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
  • A61K8/81—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
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
• • 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
  • A61Q1/02—Preparations containing skin colorants, e.g. pigments
  • A61Q1/10—Preparations containing skin colorants, e.g. pigments for eyes, e.g. eyeliner, mascara
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
  • A61Q17/04—Topical preparations for affording protection against sunlight or other radiation; Topical sun tanning preparations
• • 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
  • A61Q19/00—Preparations for care of the skin
  • A61Q19/10—Washing or bathing preparations
• • 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
  • A61Q5/02—Preparations for cleaning the hair
• • 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
  • A61Q5/04—Preparations for permanent waving or straightening the hair
• • 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
  • A61Q5/06—Preparations for styling the hair, e.g. by temporary shaping or colouring
• • 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
  • A61Q5/10—Preparations for permanently dyeing 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
  • C08F220/04—Acids; Metal salts or ammonium salts thereof
  • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K3/00—Materials not provided for elsewhere

Definitions

• the present invention relates to polymer compounds, cosmetics, and thickeners.
• a polymer exhibiting viscosity-increasing properties may be added to the cosmetic to thicken or gel the cosmetic.
• Carboxyvinyl polymers for example, are known as such polymers.
• many of the polymers that can be used as thickeners aggregate when electrolytes (especially polyelectrolytes) are added, and the viscosity drops sharply when the amount of electrolyte added exceeds 2% by mass. There is a problem that the viscosity cannot be maintained when a high-concentration electrolyte coexists.
• Patent Document 1 it is possible to form a viscous aqueous solution having a desired viscosity even in the presence of a polyelectrolyte such as L-ascorbylmagnesium phosphate.
• a polyelectrolyte such as L-ascorbylmagnesium phosphate.
• Polymers containing units are disclosed.
• the polymer disclosed in Patent Document 1 is a fluorine-containing polymer, its versatility is not necessarily high. In addition, the above fluorine-containing polymer is expensive, and the productivity is not sufficient. Therefore, the present invention can form a viscous aqueous solution having a desired viscosity even in the presence of a polyelectrolyte such as L-ascorbyl magnesium phosphate, even if it does not contain a repeating unit derived from a monomer having a fluorine atom.
• An object of the present invention is to provide a novel polymer (polymer compound). Another object of the present invention is to provide a cosmetic and a thickener containing the polymer.
• a polymer compound in which the monomer (B) includes a compound represented by formula (1) described later and a compound represented by formula (2) described later.
• R 12 is an alkyl group having 9 to 12 carbon atoms having only one specific carbon atom selected from the group consisting of a tertiary carbon atom and a quaternary carbon atom, or a carbon number having a cyclic structure
• the monomer (B) contains a compound represented by formula (3) described later, A polymer compound in which the content of repeating units derived from the monomer (B) is 8.5 to 14.0% by mass with respect to the total repeating units of the polymer compound.
• R 32 is an alkyl group having 9 to 12 carbon atoms having at least one specific carbon atom selected from the group consisting of a tertiary carbon atom and a quaternary carbon atom, or a carbon number having a cyclic structure
• viscosity a represents the viscosity at 20° C. of sample liquid A prepared by the procedure described later.
• Viscosity b represents the viscosity at 20° C. of sample liquid B prepared by the procedure described later.
• the polymer compound according to [6], wherein the viscosity c at 20°C of the sample liquid C prepared by the procedure described later is 3,000 mPa ⁇ s or more.
• the polymer according to [6] or [7], wherein the monomer (B) includes a compound represented by the formula (1) described later and a compound represented by the formula (2) described later Compound.
• the monomer (B) contains a compound represented by formula (3) described later, [6] or [7], wherein the content of the repeating unit derived from the monomer (B) is 8.5 to 14.0% by mass with respect to the total repeating units of the polymer compound. polymer compound.
• a viscous aqueous solution having a desired viscosity can be formed even in the presence of a polyelectrolyte such as L-ascorbyl magnesium phosphate, even without containing repeating units derived from a monomer having a fluorine atom.
• a novel polymer polymer compound
• cosmetics and thickeners containing the polymer can also be provided.
• a numerical range represented using “ ⁇ ” means a range including the numerical values before and after " ⁇ " as lower and upper limits.
• solid content means components other than the solvent among the components contained in the composition.
• a component other than a solvent is regarded as a solid content even if it is in a liquid state.
• (meth)acryl means “either one or both of acryl and methacryl”.
• (meth)acrylate means “either one or both of acrylate and methacrylate”.
• (meth)acryloyl means “one or both of acryloyl and methacryloyl”.
• (meth)alkylacrylamide is synonymous with N-alkyl(meth)acrylamide.
• the bonding direction of the divalent group (eg, --CO--O--) indicated is not limited unless otherwise specified.
• the compound when Y is -CO-O- in a compound represented by the formula "X-Y-Z", the compound may be "X-O-CO-Z", and "- X—CO—O—Z”.
• halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms.
• the polymer compound (hereinafter also referred to as "polymer") of the first embodiment of the present invention is a repeating unit derived from the monomer (A) having an acidic functional group and an ethylenically unsaturated double bond group (hereinafter also referred to as "repeating unit derived from the monomer (A)”); a repeating unit derived from a monomer (B) having an ethylenically unsaturated double bond group containing no fluorine atom (hereinafter also referred to as a “repeating unit derived from the monomer (B)”); a repeating unit derived from the monomer (C) having two or more ethylenically unsaturated double bond groups (hereinafter also referred to as “repeating unit derived from the monomer (C)”); hand,
• the monomer (B) includes a compound represented by the formula (1) described later and a compound represented by the formula (2) described
• the present inventors presume as follows.
• the polymer of the present invention is neutralized with an alkaline agent while being dispersed in water, the acidic functional groups in the repeating units derived from the monomer (A) are anionized, and the electrostatic repulsion between the anions The network of polymer chains spreads (swells) due to , resulting in thickening.
• polymers exhibiting a thickening effect due to the morphology described above when in their neutralized state a polyelectrolyte such as L-ascorbylmagnesium phosphate is added, the action of osmotic pressure and/or the acidic functionality of the polyelectrolyte.
• the network of polymer chains tends to shrink due to cross-linking between groups.
• the side chain of the repeating unit derived from the compound represented by the formula (1) and the side chain of the repeating unit derived from the compound represented by the formula (2) It is speculated that physical cross-linking such as hydrophobic interaction that occurs between and makes it difficult for the polymer chain network to shrink, and as a result, it is easy to suppress the decrease in the thickening action.
• the fact that the polymer of the first embodiment of the present invention can be used to form a viscous aqueous solution having a higher viscosity in the presence of a polyelectrolyte such as L-ascorbyl magnesium phosphate is referred to as "the effect of the present invention is more excellent. ” is also said.
• the polymer of the first embodiment of the invention will be described below.
• the polymer of the first embodiment has repeating units derived from the monomer (A), repeating units derived from the monomer (B), and repeating units derived from the monomer (C). First, each monomer will be described below.
• Monomer (A) is a monomer having an acidic functional group and an ethylenically unsaturated double bond group.
• the acidic functional group includes a carboxyl group, a sulfo group, a phosphoric acid group, and the like, and a carboxyl group is preferred.
• the ethylenically unsaturated double bond group means a group having an ethylenically unsaturated double bond and capable of being polymerized by irradiation with active energy rays such as ultraviolet rays or the action of radicals.
• the monomer (A) does not contain a fluorine atom.
• the monomer (A) is typically a monofunctional compound containing only one ethylenically unsaturated double bond group.
• the number of acidic functional groups in the monomer (A) is not particularly limited as long as it is 1 or more.
• Examples of the monomer (A) include compounds represented by the following formula (AX).
• R A1 represents a hydrogen atom or a methyl group.
• X A1 represents a single bond, -CO-O-, or -CO-NR A3 -.
• R A3 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• L A1 represents a single bond or an alkylene group having 1 to 10 carbon atoms.
• RA2 represents an acidic functional group.
• X A1 is preferably a single bond.
• the alkyl group having 1 to 6 carbon atoms represented by R A3 may be linear, branched or cyclic. Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R A3 include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, isobutyl group, sec- butyl group, tert-butyl group, cyclobutyl group, n-pentyl group, isopentyl group, sec-pentyl group, tert-pentyl group, neopentyl group, 2-methylbutyl group, 1,2-dimethylpropyl group, 1-ethylpropyl group , cyclopentyl group, n-hexyl group, isohexyl group, sec-hexyl
• a linear, branched or cyclic alkyl group having 1 to 3 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and a cyclopropyl group is preferred, and a methyl group is preferred. More preferred.
• R A3 is preferably a hydrogen atom or a methyl group.
• the alkylene group having 1 to 10 carbon atoms represented by L A1 is preferably linear or branched.
• the number of carbon atoms in the alkylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 2 to 4.
• the alkylene group preferably has a hydroxy group as a substituent.
• alkylene group having 1 to 10 carbon atoms represented by L A1 include, for example, a methylene group, a hydroxymethylene group, a dimethylene group (ethylene group), a hydroxydimethylene group (hydroxyethylene group), a trimethylene group, -hydroxytrimethylene group, 2-hydroxytrimethylene group, isopropylene group, hydroxyisopropylene group, tetramethylene group, hydroxytetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethyl A dimethylene group, a pentamethylene group, a hexamethylene group, and the like can be mentioned.
• L A1 is preferably a single bond.
• the monomer (A) include acrylic acid, methacrylic acid, 2-(acryloyloxy)ethanesulfonic acid, 2-(methacryloyloxy)ethanesulfonic acid, 3-(acryloyloxy)propanesulfonic acid, 3-(methacryloyloxy)propanesulfonic acid, 2-acryloyloxy-2-methylpropanesulfonic acid, 2-methacryloyloxy-2-methylpropanesulfonic acid, 3-acryloyloxy-2-hydroxypropanesulfonic acid, 3-methacryloyloxy -2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, 2-(acryloyloxy)ethyl phosphate, and 2-(methacryloyloxy)ethyl phosphate and the like.
• the monomer (A) a commercially available product may be used, or one appropriately synthesized by a known method may be used.
• the monomer (B) is a monomer having an ethylenically unsaturated double bond group containing no fluorine atoms, and is preferably an acrylate-based compound or an acrylamide-based compound. It is more preferably a compound represented by the formula (BX) shown in the form of a polymer. Note that the monomer (B) does not contain a fluorine atom. Moreover, the monomer (B) is typically a monofunctional compound containing only one ethylenically unsaturated double bond group. The ethylenically unsaturated double bond groups are as described above. Moreover, the monomer (B) is a compound different from the monomer (A).
• repeating unit derived from the monomer (B) a repeating unit derived from a compound represented by the formula (1) described later and a compound represented by the formula (2) described later containing any repeating unit derived from The compound represented by formula (1) and the compound represented by formula (2) are described below.
• R 11 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• the C 1-6 alkyl group represented by R 11 may be linear, branched, or cyclic. Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R 11 include the same as R 1 A3 in the above formula (AX), and preferred embodiments are also the same.
• R 11 is preferably a hydrogen atom or a methyl group.
• R 12 is an alkyl group having 9 to 16 carbon atoms having only one specific carbon atom selected from the group consisting of tertiary carbon atoms and quaternary carbon atoms, or has a cyclic structure. It represents an alkyl group having 9 to 16 carbon atoms.
• a tertiary carbon atom means a carbon atom in which one of four bonds is bonded to a hydrogen atom and three bonds are bonded to atoms other than hydrogen atoms.
• Specific examples of atoms other than hydrogen atoms include carbon atoms, oxygen atoms, and nitrogen atoms.
• the oxygen atom and nitrogen atom described above each mean an atom that bonds to R 12 in X 11 specified in formula (1).
• R 12 when the carbon atom at the position adjacent to X 11 specified in formula (1) in R 12 is a tertiary carbon atom, one of the four bonds of the carbon atom is a hydrogen atom.
• one bond is bonded to an oxygen atom or a nitrogen atom (the atom bonded to R 12 in X 11 specified in formula (1)), and the other two bonds are bonded to a carbon atom Combined.
• the carbon atom at a position not adjacent to X 11 specified in formula (1) in R 12 is a tertiary carbon atom
• one of the four bonds of the carbon atom is a hydrogen atom. bond and the other three bonds are attached to carbon atoms.
• a quaternary carbon atom means a carbon atom having four bonds bonded to an atom other than a hydrogen atom.
• atoms other than hydrogen atoms include carbon atoms, oxygen atoms, and nitrogen atoms.
• the oxygen atom and nitrogen atom described above each mean an atom that bonds to R 12 in X 11 specified in formula (1).
• one of the four bonds of the carbon atom is an oxygen atom Or, it is bonded to the nitrogen atom (the atom bonded to R12 in X11 specified in formula ( 1 )), and the other three bonds are bonded to carbon atoms.
• the carbon atom at the position not adjacent to X 11 specified in formula (1) in R 12 is a quaternary carbon atom, all four bonds of the carbon atom are bonded to the carbon atom there is
• the alkyl group having 9 to 16 carbon atoms and having only one specific carbon atom represented by R 12 is an alkyl group containing a branched structural site introduced by the specific carbon atom, and the total number of carbon atoms is Alkyl groups of 9 to 16 carbon atoms are contemplated. Note that the specific carbon atom does not correspond to a ring member atom constituting a cyclic structure.
• R 12 represents an alkyl group having 9 to 16 carbon atoms and having only one specific carbon atom selected from the group consisting of a tertiary carbon atom and a quaternary carbon atom
• a group represented by formula (1A) or formula (1B) can be mentioned.
• L 11 represents a single bond or a linear alkylene group.
• R 14 and R 15 each independently represent a linear alkyl group. However, the total number of carbon atoms of L 11 , R 14 and R 15 is 8-15.
• R 16 , R 17 and R 18 each independently represent a linear alkyl group. However, the total number of carbon atoms of L 12 , R 16 , R 17 and R 18 is 8-15.
• the number of carbon atoms is more preferably 9 to 12 from the viewpoint that the effects of the present invention are more excellent.
• the number of ring members of the cyclic structure is not particularly limited.
• the number of cyclic structures is 1 or more, preferably 1 or 2.
• the alkyl group having 9 to 16 carbon atoms and having a cyclic structure represented by R 12 may have a cyclic structure and may further have a linear or branched structure.
• R 12 represents an alkyl group having 9 to 16 carbon atoms and having a cyclic structure
• specific examples thereof include groups represented by the following formula (1C).
• ALi 11 and ALi 12 each independently represent a linear or branched alkyl group.
• ALc 11 represents a cycloalkylene group (eg, a cyclohexylene group).
• ALc 12 represents an r 1 +1-valent cycloalkane group (eg, r 1 +1-valent cyclohexane group).
• p 1 and q 1 each independently represent 0 or 1; r 1 represents 0-6; However, the total number of carbon atoms of ALi 11 , ALi 12 , ALc 11 and ALc 12 is 9-16.
• ALi 11 represents a single bond.
• ALi 12 represents a single bond.
• the r 1 +1 valent cycloalkane group intends a group formed by removing r 1 +1 hydrogen atoms from a cycloalkane ring.
• the number of carbon atoms is more preferably 9 to 12 from the viewpoint that the effects of the present invention are more excellent.
• X 11 represents *1-CO-O-*2 or *1-CO-NR 13 -*2.
• *1-CO-O-*2 is preferable because the effects of the present invention are more excellent.
