Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
• • 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
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/891—Polysiloxanes saturated, e.g. dimethicone, phenyl trimethicone, C24-C28 methicone or stearyl dimethicone
• • 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
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/895—Polysiloxanes containing silicon bound to unsaturated aliphatic groups, e.g. vinyl dimethicone
• • 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
  • A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
  • A61K8/89—Polysiloxanes
  • A61K8/896—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate
  • A61K8/898—Polysiloxanes containing atoms other than silicon, carbon, oxygen and hydrogen, e.g. dimethicone copolyol phosphate containing nitrogen, e.g. amodimethicone, trimethyl silyl amodimethicone or dimethicone propyl PG-betaine
• • 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
  • A61K8/91—Graft copolymers
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q19/00—Preparations for care of the skin
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/045—Polysiloxanes containing less than 25 silicon atoms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
  • C08G77/18—Polysiloxanes containing silicon bound to oxygen-containing groups to alkoxy or aryloxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
  • C08G77/26—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/38—Polysiloxanes modified by chemical after-treatment
  • C08G77/382—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon
  • C08G77/388—Polysiloxanes modified by chemical after-treatment containing atoms other than carbon, hydrogen, oxygen or silicon containing nitrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
  • A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
  • A61K2800/56—Compounds, absorbed onto or entrapped into a solid carrier, e.g. encapsulated perfumes, inclusion compounds, sustained release forms
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
  • C08G77/04—Polysiloxanes
  • C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups

Definitions

• the present disclosure relates to cosmetics containing a siloxane bond-containing polymer compound having a host group and / or a guest group.
• a film is formed by using a crosslinked polymer compound.
• a film-forming agent containing a crosslinked silicone resin is widely used as various coating agents and cosmetics.
• Patent Document 1 discloses a cosmetic containing trimethylsiloxysilicic acid or the like as a film-forming agent.
• a host body composed of a polymer compound having a host group and a guest body composed of a polymer compound having a guest group, or a host-guest body composed of a polymer compound having a host group and a guest group is the host group and the guest body. It is known that a bond can be reversibly formed by a combination of guest groups (Patent Document 2).
• Patent Document 3 discloses a method for producing an aqueous solvent solution of a host group-containing monomer, a guest group-containing monomer, and an acrylic monomer.
• Conventional cosmetics containing crosslinked polymer compounds may have insufficient usability. Specifically, conventional cosmetics containing a crosslinked polymer compound may have an undesired feeling of use in terms of adhesion, elasticity, and / or tension after application to the skin or the like. ..
• the purpose of this disclosure is to provide a cosmetic having an excellent feeling of use.
• the inventors of the present invention have made extensive studies in order to solve such a problem, and have invented the present application.
• the invention according to the present disclosure includes the following aspects: ⁇ Aspect 1> A host body composed of a polymer compound having a host group and a guest body composed of a polymer compound having a guest group, or a host-guest body composed of a polymer compound having a host group and a guest group, and containing the host body and a guest body.
• Cosmetics in which at least one of the polymer compound having a host group and the polymer compound having a guest group, or the polymer compound having the host group and the guest group contains a siloxane bond.
• the cosmetic according to aspect 1, wherein the polymer compound having a host group and the polymer compound having a guest group contain a siloxane bond.
• ⁇ Aspect 6> The polymer compound having a host group has a host group in the side chain, and the polymer compound having a guest group has a guest group at the terminal.
• ⁇ Aspect 7> The polymer compound having a host group has a host group at the terminal, and the polymer compound having a guest group has a guest group in the side chain.
• ⁇ Aspect 8> At least one of the polymer compound having a host group and the polymer compound having a guest group, or the polymer compound having the host group and the guest group is crosslinked.
• At least one of the polymer compound having a host group and the polymer compound having a guest group, or the polymer compound having the host group and the guest group has a structure represented by the following formula (1).
• R R1, R R2, and R R3 are each a carbon number of 1 to 10 alkyl or alkylene Groups;
• X 1 and X 2 are independently O, Si (OH) 2 , Si (R 10 ) 2 , N (H), or N (COCH 3 ), or urethane bonds, urea.
• R 10 is a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a cycloalkoxy group, a hydroxy group.
• R 10s may be the same or different, respectively. If there are a plurality of X 1 and X 2 , they may be the same or different; p and q each independently represent an integer greater than or equal to 0; RY is a host group; R Z. Is a guest group; h, i, j, and k each represent an integer greater than or equal to 0, which may be the same or different from each other; at least j or k is an integer greater than or equal to 1. ; N represents an integer greater than or equal to 1. ].
• ⁇ Aspect 10> The cosmetic according to aspect 9, wherein the polymer compound having a host group and the polymer compound having a guest group have a structure represented by the formula (1).
• the cosmetic according to aspect 9 or 10 which has the above-mentioned structure.
• At least one of the polymer compound having a host group and the polymer compound having a guest group, or the polymer compound having the host group and the guest group is It has a vinyl main chain, an acrylic main chain, a urethane main chain, an epoxy main chain, a polyimide main chain, a polyester main chain, a polyurea main chain, or a polycarbonate main chain, and The side chain has a structure represented by the above formula (1).
• ⁇ Aspect 13> At least one of the polymer compound having a host group and the polymer compound having a guest group, or the polymer compound having the host group and the guest group is a structural unit represented by the following formula (2).
• R 1 to R 6 are independently hydrogen atoms, or an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a cycloalkoxy group, a hydroxy group, a carboxy group, and an aldehyde group.
• R R1, R R2, and R R3 are each a carbon number of 1 to 10 alkyl or alkylene
• X 1 and X 2 are independently O, Si (OH) 2 , Si (R 10 ) 2 , NH, or N (COCH 3 ), or are urethane or urea bonds, respectively.
• R 10 is a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a cycloalkoxy group, a hydroxy group, a carboxy group.
• An aldehyde group, an aryl group, an aryloxy group, or a heterocyclic group, and these groups may have a substituent; a plurality of R 10s may be the same or different, respectively; X 1 And X 2 may be the same or different if there are more than one; p and q each independently represent an integer greater than or equal to 0; RY is the host group; R Z is the guest group. There; h, i, j, and k each represent an integer greater than or equal to 0, which may be the same or different from each other, where at least j or k is an integer greater than or equal to 1.
• R m1 to R m3 are independently hydrogen atoms or alkyl groups
• Y 1 is an ether bond, an amide bond, or an ester bond
• R m4 is.
• Y 2 is an ether bond, an amide bond, or an ester bond.
• R m5 ⁇ R m7 are each independently a hydrogen atom or an alkyl group
• Y 3 is an ether bond, amide bond, or ester bond
• R m8 is alkylene group, a cycloalkylene group, an alkenylene group, alkoxylene group, or an arylene group, which may have a substituent group
• Y 4 is a hydrogen atom, an alkyl group, a hydroxyl group, Si (OH ) 3 , Si (R 10 ) 3 , NH 2 , C (O) CH 3 , C (O) NH 2 , or N (COCH 3 ), where d and e are independently integers from 0 to 3.
• R 11 is an alkylene group having 1 to 12 carbon atoms which may have a substituent, and k is an integer of 1 or more.
• It consists of a chain alkyl group, (4) a linear alkyl group having 4 to 18 carbon atoms having an amino group, (5) a cyclic alkyl group, (6) a phenyl group, (7) an azobenzene group, and (8) a cinnamic acid group.
