WO2022225046A1 - Composition suitable for gel formation and thickening characteristics - Google Patents

Composition suitable for gel formation and thickening characteristics Download PDF

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Publication number
WO2022225046A1
WO2022225046A1 PCT/JP2022/018554 JP2022018554W WO2022225046A1 WO 2022225046 A1 WO2022225046 A1 WO 2022225046A1 JP 2022018554 W JP2022018554 W JP 2022018554W WO 2022225046 A1 WO2022225046 A1 WO 2022225046A1
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group
hydrocarbon
component
hydrogen
formula
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PCT/JP2022/018554
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French (fr)
Japanese (ja)
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恒太郎 金子
功治 河合
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ミヨシ油脂株式会社
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Publication of WO2022225046A1 publication Critical patent/WO2022225046A1/en

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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/33—Heterocyclic compounds
    • A61K31/335—Heterocyclic compounds having oxygen as the only ring hetero atom, e.g. fungichromin
    • A61K31/365—Lactones
    • A61K31/375—Ascorbic acid, i.e. vitamin C; Salts thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/08—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing oxygen, e.g. ethers, acetals, ketones, quinones, aldehydes, peroxides
    • A61K47/12—Carboxylic acids; Salts or anhydrides thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/06—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite
    • A61K47/16—Organic compounds, e.g. natural or synthetic hydrocarbons, polyolefins, mineral oil, petrolatum or ozokerite containing nitrogen, e.g. nitro-, nitroso-, azo-compounds, nitriles, cyanates
    • A61K47/18—Amines; Amides; Ureas; Quaternary ammonium compounds; Amino acids; Oligopeptides having up to five amino acids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
    • A61K47/30—Macromolecular organic or inorganic compounds, e.g. inorganic polyphosphates
    • A61K47/36—Polysaccharides; Derivatives thereof, e.g. gums, starch, alginate, dextrin, hyaluronic acid, chitosan, inulin, agar or pectin
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/36—Carboxylic acids; Salts or anhydrides thereof
    • A61K8/365—Hydroxycarboxylic acids; Ketocarboxylic acids
    • 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
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/41—Amines
    • 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
    • A61K8/73—Polysaccharides
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/06—Ointments; Bases therefor; Other semi-solid forms, e.g. creams, sticks, gels
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00—Preparations for care of the skin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/10—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic with one amino group and at least two hydroxy groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C215/00—Compounds containing amino and hydroxy groups bound to the same carbon skeleton
    • C07C215/02—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton
    • C07C215/04—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated
    • C07C215/06—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic
    • C07C215/12—Compounds containing amino and hydroxy groups bound to the same carbon skeleton having hydroxy groups and amino groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being saturated and acyclic the nitrogen atom of the amino group being further bound to hydrocarbon groups substituted by hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/01—Saturated compounds having only one carboxyl group and containing hydroxy or O-metal groups
    • C07C59/08—Lactic acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/235—Saturated compounds containing more than one carboxyl group
    • C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
    • C07C59/255—Tartaric acid
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C59/00—Compounds having carboxyl groups bound to acyclic carbon atoms and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C59/235—Saturated compounds containing more than one carboxyl group
    • C07C59/245—Saturated compounds containing more than one carboxyl group containing hydroxy or O-metal groups
    • C07C59/265—Citric acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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 compositions suitable for gel-forming or thickening properties.
  • Gels are used in biomedical fields such as cosmetics, conductive materials, thickeners, biomaterials, medical sensors, drug delivery systems, and cell culture substrates, and are expected to further improve their functionality.
  • Conventional gels include a gel composed of 1-butyl-3-methylimidazolium chloride, xanthan gum, and water (Patent Document 1), a gel using gelatin (Patent Document 2), polyacrylic acid, glycerin, and water.
  • Patent Document 3 A gel (Patent Document 3) and the like consisting of
  • a gel using a polysaccharide and an ammonium salt such as that disclosed in Patent Document 1
  • a gel using a polysaccharide and an ammonium salt can be easily and inexpensively produced as a stable hydrogel without washing with an organic solvent or the like.
  • compositions suitable for gel forming or thickening properties with improved usability in practical use.
  • Gels are expected to be applied to materials such as biomaterials, cosmetics, conductive materials, medical sensors, drug delivery systems, cell culture substrates, etc. in the field of living organisms. In the field of industrial materials, it is expected to be applied to materials such as industrial sensors, adhesives, thickeners, electrodes, and conductive materials.
  • composition of the present invention contains the following components (A) and (B), a polymer compound and water as additive components, At least one of component (A) and component (B) has a hydrogen-bonding functional group.
  • composition of the present invention contains water, a polymer compound, and at least one of component (A) and component (B) having a hydrogen-bonding functional group, and is excellent in gel-forming or thickening properties, water retention, It has excellent electrical conductivity, stabilizing effect on biomaterials including enzymes, solubility and release of active ingredients, and thixotropy.
  • composition of the present invention comprises water, a polymer compound, and the components (A) and (B), wherein at least one of component (A) and component (B) has a hydrogen-bonding functional group. have.
  • the skeleton of the amine compound of component (A) is not particularly limited. , oxazoline, thiazoline, morpholine, guanidine, pyrimidine, piperazine, triazine, quinoline, indole, quinoxaline, isoxazoline, and other cyclic amines and various amino acids, among which amines and amino acids are preferred. In addition, these may contain substituents described in the section [Substituents] below.
  • amino acids examples include, but are not limited to, glycine, alanine, glutamic acid, arginine, asparagine, aspartic acid, isoleucine, glutamine, histidine, cysteine, leucine, lysine, proline, phenylalanine, threonine, serine, tryptophan, tyrosine, and methionine.
  • valine valine, sarcosine, aminobutyric acid, methylleucine, aminocaprylic acid, aminohexanoic acid, aminocapric acid, aminolauric acid, aminomyristic acid, aminopalmitic acid, aminostearic acid, norvaline, aminovaleric acid, aminoisobutyric acid, thyroxine, Creatine, ornithine, opine, theanine, tricolamine, kainate, domoic acid, ibotenic acid, acromelic acid, cystine, hydroxyproline, hydroxylysine, thyroxine, phosphoserine, desmosine, beta-alanine, citrulline, creatine, trimethylglycine, cystathionine, methylhistidine , anserine, carnosine, aminoadipic acid, omitin and the like.
  • the ammonium compounds include salts of the above amine compounds and quaternary amine compounds.
  • Component (A) preferably has a hydrogen-bonding functional group.
  • the hydrogen-bonding functional group in component (A) is not particularly limited, but examples thereof include oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups, hydrogen atoms directly bonded to nitrogen, and the like.
  • oxygen-containing groups include, but are not limited to, hydroxyl groups, carbonyl groups, ether groups, ester groups, aldehyde groups, carboxyl groups, carboxylate groups, urea groups, urethane groups, amide groups, oxazole groups, morpholine groups, carbamine groups.
  • An acid group, a carbamate group, and the like can be mentioned. Among these, a hydroxyl group and a carboxy group are preferred, and a hydroxyl group is more preferred.
  • the nitrogen-containing group is not particularly limited, but includes, for example, an amino group, a nitro group, and the like.
  • Hydrogen-bonding functional groups in component (A) include hydroxyl, carboxy, carboxylate, ester, ether, and alkoxy groups from the viewpoint of affinity for coordination and bonding to water and polymer compounds. , hydrogen atoms directly bonded to nitrogen are preferred. Among these, a hydroxyl group, a carboxy group, a carboxylate group, an ether group, an alkoxy group, and a hydrogen atom directly bonded to nitrogen are more preferable, and a hydroxyl group, a carboxy group, a carboxylate group, and a hydrogen atom directly bonded to nitrogen are more preferable.
  • a hydrogen atom directly bonded to a hydroxyl group, a carboxy group, or nitrogen is particularly preferred, and a hydrogen atom directly bonded to a hydroxyl group or nitrogen is most preferred.
  • a preferred example of the substituent having a hydrogen-bonding functional group is a hydrocarbon group having a hydrogen-bonding functional group.
  • substituents having a hydrogen-bonding functional group include a hydrocarbon group containing a hydroxy group (hydroxy hydrocarbon group), a hydrocarbon group containing a carboxy group (carboxy hydrocarbon group), and a hydrocarbon group containing a hydroxy group and a carboxy group.
  • Examples include a hydrogen group (hydroxycarboxy hydrocarbon group), a hydrocarbon group containing a carboxylate group, a hydrocarbon group containing an ester group, a hydrocarbon group containing an ether group, a hydrocarbon group containing an alkoxy group, and the like. Among these, a hydroxy hydrocarbon group is preferred.
  • the hydrocarbon group includes a saturated or unsaturated aliphatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc., and a hydrocarbon group combining them. Common hydrocarbon groups can be used as these hydrocarbon groups. Among the above hydrocarbon groups, saturated aliphatic hydrocarbon groups are preferred. Examples of the hydrocarbon group include those described in the section [Hydrocarbon group] below.
  • the hydroxy hydrocarbon group has one or more hydroxyl groups, and the hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 12 carbon atoms. 1 to 6 linear or branched chains, and the hydrocarbon moiety may contain an oxygen atom.
  • the carboxy hydrocarbon group has one or more carboxy groups, and the hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, particularly preferably carbon atoms. It is linear or branched with numbers 1 to 6, and the hydrocarbon portion may contain an oxygen atom.
  • the hydroxycarboxy hydrocarbon group has one or more hydroxyl groups and one or more carboxy groups, and the hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, It is particularly preferably linear or branched having 1 to 6 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom.
  • the hydrocarbon group containing the carboxylate group has one or more carboxylate groups, and each hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and still more preferably 1 to 1 carbon atoms. 12, particularly preferably straight or branched having 1 to 6 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom.
  • the hydrocarbon group containing an ester group has one or more ester groups, and each hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, It is particularly preferably linear or branched having 1 to 6 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom.
  • the hydrocarbon group containing an ether group has one or more ether groups, and each hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, It is particularly preferably linear or branched having 1 to 6 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom.
  • the hydrocarbon group containing the above alkoxy group has one or more alkoxy groups, and each hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, It is particularly preferably linear or branched having 1 to 6 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom.
  • the hydrocarbon portion contains an oxygen atom
  • the oxygen atom forms, for example, an ether bond, a carbonyl group, an ester bond, an amide bond, a urea bond, or a urethane bond with the hydrocarbon portion.
  • the hydrocarbon moiety contains an oxygen atom means that the hydrocarbon moiety is interrupted by a group that may also contain a heteroatom such as a nitrogen atom as an atomic group containing an oxygen atom, or the group is Including at the ends or when a hydrogen atom is substituted in the group.
  • hydroxy hydrocarbon group a saturated or unsaturated aliphatic hydrocarbon group having one or more hydroxy groups, a saturated or unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon combination thereof groups.
  • the number of hydroxyl groups in the hydroxy hydrocarbon group is preferably 2 or more, more preferably 3 or more.
  • a hydroxy saturated aliphatic hydrocarbon group is preferable, a saturated aliphatic hydrocarbon group having one hydroxy group (monohydroxyalkyl group, etc.), a saturated aliphatic hydrocarbon group having two or more hydroxy groups (polyhydroxyalkyl group, etc.) ), a saturated aliphatic hydrocarbon group having 3 or more hydroxy groups (polyhydroxyalkyl group, etc.) is preferable, a saturated aliphatic hydrocarbon group having 2 or more hydroxy groups (polyhydroxyalkyl group, etc.), 3 hydroxy groups more preferably saturated aliphatic hydrocarbon groups having 3 or more hydroxy groups (polyhydroxyalkyl groups, etc.), more preferably saturated aliphatic hydrocarbon groups having 3 or more hydroxy groups (polyhydroxyalkyl groups, etc.), these are hydrocarbon moieties may contain the above oxygen-containing groups.
  • the saturated aliphatic hydrocarbon group having one hydroxy group is not particularly limited, and examples thereof include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropane- 1-yl group, 2-hydroxypropan-1-yl group, 3-hydroxypropan-1-yl group, 1-hydroxypropan-2-yl group, 2-hydroxypropan-2-yl group, 2-hydroxymethylpropane -2-yl group, 2-hydroxyethylpropan-2-yl group, 1-hydroxybutan-1-yl group, 2-hydroxybutan-1-yl group, 3-hydroxybutan-1-yl group, 4-hydroxy butan-1-yl group, 1-hydroxy-2-methylpropan-1-yl group, 2-hydroxy-2-methylpropan-1-yl group, 3-hydroxy-2-methylpropan-1-yl group, 1 -hydroxybutan-2-yl group, 2-hydroxybutan-2-yl group, 3-hydroxybutan-2-yl group, 4-hydroxy
  • the saturated aliphatic hydrocarbon group having two or more hydroxy groups is not particularly limited, and examples thereof include di-, tri-, tetra-, penta-, hexa-, hepta-, and octahydroxyalkyl groups. be done.
  • dihydroxyethyl groups such as 1,2-dihydroxyethyl group; 1,2-dihydroxypropan-1-yl group, 2,3-dihydroxypropan-1-yl group dihydroxypropan-1-yl group; 1,2-dihydroxypropan-2-yl group, dihydroxypropan-2-yl group such as 1,3-dihydroxypropan-2-yl group; trihydroxypropan-1-yl group; trihydroxypropan-2-yl group; trihydroxypropan-1-yl group; trihydroxypropan-1-yl group; trihydroxypropan-2-yl group; 1,2-dihydroxybutan-1-yl group, 1,3-dihydroxybutan-1-yl group , 1,4-dihydroxybutan-1-yl group, 2,3-dihydroxybutan-1-yl group, 2,4-dihydroxybutan-1-yl group, 3,4-dihydroxybutan-1-yl group, etc.
  • dihydroxyethyl groups such as 1,2-dihydroxyethyl group; 1,2-
  • dihydroxybutan-1-yl group 1,2,3 trihydroxybutan-1-yl group, 1,2,4 trihydroxybutan-1-yl group, 1,3,4 trihydroxybutan-1-yl group, trihydroxybutan-1-yl group such as 2,3,4 trihydroxybutan-1-yl group; tetrahydroxybutan-1-yl group; 1,2-dihydroxy-2-methylpropan-1-yl group, 1 , 3-dihydroxy-2-methylpropan-1-yl group, dihydroxy-2-methylpropan-1-yl group such as 2,3-dihydroxy-2-methylpropan-1-yl group; trihydroxy-2-methyl Propan-1-yl group; Tetrahydroxy-2-methylpropan-1-yl group; 1,2-dihydroxybutan-2-yl group, 1,3-dihydroxybutan-2-yl group, 1,4-dihydroxybutane -2-yl group, 2,3-dihydroxybutan-2-yl group, 2,4-dihydroxybutan-2-yl group, 3,4-dihydroxy
  • the polyhydroxy saturated aliphatic hydrocarbon group preferably has 2 to 8 hydroxyl groups, more preferably 2 to 6 hydroxyl groups.
  • the alkyl group preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, and 1 to 6 carbon atoms. is particularly preferred.
  • a branched polyhydroxy saturated aliphatic hydrocarbon group represented by the following formula is exemplified as a preferable one.
  • R 7 is a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms), or a linear alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) indicates a hydroxyalkyl group.
  • the group of the above formula is not particularly limited, but examples include 1,2-dihydroxypropan-1-yl group, 2,3-dihydroxypropan-1-yl group, 1,2-dihydroxypropan-2-yl group, 1,3-dihydroxypropan-2-yl group, trihydroxypropan-1-yl group, trihydroxypropan-2-yl group, trihydroxypropan-1-yl group, trihydroxypropan-2-yl group, 1, 2-dihydroxybutan-1-yl group, 1,3-dihydroxybutan-1-yl group, 1,4-dihydroxybutan-1-yl group, 2,3-dihydroxybutan-1-yl group, 2,4- Dihydroxybutan-1-yl group, 3,4-dihydroxybutan-1-yl group, 1,2,3-trihydroxybutan-1-yl group, 1,2,4-trihydroxybutan-1-yl group 1,3 ,4-trihydroxybutan-1-yl group, 2,3,4-trihydroxybutan-1-yl group, tetrahydroxybutan
  • 2,3-dihydroxypropan-1-yl group, 1,3-dihydroxypropan-2-yl group, 1,3-dihydroxy-2-ethylpropane-2- yl group, 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group, and pentahydroxyhexan-1-yl group are preferred, and 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group is more preferred.
  • a saturated or unsaturated aliphatic hydrocarbon group having one or more carboxy groups, a saturated or unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon combination thereof groups.
  • a monocarboxyalkyl group and a polycarboxyalkyl group, in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group) are preferred, and specific examples thereof include the mono-, di-, tri-, Examples thereof include tetra-, penta-, hexa-, hepta- or octahydroxyalkyl groups in which the hydroxyl group is substituted with a carboxy group (the alkyl moiety may contain an oxygen atom).
  • Monocarboxy saturated aliphatic hydrocarbon groups and polycarboxy saturated aliphatic hydrocarbon groups preferably have 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and even more preferably 1 to 12 carbon atoms. , and those having 1 to 6 carbon atoms are particularly preferred.
  • the hydroxycarboxy hydrocarbon group includes saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups each having one or more hydroxy groups and one or more carboxyl groups, and also and a hydrocarbon group in which Among them, those in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group) are preferable, and are not particularly limited. Examples thereof include alkyl groups in which a portion of the hydroxyl group is substituted with a carboxy group (the alkyl moiety may contain an oxygen atom).
  • the hydroxycarboxy saturated aliphatic hydrocarbon group preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, and 1 to 6 carbon atoms. Especially preferred.
  • hydrocarbon group containing an ester group examples include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups having one or more ester groups, and combinations thereof. and hydrocarbon groups. Among them, those in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group) are preferred, and are not particularly limited. is mentioned.
  • a hydrocarbon group containing an ester group preferably has 1 to 22 carbon atoms.
  • the hydrocarbon group containing an ether group includes a saturated or unsaturated aliphatic hydrocarbon group having one or more ether groups, a saturated or unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. and hydrocarbon groups.
  • hydrocarbon groups those in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group) are preferred and not particularly limited, but examples thereof include those in which an alkyl group having 2 to 22 carbon atoms is interrupted by an oxygen atom. .
  • the hydrocarbon group containing the alkoxy group includes a saturated or unsaturated aliphatic hydrocarbon group having one or more alkoxy groups, a saturated or unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. and hydrocarbon groups.
  • hydrocarbon groups those in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group) are preferable and not particularly limited, but an alkyl ether group is bonded to the base end of an alkyl group having a total of 1 to 22 carbon atoms, or Examples thereof include those in which hydrogen atoms of hydrocarbon groups are substituted with alkyl ether groups.
  • hydrocarbon group containing a carboxylate group examples include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, and aromatic hydrocarbon groups having one or more carboxylate groups. and a hydrocarbon group in which Among them, those in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group) are preferred, and are not particularly limited. Examples include those in which a hydrogen atom of a hydrocarbon group is substituted with a carboxylate group.
  • substituents other than hydrogen-bonding functional groups in component (A) and cations derived from component (A) include organic groups.
  • the organic group essentially has a carbon atom and may additionally contain at least one selected from a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a halogen atom.
  • the atomic group contained in the organic group is not particularly limited, examples thereof include hydrocarbon groups, heterocyclic groups, and substituents described in the section [Substituents] below.
  • the substituents described in the "Substituents" column below replace the hydrogen atoms of the hydrocarbon group, interrupt the hydrocarbon group, are included at the base end of the hydrocarbon group, or are combined with the aromatic hydrocarbon group.
  • Groups forming condensed rings are also included.
  • the number of carbon atoms in the organic group is not particularly limited, it is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4 in terms of affinity with water and polymer compounds.
  • the hydrocarbon group is not particularly limited, and examples include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof.
  • a hydrocarbon group etc. are mentioned.
  • it may be monovalent or polyvalent, and examples of monovalent saturated or unsaturated aliphatic hydrocarbon groups include, but are not limited to, linear or branched alkyl groups, alkenyl groups and alkynyl groups. etc.
  • Alkyl groups include linear or branched chains, but are not particularly limited.