• R13 represents a hydrogen atom or an alkyl group. *1 and *2 represent the binding position, and *2 represents the binding position with R12 .
• the alkyl group represented by R 13 may be linear, branched or cyclic, with linear or branched alkyl groups being preferred.
• the number of carbon atoms in the alkyl group represented by R 13 is, for example, preferably 1-12, more preferably 1-8, even more preferably 1-6.
• R 13 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms are the same as those for R A3 in the above formula (AX), and the preferred embodiments are also the same.
• R 21 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• the C 1-6 alkyl group represented by R 21 may be linear, branched, or cyclic. Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R 21 include those similar to those of R 11 in the above formula (1), and preferred embodiments are also the same.
• R 21 is preferably a hydrogen atom and a methyl group.
• R 22 represents a linear alkyl group having 9 to 16 carbon atoms.
• linear alkyl groups having 9 to 16 carbon atoms represented by R 22 include n-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n- A pentadecyl group, an n-hexadecyl group and the like can be mentioned.
• X 21 represents *1-CO-O-*2 or *1-CO-NR 23 -*2.
• *1-CO-O-*2 is preferable because the effects of the present invention are more excellent.
• R23 represents a hydrogen atom or an alkyl group. *1 and *2 represent the bonding position, and *2 represents the bonding position with R22 .
• the alkyl group represented by R 23 may be linear, branched or cyclic, with linear alkyl groups being preferred.
• the number of carbon atoms in the alkyl group represented by R 23 is, for example, preferably 1-8, more preferably 1-6. Among them, R 23 is preferably a hydrogen atom.
• the monomer (B) a commercially available product may be used, or one appropriately synthesized by a known method may be used.
• Monomer (C) is a monomer having two or more ethylenically unsaturated double bond groups.
• Monomer (C) can function as a so-called cross-linking agent.
• the ethylenically unsaturated double bond groups are as described above.
• Monomer (C) preferably does not contain a fluorine atom.
• monomer (C) examples include, but are not limited to, compounds represented by the following formula (CX). (Compound represented by the following formula (CX))
• M C1 represents an n-valent linking group.
• L C1 represents a single bond or a divalent linking group.
• R C1 represents an ethylenically unsaturated double bond group.
• n represents an integer from 2 to 120;
• the n-valent linking group represented by M C1 is not particularly limited, and examples include -O-, -NR C2 -, -CO-, -CO-NR C3 -CO-, 2- A hexavalent aromatic hydrocarbon ring group, a divalent to hexavalent aliphatic hydrocarbon ring group, an alkylene group, an oxyalkylene group, a group represented by any of the formulas (A) to (I) described below, and A group formed by removing an n-valent hydrogen atom from sugar, and the like.
• Each of R 1 C2 and R 1 C3 described above independently represents a single bond, a hydrogen atom, or an alkyl group having 1 to 6 carbon atoms.
• R C2 is a single bond
• -NR C2 - intends >N-.
• the same intention applies to the case where R C3 is a single bond.
• the alkyl group having 1 to 6 carbon atoms represented by R C2 and R C3 is preferably linear or branched.
• the number of carbon atoms in the alkylene group is more preferably 1 to 3.
• a hydrogen atom is preferable as R C2 and R C3 .
• the number of carbon atoms in the divalent to hexavalent aromatic hydrocarbon ring group represented by M C1 is preferably 6 to 10, more preferably 6.
• the aromatic hydrocarbon ring constituting the divalent to hexavalent aromatic hydrocarbon ring group include a benzene ring.
• a bivalent to hexavalent aromatic hydrocarbon ring group can be formed by removing 2 to 6 hydrogen atoms from the aromatic hydrocarbon ring.
• the number of carbon atoms in the divalent to hexavalent aliphatic hydrocarbon ring group represented by M C1 is preferably 6 to 10, more preferably 6.
• divalent to hexavalent aliphatic hydrocarbon ring groups include cyclohexane ring and tricyclodecane ring.
• a divalent to hexavalent aliphatic hydrocarbon ring group can be formed by removing 2 to 6 hydrogen atoms from the aliphatic hydrocarbon ring.
• the alkylene group represented by M C1 is preferably linear or branched.
• the number of carbon atoms in the alkylene group is, for example, preferably 1 to 50, more preferably 1 to 30, still more preferably 1 to 10, and particularly preferably 1 to 6.
• the alkylene group may have a substituent such as a hydroxyl group.
• the oxyalkylene group represented by M C1 is preferably a group represented by -(O-AL)n-.
• AL represents an alkylene group.
• n represents the average number of additions and is an integer of 1 or more.
• the number of carbon atoms in the alkylene group represented by AL is preferably 1-6, more preferably 2-4, and still more preferably 2 or 3.
• the alkylene group is preferably linear or branched, and specific examples thereof include ethylene, propylene, isopropylene, butylene and the like.
• the alkylene group may have a substituent such as a hydroxyl group.
• the upper limit of the average addition number represented by n is not particularly limited, and is preferably 50 or less, more preferably 30 or less. When n is an integer of 2 or more, multiple ALs may be the same or different.
• R S represents a hydrogen atom or a substituent.
• substituents represented by R S include, for example, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms which may be substituted with a hydroxyl group, an alkoxycarbonyl group having 2 to 7 carbon atoms, and 2 to 7 carbon atoms. 7 alkylaminocarbonyl group, and the like.
• Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group and an ethyl group.
• Examples of the alkoxycarbonyl group having 2 to 7 carbon atoms include a methoxycarbonyl group and an ethoxycarbonyl group.
• Examples of the alkoxycarbonyl group having 2 to 7 carbon atoms include a methylaminocarbonyl group and an ethylaminocarbonyl group.
• RT represents a substituent.
• AL 1 and AL 2 each independently represent an alkylene group.
• n1a and n1b each independently represent the average number of additions and are an integer of 0 or more.
• n2 represents an integer from 0 to 4;
• multiple AL 1 may be the same or different.
• multiple n2's may be the same or different.
• a plurality of RT 's may be the same or different.
• the number of carbon atoms in the alkylene group represented by AL 1 is preferably 1-6, more preferably 2-4, and even more preferably 2 or 3.
• the alkylene group is preferably linear or branched, and specific examples thereof include ethylene, propylene, isopropylidene, isopropylidene, and butylene groups. Moreover, the alkylene group may have a substituent such as a hydroxyl group.
• the upper limit of the average number of additions represented by n 1a and n 1b is not particularly limited, and is preferably 50 or less, more preferably 30 or less. Among them, the total number of n 1a and n 1b is preferably 2-30, more preferably 2-20.
• the alkylene group represented by AL2 is preferably linear or branched. The alkylene group may have a substituent such as a hydroxyl group.
• the alkylene group is preferably an alkylene group having 1 to 3 carbon atoms, such as -C(CH 3 ) 2 -. As n2, 0 is preferred.
• Substituents represented by RT include, for example, a hydroxyl group and a halogeno group such as a fluoro group or a chloro group.
• AL 3 represents an alkylene group.
• Each of n 3a to n 3d independently represents an average addition number and is an integer of 0 or more. However, the total number of n 3a to n 3d is 2 or more. In addition, multiple ALs 3 may be the same or different.
• the number of carbon atoms in the alkylene group represented by AL 3 is preferably 1-6, more preferably 2-4, and still more preferably 2 or 3.
• the alkylene group is preferably linear or branched, and specific examples thereof include ethylene, propylene, isopropylene, butylene and the like. Moreover, the alkylene group may have a substituent such as a hydroxyl group.
• the upper limit of the average number of additions represented by n 3a to n 3d is not particularly limited, and is preferably 50 or less, more preferably 30 or less, independently.
• the total number of n 3a to n 3d is preferably 2-30.
• AL 4 represents an alkylene group.
• n 4a to n 4d independently represents an average addition number and is an integer of 0 or more. However, the total number of n 4a to n 4c is 2 or more. In addition, multiple ALs 4 may be the same or different.
• R U represents a hydrogen atom or a substituent.
• the number of carbon atoms in the alkylene group represented by AL 4 is preferably 1-6, more preferably 2-4, and still more preferably 2 or 3.
• the alkylene group is preferably linear or branched, and specific examples thereof include ethylene, propylene, isopropylene, butylene and the like.
• the alkylene group may have a substituent such as a hydroxyl group.
• the upper limit of the average addition number represented by n 4a to n 4c is not particularly limited, and is preferably 50 or less, more preferably 30 or less, independently.
• the total number of n 4a to n 4c is preferably 2 to 30.
• the substituent represented by R U is not particularly limited, and examples include acryloyloxy group, methacryloyloxy group, acryloylamino group, methacryloylamino group, and R S in the above formulas (A) to (E). The same can be mentioned.
• n5 represents the average number of additions and is an integer of 1 or more.
• the substituent represented by R V is not particularly limited, and includes, for example, the same groups as R S in formulas (A) to (E) above.
• the upper limit of the average addition number represented by n5 is not particularly limited, and is preferably, for example, 50 or less, more preferably 30 or less.
• the divalent linking group represented by L C1 is not particularly limited, but examples include -O-, -CO-, -NR C4 -, and an alkylene group having 1 to 6 carbon atoms (preferably is preferably one or a combination thereof selected from the group consisting of alkylene groups having 1 to 3 carbon atoms). Moreover, the alkylene group may have a substituent such as a hydroxyl group.
• Examples of the divalent linking group represented by L C1 include -CH 2 CH 2 OCH 2 -, -OCH 2 -, -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 - , -O-, -CO-, -NR C4 -, -NR C4 -CH 2 -, -NR C4 -CH 2 CH 2 -, -NR C4 -CH 2 CH 2 CH 2 -, -NR C4 -CO- , -CO-O-, -CO-O-CH 2 -, -O-CO-CH 2 -, and -CO-NR C4 -CH 2 -.
• R C4 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• the alkyl group having 1 to 6 carbon atoms represented by R C4 is preferably linear or branched.
• the number of carbon atoms in the alkylene group is more preferably 1 to 3.
• R C4 is preferably a hydrogen atom.
• n is preferably from 2 to 100, more preferably from 2 to 60, still more preferably from 2 to 30, and particularly preferably from 2 to 10.
• Examples of the compound represented by Formula (C) are shown below, but are not limited thereto.
• Examples of compounds represented by formula (C) include 1,6-hexanediol di(meth)acrylate, glycerin tri(meth)acrylate, pentaerythritol diallyl ether, polyallyl saccharose, isopropenyl (meth)acrylate, butenyl (meth)acrylate, pentenyl (meth)acrylate, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, N-methylol (meth)acrylamide, N-methoxyalkyl (meth)acrylate and the like.
• the following compounds are also mentioned as a compound represented by Formula (C).
• a, b, c, d, l, n, and m written in parentheses each represent the average number of additions.
• the monomer (C) a commercially available product may be used, or one appropriately synthesized by a known method may be used.
• the content of repeating units derived from the monomer (A) is More than 69.5% by mass and 97.9999% by mass or less are preferable with respect to the total repeating units of the polymer, and more than 79.5% by mass and 95.9999% by mass or less are more preferable in that the effect of the present invention is more excellent. More than 82.6 mass % and 91.999 mass % or less are more preferable, and more than 85.7 mass % and 91.49 mass % or less are particularly preferable.
• the content of repeating units derived from the monomer (B) is It is preferably 2.0 to 30.0% by mass, more preferably 4.0 to 20.0% by mass, and 8.0 to 17.0% by mass, based on the total repeating units of the polymer. 0% by mass is more preferred, and 8.5 to 14.0% by mass is particularly preferred.
• the content of repeating units derived from the monomer (C) (the total content when multiple types of repeating units derived from the monomer (C) are included) is 0.0001% by mass or more and less than 0.5% by mass is preferable with respect to all repeating units of the polymer, and 0.001% by mass or more and less than 0.4% by mass is more preferable in that the effect of the present invention is more excellent, 0.01% by mass or more and less than 0.3% by mass is more preferable.
• the total content of repeating units derived from the compound represented by formula (1) and repeating units derived from the compound represented by formula (2) is It is preferably 80 to 100% by mass, more preferably 90 to 100% by mass, based on the repeating unit derived from the body (B).
• the polymer compound (hereinafter also referred to as "polymer") of the second embodiment of the present invention is a repeating unit derived from the monomer (A) having an acidic functional group and an ethylenically unsaturated double bond group (hereinafter also referred to as "repeating unit derived from the monomer (A)”); a repeating unit derived from a monomer (B) having an ethylenically unsaturated double bond group containing no fluorine atom (hereinafter also referred to as a “repeating unit derived from the monomer (B)”); a repeating unit derived from the monomer (C) having two or more ethylenically unsaturated double bond groups (hereinafter also referred to as “repeating unit derived from the monomer (C)”); hand,
• the monomer (B) contains a compound represented by formula (3) described later, The content of repeating units derived from the monomer (
• the present inventors presume as follows.
• the polymer of the present invention is neutralized with an alkaline agent while being dispersed in water, the acidic functional groups in the repeating units derived from the monomer (A) are anionized, and the electrostatic repulsion between the anions The network of polymer chains spreads (swells) due to , resulting in thickening.
• polymers exhibiting viscosity-thickening properties due to the morphology described above are added to polyelectrolytes such as magnesium L-ascorbyl phosphate in their neutralized state, resulting in the formation of acidic functional groups by the action of osmotic pressure and/or polyelectrolytes.
• the network of polymer chains tends to shrink due to cross-linking between them.
• the content of repeating units derived from the monomer (B) is adjusted to a predetermined amount, and the monomer (B) is represented by formula (3)
• the repeating unit derived from the represented compound By containing the repeating unit derived from the represented compound, the polymer chain network is less likely to shrink due to physical cross-linking such as hydrophobic interaction occurring between the side chains of the repeating unit derived from the monomer (B). As a result, it is assumed that the decrease in the thickening action is likely to be suppressed.
• the fact that the polymer of the second embodiment of the present invention can be used to form a viscous aqueous solution having a higher viscosity in the presence of a polyelectrolyte such as L-ascorbyl magnesium phosphate is referred to as "the effect of the present invention is more excellent. ” is also said.
• the polymer of the second embodiment of the invention will be described below.
• the polymer of the second embodiment has repeating units derived from the monomer (A), repeating units derived from the monomer (B), and repeating units derived from the monomer (C).
• the composition and the like of the repeating units derived from the monomer (A) and the repeating units derived from the monomer (C) in the polymer of the second embodiment are the same as those of the polymer of the first embodiment of the present invention. are the same. Only the monomer (B) will be described below.
• Monomer (B) is a monomer having an ethylenically unsaturated double bond group containing no fluorine atoms.
• the ethylenically unsaturated double bond groups are as described above.
• the monomer (B) for example, a monomer represented by the following formula (BX) is preferable.
• R B1 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• the C 1-6 alkyl group represented by R 1 B1 may be linear, branched, or cyclic.
• Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R 1 B1 include the same as R 1 A3 in the above formula (AX), and preferred embodiments are also the same.
• R B2 represents an alkyl group having 8 to 20 carbon atoms.
• the alkyl group represented by R B2 may be linear, branched, or cyclic.
