze and dried with hot air at 170° C. for 70 minutes to obtain a dry polymer.
  • the obtained dried polymer was pulverized using a vibration mill, and then classified using a JIS standard sieve with an opening of 850 ⁇ m to obtain a sieve-passed material. Through this series of operations, a pulverized intermediate (1) was obtained.
  • a reaction solution was prepared by dissolving 7.5 g of polyethylene glycol diacrylate (average number of added moles of ethylene oxide: 9) in 5500 g of an aqueous solution of sodium acrylate (monomer concentration 38% by mass) having a neutralization rate of 75 mol%.
  • the reaction solution was supplied to a reactor formed by attaching a lid to a jacketed stainless steel double-arm kneader having an internal volume of 10 L and having two sigma-type blades, and the system was flushed with nitrogen while keeping the reaction solution at 30°C. Dissolved oxygen was removed by gas replacement.
  • This finely divided hydrogel crosslinked polymer (particulate hydrogel) was spread on a 50 mesh wire mesh (opening size 300 ⁇ m) and dried with hot air at 160° C. for 60 minutes to obtain a dry polymer.
  • the obtained dried polymer was pulverized using a roll mill, and further classified using a JIS standard sieve with an opening of 450 ⁇ m. Particles of 450 ⁇ m or more were ground again using a roll mill, classified using a JIS standard sieve with an opening of 450 ⁇ m, and the materials passing through the two sieves were combined. Through this series of operations, a pulverized intermediate (3) was obtained.
  • a surface crosslinking agent consisting of 100 parts by mass of the pulverized intermediate (3) obtained in Production Example 3, 0.1 part by mass of ethylene glycol diglycidyl ether, 0.3 parts by mass of propylene glycol, and 0.3 parts by mass of water. 0.7 parts by mass of an aqueous solution was mixed. The above mixture was heat-treated for 20 minutes in a mortar mixer heated to 210°C to obtain a surface-crosslinked pulverized intermediate (3).
  • the temperature of the monomer aqueous solution (a') rose to 62.9° C. due to the heat of neutralization in the first stage immediately after preparation.
  • the monomer aqueous solution (a') was cooled while stirring.
  • 211.9 g of a 48.5% by weight aqueous sodium hydroxide solution adjusted to 40°C is added to the monomer aqueous solution (a') and mixed to form a monomer.
  • An aqueous solution (a) was prepared.
  • the temperature of the monomer aqueous solution (a) rose to 81.7° C. due to the heat of neutralization in the second stage immediately after preparation.
  • the time from the start of the second stage neutralization until the monomer aqueous solution (a) is poured into the vat-shaped container is 55 seconds, and the vat-shaped container is equipped with a hot plate (NEOHOT PLATE HI-1000/Iuchi Seieido Co., Ltd.). was heated until the surface temperature reached 40°C.
  • the polymerization reaction started 60 seconds after the monomer aqueous solution (a) was poured into the vat-shaped container.
  • the polymerization reaction progressed by expanding and foaming in all directions while generating steam, and then the container contracted to a size slightly larger than the vat-shaped container.
  • hydrogel three minutes after the start of the polymerization reaction, the hydrogel crosslinked polymer (hereinafter referred to as "hydrogel") was taken out. Note that these series of operations were performed in a system open to the atmosphere. Moreover, the peak temperature during polymerization was 108°C.
  • the hydrous gel obtained in the polymerization reaction was crushed into particulate hydrogel using a meat chopper (HL-3225N, plate pore size: 8.0 mm/Remacom Co., Ltd.).
  • the input amount of the hydrogel was 230 g/min, and gel crushing was performed while adding deionized water whose temperature was controlled to 90°C at a rate of 50 g/min in parallel with the input of the hydrogel.
  • the resulting particulate water-containing gel was spread and placed on a stainless wire mesh with an opening of 850 ⁇ m, and dried by blowing hot air at 180° C. for 30 minutes to obtain a dry polymer.
  • the dried polymer obtained in the drying operation was pulverized using a roll mill (WL type roll pulverizer/Inoguchi Giken Co., Ltd.), classified using a JIS standard sieve with an opening of 710 ⁇ m, and passed through the sieve. I got something. Through this series of operations, a pulverized intermediate (5) was obtained.