• the host group is ⁇ -cyclodextrin and The guest group is a (1') t-butyl group, a (2') adamantyl group, a (3') aryl group, an aryl group having a (4') hydroxyl group, an aryl group having a (5') carboxyl group, ( At least one selected from the group consisting of an aryl group having a 6') amino group, a (7') ferrosenyl group, an (8') azobenzene group, and a (9') dansyl group;
• the host group is ⁇ -cyclodextrin and The guest group is an alkyl group having a (1 ′′) up to 18 carbon atoms, an alkyl group having a (2 ′′) hydroxyl group up to 18 carbon atoms, and an alkyl group having a (3 ′′) carboxyl group up to 18 carbon atoms.
• cosmetics having an excellent usability are provided.
• the cosmetics according to this disclosure are A host body composed of a polymer compound having a host group and a guest body composed of a polymer compound having a guest group, or a host-guest body composed of a polymer compound having a host group and a guest group, and containing the host body and a guest body. At least one of the polymer compound having a host group and the polymer compound having a guest group, or the polymer compound having a host group and a guest group contains a siloxane bond.
• cosmetics containing a polymer compound having a host group and / or a guest group have an excellent usability as compared with conventional cosmetics. I found it. Specifically, it has been found that a cosmetic containing a siloxane bond-containing polymer compound having a host group and / or a guest group has excellent properties in terms of adhesion, elasticity, and tension. Further, the cosmetics according to the present disclosure are also excellent in long-lasting makeup.
• the cosmetics according to the present disclosure contain a polymer compound having a host group and / or a guest group, and therefore, when applied to the skin or the like, a host-guest interaction. It is considered that the polymer compounds are bonded to each other via the above to form a film (decorative coating film). Therefore, it is considered that the cosmetics according to the present disclosure exhibit excellent properties in terms of elasticity.
• the cosmetic coating film formed by the cosmetics according to the present disclosure is high due to the covalent bond. It is considered that the elasticity is relatively high (the Young's modulus is small) as compared with the decorative coating film formed by bonding the molecules, and as a result, excellent properties are exhibited in terms of adhesion and tension.
• the cosmetics according to the present disclosure use a polymer compound having a siloxane bond, it is possible to provide a chemically stable cosmetic.
• cosmetics containing a polymer compound having a siloxane bond are relatively highly soluble in non-polar solvents such as hydrocarbon oil and silicone oil.
• non-polar solvents such as hydrocarbon oil and silicone oil.
• Conventional polymer compounds having a host group and / or a guest group may have insufficient solubility in a solvent.
• the polymer compound contained in the cosmetics according to the present disclosure has a siloxane bond, thereby improving the solubility.
• the solubility in a volatile non-polar solvent is relatively high, it becomes easy to apply the cosmetic to the skin or the like by applying the cosmetic, and it is possible to form a uniform and thin film relatively easily. become.
• the cosmetics according to the present disclosure include, in particular, sunscreen emulsions and ultraviolet protective cosmetics such as sunscreen creams; makeup bases (base makeup), foundations, concealers, lipsticks, eye shadows, mascara, eyeliners. , Eyebrow, overcoating agent, and make-up cosmetics such as lipstick can be suitably used.
• Host-guest interaction refers to the bond formed between a host group and a guest group.
• the host group is attached to the guest group by including the guest group.
• the size of the guest group is suitable for being incorporated into the internal space of the host group, and the host group and the guest group are of among hydrophobic interaction, hydrogen bond, electrostatic interaction, and coordination bond.
• a host-guest interaction occurs when there is an interaction involving at least one of the above.
• host group examples include cyclodextrin (CD). Specific examples thereof include ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin. When these groups are used as host groups, stable host-guest interactions can be formed.
• the guest group is not particularly limited as long as it can be a guest group with respect to the corresponding host group.
• the guest group include an alkyl group which may have a substituent and an aryl group which may have a substituent.
• the alkyl group which may have a substituent as a guest group and the aryl group which may have a substituent have 1 to 18, preferably 3 to 12, and more preferably 3 to 9 carbon atoms.
• examples of the guest group include a trialkylsilyl group (for example, a trimethylsilyl group, a triethylsilyl group, and a tripropylsilyl group, particularly a trimethylsilyl group).
• alkyl group which may have a substituent examples include linear, branched or cyclic C1-18 alkyl groups. Specifically, alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl, dodecyl, octadecyl, and adamantyl. Can be mentioned.
• an adamantyl group or a butyl group is preferable, and an adamantyl group is particularly preferable.
• This alkyl group may have, for example, 1 to 3 substituents such as a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group, an amide group, and a hydroxyl group which may be protected. good. It may be an alkyl group to which ferrocene, which is an organometallic complex, is bonded as a substituent.
• examples of the aryl group which may have a substituent include a single ring or an aryl group having two or more rings, and specific examples thereof include phenyl, toluyl, xsilyl, naphthyl, anthryl, phenanthryl and the like.
• the aryl group is, for example, an alkyl group (for example, C1-18 alkyl group, etc.), a halogen atom (for example, fluorine, chlorine, bromine, etc.), a carboxyl group, an ester group, an amide group, an azo group having an aryl group, and protection. It may have 1 to 3 substituents such as hydroxyl groups.
• the host group and guest group in the cosmetics are any one of the following combinations (a) to (c):
• the host group is ⁇ -cyclodextrin and
• the guest groups are (1) a linear alkyl group having 4 to 18 carbon atoms, (2) a linear alkyl group having 4 to 18 carbon atoms having a hydroxyl group, and (3) a linear alkyl group having 4 to 18 carbon atoms having a carboxyl group.
• the host group is ⁇ -cyclodextrin and
• the guest groups are (1') t-butyl group, (2') adamantyl group, (3') aryl group, (4') hydroxyl group-bearing aryl group, (5') carboxyl group-bearing aryl group, (6').
• the host group is ⁇ -cyclodextrin and The guest group is an alkyl group having a (1 ′′) up to 18 carbon atoms, an alkyl group having a (2 ′′) hydroxyl group up to 18 carbon atoms, an alkyl group having a (3 ′′) carboxyl group up to 18 carbon atoms, and the like.
• the “polymer compound” means a polymer composed of one or more kinds of monomers, and in particular, has a molecular weight distribution and has a polystyrene-equivalent number average molecular weight of 1 ⁇ 10 3 or more (for example, 1 ⁇ 10 3 to 1). It is a polymer of 1 ⁇ 10 8).
• the polymer compound may be a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, or any other embodiment.
• the polymer compound having a host group and / or a guest group according to the present disclosure may be a polymer composed of a single monomer, or may be a copolymer, a block copolymer, or a graft copolymer. May be good.
• the silicon atom (Si) constituting the siloxane bond is preferably represented by a hydrogen atom or RS.
• RS is an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a cycloalkoxy group, a hydroxy group, a carboxy group, an aldehyde group, an aryl group, an aryloxy group, or a monovalent heterocyclic group.
• these groups may have a substituent group, if R S there are a plurality, or different in each of them the same.
• RS may be an alkyl group having 1 to 12 carbon atoms or an aryl group which may have a substituent.
• RS is preferably an alkyl group having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, and particularly preferably 1 or 2 carbon atoms.
• At least one of the polymer compound having a host group and the polymer compound having a guest group, or the polymer compound having a host group and a guest group contains a polyorganosiloxane main chain.
• the polymer compound contained in the cosmetics according to the present disclosure contains a siloxane bond in the main chain, or when the polyorganosiloxane main chain is contained, the chemical stability of the cosmetics is further improved. It is preferable because it may be used, and it is preferable because it exhibits better solubility in hydrocarbon oils, silicone oils, and the like.