  • Alkenyl groups include linear or branched chains, and are not particularly limited, but examples include vinyl, prop-1-en-1-yl, allyl, isopropenyl, but-1-en-1-yl. group, but-2-en-1-yl group, but-3-en-1-yl group, 2-methylprop-2-en-1-yl group, 1-methylprop-2-en-1-yl group, pent-1-en-1-yl group, pent-2-en-1-yl group, pent-3-en-1-yl group, pent-4-en-1-yl group, 3-methylbut-2- En-1-yl group, 3-methylbut-3-en-1-yl group, hex-1-en-1-yl group, hex-2-en-1-yl group, hex-3-en-1- yl group, hex-4-en-1-yl group, hex-5-en-1-yl group, 4-methylpent-3-en-1-yl group, 4-methylpent-3-en-1-yl group,
  • Alkynyl groups include straight or branched chains, and are not particularly limited and include, but are not limited to, ethynyl, prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn- 1-yl group, but-3-yn-1-yl group, 1-methylprop-2-yn-1-yl group, pent-1-yn-1-yl group, pent-4-yn-1-yl group , hex-1-yn-1-yl group, hex-5-yn-1-yl group, hept-1-yn-1-yl group, hept-6-yn-1-yl group, octa-1-yne -1-yl group, octa-7-yn-1-yl group, non-1-yn-1-yl group, non-8-yn-1-yl group, deca-1-yn-1-yl group, Dec-9-yn-1-yl group, undec-1-yn-1-y
  • the saturated or unsaturated alicyclic hydrocarbon group is preferably a saturated alicyclic hydrocarbon group and is not particularly limited.
  • monovalent groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo A heptyl group, a cyclooctyl group, and a group containing an alicyclic residue such as those residues are included.
  • the aromatic hydrocarbon group is not particularly limited, but includes, for example, a phenyl group, a naphthalene group, an anthracene group, and groups containing aromatic ring residues such as residues thereof.
  • a condensed ring may be formed together with the substituents described in [Substituent] below.
  • Examples of monovalent aromatic hydrocarbon groups include, but are not limited to, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5 -dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4-propyl phenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4-pentylphenyl group, 4-tert-pentylphenyl group, 2,4-bis(4-tert-pentyl)phenyl group, 1,1,3,3-tetramethylbutylphenyl group, 2-methyl-5-tert-butylphenyl group, 4-pentylphenyl group, 4-hexylphenyl group, 4-hepty
  • divalent hydrocarbon groups examples include groups obtained by removing one hydrogen atom from the above groups.
  • substituents examples include, but are not limited to, hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups, and halogens. Substituents also include groups to which these substituents are bonded.
  • hydrocarbon group examples include those listed in the above [hydrocarbon group].
  • oxygen-containing groups include, but are not limited to, hydroxyl groups, alkoxy groups, acetoxy groups, acetyl groups, aldehyde groups, carboxyl groups, carboxylate groups, urea groups, urethane groups, amide groups, imide groups, ether groups, carbonyl group, ester group, oxazole group, morpholine group, carbamate group, carbamoyl group, polyoxyethylene group, tocopheryl group, chroman group, dihydropyran group, glyceryl group, glyceryl ether group and the like.
  • nitrogen-containing groups include, but are not limited to, cyano groups, cyanato groups, isocyanate groups, nitro groups, nitroalkyl groups, amide groups, urea groups, urethane groups, imide groups, carbodiimide groups, azo groups, pyridine groups, imidazole group, primary amino group, secondary amino group, tertiary amino group, quaternary ammonium group, aminoalkyl group and the like.
  • sulfur-containing groups include, but are not limited to, sulfuric acid group, sulfonyl group, sulfonic acid group, mercapto group, thioether group, thiocarbonyl group, thiourea group, thiocarboxy group, thiocarboxylate group, dithiocarboxy group, Dithiocarboxylate group, sulfate ester, thiophene group, thiazole group, thiol group, sulfo group, sulfide group, disulfide group, thioester group, thioamide group, thiocarbamate group, dithiocarbamate group and esters thereof.
  • Examples of phosphorus-containing groups include, but are not limited to, phosphoric acid group, phosphorous acid group, phosphonic acid group, phosphinic acid group, phosphonous acid group, phosphinic acid group, pyrophosphate group, phosphate ester group, Phosphate ester group, phosphonate ester group, pyrophosphate group, ester group thereof and the like.
  • Halogen includes fluorine, chlorine, bromine, and iodine.
  • Examples of the organic group include hydrocarbon groups that may have a substituent and whose hydrocarbon portion may contain an oxygen atom.
  • hydrocarbon group the contents described in the above [Hydrocarbon group] column are referred to.
  • the hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group (such as an alkyl group).
  • the saturated aliphatic hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms, from the viewpoint of affinity with water.
  • the hydrocarbon group may have a substituent, and the substituent is not particularly limited, but includes, for example, those described in the above [Substituent] column.
  • substituents those having an oxygen-containing group are preferred, and among these, a hydroxyl group, a carboxyl group, a carboxylate group, an ester group, an ether group, and an alkoxy group are preferred.
  • hydroxyl group, carboxy group, carboxylate group, ether group, and alkoxy group are more preferable, hydroxyl group, carboxy group, and carboxylate group are more preferable, hydroxyl group and carboxylate group are particularly preferable, and hydroxyl group is particularly preferable.
  • the hydrocarbon moiety may contain an oxygen atom.
  • the hydrocarbon moiety contains the oxygen-containing group described above, for example, an ether bond, a carbonyl group, a hydroxyl group, a carboxylate group, an ester bond, an amide bond, a urea Forms or contains a bond or a urethane bond. Therefore, in the present invention, "the hydrocarbon moiety contains an oxygen atom” means that the hydrocarbon moiety is interrupted by a group that may also contain a heteroatom such as a nitrogen atom as an atomic group containing an oxygen atom, or the group is Including at the ends or when a hydrogen atom is substituted in the group.
  • Component (A) has at least one hydrogen-bonding functional group (hydroxyl and carboxy It is one of preferred embodiments to have a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) having a hydroxyl group is more preferable).
  • one or more of the moieties (atoms contained in the basic skeleton chemical structure, such as nitrogen moieties and carbon moieties that form a ring together with nitrogen) to which functional groups can be introduced in component (A) are hydrogen It is preferably substituted with a hydrocarbon group having a bonding functional group, and if there are other sites, they are each independently a hydrogen atom or a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group). preferably substituted with an organic group such as a hydrogen group). It is also preferred that the site is composed only of hydrogen atoms directly bonded to nitrogen.
  • the amine of component (A) is an amine composed only of a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) having a hydrogen-bonding functional group and a hydrogen atom directly bonded to nitrogen; Hydrocarbon groups having hydrogen-bonding functional groups (more preferably saturated aliphatic hydrocarbon groups) and amines composed only of hydrocarbon groups (more preferably saturated aliphatic hydrocarbon groups), having hydrogen-bonding functional groups Amines composed only of hydrocarbon groups (more preferably saturated aliphatic hydrocarbon groups), amines composed only of hydrogen atoms are preferred, and hydrocarbon groups having hydrogen-bonding functional groups (more preferably saturated aliphatic hydrocarbon groups) are preferred.
  • Hydrogen groups (more preferably saturated aliphatic hydrocarbon groups) and amines composed only of hydrogen atoms directly bonded to nitrogen, hydrocarbon groups having hydrogen-bonding functional groups (more preferably saturated aliphatic hydrocarbon groups) and An amine composed only of a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) is more preferable, and a hydrocarbon group having a hydrogen-bonding functional group (more preferably a saturated aliphatic hydrocarbon group) and a direct bond to nitrogen Amines composed only of hydrogen atoms are particularly preferred.
  • the hydrogen-bonding functional group is preferably a hydroxyl group.
  • the amine of component (A) has 3 hydroxyl groups.
  • component (A) has a monohydroxyalkyl group
  • triethanolamine and diethanolamine are preferred, and triethanolamine is particularly preferred.
  • component (A) is specified in the Standards for Quasi-drug Ingredients (Quasi-drugs Ingredients), Standards for Quasi-drug Additives, Japanese Pharmacopoeia (Japanese Pharmacopoeia), Japanese Pharmacopoeia Drugs It is preferable to use compounds listed in the Standards for Quasi-Drugs (Regulations), Pharmaceutical Additives Standards (Medicine Additives), and Food Additives Standards (Food Additives) as raw materials (for example, acids and bases).
  • Such compounds include, but are not limited to, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-methyl-1- Propanol, 2-amino-2-methyl-1,3-propanediol, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-acetamidoethanolamine, N-lauryldiethanolamine, dimethyloctadecylamine are preferred, from the viewpoint of low odor.
  • 2-amino-2-hydroxymethyl-1,3-propanediol 2-amino-2-methyl-1,3-propanediol are more preferable, and 2-amino-2-hydroxymethyl-1,3-propane Diols are more preferred.
  • the cations derived from component (A) are preferably those in which a cationic residue such as a hydrogen atom is bound to the above amine compound. ) may be derived from
  • the residue in the component (B) refers to an uncharged atom or atomic group (group), a cationic residue having a charge that becomes a cation, and an anionic residue that becomes an anion.
  • the anion is not particularly limited, but examples include hydroxide anions, halogen anions, sulfur anions, phosphorus anions, cyanide anions, and boron anions. , fluorine-based anions, nitrogen oxide-based anions, carboxylic acid-based anions, and the like, and among these, hydroxide anions are preferred.
  • component (A) is preferably an amine compound represented by the following formula (I).
  • each R 1 independently has one or more hydroxyl groups, the hydrocarbon moiety is linear or branched with 1 to 22 carbon atoms, and the hydrocarbon moiety contains an oxygen atom.
  • each R 2 is independently a hydrogen atom or an organic group having 1 to 22 carbon atoms
  • m represents an integer of 0 to 3.
  • m is preferably an integer of 1-3.
  • R 2 are preferably hydrogen atoms.
  • R 1 is preferably a linear or branched hydroxy hydrocarbon group having 1 to 22 carbon atoms in the hydrocarbon moiety.
  • the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon.
  • At least one of R 1 preferably has one hydroxyl group, and the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon hydroxy hydrocarbon group.
  • At least one of R 1 preferably has two or more hydroxyl groups, and the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon hydroxy hydrocarbon group.
  • At least one of R 1 has one or more hydroxyl groups
  • the hydrocarbon moiety is a branched chain having 3 to 22 carbon atoms
  • the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon. It is preferably a hydrogen hydroxy hydrocarbon group.
  • R 1 is a hydroxyalkyl group having one or more hydroxyl groups, a branched hydrocarbon moiety having 3 to 6 carbon atoms, and the hydrocarbon moiety being an alkyl group; is a hydrogen atom and m is an integer of 1 in one preferred embodiment.
  • R 1 is a hydroxyalkyl group having one hydroxyl group, a linear hydrocarbon moiety having 1 to 6 carbon atoms, the hydrocarbon moiety being an alkyl group, and m being an integer of 3. It is one of preferred embodiments.
  • a combination of at least one of the above preferred examples shown in formula (I) can be a more preferred embodiment.
  • component (A) is an ammonium compound
  • said component (A) is preferably an ammonium compound represented by the following formula (II).
  • each R 3 independently has one or more hydroxyl groups, the hydrocarbon moiety is linear or branched with 1 to 22 carbon atoms, and the hydrocarbon moiety contains an oxygen atom.
  • each R 4 is independently a hydrogen atom or an organic group having 1 to 22 carbon atoms
  • n represents an integer of 0 to 4
  • X ⁇ represents an anion.
  • n is preferably an integer of 1-4.
  • R 4 are preferably hydrogen atoms.
  • R 3 is preferably a linear or branched hydroxy hydrocarbon group having 1 to 22 carbon atoms in the hydrocarbon moiety.
  • the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon.
  • At least one of R 3 preferably has one hydroxyl group, and the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon hydroxy hydrocarbon group.
  • At least one of R 3 preferably has two or more hydroxyl groups, and the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon hydroxy hydrocarbon group.
  • At least one of R 3 has one or more hydroxyl groups
  • the hydrocarbon moiety is a branched chain having 3 to 22 carbon atoms
  • the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon. It is preferably a hydrogen hydroxy hydrocarbon group.
  • the anion represented by X ⁇ is preferably a hydroxide ion.
  • R 3 is a hydroxyalkyl group having one or more hydroxyl groups, a branched hydrocarbon moiety having 3 to 6 carbon atoms, and the hydrocarbon moiety being an alkyl group; is a hydrogen atom and n is an integer of 1 in one preferred embodiment.
  • R 3 is a hydroxyalkyl group having one hydroxyl group, a straight-chain hydrocarbon moiety having 1 to 6 carbon atoms, the hydrocarbon moiety being an alkyl group, and n being an integer of 3. It is one of preferred embodiments.
  • ammonium salt formed by component (A) and component (B) is also one preferred embodiment of the composition of the present invention.
  • an ammonium salt formed by a cation derived from the component (A), which may have a cationic residue of the component (B), and an anion derived from the anionic residue of the component (B). contains.
  • the residue in the component (B) refers to an uncharged atom or atomic group (group), a cationic residue having a charge that becomes a cation, and an anionic residue that becomes an anion.
  • the acid of component (B) or a salt thereof has a cationic residue and an anionic residue.
  • the cationic residue is a hydrogen atom or a group (atomic group) that combines with the nitrogen atom of component (A) to form a hydrogen-bonding functional group or an organic group.
  • the acid of component (B) is a compound composed of protonated hydrogen and an anionic residue.
  • the cation is preferably an ammonium cation.
  • ammonium salts include organic cations or NH 4 + having a nitrogen atom as the ion center, and anions.
  • organic cations and organic anions include organic cations and organic anions.
  • organic is meant to include carbon and hydrogen as elements.
  • the cations derived from the component (A) are not particularly limited, but examples include ammonium cations (NH 4 + , primary ammonium cations, secondary ammonium cations, tertiary ammonium cations), imidazolium cations, pyridinium cations, pyrrolidinium cations, cation, piperidinium cation, pyrrolinium cation, pyrazinium cation, triazolium cation, isoquinolinium cation, oxazolinium cation, thiazolinium cation, morpholinium cation, guanidinium cation, pyrimidinium cation cations derived from cyclic amines such as nium cations, piperazinium cations, triazinium cations, quinolinium cations, indolinium cations, quinoxalinium cations, isoxazolium cations, and cati
  • ammonium cation imidazolium cation, pyridinium cation, pyrrolidinium cation, piperidinium cation, and morpholinium cation are preferred, and ammonium cation is more preferred.
  • the cation of the ammonium salt formed by the component (A) and the component (B) is preferably a cation represented by the following formula (III). Moreover, when the component (A) is an ammonium compound, its cation is also preferably a cation represented by the following formula (III).
  • each R 5 independently has one or more hydroxyl groups, the hydrocarbon moiety is linear or branched with 1 to 22 carbon atoms, and the hydrocarbon moiety contains an oxygen atom.
  • each R 6 is independently a hydrogen atom or an organic group having 1 to 22 carbon atoms, and o represents an integer of 0 to 4.
  • o is preferably an integer of 1-4.
  • R 6 are preferably hydrogen atoms.
  • R 5 is preferably a hydroxy hydrocarbon group.
  • the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon.
  • At least one of R 5 has one hydroxyl group, and the hydrocarbon in the hydrocarbon moiety is preferably a hydroxy hydrocarbon group of saturated aliphatic hydrocarbon.
  • At least one of R 5 preferably has two or more hydroxyl groups, and the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon hydroxy hydrocarbon group.
  • At least one of R 5 has one or more hydroxyl groups
  • the hydrocarbon moiety is a branched chain having 3 to 22 carbon atoms
  • the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon. It is preferably a hydrogen hydroxy hydrocarbon group.
  • R 6 of the cation represented by the formula (III) is a hydrogen atom
  • the proton corresponding to the hydrogen atom is preferably derived from the component (B).
  • R 5 is a hydroxyalkyl group having one or more hydroxyl groups, a branched hydrocarbon moiety having 3 to 6 carbon atoms, and the hydrocarbon moiety being an alkyl group; is a hydrogen atom and o is an integer of 1 in one preferred embodiment.
  • R 5 is a hydroxyalkyl group having one hydroxyl group, a linear hydrocarbon moiety having 1 to 6 carbon atoms, the hydrocarbon moiety being an alkyl group, and o being an integer of 3. It is one of preferred embodiments.
  • a combination of at least one of the above preferred examples shown in formula (III) can be a more preferred embodiment.
  • the cation derived from component (A) (the cation of the ammonium compound of component (A)) has the effects of the present invention, namely gel formation, thickening effect, water retention, electrical conductivity, and stability to biomaterials such as enzymes. From the viewpoints of synergizing effect, solubility and releasability of active ingredients, and thixotropy, it is preferable to have a hydrocarbon group having one or more hydrogen-bonding functional groups (more preferably a saturated aliphatic hydrocarbon group). one of.
  • the cation derived from the component (A) (the cation of the ammonium compound of the component (A)) into which a functional group can be introduced (such as a nitrogen site or a carbon site that forms a ring together with nitrogen) becomes a basic skeleton.
  • atoms contained in the chemical structure one or more of which is preferably substituted with a hydrocarbon group having a hydrogen-bonding functional group. It is preferably present or substituted with an organic group such as a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group). It is also preferred that the site is composed only of hydrogen atoms directly bonded to nitrogen.
  • the cation derived from component (A) is a hydrocarbon group having a hydrogen-bonding functional group (more preferably a saturated aliphatic hydrocarbon group) and nitrogen A cation composed only of hydrogen atoms directly bonded to, a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) having a hydrogen-bonding functional group, and a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) only A cation composed of, a cation composed only of a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) having a hydrogen-bonding functional group, a cation composed only of hydrogen atoms is preferable, and a hydrogen-bonding functional group A hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) with a cation composed only of hydrogen atoms directly bonded to nitrogen, a hydrocarbon group with a hydrogen-bonding functional group (more
  • the cation represented by the formula (III) is obtained by bonding a cationic residue such as a hydrogen atom to the amine of the component (A), and the cationic residue such as a hydrogen atom is derived from the component (B). is a preferred embodiment.
  • the total carbon number of the hydrocarbon groups (such as alkyl groups) in component (A), formulas (I), (II), and (III) is 1 to 12. is preferred, 1 to 8 are more preferred, 1 to 6 are even more preferred, and 1 to 4 are particularly preferred.
  • the acid of component (B) or a salt thereof has a cationic residue and an anionic residue.
  • the cationic residue is a hydrogen atom or a group (atomic group) that combines with the nitrogen atom of component (A) to form a hydrogen-bonding functional group or an organic group.
  • the hydrogen-bonding functional group in component (B) may be one possessed by an anionic residue, or may be hydrogen that becomes a proton in an acid.
  • at least the anionic residue has a hydrogen-bonding functional group.
  • the component (B) acid is a compound composed of protonated hydrogen and an anionic residue (e.g., the anion shown below), as well as a Lewis acid in a salt-forming reaction with component (A).
  • Acid-acting compounds are not excluded, for example, halogenated hydrocarbons, dialkylsulfuric acids, dialkylcarbonates, alkylsulfonic acids, which may have the above substituents (preferably oxygen-containing groups) on the hydrocarbon moiety , phosphate alkyl esters, and the like.
  • the acid of component (B) is a compound composed of protonated hydrogen and an anionic residue.
  • the anion derived from the anionic residue of component (B) is not particularly limited, but examples include halogen anions, sulfur anions, phosphorus anions, cyanide anions, boron anions, fluorine anions, Nitrogen oxide-based anions, carboxylic acid-based anions, and the like are included. These may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, halogen-based anions, sulfur-based anions, phosphorus-based anions, boron-based anions, fluorine-based anions, nitrogen oxide-based anions, and carboxylic acid-based anions are preferable. Acid anions are more preferred, and carboxylate anions are even more preferred.
  • the anionic residue of component (B) preferably has a hydrogen-bonding functional group, and examples of the hydrogen-bonding functional group include the aforementioned hydrogen-bonding functional groups.