• Specific examples of the alkyl group having 8 to 20 carbon atoms represented by R B2 include n-octyl group, isooctyl group, cyclooctyl group, n-nonyl group, isononyl group, cyclononyl group, n-decyl group, isodecyl group, cyclodecyl group, decahydronaphthyl group, n-undecyl group, isoundecyl group, cycloundecyl group, n-dodecyl group, isododecyl group, cyclododecyl group, tridecyl group, isotridecyl group, cyclotridecyl group, tetradecyl group,
• X B1 represents *1-CO-O-*2 or *1-CO-NR B3 -*2.
• R B3 represents a hydrogen atom or an alkyl group. *1 and *2 represent the bonding positions, and *2 represents the bonding position with RB2 .
• the alkyl group represented by R B3 may be linear, branched, or cyclic.
• the number of carbon atoms in the alkyl group represented by R B3 is, for example, preferably 1-8, more preferably 1-6.
• R B3 is preferably a hydrogen atom.
• the monomer (B) contains the compound represented by formula (3).
• the compound represented by formula (3) is described below.
• R 31 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
• the C 1-6 alkyl group represented by R 31 may be linear, branched, or cyclic. Specific examples of the alkyl group having 1 to 6 carbon atoms represented by R 31 include the same as R 3 A3 in the above formula (AX), and preferred embodiments are also the same.
• R 31 is preferably a hydrogen atom and a methyl group.
• R 32 is an alkyl group having 9 to 16 carbon atoms having at least one specific carbon atom selected from the group consisting of tertiary carbon atoms and quaternary carbon atoms, or has a cyclic structure. It represents an alkyl group having 9 to 16 carbon atoms.
• a tertiary carbon atom means a carbon atom in which one of four bonds is bonded to a hydrogen atom and three bonds are bonded to atoms other than hydrogen atoms.
• Specific examples of atoms other than hydrogen atoms include carbon atoms, oxygen atoms, and nitrogen atoms.
• the oxygen atom and nitrogen atom described above each mean an atom that bonds to R 32 in X 31 specified in formula (3).
• R 32 is a tertiary carbon atom
• one of the four bonds of the carbon atom is a hydrogen atom.
• the other one bond is bonded to an oxygen atom or a nitrogen atom (the atom bonded to R 32 in X 31 specified in formula (3)), and the other two bonds are bonded to a carbon atom Combined.
• the carbon atom at a position not adjacent to X 31 specified in formula (3) in R 32 is a tertiary carbon atom
• one of the four bonds of the carbon atom is a hydrogen atom.
• the other three bonds are attached to carbon atoms.
• a quaternary carbon atom means a carbon atom having four bonds bonded to an atom other than a hydrogen atom.
• atoms other than hydrogen atoms include carbon atoms, oxygen atoms, and nitrogen atoms.
• the oxygen atom and nitrogen atom described above each mean an atom that bonds to R 32 in X 31 specified in formula (3).
• one of the four bonds of the carbon atom is an oxygen atom Or it is bonded to the nitrogen atom (the atom bonded to R 32 in X 31 specified in formula (3)), and the other three bonds are bonded to carbon atoms.
• the carbon atom at a position not adjacent to X 31 specified in formula (3) in R 32 is a quaternary carbon atom, all four bonds of the carbon atom are bonded to the carbon atom there is
• the alkyl group having 9 to 16 carbon atoms and having at least one specific carbon atom represented by R 32 is an alkyl group containing a branched structural site introduced by the specific carbon atom, and the total number of carbon atoms is Alkyl groups of 9 to 16 carbon atoms are contemplated. Note that the specific carbon atom does not correspond to a ring member atom constituting a cyclic structure.
• R 32 represents an alkyl group having 9 to 16 carbon atoms and having at least one specific carbon atom selected from the group consisting of a tertiary carbon atom and a quaternary carbon atom
• specific examples thereof include the following A group represented by formula (3A) or formula (3B) can be mentioned.
• L 31 represents a single bond or a linear or branched alkylene group.
• R 34 and R 35 each independently represent a linear or branched alkyl group. However, the total number of carbon atoms of L 31 , R 34 and R 35 is 8-15.
• L 32 represents a single bond or a linear or branched alkylene group.
• R 36 , R 37 and R 38 each independently represent a linear or branched alkyl group. However, the total number of carbon atoms of L 32 , R 36 , R 37 and R 38 is 8-15.
• the number of carbon atoms is more preferably 9 to 12 from the viewpoint that the effects of the present invention are more excellent.
• the number of ring members of the cyclic structure is not particularly limited, and examples thereof include 6 to 10, with 6 being preferred.
• the number of cyclic structures is 1 or more, preferably 1 or 2.
• the alkyl group having 9 to 16 carbon atoms and having a cyclic structure represented by R 32 may have a cyclic structure and may further have a linear or branched structure.
• R 32 represents an alkyl group having 9 to 16 carbon atoms and having a cyclic structure
• specific examples thereof include groups represented by the following formula (3C).
• ALi 31 and ALi 32 each independently represent a linear or branched alkyl group.
• ALc 31 represents a cycloalkylene group (eg, a cyclohexylene group).
• ALc 32 represents an r 3 +1-valent cycloalkane group (eg, r 3 +1-valent cyclohexane group).
• p3 and q3 each independently represent 0 or 1 ; r 3 represents 0-6.
• the total number of carbon atoms of ALi 31 , ALi 32 , ALc 31 and ALc 32 is 9-16.
• ALi31 represents a single bond.
• q3 represents 0, ALi32 represents a single bond.
• the r 3 +1 valent cycloalkane group intends a group formed by removing r 3 +1 hydrogen atoms from a cycloalkane ring.
• the number of carbon atoms is more preferably 9 to 12 from the viewpoint that the effects of the present invention are more excellent.
• X 31 represents *1-CO-O-*2 or *1-CO-NR 33 -*2.
• *1-CO-O-*2 is preferable because the effects of the present invention are more excellent.
• R33 represents a hydrogen atom or an alkyl group. *1 and *2 represent the binding position, and *2 represents the binding position with R32 .
• the alkyl group represented by R 33 may be linear, branched or cyclic, with linear alkyl groups being preferred.
• the number of carbon atoms in the alkyl group represented by R 33 is, for example, preferably 1-12, more preferably 1-8, even more preferably 1-6.
• R 33 is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Specific examples of the alkyl group having 1 to 6 carbon atoms are the same as those for R A3 in the above formula (AX), and the preferred embodiments are also the same.
• Specific examples of the compound represented by formula (3) include compounds similar to the specific examples of the compound represented by formula (1) in the polymer of the first embodiment of the present invention, in addition to the compounds shown below. However, the invention is not limited to this.
• the monomer (B) a commercially available product may be used, or one appropriately synthesized by a known method may be used.
• the content of repeating units derived from the monomer (B) (the total content when multiple types of repeating units derived from the monomer (B) are included) is It is 8.5 to 14.0% by mass, preferably 9.0 to 14.0% by mass, based on the total repeating units of the polymer, from the viewpoint that the effects of the present invention are more excellent.
• the content of repeating units derived from the monomer (A) is More than 85.5% by mass and 91.4999% by mass or less is preferable with respect to the total repeating units of the polymer, and more than 85.5% by mass and 90.9999% by mass or less is more preferable in that the effect of the present invention is more excellent. preferable.
• the content of repeating units derived from the monomer (C) (the total content when multiple types of repeating units derived from the monomer (C) are included) is 0.0001% by mass or more and less than 0.5% by mass is preferable with respect to all repeating units of the polymer, and 0.001% by mass or more and less than 0.4% by mass is more preferable in that the effect of the present invention is more excellent, 0.01% by mass or more and less than 0.3% by mass is more preferable.
• repeating units other than repeating units derived from the compound represented by formula (3) may be contained as repeating units derived from the monomer (B),
• the content of the repeating unit derived from the compound represented by formula (3) is preferably 30 to 100% by mass, more preferably 40 to 90% by mass, based on the repeating unit derived from the monomer (B).
• the polymer compound (hereinafter also referred to as "polymer”) of the third embodiment of the present invention is a repeating unit derived from the monomer (A) having an acidic functional group and an ethylenically unsaturated double bond group (hereinafter also referred to as “repeating unit derived from the monomer (A)”);
• viscosity a represents the viscosity at 20° C. of sample liquid A prepared by the procedure described later.
• Viscosity b represents the viscosity at 20° C. of sample liquid B prepared by the procedure described later.
• the polymer of the third embodiment of the invention preferably does not contain fluorine atoms.
• a water-soluble polymer exhibiting a thickening action is typically neutralized with an alkaline agent in a state of being dispersed in water, anionizing the acidic functional group in the repeating unit derived from the monomer (A),
• the polymer chain network expands (swells) due to electrostatic repulsion between anions, resulting in thickening.
• a polyelectrolyte such as L-ascorbylmagnesium phosphate
• the polymer chain becomes soluble due to the action of osmotic pressure and/or cross-linking of the acidic functional groups by the polyelectrolyte. networks tend to shrink.
• the present inventors have recently investigated the thickening action of a polymer containing repeating units derived from monomers (A) to (C), and found that magnesium L-ascorbyl phosphate in its neutralized state
• the present inventors have discovered a polymer whose thickening effect is less likely to decrease even when 2% by mass of a polyelectrolyte such as polyelectrolyte is added.
• the fact that the polymer of the third embodiment of the present invention can be used to form a viscous aqueous solution having a higher viscosity in the presence of a polyelectrolyte such as L-ascorbyl magnesium phosphate is referred to as "the effect of the present invention is more excellent. ” is also said.
• the value represented by viscosity b/viscosity a of the polymer of the third embodiment of the present invention is preferably 5.0 or more, more preferably 8.0 or more, and 10.0 or more. It is even more preferable to have In addition, as an upper limit, it is 1,000 or less, for example.
• One aspect of the upper limit includes, for example, 300 or less, 200 or less, and 70 or less.
• the polymer of the third embodiment of the present invention preferably has a viscosity c of 500 mPa ⁇ s or more at 20° C. of the sample liquid C prepared by the procedure described later, because the effect of the present invention is more excellent. , more preferably 2,000 mPa ⁇ s or more, and even more preferably 3,000 mPa ⁇ s or more.
• the upper limit of the viscosity may vary depending on the use of the cosmetic, but for example, 300,000 mPa ⁇ s or less can be mentioned. One aspect of the upper limit is, for example, 10,000 mPa ⁇ s or less.
• Procedure for preparing sample solution A 0.5 g of the polymer of the third embodiment of the invention is dispersed in 24.5 g of deionized water to prepare 25.0 g of dispersion. Next, to the above dispersion, a 2N sodium hydroxide aqueous solution is added in such an amount that the pH of the above dispersion becomes 7.5 ⁇ 0.5, and the mixture is stirred. After stirring, deionized water is added to the resulting aqueous solution so that the total amount becomes 50 g, and the mixture is stirred to obtain a sample liquid A.
• Procedure for preparing sample solution B 0.5 g of the polymer of the third embodiment of the invention is dispersed in 24.5 g of deionized water to prepare 25.0 g of dispersion. Next, to the above dispersion, 2N aqueous sodium hydroxide solution and 1 g of magnesium L-ascorbyl phosphate n-hydrate are added in such an amount that the pH of the above dispersion becomes 7.5 ⁇ 0.5, and further , Deionized water is added so that the total amount becomes 50 g, and the mixture is stirred to obtain a sample liquid B containing L-ascorbyl magnesium phosphate n-hydrate at a concentration of 2% by mass.
• Procedure for preparing sample liquid C 0.5 g of the polymer of the third embodiment of the invention is dispersed in 24.5 g of deionized water to prepare 25.0 g of dispersion. Then, to the above dispersion, 2N sodium hydroxide aqueous solution and 1.5 g of magnesium L-ascorbyl phosphate n-hydrate were added in such an amount that the pH of the above dispersion becomes 7.5 ⁇ 0.5. Furthermore, deionized water is added so that the total amount becomes 50 g, and the mixture is stirred to obtain a sample liquid C containing L-ascorbyl magnesium phosphate n-hydrate at a concentration of 3% by mass.
• the amount of 2N sodium hydroxide aqueous solution that makes the pH of the dispersion 7.5 ⁇ 0.5 means that the pH of the dispersion during preparation (dispersion containing 0.5 g of polymer and 24.5 g of deionized water) is The theoretical amount of 2N aqueous sodium hydroxide solution required to achieve 7.5 ⁇ 0.5 is intended, and the dispersion after preparation (polymer, deionized water, and L-ascorbyl magnesium phosphate n water The amount of theoretical 2N aqueous sodium hydroxide solution required for pH of 7.5 ⁇ 0.5 in sample liquids A to C) containing hydrates is not intended.
• the acidic functional group contained in the repeating unit derived from the monofunctional (A) contained in the polymer reacts with an alkaline agent such as sodium hydroxide. It is harmonized.
• the degree of neutralization of the polymer (the degree of loss of the acidic functional group among the repeating units derived from the monofunctional (A) contained in the polymer by reaction with an alkaline agent such as sodium hydroxide (the acidity )) based on the number of moles of functional groups is typically 30 to 100 mol %, depending on the type of polymer.
• the pH of the dispersion prior to neutralization is typically less than 5.0 (eg, 2.5-3.5).
• the stirring time after adding the alkali and the stirring time after adding deionized water so that the total amount becomes 50 g are preferably, for example, 5 minutes to 30 hours.
• Stirring can also be carried out under atmospheric pressure using a kneader. Viscosities a to c measured with sample liquids A to C were measured using a B-type rotational viscometer and rotor No. 4 at a temperature of 20° C. and a rotation speed of 30 rpm.
• the polymer of the third embodiment of the present invention has repeating units derived from the monomer (A), repeating units derived from the monomer (B), and repeating units derived from the monomer (C).
• the composition and the like of the repeating unit derived from the monomer (A) and the repeating unit derived from the monomer (C) in the polymer of the third embodiment are all the same as the polymer of the first embodiment of the present invention, and are suitable The mode is also the same. Only the monomer (B) will be described below.
• the monomer (B) is one or more monomers selected from the group consisting of fluorine-free (meth)acrylate-based monomers and fluorine-free (meth)alkylacrylamide-based monomers.
• the "(meth)acrylate-based monomer” refers to acrylates, and monomers in which the carbon atom at the ⁇ -position of the acrylate is substituted with an alkyl group such as a methyl group (preferably having 1 to 6 carbon atoms), and the like. is applicable.
• (meth)alkylacrylamide-based monomer refers to alkylacrylamide, and a unit in which the carbon atom at the ⁇ -position of alkylacrylamide is substituted with an alkyl group such as a methyl group (preferably having 1 to 6 carbon atoms). Quantities and the like fall under this category.
• Monomer (B) is one or more monomers selected from the group consisting of fluorine-free (meth)acrylate-based monomers and fluorine-free (meth)alkylacrylamide-based monomers is preferably a compound represented by the formula (BX) shown in the polymer of the second embodiment of the present invention described above.
• Monomer (B) is typically a monofunctional compound containing only one ethylenically unsaturated double bond group.
• the monomer (B) is a compound different from the monomer (A).
• the repeating unit derived from the monomer (B) in the polymer of the third embodiment of the present invention preferably satisfies the following aspects in that the viscosity characteristics of the present invention can be easily obtained.
• Mode 1 Both the compound represented by the formula (1) and the compound represented by the formula (2) are included as the monomer (B).
• Aspect 2 The content of the monomer (B) is 8.5 to 14.0% by mass with respect to the total repeating units of the polymer of the third embodiment of the present invention, and the monomer (B) contains compounds represented by formula (3).