• the polymer compound according to the present disclosure may have a polyorganosiloxane unit in the main chain or side chain.
• the proportion of the polyorganosiloxane unit is 20% by weight or more, 30% by weight or more, or 40% by weight or more with respect to the entire polymer compound. It may be 100% by weight or less, 90% by weight or less, 80% by weight or less, 70% by weight or less, or 60% by weight or less.
• the proportion of the polyorganosiloxane unit is in this range, the chemical stability and solubility of the polymer compound are further improved.
• both the polymer compound having a host group and the polymer compound having a guest group contain a siloxane bond in the main chain.
• the present invention for hydrocarbon oil, silicone oil, etc. The solubility of the disclosed cosmetics is further improved.
• siloxane polymer compound may be, for example, poly. Organosiloxane; Block copolymer of polyorganosiloxane and vinyl resin, acrylic resin, urethane resin, epoxy resin, polyimide resin, polyester resin, or polycarbonate resin; vinyl resin, acrylic resin, urethane resin, epoxy resin, polyimide resin , Polyimide resin, or a graft copolymer in which polyorganosiloxane is grafted on a polycarbonate resin.
• These resins and / or polyorganosiloxanes may have substituents other than host and / or guest groups.
• examples of such a polymer compound include an acrylic silicone resin and an acrylic-silicone graft copolymer. , A copolymer of polynorbornene and silicone, a copolymer of pullulan and silicone, and the like.
• polyorganosiloxane examples include methylpolysiloxane, phenylpolysiloxane, and methylphenylpolysiloxane, and these polysiloxanes may have a substituent other than a host group and / or a guest group.
• the polymer compound according to the present disclosure particularly preferably has a methylpolysiloxane skeleton.
• At least one of the polymer compound having a host group and the polymer compound having the guest group, or the polymer compound having the host group and the guest group is represented by the following formula (1).
• R R1, R R2, and R R3 are each a carbon number of 1 to 10 alkyl or alkylene
• X 1 and X 2 are independently O, Si (OH) 2 , Si (R 10 ) 2 , NH, or N (COCH 3 ), or are urethane or urea bonds, respectively.
• R 10 is a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a cycloalkoxy group, a hydroxy group, a carboxy group.
• An aldehyde group, an aryl group, an aryloxy group, or a heterocyclic group, and these groups may have a substituent; a plurality of R 10s may be the same or different, respectively; X 1 And X 2 may be the same or different if there are more than one; p and q each independently represent an integer greater than or equal to 0; RY is the host group; R Z is the guest.
• the groups; h, i, j, and k each represent an integer greater than or equal to 0, which may be the same or different from each other; at least j or k is an integer greater than or equal to 1.
• n represents an integer of 1 or more. ].
• the polymer compound having a host group and the polymer compound having a guest group have a structure represented by the above formula (1).
• the polymer compound contained in the resin composition according to the present disclosure has a structure represented by the above formula (1)
• the polymer compound is applied to both ends of the structure represented by the above formula (1). It may have a structure in which end groups are bonded.
• the terminal group (RE ) that can be bonded to the end of the structure represented by the above formula (1) is an alkyl group having 1 to 10 carbon atoms, particularly an alkyl group having 1 to 6 carbon atoms, or Si.
• RE1 Examples thereof include a group represented by 3 ⁇ , wherein RE1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an aryl group.
• At least one of a polymer compound having a host group and a polymer compound having a guest group, or a polymer compound having a host group and a guest group is placed in the main chain. It has a structure represented by the above formula (1).
• the polymer compound according to the present disclosure includes, for example, a vinyl resin, an acrylic resin, a urethane resin, an epoxy resin, a polyimide resin, a polyester resin, or a polycarbonate resin, and a polyorganosiloxane having a structure represented by the above formula (1). It may be a block copolymer with.
• the polymeric compound contained in the cosmetic is. It has a vinyl main chain, an acrylic main chain, a urethane main chain, an epoxy main chain, a polyimide main chain, a polyester main chain, a polyurea main chain, or a polycarbonate main chain, and
• the side chain has a structure represented by the above formula (1).
• the polymer compound according to the present disclosure is, for example, a vinyl resin, an acrylic resin, a urethane resin, an epoxy resin, a polyurea resin, a polyimide resin, a polyester resin, a polycarbonate resin, or the like, according to the above formula (1). It may be a graft polymer grafted with a polyorganosiloxane having the structure represented.
• At least one of a polymer compound having a host group and a polymer compound having a guest group, or a polymer compound having a host group and a guest group is represented by the following formula ( Has a structural unit represented by 2): [In the formula (2), R 1 to R 6 are independently hydrogen atoms, or an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a cycloalkoxy group, a hydroxy group, a carboxy group, and an aldehyde group.
• X 1 and X 2 are independently O, Si (OH) 2 , Si (R 10 ) 2 , N (H), or N (COCH 3). ), Urethane bond, urea bond, ether bond, amide bond, or ester bond, or carbonyl group, alkylene group, cycloalkylene group, alkenylene group, alkoxylen group, divalent complex It is a ring group, a urethane group, a urea group, or an arylene group, and these groups may have a substituent; R 10 is a hydrogen atom or an alkyl group, a cycloalkyl group, an alkenyl group.
• R m4 is an alkylene group, a cycloalkylene group, an alkenylene group, an alkoxylen group, or an arylene group, and these groups may have a substituent and Y 2 Is an ether bond, an amide bond, or an ester bond, O, Si (OH) 2 , Si (R 10 ) 2. , N (H), or N (COCH 3 ), where a, b, and c each independently represent an integer of 0 to 3; * represents a single bond constituting the main chain of the polymer compound. .. ]
• At least one of a polymer compound having a host group and a polymer compound having a guest group, or a polymer compound having a host group and a guest group is the above-mentioned formula (2).
• R m5 ⁇ R m7 are each independently a hydrogen atom or an alkyl group
• Y 3 is an ether bond, amide bond, or ester bond
• R m8 is alkylene group, a cycloalkylene group, an alkenylene group, alkoxylene group, or an arylene group, which may have a substituent group
• Y 4 is a hydrogen atom, an alkyl group, a hydroxyl group, Si (OH ) 3 , Si (R 10 ) 3 , NH 2 , C (O) CH 3 , C (O) NH 2 , or N (COCH 3 ), where d and e are independently integers from 0 to 3.
• the polymer compound having a host group and the polymer compound having a guest group have a structural unit represented by the above formula (2) and optionally a structural unit represented by the above formula (3).
• a terminal group (RE ) may be bonded to the end of the polymer compound having the structural unit represented by the above formula (2).
• Examples of the terminal group include an alkyl group having 1 to 10 carbon atoms or a group represented by Si (RE1 ) 3- , where RE1 is a hydrogen atom or a carbon atom. It is an alkyl group or an aryl group having a number of 1 to 10, 1 to 6, 1 to 3, or 1 to 2.
• the polymer compound having the structural units represented by the above formulas (2) and (3) may be a random copolymer, a block copolymer, an alternating sequence copolymer or the like, and the arrangement order of the constituent units is not particularly limited.
• the content ratio of the structural unit in the polymer compound having the structural unit represented by the above formula (2) is not particularly limited.
• the content ratio of the structural unit represented by the above formula (2) is set with respect to the entire structural unit (monomer unit) constituting the polymer compound having the structural unit represented by the above formula (2). 0.01 mol% or more, 0.1 mol% or more, 1.0 mol% or more, 5 mol% or more, 10 mol% or more, or 15 mol% or more, and / or 90 mol% or less, It may be 75 mol% or less, 50 mol% or less, 25 mol% or less, or 20 mol% or less.