  • a carboxylate group, an ether group and an alkoxy group are preferred, and a hydroxyl group is more preferred.
  • halogen-based anions are not particularly limited, but include, for example, fluorine ions, chloride ions, bromide ions, iodine ions, fluorine-based anions, and the like.
  • the sulfur-based anion is not particularly limited. p-toluenesulfonate anion, 2,4,6-trimethylbenzenesulfonate anion, styrenesulfonate anion, 3-sulfopropyl methacrylate anion, 3-sulfopropyl acrylate anion, etc.), sulfate anion, hydrogen sulfate anion, alkyl Sulfate anions (eg, methylsulfate anion, ethylsulfate anion, butylsulfate anion, octylsulfate anion, 2-(2-methoxyethoxy)ethylsulfate anion, etc.) and the like.
  • alkyl Sulfate anions eg, methylsulfate anion, ethylsulfate anion, butylsulfate anion, octylsulfate anion, 2-(2-me
  • Examples of the phosphorus-based anion include, but are not limited to, phosphate anion, hydrogen phosphate anion, dihydrogen phosphate anion, phosphonate anion, hydrogen phosphonate anion, dihydrogen phosphonate anion, phosphinate anion, hydrogen Phosphinate anions, alkyl phosphate anions (e.g. dimethyl phosphate anion, diethyl phosphate anion, dipropyl phosphate anion, dibutyl phosphate anion, etc.), alkyl phosphonate anions (e.g.
  • methyl phosphonate anions ethyl phosphonate anions anion, propylphosphonate anion, butylphosphonate anion, methylmethylphosphonate anion, etc.
  • alkylphosphinate anion hexaalkylphosphate anion and the like.
  • the cyan anion is not particularly limited, but includes, for example, tetracyanoborate anion, dicyanamide anion, thiocyanate anion, isothiocyanate anion, and the like.
  • the boron-based anion is not particularly limited, but includes, for example, a tetraalkylborate anion such as a tetrafluoroborate anion, a bisoxalateborate anion, and a tetraphenylborate anion.
  • a tetraalkylborate anion such as a tetrafluoroborate anion, a bisoxalateborate anion, and a tetraphenylborate anion.
  • the fluorine-based anion is not particularly limited. ) imide, bis(heptafluoropropanesulfonyl)imide anion, bis(nonafluorobutylsulfonyl)imide, etc.), perfluoroalkylsulfonate anion (e.g., trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate phosphate anion, nonaflate anion, perfluorooctanesulfonate anion, etc.), fluorophosphate anion (e.g., hexafluorophosphate anion, tri(pentafluoroethyl)trifluorophosphate anion, etc.), tris (perfluoroalkylsulfonyl ) methide anion (e.g., tris(trifluoromethanesulfony
  • the nitrogen oxide anion is not particularly limited, but includes, for example, nitrate anion and nitrite anion.
  • the carboxylate anion is an organic acid anion having at least one carboxylate anion (—COO ⁇ ) in the molecule, and includes an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, and a hydrocarbon. You may have a group or the like.
  • Carboxylic acid anions include, but are not limited to, saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups, etc., and hydrocarbons combining them.
  • Anions having a group and a carboxylate anion include, for example, saturated aliphatic carboxylate anions, unsaturated aliphatic carboxylate anions, saturated or unsaturated alicyclic carboxylate anions, aromatic carboxylate anions, saturated aliphatic hydroxy Carboxylate anion, unsaturated aliphatic hydroxycarboxylate anion, saturated or unsaturated alicyclic hydroxycarboxylate anion, aromatic hydroxycarboxylate anion, carbonylcarboxylate anion, alkyl ether carboxylate anion, halogen carboxylate anion, amino acid anion etc. (The number of carbon atoms in the carboxylate anions listed below includes the carbon atoms in the carboxy group.).
  • the saturated aliphatic carboxylate anion consists of a linear or branched saturated aliphatic hydrocarbon group and one or more carboxylate anions, may contain a carboxy group or a carboxylate group, and has 1 to 22 carbon atoms. is preferred.
  • formic acid acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid , margaric acid, stearic acid, arachidic acid, henicosyl acid, behenic acid, isobutyric acid, 2-methylbutyric acid, isovaleric acid, 2-ethylhexanoic acid, isononanoic acid, isopalmitic acid, isostearic acid, oxalic acid, malonic acid,
  • Examples include anions obtained by dissociating protons from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like.
  • the unsaturated aliphatic carboxylate anion consists of a linear or branched unsaturated aliphatic hydrocarbon group and one or more carboxylate anions, may contain a carboxy group or a carboxylate group, and has 3 carbon atoms. ⁇ 22 is preferred. Specifically, but not limited to, acrylic acid, methacrylic acid, crotonic acid, palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, maleic acid, fumaric acid, etc. Anions in which protons are dissociated from are exemplified.
  • the saturated or unsaturated alicyclic carboxylate anion consists of a saturated or unsaturated carbocyclic ring having no aromaticity and one or more carboxylate anions, may contain a carboxy group or a carboxylate group, and has a carbon number of 6 to 20 are preferred.
  • a saturated alicyclic carboxylic acid anion having a cyclohexane ring skeleton is preferable, and specific examples include, but are not particularly limited to, anions in which protons are dissociated from cyclohexanecarboxylic acid and cyclohexanedicarboxylic acid.
  • the aromatic carboxylate anion consists of a single ring or a plurality of aromatic rings and one or more carboxylate anions, may contain a carboxy group or a carboxylate group, and preferably has 6 to 20 carbon atoms.
  • aromatic carboxylate anions having a benzene ring skeleton are preferred, and specific examples thereof include, but are not limited to, anions in which protons are dissociated from benzoic acid, cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like. be done.
  • the saturated aliphatic hydroxycarboxylic acid anion consists of a linear or branched saturated aliphatic hydrocarbon group, one or more carboxylic acid anions and one or more hydroxyl groups, and may include a carboxy group and a carboxylate group. Well, preferably 2 to 24 carbon atoms. Among them, saturated aliphatic hydroxycarboxylic acid anions having 2 to 7 carbon atoms and 1 to 4 hydroxyl groups are preferred. Specific examples include, but are not limited to, glycolic acid, lactic acid, tartronic acid, glyceric acid, hydroxyacetic acid, hydroxybutyric acid, 2-hydroxydecanoic acid, 3-hydroxydecanoic acid, 12-hydroxystearic acid, and dihydroxystearic acid. , cerebronic acid, malic acid, tartaric acid, citramaric acid, citric acid, isocitric acid, leucic acid, mevalonic acid, pantoic acid, and the like.
  • the unsaturated aliphatic hydroxycarboxylate anion consists of a linear or branched unsaturated aliphatic sum hydrocarbon group, one or more carboxylate anions and one or more hydroxyl groups, a carboxy group, a carboxylate group and preferably has 3 to 22 carbon atoms.
  • Specific examples include, but are not particularly limited to, anions obtained by dissociating protons from ricinoleic acid, ricinoleic acid, ricineraidic acid, and the like.
  • the saturated or unsaturated alicyclic hydroxycarboxylate anion is composed of a saturated or unsaturated carbocyclic ring having no aromaticity, one or more carboxylate anions and one or more hydroxyl groups, and includes a carboxy group, a carboxylate It may contain a group, and preferably has 4 to 20 carbon atoms.
  • a saturated alicyclic hydroxycarboxylic acid anion having a 6-membered ring skeleton having 1 to 4 hydroxyl groups is preferable.
  • examples include hydroxycyclohexanecarboxylic acid, dihydroxycyclohexanecarboxylic acid, and quinic acid.
  • the aromatic hydroxycarboxylic acid anion consists of a single ring or a plurality of rings having aromaticity, one or more carboxylic acid anions and one or more hydroxyl groups, and may contain a carboxy group and a carboxylate group. 6 to 20 are preferred.
  • an aromatic carboxylic acid anion having a benzene ring skeleton having 1 to 3 hydroxyl groups is preferable, and specific examples thereof include, but are not limited to, salicylic acid, hydroxybenzoic acid, dihydroxybenzoic acid, trihydroxybenzoic acid, hydroxy Protons are released from methylbenzoic acid, vanillic acid, syringic acid, pyrotocatechuic acid, gentisic acid, orceric acid, mandelic acid, benzilic acid, atrolactinic acid, phloretic acid, coumaric acid, umberic acid, caffeic acid, ferulic acid, sinapic acid, etc. Dissociated anions are included.
  • the carbonyl carboxylate anion is a carboxylate anion having 3 to 22 carbon atoms having a carbonyl group in the molecule, may contain a carboxy group and a carboxylate group, and has 1 to 2 carbonyl groups and has 3 to 2 carbon atoms.
  • a carbonyl carboxylate anion of 7 is preferred.
  • a carbonyl carboxylate anion represented by CH 3 ((CH 2 ) p CO(CH 2 ) q )COO - (p and q are integers of 0 to 2) is preferred. Specific examples thereof include, but are not particularly limited to, anions in which protons are dissociated from pyruvic acid or the like.
  • the alkyl ether carboxylate anion is a carboxylate anion having 2 to 22 carbon atoms having an ether group in the molecule, including a polyoxyalkylene alkyl ether carboxylate anion, and may contain a carboxy group and a carboxylate group.
  • C2-C12 alkyl carboxylate anions with ⁇ 2 ether groups are preferred, especially CH3 ( CH2 ) rO ( CH2 ) sCOO- ( r and s are integers from 0 to 4 ), and more preferably polyoxyethylene alkyl ether carboxylate anions.
  • Alkyl ether carboxylate anions are not particularly limited, but include, for example, anions in which protons are dissociated from methoxyacetic acid, ethoxyacetic acid, methoxybutyric acid, ethoxybutyric acid, and the like.
  • the halogen carboxylate anion is a carboxylate anion having 2 to 22 carbon atoms having a halogen atom in the molecule, and may contain a carboxy group or a carboxylate group, preferably a halogen carboxylate anion having 2 to 22 carbon atoms.
  • a carboxylate anion having 2 to 22 carbon atoms preferably a halogen carboxylate anion having 2 to 22 carbon atoms.
  • the amino acid anion is a carboxylate anion having 2 to 22 carbon atoms and having an amino group in the molecule, and may contain a carboxy group or a carboxylate group.
  • Amino acid anions are preferred. Specifically, but not limited to, for example, glycine, alanine, glutamic acid, arginine, asparagine, aspartic acid, isoleucine, glutamine, histidine, cysteine, leucine, lysine, proline, phenylalanine, threonine, serine, tryptophan, tyrosine, methionine , valine, sarcosine, aminobutyric acid, methylleucine, aminocaprylic acid, aminohexanoic acid, aminocapric acid, aminolauric acid, aminomyristic acid, aminopalmitic acid, aminostearic acid, norvaline, aminovaleric acid, aminoisobutyric acid, thyroxine, Creatine,
  • Salts of component (B) include salts of the above anions and cations (alkali metal cations, alkaline earth metal cations, ammonium cations, etc.).
  • the amine or ammonium compound as component (A), the acid or its salt as component (B), and the ammonium salt formed by component (A) and component (B) may be used singly. More than one species may be used in combination.
  • component (B) is a polybasic acid
  • component (A) and component (B) may be blended so that the valence of component (A) is equivalent to that of component (B).
  • the composition may be less than equivalent, or more than equivalent (when component (B) is a polybasic acid, it may be a partially neutralized salt or a completely neutralized salt).
  • component (B) is a dibasic acid and component (A) has a valence of 1, the blending molar ratio of component (A) and component (B) should be 1:1 mol to 2:1 mol. can be done.
  • Two or more kinds of components (A) may be used.
  • component (A) has hydrogen-bonding functional groups, the effects of those hydrogen-bonding functional groups can be enhanced.
  • component (A) and component (B) form an ammonium salt, two molecules of cations derived from component (A) can be introduced into one molecule of salt. The effect of the functional group can be further enhanced.
  • component (A) and component (B) In order to improve gel formability, thickening effect, water retention, electrical conductivity, stabilizing effect on biomaterials such as enzymes, solubility and release of active ingredients, and thixotropy, component (A) and In the case of a mixture of component (B) or a salt of component (A) and component (B), either the cation or the anion of the salt of component (A) and component (B) or component (A) and component (B) One of them preferably has a hydrogen-bonding functional group, and both preferably have a hydrogen-bonding functional group.
  • hydrogen-bonding functional groups for component (A) are those listed above, and hydrogen-bonding functional groups for component (B) include oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups, and the like. mentioned.
  • element-containing groups a hydroxyl group, a carboxy group, a carboxylate group, an ester group, an ether group, an alkoxy group, a carbonyl group, an amino group, a sulfonyl group, a sulfate ester group, a phosphate group, and a phosphate ester group are preferred.
  • a hydroxyl group preferably a hydroxyl group, a carboxyl group, a carboxylate group, an ester group, an ether group, an alkoxy group, or a carbonyl group, more preferably a hydroxyl group, a carboxyl group, a carboxylate group, an ester group, an ether group, or an alkoxy group, and particularly preferably a hydroxyl group .
  • composition of the present invention has a hydrogen-bonding functional group in at least one of component (A) and component (B), and it is one of preferred embodiments that this hydrogen-bonding functional group is a hydroxyl group.
  • component (B) may be Compounds listed in the Pharmacopoeial Standards for Quasi-Drugs (Regulations), Pharmaceutical Additives Standards (Medicine Additives), and Food Additives Standards (Food Additives) are preferably used as raw materials, but are not particularly limited.
  • acetic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, lactic acid, glycolic acid, succinic acid, citric acid, hydrochloric acid, fumaric acid, phosphoric acid, ascorbic acid, etc. is mentioned.
  • Amino acids that can be used for component (A) and component (B) include glycine, alanine, arginine, aspartic acid, histidine, cysteine, proline, serine, tryptophan, tyrosine, methionine, aminobutyric acid, aminohexanoic acid, Cystine, glutamic acid, isoleucine, phenylalanine, threonine, tryptophan, methionine, valine, theanine and the like.
  • composition of the present invention provides gel formability, thickening properties, water retention, electrical conductivity, stabilizing effect on biomaterials such as enzymes, solubility and release of active ingredients, and thixotropy.
  • the mixture of component (A) and component (B) or the salt of component (A) and component (B) may be in an anhydrous state (anhydrous), and the moisture in the air may be It may be an absorbed hydrate.
  • a hydrate refers to a compound that, when left in the air at 25°C, absorbs water and has a saturated moisture content. Compounds that do not absorb water when left in air at 25° C. are non-hydrated and anhydrous.
  • the mixture of components (A) and (B) or the salt of (A) and (B) is an anhydride and/or hydrate that is liquid or solid at 25°C.
  • it is preferably liquid at 25 ° C.
  • the freezing point of the anhydride and / or hydrate is preferably less than 25 ° C., more preferably less than -5 ° C. It is preferred, and less than -10°C is more preferred.
  • the composition of the present invention is mainly intended for a composition that is blended in an arbitrary step when manufacturing a desired composition.
  • the composition of the present invention contains components (A) and (B), a polymer compound and water.
  • “adding" components (A), (B), a polymer compound, and water means that components (A), (B), a polymer compound, and water are added until the final composition is prepared.
  • Salts or salts formed with components (A), (B) or components (A), (B) or components (A), (B) and water using these and water as starting materials It includes the case where an aqueous solution is synthesized and the salt or salt solution is used as an additive, and the case where the salt or salt solution is optionally mixed with water and/or components such as a polymer compound to form a composition.
  • the composition of the present invention may be a mixture (including a salt thereof) consisting only of components (A), (B), a polymer compound and water, and (A), (B) ( Alternatively, it may be a composition containing components other than (A) and (B)), a polymer compound and water.
  • the composition of the present invention also primarily targets the desired final composition.
  • the composition of the present invention includes the final composition produced by adding the component (A), the component (B), the polymer compound and water in any step thereof, and only using the composition of the present invention Instead, it may contain components (A), (B), a polymer compound, and water.
  • the gel composition of the present invention is a gel-like composition among the compositions suitable for the above gel-forming or thickening properties.
  • the thickened or to-be-thickened compositions of the present invention contain, among other compositions suitable for gel-forming or thickening properties as described above, components (A), (B) and polymeric compounds. Thickening is caused by the action of the component (A), the component (B), and the polymer compound added when preparing the composition thickened by the action or the intended thickened composition. possible compositions.
  • the component (A), the component (B), the polymer compound and water it is preferable to heat and dissolve the component (A), the component (B), the polymer compound and water at, for example, 50° C. or higher, and then slowly cool to room temperature. , preferably 15 minutes or more, more preferably 30 minutes or more.
  • the polymer compound used in the composition of the present invention is not particularly limited, but includes synthetic polymer compounds, semi-synthetic polymer compounds, natural polymer compounds, and the like.
  • synthetic polymer compounds when the polymer compound has a hydrogen-bonding functional group, it can interact with water, the component (A) and/or the component (B), and the affinity increases, so the compound having a hydrogen-bonding functional group is preferred, and polymer compounds containing at least one selected from a hydroxyl group, a carbonyl group, a carboxy group, and a carboxylate group are particularly preferred.
  • semi-synthetic polymer compounds and natural polymer compounds are preferred, and natural polymer compounds are more preferred. These may be used individually by 1 type, and may be used in combination of 2 or more type.
  • Examples of synthetic polymer compounds include, but are not limited to, polyacrylic acid, vinyl acetate copolymer, maleic anhydride copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide, and polyester. , polyacrylonitrile-based, polyamide-based, polyimide-based, polyamideimide-based, polymaleimide-based, polyurethane-based, polycarbonate-based, and polyarylate-based high molecular compounds.
  • semisynthetic polymer compounds include, but are not limited to, cellulose derivatives (sodium carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, nitrocellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, crystalline cellulose), sodium alginate, ester gum, Soluble starch etc. are mentioned.
  • natural polymer compounds include, but are not limited to, polysaccharides, cellulose, nucleic acids or salts thereof, ribonucleic acids or salts thereof, water-soluble proteins (casein, collagen, gelatin, albumin, fibroin, elastin, keratin, sericin, etc.), hyaluronic acid or its salts, mucopolysaccharides (such as chondroitin sulfate), etc., and polysaccharides are particularly preferred.
  • polysaccharides include, but are not limited to, xanthan gum, carrageenan, tamarind sea gum, gellan gum, guar gum, pectin, gum arabic, karaya gum, locust bean gum, daiutang gum, sodium alginate, agarose, hyaluronic acid, polygalactose.
  • Natural polysaccharides such as uronic acid, carboxymethyl pullulan, carboxymethyl chitin, carboxymethyl chitosan, carboxymethyl mannan, carboxymethyl starch, carboxymethyl dextran, carboxyethyl cellulose, carboxy alkyl polysaccharides such as carboxymethyl pullulan, oxidized cellulose and oxidized starch and polysaccharides containing sulfate groups such as chondroitin sulfate, dermatan sulfate, heparin and heparan sulfate.
  • polymer compounds having hydrogen-bonding functional groups are preferred, and water-soluble polymer compounds are more preferred.
  • Such polymer compounds are preferably xanthan gum, carrageenan, gellan gum, guar gum, diutane gum and sodium alginate, more preferably xanthan gum, carrageenan, gellan gum, guar gum and diutane gum, and still more preferably xanthan gum and guar gum.
  • compositions Compositions, Gel Compositions, and Thickened or To Thicken Compositions
  • component (A), component (B), polymer compound, and water are blended in any ratio.
  • the amount thereof is not particularly limited, for example, the total amount of component (A) and component (B) in the composition is preferably 90% by mass or less, and 50% by mass or less, from the viewpoint of being suitable for gel formation or thickening properties. is more preferable, 30% by mass or less is even more preferable, and 10% by mass or less is particularly preferable.
  • the polymer compound in the composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more.
  • composition of the present invention forms a gel through the interaction of component (A), component (B), water, and a polymer compound having hydrogen-bonding functional groups, and has a thickening effect.
  • a polymer compound having a functional group such as a polysaccharide, is more likely to form a gel composition and is suitable for imparting a thickening effect and thixotropy.