• the compound represented by formula (1) and the compound represented by formula (2) in aspect 1 are as described in the polymer of the first embodiment of the present invention above, and the preferred aspect thereof is also are the same.
• the compound represented by formula (3) in aspect 2 is as described in the polymer of the second embodiment of the present invention above, and the preferred aspects thereof are also the same.
• the content of repeating units derived from the monomer (A) is More than 69.5% by mass and 97.9999% by mass or less is preferable with respect to all repeating units of the polymer, and more than 82.6% by mass and 91.999% by mass or less is more preferable in that the effect of the present invention is more excellent. More than 85.7 mass % and 91.49 mass % or less are more preferable.
• the content of repeating units derived from the monomer (B) is It is preferably 2.0 to 30.0% by mass, more preferably 8.0 to 17.0% by mass, and 8.5 to 14.0% by mass, based on the total repeating units of the polymer. 0% by mass is more preferred.
• the content of repeating units derived from the monomer (C) (the total content when multiple types of repeating units derived from the monomer (C) are included) is 0.0001% by mass or more and less than 0.5% by mass is preferable with respect to all repeating units of the polymer, and 0.001% by mass or more and less than 0.4% by mass is more preferable in that the effect of the present invention is more excellent, 0.01% by mass or more and less than 0.3% by mass is more preferable.
• the method for producing the polymer of the first to third embodiments is not particularly limited. A method of producing by polymerization using an initiator, and the like.
• inert gases examples include nitrogen gas and argon gas.
• the solvent is not particularly limited as long as it does not react with each component of the monomers (A) to (C) and does not inhibit their polymerization reaction.
• Specific examples of the solvent include distilled water, purified water such as deionized water, water such as ultrapure water; Aliphatic hydrocarbon solvents such as ether; halogenated aliphatic hydrocarbon solvents such as dichloromethane, trichloromethane (chloroform), and tetrachloromethane (carbon tetrachloride); aromatic hydrocarbon solvents; ether solvents such as diethyl ether, diisopropyl ether, methyl-tert-butyl ether, cyclopentyl methyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, and 1,4-dioxane; Glycol ether solvents such as propylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol diethyl
• the total content of the monomer (A), the monomer (B), the monomer (C), and the solvent is The content of is preferably 50 to 99% by mass, more preferably 66 to 96% by mass.
• the polymerization initiator is not particularly limited, and includes persulfates such as persulfate, sodium persulfate, potassium persulfate, and ammonium persulfate; hydroperoxides such as hydrogen peroxide and tert-butyl hydroperoxide. ; for example, peroxydicarbonates such as di(4-tert-butylcyclohexyl) peroxydicarbonate; methylbutyronitrile), 2,2′-azobis(2,4-dimethylvaleronitrile), 2,2′-azobis(N-butyl-2-methylpropionamide), and dimethyl 2,2-azobis(2- and radical polymerization initiators such as azo compounds such as methyl propionate).
• persulfates such as persulfate, sodium persulfate, potassium persulfate, and ammonium persulfate
• hydroperoxides such as hydrogen peroxide and tert-butyl hydroperoxide.
• the amount of the polymerization initiator to be used is usually 0.001 to 1 mol % with respect to the total mol of the monomer (A), the monomer (B) and the monomer (C). 01 to 0.1 mol % is preferred.
• the polymerization in the production of the polymers of the first to third embodiments be carried out under heating conditions and/or under light (active energy ray) irradiation conditions.
• the reaction temperature for polymerization under heating conditions is, for example, usually 40 to 120°C, preferably 45 to 110°C, more preferably 50 to 105°C.
• the reaction time varies depending on the reaction temperature, it cannot be generalized, but it is usually 0.5 to 12 hours.
• the wavelength of light (active energy ray) when polymerization is carried out under light (active energy ray) irradiation conditions is not particularly limited as long as the polymerization reaction proceeds well.
• a specific example of the wavelength of such light (active energy ray) is, for example, usually 1 to 1,000 nm.
• examples of types of light (active energy rays) include X-rays, ultraviolet rays, visible rays, and infrared rays.
• the amount of light (active energy ray) irradiation (accumulated exposure amount) is not particularly limited as long as the polymerization reaction proceeds satisfactorily.
• Examples of light sources for light include high-pressure mercury lamps, and the wattage (W) is usually 10 to 100,000 W, preferably 100 to 10,000 W.
• the reaction temperature in the case of performing polymerization under light (active energy ray) irradiation conditions may be appropriately set.
• the reaction time varies depending on the wavelength of light (active energy ray) and the amount of irradiation (accumulated exposure amount), so it cannot be generalized, but it is usually 0.5 to 12 hours.
• the post-treatment method and purification method when producing the polymers of the first to third embodiments general methods that are usually performed in this field may be used.
• the post-treatment method and the purification method include, for example, a method of cooling the reaction solution after completion of the polymerization, filtering the polymer precipitated in the solution, and drying the filtered polymer. be done.
• the polymer may be purified by putting the filtered polymer into a suitable precipitant.
• the polymers of the first to third embodiments are the loss tangent tan ⁇ (loss elastic modulus G''/storage elastic modulus G' ) is preferably less than 0.6, more preferably 0.4 or less.
• the lower limit is not particularly limited, it is preferably 0.001 or more.
• Procedure for preparing sample solution D Disperse 0.5 g of the polymer of the present invention (of any of the first to third embodiments) in 24.5 g of deionized water to prepare 25.0 g of dispersion. Then, to the above dispersion, 2N sodium hydroxide aqueous solution and 1.0 g of magnesium L-ascorbyl phosphate n-hydrate were added in such an amount that the pH of the above dispersion becomes 7.5 ⁇ 0.5. Furthermore, deionized water is added so that the total amount becomes 50 g, and the mixture is stirred to obtain a sample liquid D containing L-ascorbyl magnesium phosphate n-hydrate at a concentration of 2% by mass.
• the amount of 2N sodium hydroxide aqueous solution that makes the pH of the dispersion liquid 7.5 ⁇ 0.5 is the dispersion liquid during preparation (containing 0.5 g of polymer and 24.5 g of deionized water
• the amount of theoretical 2N aqueous sodium hydroxide solution required for the pH of the dispersion) to be 7.5 ⁇ 0.5 is intended, and the dispersion after preparation (polymer, deionized water, phosphoric acid
• the amount of theoretical 2N aqueous sodium hydroxide solution required for the pH of the sample liquid D) containing L-ascorbylmagnesium n-hydrate to be 7.5 ⁇ 0.5 is not intended.
• the acidic functional group contained in the repeating unit derived from the monofunctional (A) contained in the polymer reacts with an alkaline agent such as sodium hydroxide. It is harmonized.
• the degree of neutralization of the polymer (the degree of loss of the acidic functional group among the repeating units derived from the monofunctional (A) contained in the polymer by reaction with an alkaline agent such as sodium hydroxide (the acidity )) based on the number of moles of functional groups is typically 30 to 100 mol %, depending on the type of polymer.
• the pH of the dispersion prior to neutralization is typically less than 5.0 (eg, 2.5-3.5).
• the stirring time after adding the alkali and the stirring time after adding deionized water so that the total amount becomes 50 g are preferably, for example, 5 minutes to 30 hours. Stirring can also be carried out under atmospheric pressure using a kneader.
• the viscosity d measured with the sample liquid D was measured using a B-type rotational viscometer and a rotor No. 4 at a temperature of 20° C. and a rotation speed of 30 rpm.
• the loss tangent tan ⁇ (loss elastic modulus G''/storage elastic modulus G') at a temperature of 25 ° C., a frequency of 1 Hz, and a strain of 50% of the sample liquid D was measured using a rheometer (for example, "MCR102" manufactured by Anton Paar). Using, strain dispersion measurement was performed at 25 ° C., frequency 1 Hz, strain amount in the range of 10 -2 to 10 3 %, and the storage elastic modulus G' and loss elastic modulus G obtained when the strain amount was 50% It can be obtained from the value of ''.
• the polymer of the first and second embodiments can be thickened with a small addition amount, and has excellent usability and applicability, and can provide a cosmetic having a unique touch. It is preferable to satisfy viscosity characteristics similar to those of the polymer. Specifically, it is preferable that the viscosity characteristic represented by the above-described formula (X1) is satisfied and/or the viscosity c at 20°C of the sample liquid C prepared by the above-described procedure satisfies a predetermined numerical range. .
• the polymers according to the first to third embodiments of the present invention can be used for various uses other than the cosmetic uses described below.
• Applications of the polymers of the first to third embodiments of the present invention include, for example, pharmaceuticals (antibacterial agents, antifungal agents, caries preventive agents, anticalculus agents, antiplaque agents, cataplasms, ointments, etc.).
• paints water-based paints, oil-based paints, antiseptic paints, ship bottom paints, emulsion paints, exterior wall paints, heat dissipation paints, heat shielding paints, antifouling coating agents , matting agents, etc.
• ink water-based / oil-based paint, spray ink, inkjet ink, UV curing ink
• writing instruments water-based / oil-based ballpoint pens, gel ink ballpoint pens, emulsion ballpoint pens, friction ballpoint pens, felt pens, brush pens, line markers, fluorescent pens, water-based and oil-based paints
• storage agents biners for electrodes, polymer electrolytes, electrolytic solutions, nano-titanium oxide pastes for dye-sensitized solar cells, electrode materials for fuel cells, solid polymer fuels
• Proton conductive membrane for batteries, gel electrolyte for electric double layer capacitor Proton conductive membrane for batteries, gel electrolyte for electric double layer capacitor
• the polymers of the first to third embodiments of the present invention may be included in any proportion in the compositions prepared for the applications described above. It may be More specifically, the content of the polymer of the first to third embodiments of the present invention in the composition for the above applications is preferably 0.01 to 50% by mass, more preferably 0.05 to 25% by mass. Preferably, 0.1 to 10% by mass is more preferable.
• the polymers of the first to third embodiments of the present invention are used for the above applications, they can be used in combination with organic and inorganic particles.
• the particles include resin particles, organic pigments, inorganic pigments, and extender pigments. These pigments may be used singly or in combination of two or more.
• the resin particles include polycondensation resins using acidic group-containing compounds such as polyamides, polyesters, polyarylates, polyphenylene sulfides, polysulfones, and polyethersulfones as monomer components; styrene resins having styrene as the main monomer; Acrylic resins whose main monomers are (meth)acrylic acid esters and polyacrylonitrile, olefin resins whose main monomers are olefins, vinyl chloride resins whose main monomer is vinyl chloride, and polyvinyl alcohol whose main monomer is vinyl alcohol.
• acidic group-containing compounds such as polyamides, polyesters, polyarylates, polyphenylene sulfides, polysulfones, and polyethersulfones as monomer components
• styrene resins having styrene as the main monomer styrene as the main monomer
• Acrylic resins whose main monomers are (
• resins vinyl resins such as fluorine resins containing tetrafluoroethylene as a main monomer
• particles made of other resins such as polyethers, cellulose resins, polycarbonates, polyphenylene ethers, and polyether ether ketones.
• Colored resin particles may also be used as the resin particles.
• Colored resin particles can be obtained by coloring various resin particles with a coloring material such as a dye.
• a coloring material such as a dye.
• resin particles such as amino resins, acrylic resins, styrene resins, polyester resins, and polyamide resins are colored with coloring materials such as dyes. mentioned.
• styrene-based resin particles are preferably colored with a coloring material
• styrene-acrylonitrile resin particles are colored with a coloring material, since they have good compatibility with silicone and are easy to obtain excellent stability over time. is more preferred.
• the colorant used for the colored resin particles is not particularly limited as long as the resin particles can be colored, and conventionally known dyes and pigments can be appropriately used depending on the resin particles to be used.
• dyes are particularly preferable because they tend to provide better color development.
• basic dyes, acid dyes, direct dyes, disperse dyes, solvent dyes, and the like can be preferably used.
• Examples of commercially available products containing colored resin particles include Shinroihi Color Series (manufactured by Shinroihi Co., Ltd.), Lumicol Series (manufactured by Nihon Shokuryo Kagaku Co., Ltd.), LM Series (manufactured by Fuji Pigment Co., Ltd.), and Epocolor series (manufactured by Nippon Shokubai Co., Ltd.).
• the average particle size of the colored resin particles is not particularly limited, it is preferably 0.001 to 30 ⁇ m, more preferably 0.05 to 1 ⁇ m.
• the average particle size of the colored resin particles is measured using, for example, a dynamic light scattering (DLS) particle size distribution analyzer (trade name: Nanotrac NANO-flex, manufactured by Microtrac Bell Co., Ltd.). Based on values calibrated using a sample or other measuring method, the particle diameter (D50) at 50% cumulative volume in the particle size distribution measured by the dynamic light scattering method can be measured.
• DLS dynamic light scattering
• organic pigments include azo pigments, polycyclic pigments, lake pigments, nitro pigments, nitroso pigments, and aniline black.
• azo pigments include azo lake pigments, insoluble azo pigments, condensed azo pigments, and chelate azo pigments.
• polycyclic pigments include phthalocyanine pigments, perylene pigments, perinone pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, diketopyrrolopyrrole pigments, indigo pigments, thioindigo pigments, isoindolinone pigments, and quinophthalone pigments. is mentioned.
• lake pigments examples include basic dye lake pigments and acid dye lake pigments. These organic pigments may be used singly or in combination of two or more.
• the content of the organic pigment in the composition is preferably 0.01 to 70% by mass, more preferably 0.1 to 60% by mass, and 0.5 to 50% by mass, based on the total mass of the composition. More preferred.
• inorganic pigments include composite metal oxide pigments such as titanium yellow; zirconium oxide, titanium oxide, hafnium oxide, zinc oxide, tin oxide, tungsten oxide, iron oxide, aluminum oxide, silicon oxide, molybdenum oxide, vanadium oxide, metal oxides such as cobalt oxide, copper oxide, silver oxide, indium tin oxide, indium oxide, and antimony oxide; metal sulfides such as zinc sulfide and cadmium sulfide; metal hydroxides such as aluminum hydroxide; calcium carbonate and sulfuric acid carbonates and sulfates of alkaline earth metals such as barium; barium yellow (barium chromate); cadmium red; Examples include natural inorganic pigments such as ultramarine blue and dark blue.
• the inorganic pigments may be used individually by 1 type, and may use 2 or more types together.
• the content of the inorganic pigment in the composition is preferably 0.01 to 70% by mass, more preferably 0.1 to 60% by mass, and 0.5 to 50% by mass, based on the total mass of the composition. More preferred.
• extender pigments examples include talc, silica, calcium carbonate, barium sulfate, and zinc white (zinc oxide). These extender pigments may be used singly or in combination of two or more.
• the content of the extender pigment in the composition is preferably 0.01 to 70% by mass, more preferably 0.1 to 60% by mass, more preferably 0.5 to 50% by mass, based on the total mass of the composition. More preferred. Also, two or more selected from the group consisting of inorganic pigments, organic pigments and extender pigments may be used in combination.
• the aqueous ink compositions contain the polymers of the first to third embodiments of the present invention as well as colored agents, water-soluble solvents, pigment dispersants, lubricants, pH adjusters, rust inhibitors, preservatives, thickeners, evaporation inhibitors, surfactants, light stabilizers, moisturizing agents, and resin particles. Materials used in the field may be included as appropriate.
• the content of the polymers of the first to third embodiments of the present invention is 0.05% relative to the total mass of the composition. 05 to 20 mass % is preferred.