• the structural unit represented by the above formula (2) The content ratio may be 0.01 mol% or more, 0.1 mol% or more, 1.0 mol% or more, 5 mol% or more, 10 mol% or more, or 15 mol% or more, and / or 30 It may be mol% or less, 25 mol% or less, or 20 mol% or less, and the content ratio of the structural unit represented by the above formula (3) is 70 mol% or more, 75 mol% or more, or 80. It may be mol% or more and / or 99.99 mol% or less, 99.9 mol% or less, 99 mol% or less, 95 mol% or less, or 90 mol% or less.
• R m1 to R m3 are independently hydrogen atoms or alkyl groups, preferably hydrogen atoms or carbon atoms 1 to 12, 1 to 6 or 1 to 1. It is an alkyl group of 3, and is particularly preferably a hydrogen atom. R m1 to R m3 are preferably the same as each other.
• R m4 is preferably an alkylene group having 1 to 12, 1 to 6 or 1 to 3 carbon atoms, or an arylene group having 6 to 12 carbon atoms, and is particularly preferably. , 1 to 12, 1 to 6 or 1 to 3 alkylene groups having 1 to 3 carbon atoms.
• Y 2 is preferably an ether bond, an amide bond, an ester bond, N (H), or N (COCH 3 ), and particularly preferably an ether bond, an amide bond, or an ester. It is a bond.
• a, b, and c are preferably integers of 0 to 2 independently of each other, and particularly preferably 0 or 1.
• R m5 to R m7 are independently hydrogen atoms or alkyl groups, preferably hydrogen atoms or carbon atoms 1 to 12, 1 to 6 or 1 to 1. It is an alkyl group of 3, and is particularly preferably a hydrogen atom.
• R m1 to R m3 are preferably the same as each other.
• R m8 is preferably an alkylene group having 1 to 12, 1 to 6 or 1 to 3 carbon atoms, or an arylene group having 6 to 12 carbon atoms, and is particularly preferably. , 1 to 12, 1 to 6 or 1 to 3 alkylene groups having 1 to 3 carbon atoms.
• Y 4 is preferably an alkyl group having 1 to 12, 1 to 6 or 1 to 3 carbon atoms, C (O) CH 3 , C (O) NH 2 , or N (COCH). 3 ).
• d and e are preferably integers of 0 to 2 independently of each other, and particularly preferably 0 or 1.
• R m1 , R m2 , R m3 , R m4 , Y 1 , a, and b in the above formula (2) are R m5 , R m6 , respectively in the above formula (3).
• the host group represented by RY is preferably ⁇ -cyclodextrin, ⁇ -cyclodextrin, or ⁇ -cyclodextrin.
• the guest group represented by R Z is preferably an alkyl group which may have a substituent or an aryl group which may have a substituent.
• Each of R 1 to R 5 is independently a hydrogen atom, or an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a cycloalkoxy group, a hydroxy group, a carboxy group, an aldehyde group, an aryl group, or an aryloxy. It is preferably a group, more preferably an alkyl group, a cycloalkyl group, an alkenyl group, an alkoxy group, a cycloalkoxy group, a hydroxy group, a carboxy group, an aldehyde group, or an aryl group or an aryloxy group.
• R 1 to R 5 preferably have 1 to 10, more preferably 1 to 6, particularly preferably 1 to 3, and most preferably 1 to 2 carbon atoms.
• R 1 , R 2 , R 3 , R 4 and R 5 are preferably methyl groups or phenyl groups, and particularly preferably methyl groups. ..
• R 1 , R 2 , R 3 , R 4 and R 5 are methyl groups, the solubility in a non-polar solvent such as a hydrocarbon compound or silicone is further improved.
• R 6 is a group represented by -R R1 -COOH, or -R R2- COO-R R3, because the synthesis becomes easier.
• These groups may have a substituent, and RR1 , RR2 , and RR3 are alkyl groups or alkylene groups having 1 to 10 carbon atoms, respectively. .. RR1 , RR2 , and RR3 may be alkyl or alkylene groups having 1 to 8 carbon atoms, 1 to 6 carbon atoms, or 1 to 3 carbon atoms, respectively.
• R 1 to R 5 may be a methyl group and / or R 6 is a group represented by -R R1-COOH or it may be a group represented by -R R2 -COO-R R3.
• the cosmetics according to the present disclosure may bring about excellent physical properties such as improved makeup retention due to self-healing properties based on host-guest interaction.
• the cosmetics according to the present disclosure are used as a cosmetic coating film, the cosmetics are made up by reversibly rebinding the polymer compounds via a host-guest interaction. It is conceivable that the scratches on the coating film (including minute scratches that cannot be seen) are closed, and as a result, the longevity of the cosmetics is further improved.
• a k 0, and, R 1 ⁇ R 3, R 5, and R 6, It is an alkyl group.
• a cosmetic having a particularly excellent makeup retention may be obtained.
• the Si atom constituting the main chain or side chain of a polymer compound having a host group is modified with an alkyl group, it is modified with a substituent having a relatively high polarity.
• the compatibility between the polymer compound having a host group and the polymer compound having a guest group is improved, and as a result, the bond (rebonding) based on the host-guest interaction is promoted. Therefore, it is considered that the self-healing property of the cosmetic is further improved.
• R 1 ⁇ R 3 and R 5 is a methyl group
• R 6 is a alkyl group having 2 or more carbon atoms, more preferably a alkyl group having 4 or more carbon atoms, More preferably, it is an alkyl group having 4 to 30 carbon atoms, 4 to 24 carbon atoms, 4 to 18 carbon atoms, 4 to 12 carbon atoms, or 4 to 8 carbon atoms, and particularly a pentyl group. .. In this case, a cosmetic having particularly excellent self-healing property can be obtained.
• p and / or q are preferably 1 to 3, respectively, and more preferably 1 or 2, respectively, because the synthesis becomes easier. ..
• X 1 and X 2 are independently Si (OH) 2 , N (H), or N (COCH 3 ), an amide bond, or an ester bond, or a carbonyl group, an alkylene group, or a cyclo. It is preferably an alkylene group or an arylene group, and more preferably an N (H) or N (COCH 3 ), an amide bond, an ester bond, or an alkylene group.
• R 10 is preferably a hydrogen atom or is preferably an alkyl group, a cycloalkyl group, a carboxy group, an aldehyde group or an aryl group, and is a hydrogen atom or an alkyl group, a cycloalkyl group or an aryl group. It is more preferable, and it is particularly preferable that it is a hydrogen atom or an alkyl group.
• R 10 as an alkyl group preferably has 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms.
• X 1 is an alkylene group having 1 to 10 carbon atoms, an N (COCH 3 ), an amide bond, or a carbonyl group because the synthesis becomes easier. Is preferable.
• X 1 as an alkylene group preferably has 1 to 6, more preferably 1 to 4, and particularly preferably 1 to 2 carbon atoms.
• (X 1) p is, R P1 -N (COCH 3) or (CH 2) 2 -N (COCH 3).
• - (X 1) p -R Y is represented by -R P1 -N (COCH 3) -R Y.
• RP1 is an alkylene group which may have a substituent and preferably has 1 to 10, more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms.
• R P1 preferably has no substituents.
• (X 1 ) p is (CH 2 ) 3- N (COCH 3 ).
• X 2 may have a substituent, an alkylene group having 1 to 12 carbon atoms, an amide bond, or a carbonyl, because the synthesis becomes easier. It is preferably a group.