  • composition of the present invention forms a hydrogen bond with water by using the component (A) or the component (A) and the component (B) having a hydrogen-bonding functional group, and further by using a polymer compound. can be enhanced. Also, the interaction between the component (A) and the component (B) and the dense arrangement of the component (A) and the component (B) result in the development of electrical conductivity.
  • the hydrogen-bonding functional group in component (A) or component (A) and component (B) further includes a hydrogen-bonding functional group when the polymer compound has a hydrogen-bonding functional group. interacts with enzymes and other biomaterials to stabilize them.
  • composition of the present invention has good affinity between the composition and water, is suitable for gel formation, and has an excellent thickening effect. and both component (A) and component (B) preferably have a hydrogen-bonding functional group. On the other hand, it is preferable that the polymer compound has a hydrogen-bonding functional group. A composition that forms a gel has an excellent thickening effect.
  • the composition of the present invention is excellent in that the viscosity decreases when a shearing force is applied, making it easy to apply to an object, and then the viscosity increases when the shearing force is not applied, making it difficult for dripping to occur on the application surface.
  • component (A) or component (B) has a hydrogen-bonding functional group, and both component (A) and component (B) have a hydrogen-bonding functional group. It is preferable to have On the other hand, it is preferable that the polymer compound has a hydrogen-bonding functional group.
  • composition of the present invention comprises an active ingredient made of an organic material or an inorganic material, in particular, hydrogen Excellent compatibility with active ingredients consisting of organic or inorganic materials with bonding functional groups (hydroxyl, carbonyl, carboxyl, carboxylate, amino, hydrogen atoms, etc.), and their solubility and dispersibility Furthermore, they are excellent in release properties and sustained release properties of their active ingredients.
  • composition of the present invention is expected to have superior development in various uses.
  • biomaterials such as water retention, conductivity, living organisms and enzymes
  • examples include proteins, enzymes, amino acids and salts thereof, nucleic acids, antibodies / antigens, cells, (animals, plants, living tissues such as organs, biological and natural materials such as cellulose), solubility, dispersibility, release and sustained release, thickening and thixotropic properties of inorganic and organic materials , High specific heat, high thermal conductivity, lubricity, freezing point depression, boiling point elevation, vapor pressure depression, permeability, hydrophilicity, adsorptivity, reactivity, moisture retention, safety, etc.
  • water retention / moisturizing agents for example, water retention / moisturizing agents, conductive materials, electrolyte materials, antistatic agents, biomaterial dissolution solvents, dispersion solvents, storage solvents and culture media, thickeners, organic materials or inorganic materials
  • metals, metal oxides but not particularly limited, for example, silica, aluminum oxide (alumina), zirconia, titanium oxide, magnesium oxide, indium tin oxide (ITO), cobalt blue (CoO Al 2 O 3 ), antimony oxide, zinc oxide, cesium oxide, zirconium oxide, yttrium oxide, tungsten oxide, vanadium oxide, cadmium oxide, tantalum oxide, niobium oxide, tin oxide, bismuth oxide, cerium oxide, copper oxide, iron oxide, indium oxide , boron oxide, calcium oxide, barium oxide, thorium oxide, indium tin oxide, ferrite, etc.), carbon materials), dissolution solvents, dispersion solvents,
  • each of the above preferred examples shown in formula (I), each of the above preferred examples shown in formula (II), and each of the above preferred examples shown in formula (III) are at least any of them. Any combination can be a more preferable embodiment based on the results of the examples. At least one combination of all of the above preferred examples shown in formulas (I) to (III) can be a more preferred embodiment based on the results of the examples.
  • 2-Amino-2-hydroxymethyl-1,3-propanediol (Fuji Film Wako Pure Chemical Industries, Ltd.) and triethanolamine (Kanto Chemical Co., Ltd.) are used as the amine compound of component (A). Lactic acid, malic acid, and citric acid (Kanto Kagaku Co., Ltd.) are used as acids, and xanthan gum (Echo Gum T: manufactured by DSP Gokyo Food & Chemical) and carrageenan (Ceepigum FA: manufactured by DSP Gokyo Food & Chemical) are used as polymer compounds.
  • gellan gum (Kelcogel: manufactured by Saneigen FFI), guar gum (SUPERGEL CSA 200/50: manufactured by Sankei), diutan gum (KELCO-VIS DG: manufactured by Sankei), the ammonium compound of component (A) Choline hydroxide (Tokyo Chemical Industry Co., Ltd.) was used as the solvent.
  • guar gum SUPERGEL CSA 200/50: manufactured by Sankei
  • diutan gum KELCO-VIS DG: manufactured by Sankei
  • the ammonium compound of component (A) Choline hydroxide (Tokyo Chemical Industry Co., Ltd.) was used as the solvent.
  • 1-butyl-3-methylimidazolium chloride (BMI-Cl) in Comparative Examples was manufactured by Tokyo Chemical Industry Co., Ltd., and glycerin was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
  • composition was prepared by the following method (Tables 1A, B to 4A, B, Table 5).
  • Tables 1A, B to 4A, B, Table 5 After mixing the component (A) and the component (B) described in Tables 1A, B to 4A, B, and Table 5 in water, the water is distilled off, and the resulting mixture or salt is a hydrate. and was liquid at 25°C.
  • Examples 2 to 100 Compositions 2 to 100 Similarly, predetermined amounts of an amine compound (component (A)), an acid (component (B)), and a polymer compound listed in Tables 1A and B to Table 4A and B were prepared under the same conditions as in Example 1, Gel compositions 2 to 100 were obtained. In addition, each amine compound (component (A)), acid (component (B)) and water described in Examples 1 to 100 were premixed in the same amount as above to synthesize an ammonium salt, and then a polymer compound was added. It was confirmed that a gel composition was similarly obtained by adding, heating, stirring, dissolving, and cooling under the same conditions as in Example 1.
  • compositions 102-106 Similarly, predetermined amounts of ammonium compound, acid, and polymer compound shown in Table 5 were prepared under the same conditions as in Example 101 to obtain gel compositions 102-106. Further, each ammonium compound, acid and water described in Examples 101 to 106 are premixed in the same charge amount as above, the polymer compound is added, and the mixture is heated and stirred under the same conditions as in Example 101, dissolved, and cooled. , confirmed that a gel-like composition was similarly obtained.
  • Composition 107 1-butyl-3-methylimidazolium chloride 1.0 g (concentration in composition: 10% by mass), polymer compound xanthan gum 0.1 g (polymer compound concentration in composition: 1% by mass) and water 8 9 g was mixed, heated and stirred at 50° C. for 30 minutes to dissolve, and then cooled to room temperature over 60 minutes to obtain a gel composition 107 .
  • Composition 108 1.0 g of glycerin (concentration in the composition: 10% by mass), 0.1 g of high molecular compound xanthan gum (concentration of high molecular compound in the composition: 1% by mass) and 8.9 g of water were mixed and heated at 50°C. After heating and stirring for 30 minutes for dissolution, the mixture was cooled to room temperature over 60 minutes to obtain a gel composition 108 .
  • Composition 109 0.1 g of xanthan gum, which is a polymer compound (concentration of polymer compound in the composition: 1% by mass) and 9.9 g of water are mixed, heated and stirred at 50° C. for 30 minutes to dissolve, and then cooled to room temperature over 60 minutes. After cooling, a gel composition 109 was obtained.
  • xanthan gum which is a polymer compound (concentration of polymer compound in the composition: 1% by mass) and 9.9 g of water are mixed, heated and stirred at 50° C. for 30 minutes to dissolve, and then cooled to room temperature over 60 minutes. After cooling, a gel composition 109 was obtained.
  • the moisture content of the gel composition was measured with a Karl Fischer moisture meter, and 1.0 g of the sample was added to the screw tube without a lid, and the temperature and humidity were set to 40 ° C. and 40% RH. It was allowed to stand in a vessel (KCL-2000W manufactured by Tokyo Rikakikai Co., Ltd.) for 24 hours. The moisture content after 24 hours was measured (moisture content after test), and the water retention rate was calculated using the following formula to evaluate water retention (Table 6).
  • B Moisture content after test (%)
  • Moisture reduction rate (%) [(A (%) - B (%)) / A (%)] ⁇ 100
  • Table 6 shows the moisture reduction rate.
  • Compositions 20 to 24, 42, 66 and 93 (Examples 107 to 111 and 116 to 118) had a smaller water loss rate and better water retention than Compositions 107 to 109 (Comparative Examples 1 to 3).
  • Composition 20 (Example 107) has higher moisturizing properties than Composition 107 (Comparative Example 1), and the hydrogen-bonding functional groups present in component (A) and/or component (B) in the composition according to the present invention was suggested to contribute to water retention.
  • Composition 20 (Example 107) has better water retention than Composition 108 (Comparative Example 2) containing glycerin having a hydrogen-bonding functional group (hydroxyl group). It was confirmed that A) and component (B) (the ammonium salt formed from component (A) and component (B)) are effective in retaining water.
  • ⁇ Hydrolytic enzyme activity measurement of urease> Urease activity was measured by quantifying the amount of ammonium ions produced from urea by the enzymatic reaction of urease by the indophenol method.
  • a 1 mM substrate solution prepared by dissolving urea as a substrate in a pH 7.5 10 mM phosphate buffer
  • 100 mL of a 1 mM substrate solution was placed in an Erlenmeyer flask and preheated at 30°C for about 30 minutes.
  • the sample containing 0.5 mg of enzyme was added to the substrate solution and allowed to react at 30° C. for 60 minutes.
  • a phenol solution (10 g of phenol and 50 mg of sodium pentacyanonitrosylferrate(III) were dissolved in ion-exchanged water, and then diluted to 1000 mL with ion-exchanged water to prepare).
  • 2 mL and sodium hypochlorite solution (prepared by dissolving 5 g of sodium hydroxide and 8.4 mL of 5% sodium hypochlorite solution in ion-exchanged water, and then diluting to 1000 mL with ion-exchanged water). In addition, they were reacted for 20 minutes in a constant temperature bath at 37°C.
  • the amount of ammonium ions produced was determined from the amount of indophenol obtained by measuring the absorbance at a wavelength of 635 nm (V-550: JASCO Corporation) of the reaction solution, and the urease activity was measured. Calculated. Ammonium ion was quantified using a calibration curve obtained by preparing an ammonium ion solution in the concentration range of 0.1 to 3.0 mM and quantifying by the indophenol method in the same manner as described above.
  • Table 6 shows the enzyme activity retention rate.
  • Compositions 20 to 24 (Examples 107 to 111) had a higher enzymatic activity retention rate and were superior in enzyme stabilizing effect than Compositions 107 to 109 (Comparative Examples 1 to 3).
  • Composition 20 (Example 107) has a higher enzymatic activity retention rate than Composition 107 (Comparative Example 1), and the hydrogen-bonding functionality of component (A) and/or component (B) in the composition according to the present invention It was suggested that the groups contributed to the enzyme stabilizing effect.
  • Composition 20 (Example 107) has better water retention than Composition 108 (Comparative Example 2) containing glycerin having a hydrogen-bonding functional group (hydroxyl group). It was confirmed that A) and component (B) (the ammonium salt formed from component (A) and component (B)) are effective in stabilizing the enzyme.
  • the samples of gel compositions 20 to 24 are all viscous and have higher conductivity (lower surface resistivity) than composition 107 (Comparative Example 1). , it was confirmed that the antistatic effect is excellent. That is, the hydrogen-bonding functional groups in component (A) and/or component (B) in the composition according to the present invention, component (A) and component (B) (component (A) and component (B) It was suggested that the ammonium salt formed from ) is liquid at 25°C.
  • composition according to the present invention has higher conductivity than the comparative example composition, it is suggested that the surface of the application object is uniformly coated, and other effects other than conductivity and antistatic effects It can be effectively applied to the target object.
  • composition 111 (Comparative Example 4) 1-butyl-3-methylimidazolium chloride (BMI-Cl) 1.0 g, polymer compound xanthan gum 0.1 g (composition (BMI-Cl, polymer compound, water ), 8.9 g of water, and 0.1 g of ascorbic acid as an active ingredient (1% by mass of the composition (BMI-Cl, polymer compound, water)) were mixed. , at 50° C. for 30 minutes to dissolve the mixture, and then cooled to room temperature over 60 minutes to obtain a gel composition 111 containing an active ingredient.
  • BMI-Cl 1-butyl-3-methylimidazolium chloride
  • a Pierce vial (2 mL) was filled with a buffer (phosphate-buffered saline (PBS) solution), Lab Skin (Hoshino Laboratory Animal Breeding Co., Ltd.) was placed in the Pierce vial, and maintained at 32°C.
  • a buffer phosphate-buffered saline (PBS) solution
  • Lab Skin Hoshino Laboratory Animal Breeding Co., Ltd.
  • 0.1 g of each of the gel compositions 110 and 111 described above was added to the surface of the lab skin (the amount of ascorbic acid in the added gel composition: 1.0 mg), and the mixture was heated at 32° C.
  • compositions obtained by changing the order of addition of component (A), component (B), and polymer compound have the same thickening effect and thixotropy.
  • the target product contained component (A), component (B), a polymer compound, and water, it had a thickening effect and thixotropy.
  • the gel composition 112 (Comparative Example 5) did not become a gel even after standing for 60 minutes after the viscosity measurement, and did not exhibit thixotropy.
  • none of the compositions 113 and 114 of Comparative Examples 6 and 7 were gelled, and a gel composition was not obtained.
  • compositions 20, 66, and 93 as examples, 18 g of compositions 114, 115, 116, and 117 as comparative examples, and methyl ethyl ketone and 2 g of isopropanol as active ingredients were mixed and placed in a constant temperature bath at a temperature of 25°C and a humidity of 60% RH. placed. After 2.5 hours, 6 hours, 8 hours, and 24 hours, the weight of the composition in which the active ingredient was dissolved was measured, and the evaporation rate was calculated from the following formula.
  • Evaporation rate formula [(G - H) / I x 100] - J
  • G Weight (g) of the composition in which the active ingredient is dissolved before the test
  • H Weight (g) of the composition in which the active ingredient was dissolved after each hour
  • I Charged amount of active ingredient: 2 g
  • J Evaporation rate of the composition after each time when the active ingredient is water
  • Examples 119 to 121 had lower evaporation rates after 2.5 hours, 6 hours, 8 hours, and 24 hours than Comparative Examples 8 to 12. The sustained release of the substance was confirmed. Also, from Tables 10A and B, Examples 122 to 124 had lower evaporation rates after 2.5 hours, 6 hours, 8 hours, and 24 hours than Comparative Examples 13 to 17. confirmed the sustained release properties of the composition.

Abstract

Provided is a composition which has excellent gel formation and thickening characteristics, excellent water retention and conductivity, an excellent stabilization effect in biological materials such as enzymes, in which active ingredients have excellent solubility and releasability, and which has excellent thixotropy.　The composition according to the present invention includes, as added components, the following components (A) and (B), a polymer compound, and water, where at least one of component (A) and component (B) has a hydrogen-bonding functional group. (A) an amine or an ammonium compound; (B) an acid or a salt thereof.

Description

ゲルの形成又は増粘特性に適した組成物Compositions suitable for gel-forming or thickening properties
　本発明は、ゲルの形成又は増粘特性に適した組成物に関する。 The present invention relates to compositions suitable for gel-forming or thickening properties.
　ゲルは、化粧品、導電材料、増粘剤をはじめ、生体材料、医療用センサー、ドラックデリバリーシステム、細胞培養基材等の生体関連分野で利用され、更に機能性の向上が期待されている。従来、ゲルとしては、塩化－１－ブチル－３－メチルイミダゾリウム、キサンタンガム、及び水からなるゲル（特許文献１）、ゼラチンを用いたゲル（特許文献２）、ポリアクリル酸、グリセリン、及び水からなるゲル（特許文献３）等が提案されている。 Gels are used in biomedical fields such as cosmetics, conductive materials, thickeners, biomaterials, medical sensors, drug delivery systems, and cell culture substrates, and are expected to further improve their functionality. Conventional gels include a gel composed of 1-butyl-3-methylimidazolium chloride, xanthan gum, and water (Patent Document 1), a gel using gelatin (Patent Document 2), polyacrylic acid, glycerin, and water. A gel (Patent Document 3) and the like consisting of
特開２０１０－１７４１４５号公報JP 2010-174145 A 特開２０１６－１８５９３３号公報JP 2016-185933 A 国際公開第２０１２／０３６０６４号WO2012/036064
　従来知られているゲルの中でも、特許文献１のような多糖類とアンモニウム塩を用いたゲルは有機溶媒等で洗浄することなく、簡便かつ安価に安定なハイドロゲルを製造することができるが、更に、実際に使用するときの有用性を改良したゲルの形成又は増粘特性に適した組成物が望まれていた。ゲルは、生体関連分野として生体材料、化粧品、導電性材料、医療用センサー、ドラックデリバリーシステム、細胞培養基材等の材料での応用が期待されている。また、工業材料分野では、工業用センサー、粘着剤、増粘剤、電極、導電材料等の材料での応用が期待されている。これらの分野では、高い安全性の他、保水性、導電性、酵素をはじめとする生体材料に対する安定化効果、有効成分の溶解性と放出性、及びチクソ性を有するゲルの形成又は増粘特性に適した組成物が望まれてきた。 Among conventionally known gels, a gel using a polysaccharide and an ammonium salt, such as that disclosed in Patent Document 1, can be easily and inexpensively produced as a stable hydrogel without washing with an organic solvent or the like. Further, there is a need for compositions suitable for gel forming or thickening properties with improved usability in practical use. Gels are expected to be applied to materials such as biomaterials, cosmetics, conductive materials, medical sensors, drug delivery systems, cell culture substrates, etc. in the field of living organisms. In the field of industrial materials, it is expected to be applied to materials such as industrial sensors, adhesives, thickeners, electrodes, and conductive materials. In these fields, in addition to high safety, water retention, electrical conductivity, stabilizing effect on enzymes and other biomaterials, solubility and release of active ingredients, and formation or thickening properties of gels with thixotropic properties. There has been a desire for a composition suitable for
　上記の課題を解決するために、本発明の組成物は、次の成分（Ａ）、（Ｂ）、高分子化合物及び水を添加成分として含み、
　成分（Ａ）と成分（Ｂ）の少なくともいずれかに水素結合性官能基を有することを特徴としている。
（Ａ）アミンもしくはアンモニウム化合物
（Ｂ）酸もしくはその塩 In order to solve the above problems, the composition of the present invention contains the following components (A) and (B), a polymer compound and water as additive components,
At least one of component (A) and component (B) has a hydrogen-bonding functional group.
(A) amine or ammonium compound (B) acid or salt thereof
　本発明の組成物は、水、高分子化合物と、少なくともいずれかに水素結合性官能基を有する成分（Ａ）及び成分（Ｂ）を含み、ゲルの形成又は増粘特性に優れ、保水性、導電性、酵素をはじめとする生体材料に対する安定化効果、有効成分の溶解性と放出性、及びチクソ性に優れる。 The composition of the present invention contains water, a polymer compound, and at least one of component (A) and component (B) having a hydrogen-bonding functional group, and is excellent in gel-forming or thickening properties, water retention, It has excellent electrical conductivity, stabilizing effect on biomaterials including enzymes, solubility and release of active ingredients, and thixotropy.
　以下に、本発明を詳細に説明する。 The present invention will be described in detail below.
　本発明の組成物は、水、高分子化合物、前記成分（Ａ）及び（Ｂ）を含む組成物であって、成分（Ａ）と成分（Ｂ）の少なくともいずれかに水素結合性官能基を有する。 The composition of the present invention comprises water, a polymer compound, and the components (A) and (B), wherein at least one of component (A) and component (B) has a hydrogen-bonding functional group. have.