  • the obtained surface-crosslinked pulverized intermediate (5) was crushed until it passed through a JIS standard sieve with an opening of 850 ⁇ m to obtain a pulverized intermediate (6).
  • a reaction solution was prepared by dissolving 2.83 g of trimethylolpropane triacrylate as an internal crosslinking agent in 5,500 g of a 33% by weight aqueous solution of sodium acrylate with a neutralization rate of 75 mol%. Next, this reaction solution was degassed for 30 minutes under a nitrogen gas atmosphere (dissolved oxygen in the reaction solution was expelled by blowing nitrogen gas into this reaction solution for 30 minutes). Next, the above reaction liquid was supplied to a reactor formed by attaching a lid to a jacketed stainless steel double-arm kneader having an internal volume of 10 L and having two sigma type blades, and the system was heated while keeping the reaction liquid at 25°C. Replaced with nitrogen gas.
  • hydrogel crosslinked polymer was subdivided into pieces with a diameter of about 5 mm.
  • This finely divided hydrogel-like crosslinked polymer (particulate hydrogel) was spread on a 50-mesh (opening size: 300 ⁇ m) wire gauze and dried with hot air at 170° C. for 70 minutes to obtain a dry polymer.
  • the obtained dried polymer was pulverized using a vibration mill, and then classified using a JIS standard sieve with an opening of 850 ⁇ m to obtain a sieve-passed material. Through this series of operations, a pulverized intermediate (7) was obtained.
  • Comparative production example 1 Crosslinked polymer particles were obtained by a reverse phase suspension polymerization method with reference to Production Examples 2 to 7 of JP 2015-151336A, and comparative crosslinked polymer particles 1 were produced without going through a pulverization step.
  • the volume average particle diameter of the obtained comparative crosslinked polymer particles 1 was 26.51 ⁇ m, and the half width was 21.18 ⁇ m.
  • Comparative production example 2 Crosslinked polymer particles were obtained by a reverse phase suspension polymerization method with reference to Examples 1 to 11 of Japanese Patent No. 3023110, and Comparative Crosslinked Polymer Particles 2 were produced without going through a pulverization step.
  • the volume average particle diameter of the obtained comparative crosslinked polymer particles 2 was 7.59 ⁇ m, and the half width was 2.51 ⁇ m.
  • Turbidity and viscosity measurements and sensory evaluations were performed by adjusting the pH of a 1% mass aqueous solution of Comparative Crosslinked Polymer Particles 2 prepared to 5 to 8 with a 10% NaOH aqueous solution.
  • Measurement method of volume average particle diameter and half width Measurement was performed using a laser diffraction scattering particle size distribution analyzer LA-950 manufactured by HORIBA. Ethyl acetate was used as the circulating solvent during the measurement, and the refractive index of the dispersion was 1.59, and the refractive index of the dispersion medium was 1.371. The median diameter ( ⁇ m) was calculated from the volume-based particle size distribution obtained by the measurement, and was defined as the volume average particle diameter D50.
  • the half-width was calculated based on the particle size distribution graph obtained from the volume average particle diameter measurement. Specifically, the half-value of the frequency was calculated from the value of the maximum frequency, the particle diameter at the half-value was calculated from the approximate curve equation of the region including the half-value, and the difference between the particle diameters at two points was taken as the half-value width.
  • Measurement was performed using a haze meter NDH7000 manufactured by Nippon Denshokusha. A 1% aqueous solution of crosslinked polymer particles was prepared, filled in a quartz cell with an optical path length of 10 mm, and measured at a measurement temperature of 25° C. using a haze meter NDH7000 manufactured by Nippon Denshoku Co., Ltd.
  • the method of sensory evaluation is as follows. A 1% by mass aqueous solution of each of the obtained crosslinked polymer particles was prepared and subjected to sensory evaluation when applied to the inner side of the forearm by a specialized panel. Scoring on a 5-point scale (5: very good, 4: good, 3: average, 2: bad, 1: very bad) for spreadability during application, skin adhesion, freshness, sliminess, stickiness when drying, and squeakiness. The average value (rounded up) was used as the overall evaluation.
  • crosslinked polymer particles 1 to 8 which have a volume average particle diameter of 8 ⁇ m or more and 20 ⁇ m or less and a half width of 3 ⁇ m or more and less than 20 ⁇ m, were used in the sensory evaluation when applied to the skin. It was found that the texture was excellent. In particular, it was found to be excellent in that there is no slimy feeling when applied, no stickiness when drying, and no squeaky feeling.