• X 2 as an alkylene group preferably has 1 to 8, more preferably 1 to 6, and particularly preferably 1 to 3 carbon atoms.
• (X 2) q is particularly preferably, -R 11 -CO-O-or -R 11 -CO-N (H) - is.
• -(X 2 ) q- R Z is -R 11- CO- OR Z , or -CO-N (H).
• R 11 is an alkylene group having 1 to 12 carbon atoms which may have a substituent, preferably 1 to 10, more preferably 1 to 6, particularly preferably 2 to 4, and most preferably 3. It has a carbon number. R 11 preferably has no substituents.
• (X 1 ) p is-(CH 2 ) 3- N (COCH 3 )-and j is an integer greater than or equal to 1, and / or (X 2 ) q is -R 11- CO-O.
• R 11 is an alkylene group having 1 to 12 carbon atoms which may have a substituent, particularly an alkylene group having 3 to 6 carbon atoms.
• k is an integer of 1 or more.
• n may be an integer of 5 or more, 10 or more, 20 or more, or 50 or more, and / or an integer of 1000 or less, 500 or less, 250 or less, 200 or less, 150 or less, or 100 or less. ..
• examples of the alkyl group include an alkyl group which may have a substituent and a linear, branched or cyclic C1 to 18 alkyl group.
• alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, isohexyl, dodecyl, octadecyl, and adamantyl.
• Examples of the alkylene group include linear, branched or cyclic C1-18 alkylene groups, methylene, ethylene, n-propylene, isopropylene, n-butylene and isobutylene.
• examples of the aryl group include an aryl group which may have a substituent, and specific examples thereof include an aryl group having a single ring or two or more rings. Specific examples thereof include phenyl, toluyl, xylyl, naphthyl, anthryl, phenanthryl and the like. Examples of the arylene group include a monocyclic or bicyclic arylene group, phenylene and the like.
• the alkenyl group is a linear or branched alkenyl group having 2 to 20 carbon atoms, for example, vinyl, 1-propene-1-yl, 2-propene-1. -Il, isopropenyl, 2-butene-1-yl, 4-pentene-1-yl, and 5-hexene-1-yl can be mentioned.
• the alkoxy group includes an alkoxy group having 1 to 10 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, and sec-butoxy.
• Examples include a group, a pentyloxy group, and a hexyloxy group.
• examples of the substituent include an alkyl group such as a methyl group and an ethyl group, a halogen atom, a carboxyl group, an ester group, an amide group, and a hydroxyl group.
• Ph 100 x h / (h + i + j + k)
• P i 100 x i / (h + i + j + k)
• P j 100 x j / (h + i + j + k)
• P k 100 x k / (h + i + j + k)
• P h , P i , P j , and P k are h, i, j, with respect to the total number of moles of all the structural units constituting the structure represented by the above formula (1) or (2). It represents the ratio of the number of moles of each constituent unit subscripted by each of and k.
• the value of P h may be 70 mol% ⁇ 100 mol%, is preferably 90 mol% ⁇ 100 mol%, more preferably 95 mol% ⁇ 98 mol%, further preferably 96 mol% ⁇ 97 mol% ..
• the value of P i may be 0 mol% ⁇ 30 mol%, is preferably from 0 mol% ⁇ 20 mol%, more preferably from 0.5 mol% ⁇ 10 mol%, it is 1 mol% ⁇ 5 mol% More preferred.
• the value of P j may be 0.01 mol% to 25 mol%, 0.01 mol% to 10 mol%, 0.1 mol% to 5 mol%, or 0.1 mol% to 2 mol%.
• the value of P j is, 0.1mol% ⁇ 0.9mol%, 0.2mol % ⁇ 0.8mol%, 0.3mol% ⁇ 0.7mol%, or 0.4 mol% ⁇ 0.6 mol% Yes, in this case the membranous or film-like cosmetics may have particularly good elasticity.
• the value of P k may be 0.01 mol% to 25 mol%, 0.01 mol% to 10 mol%, 0.1 mol% to 5 mol%, or 0.5 mol% to 3 mol%.
• P h, P i, P j , and the value of P k is, h, i, j, and k charged amount of the raw materials used to manufacture each of the structural units which are indices by each, and, a polymer It can be calculated from 1 1 H-NMR measurement data relating to the compound.
• the polymer compound having a host group contained in the cosmetic has a host group in the side chain
• the polymer compound having a guest group contained in the cosmetic has a guest group in the side chain
• the polymer compound having a host group contained in the cosmetic has a host group in the side chain, and the polymer compound having a guest group contained in the cosmetic has a guest group at the terminal.
• the polymer compound having a host group contained in the cosmetic has a host group at the terminal, and the polymer compound having a guest group contained in the cosmetic has a guest group in the side chain.
• the polymer compound having a host group or the polymer compound having a guest group contained in the cosmetic does not contain a siloxane bond.
• examples of the polymer compound containing no siloxane bond include vinyl compounds, acrylic compounds, olefins, styrenes, acrylic acid esters, and methacrylic acid. Examples include polymers and copolymers of at least one monomer selected from esters, and block copolymers containing these polymers and copolymers, such as vinyl resins, acrylic resins, urethane resins, and epoxy resins.
• Siloxane resin polyester resin, or polycarbonate resin.
• These resins may have substituents other than host and / or guest groups.
• the description in Patent Document 2 can be referred to.
• the cosmetic according to the present disclosure may have at least one of the following polymer compounds (i) to (iv): (I) Non-siloxane polymer compound having a host group and siloxane polymer compound having a guest group; (Ii) A siloxane polymer compound having a host group and a non-siloxane polymer compound having a guest group; (Iii) A siloxane polymer compound having a host group and a siloxane polymer compound having a guest group; (Iv) A siloxane polymer compound having a host group and a guest group.
• the content ratio of each in the cosmetic is not particularly limited.
• the content of the polymer compound having a host group may be 10 to 90% by mass with respect to the total of the polymer compound having a host group and the polymer compound having a guest group, and the content is high having a guest group.
• the content of the molecular compound may be 90% by mass to 10% by mass.
• the amount of host groups and the ratio of guest groups contained in cosmetics are not particularly limited.
• the molar ratio of host group to guest group contained in the cosmetic may be 0.1: 1 to 1: 0.1.
• the cosmetic may contain 1 part by mass or more, 10 parts by mass or more, or 20 parts by mass or more of the polymer compound having a guest group with respect to 100 parts by mass of the polymer compound having a host group. And / or 1000 parts by mass or less, 250 parts by mass or less, or 100 parts by mass or less may be contained.
• non-siloxane polymer compounds having a host group A polymer compound having a host group and not containing a siloxane bond (non-siloxane polymer compound having a host group) can be produced by a known method, for example, the method described in Patent Document 2. Can be manufactured by.
• non-siloxane polymer compounds having guest groups A polymer compound having a guest group and not containing a siloxane bond (non-siloxane polymer compound having a guest group) can be produced by a known method, for example, the method described in Patent Document 2. Can be manufactured by.
• the siloxane polymer compound having a host group can be produced, for example, by a method having the following steps: (I) A polymer providing step of providing a polymer compound having a siloxane bond (siloxane polymer compound). (Ii) Host group precursor providing step of providing a host group precursor compound (iii) A siloxane polymer compound and a host group precursor compound are reacted in the presence of a metal catalyst to cause a siloxane polymer having a host group. Host group addition reaction step to obtain a compound.
• a polymer compound having a siloxane bond (siloxane polymer compound) is provided.
• the polymer compound having a siloxane bond is preferably a polyorganosiloxane.