• the water-based ink composition includes, as components other than the polymer of the first to third embodiments of the present invention, a pigment or dye (preferably 1 to 40% by mass relative to the total mass of the composition), a water-soluble solvent (preferably 1 to 40% by weight relative to the total weight of the composition), moisturizing agents (preferably 0.1 to 20% by weight relative to the total weight of the composition), preservatives (preferably the composition 0.01 to 5% by weight based on the total weight of the composition), a surfactant (preferably 0.05 to 10% by weight based on the total weight of the composition), and resin particles (preferably, the total weight of the composition 0.05 to 10% by mass based on the mass).
• a pigment or dye preferably 1 to 40% by mass relative to the total mass of the composition
• a water-soluble solvent preferably 1 to 40% by weight relative to the total weight of the composition
• moisturizing agents preferably 0.1 to 20% by weight relative to the total weight of the composition
• preservatives preferably the composition 0.01 to 5% by weight based on the total weight
• the content of the polymer of the first to third embodiments of the present invention is relative to the total weight of the water-based paint. 0.01 to 30% by mass is preferable.
• the water-based paint contains, as components other than the polymers of the first to third embodiments of the present invention, pigments or dyes (preferably 1 to 40% by mass with respect to the total weight of the water-based paint), the first -A resin component other than the polymer of the third embodiment (preferably, 1 to 40% by mass with respect to the total weight of the water-based paint), and a dispersion medium (preferably, 10 to 90% by weight with respect to the total weight of the water-based paint)
• the dispersion medium includes, for example, an organic solvent and water.When the dispersion medium contains two or more components, the above content means the total content.) It is also preferred to include
• the polymer of the first to third embodiments of the present invention when used as a binder for electrodes, it can be used as a binder for negative electrodes or positive electrodes such as primary batteries, secondary batteries, and all-solid-state batteries.
• the content thereof is the active material, conductive aid, binder, and, if necessary, the electrode mixture constituting the electrode composition. Accordingly, it is preferably 0.1 to 60% by mass with respect to 100% by mass of the total amount of the dispersing aid.
• the electrode mixture can be produced by a known method using the polymers (binders) of the first to third embodiments of the present invention.
• a specific method for producing the electrode mixture for example, an active material is added with a conductive aid, the polymer (binder) of the first to third embodiments of the present invention, a dispersing aid if necessary, and water. and a method of obtaining a paste-like slurry.
• the timing of adding water is not particularly limited, and the polymer (binder) of the first to third embodiments of the present invention may be added by dissolving it in water in advance, or the active material and conductive aid , if necessary, a dispersing aid, and the polymer (binder) of the first to third embodiments of the present invention are mixed in a solid state, and then water may be added thereto.
• the amount of water used is, for example, 40 to 2000 parts per 100 parts by mass in total of the active material, the conductive aid, and the polymer (binder) of the first to third embodiments of the present invention.
• the amount is preferably parts by mass, more preferably 50 to 1000 parts by mass.
• positive electrode active materials used in technical fields such as primary batteries, secondary batteries, and all-solid-state batteries can be used as positive electrode active materials.
• positive electrode active materials include lithium iron phosphate (LiFePO 4 ), lithium manganese phosphate (LiMnPO 4 ), lithium cobalt phosphate (LiCoPO 4 ), iron pyrophosphate (Li 2 FeP 2 O 7 ), and lithium cobaltate.
• LiCoO 2 spinel-type lithium manganate composite oxide (LiMn 2 O 4 ), lithium manganate composite oxide (LiMnO 2 ), lithium nickelate composite oxide (LiNiO 2 ), lithium niobate composite oxide (LiNbO 2 ), lithium ferrate composite oxide (LiFeO 2 ), lithium magnesium oxide composite oxide (LiMgO 2 ), lithium calcium oxide composite oxide (LiCaO 2 ), lithium cuprate composite oxide (LiCuO 2 ), lithium zincate Composite oxide (LiZnO 2 ), lithium molybdate composite oxide (LiMoO 2 ), lithium tantalate composite oxide (LiTaO 2 ), lithium tungstate composite oxide (LiWO 2 ), lithium-nickel-cobalt-aluminum composite oxide (LiNi 0.8 Co 0.15 Al 0.05 O 2 ), lithium-nickel-cobalt-manganese composite oxide ((LiNi x Co y Mn 1-x-y O 2 ), lithium
• negative electrode active materials used in technical fields such as primary batteries, secondary batteries, and all-solid-state batteries can be used as negative electrode active materials.
• the negative electrode active material for example, carbon materials, silicon (Si), tin (Sn), lithium titanate, and other materials capable of intercalating and deintercalating a large amount of lithium ions can be suitably used. Such a material can exert its effect regardless of whether it is a simple substance, an alloy, a compound, a solid solution, or a composite active material containing a silicon-containing material or a tin-containing material.
• the carbon material crystalline carbon, amorphous carbon, or the like can be used.
• Examples of crystalline carbon include amorphous, platy, flake, and spherical or fibrous graphite, such as natural or artificial graphite.
• Examples of amorphous carbon include soft carbon (easy-to-carbonize graphite) or hard carbon (hard-to-carbonize graphite), mesophase pitch carbide, and calcined coke.
• Silicon-containing materials include Si, SiOx (0.05 ⁇ x ⁇ 1.95), and any of these containing B, Mg, Ni, Ti, Mo, Co, Ca, Cr, Cu, Fe, Mn, Examples include alloys, compounds, solid solutions, etc. in which Si is partially substituted with at least one or more elements selected from the group consisting of Nb, Ta, V, W, Zn, C, N, and Sn.
• Tin-containing materials include Ni 2 Sn 4 , Mg 2 Sn, SnO x (0 ⁇ x ⁇ 2), SnO 2 , SnSiO 3 , LiSnO, and the like. These materials may be used singly or in combination of two or more. Among these, graphite is preferable as the negative electrode active material.
• the binder By using the polymer (binder) of the first to third embodiments of the present invention, even when graphite is used as the negative electrode active material, the binder exhibits sufficient binding power, and for example, a non-aqueous electrolyte secondary battery can be suitably reduced in resistance.
• the content of the polymer (binder) of the first to third embodiments of the present invention is an inorganic It is preferably 0.01 to 40% by mass with respect to the total mass of the particle-dispersed slurry composition.
• the inorganic particle-dispersed slurry composition may contain inorganic particles as a component other than the polymer of the first to third embodiments of the present invention.
• the content of inorganic particles is preferably 10 to 70% by mass with respect to the total mass of the inorganic particle-dispersed slurry composition.
• the inorganic particle-dispersed slurry composition contains a dispersion medium (preferably, 10 to 10 to the total mass of the inorganic particle-dispersed slurry composition) as a component other than the polymer and the inorganic particles of the first to third embodiments of the present invention.
• a dispersion medium preferably, 10 to 10 to the total mass of the inorganic particle-dispersed slurry composition
• the dispersion medium includes, for example, an organic solvent and water.When the dispersion medium contains two or more components, the above content means the total content.), a surfactant (preferably is 0.01 to 10% by mass relative to the total mass of the inorganic particle-dispersed slurry composition), and a plasticizer (preferably 0.01 to 20% by mass relative to the total mass of the inorganic particle-dispersed slurry composition) It is also preferable to contain one or more selected from the group consisting of
• the polymer of the first to third embodiments of the present invention when used as a binder in a conductive paste for forming an internal electrode of a laminated ceramic capacitor, the polymer of the first to third embodiments of the present invention is contained.
• the amount is preferably 0.001 to 30 mass % with respect to the total mass of the conductive paste.
• the conductive paste includes, as components other than the polymer of the first to third embodiments of the present invention, a conductive powder (preferably 10 to 90% by mass with respect to the total mass of the conductive paste), and a dispersion A medium (preferably 5 to 80% by mass relative to the total mass of the conductive paste.
• the dispersion medium include organic solvents and water.
• the polymer of the first to third embodiments of the present invention when applying the polymer of the first to third embodiments of the present invention to a polishing composition used in chemical mechanical polishing (CMP) in a semiconductor manufacturing process, the polymer of the first to third embodiments of the present invention
• the content is preferably 0.0001 to 5% by mass with respect to the total mass of the composition.
• the composition preferably contains abrasive particles as a component other than the polymer of the first to third embodiments of the present invention.
• abrasive particles include inorganic metal particles such as silica particles, ceria particles, alumina particles, zirconia particles, titania particles, diamond particles, and silicon carbide particles; fullerene derivatives, polystyrene particles, polyethylene particles, polypropylene particles, polyacrylic acid polymer compound particles such as particles, polymethacrylic acid particles, polymethyl methacrylate particles, polyacrylamide particles, polymethacrylamide particles, and polyacrylonitrile particles.
• the content of abrasive particles is preferably 0.0001 to 30% by mass with respect to the total mass of the composition.
• the content of the polymers of the first to third embodiments of the present invention is 0.0001 to 5% by weight is preferred relative to the total weight of the composition.
• the composition preferably contains abrasive particles as a component other than the polymer of the first to third embodiments of the present invention.
• abrasive particles include inorganic metal particles such as silica particles, ceria particles, alumina particles, zirconia particles, titania particles, diamond particles, and silicon carbide particles; fullerene derivatives, polystyrene particles, polyethylene particles, polypropylene particles, polyacrylic acid polymer compound particles such as particles, polymethacrylic acid particles, polymethyl methacrylate particles, polyacrylamide particles, polymethacrylamide particles, and polyacrylonitrile particles.
• the content of abrasive particles is preferably 0.0001 to 30% by mass with respect to the total mass of the composition.
• the content of the polymer of the first to third embodiments of the present invention is the total mass of the composition. 0.1 to 30% by mass is preferable.
• the composition contains, as components other than the polymer of the first to third embodiments of the present invention, a polyvinyl alcohol-based polymer and/or a water-soluble ethylene-vinyl alcohol-based copolymer having a degree of saponification of 50 to 100 mol%.
• water-soluble polymers examples include hydroxyethyl cellulose, hydroxypropyl cellulose, polyvinylpyrrolidone, water-soluble nylon, polyvinyl alcohol, and polyvinyl alcohol derivatives.
• a polyvinyl alcohol derivative which is a saponified product of polyvinyl acetate or a copolymer of vinyl acetate and olefin, is preferable.
• olefins that form copolymers with vinyl acetate include ethylene, butenediol, acrylic acid derivatives, maleic acid derivatives, and the like.
• the vinyl alcohol unit in the polyvinyl alcohol derivative corresponds to a saponified vinyl acetate unit, and the degree of saponification is preferably 50 to 100%.
• the degree of polymerization is not limited, and may be from 300 to 4,000.
• the composition may contain two or more polyvinyl alcohol derivatives with different degrees of saponification and polymerization. Cation-modified, anion-modified, carboxylic acid-modified, partially acetalized-modified, or acetoacetate-modified polyvinyl alcohol may also be used.
• these water-soluble polymers may have a photocrosslinkable group.
• a water-soluble polymer having a styrylpyridinium group or a styrylquinolinium group is preferable as the water-soluble polymer having a photocrosslinkable group.
• a water-soluble polymer having such a photocrosslinkable group is obtained, for example, by adding a formylstyrylpyridinium salt or a formylstyrylquinolinium salt to an alcoholic OH group contained in a polyvinyl alcohol-based polymer by an acetalization reaction. obtained by A method for synthesizing a water-soluble polymer having such a photocrosslinkable group is disclosed, for example, in Japanese Patent Application Laid-Open Nos. 55-023163, 55-062905, and 56-011906. Are listed.
• One or more photocrosslinkable groups may be introduced into the water-soluble polymer, if desired. This photocrosslinkable group is preferably added in an amount of 0.3 to 20 mol %, particularly 0.5 to 10 mol %, to the water-soluble polymer.
• photocrosslinking agents examples include water-soluble diazo resins and bichromates, among which water-soluble diazo resins are preferred.
• water-soluble diazo resins include sulfates, phosphates, zinc chloride double salts, and the like, which are condensates obtained by condensing diazo compounds of diphenylamines such as para-aminodiphenylamine with aldehydes such as paraformaldehyde.
• a water-soluble diazonium resin made into an anion complex and the like can be mentioned.
• ammonium dichromate, potassium dichromate, sodium dichromate, etc. are mentioned as a dichromate.
• the content of the photocrosslinking agent is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the water-soluble polymer and the water-insoluble polymer in the composition.
• the radical polymerizable compound is not particularly limited as long as it is a compound having at least one unsaturated bond with radical polymerizability.
• the monomers and oligomers described in "Photocuring Technical Data Book” (Technonet, 2000) can be mentioned.
• unsaturated bonds include allyl ether groups, allyl ester groups, vinyl ester groups, (meth)acrylate groups, and (meth)acrylamide groups.
• Sensitizers and/or photopolymerization initiators include, for example, benzoin alkyl ether, Michler's ketone, di-tert-butyl peroxide, anthraquinone derivatives such as tribromoacetophenone and tert-butylanthraquinone, and thioxanthone derivatives such as chlorothioxanthone. is mentioned.
• these photopolymerization initiators are known photopolymerization accelerators and sensitizers such as benzoic acid and tertiary amines such as p-dimethylaminobenzoic acid ethyl ester and 2-dimethylaminoethylbenzoate. etc. may be used together.
• the content of the sensitizer and/or photopolymerization initiator is preferably 0.1 to 15 parts by mass, more preferably 0.3 to 10 parts by mass, based on 100 parts by mass of the radically polymerizable compound.
• a sensitizer and/or a photoinitiator contain 2 or more types of components, the said content intends total content.
• a photoacid generator can also be used as a photoradical polymerization aid.
• photoacid generators include, but are not limited to, phenyltribromomethylsulfone, 2,4-bis(trichloromethyl)-6-p-methoxystyryl-s-triazine, and 2,6-bis(trichloromethyl).
• -polyhalogen compounds such as 4-(3,4-methylenedioxyphenyl)-1,3,5-triazine; 2-nitrobenzyl-p-toluenesulfonate, 2,6-dinitrobenzyl-p-toluenesulfonate, 10 -(p-toluenesulfonylimino)thioxanthone, 2-p-toluenesulfonyloxy-2-benzoylpropane, N-trifluoromethanesulfonyloxydiphenylmaleimide, Np-toluenesulfonyloxysuccinimide, Np-toluenesulfonyloxyphthalimide, and sulfonates such as Np-toluenesulfonyloxy-1,8-naphthalenecarboximide; benzyldiphenylsulfonium, p-methoxyphenyldiphenyl
• water-insoluble polymers examples include polyvinyl acetate, vinyl acetate/ethylene copolymer, vinyl acetate/acrylate copolymer, (meth)acrylic acid polymer, styrene/butadiene copolymer, and methyl methacrylate. /butadiene copolymer, acrylonitrile/butadiene copolymer, chloroprene polymer, isoprene polymer, polyvinyl chloride, polyvinylidene chloride, polystyrene, silicone resin, polyethylene, polyurethane, fluorine resin, and the like.
• water-insoluble polymers are polyvinyl acetate emulsions, ethylene/vinyl acetate copolymer emulsions, vinyl acetate/acrylic copolymer emulsions, ethylene/vinyl acetate/acrylic terpolymer emulsions, vinyl chloride/acetic acid obtained during the polymerization process.