　成分（Ａ）のうちアミン化合物の骨格は特に限定されず、例えば、アミン（アンモニア、１級アミン、２級アミン、３級アミン）、イミダゾール、ピリジン、ピロリジン、ピペリジン、ピロリン、ピラジン、トリアゾール、イソキノリン、オキサゾリン、チアゾリン、モルホリン、グアニジン、ピリミジン、ピペラジン、トリアジン、キノリン、インドール、キノキサリン、イソオキサゾリン等をはじめとする環状アミン、各種アミノ酸等が挙げられ、これらの中でもアミン、アミノ酸が好ましい。また、これらに後記［置換基］の欄に記載の置換基等を含んでもよい。 The skeleton of the amine compound of component (A) is not particularly limited. , oxazoline, thiazoline, morpholine, guanidine, pyrimidine, piperazine, triazine, quinoline, indole, quinoxaline, isoxazoline, and other cyclic amines and various amino acids, among which amines and amino acids are preferred. In addition, these may contain substituents described in the section [Substituents] below.
　前記アミノ酸としては、特に限定されないが、例えば、グリシン、アラニン、グルタミン酸、アルギニン、アスパラギン、アスパラギン酸、イソロイシン、グルタミン、ヒスチジン、システイン、ロイシン、リシン、プロリン、フェニルアラニン、トレオニン、セリン、トリプトファン、チロシン、メチオニン、バリン、サルコシン、アミノ酪酸、メチルロイシン、アミノカプリル酸、アミノヘキサン酸、アミノカプリン酸、アミノラウリン酸、アミノミリスチン酸、アミノパルミチン酸、アミノステアリン酸、ノルバリン、アミノ吉草酸、アミノイソ酪酸、チロキシン、クレアチン、オルニチン、オパイン、テアニン、トリコロミン、カイニン酸、ドウモイ酸、イボテン酸、アクロメリン酸、シスチン、ヒドロキシプロリン、ヒドロキシリシン、サイロキシン、ホスホセリン、デスモシン、βアラニン、シトルリン、クレアチン、トリメチルグリシン、シスタチオニン、メチルヒスチジン、アンセリン、カルノシン、アミノアジピン酸、オミチン等が挙げられる。 Examples of the amino acids include, but are not limited to, glycine, alanine, glutamic acid, arginine, asparagine, aspartic acid, isoleucine, glutamine, histidine, cysteine, leucine, lysine, proline, phenylalanine, threonine, serine, tryptophan, tyrosine, and methionine. , valine, sarcosine, aminobutyric acid, methylleucine, aminocaprylic acid, aminohexanoic acid, aminocapric acid, aminolauric acid, aminomyristic acid, aminopalmitic acid, aminostearic acid, norvaline, aminovaleric acid, aminoisobutyric acid, thyroxine, Creatine, ornithine, opine, theanine, tricolamine, kainate, domoic acid, ibotenic acid, acromelic acid, cystine, hydroxyproline, hydroxylysine, thyroxine, phosphoserine, desmosine, beta-alanine, citrulline, creatine, trimethylglycine, cystathionine, methylhistidine , anserine, carnosine, aminoadipic acid, omitin and the like.
　成分（Ａ）のうちアンモニウム化合物は、上記のアミン化合物の塩又は、アミン化合物を４級化したものが挙げられる。 Among the components (A), the ammonium compounds include salts of the above amine compounds and quaternary amine compounds.
　成分（Ａ）は、水素結合性官能基を有することが好ましい。
　成分（Ａ）に有する水素結合性官能基としては、特に限定されないが、例えば、酸素含有基、窒素含有基、硫黄含有基、リン含有基、窒素に直接結合した水素原子等が挙げられる。 Component (A) preferably has a hydrogen-bonding functional group.
The hydrogen-bonding functional group in component (A) is not particularly limited, but examples thereof include oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups, hydrogen atoms directly bonded to nitrogen, and the like.
　酸素含有基としては、特に限定されないが、例えば、水酸基、カルボニル基、エーテル基、エステル基、アルデヒド基、カルボキシ基、カルボキシレート基、尿素基、ウレタン基、アミド基、オキサゾール基、モルホリン基、カルバミン酸基、カルバメート基等が挙げられる。これらの中でも水酸基、カルボキシ基が好ましく、水酸基がより好ましい。 Examples of oxygen-containing groups include, but are not limited to, hydroxyl groups, carbonyl groups, ether groups, ester groups, aldehyde groups, carboxyl groups, carboxylate groups, urea groups, urethane groups, amide groups, oxazole groups, morpholine groups, carbamine groups. An acid group, a carbamate group, and the like can be mentioned. Among these, a hydroxyl group and a carboxy group are preferred, and a hydroxyl group is more preferred.
　窒素含有基としては、特に限定されないが、例えば、アミノ基、ニトロ基等が挙げられる。 The nitrogen-containing group is not particularly limited, but includes, for example, an amino group, a nitro group, and the like.
　硫黄含有基としては、特に限定されないが、例えば、硫酸基（－Ｏ－Ｓ（＝Ｏ）2－Ｏ－）、スルホニル基（－Ｓ（＝Ｏ）2Ｏ－）、スルホン酸基（－Ｓ（＝Ｏ）2－）、メルカプト基（－ＳＨ）、チオエーテル基（－Ｓ－）、チオカルボニル基（－Ｃ（＝Ｓ）－）、チオ尿素基（－Ｎ－Ｃ（＝Ｓ）－Ｎ－）、チオカルボキシ基（－Ｃ（＝Ｓ）ＯＨ）、チオカルボキシレート基（－Ｃ（＝Ｓ）Ｏ－）、ジチオカルボキシ基（－Ｃ（＝Ｓ）ＳＨ）、ジチオカルボキシレート基（－Ｃ（＝Ｓ）Ｓ－）等が挙げられる。 The sulfur-containing group is not particularly limited, but examples include a sulfate group (--O--S(=O) 2 --O--), a sulfonyl group (--S(=O) 2 O--), a sulfonic acid group (--S (=O) 2 -), mercapto group (-SH), thioether group (-S-), thiocarbonyl group (-C(=S)-), thiourea group (-N-C(=S)-N -), thiocarboxy group (-C (=S) OH), thiocarboxylate group (-C (=S) O-), dithiocarboxy group (-C (=S) SH), dithiocarboxylate group (- C(=S)S-) and the like.
　リン含有基としては、特に限定されないが、例えば、リン酸基（－Ｏ－Ｐ（＝Ｏ）（－Ｏ－）－Ｏ－）、ホスホン酸基（－Ｐ（＝Ｏ）（－Ｏ－）－Ｏ－）、ホスフィン酸基（－Ｐ（＝Ｏ）－Ｏ－）、亜リン酸基（－Ｏ－Ｐ（－Ｏ－）－Ｏ－）、亜ホスホン酸基（－Ｐ（－Ｏ－）－Ｏ－）、亜ホスフィン酸基（－Ｐ－Ｏ－）ピロホスフェート基[（－Ｏ－Ｐ（＝Ｏ）（－Ｏ－））2－Ｏ－]等が挙げられる。 The phosphorus-containing group is not particularly limited. -O-), phosphinic acid group (-P (=O) -O-), phosphorous acid group (-OP (-O-) -O-), phosphonous acid group (-P (-O- )--O--), phosphite group (--PO--), pyrophosphate group [(--OP(=O)(--O--)) 2 --O--] and the like.
　成分（Ａ）に有する水素結合性官能基としては、水、高分子化合物への配位、結合等の親和性の観点から、水酸基、カルボキシ基、カルボキシレート基、エステル基、エーテル基、アルコキシ基、窒素に直接結合した水素原子が好ましい。これらの中でも、水酸基、カルボキシ基、カルボキシレート基、エーテル基、アルコキシ基、窒素に直接結合した水素原子がより好ましく、水酸基、カルボキシ基、カルボキシレート基、窒素に直接結合した水素原子が更に好ましく、水酸基、カルボキシ基、窒素に直接結合した水素原子が特に好ましく、水酸基、窒素に直接結合した水素原子が最も好ましい。水素結合性官能基を持つ置換基の好ましい例として、水素結合性官能基を有する炭化水素基が挙げられる。例えば、水素結合性官能基を持つ置換基としては、ヒドロキシ基を含む炭化水素基（ヒドロキシ炭化水素基）、カルボキシ基を含む炭化水素基（カルボキシ炭化水素基）、ヒドロキシ基とカルボキシ基を含む炭化水素基（ヒドロキシカルボキシ炭化水素基）、カルボキシレート基を含む炭化水素基、エステル基を含む炭化水素基、エーテル基を含む炭化水素基、アルコキシ基を含む炭化水素基等が挙げられる。これらの中でも、ヒドロキシ炭化水素基が好ましい。 Hydrogen-bonding functional groups in component (A) include hydroxyl, carboxy, carboxylate, ester, ether, and alkoxy groups from the viewpoint of affinity for coordination and bonding to water and polymer compounds. , hydrogen atoms directly bonded to nitrogen are preferred. Among these, a hydroxyl group, a carboxy group, a carboxylate group, an ether group, an alkoxy group, and a hydrogen atom directly bonded to nitrogen are more preferable, and a hydroxyl group, a carboxy group, a carboxylate group, and a hydrogen atom directly bonded to nitrogen are more preferable. A hydrogen atom directly bonded to a hydroxyl group, a carboxy group, or nitrogen is particularly preferred, and a hydrogen atom directly bonded to a hydroxyl group or nitrogen is most preferred. A preferred example of the substituent having a hydrogen-bonding functional group is a hydrocarbon group having a hydrogen-bonding functional group. For example, substituents having a hydrogen-bonding functional group include a hydrocarbon group containing a hydroxy group (hydroxy hydrocarbon group), a hydrocarbon group containing a carboxy group (carboxy hydrocarbon group), and a hydrocarbon group containing a hydroxy group and a carboxy group. Examples include a hydrogen group (hydroxycarboxy hydrocarbon group), a hydrocarbon group containing a carboxylate group, a hydrocarbon group containing an ester group, a hydrocarbon group containing an ether group, a hydrocarbon group containing an alkoxy group, and the like. Among these, a hydroxy hydrocarbon group is preferred.
　前記炭化水素基は、飽和又は不飽和脂肪族炭化水素基、飽和又は不飽和脂環式炭化水素基、芳香族炭化水素基等、また、それらを組み合わせた炭化水素基が挙げられる。これらの炭化水素基は、一般的なものを用いることができる。前記炭化水素基の中でも、飽和脂肪族炭化水素基が好ましい。前記炭化水素基としては、後記［炭化水素基］の欄に記載のものが挙げられる。 The hydrocarbon group includes a saturated or unsaturated aliphatic hydrocarbon group, a saturated or unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, etc., and a hydrocarbon group combining them. Common hydrocarbon groups can be used as these hydrocarbon groups. Among the above hydrocarbon groups, saturated aliphatic hydrocarbon groups are preferred. Examples of the hydrocarbon group include those described in the section [Hydrocarbon group] below.
　上記ヒドロキシ炭化水素基は、水酸基を１個以上有し、炭化水素部位が好ましくは炭素数１～２２、より好ましくは炭素数１～１８、更に好ましくは炭素数１～１２、特に好ましくは炭素数１～６の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよい。 The hydroxy hydrocarbon group has one or more hydroxyl groups, and the hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 12 carbon atoms. 1 to 6 linear or branched chains, and the hydrocarbon moiety may contain an oxygen atom.
　上記カルボキシ炭化水素基は、カルボキシ基を１個以上有し、炭化水素部位が好ましくは炭素数１～２２、より好ましくは炭素数１～１８、更に好ましくは炭素数１～１２、特に好ましくは炭素数１～６の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよい。 The carboxy hydrocarbon group has one or more carboxy groups, and the hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, particularly preferably carbon atoms. It is linear or branched with numbers 1 to 6, and the hydrocarbon portion may contain an oxygen atom.
　上記ヒドロキシカルボキシ炭化水素基は、水酸基及びカルボキシ基を各々１個以上有し、炭化水素部位が好ましくは炭素数１～２２、より好ましくは炭素数１～１８、更に好ましくは炭素数１～１２、特に好ましくは炭素数１～６の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよい。 The hydroxycarboxy hydrocarbon group has one or more hydroxyl groups and one or more carboxy groups, and the hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, It is particularly preferably linear or branched having 1 to 6 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom.
　上記カルボキシレート基を含む炭化水素基は、カルボキシレート基を１個以上有し、各炭化水素部位が好ましくは炭素数１～２２、より好ましくは炭素数１～１８、更に好ましくは炭素数１～１２、特に好ましくは炭素数１～６の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよい。 The hydrocarbon group containing the carboxylate group has one or more carboxylate groups, and each hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and still more preferably 1 to 1 carbon atoms. 12, particularly preferably straight or branched having 1 to 6 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom.
　上記エステル基を含む炭化水素基は、エステル基を１個以上有し、各炭化水素部位が好ましくは炭素数１～２２、より好ましくは炭素数１～１８、更に好ましくは炭素数１～１２、特に好ましくは炭素数１～６の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよい。 The hydrocarbon group containing an ester group has one or more ester groups, and each hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, It is particularly preferably linear or branched having 1 to 6 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom.
　上記エーテル基を含む炭化水素基は、エーテル基を１個以上有し、各炭化水素部位が好ましくは炭素数１～２２、より好ましくは炭素数１～１８、更に好ましくは炭素数１～１２、特に好ましくは炭素数１～６の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよい。 The hydrocarbon group containing an ether group has one or more ether groups, and each hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, It is particularly preferably linear or branched having 1 to 6 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom.
　上記アルコキシ基を含む炭化水素基は、アルコキシ基を１個以上有し、各炭化水素部位が好ましくは炭素数１～２２、より好ましくは炭素数１～１８、更に好ましくは炭素数１～１２、特に好ましくは炭素数１～６の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよい。 The hydrocarbon group containing the above alkoxy group has one or more alkoxy groups, and each hydrocarbon moiety preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, It is particularly preferably linear or branched having 1 to 6 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom.
　ここで、炭化水素部位が酸素原子を含む場合、該酸素原子は、例えば、炭化水素部位にエーテル結合、カルボニル基、エステル結合、アミド結合、尿素結合又はウレタン結合を形成する。したがって本発明において「炭化水素部位が酸素原子を含む」とは、酸素原子を含む原子団として窒素原子等のヘテロ原子をも含んでよい基によって炭化水素部位が中断されるか、当該基を基端に含むか、あるいは当該基で水素原子が置換される場合を包含する。 Here, when the hydrocarbon portion contains an oxygen atom, the oxygen atom forms, for example, an ether bond, a carbonyl group, an ester bond, an amide bond, a urea bond, or a urethane bond with the hydrocarbon portion. Therefore, in the present invention, "the hydrocarbon moiety contains an oxygen atom" means that the hydrocarbon moiety is interrupted by a group that may also contain a heteroatom such as a nitrogen atom as an atomic group containing an oxygen atom, or the group is Including at the ends or when a hydrogen atom is substituted in the group.
　上記ヒドロキシ炭化水素基としては、ヒドロキシ基を１個以上有する飽和又は不飽和脂肪族炭化水素基、飽和又は不飽和脂環式炭化水素基、芳香族炭化水素基、また、それらを組み合わせた炭化水素基が挙げられる。ヒドロキシ炭化水素基中の水酸基の数は、２個以上が好ましく、３個以上がより好ましい。更にヒドロキシ飽和脂肪族炭化水素基が好ましく、ヒドロキシ基を１個有する飽和脂肪族炭化水素基（モノヒドロキシアルキル基等）、ヒドロキシ基を２個以上有する飽和脂肪族炭化水素基（ポリヒドロキシアルキル基等）、ヒドロキシ基を３個以上有する飽和脂肪族炭化水素基（ポリヒドロキシアルキル基等）が好ましく、ヒドロキシ基を２個以上有する飽和脂肪族炭化水素基（ポリヒドロキシアルキル基等）、ヒドロキシ基を３個以上有する飽和脂肪族炭化水素基（ポリヒドロキシアルキル基等）がより好ましく、ヒドロキシ基を３個以上有する飽和脂肪族炭化水素基（ポリヒドロキシアルキル基等）が、更に好ましく、これらは炭化水素部位が上記酸素含有基を含んでもよい。 As the hydroxy hydrocarbon group, a saturated or unsaturated aliphatic hydrocarbon group having one or more hydroxy groups, a saturated or unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon combination thereof groups. The number of hydroxyl groups in the hydroxy hydrocarbon group is preferably 2 or more, more preferably 3 or more. Furthermore, a hydroxy saturated aliphatic hydrocarbon group is preferable, a saturated aliphatic hydrocarbon group having one hydroxy group (monohydroxyalkyl group, etc.), a saturated aliphatic hydrocarbon group having two or more hydroxy groups (polyhydroxyalkyl group, etc.) ), a saturated aliphatic hydrocarbon group having 3 or more hydroxy groups (polyhydroxyalkyl group, etc.) is preferable, a saturated aliphatic hydrocarbon group having 2 or more hydroxy groups (polyhydroxyalkyl group, etc.), 3 hydroxy groups more preferably saturated aliphatic hydrocarbon groups having 3 or more hydroxy groups (polyhydroxyalkyl groups, etc.), more preferably saturated aliphatic hydrocarbon groups having 3 or more hydroxy groups (polyhydroxyalkyl groups, etc.), these are hydrocarbon moieties may contain the above oxygen-containing groups.