• the polymer compound having a siloxane bond preferably has a structure suitable for reaction with the host group precursor compound, and has, for example, a hydrogen atom directly bonded to Si.
• the siloxane polymer compound provided in the polymer providing step may be, for example, SiH-containing silicone, and specifically, for example, a polymer having a structure represented by the following formula (4). :
• X may be 2 or more, 5 or more, 10 or more, or 20 or more, and / or 95 or less, 90 or less, 75 or less, or 50 or less.
• n may be 5 or more, 10 or more, or 50 or more, and / or 1000 or less, 500 or less, 250 or less, 100 or less, or 75 or less.
• the host group precursor compound is provided.
• the host group precursor compound preferably has a linker structure for binding to a polymer compound having a siloxane bond.
• Examples of the host group precursor compound include cyclodextrin having a linker structure.
• Examples of the linker structure include vinyl groups, and in particular, groups represented by the following formula (XL).
• C (H) 2 C ( H) -C (H) 2 -N (COCH 3) - * ⁇ (X L) [In formula ( XL ), * represents a single bond with cyclodextrin. ]
• the siloxane polymer compound and the host precursor compound are reacted in the presence of a metal catalyst to obtain a siloxane polymer compound having a host group.
• a metal catalyst for example, by reacting a siloxane polymer compound having a hydrogen atom directly bonded to Si in the main chain with cyclodextrin having a vinyl group as a linker structure in the presence of a metal catalyst, cyclodextrin is transmitted through the linker structure.
• a siloxane polymer compound bonded to the Si atom of the main chain can be obtained.
• the hydrogen atom directly bonded to the Si atom is substituted in the polymer compound.
• the compound that can be used for this substitution include an acrylic acid ester and an alkene having 2 or more carbon atoms.
• an alkene having 2 or more carbon atoms is used, the self-repairing property of the obtained cosmetic is particularly excellent, which is preferable.
• a more preferable compound is an alkene having 5 or more carbon atoms, and further preferable compounds are 5 to 30 carbon atoms, 5 to 24 carbon atoms, 5 to 18 carbon atoms, and 5 to 5 carbon atoms. It is an alkene with 12 or 5 to 8 carbon atoms, especially 1-pentene.
• Metal catalyst examples of the metal catalyst used in the above-mentioned host group addition reaction step include platinum (Pt).
• the siloxane polymer compound having a guest group can be produced, for example, by a method having the following steps: (I) A polymer providing step of providing a polymer compound having a siloxane bond (siloxane polymer compound). (Ii) A guest group precursor providing step, which provides a guest group precursor compound. (Iii) A reaction step of reacting a siloxane polymer compound and a guest group precursor compound in a solvent to obtain a siloxane polymer compound having a guest group.
• a polymer compound having a siloxane bond having a carboxy group is provided.
• the polymer compound having a siloxane bond is preferably a polyorganosiloxane.
• the polymer compound having a siloxane bond provided in the polymer providing step preferably has a structure suitable for reacting with the guest group precursor compound to produce a siloxane polymer compound having a guest group. For example, it has a carboxy group bonded to Si in the main chain via an alkylene group having 1 to 12 carbon atoms.
• the guest group precursor compound In the guest group precursor providing step, the guest group precursor compound is provided.
• the guest group precursor compound preferably has a linker structure for binding to a polymer compound having a siloxane bond.
• Specific examples of the guest group precursor compound include adamantyl having a linker structure.
• Examples of the linker structure include an amino group.
• reaction process In the reaction step, the siloxane polymer compound and the guest group precursor compound are reacted in a solvent to obtain a siloxane polymer compound having a guest group.
• a siloxane polymer compound having a carboxy group bonded to Si in the main chain via an alkyl group and adamantyl having an amino group as a linker structure are reacted in a solvent in the presence of a condensing agent to cause a guest.
• a siloxane polymer compound having a group can be obtained.
• the siloxane polymer compound having a guest group has a structure in which adamantyl is bonded to a Si atom constituting the main chain of the siloxane polymer compound via a linker structure.
• the condensing agent include 1-hydroxybenzotriazole (HOBt; Tokyo Chemical Industry Co., Ltd., H0468, Cas: 80029-43-2) and N, N'-dicyclohexylcarbodiimide (DCC; Nacalai Tesque Co., Ltd., 11913-52). , Cas: 538-75-0).
• siloxane polymer compounds having host and guest groups The siloxane polymer compound having a host group and a guest group is obtained by, for example, polymerizing a siloxane polymer compound having a host group produced by the above method and a siloxane polymer compound having a guest group produced by the above method. It can be obtained by forming a block copolymer.
• a polymer compound having a host group and / or a guest group and having a siloxane bond is produced, for example, by polymerizing a monomer represented by the following formula (5) and a monomer represented by the formula (6). You can also do it.
• the mode of the polymerization reaction is not particularly limited, and a known method can be used.
• R E represents a terminal group.
• R E reference may be made to the above description.
• Cross-linking may be a cross-linking other than the host-guest interaction, for example by a covalent bond (eg, a siloxane cross-link).
• a polymer compound having a host group may form a host body by being crosslinked, and / or a polymer compound having a guest group may form a guest body by being crosslinked.
• cross-linking the polymer compound and the cross-linking agent known ones may be used depending on the type of the polymer compound.
• the crosslinks may be formed, for example, by irradiation with light.
• the cross-linking agent include N, N'-methylenebisacrylamide (MBAAm) and ethylene glycol dimethacrylate (EDMA).
• the cosmetics according to the present disclosure have a polymer compound having a host group and a polymer compound having a guest group, which are obtained by individually producing a polymer compound having a host group and a guest group. It can be prepared by mixing each with a polymer compound.
• a polymer compound having a host group and the polymer compound having a guest group for example, both may be mixed in a solid state, one or both may be mixed in a liquid state, or , One or both may be mixed in a solution.
• a method of adding the other polymer compound in a solid state to a solution of one polymer compound may also be used.
• the conditions for mixing the polymer compound having a host group and the polymer compound having a guest group are not particularly limited.
• the temperature at the time of mixing, the mixing time, the mixing means, and the like can be performed under appropriate conditions.
• the cosmetics are paste-like at room temperature.
• a paste-like cosmetic can be obtained by selecting a paste-like compound at room temperature as the polymer compound contained in the cosmetic.
• a liquid cosmetic may be obtained by dissolving the polymer compound in a solvent.
• Cosmetics that are liquid or paste at room temperature are particularly preferable because they are relatively easy to form.
• Examples of the polymer compound that is liquid at room temperature include a polymer compound having polyorganosiloxane in the main chain, particularly dimethylpolysiloxane.
• the solvent for dissolving the polymer compound in the production of cosmetics is not particularly limited, and examples thereof include silicone oil and hydrocarbon oil.
• silicone oil one or more selected from octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, dimethylpolysiloxane, and caprylylmethicone are preferable, and decamethylcyclopentasiloxane and dimethylpoly
• siloxanes are more preferable, and dimethylpolysiloxane having a degree of polymerization of 10 or less is further preferable.
• hydrocarbon oil agent include toluene and isododecane, and isododecane is preferable.
• the polymer compounds contained in the cosmetics according to the present disclosure may be bound to each other by a host-guest interaction, or may not be bound to each other by a host-guest interaction.
• Cosmetics can be formed into a film. If the cosmetic is in the form of a film, it can be used as a cosmetic coating applied on the skin or the like.
• the thickness is not particularly limited and can be set to an appropriate thickness according to the intended use.