  • Comparative Crosslinked Polymer Particles 1 which was used as a comparative product and has a volume average particle diameter of more than 20 ⁇ m and a half-width of 20 ⁇ m or more, sensory evaluation showed that it did not blend well with the skin when applied to the skin, and that it felt slimy and sticky when dry. It was found that the feel of the product was not excellent in that it felt squeaky. Furthermore, Comparative Crosslinked Polymer Particles 2, which has a volume average particle diameter of less than 8 ⁇ m and a half width of less than 3 ⁇ m, does not have an excellent feel in use in terms of feeling slimy when applied to the skin and sticky when dry, according to sensory evaluation. I understand.
  • Tables 7 and 8 show the results of appearance evaluation and sensory evaluation of sun care formulations 1 to 10 prepared with the formulations shown in Tables 5 and 6.
  • sun care preparations 1 to 8 containing crosslinked polymer particles 1 to 8 having a volume average particle diameter of 8 ⁇ m or more and 20 ⁇ m or less and a half width of 3 ⁇ m or more and less than 20 ⁇ m. It was revealed that the product has excellent dispersibility of titanium dioxide, has a unique appearance similar to whipped cream, and has a smooth feeling when applied.
  • sun care formulation 9 which was used as a comparative product and contained comparative crosslinked polymer particles 1 with a volume average particle diameter of more than 20 ⁇ m and a half width of 20 ⁇ m or more, a gel-like dispersion was obtained, but when applied, There was a tendency for the sliminess to become stronger.
  • sun care formulation 10 containing Comparative Crosslinked Polymer Particles 2 with a volume average particle diameter of less than 8 ⁇ m and a half-width of less than 3 ⁇ m yields a gel-like dispersion, but it is clear that it has a strong squeaky feeling when applied. Became.
  • each crosslinked polymer particle formulation and the comparative crosslinked polymer particle 2 formulation maintained the same viscosity at the start of measurement, which clearly indicates that the UV light resistance is improved by the effect of the chelating agent. became.
  • Comparative Crosslinked Polymer Particle 1 formulation the thickening property was lost due to the addition of 0.1% of EDTA/2Na, which is a chelating agent.
  • each crosslinked polymer particle formulation and the comparative crosslinked polymer particle 1 formulation showed a decrease in viscosity over time.
  • Comparative Crosslinked Polymer Particle 2 formulation showed high stability as the viscosity was maintained before and after initiation.
  • each crosslinked polymer particle formulation and the comparative crosslinked polymer particle 2 formulation maintained the viscosity at the start of the measurement, indicating that the light resistance under fluorescent lighting was improved due to the effect of the chelating agent. It became clear that On the other hand, in Comparative Crosslinked Polymer Particle 1 formulation, the thickening property was lost due to the addition of 0.1% of EDTA/2Na as a chelating agent.
  • each component listed in Table 12 was mixed uniformly in each section to obtain a mixture (Parts A to C).
  • Part A and Part C were dissolved at 80°C.
  • Part B was gradually added to part A and mixed while stirring, then part C was added and stirred to make the mixture uniform, and then cooled to obtain a beauty serum.
  • This serum had a high moisturizing effect, softened the skin, kept the skin fresh, smooth, and moisturized, and lasted for a long time.
  • Preparation method Components 1 to 10 in Table 15 were added and heated to about 80° C. to dissolve them (Part A). Components 11 to 15 were placed in a separate container and heated to about 80°C to uniformly dissolve them (Part B). Part B was added to part A, emulsified using a homomixer, and then cooled to 40°C to obtain an emollient cream. This emollient cream was excellent in the effect of imparting a moist feeling.
  • Anti-aging cream Using the obtained crosslinked polymer particles 8, an anti-aging cream having the formulation shown in Table 16 below was prepared.
  • Preparation method Components 1 to 6 in Table 24 were heated to about 80° C. and uniformly dissolved (Part A). Next, components 7 to 11 were heated to about 80° C. to uniformly dissolve them (Part B). A treatment was obtained by adding part B to part A, stirring and mixing uniformly, and then cooling to room temperature. This treatment was able to impart a moist and soft feel to the hair.
  • Preparation method 1 liquid
  • Most of component 15 in Table 26 was heated to about 80°C (Part A).