　ヒドロキシ基を１個有する飽和脂肪族炭化水素基（モノヒドロキシアルキル基等）としては、特に限定されないが、例えば、ヒドロキシメチル基、１－ヒドロキシエチル基、２－ヒドロキシエチル基、１－ヒドロキシプロパン－１－イル基、２－ヒドロキシプロパン－１－イル基、３－ヒドロキシプロパン－１－イル基、１－ヒドロキシプロパン－２－イル基、２－ヒドロキシプロパン－２－イル基、２－ヒドロキシメチルプロパン－２－イル基、２－ヒドロキシエチルプロパン－２－イル基、１－ヒドロキシブタン－１－イル基、２－ヒドロキシブタン－１－イル基、３－ヒドロキシブタン－１－イル基、４－ヒドロキシブタン－１－イル基、１－ヒドロキシ－２－メチルプロパン－１－イル基、２－ヒドロキシ－２－メチルプロパン－１－イル基、３－ヒドロキシ－２－メチルプロパン－１－イル基、１－ヒドロキシブタン－２－イル基、２－ヒドロキシブタン－２－イル基、３－ヒドロキシブタン－２－イル基、４－ヒドロキシブタン－２－イル基、１－ヒドロキシ－２－メチルプロパン－２－イル基、５－ヒドロキシペンタン－１－イル基、２－ヒドロキシメチルペンタン－２－イル基、２－ヒドロキシエチルペンタン－２－イル基、６－ヒドロキシヘキサン－１－イル基、７－ヒドロキシヘプタン－１－イル基、８－ヒドロキシオクタン－１－イル基、９－ヒドロキシノナン－１－イル基、１０－ヒドロキシデカン－１－イル基、２－メチル－１－ヒドロキシプロパン－２－イル基、２－メチル－１－プロパン－２－イル基、１－ヒドロキシ－２－メチルプロパン－２－イル基、１－ヒドロキシ－３－メチルブタン－２－イル基、２－ヒドロキシ－２－メチルプロパン－２－イル基、２－ヒドロキシ－２－メチルブタン－２－イル基、２－エチル－２－ヒドロキシブタン－２－イル基、２－ヒドロキシ－３－メチルペンタン－２－イル基、３－エチル－２－ヒドロキシペンタン－２－イル基、２－エチル－１－ヒドロキシ－３－メチルブタン－２－イル基、１－ヒドロキシ－３－メチル－２－（１－メチルエチル）ブタン－２－イル基、２－エチル－１－ヒドロキシペンタン－２－イル基、１－ヒドロキシ－２－プロピルペンタン－２－イル基、４－エチル－３－ヒドロキシヘキサン－４－イル基、３－エチル－２－ヒドロキシ－２－メチルペンタン－３－イル基、２－エチル－１－ヒドロキシヘキサン－２－イル基、１－ヒドロキシ－２－プロピルヘキサン－２－イル基、２－エチル－１－ヒドロキシヘプタン－２－イル基、２－エチル－１－ヒドロキシ－４－メチルペンタン－２－イル基、１－ヒドロキシ－２－（１－メチルエチル）ペンタン－２－イル基、３－エチル－４－ヒドロキシヘプタン－３－イル基等が挙げられる。モノヒドロキシ飽和脂肪族炭化水素基は、炭素数１～２２のものが好ましく、炭素数１～１８のものがより好ましく、炭素数１～１２のものが更に好ましく、炭素数１～６のものが特に好ましい。 The saturated aliphatic hydrocarbon group having one hydroxy group (such as a monohydroxyalkyl group) is not particularly limited, and examples thereof include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropane- 1-yl group, 2-hydroxypropan-1-yl group, 3-hydroxypropan-1-yl group, 1-hydroxypropan-2-yl group, 2-hydroxypropan-2-yl group, 2-hydroxymethylpropane -2-yl group, 2-hydroxyethylpropan-2-yl group, 1-hydroxybutan-1-yl group, 2-hydroxybutan-1-yl group, 3-hydroxybutan-1-yl group, 4-hydroxy butan-1-yl group, 1-hydroxy-2-methylpropan-1-yl group, 2-hydroxy-2-methylpropan-1-yl group, 3-hydroxy-2-methylpropan-1-yl group, 1 -hydroxybutan-2-yl group, 2-hydroxybutan-2-yl group, 3-hydroxybutan-2-yl group, 4-hydroxybutan-2-yl group, 1-hydroxy-2-methylpropane-2- yl group, 5-hydroxypentan-1-yl group, 2-hydroxymethylpentan-2-yl group, 2-hydroxyethylpentan-2-yl group, 6-hydroxyhexan-1-yl group, 7-hydroxyheptane- 1-yl group, 8-hydroxyoctan-1-yl group, 9-hydroxynonan-1-yl group, 10-hydroxydecan-1-yl group, 2-methyl-1-hydroxypropan-2-yl group, 2 -methyl-1-propan-2-yl group, 1-hydroxy-2-methylpropan-2-yl group, 1-hydroxy-3-methylbutan-2-yl group, 2-hydroxy-2-methylpropane-2- yl group, 2-hydroxy-2-methylbutan-2-yl group, 2-ethyl-2-hydroxybutan-2-yl group, 2-hydroxy-3-methylpentan-2-yl group, 3-ethyl-2- Hydroxypentan-2-yl group, 2-ethyl-1-hydroxy-3-methylbutan-2-yl group, 1-hydroxy-3-methyl-2-(1-methylethyl)butan-2-yl group, 2- ethyl-1-hydroxypentan-2-yl group, 1-hydroxy-2-propylpentan-2-yl group, 4-ethyl-3-hydroxyhexan-4-yl group, 3-ethyl-2-hydroxy-2- methylpentan-3-yl group, 2-ethyl-1-hydroxyhexane-2- yl group, 1-hydroxy-2-propylhexan-2-yl group, 2-ethyl-1-hydroxyheptan-2-yl group, 2-ethyl-1-hydroxy-4-methylpentan-2-yl group, 1 -hydroxy-2-(1-methylethyl)pentan-2-yl group, 3-ethyl-4-hydroxyheptan-3-yl group and the like. The monohydroxy saturated aliphatic hydrocarbon group preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, and 1 to 6 carbon atoms. Especially preferred.
　ヒドロキシ基を２個以上有する飽和脂肪族炭化水素基（ポリヒドロキシアルキル基等）としては、特に限定されないが、例えば、ジ、トリ、テトラ、ペンタ、ヘキサ、ヘプタ、又はオクタヒドロキシアルキル基等が挙げられる。具体的には、特に限定されないが、例えば、１，２－ジヒドロキシエチル基等のジヒドロキシエチル基；１，２－ジヒドロキシプロパン－１－イル基、２，３－ジヒドロキシプロパン－１－イル基等のジヒドロキシプロパン－１－イル基;１，２－ジヒドロキシプロパン－２－イル基、１，３－ジヒドロキシプロパン－２－イル基等のジヒドロキシプロパン－２－イル基；トリヒドロキシプロパン－１－イル基；トリヒドロキシプロパン－２－イル基；トリヒドロキシプロパン－１－イル基；トリヒドロキシプロパン－２－イル基；１，２－ジヒドロキシブタン－１－イル基、１，３－ジヒドロキシブタン－１－イル基、１，４－ジヒドロキシブタン－１－イル基、２，３－ジヒドロキシブタン－１－イル基、２，４－ジヒドロキシブタン－１－イル基、３，４－ジヒドロキシブタン－１－イル基等のジヒドロキシブタン－１－イル基；１，２，３トリヒドロキシブタン－１－イル基、１，２，４トリヒドロキシブタン－１－イル基、１，３，４トリヒドロキシブタン－１－イル基、２，３，４トリヒドロキシブタン－１－イル基等のトリヒドロキシブタン－１－イル基；テトラヒドロキシブタン－１－イル基；１，２－ジヒドロキシ－２－メチルプロパン－１－イル基、１，３－ジヒドロキシ－２－メチルプロパン－１－イル基、２，３－ジヒドロキシ－２－メチルプロパン－１－イル基等のジヒドロキシ－２－メチルプロパン－１－イル基；トリヒドロキシ－２－メチルプロパン－１－イル基；テトラヒドロキシ－２－メチルプロパン－１－イル基；１，２－ジヒドロキシブタン－２－イル基、１，３－ジヒドロキシブタン－２－イル基、１，４－ジヒドロキシブタン－２－イル基、２，３－ジヒドロキシブタン－２－イル基、２，４－ジヒドロキシブタン－２－イル基、３，４－ジヒドロキシブタン－２－イル基等のジヒドロキシブタン－２－イル基；テトラヒドロキシブタン－２－イル基；１，３－ジヒドロキシ－２－メチルプロパン－２－イル基、１，３－ジヒドロキシ－２－エチルプロパン－２－イル基、１，３－ジヒドロキシ－２－ヒドロキシメチルプロパン－２－イル基；テトラヒドロキシブタン－２－イル基；１，３－ジヒドロキシ－２－メチルプロパン－２－イル基、１，３－ジヒドロキシ－２－エチルプロパン－２－イル基、１，３－ジヒドロキシ－２－ヒドロキシメチルプロパン－２－イル基、１，２－ジヒドロキシプロパン－３－イル基、１，１－ジヒドロキシブタン－２－イル基、１，１－ジヒドロキシペンタン－２－イル基、１，１－ジヒドロキシ－５－メチルヘキサン－２－イル基、１，１－ジヒドロキシプロパン－２－イル基、１，１－ジヒドロキシ－４－（－４－ヒドロキシフェニル）ブタン－２－イル基；ジ、トリ、テトラ、又はペンタヒドロキシペンタン－１－イル基；ジ、トリ、テトラ、ペンタ、又はヘキサヒドロキシヘキサン－１－イル基；ジ、トリ、テトラ、ペンタ、ヘキサ、又はヘプタヒドロキシヘプタン－１－イル基；ジ、トリ、テトラ、ペンタ、ヘキサ、ヘプタ、又はオクタヒドロキシオクタン－１－イル基等が挙げられる。ポリヒドロキシ飽和脂肪族炭化水素基は、水酸基を２～８個有するものが好ましく、２～６個有するものがより好ましい。ポリヒドロキシ飽和脂肪族炭化水素基は、アルキル基が炭素数１～２２のものが好ましく、炭素数１～１８のものがより好ましく、炭素数１～１２のものが更に好ましく、炭素数１～６のものが特に好ましい。また、次式で表わされる分岐鎖状のポリヒドロキシ飽和脂肪族炭化水素基は好ましいものとして例示される。 The saturated aliphatic hydrocarbon group having two or more hydroxy groups (polyhydroxyalkyl group, etc.) is not particularly limited, and examples thereof include di-, tri-, tetra-, penta-, hexa-, hepta-, and octahydroxyalkyl groups. be done. Specifically, although not particularly limited, for example, dihydroxyethyl groups such as 1,2-dihydroxyethyl group; 1,2-dihydroxypropan-1-yl group, 2,3-dihydroxypropan-1-yl group dihydroxypropan-1-yl group; 1,2-dihydroxypropan-2-yl group, dihydroxypropan-2-yl group such as 1,3-dihydroxypropan-2-yl group; trihydroxypropan-1-yl group; trihydroxypropan-2-yl group; trihydroxypropan-1-yl group; trihydroxypropan-2-yl group; 1,2-dihydroxybutan-1-yl group, 1,3-dihydroxybutan-1-yl group , 1,4-dihydroxybutan-1-yl group, 2,3-dihydroxybutan-1-yl group, 2,4-dihydroxybutan-1-yl group, 3,4-dihydroxybutan-1-yl group, etc. dihydroxybutan-1-yl group; 1,2,3 trihydroxybutan-1-yl group, 1,2,4 trihydroxybutan-1-yl group, 1,3,4 trihydroxybutan-1-yl group, trihydroxybutan-1-yl group such as 2,3,4 trihydroxybutan-1-yl group; tetrahydroxybutan-1-yl group; 1,2-dihydroxy-2-methylpropan-1-yl group, 1 , 3-dihydroxy-2-methylpropan-1-yl group, dihydroxy-2-methylpropan-1-yl group such as 2,3-dihydroxy-2-methylpropan-1-yl group; trihydroxy-2-methyl Propan-1-yl group; Tetrahydroxy-2-methylpropan-1-yl group; 1,2-dihydroxybutan-2-yl group, 1,3-dihydroxybutan-2-yl group, 1,4-dihydroxybutane -2-yl group, 2,3-dihydroxybutan-2-yl group, 2,4-dihydroxybutan-2-yl group, 3,4-dihydroxybutan-2-yl group and other dihydroxybutan-2-yl groups ; tetrahydroxybutan-2-yl group; 1,3-dihydroxy-2-methylpropan-2-yl group, 1,3-dihydroxy-2-ethylpropan-2-yl group, 1,3-dihydroxy-2- hydroxymethylpropan-2-yl group; tetrahydroxybutan-2-yl group; 1,3-dihydroxy-2-methylpropan-2-yl group, 1,3-dihydroxy-2-ethylpropan-2-yl group, 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group, 1 , 2-dihydroxypropan-3-yl group, 1,1-dihydroxybutan-2-yl group, 1,1-dihydroxypentan-2-yl group, 1,1-dihydroxy-5-methylhexan-2-yl group , 1,1-dihydroxypropan-2-yl group, 1,1-dihydroxy-4-(-4-hydroxyphenyl)butan-2-yl group; di-, tri-, tetra-, or pentahydroxypentan-1-yl group di, tri, tetra, penta, or hexahydroxyhexan-1-yl group; di, tri, tetra, penta, hexa, or heptahydroxyheptan-1-yl group; di, tri, tetra, penta, hexa, hepta , or an octahydroxyoctan-1-yl group. The polyhydroxy saturated aliphatic hydrocarbon group preferably has 2 to 8 hydroxyl groups, more preferably 2 to 6 hydroxyl groups. In the polyhydroxy saturated aliphatic hydrocarbon group, the alkyl group preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, and 1 to 6 carbon atoms. is particularly preferred. Also, a branched polyhydroxy saturated aliphatic hydrocarbon group represented by the following formula is exemplified as a preferable one.
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（式中、Ｒ7は水素原子、炭素数１～８（好ましくは炭素数１～４）の直鎖状のアルキル基、又は炭素数１～８（好ましくは炭素数１～４）の直鎖状のヒドロキシアルキル基を示す。） (Wherein, R 7 is a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms), or a linear alkyl group having 1 to 8 carbon atoms (preferably 1 to 4 carbon atoms) indicates a hydroxyalkyl group.)
　上記式の基としては、特に限定されないが、例えば、１，２－ジヒドロキシプロパン－１－イル基、２，３－ジヒドロキシプロパン－１－イル基、１，２－ジヒドロキシプロパン－２－イル基、１，３－ジヒドロキシプロパン－２－イル基、トリヒドロキシプロパン－１－イル基、トリヒドロキシプロパン－２－イル基、トリヒドロキシプロパン－１－イル基、トリヒドロキシプロパン－２－イル基、１，２－ジヒドロキシブタン－１－イル基、１，３－ジヒドロキシブタン－１－イル基、１，４－ジヒドロキシブタン－１－イル基、２，３－ジヒドロキシブタン－１－イル基、２，４－ジヒドロキシブタン－１－イル基、３，４－ジヒドロキシブタン－１－イル基、１，２，３トリヒドロキシブタン－１－イル基、１，２，４トリヒドロキシブタン－１－イル基１，３，４トリヒドロキシブタン－１－イル基、２，３，４トリヒドロキシブタン－１－イル基、テトラヒドロキシブタン－１－イル基、１，２－ジヒドロキシ－２－メチルプロパン－１－イル基、１，３－ジヒドロキシ－２－メチルプロパン－１－イル基、２，３－ジヒドロキシ－２－メチルプロパン－１－イル基、トリヒドロキシ－２－メチルプロパン－１－イル基、テトラヒドロキシ－２－メチルプロパン－１－イル基、１，２－ジヒドロキシブタン－２－イル基、１，３－ジヒドロキシブタン－２－イル基、１，４－ジヒドロキシブタン－２－イル基、２，３－ジヒドロキシブタン－２－イル基、２，４－ジヒドロキシブタン－２－イル基、３，４－ジヒドロキシブタン－２－イル基、テトラヒドロキシブタン－２－イル基、１，３－ジヒドロキシ－２－メチルプロパン－２－イル基、１，３－ジヒドロキシ－２－エチルプロパン－２－イル基、１，３－ジヒドロキシ－２－ヒドロキシメチルプロパン－２－イル基、テトラヒドロキシブタン－２－イル基、１，３－ジヒドロキシ－２－メチルプロパン－２－イル基、１，３－ジヒドロキシ－２－エチルプロパン－２－イル基、１，３－ジヒドロキシ－２－ヒドロキシメチルプロパン－２－イル基、１，２－ジヒドロキシプロパン－３－イル基、１，１－ジヒドロキシブタン－２－イル基、１，１－ジヒドロキシペンタン－２－イル基、１，１－ジヒドロキシ－５－メチルヘキサン－２－イル基、１，１－ジヒドロキシプロパン－２－イル基、１，１－ジヒドロキシ－４－（－４－ヒドロキシフェニル）ブタン－２－イル基、ジ、トリ、テトラ、又はペンタヒドロキシペンタン－１－イル基、ジ、トリ、テトラ、ペンタ、又はヘキサヒドロキシヘキサン－１－イル基、ジ、トリ、テトラ、ペンタ、ヘキサ、又はヘプタヒドロキシヘプタン－１－イル基、ジ、トリ、テトラ、ペンタ、ヘキサ、ヘプタ、又はオクタヒドロキシオクタン－１－イル基が挙げられる。 The group of the above formula is not particularly limited, but examples include 1,2-dihydroxypropan-1-yl group, 2,3-dihydroxypropan-1-yl group, 1,2-dihydroxypropan-2-yl group, 1,3-dihydroxypropan-2-yl group, trihydroxypropan-1-yl group, trihydroxypropan-2-yl group, trihydroxypropan-1-yl group, trihydroxypropan-2-yl group, 1, 2-dihydroxybutan-1-yl group, 1,3-dihydroxybutan-1-yl group, 1,4-dihydroxybutan-1-yl group, 2,3-dihydroxybutan-1-yl group, 2,4- Dihydroxybutan-1-yl group, 3,4-dihydroxybutan-1-yl group, 1,2,3-trihydroxybutan-1-yl group, 1,2,4-trihydroxybutan-1-yl group 1,3 ,4-trihydroxybutan-1-yl group, 2,3,4-trihydroxybutan-1-yl group, tetrahydroxybutan-1-yl group, 1,2-dihydroxy-2-methylpropan-1-yl group, 1,3-dihydroxy-2-methylpropan-1-yl group, 2,3-dihydroxy-2-methylpropan-1-yl group, trihydroxy-2-methylpropan-1-yl group, tetrahydroxy-2- methylpropan-1-yl group, 1,2-dihydroxybutan-2-yl group, 1,3-dihydroxybutan-2-yl group, 1,4-dihydroxybutan-2-yl group, 2,3-dihydroxybutane -2-yl group, 2,4-dihydroxybutan-2-yl group, 3,4-dihydroxybutan-2-yl group, tetrahydroxybutan-2-yl group, 1,3-dihydroxy-2-methylpropane- 2-yl group, 1,3-dihydroxy-2-ethylpropan-2-yl group, 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group, tetrahydroxybutan-2-yl group, 1,3 -dihydroxy-2-methylpropan-2-yl group, 1,3-dihydroxy-2-ethylpropan-2-yl group, 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group, 1,2- dihydroxypropan-3-yl group, 1,1-dihydroxybutan-2-yl group, 1,1-dihydroxypentan-2-yl group, 1,1-dihydroxy-5-methylhexan-2-yl group, 1, 1-dihydroxypropan-2-yl group, 1,1-dihydroxy-4-(-4-hydroxyphenyl ) butan-2-yl group, di, tri, tetra, or pentahydroxypentan-1-yl group, di, tri, tetra, penta, or hexahydroxyhexan-1-yl group, di, tri, tetra, penta, A hexa or heptahydroxyheptan-1-yl group, a di-, tri-, tetra-, penta-, hexa-, hepta- or octahydroxyoctan-1-yl group.
　以上のポリヒドロキシ飽和脂肪族炭化水素基の中でも、２，３－ジヒドロキシプロパン－１－イル基、１，３－ジヒドロキシプロパン－２－イル基、１，３－ジヒドロキシ－２－エチルプロパン－２－イル基、１，３－ジヒドロキシ－２－ヒドロキシメチルプロパン－２－イル基、ペンタヒドロキシヘキサン－１－イル基が好ましく、１，３－ジヒドロキシ－２－ヒドロキシメチルプロパン－２－イル基がより好ましい。 Among the above polyhydroxy saturated aliphatic hydrocarbon groups, 2,3-dihydroxypropan-1-yl group, 1,3-dihydroxypropan-2-yl group, 1,3-dihydroxy-2-ethylpropane-2- yl group, 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group, and pentahydroxyhexan-1-yl group are preferred, and 1,3-dihydroxy-2-hydroxymethylpropan-2-yl group is more preferred. .
　上記カルボキシ炭化水素基としては、カルボキシ基を１個以上有する飽和又は不飽和脂肪族炭化水素基、飽和又は不飽和脂環式炭化水素基、芳香族炭化水素基、また、それらを組み合わせた炭化水素基が挙げられる。その中でも、炭化水素基が飽和脂肪族炭化水素基（アルキル基等）である、モノカルボキシアルキル基、ポリカルボキシアルキル基が好ましく、これらの具体例としては、上記において例示したモノ、ジ、トリ、テトラ、ペンタ、ヘキサ、ヘプタ、又はオクタヒドロキシアルキル基の水酸基をカルボキシ基に置換したもの（アルキル部位に酸素原子を含んでもよい）が挙げられる。 As the carboxy hydrocarbon group, a saturated or unsaturated aliphatic hydrocarbon group having one or more carboxy groups, a saturated or unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon combination thereof groups. Among them, a monocarboxyalkyl group and a polycarboxyalkyl group, in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group), are preferred, and specific examples thereof include the mono-, di-, tri-, Examples thereof include tetra-, penta-, hexa-, hepta- or octahydroxyalkyl groups in which the hydroxyl group is substituted with a carboxy group (the alkyl moiety may contain an oxygen atom).
　モノカルボキシ飽和脂肪族炭化水素基、ポリカルボキシ飽和脂肪族炭化水素基は、炭素数１～２２のものが好ましく、炭素数１～１８のものがより好ましく、炭素数１～１２のものが更に好ましく、炭素数１～６のものが特に好ましい。 Monocarboxy saturated aliphatic hydrocarbon groups and polycarboxy saturated aliphatic hydrocarbon groups preferably have 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, and even more preferably 1 to 12 carbon atoms. , and those having 1 to 6 carbon atoms are particularly preferred.