• the cosmetic can be adjusted to 1 nm to 1 cm, and can be adjusted to 1 ⁇ m to 100 ⁇ m in terms of good film forming property.
• a cosmetic coating film can be formed by preparing a solution or dispersion of a polymer compound and applying this solution or dispersion.
• the method for producing a cosmetic may include, for example, the following steps: To prepare a host solution by dissolving a polymer compound having a host group in a solvent, and to prepare cosmetic A by adding a polymer compound having a guest group to this host solution.
• cosmetic A is prepared by dissolving a polymer compound having a guest group in a solvent to prepare a guest solution, and adding the polymer compound having a host group to the guest solution. May be produced.
• the step of forming the cosmetic coating film A produced as described above may include, for example, the following operations: Applying cosmetic A to an object with a finger and drying it to form a cosmetic coating film.
• the method for producing a cosmetic may include, for example, the following steps: To prepare a cosmetic B by mixing a polymer compound having a paste-like or liquid host group and a polymer compound having a paste-like or liquid guest group.
• the step of converting the cosmetic B produced as described above into a decorative coating film may include, for example, the following operations: Applying the above cosmetic B to an object to form a decorative coating film.
• either the polymer compound having a host group or the polymer compound having a guest group may be in the form of a paste or a liquid.
• the cosmetics according to the present disclosure may further contain a solvent in addition to the above-mentioned components. By further having a solvent, it is possible to provide a cosmetic having particularly excellent applicability to the skin or the like.
• the solvent that can be contained in the cosmetics according to the present disclosure is not particularly limited, and examples thereof include water, alcohols, silicones, hydrocarbon compounds, ester compounds, ethers, and waxes.
• alcohols examples include glycerin, butylene glycol (BG), propylene glycol (PG), dipropylene glycol (DPG), polyethylene glycol (PEG), ethanol, and oleyl alcohol.
• Silicones include dodecamethylcyclohexasiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dimethylpolysiloxane, caprylylmethicone, methylpolysiloxane, methylphenylpolysiloxane, cyclopentasiloxane, aminoethylaminopropylmethylsiloxane.
• Examples include dimethylsiloxane copolymer, aminopropyldimethicone, methyltrimethicone, tris (trimethylsilyl) methylsilane, tetrakis (trimethylsilyl) silane, amodimethicone, cyclomethicone, and phenyltrimethicone.
• dimethylsiloxane copolymer aminopropyldimethicone, methyltrimethicone, tris (trimethylsilyl) methylsilane, tetrakis (trimethylsilyl) silane, amodimethicone, cyclomethicone, and phenyltrimethicone.
• decamethylcyclopentasiloxane and dimethylpolysiloxane are more preferable, and dimethylpolysiloxane having a degree of polymerization of 10 or less is further preferable.
• hydrocarbon compound examples include hydrogenated polyisobutene, vaseline, mineral oil, squalane, paraffin, isoparaffin, alkyl benzoate, polyisobutene, isododecane, isotridecane, and isohexadecane light isoparaffin, and isododecane is preferable.
• ester compound examples include isopropyl palmitate, ethylhexyl palmitate, isopropyl myristate, and octyldodecyl myristate.
• ethers examples include ethyl perfluorobutyl ether.
• the solvent is volatile.
• the solvent volatilizes when the cosmetic is applied to the skin or the like, so that the cosmetic becomes a film, so that a decorative coating film can be easily formed. can do.
• volatile solvents include dimethylpolysiloxane, methyltrimethicone, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tris (trimethylsilyl) methylsilane, and tetrakis (trimethylsilyl).
• silicones such as silane, hydrocarbon compounds such as isododecane, isotridecane, isohexadecane, light isoparaffin, and hydrogenated polyisobutene, and ethers such as ethyl perfluorobutyl ether.
• the cosmetics according to the present disclosure can contain each main component other than the above-mentioned components to the extent that the effects of the present invention are not impaired.
• each main component other than the above-mentioned components for example, lower alcohols, higher alcohols, spherical powders, film-forming agents, and refreshing agents.
• Lower alcohol is widely used in cosmetics as a usability adjuster and an antiseptic aid.
• Examples of the lower alcohol include ethanol and isopropyl alcohol.
• spherical powder examples include inorganic powders such as spherical anhydrous silicic acid, spherical polymethylmethacrylate, spherical cellulose, spherical nylon, spherical polyethylene, and spherical silicone powder.
• examples of the film-forming agent include latexes such as polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl acetate and alkyl polyacrylate, and cellulose derivatives such as dextrin, alkyl cellulose and nitrocellulose. ..
• Examples of the refreshing agent include menthol derivatives, camphor derivatives, and essential oils.
• ⁇ MALDI-TOF MAS> The MALDI-TOF MS spectrum was measured using a Bruker autoflex maX LRF as an instrument.
• Elemental analysis was performed using an elemental analyzer (manufactured by Yanaco, CHN coder) based on the differential thermal conductivity method.
• Host precursor compound 2 was prepared according to the method below: 20 g (17.0 mmol) of Compound 1 obtained by the above method is prepared, and 300 mL (300 g, 3.8 mol) of dry pyridine and 170 mL (184 g, 1.8 mol) of acetic anhydride are added thereto. , 70 ° C. overnight. Then, 60 mL of methanol was added dropwise while cooling the reaction solution with ice. Then, the reaction solution was dried under reduced pressure with an evaporator to obtain a dry product. The obtained dry matter was dissolved in 100 mL of acetone and added dropwise to 2 L of water.
• the precipitate in the solution was collected by suction filtration, and the solution obtained by dissolving it in 100 mL of acetone was added dropwise to 1.5 L of water. Then, the precipitate in the solution was collected by suction filtration and dried under reduced pressure in a vacuum oven at 70 ° C. for 1 day to obtain the host precursor compound 2.
• the synthesis of host precursor compound 2 was confirmed by MALDI-TOFMS, 1 H-NMR, and elemental analysis.
• the polymer compound H1 having a host group was produced by the following method: 1.8 g (0.9 mmol) of the host precursor compound 2 was dissolved in 400 ml of toluene, substituted with nitrogen, and stirred at 105 ° C. There, 12.0 g (14.4 mmol) of methylhydrogen polysiloxane (dynamic viscosity 20 mm 2 / s, effective hydrogen amount 7.5 mol%) and 165 ⁇ L of Carlstead platinum solution were dissolved in 400 mL toluene. The solution was added dropwise over 1 hour.
• the Carlstead platinum solution is platinum (0) -1,3-divinyltetramethyldisiloxane complex (Platinum (0) -1,3-Divinyltetramethylloxane Complex (19.0% -21.5% as Pt), TCI. , P2075, Cas: 68478-92-2 Product code: P2075).
• the weight of Pt used was 28.5 mg.
• 4.8 g (48 mmol) of ethyl acrylate manufactured by Tokyo Chemical Industry Co., Ltd., Cas: 140-88-5) was added by a syringe.
• the obtained polymer compound H1 was analyzed by 1 H-NMR and IR spectrum, and it was confirmed that the desired product was obtained.
• the host group introduction rate measured by 1 H-NMR was 0.32 mol%.
• ⁇ Production Example 4 Production of Polymer Compound H2 Having a Host Group> It has the above host groups, except that 0.6 g (0.3 mmol) of the host precursor compound 2, 4.0 g (4.8 mmol) of methylhydrogenpolysiloxane, and 55 ⁇ L of Carlstead platinum solution were used. A polymer compound H2 having a host group was produced in the same manner as in the production of the polymer compound H1.
• the host group introduction rate measured by 1 H-NMR was 0.31 mol%.