  • Ingredients 1 to 8 in a separate container was added and heated to dissolve (Part B).
  • Part C the remainder of component 15 and components 9 to 13 were added to another container and uniformly dissolved
  • Part B was added to part A, mixed and stirred, and at about 45°C, part C was added and mixed uniformly.
  • component 14 was further added to obtain one liquid of straight perm agent.
  • hair bleaching agent (2-drug formula) Using the obtained crosslinked polymer particles 3, hair bleaching agents (two-component type) having the formulations shown in Tables 28 and 29 below were prepared.
  • a hair bleaching agent was obtained by uniformly stirring and mixing each component listed in Table 28.
  • a hair bleaching agent was obtained by blending the first agent and the second agent obtained in the following blending ratio.
  • This hair bleaching agent (two-component formula) is a bleaching agent that, when applied to the hair, can reduce the feeling of damage to the hair after bleaching, and give the hair a good feel such as flexibility, moisture, and smoothness. there were.
  • oxidative hair dye [Oxidative hair dye] Using the obtained crosslinked polymer particles 4, oxidative hair dyes (two-component type) having the formulations shown in Tables 30 and 31 below were prepared.
  • This oxidative hair dye (two-component formula) is an oxidative hair dye that can be applied to hair to reduce the feeling of damage to the hair after dyeing, and to give the hair a good feel such as flexibility, moisture, and smoothness. It was hair dye.
  • a hair growth agent was obtained by uniformly stirring and mixing each component listed in Table 37. This hair growth agent was able to prevent hair loss, dandruff, and itchiness.
  • perm agent Using the obtained crosslinked polymer particles 2, perm agents having the formulations shown in Tables 38 and 39 below were prepared.
  • This perm agent was a perm agent that gave the hair a smooth and soft feel when applied to the hair.
  • a cleansing oil was obtained by heating, dissolving, and mixing all the components listed in Table 41. This cleansing oil was transparent, viscous, did not drip during use, had a refreshing feel, blended well with foundation, makeup, etc., and could quickly remove them.
  • Part A Component 1 and some component 11 in Table 43 were heated at about 80° C. and mixed uniformly
  • Part B Components 2 to 10 and the remainder of component 11 were heated at about 80° C. and mixed uniformly
  • a body soap was obtained by gradually adding part A to part B and mixing uniformly while stirring.
  • a formulation in which only component 8 was removed was used as a blank.
  • Ten panelists evaluated the feel of the skin after using the body shampoo. The results were superior to the blank in both evaluation items of slippery feeling and moist feeling.
  • soaps having the formulations shown in Table 44 below were prepared.
  • a soap was obtained by heating and dissolving all the components listed in Table 44 at 80°C, cooling while stirring, pouring into a mold and leaving to stand.
  • an unblended soap was prepared using a formulation in which only component 1 was removed. Soaps containing component 1 (cross-linked polymer particles 7) can give the skin a moisturizing and smooth feeling compared to soaps that do not contain component 1 (crosslinked polymer particles 7), and are also excellent as fat-adding agents. Recognize.

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WO2016039357A1 (ja) * 2014-09-11 2016-03-17 積水化成品工業株式会社 高復元性樹脂粒子及びその用途
JP2016518427A (ja) * 2013-05-16 2016-06-23 ディーエスエム アイピー アセッツ ビー．ブイ． 局所組成物
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JP2015155519A (ja) 2014-01-16 2015-08-27 住友精化株式会社 増粘組成物
JP6548866B2 (ja) 2014-02-10 2019-07-24 住友精化株式会社 弱酸性化粧料用増粘剤、及び当該増粘剤を配合してなる弱酸性化粧料
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JP2016518427A (ja) * 2013-05-16 2016-06-23 ディーエスエム アイピー アセッツ ビー．ブイ． 局所組成物
JP2016518431A (ja) * 2013-05-16 2016-06-23 ディーエスエム アイピー アセッツ ビー．ブイ． シリコーンオイルおよびポリメチルメタクリレート粒子を含む化粧料組成物
WO2016039357A1 (ja) * 2014-09-11 2016-03-17 積水化成品工業株式会社 高復元性樹脂粒子及びその用途
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WO2025216310A1 (ja) * 2024-04-11 2025-10-16 株式会社日本触媒 （メタ）アクリル酸の製造方法

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