　上記ヒドロキシカルボキシ炭化水素基としては、ヒドロキシ基及びカルボシキ基をそれぞれ１個以上有する飽和又は不飽和脂肪族炭化水素基、飽和又は不飽和脂環式炭化水素基、芳香族炭化水素基、また、それらを組み合わせた炭化水素基が挙げられる。その中でも、炭化水素基が飽和脂肪族炭化水素基（アルキル基等）であるものが好ましく、特に限定されないが、例えば、上記において例示したジ、トリ、テトラ、ペンタ、ヘキサ、ヘプタ、又はオクタヒドロキシアルキル基の水酸基の一部をカルボキシ基に置換したもの（アルキル部位に酸素原子を含んでもよい）が挙げられる。ヒドロキシカルボキシ飽和脂肪族炭化水素基は、炭素数１～２２のものが好ましく、炭素数１～１８のものがより好ましく、炭素数１～１２のものが更に好ましく、炭素数１～６のものが特に好ましい。 The hydroxycarboxy hydrocarbon group includes saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups each having one or more hydroxy groups and one or more carboxyl groups, and also and a hydrocarbon group in which Among them, those in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group) are preferable, and are not particularly limited. Examples thereof include alkyl groups in which a portion of the hydroxyl group is substituted with a carboxy group (the alkyl moiety may contain an oxygen atom). The hydroxycarboxy saturated aliphatic hydrocarbon group preferably has 1 to 22 carbon atoms, more preferably 1 to 18 carbon atoms, still more preferably 1 to 12 carbon atoms, and 1 to 6 carbon atoms. Especially preferred.
　上記エステル基を含む炭化水素基としては、エステル基を１個以上有する飽和又は不飽和脂肪族炭化水素基、飽和又は不飽和脂環式炭化水素基、芳香族炭化水素基、また、それらを組み合わせた炭化水素基が挙げられる。その中でも、炭化水素基が飽和脂肪族炭化水素基（アルキル基等）であるものが好ましく、特に限定されないが、例えば、上記において例示したカルボキシ飽和脂肪族炭化水素基のカルボキシ基をエステル化したものが挙げられる。エステル基を含む炭化水素基は、炭素数１～２２のものが好ましい。 Examples of the hydrocarbon group containing an ester group include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups having one or more ester groups, and combinations thereof. and hydrocarbon groups. Among them, those in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group) are preferred, and are not particularly limited. is mentioned. A hydrocarbon group containing an ester group preferably has 1 to 22 carbon atoms.
　上記エーテル基を含む炭化水素基としては、エーテル基を１個以上有する飽和又は不飽和脂肪族炭化水素基、飽和又は不飽和脂環式炭化水素基、芳香族炭化水素基、また、それらを組み合わせた炭化水素基が挙げられる。その中でも、炭化水素基が飽和脂肪族炭化水素基（アルキル基等）であるものが好ましく、特に限定されないが、例えば、炭素数２～２２のアルキル基が酸素原子で中断されたものが挙げられる。 The hydrocarbon group containing an ether group includes a saturated or unsaturated aliphatic hydrocarbon group having one or more ether groups, a saturated or unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. and hydrocarbon groups. Among them, those in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group) are preferred and not particularly limited, but examples thereof include those in which an alkyl group having 2 to 22 carbon atoms is interrupted by an oxygen atom. .
　上記アルコキシ基を含む炭化水素基としては、アルコキシ基を１個以上有する飽和又は不飽和脂肪族炭化水素基、飽和又は不飽和脂環式炭化水素基、芳香族炭化水素基、また、それらを組み合わせた炭化水素基が挙げられる。その中でも、炭化水素基が飽和脂肪族炭化水素基（アルキル基等）であるものが好ましく、特に限定されないが、総炭素数１～２２のアルキル基の基端にアルキルエーテル基が結合したもの又は炭化水素基の水素原子がアルキルエーテル基で置換したものが挙げられる。 The hydrocarbon group containing the alkoxy group includes a saturated or unsaturated aliphatic hydrocarbon group having one or more alkoxy groups, a saturated or unsaturated alicyclic hydrocarbon group, an aromatic hydrocarbon group, or a combination thereof. and hydrocarbon groups. Among them, those in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group) are preferable and not particularly limited, but an alkyl ether group is bonded to the base end of an alkyl group having a total of 1 to 22 carbon atoms, or Examples thereof include those in which hydrogen atoms of hydrocarbon groups are substituted with alkyl ether groups.
　上記カルボキシレート基を含む炭化水素基としては、カルボキシレート基を１個以上有する飽和又は不飽和脂肪族炭化水素基、飽和又は不飽和脂環式炭化水素基、芳香族炭化水素基、また、それらを組み合わせた炭化水素基が挙げられる。その中でも、炭化水素基が飽和脂肪族炭化水素基（アルキル基等）であるものが好ましく、特に限定されないが、総炭素数１～２２のアルキル基の基端にカルボキシレート基が結合したもの又は炭化水素基の水素原子をカルボキシレート基で置換したものが挙げられる。 Examples of the hydrocarbon group containing a carboxylate group include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, and aromatic hydrocarbon groups having one or more carboxylate groups. and a hydrocarbon group in which Among them, those in which the hydrocarbon group is a saturated aliphatic hydrocarbon group (such as an alkyl group) are preferred, and are not particularly limited. Examples include those in which a hydrogen atom of a hydrocarbon group is substituted with a carboxylate group.
　成分（Ａ）、及び成分（Ａ）由来のカチオンにおける水素結合性官能基以外の置換基としては、例えば、有機基を挙げることができる。 Examples of substituents other than hydrogen-bonding functional groups in component (A) and cations derived from component (A) include organic groups.
［有機基］
　本明細書において有機基は、炭素原子を必須とし、その他に水素原子、酸素原子、窒素原子、硫黄原子、リン原子、及びハロゲン原子から選ばれる少なくとも１種を含んでもよい。有機基に含まれる原子団は、特に限定されないが、例えば、炭化水素基、複素環基、及び後記［置換基］の欄に記載の置換基等が挙げられる。例えば、後記［置換基］の欄に記載の置換基等が、炭化水素基の水素原子と置換し、炭化水素基を中断し、炭化水素基の基端に含み、あるいは芳香族炭化水基と縮合環を形成した基も含まれる。 [Organic group]
In the present specification, the organic group essentially has a carbon atom and may additionally contain at least one selected from a hydrogen atom, an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, and a halogen atom. Although the atomic group contained in the organic group is not particularly limited, examples thereof include hydrocarbon groups, heterocyclic groups, and substituents described in the section [Substituents] below. For example, the substituents described in the "Substituents" column below replace the hydrogen atoms of the hydrocarbon group, interrupt the hydrocarbon group, are included at the base end of the hydrocarbon group, or are combined with the aromatic hydrocarbon group. Groups forming condensed rings are also included.
　有機基における炭素数は、特に限定されないが、例えば、水、高分子化合物との親和性から、１～８が好ましく、１～６がより好ましく、１～４が更に好ましい。 Although the number of carbon atoms in the organic group is not particularly limited, it is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4 in terms of affinity with water and polymer compounds.
［炭化水素基］
　本明細書において炭化水素基としては、特に限定されないが、例えば、飽和又は不飽和脂肪族炭化水素基、飽和又は不飽和脂環式炭化水素基、芳香族炭化水素基、また、それらを組み合わせた炭化水素基等が挙げられる。文脈に応じて１価でも多価でもよく、１価の飽和又は不飽和脂肪族炭化水素基としては、特に限定されないが、例えば、直鎖状もしくは分岐鎖状のアルキル基、アルケニル基、アルキニル基等が挙げられる。アルキル基は、直鎖状もしくは分岐鎖状を含み、特に限定されないが、例えば、メチル基、エタン－１－イル基、プロパン－１－イル基、１－メチルエタン－１－イル基、ブタン－１－イル基、ブタン－２－イル基、２－メチルプロパン－１－イル基、２－メチルプロパン－２－イル基、ペンタン－１－イル基、ペンタン－２－イル基、ヘキサン－１－イル基、ヘプタン－１－イル基、オクタン－１－イル基、２－エチルヘキサン－１－イル基、１，１，３，３－テトラメチルブタン－１－イル基、ノナン－１－イル基、デカン－１－イル基、ウンデカン－１－イル基、ドデカン－１－イル基、トリデカン－１－イル基、テトラデカン－１－イル基、ペンタデカン－１－イル基、ヘキサデカン－１－イル基、２－ヘキシルデカン－１－イル基、ヘプタデカン－１－イル基、オクタデカン－１－イル基、ノナデカン－１－イル基、イコサン－１－イル基、ヘンイコサン－１－イル基、ドコサン－１－イル基、４，８，１２－トリメチルトリデカン－１－イル基、ベンジル基、α，α－ジメチルベンジル基等が挙げられる。アルケニル基は直鎖状もしくは分岐鎖状を含み、特に限定されないが、例えば、ビニル基、プロパ－１－エン－１－イル基、アリル基、イソプロペニル基、ブタ－１－エン－１－イル基、ブタ－２－エン－１－イル基、ブタ－３－エン－１－イル基、２－メチルプロパ－２－エン－１－イル基、１－メチルプロパ－２－エン－１－イル基、ペンタ－１－エン－１－イル基、ペンタ－２－エン－１－イル基、ペンタ－３－エン－１－イル基、ペンタ－４－エン－１－イル基、３－メチルブタ－２－エン－１－イル基、３－メチルブタ－３－エン－１－イル基、ヘキサ－１－エン－１－イル基、ヘキサ－２－エン－１－イル基、ヘキサ－３－エン－１－イル基、ヘキサ－４－エン－１－イル基、ヘキサ－５－エン－１－イル基、４－メチルペンタ－３－エン－１－イル基、４－メチルペンタ－３－エン－１－イル基、ヘプタ－１－エン－１－イル基、ヘプタ－６－エン－１－イル基、オクタ－１－エン－１－イル基、オクタ－７－エン－１－イル基、ノナ－１－エン－１－イル基、ノナ－８－エン－１－イル基、デカ－１－エン－１－イル基、デカ－９－エン－１－イル基、ウンデカ－１－エン－１－イル基、ウンデカ－１０－エン－１－イル基、ドデカ－１－エン－１－イル基、ドデカ－１１－エン－１－イル基、トリデカ－１－エン－１－イル基、トリデカ－１２－エン－１－イル基、テトラデカ－１－エン－１－イル基、テトラデカ－１３－エン－１－イル基、ペンタデカ－１－エン－１－イル基、ペンタデカ－１４－エン－１－イル基、ヘキサデカ－１－エン－１－イル基、ヘキサデカ－１５－エン－１－イル基、ヘプタデカ－１－エン－１－イル基、ヘプタデカ－１６－エン－１－イル基、オクタデカ－１－エン－１－イル基、オクタデカ－９－エン－１－イル基、オクタデカ－１７－エン－１－イル基、ノナデカ－１－エン－１－イル基、イコサ－１－エン－１－イル基、ヘンイコサ－１－エン－１－イル基、ドコサ－１－エン－１－イル基等が挙げられる。アルキニル基は直鎖状もしくは分岐鎖状を含み、特に限定されないが、例えば、エチニル、プロパ－１－イン－１－イル基、プロパ－２－イン－１－イル基、ブタ－１－イン－１－イル基、ブタ－３－イン－１－イル基、１－メチルプロパ－２－イン－１－イル基、ペンタ－１－イン－１－イル基、ペンタ－４－イン－１－イル基、ヘキサ－１－イン－１－イル基、ヘキサ－５－イン－１－イル基、ヘプタ－１－イン－１－イル基、ヘプタ－６－イン－１－イル基、オクタ－１－イン－１－イル基、オクタ－７－イン－１－イル基、ノナ－１－イン－１－イル基、ノナ－８－イン－１－イル基、デカ－１－イン－１－イル基、デカ－９－イン－１－イル基、ウンデカ－１－イン－１－イル基、ウンデカ－１０－イン－１－イル基、ドデカ－１－イン－１－イル基、ドデカ－１１－イン－１－イル基、トリデカ－１－イン－１－イル基、トリデカ－１２－イン－１－イル基、テトラデカ－１－イン－１－イル基、テトラデカ－１３－イン－１－イル基、ペンタデカ－１－イン－１－イル基、ペンタデカ－１４－イン－１－イル基、ヘキサデカ－１－イン－１－イル基、ヘキサデカ－１５－イン－１－イル基、ヘプタデカ－１－イン－１－イル基、ヘプタデカ－１６－イン－１－イル基、オクタデカ－１－イン－１－イル基、オクタデカ－１７－イン－１－イル基、ノナデカ－１－イン－１－イル基、イコサ－１－イン－１－イル基、ヘンイコサ－１－イン－１－イル基、ドコサ－１－イン－１－イル基等が挙げられる。 [Hydrocarbon group]
In the present specification, the hydrocarbon group is not particularly limited, and examples include saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and combinations thereof. A hydrocarbon group etc. are mentioned. Depending on the context, it may be monovalent or polyvalent, and examples of monovalent saturated or unsaturated aliphatic hydrocarbon groups include, but are not limited to, linear or branched alkyl groups, alkenyl groups and alkynyl groups. etc. Alkyl groups include linear or branched chains, but are not particularly limited. -yl group, butan-2-yl group, 2-methylpropan-1-yl group, 2-methylpropan-2-yl group, pentan-1-yl group, pentan-2-yl group, hexan-1-yl group, heptane-1-yl group, octan-1-yl group, 2-ethylhexan-1-yl group, 1,1,3,3-tetramethylbutan-1-yl group, nonan-1-yl group, decan-1-yl group, undecane-1-yl group, dodecane-1-yl group, tridecane-1-yl group, tetradecane-1-yl group, pentadecane-1-yl group, hexadecane-1-yl group, 2 -hexyldecane-1-yl group, heptadecan-1-yl group, octadecane-1-yl group, nonadecan-1-yl group, icosan-1-yl group, henicosan-1-yl group, docosan-1-yl group, 4,8,12-trimethyltridecan-1-yl group, benzyl group, α,α-dimethylbenzyl group and the like. Alkenyl groups include linear or branched chains, and are not particularly limited, but examples include vinyl, prop-1-en-1-yl, allyl, isopropenyl, but-1-en-1-yl. group, but-2-en-1-yl group, but-3-en-1-yl group, 2-methylprop-2-en-1-yl group, 1-methylprop-2-en-1-yl group, pent-1-en-1-yl group, pent-2-en-1-yl group, pent-3-en-1-yl group, pent-4-en-1-yl group, 3-methylbut-2- En-1-yl group, 3-methylbut-3-en-1-yl group, hex-1-en-1-yl group, hex-2-en-1-yl group, hex-3-en-1- yl group, hex-4-en-1-yl group, hex-5-en-1-yl group, 4-methylpent-3-en-1-yl group, 4-methylpent-3-en-1-yl group , hept-1-en-1-yl group, hept-6-en-1-yl group, octa-1-en-1-yl group, octa-7-en-1-yl group, non-1-ene -1-yl group, non-8-en-1-yl group, dec-1-en-1-yl group, dec-9-en-1-yl group, undec-1-en-1-yl group, undec-10-en-1-yl group, dodec-1-en-1-yl group, dodec-11-en-1-yl group, tridec-1-en-1-yl group, tridec-12-en- 1-yl group, tetradeca-1-en-1-yl group, tetradeca-13-en-1-yl group, pentadeca-1-en-1-yl group, pentadec-14-en-1-yl group, hexadecaco -1-en-1-yl group, hexadec-15-en-1-yl group, heptadecan-1-en-1-yl group, heptadedec-16-en-1-yl group, octadec-1-en-1 -yl group, octadec-9-en-1-yl group, octadec-17-en-1-yl group, nonadecan-1-en-1-yl group, icosa-1-en-1-yl group, henicosa- 1-en-1-yl group, docos-1-en-1-yl group and the like. Alkynyl groups include straight or branched chains, and are not particularly limited and include, but are not limited to, ethynyl, prop-1-yn-1-yl, prop-2-yn-1-yl, but-1-yn- 1-yl group, but-3-yn-1-yl group, 1-methylprop-2-yn-1-yl group, pent-1-yn-1-yl group, pent-4-yn-1-yl group , hex-1-yn-1-yl group, hex-5-yn-1-yl group, hept-1-yn-1-yl group, hept-6-yn-1-yl group, octa-1-yne -1-yl group, octa-7-yn-1-yl group, non-1-yn-1-yl group, non-8-yn-1-yl group, deca-1-yn-1-yl group, Dec-9-yn-1-yl group, undec-1-yn-1-yl group, undec-10-yn-1-yl group, dodec-1-yn-1-yl group, dodec-11-yn- 1-yl group, tridec-1-yn-1-yl group, tridec-12-yn-1-yl group, tetradeca-1-yn-1-yl group, tetradeca-13-yn-1-yl group, pentadeca -1-yn-1-yl group, pentadeca-14-yn-1-yl group, hexadec-1-yn-1-yl group, hexadec-15-yn-1-yl group, heptadeca-1-yn-1 -yl group, heptadeca-16-yn-1-yl group, octadec-1-yn-1-yl group, octadec-17-yn-1-yl group, nonadeca-1-yn-1-yl group, icosa- 1-yn-1-yl group, henicosa-1-yn-1-yl group, docos-1-yn-1-yl group and the like.
　飽和又は不飽和脂環式炭化水素基としては、飽和脂環式炭化水素基が好ましく、特に限定されないが、例えば、１価の基としてはシクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、また、それらの残基等の脂環残基を含む基が挙げられる。 The saturated or unsaturated alicyclic hydrocarbon group is preferably a saturated alicyclic hydrocarbon group and is not particularly limited. Examples of monovalent groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo A heptyl group, a cyclooctyl group, and a group containing an alicyclic residue such as those residues are included.
　芳香族炭化水素基としては、特に限定されないが、例えば、フェニル基、ナフタレン基、アントラセン基、また、それらの残基等の芳香環残基を含む基が挙げられる。後記［置換基］に記載された置換基等と一緒になって縮合環を形成してもよい。１価の芳香族炭化水素基としては、特に限定されないが、例えば、フェニル基、２－メチルフェニル基、３－メチルフェニル基、４－メチルフェニル基、２，４－ジメチルフェニル基、２，５－ジメチルフェニル基、３，４－ジメチルフェニル基、３，５－ジメチルフェニル基、２，４，５－トリメチルフェニル基、２，４，６－トリメチルフェニル基、４－エチルフェニル基、４－プロピルフェニル基、４－イソプロピルフェニル基、４－ブチルフェニル基、４－ｔｅｒｔ－ブチルフェニル基、４－ペンチルフェニル基、４－ｔｅｒｔ－ペンチルフェニル基、２，４－ビス（４－ｔｅｒｔ－ペンチル）フェニル基、１，１，３，３－テトラメチルブチルフェニル基、２－メチル－５－ｔｅｒｔ－ブチルフェニル基、４－ペンチルフェニル基、４－ヘキシルフェニル基、４－ヘプチルフェニル基、４－オクチルフェニル基、４－ノニルフェニル基、４－デカニルフェニル基、４－ウンデシルフェニル基、４－ドデシルフェニル基、４－トリデシルフェニル基、４－テトラデシルフェニル基、４－ペンタデシルフェニル基、４－ヘキサデシルフェニル基、４－ヘプタデシルフェニル基、４－オクタデシルフェニル基、４－ビフェニル基、２－メトキシフェニル基、３－メトキシフェニル基、４－メトキシフェニル基、２－エトキシフェニル基、３－エトキシフェニル基、４－エトキシフェニル基、２－クロロフェニル基、２－フルオロフェニル基、４－フルオロフェニル基、２－トリフルオロメチルフェニル基、４－トリフルオロメチルフェニル基、４－ヒドロキシフェニル基、１－ナフチル基、２－ナフチル基、１－アントラセニル基、２－アントラセニル基、９－アントラセニル基等が挙げられる。 The aromatic hydrocarbon group is not particularly limited, but includes, for example, a phenyl group, a naphthalene group, an anthracene group, and groups containing aromatic ring residues such as residues thereof. A condensed ring may be formed together with the substituents described in [Substituent] below. Examples of monovalent aromatic hydrocarbon groups include, but are not limited to, phenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dimethylphenyl, 2,5 -dimethylphenyl group, 3,4-dimethylphenyl group, 3,5-dimethylphenyl group, 2,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 4-ethylphenyl group, 4-propyl phenyl group, 4-isopropylphenyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4-pentylphenyl group, 4-tert-pentylphenyl group, 2,4-bis(4-tert-pentyl)phenyl group, 1,1,3,3-tetramethylbutylphenyl group, 2-methyl-5-tert-butylphenyl group, 4-pentylphenyl group, 4-hexylphenyl group, 4-heptylphenyl group, 4-octylphenyl group, 4-nonylphenyl group, 4-decanylphenyl group, 4-undecylphenyl group, 4-dodecylphenyl group, 4-tridecylphenyl group, 4-tetradecylphenyl group, 4-pentadecylphenyl group, 4 -hexadecylphenyl group, 4-heptadecylphenyl group, 4-octadecylphenyl group, 4-biphenyl group, 2-methoxyphenyl group, 3-methoxyphenyl group, 4-methoxyphenyl group, 2-ethoxyphenyl group, 3- ethoxyphenyl group, 4-ethoxyphenyl group, 2-chlorophenyl group, 2-fluorophenyl group, 4-fluorophenyl group, 2-trifluoromethylphenyl group, 4-trifluoromethylphenyl group, 4-hydroxyphenyl group, 1 -naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group and the like.