• Vinyl copolymer emulsions acrylic emulsions, styrene-butadiene latex emulsions, MBR latex emulsions, acrylonitrile-butadiene rubber latex emulsions, chloroprene rubber latex emulsions, vinylidene chloride emulsions, and the like may also be included.
• an aqueous emulsion of a polymer having a crosslinked structure obtained by emulsion polymerization of an aqueous emulsion prepared from a polyfunctional (meth)acrylate with a thermal polymerization initiator or a photopolymerization initiator can also be used.
• the content of these water-insoluble polymers is preferably 0.3 to 7 parts by mass, more preferably 0.5 to 5 parts by mass, per 1 part by mass of the water-soluble polymer.
• the content of the polymers of the first to third embodiments of the present invention is the same as that of the first to third embodiments of the present invention.
• the volume ratio of Ag to the polymer of the third embodiment is preferably 1/4 to 100, more preferably 1/3 to 10, more preferably 1/2 to 2, especially Preferably, the amount is 1/1 to 2.
• the polymers of the first to third embodiments of the present invention may be used in combination with a latex or polymer dispersible in an aqueous solvent.
• the content of the polymer of the first to third embodiments of the present invention is preferably 30% by mass or less, more preferably 20% by mass or less, of the total binder component contained in the photosensitive silver halide emulsion composition. is more preferred.
• the photosensitive silver halide contained in the photosensitive silver halide emulsion composition is not particularly limited as a halogen composition, and includes silver chloride, silver chlorobromide, silver bromide, silver iodobromide, silver iodochlorobromide, and silver iodide, of which silver bromide, silver iodobromide, or silver iodide is preferred.
• the polymers of the first to third embodiments of the present invention are used as polymers for sanitary products
• the polymers of the first to third embodiments of the present invention are used as surface materials or absorbents for sanitary products.
• the content of the polymer of the first to third embodiments of the present invention is preferably 0.01 to 40% by mass with respect to 100% by mass of the surface material or absorbent.
• Examples of surface materials include nonwoven fabrics containing natural fibers such as cotton, and nonwoven fabrics containing various synthetic fibers that have been subjected to hydrophilic treatment.
• a core-sheath structure type including side-by-side type conjugate fiber using polypropylene or polyester as a core component and polyethylene as a sheath component is formed into a web by carding, and then a non-woven fabric is produced by an air-through method. (After this, hole opening treatment may be performed at predetermined locations.) is also preferable.
• a perforated sheet-like nonwoven fabric made of polyolefin such as low-density polyethylene is also preferable from the viewpoint of high liquid permeability (dry feeling).
• Absorbent materials include, for example, pulverized wood pulp called airfelt, crimped cellulose mass, absorbent gelling materials containing superabsorbent polymers such as hydrogel-forming polymer gelling agents, chemically hardened, modified, or crosslinked cellulose fibers, meltblown polymers including coforms, synthetic fibers including crimped polyester fibers, tissues including tissue wraps and tissue laminates, capillary tract fibers, absorbent foams, absorbent sponges, synthetic staple fibers, peat moss, In addition, materials equivalent to those are also included. These absorbers may be used individually by 1 type, and may use 2 or more types together.
• superabsorbent polymers such as hydrogel-forming polymer gelling agents, chemically hardened, modified, or crosslinked cellulose fibers, meltblown polymers including coforms, synthetic fibers including crimped polyester fibers, tissues including tissue wraps and tissue laminates, capillary tract fibers, absorbent foams, absorbent sponges, synthetic staple fibers, peat moss, In addition,
• Superabsorbent polymers used as absorbents include, for example, particulate or fibrous polymers. Moreover, the particulate polymer includes not only spherical ones, but also lumps, bales, and irregularly shaped ones. Specific examples of superabsorbent polymers include homopolymers of (meth)acrylic acid or alkali metal (meth)acrylates such as polyacrylic acid, polymethacrylic acid, sodium polyacrylate, and sodium polymethacrylate; For example, acrylic or methacrylic acid, maleic acid, itaconic acid, acrylamide, 2-acrylamido-2-methylpropanesulfonic acid, 2-(meth)acryloylethanesulfonic acid, 2-hydroxyethyl (meth)acrylate, or styrenesulfone Examples thereof include copolymers of (meth)acrylic acid or alkali metal (meth)acrylic acid obtained by copolymerizing comonomers such as acids.
• the method of adding the polymer of the first to third embodiments of the present invention to the surface material or absorbent body is not particularly limited, and examples thereof include methods such as coating, coating, spraying, and kneading.
• the invention also relates to thickeners comprising the polymers of the first to third embodiments of the invention.
• the polymers of the first to third embodiments of the present invention are dissolved, for example, in pure water such as deionized water, and an alkaline agent is used to obtain a polymer concentration of about 1% by mass and a pH of 5 to 11. It can be used as a thickening agent for cosmetics and the like by making it into a viscous aqueous solution of weakly acidic to alkaline agents.
• the alkaline agent is not particularly limited, and examples include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkaline earth metal hydroxides such as magnesium hydroxide and calcium hydroxide; Amines such as amines, diethanolamine, triethanolamine, 2-amino-2-methylpropanol, 2-amino-2-methyl-1,3-propanediol, diisopropanolamine, tromethamine, and cocamidomethylmonoethanolamine, etc. is mentioned.
• Sodium hydroxide is particularly preferred as the alkaline agent.
• the content of the polymer of the first to third embodiments of the present invention is not particularly limited, but the thickening effect is more excellent, For example, it is preferably 0.01 to 70% by mass, more preferably 0.05 to 50% by mass, even more preferably 0.1 to 50% by mass, based on the total mass of the thickener.
• the degree of neutralization of the polymer in the weakly acidic to alkaline thickener (viscous aqueous solution) having a pH of 5 to 11 and containing the polymer of the first to third embodiments of the present invention is, for example, 30 to 100 mol%. be.
• the degree of neutralization of the polymer means that the acidic functional groups contained in the repeating units derived from the monofunctional (A) contained in the polymer are lost by reaction with an alkaline agent such as sodium hydroxide.
• the degree (expressed in % based on the number of moles of the acid functional groups) is indicated.
• Electrolytes include, but are not limited to, magnesium L-ascorbyl phosphate.
• Types of electrolytes include, for example, acetic acid, lactic acid, gluconic acid, succinic acid, glutaric acid, adipic acid, malic acid, tartaric acid, maleic acid, fumaric acid, itaconic acid, citric acid, phthalic acid, benzoic acid, salicylic acid, and gallic acid.
• carboxylic acids such as acid, DL-pyrrolidone carboxylic acid, diethylbarbituric acid, ascorbic acid, pantothenic acid, and thioglycolic acid; amino acids such as glycine, alanine, valine, leucine, serine, glutamic acid, and aspartic acid; organic sulfonic acids such as ethanesulfonic acid, phenolsulfonic acid, p-toluenesulfonic acid, and m-xylenesulfonic acid; aminosulfonic acids such as taurine; hydrochloric acid, sulfuric acid, nitric acid, carbonic acid, and phosphoric acid acid agents such as inorganic acids such as; , cocamidomethylmonoethanolamine, trimethylamine, triethylamine, and other amines with acid agents such as the above-mentioned carboxylic acids, organic sulfonic acids, and inorganic acids; for example, basic amino acids such
• the amount of the electrolyte compounded is preferably 1 to 3,000 parts by mass, more preferably 5 to 2,000 parts by mass, based on 100 parts by mass of the polymer of the first to third embodiments of the present invention.
• the polymers of the first to third embodiments of the present invention can form viscous aqueous solutions with desired viscosities even in the presence of such polyelectrolytes.
• the thickener of the present invention may contain additives or the like that are commonly used in the fields of pharmaceuticals, agriculture and horticulture. Any of these additives can be used as long as they are known in this field.
• the thickener of the present invention has a relatively low viscosity in the absence of an electrolyte, so it can be said that it is a very useful thickener in terms of production efficiency of cosmetics and the like. That is, in the various manufacturing processes of the product, the viscosity of the solution before addition of the (polyvalent) electrolyte is low, and the process of adding the electrolyte is performed at a later stage, so that the reaction process, the transfer process, and the heating process before the addition of the electrolyte are performed. It is possible to significantly improve the working efficiency of processes, preparation processes, and the like.
• the thickener of the present invention can be used for various uses other than the cosmetics use described below.
• the thickener of the present invention can be applied, for example, to the various uses exemplified as the uses of the polymers of the first to third embodiments of the present invention in the upper section.
• Cosmetics of the present invention include lotions, milky lotions, serums, creams, cream packs, massage creams, cleansing creams, cleansing gels, facial cleansing foams, body shampoos, body lotions, styling gels, hair growth agents, and hair growth agents. , anti-dandruff agents, hair dyes, hair styling agents, eyeliners, mascara, foundations, sunscreens, moisturizers, antiperspirants, whitening agents, UV inhibitors, anti-aging agents, anti-wrinkle agents, etc. mentioned.
• the polymers of the first to third embodiments of the present invention can be used for various cosmetic applications as described above, and can be blended with known substances described later to prepare cosmetics.
• the content of the polymer of the first to third embodiments of the present invention is not particularly limited, but the thickening effect is more excellent, and From the viewpoint of better usability and applicability, for example, 0.01 to 10% by mass is preferable, 0.05 to 7.0% by mass is more preferable, and 0.1 to 4% is more preferable with respect to the total mass of the cosmetic. 0 mass % is more preferred.
• the degree of neutralization of the polymer in weakly acidic to alkaline cosmetics having a pH of 5 to 11 and containing the polymers of the first to third embodiments of the present invention is, for example, 30 to 100 mol %.
• the degree of neutralization of the polymer means that the acidic functional groups contained in the repeating units derived from the monofunctional (A) contained in the polymer are lost by reaction with an alkaline agent such as sodium hydroxide.
• the degree (expressed in % based on the number of moles of the acid functional groups) is indicated.
• Components contained in the cosmetic of the present invention, other than the polymers of the first to third embodiments, are not particularly limited as long as they do not impair the effects of the present invention, as long as they are known components blended in the cosmetic.
• water, waxes, hydrocarbon oils, fatty acids, lower alcohols, higher alcohols, polyhydric alcohols, ester oils, silicone oils, animal and vegetable oils anionic surfactants, cationic surfactants, Amphoteric surfactants, nonionic surfactants, moisturizers, water-soluble polymers, film agents, UV absorbers, sequestering agents, sugars, amino acids, organic amines, polymer emulsions, pH adjusters, buffers, Emulsifiers, dispersants, viscosity modifiers, skin nutrients, vitamins, antioxidants, antioxidant aids, colorants, fragrances, antacids, foam boosters, foam improvers, softeners, preservatives, antibacterial agents , antistatic agents, hair dyes, hair styling agents,
• waxes include, for example, beeswax, high acid value beeswax, carnauba wax, candelilla wax, gay wax, shellac, mink wax, lanolin, liquid lanolin, rice bran wax, Japanese wax, cotton wax, bayberry wax, wart wax, montan wax, kabok wax, and jojo wax. Barlow, sugarcane wax, lanolin fatty acid isopropyl, reduced lanolin, hard lanolin, and the like.
• hydrocarbon oils include liquid paraffin, liquid isoparaffin, olefin oligomer, squalane, olive squalane, rice squalane, dioctylcyclohexane, polybutene, hydrogenated polyisobutene, isododecane, isohexadecane, ozokerite, pristane, paraffin wax, and ceresin. wax, microcrystalline wax, petrolatum, polyethylene wax, Fischer-Tropsch wax, and the like.
• fatty acids include caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, behenic acid, undecylenic acid, oleic acid, linoleic acid, linolenic acid, arachidonic acid, and coconut oil fatty acids and the like.
• higher alcohols include cetyl alcohol, stearyl alcohol, isostearyl alcohol, and oleyl alcohol.
• polyhydric alcohols include glycerin, diglycerin, polyglycerin, methylgluceth, trehalose, 1,3-butylene glycol, and 1,2-pentanediol.
• ester oils include dialkyl carbonate, alkyl benzoate, octyl paramethoxycinnamate, lanolin acetate, cetyl octanoate, cetyl isooctanoate, cetyl 2-ethylhexanoate, 2-ethylhexyl isononanoate, and nonyl isononanoate.
• isononyl isononanoate isodecyl isononanoate, isotridecyl isononanoate, cetostearyl isononanoate, hexyldecyl dimethyloctanoate, octyldodecyl dimethyloctanoate, ethyl laurate, isopropyl laurate, hexyl laurate, hexyldecyl laurate, isopropyl myristate , butyl myristate, myristyl myristate, isocetyl myristate (2-hexyldecyl myristate), isostearyl myristate, 2-octyldodecyl myristate, isopropyl palmitate, octyl palmitate, 2-ethylhexyl palmitate, cetyl palmitate, 2-hexyldecy
• silicone oils include dimethylpolysiloxane, methylphenylpolysiloxane, methylcetylpolysiloxane, diphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane (cyclomethicone), dodecamethylcyclohexasiloxane, Highly polymerized methylpolysiloxane, dimethicone, highly polymerized methylphenylpolysiloxane, alkyl-modified polysiloxane, fluorine-modified polysiloxane, amino-modified polysiloxane, oleyl-modified methylpolysiloxane, trimethylsiloxysilicate, alkyl-modified silicone, alkoxy-modified silicone, fluorine Examples include modified silicone and acrylic-modified silicone.
• animal and vegetable fats and oils include avocado oil, linseed oil, almond oil, olive oil, linseed oil, sesame oil, rice germ oil, wheat germ oil, germ oil, rice bran oil, safflower oil, soybean oil, and corn oil.
• jojoba oil macadamia nut oil, cottonseed oil, coconut oil, hydrogenated coconut oil, castor oil, sunflower oil, rapeseed oil, meadowfoam oil, evening primrose oil, shea oil, tall oil, mink oil, camellia oil, persic oil, sasanqua oil, Eno oil, peanut oil, tea seed oil, kaya oil, sinagiri oil, Japanese paulownia oil, palm oil, palm kernel oil, coconut oil, peanut oil, hazelnut oil, walnut oil, grape seed oil, turtle oil, fish oil, etc. Refined oil or hardened (hydrogenated) oil.
• anionic surfactants include sodium polyoxyethylene lauryl ether sulfate, ammonium polyoxyethylene lauryl ether sulfate, triethanolamine polyoxyethylene lauryl ether sulfate, and polyoxyethylene alkyl (C12-13) ether sulfate.
• Polyoxyethylene alkyl ether sulfates such as sodium, ammonium polyoxyethylene alkyl (C12-13) ether sulfate, and triethanolamine polyoxyethylene alkyl (C12-13) ether sulfate; sodium lauryl sulfate, ammonium lauryl sulfate, and lauryl sulfate Alkyl sulfates such as triethanolamine;
• Sodium polyoxyethylene alkyl ether acetates such as sodium polyoxyethylene lauryl ether acetate, sodium polyoxyethylene tridecyl ether acetate, and sodium polyoxyethylene coconut oil fatty acid acetate; dioctyl sodium sulfosuccinate , disodium lauryl sulfosuccinate, dialkyl sulfosuccinate, disodium lauryl sulfosuccinate, polyoxyethylene alkyl (C12-13) disodium sulfosuccinate, disodium polyoxy
• nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene behenyl ether, and polyoxyethylene octyldodecyl ether.