• the host group introduction rate measured by 1 H-NMR was 0.20 mol%.
• the host group introduction rate measured by 1 H-NMR was 0.37 mol%.
• ⁇ Production Example 7 Production of Polymer Compound H5 Having a Host Group> It has the above host groups, except that 0.6 g (0.3 mmol) of the host precursor compound 2, 2.0 g (2.4 mmol) of methylhydrogenpolysiloxane, and 55 ⁇ L of Carlstead platinum solution were used. A polymer compound H5 having a host group was produced in the same manner as in the production of the polymer compound H1.
• the host group introduction rate measured by 1 H-NMR was 1.0 mol%.
• ⁇ Production Example 8 Production of Polymer Compound H6 Having a Host Group> It has the above host groups, except that 0.6 g (0.3 mmol) of the host precursor compound 2, 4.0 g (4.8 mmol) of methylhydrogenpolysiloxane, and 55 ⁇ L of Carlstead platinum solution were used. A polymer compound H6 having a host group was produced in the same manner as in the production of the polymer compound H1.
• the host group introduction rate measured by 1 H-NMR was 0.5 mol%.
• the polymer compound H7 having a host group was produced by the following method: 1.8 g (0.9 mmol) of the host precursor compound 2 was dissolved in 900 ml of toluene, substituted with nitrogen, and stirred at 105 ° C. A solution prepared by dissolving 12.0 g (11.48 mmol) of methylhydrogenpolysiloxane and 165.0 ⁇ L of Carlstead platinum solution in 250 mL of toluene was added thereto by dropping over 30 minutes.
• the Carlstead platinum solution is platinum (0) -1,3-divinyltetramethyldisiloxane complex (Platinum (0) -1,3-Divinyltetramethylloxane Complex (19.0% -21.5% as Pt), TCI. , P2075, Cas: 68478-92-2 Product code: P2075).
• 2.0 g (29.0 mmol) of 1-Pentene manufactured by Tokyo Chemical Industry Co., Ltd.
• Reflux was carried out overnight, toluene was distilled off by an evaporator, the mixture was dissolved in hexane, and the precipitate was removed by a centrifuge to obtain a polymer compound H7 having a host group dissolved in hexane.
• the obtained polymer compound H7 was analyzed by 1 H-NMR and IR spectrum, and it was confirmed that the desired product was obtained.
• the host group introduction rate measured by 1 H-NMR was 0.47 mol%.
• the polymer compound having a host group is the same as the above-mentioned production of the polymer compound H7 having a host group, except that the host precursor compound of 3.6 g (1.8 mmol) of the host precursor compound 2 is used. H8 was manufactured. The host group introduction rate of the polymer compound H8 was 0.63 mol%.
• N-octylamine Nacalai Tesque, Inc., 25512-72, Cas: 111-86-4
• the solution 4 was stirred overnight to give a clear supernatant and a white precipitate.
• This white precipitate was removed by filtration to give a clear filtrate.
• This clear filtrate was washed with saturated aqueous sodium hydrogen carbonate and dehydrated with anhydrous sodium sulfate.
• Toluene was removed by an evaporator to obtain a colorless and transparent oil. This colorless and transparent oil was vacuum dried at 85 ° C. overnight to obtain a polymer compound G1 having a guest group.
• the obtained polymer compound G1 was analyzed by 1 H-NMR spectrum (500 MHz) measurement.
• the guest group introduction rate measured by 1 1 H-NMR was 0.46 mol%.
• ⁇ Production Example 12 Production of Polymer Compound G1'with Guest Group>
• the polymer compound G1' was obtained by the same method as in Production Example 11.
• the guest group introduction rate in the polymer compound G1' was 0.51 mol%.
• the guest group introduction rate measured by 1 1 H-NMR was 1.3 mol%.
• Polymer compound A2 was produced using methylhydrogenpolysiloxane, Carlstead platinum solution, and 1-Pentene (manufactured by Tokyo Chemical Industry Co., Ltd.).
• ⁇ Production Example 15 Production of Polymer Compound CH-4 Having a Host Group> Macromolecules CH-4 having a polyethyl acrylate backbone and having ⁇ -cyclodextrin as a host group was produced according to the method described in Macromolecules 2019, 52 (7), 2659-2668. The production was carried out so that the unit having a host group was 1.0 mol% in the obtained polymer compound.
• Example 1 >> The polymer compound H5 having a host group produced as described in Production Example 7 described above and the polymer compound G1 having a guest group produced as described in Production Example 11 described above are dissolved in isododecane and in Table 1 below.
• the cosmetic according to Example 1 was produced by adding the additional compounds shown in Table 1 in the amounts shown in Table 1.
• the polymer compound H5 and the polymer compound G1 having a polymethylsiloxane main chain showed good solubility in isododecane used as a solvent.
• the cosmetic according to Example 1 was applied to the cheeks with a finger to form a decorative coating film. Then, the following items were evaluated: (A) Tightness (b) Adhesion (c) Elasticity (d) Makeup lasting.
• Table 2 shows the evaluation results of Example 1.
• Example 2 >> The polymer compound H5 having a host group produced as described in Production Example 7 described above and the polymer compound G2 having a guest group produced as described in Production Example 13 described above are dissolved in isododecane and in Table 1 below.
• the cosmetic according to Example 2 was produced by adding the additional compounds shown in Table 1 in the amounts shown in Table 1.
• the polymethylsiloxane main chain polymer compound H5 and the polymer compound G2 showed good solubility in isododecane used as a solvent.
• Example 2 The feeling of use of the cosmetics according to Example 2 was evaluated in the same manner as in Example 1. The results are shown in Table 2.
• Example 3 >> The polymer compound H7 having a host group produced as described in Production Example 9 and the polymer compound G1 having a guest group produced as described in Production Example 11 above are dissolved in isododecane and in Table 1 below.
• the cosmetic according to Example 3 was produced by adding the additional compounds shown in Table 1 in the amounts shown in Table 1.
• the polymethylsiloxane main chain polymer compound H7 and the polymer compound G1 showed good solubility in isododecane used as a solvent.
• Comparative Example 1 A cosmetic according to Comparative Example 1 was produced in the same manner as in Example 1 except that trimethylsiloxysilicic acid (manufactured by MOMENTIVE, SR1000) was used instead of the isododecane solution of the polymer compound H5 and the polymer compound G1. bottom.
• trimethylsiloxysilicic acid manufactured by MOMENTIVE, SR1000
• Comparative Example 2 Comparison was performed in the same manner as in Example 1 except that a silicone resin (siloxane crosslinked product, Silicon Flexible Resin (trade name) (manufactured by MOMENTIVE)) was used instead of the isododecane solution of the polymer compound H5 and the polymer compound G1. The cosmetic according to Example 2 was produced.
• a silicone resin silicone resin (siloxane crosslinked product, Silicon Flexible Resin (trade name) (manufactured by MOMENTIVE)) was used instead of the isododecane solution of the polymer compound H5 and the polymer compound G1.
• the cosmetic according to Example 2 was produced.
• Example 4 Production of cosmetics in the same manner as in Example 1 using the polymer compound CH-4 having a host group according to Production Example 15 described above and the same siloxane crosslinked product used in Comparative Example 2 described above. And evaluation was performed. The results are shown in Table 3 below.
• Example 5 Using the polymer compound CH-4 having a host group according to Production Example 15 and the polymer compound G2 having a guest group according to Production Example 13 described above, in the same manner as in Example 1, cosmetics were prepared. Manufactured and evaluated. The results are shown in Table 3 below.

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