• polyoxyethylene alkyl ethers such as polyoxyethylene decyltetradecyl ether; polyoxyethylene polyoxypropylene decyl ether, polyoxyethylene polyoxypropylene cetyl ether, and polyoxyethylene polyoxypropylene decyltetradecyl ether Oxyethylene polyoxypropylene alkyl ethers; lauric acid monoethanolamide, myristic acid monoethanolamide, palmitic acid monoethanolamide, stearic acid monoethanolamide, isostearic acid monoethanolamide, oleic acid monoethanolamide, and coconut oil fatty acid monoethanolamide Monoethanolamides such as ethanolamide; lauric acid diethanolamide, myristic acid diethanolamide, palmitic acid diethanolamide, stearic acid diethanolamide, isostearic acid diethanolamide, oleic acid diethanolamide, coconut oil fatty acid diethanolamide, and palm kernel oil fatty acid diethanolamides such as diethanolamide; isopropanolamides such as la
• alkyl group of cosides alkyldimethylamine oxides such as lauryldimethylamine oxide and stearyldimethylamine oxide; sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan tristearate, sorbitan sesquistearate, sorbitan monoisostearate, sesqui Sorbitan fatty acid esters such as sorbitan isostearate, sorbitan monooleate, sorbitan trioleate, and sorbitan sesquioleate; polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, Polyoxyethylene sorbitan stearate, polyoxyethylene sulbitan monoisostearate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, and coconut oil fatty acid polyoxyethylene sorbit
• polyoxyethylene lanolin alcohols modified polysiloxanes such as polyether-modified polysiloxane and polyvinylpyrrolidone-modified methylpolysiloxane; sugar derivatives such as maltitol hydroxy fatty acid alkyl ether, alkylated polysaccharide, and sucrose fatty acid ester, etc. mentioned.
• sugars include sugar alcohols such as sorbitol, maltitol and mannitol; monosaccharides such as glucose; mucopolysaccharides such as hyaluronic acid, sodium hyaluronate and acetylated hyaluronic acid. mentioned.
• amino acids include valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, glycine, alanine, asparagine, glutamine, serine, cysteine, cystine, tyrosine, proline, hydroxyproline, aspartic acid, and glutamic acid. , hydroxylysine, arginine, ornithine, and histidine.
• viscosity modifiers include carboxymethylcellulose, hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, carboxymethylcellulose, carboxyethylcellulose, cationized cellulose, gum arabic, carrageenan, starch, agar, mannan, guar gum.
• quince seed (quince), tamarind gum, locust bean gum, karaya gum, tragacanth gum, pectin, xanthan gum, gellan gum, alginic acid or its salts, hyaluronic acid or its salts, sodium chondroitin sulfate, collagen, casein, albumin, gelatin, chitosan, saku Synoglycan, dextran, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, acrylic acid methacrylate copolymer, polyacrylamide, polyvinyl alcohol, polyvinylpyrrolidone, highly polymerized polyethylene glycol, hydrophobically modified polyurethane, cellulose nanofiber, bentonite, silicon magnesium aluminum oxide, labonite, hectorite, and the like.
• a water-soluble compound described in JP-A-2021-123592 can be used as a viscosity modifier.
• compositions of the polymers of the first to third embodiments are shown below. Note that the following are representative examples, and are not limited to these.
• Examples of polymer compositions of the first to third embodiments the repeating unit constituting the polymer is indicated by the name of the monomer that induces the repeating unit.
• AA:IDMA:DGBA in Polymer Example 1 means that Polymer Example 1 is composed of repeating units derived from the AA, IDMA, and DGBA monomers.
• each numerical value in Polymer Example 1 indicates the content (% by mass) of each repeating unit in the polymer.
• AA acrylic acid NA: nonyl acrylate INA: isononyl acrylate IDMA: isodecyl methacrylate IDA: isodecyl acrylate LMA: lauryl methacrylate LA: lauryl acrylate SMA: stearyl methacrylate SA: stearyl acrylate ISA: isostearyl acrylate CHCHMA: 4-cyclohexylcyclohexyl Methacrylate CHCHA: 4-cyclohexylcyclohexyl acrylate DGBA: Diethylene glycol bisallyl ether P-30M: Pentaerythritol triallyl ether
• Preparation examples of Cosmetics using the polymer of the present invention include formulations shown below.
• prescription examples are not limited to the examples shown in the following table.
• ⁇ Prescription Example 1 Preparation of cream pack using Polymer Example 1> A solution A obtained by stirring and mixing components 1 to 3 in respective proportions and heating to 80 ° C., and a part of component 11 and components 4 to 6 and 9 in respective proportions by stirring and mixing 80 A solution B obtained by heating to ° C. is prepared. Next, the solution B is added dropwise to the solution A, and then emulsified by stirring. Then, a part of component 11 and component 7 are added to the resulting emulsion to adjust the viscosity to pH 8.0, a part of component 11 and component 8 are added and cooled, and finally component 11 A cream pack can be prepared by adding the rest of and ingredient 10. Table 1 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 1.
• ⁇ Prescription Example 2 Preparation of Body Shampoo Using Polymer Example 2> Components 1 to 3 were mixed in their respective proportions and heated to 80° C., then a part of component 13 and components 5 to 7, 10 and 11 previously uniformly mixed were gradually added and stirred until uniform. do. Then, a part of component 13 and component 8 are added to the obtained solution to adjust the viscosity to pH 8.5, and a part of component 13 and components 4 and 9 are added and the mixture is heated to 30°C while stirring. A body shampoo can be prepared by cooling and finally adding the remainder of component 13 and component 12. Table 2 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 2.
• ⁇ Prescription Example 3 Preparation of massage cream using Polymer Example 3> Solution A obtained by stirring and mixing components 1 to 7 in respective proportions and heating to 80 ° C., and a part of component 14 and components 8, 10 and 12 in respective proportions by stirring and mixing 80 A solution B obtained by heating to ° C. is prepared. Next, the solution B is added dropwise to the solution A, and then emulsified by stirring. Then, a portion of component 14 and component 9 are added to the resulting emulsion to adjust the viscosity to pH 8.0, and a portion of component 14 and component 11 are added and cooled.
• a massage cream can be prepared by adding the remainder of and component 13. Table 3 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 3.
• ⁇ Prescription Example 4 Preparation of lotion using Polymer Example 4> After component 1 is added to a portion of component 11 and allowed to swell, component 2 is added with stirring to adjust the pH to 8.0. Next, components 3 to 9 are added to the resulting solution, and the mixture is uniformly stirred and mixed. Finally, the rest of component 11 and component 10 are added to prepare a lotion. Table 4 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 4.
• ⁇ Formulation Example 5 Preparation of paraphenylenediamine-based oxidative hair dye using Polymer Example 5> Part of component 6, components 1 to 5, 12, 13, and 15 to 18 are stirred and mixed in respective proportions, solution A obtained by heating to 90 ° C., and components 8 to 11 in respective proportions A solution B obtained by stirring and mixing at , and heating to 90° C. is prepared. Next, the solution A and the solution B are mixed at 90°C to prepare a mixed solution, which is then cooled to 60°C. Next, component 7 is added to the obtained solution, the mixture is further cooled to 45° C., and finally the remainder of component 6 and component 14 are added to prepare a paraphenylenediamine-based oxidative hair dye. Table 5 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 5.
• ⁇ Prescription Example 6 Preparation of emulsion using Polymer Example 6> A solution A obtained by stirring and mixing components 1 to 7 in respective proportions and heating to 80 ° C., and a part of component 16 and components 8, 13, and 14 in respective proportions by stirring and mixing 80 A solution B obtained by heating to ° C. is prepared. Next, the solution B is added dropwise to the solution A, and then emulsified by stirring. Next, component 9 is added to the resulting emulsion to adjust the viscosity to pH 8.0, components 10 to 12 are added and cooled, and finally the remainder of component 16 and component 15 are added to obtain an emulsion. can be prepared. Table 6 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 6.
• a serum can be prepared by adding Table 7 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 7.
• ⁇ Prescription Example 8 Preparation of facial cleansing foam using Polymer Example 8> Components 1 to 6 are stirred and mixed in respective proportions and heated to 80°C. Next, a mixture obtained by stirring and mixing a part of component 15 and components 7 to 9, 12 and 13 in respective proportions is added to the obtained solution while being heated to 80° C. and mixed. Next, a part of component 15 and component 10 are added to the obtained solution to adjust the viscosity, and a part of component 15 and component 11 are added with stirring to adjust the pH to 8.5 and cooled, Finally, the rest of component 15 and component 14 are added to prepare a cleansing foam. Table 8 shows the name of each component and the ratio (% by mass) of each component in Polymer Example 8.
• Example 9 Preparation of Styling Gel Using Polymer Example 9> A portion of component 8 and components 1, 2, 4 and 6 are dissolved at room temperature in respective proportions, then a portion of component 8 and component 3 are added to the resulting solution to adjust the pH to 8.0, and further components Add a portion of 8 and ingredient 5 and mix. Finally, a styling gel can be prepared by adding the rest of component 8 and component 7 to the resulting solution. Table 9 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 9.
• ⁇ Formulation Example 10 Preparation of eyeliner using Polymer Example 10> A part of component 10 and components 1, 2, 4, 6, and 8 are dissolved in respective proportions at room temperature, then component 5 is added to the resulting solution to adjust the pH to 8.0, and one part of component 10 is dissolved. Part and ingredients 3 and 7 are added and mixed. Finally, an eyeliner can be prepared by adding the rest of component 10 and component 9 to the resulting solution. Table 10 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 10.
• ⁇ Prescription Example 11 Preparation of mascara using Polymer Example 11> A solution A obtained by stirring and mixing components 1 to 5 in respective proportions and heating to 80° C., and a part of component 16 and components 6, 8, 11 to 14 in respective proportions are stirred and mixed. Prepare a solution B obtained by heating to 80° C. with a Next, the solution B is added dropwise to the solution A, and then emulsified by stirring. Then, a part of component 16 and component 7 are added to the resulting emulsion to adjust the viscosity to pH 8.0, components 9 and 10 are added and cooled, and finally the remainder of component 16 and component 15 are added.
• Mascara can be prepared by adding Table 11 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 11.
• ⁇ Prescription Example 12 Preparation of cleansing gel using Polymer Example 12> A solution A obtained by stirring and mixing components 4 and 5 in their respective proportions and heating to 80 ° C., and a part of component 9 and components 1, 6 and 7 in their respective proportions and stirring and mixing 80 A solution B obtained by heating to ° C. is prepared. Next, the solution B is added dropwise to the solution A, and then emulsified by stirring. Then, a part of component 9 and component 2 are added to the resulting emulsion to adjust the viscosity to pH 8.0, a part of component 9 and component 3 are added and cooled, and finally component 9 is added.
• a cleansing gel can be prepared by adding the balance and ingredient 8. Table 12 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 12.
• ⁇ Prescription Example 13 Preparation of facial cleansing foam using Polymer Example 13> Components 1 to 6 are mixed in respective proportions and heated to 80° C. To the obtained solution, a part of component 13 and components 7, 8 and 10 are added and stirred. Next, a part of component 13 and component 9 are added to the obtained solution to adjust the viscosity to pH 8.0, and a part of component 13 and component 11 are added and cooled to 30° C. while stirring, Finally, the rest of component 13 and component 12 are added to prepare a cleansing foam. Table 13 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 13.
• ⁇ Prescription Example 14 Preparation of Cream Using Polymer Example 14> A solution A obtained by stirring and mixing components 1 to 6 in respective proportions and heating to 80° C., and a part of component 15 and components 7, 9 to 11, and 13 in respective proportions are stirred and mixed. Prepare a solution B obtained by heating to 80° C. with a Next, the solution B is added dropwise to the solution A, and then emulsified by stirring. Then, a part of component 15 and component 12 are added to the resulting emulsion to adjust the viscosity to pH 8.0, and a part of component 15 and component 8 are added and cooled. A cream can be prepared by adding the remainder and ingredient 14. Table 14 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 14.
• ⁇ Prescription Example 15 Preparation of foundation using Polymer Example 15> A solution A obtained by stirring and mixing components 1 to 5 and 11 in respective proportions and heating to 80° C., and a part of component 17 and components 12, 13 and 15 were stirred and mixed in respective proportions. Prepare a solution B obtained by heating to 80° C. with a Solution B is then added to solution A and mixed. Then, a part of component 17 and component 14 are added to the resulting solution to adjust the pH to 8.0, and a part of component 17 and components 6 to 10 are added with stirring and cooled, and finally the remainder of component 17. and component 16 can be added to prepare a foundation. Table 15 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 15.
• ⁇ Prescription Example 16 Preparation of facial cleansing foam using Polymer Example 1> Components 1 and 2 are mixed in their respective proportions and heated to 80° C. A part of component 12 and components 4 and 7 to 10 previously uniformly mixed are added to the resulting solution and stirred. Then, a part of component 12 and component 5 are added to the resulting solution to adjust the viscosity, and then a part of component 12 and components 3 and 6 are added and cooled to 30° C. while stirring. A cleansing foam can be prepared by adding the rest of component 12 and component 11. Table 16 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 16.
• ⁇ Prescription Example 17 Preparation of color treatment using Polymer Example 2> A solution A obtained by stirring and mixing components 2 to 9 and 11 in respective proportions and heating to 90° C., and a part of component 1 and components 10 and 13 to 31 in respective proportions are stirred and mixed. Prepare a solution B obtained by heating to 90° C. Next, the solution B and the solution A are mixed at 90°C to prepare a mixed solution, which is then cooled to 60°C. A color treatment can then be prepared by adding component 12 to the resulting solution, further cooling to 45° C., and finally adding the remainder of component 1 and component 32. Table 17 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 17.
• ⁇ Prescription Example 18 Preparation of amino acid-based shampoo using Polymer Example 3> Components 3 to 10 were mixed in respective proportions and heated to 80° C., and a part of component 1 and components 2, 12 to 17, and 19 to 23 previously uniformly mixed in the resulting solution were gradually added. Add and stir until uniform. Next, after cooling the obtained solution to 60° C., component 18 is added to the obtained solution to adjust the viscosity to pH 8.0, and after cooling to 30° C. with stirring, component 11 is further added, Finally, ingredients 1 and 24 are added to prepare an amino acid shampoo. Table 18 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 18.
• ⁇ Formulation Example 19 Preparation of cleansing gel using Polymer Example 4> A portion of component 10 and components 1, 5 to 8 are mixed in their respective proportions and stirred until uniform. Next, component 2 is added to the obtained solution so as to have a pH of 8.0, and the mixture is stirred until it becomes a uniform gel. Finally, a cleansing gel can be prepared by adding the rest of component 10 and component 9. Table 19 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 19.
• ⁇ Prescription Example 20 Preparation of sulfite-based shampoo using Polymer Example 5> Components 2 to 4 and 7 were mixed in respective proportions and heated to 80° C., and a part of component 1 and components 5, 8, 10 to 14 previously uniformly mixed in the resulting solution were gradually added. Add and stir until uniform. Next, add component 9 to the resulting solution to adjust the viscosity to pH 8.0, cool to 30° C. while stirring, then add component 6, and finally add the remainder of component 1 and component 15.
• a sulfite-based shampoo can be prepared with Table 20 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 20.
• ⁇ Formulation Example 21 Preparation of sunscreen using Polymer Example 6> Solution A obtained by stirring and mixing part of component 1 and components 4 to 8 in respective proportions and heating to 90° C., and stirring and mixing the remainder of component 1 and components 9 to 13 in respective proportions. and a solution B obtained by heating to 80°C. Next, the solution B is added dropwise to the solution A, and then emulsified by stirring. Then, a part of component 16 and component 2 are added to the obtained emulsion to adjust the viscosity to pH 8.0, and a part of component 16 and component 3 are added and cooled, and finally component 16 and ingredients 14 and 15 to prepare a sunscreen.
• Table 21 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 21.
• ⁇ Prescription Example 22 Preparation of deodorant gel using Polymer Example 7> After components 5 and 6 are mixed with a portion of component 15 and allowed to swell, a portion of component 15 and component 7 are added and neutralized. Next, a part of component 15 and components 8 to 13 are added and mixed, and then components 1 to 4 are added and mixed uniformly. Finally, a deodorant gel can be prepared by adding the remainder of component 15 and component 14 to the resulting solution. Table 22 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 22.
• ⁇ Prescription Example 23 Preparation of toluenediamine-based oxidative hair dye using Polymer Example 8> A part of component 24 and components 1 to 5 and 12 to 20 are stirred and mixed in respective proportions, and a solution A obtained by heating to 90° C. and components 6 to 11 are stirred and mixed in respective proportions. Prepare a solution B obtained by heating to 90° C. Next, the solution A and the solution B are mixed at 90°C to prepare a mixed solution, which is then cooled to 60°C. Next, components 22 and 23 are added to the resulting solution, the mixture is further cooled to 45° C., and finally components 21 and 24 are added to prepare a toluenediamine-based oxidative hair dye. Table 23 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 23.
• ⁇ Prescription Example 24 Preparation of thioglycolic acid-based permanent wave solution using Polymer Example 9> A part of component 5 and components 1 to 3 are mixed in their respective proportions, and the remainder of component 5 and component 4 are added to the resulting solution to adjust the pH to 8.5 and adjust the viscosity to obtain a first solution. Next, components 6 to 9 are mixed to prepare a second liquid. Then, the first liquid and the second liquid are mixed at the same ratio to prepare a thioglycolic acid-based permanent wave liquid. Table 24 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 24.
• ⁇ Prescription Example 25 Preparation of cysteamine-based curling agent using Polymer Example 10> Part of component 5 and components 1 to 3 are mixed in their respective proportions, and the remainder of component 5 and component 4 are added to the resulting solution to adjust the viscosity to pH 9.0 to prepare a first solution. Next, components 6 to 9 are mixed to prepare a second liquid. Next, a cysteamine-based curling agent is prepared by mixing the first liquid and the second liquid at the same ratio. Table 25 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 25.
• ⁇ Prescription Example 26 Preparation of gel cream using Polymer Example 11> A part of component 19 and component 1 are mixed and heated to 70 ° C., a solution of component 2 dissolved in component 3 and components 4 to 6 are added to the resulting solution and stirred, and aqueous phase A is obtained. get Separately, components 7 to 14 are mixed in respective proportions and heated to 70° C. to obtain oil phase B. Next, oil phase B and components 15 and 16 are added to water phase A and stirred, then cooled, components 17 and 18 are added, and finally the rest of component 19 is added and stirred to prepare a gel cream. can.
• Table 26 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 26.
• ⁇ Prescription Example 27 Preparation of gel cream using Polymer Example 12> Part of component 1 and components 2 to 4 are stirred and mixed in respective proportions and heated to 75°C. To the obtained solution, component 5 is added and cooled to 30°C while stirring. Next, component 6 is added and the mixture is heated to 80° C. to obtain aqueous phase A. Separately, components 7 to 11 are mixed in respective proportions and heated to 80° C. to obtain oil phase B. Next, the oil phase B is added to the aqueous phase A at 80° C. and stirred, then cooled, and a solution obtained by dissolving components 12 and 13 in a part of component 1 and components 14 to 18 are added while stirring. A cosmetic gel cream can be prepared. Table 27 shows the name of each component and the ratio (% by mass) of each component in Formulation Example 27.
• Example 1 341 parts by mass of heptane, 53.4 parts by mass of acrylic acid (manufactured by Toagosei Co., Ltd.), isodecyl methacrylate (product Name: Light Ester ID, Kyoeisha Chemical Co., Ltd.) 6.6 parts by mass, diethylene glycol bisallyl ether (Soda Aroma Co., Ltd.) 0.132 parts by mass, and dimethyl 2,2'-azobis (2- 0.106 parts by mass of methyl propionate (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) was added, and the atmosphere in the flask was replaced with nitrogen for 30 minutes.
• acrylic acid manufactured by Toagosei Co., Ltd.
• isodecyl methacrylate product Name: Light Ester ID, Kyoeisha Chemical Co., Ltd.
• diethylene glycol bisallyl ether soda Aroma Co., Ltd.
• Example 2 359 parts by mass of heptane, 30.5 parts by mass of acrylic acid, 5.4 parts by mass of octyl methacrylate obtained in Synthesis Example 1 in place of isodecyl methacrylate, and 0.5 parts by mass of diethylene glycol bisallyl ether were used.
• Polymer 2 of the present invention was obtained in the same manner as in Example 1, except that 193 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) was used and 0.062 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) was used.
• Example 3 341 parts by mass of heptane, 54.0 parts by mass of acrylic acid (manufactured by Toagosei Co., Ltd.), isodecyl methacrylate (product Name: Light Ester ID, Kyoeisha Chemical Co., Ltd.) 4.80 parts by mass, lauryl methacrylate (Mitsubishi Chemical Co., Ltd.) 1.20 parts by mass, diethylene glycol bisallyl ether (Soda Aromatic Co., Ltd.) 0.132 parts by mass and 0.108 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added, and the atmosphere in the flask was replaced with nitrogen for 30 minutes.
• acrylic acid manufactured by Toagosei Co., Ltd.
• isodecyl methacrylate product Name: Light Ester ID, Kyoeisha Chemical Co., Ltd.
• lauryl methacrylate Mitsubishi Chemical Co., Ltd.
• Example 4 54.3 parts by mass of acrylic acid, 3.30 parts by mass of isodecyl methacrylate, 2.40 parts by mass of lauryl methacrylate, and 0.117 parts by mass of diethylene glycol bisallyl ether were used. In the same manner as in Example 3, Polymer 4 of the present invention was obtained.
• Example 5 273 parts by mass of heptane, 68.1 parts by mass of butyl acetate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), acrylic acid (Toagosei Co., Ltd.) 54.3 parts by mass, isodecyl methacrylate (trade name: Light Ester ID, Kyoeisha Chemical Co., Ltd.) 3.99 parts by mass, lauryl methacrylate (Mitsubishi Chemical Co., Ltd.) 1.71 parts by mass, 0.116 parts by mass of diethylene glycol bisallyl ether (manufactured by Soda Perfumery Co., Ltd.), and dimethyl 2,2'-azobis (2-methylpropionate) (Fujifilm Wako Pure Chemical Industries, Ltd.
• Example 6 255 parts by mass of heptane, 28.3 parts by mass of butyl acetate, 44.8 parts by mass of acrylic acid, 3.83 parts by mass of isodecyl methacrylate, and 1.43 parts by mass of lauryl methacrylate
• 0.042 parts by mass of pentaerythritol triallyl ether (trade name: Neoallyl P-30M, manufactured by Osaka Soda Co., Ltd.) was used instead of diethylene glycol bisallyl ether. , to obtain polymer 6 of the invention.
• Example 7 Using 227 parts by mass of heptane, using 36.0 parts by mass of acrylic acid, using 2.00 parts by mass of isodecyl methacrylate, and using decyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) instead of lauryl methacrylate.
• Example 3 except that 2.00 parts by mass was used, 0.0871 parts by mass of diethylene glycol bisallyl ether was used, and 0.733 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) was used.
• a polymer 7 of the present invention was obtained by the same method as above.
• Example 8 1.20 parts by mass of stearyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of lauryl methacrylate, and 0.107 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) was used.
• Polymer 8 of the present invention was obtained in the same manner as in Example 3, except for the above.
• Example 9 In the same manner as in Example 3, except that 1.20 parts by mass of lauryl acrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was used instead of lauryl methacrylate, and 0.133 parts by mass of diethylene glycol bisallyl ether was used. , to obtain polymer 9 of the invention.
• Example 10 Using 450 parts by mass of heptane, using 41.3 parts by mass of acrylic acid, using 3.71 parts by mass of isodecyl methacrylate, using 0.252 parts by mass of diethylene glycol bisallyl ether, and adding dimethyl 2,2'- Polymer 10 of the present invention was obtained in the same manner as in Example 1, except that 0.081 parts by mass of azobis(2-methylpropionate) was used.
• Example 12 Using 53.1 parts by mass of acrylic acid, using 5.19 parts by mass of isodecyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of isodecyl methacrylate, using 1.71 parts by mass of lauryl methacrylate, diethylene glycol Polymer 12 of the present invention was obtained in the same manner as in Example 5, except that 0.115 parts by mass of bisallyl ether was used.
• Example 13 Using 51.9 parts by mass of acrylic acid, using 6.39 parts by mass of isodecyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of isodecyl methacrylate, using 1.71 parts by mass of lauryl methacrylate, diethylene glycol In the same manner as in Example 5, except that 0.113 parts by mass of bisallyl ether was used and 0.105 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) was used. Polymer 13 was obtained.
• Example 14 Using 50.7 parts by mass of acrylic acid, using 7.59 parts by mass of isodecyl acrylate (manufactured by Tokyo Chemical Industry Co., Ltd.) instead of isodecyl methacrylate, using 1.71 parts by mass of lauryl methacrylate, diethylene glycol In the same manner as in Example 5, except that 0.112 parts by mass of bisallyl ether was used and 0.104 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) was used. Polymer 14 was obtained.
• Comparative Example 1 38.2 parts by mass of acrylic acid was used, 6.85 parts by mass of 2-perfluorohexylethyl acrylate (manufactured by Unimatec Co., Ltd.) was used instead of isodecyl methacrylate, and 0.234 parts by mass of diethylene glycol bisallyl ether was used. Comparative polymer 1 was obtained in the same manner as in Example 1, except that 0.0754 parts by mass of dimethyl 2,2'-azobis(2-methylpropionate) was used.
• Comparative polymer 2 was Ultrez 20 (manufactured by Lubrizol), which is a commercial product.
• Viscosity was measured using a B-type rotational viscometer and rotor No. 4 at a temperature of 20° C. and a rotation speed of 30 rpm. The results are shown in Table 28 (see “viscosity b (evaluation (2))" in Table 28).
• Viscosity was measured using a B-type rotational viscometer and rotor No. 4 at a temperature of 20° C. and a rotation speed of 30 rpm. The results are shown in Table 28 (see “viscosity c (evaluation (3))" in Table 28).
• Tables 28 and 29 are shown below.
• the "viscosity b/viscosity a" column shows the value obtained by dividing the value of viscosity b by viscosity a.
• “A” means that the viscosity b/viscosity a is >3.0
• “B” means that the viscosity b/viscosity a is ⁇ 3.0 is meant.
• the content of repeating units derived from monomer (B) in the polymer was 8.0% relative to all repeating units.
• the "presence or absence of compound represented by formula (3)” column indicates whether or not the monomer (B) contains the compound represented by formula (3).
• the case where the monomer (B) contains the compound represented by formula (3) is indicated as "A", and the case where it does not is indicated as "B".
• each monomer shown in the "Structure of Polymer” column in Table 28 represents a monomer that derives the repeating unit contained in each polymer of Examples and Comparative Examples.
• each polymer in Table 28 is composed of repeating units derived from each monomer shown in the "Structure of polymer” column. Abbreviations for each monomer are as follows.
• AA acrylic acid
• OMA octyl methacrylate
• IDMA isodecyl methacrylate
• DMA decyl methacrylate
• IDA isodecyl acrylate
• LMA lauryl methacrylate (also known as dodecyl methacrylate)
• LA Lauryl acrylate (also known as dodecyl acrylate)
• SA stearyl acrylate
• FAAC6 2-perfluorohexylethyl acrylate
• DGBA diethylene glycol bisallyl ether
• P-30M pentaerythritol triallyl ether
• an electrolyte such as magnesium L-ascorbyl phosphate (concentration of magnesium L-ascorbyl phosphate: 2% by mass).
• Requirement (A1) The monomer (B) from which the repeating unit of the polymer is derived contains the compound represented by the formula (1) and the compound represented by the formula (2).
• Comparative Examples 2 to 5 when mixed with the neutralized aqueous solution and L-ascorbylmagnesium phosphate, could not maintain the viscosity before addition of an electrolyte such as L-ascorbylmagnesium phosphate.
• a composition with a viscosity suitable for cosmetics could not be prepared (that is, viscosity b/viscosity a>3.0 was not satisfied).
• the polymer of the comparative example was a composition obtained by mixing the neutralized aqueous solution and L-ascorbyl magnesium phosphate (concentration of L-ascorbyl magnesium phosphate: 2% by mass) at a temperature of 25 ° C., a frequency of 1 Hz, and a strain amount of The ratio of storage modulus to loss modulus (tan ⁇ ) at 50% was relatively high, and the sagging property did not meet the desired level in some cases. Further, regarding the polymer of the comparative example, cloudiness was also confirmed in a composition obtained by mixing the neutralized aqueous solution and L-ascorbylmagnesium phosphate (concentration of L-ascorbylmagnesium phosphate: 2% by mass). In addition, the polymer of Comparative Example 1 satisfies the desired levels of both dripping property and transparency, but corresponds to a fluorine-containing polymer.
• aqueous solution was prepared in the same manner as in Evaluation (3) except that 0.5 g (1% by mass with respect to the total amount of the solution of 50 g) was used, and the viscosity of the aqueous solution (viscosity d) was measured by the same method. .
• the results are shown in Table 30 (see “viscosity d (evaluation (7))" in each table).
• Tables 30, 31, and 32 are shown below.
• "viscosity a" is the viscosity measured in Evaluation (1) of each polymer used in Examples 3, 6, 7, 13, and Comparative Example 2. represents a.
• evaluation (1) is as stated above.
• the "viscosity d/viscosity a” column shows the value obtained by dividing the viscosity d by the viscosity a.
• the "viscosity e/viscosity a” column shows the value obtained by dividing the value of viscosity e by viscosity a.
• the "viscosity f/viscosity a” column shows the value obtained by dividing the viscosity f value by the viscosity a.
• the polymers of the examples are excellent in dispersibility due to good agitation in the neutralized aqueous solution state when not mixed with various electrolytes.
• concentration of electrolyte 1% by mass, 0.9% by mass, or 6% by mass
• the viscosity does not decrease compared to before the addition of the electrolyte
• the viscosity is optimal as a cosmetic ( That is, it is clear that the viscosity after addition of the electrolyte (viscosity d, viscosity e, or viscosity f)/viscosity before addition of the electrolyte (viscosity a)>3.0).
• the polymer of the present invention can form a viscous aqueous solution with a desired viscosity even in the presence of a polyelectrolyte such as L-ascorbylmagnesium phosphate. Therefore, the polymer of the present invention can be applied as a thickening agent to various cosmetics such as lotions, emulsions, serums, creams, cleansing creams, cleansing gels, styling gels, eyeliners, mascara, foundations, and body shampoos. can.
• Various cosmetics containing the polymer of the present invention are excellent in usability and applicability.

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• 2022
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