　２価の炭化水素基としては、上記の基から水素原子を１個除いた基が挙げられる。 Examples of divalent hydrocarbon groups include groups obtained by removing one hydrogen atom from the above groups.
［置換基］
　上記置換基としては、特に限定されないが、例えば、炭化水素基、酸素含有基、窒素含有基、硫黄含有基、リン含有基、ハロゲン等が挙げられる。置換基には、これらの置換基が結合した基も含まれる。 [Substituent]
Examples of the substituent include, but are not limited to, hydrocarbon groups, oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups, and halogens. Substituents also include groups to which these substituents are bonded.
　炭化水素基としては、上記［炭化水素基］に挙げたものが挙げられる。 Examples of the hydrocarbon group include those listed in the above [hydrocarbon group].
　酸素含有基としては、特に限定されないが、例えば、水酸基、アルコキシ基、アセトキシ基、アセチル基、アルデヒド基、カルボキシ基、カルボシキレート基、尿素基、ウレタン基、アミド基、イミド基、エーテル基、カルボニル基、エステル基、オキサゾール基、モルホリン基、カルバメート基、カルバモイル基、ポリオキシエチレン基、トコフェリル基、クロマン基、ジヒドロピラン基、グリセリル基、グリセリルエーテル基等が挙げられる。 Examples of oxygen-containing groups include, but are not limited to, hydroxyl groups, alkoxy groups, acetoxy groups, acetyl groups, aldehyde groups, carboxyl groups, carboxylate groups, urea groups, urethane groups, amide groups, imide groups, ether groups, carbonyl group, ester group, oxazole group, morpholine group, carbamate group, carbamoyl group, polyoxyethylene group, tocopheryl group, chroman group, dihydropyran group, glyceryl group, glyceryl ether group and the like.
　窒素含有基としては、特に限定されないが、例えば、シアノ基、シアナト基、イソシアネート基、ニトロ基、ニトロアルキル基、アミド基、尿素基、ウレタン基、イミド基、カルボジイミド基、アゾ基、ピリジン基、イミダゾール基、１級アミノ基、２級アミノ基、３級アミノ基、４級アンモニウム基、アミノアルキル基等が挙げられる。 Examples of nitrogen-containing groups include, but are not limited to, cyano groups, cyanato groups, isocyanate groups, nitro groups, nitroalkyl groups, amide groups, urea groups, urethane groups, imide groups, carbodiimide groups, azo groups, pyridine groups, imidazole group, primary amino group, secondary amino group, tertiary amino group, quaternary ammonium group, aminoalkyl group and the like.
　硫黄含有基としては、特に限定されないが、例えば、硫酸基、スルホニル基、スルホン酸基、メルカプト基、チオエーテル基、チオカルボニル基、チオ尿素基、チオカルボキシ基、チオカルボキシレート基、ジチオカルボキシ基、ジチオカルボキシレート基、硫酸エステル、チオフェン基、チアゾール基、チオール基、スルホ基、スルフィド基、ジスルフィド基、チオエステル基、チオアミド基、チオカルバメート基、ジチオカルバメート基やそれらのエステル等が挙げられる。 Examples of sulfur-containing groups include, but are not limited to, sulfuric acid group, sulfonyl group, sulfonic acid group, mercapto group, thioether group, thiocarbonyl group, thiourea group, thiocarboxy group, thiocarboxylate group, dithiocarboxy group, Dithiocarboxylate group, sulfate ester, thiophene group, thiazole group, thiol group, sulfo group, sulfide group, disulfide group, thioester group, thioamide group, thiocarbamate group, dithiocarbamate group and esters thereof.
　リン含有基としては、特に限定されないが、例えば、リン酸基、亜リン酸基、ホスホン酸基、ホスフィン酸基、亜ホスホン酸基、亜ホスフィン酸基、ピロホスフェート基、リン酸エステル基、亜リン酸エステル基、ホスホン酸エステル基、ピロホスファート基やそれらのエステル基等が挙げられる。 Examples of phosphorus-containing groups include, but are not limited to, phosphoric acid group, phosphorous acid group, phosphonic acid group, phosphinic acid group, phosphonous acid group, phosphinic acid group, pyrophosphate group, phosphate ester group, Phosphate ester group, phosphonate ester group, pyrophosphate group, ester group thereof and the like.
　ハロゲンとしては、フッ素、塩素、臭素、ヨウ素が挙げられる。 　Halogen includes fluorine, chlorine, bromine, and iodine.
　前記有機基は、置換基を有していてもよく炭化水素部位が酸素原子を含んでいてもよい炭化水素基等が挙げられる。炭化水素基としては、上記［炭化水素基］の欄に記載した内容が参照される。炭化水素基は脂肪族炭化水素基が好ましく、飽和脂肪族炭化水素基（アルキル基等）がより好ましい。飽和脂肪族炭化水素基は、水との親和性の点から、炭素数は、1～８が好ましく、1～６がより好ましく、１～４が更に好ましい。 Examples of the organic group include hydrocarbon groups that may have a substituent and whose hydrocarbon portion may contain an oxygen atom. As for the hydrocarbon group, the contents described in the above [Hydrocarbon group] column are referred to. The hydrocarbon group is preferably an aliphatic hydrocarbon group, more preferably a saturated aliphatic hydrocarbon group (such as an alkyl group). The saturated aliphatic hydrocarbon group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms, from the viewpoint of affinity with water.
　上記炭化水素基は置換基を有していてもよく、ここで置換基としては、特に限定されないが、例えば、上記［置換基］の欄に記載したものが挙げられる。置換基の中でも酸素含有基を有するものが好ましく、その中でも水酸基、カルボキシ基、カルボキシレート基、エステル基、エーテル基、アルコキシ基が好ましい。これらの中でも、水酸基、カルボキシ基、カルボキシレート基、エーテル基、アルコキシ基がより好ましく、水酸基、カルボキシ基、カルボキシレート基が更に好ましく、水酸基、カルボキシ基が特に好ましく、水酸基が殊更好ましい。 The hydrocarbon group may have a substituent, and the substituent is not particularly limited, but includes, for example, those described in the above [Substituent] column. Among the substituents, those having an oxygen-containing group are preferred, and among these, a hydroxyl group, a carboxyl group, a carboxylate group, an ester group, an ether group, and an alkoxy group are preferred. Among these, hydroxyl group, carboxy group, carboxylate group, ether group, and alkoxy group are more preferable, hydroxyl group, carboxy group, and carboxylate group are more preferable, hydroxyl group and carboxy group are particularly preferable, and hydroxyl group is particularly preferable.
　上記炭化水素部位は酸素原子を含んでいてもよく、この場合、炭化水素部位に上記の酸素含有基を含み、例えば、エーテル結合、カルボニル基、水酸基、カルボキシレート基、エステル結合、アミド結合、尿素結合又はウレタン結合を形成もしくは含有する。従って本発明において「炭化水素部位が酸素原子を含む」とは、酸素原子を含む原子団として窒素原子等のヘテロ原子をも含んでよい基によって炭化水素部位が中断されるか、当該基を基端に含むか、あるいは当該基で水素原子が置換される場合を包含する。 The hydrocarbon moiety may contain an oxygen atom. In this case, the hydrocarbon moiety contains the oxygen-containing group described above, for example, an ether bond, a carbonyl group, a hydroxyl group, a carboxylate group, an ester bond, an amide bond, a urea Forms or contains a bond or a urethane bond. Therefore, in the present invention, "the hydrocarbon moiety contains an oxygen atom" means that the hydrocarbon moiety is interrupted by a group that may also contain a heteroatom such as a nitrogen atom as an atomic group containing an oxygen atom, or the group is Including at the ends or when a hydrogen atom is substituted in the group.
　成分（Ａ）は、水及び高分子化合物との親和性と結合性が良くなるように本発明の組成物を形成するためには、１個以上の水素結合性官能基（水酸基及びカルボキシ基が好ましく、水酸基がより好ましい）を有する炭化水素基（飽和脂肪族炭化水素基がより好ましい）を持つことが好ましい態様の一つである。 Component (A) has at least one hydrogen-bonding functional group (hydroxyl and carboxy It is one of preferred embodiments to have a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) having a hydroxyl group is more preferable).
　この場合、成分（Ａ）における官能基を導入可能な部位（窒素部位や、窒素と共に環を構成する炭素部位などの、基本骨格となる化学構造に含まれる原子）が、その１つ以上が水素結合性官能基を持つ炭化水素基で置換されることが好ましく、それ以外の当該部位がある場合には、それぞれ独立に、水素原子であるか、又は炭化水素基（より好ましくは飽和脂肪族炭化水素基）等の有機基で置換されることが好ましい。また当該部位が窒素に直接結合した水素原子のみで構成されることも好ましい。 In this case, one or more of the moieties (atoms contained in the basic skeleton chemical structure, such as nitrogen moieties and carbon moieties that form a ring together with nitrogen) to which functional groups can be introduced in component (A) are hydrogen It is preferably substituted with a hydrocarbon group having a bonding functional group, and if there are other sites, they are each independently a hydrogen atom or a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group). preferably substituted with an organic group such as a hydrogen group). It is also preferred that the site is composed only of hydrogen atoms directly bonded to nitrogen.
　より具体的には、成分（Ａ）のアミンは、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び窒素に直接結合した水素原子のみで構成されるアミン、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び炭化水素基（より好ましくは飽和脂肪族炭化水素基）のみで構成されるアミン、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）のみで構成されるアミン、水素原子のみで構成されるアミンが好ましく、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び窒素に直接結合した水素原子のみで構成されるアミン、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び炭化水素基（より好ましくは飽和脂肪族炭化水素基）のみで構成されるアミン、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）のみで構成されるアミンがより好ましく、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び窒素に直接結合した水素原子のみで構成されるアミン、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び炭化水素基（より好ましくは飽和脂肪族炭化水素基）のみで構成されるアミンが更に好ましく、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び窒素に直接結合した水素原子のみで構成されるアミンが特に好ましい。
　上記水素結合性官能基は、水酸基が好ましい。 More specifically, the amine of component (A) is an amine composed only of a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) having a hydrogen-bonding functional group and a hydrogen atom directly bonded to nitrogen; Hydrocarbon groups having hydrogen-bonding functional groups (more preferably saturated aliphatic hydrocarbon groups) and amines composed only of hydrocarbon groups (more preferably saturated aliphatic hydrocarbon groups), having hydrogen-bonding functional groups Amines composed only of hydrocarbon groups (more preferably saturated aliphatic hydrocarbon groups), amines composed only of hydrogen atoms are preferred, and hydrocarbon groups having hydrogen-bonding functional groups (more preferably saturated aliphatic hydrocarbon groups) are preferred. hydrogen group) and an amine composed only of hydrogen atoms directly bonded to nitrogen, a hydrocarbon group having a hydrogen-bonding functional group (more preferably a saturated aliphatic hydrocarbon group) and a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) Hydrocarbon groups), amines composed only of hydrocarbon groups having hydrogen-bonding functional groups (more preferably saturated aliphatic hydrocarbon groups) are more preferable, and hydrocarbon groups having hydrogen-bonding functional groups are more preferable. Hydrogen groups (more preferably saturated aliphatic hydrocarbon groups) and amines composed only of hydrogen atoms directly bonded to nitrogen, hydrocarbon groups having hydrogen-bonding functional groups (more preferably saturated aliphatic hydrocarbon groups) and An amine composed only of a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) is more preferable, and a hydrocarbon group having a hydrogen-bonding functional group (more preferably a saturated aliphatic hydrocarbon group) and a direct bond to nitrogen Amines composed only of hydrogen atoms are particularly preferred.
The hydrogen-bonding functional group is preferably a hydroxyl group.
　また、別の好ましい態様では、成分（Ａ）のアミンは３個の水酸基を有する。 In another preferred embodiment, the amine of component (A) has 3 hydroxyl groups.
　安全性の観点において、成分（Ａ）がモノヒドロキシアルキル基を有する場合、トリエタノールアミン、ジエタノールアミンが好ましく、特にトリエタノールアミンが好ましい。 From the viewpoint of safety, when component (A) has a monohydroxyalkyl group, triethanolamine and diethanolamine are preferred, and triethanolamine is particularly preferred.
　また、安全性、使用上の観点から、成分（Ａ）は、医薬部外品原料規格（外原規）、医薬部外品添加物規格、日本薬局方（日局）、日本薬局方外医薬部外品規格（局外規）、医薬品添加物規格（薬添規）、食品添加物公定書（食添）に記載された化合物を原料（例えば、酸、塩基）に用いることが好まし。そのような化合物としては、特に限定されないが、例えば、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、２－アミノ－２－ヒドロキシメチル－１、３－プロパンジオール、２－アミノ－２－メチル－１－プロパノール、２－アミノ－２－メチル－１、３－プロパンジオール、モノイソプロパノールアミン、ジイソプロパノールアミン、トリイソプロパノールアミン、２－アセトアミドエタノールアミン、Ｎ－ラウリルジエタノールアミン、ジメチルオクタデシルアミンが好ましく、低臭気の観点から、２－アミノ－２－ヒドロキシメチル－１、３－プロパンジオール、２－アミノ－２－メチル－１、３－プロパンジオールがより好ましく、２－アミノ－２－ヒドロキシメチル－１、３－プロパンジオールが更に好ましい。 In addition, from the viewpoint of safety and use, component (A) is specified in the Standards for Quasi-drug Ingredients (Quasi-drugs Ingredients), Standards for Quasi-drug Additives, Japanese Pharmacopoeia (Japanese Pharmacopoeia), Japanese Pharmacopoeia Drugs It is preferable to use compounds listed in the Standards for Quasi-Drugs (Regulations), Pharmaceutical Additives Standards (Medicine Additives), and Food Additives Standards (Food Additives) as raw materials (for example, acids and bases). Examples of such compounds include, but are not limited to, monoethanolamine, diethanolamine, triethanolamine, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-methyl-1- Propanol, 2-amino-2-methyl-1,3-propanediol, monoisopropanolamine, diisopropanolamine, triisopropanolamine, 2-acetamidoethanolamine, N-lauryldiethanolamine, dimethyloctadecylamine are preferred, from the viewpoint of low odor. From, 2-amino-2-hydroxymethyl-1,3-propanediol, 2-amino-2-methyl-1,3-propanediol are more preferable, and 2-amino-2-hydroxymethyl-1,3-propane Diols are more preferred.
　安全性、使用上の観点から、成分（Ａ）由来のカチオンは、上記アミン化合物に水素原子等のカチオン性残基が結合したものが好ましく、これら水素原子等のカチオン性残基は成分（Ｂ）由来のものであってもよい。 From the viewpoint of safety and usability, the cations derived from component (A) are preferably those in which a cationic residue such as a hydrogen atom is bound to the above amine compound. ) may be derived from
　本発明において、成分（Ｂ）中の残基は電荷を有さない原子又は原子団（基）を指し、電荷を持ちカチオンとなるものをカチオン性残基、アニオンとなるものをアニオン性残基とする。 In the present invention, the residue in the component (B) refers to an uncharged atom or atomic group (group), a cationic residue having a charge that becomes a cation, and an anionic residue that becomes an anion. and
　成分（Ａ）がアンモニウム化合物である場合、アニオンとしては、特に限定されるものではないが、例えば、水酸化物アニオン、ハロゲン系アニオン、硫黄系アニオン、リン系アニオン、シアン系アニオン、ホウ素系アニオン、フッ素系アニオン、窒素酸化物系アニオン、カルボン酸系アニオン等が挙げられ、これらの中でも水酸化物アニオンが好ましい。 When the component (A) is an ammonium compound, the anion is not particularly limited, but examples include hydroxide anions, halogen anions, sulfur anions, phosphorus anions, cyanide anions, and boron anions. , fluorine-based anions, nitrogen oxide-based anions, carboxylic acid-based anions, and the like, and among these, hydroxide anions are preferred.
　成分（Ａ）のアミンもしくはアンモニウム化合物がアミン化合物である場合、前記成分（Ａ）は、下記式（Ｉ）で表されるアミン化合物が好ましい。 When the amine or ammonium compound of component (A) is an amine compound, said component (A) is preferably an amine compound represented by the following formula (I).
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（式中、Ｒ1はそれぞれ独立に、水酸基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシ炭化水素基、カルボキシ基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいカルボキシ炭化水素基、又は水酸基及びカルボキシ基を各々１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシカルボキシ炭化水素基を示し、Ｒ2はそれぞれ独立に、水素原子又は炭素数１～２２の有機基であり、ｍは０～３の整数を示す。） (In the formula, each R 1 independently has one or more hydroxyl groups, the hydrocarbon moiety is linear or branched with 1 to 22 carbon atoms, and the hydrocarbon moiety contains an oxygen atom. a hydroxy hydrocarbon group, a carboxy hydrocarbon having one or more carboxy groups, having a straight or branched hydrocarbon portion having 1 to 22 carbon atoms, and the hydrocarbon portion optionally containing an oxygen atom; or one or more each of a hydroxyl group and a carboxy group, the hydrocarbon moiety being linear or branched having 1 to 22 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom. represents a hydrogen group, each R 2 is independently a hydrogen atom or an organic group having 1 to 22 carbon atoms, and m represents an integer of 0 to 3.)
　前記式（Ｉ）において、ｍは１～３の整数であることが好ましい。 In the above formula (I), m is preferably an integer of 1-3.
　前記式（Ｉ）において、全てのＲ2が水素原子であることが好ましい。 In formula (I) above, all R 2 are preferably hydrogen atoms.
　前記式（Ｉ）において、Ｒ1は炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状のヒドロキシ炭化水素基であることが好ましい。 In the above formula (I), R 1 is preferably a linear or branched hydroxy hydrocarbon group having 1 to 22 carbon atoms in the hydrocarbon moiety.
　前記式（Ｉ）において、前記炭化水素部位における炭化水素が飽和脂肪族炭化水素であることが好ましい。 In the formula (I), the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon.
　前記式（Ｉ）において、Ｒ1のうち少なくとも１つが、水酸基を１個有し、前記炭化水素部位における炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基であることが好ましい。 In formula (I), at least one of R 1 preferably has one hydroxyl group, and the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon hydroxy hydrocarbon group.
　前記式（Ｉ）において、Ｒ1のうち少なくとも１つが、水酸基を２個以上有し、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基であることが好ましい。 In formula (I), at least one of R 1 preferably has two or more hydroxyl groups, and the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon hydroxy hydrocarbon group.
　前記式（Ｉ）において、Ｒ1のうち少なくとも１つが、水酸基を１個以上有し、炭化水素部位が炭素数３～２２の分岐鎖状で、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基であることが好ましい。 In the formula (I), at least one of R 1 has one or more hydroxyl groups, the hydrocarbon moiety is a branched chain having 3 to 22 carbon atoms, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon. It is preferably a hydrogen hydroxy hydrocarbon group.
　式（Ｉ）において、Ｒ1が、水酸基を１個以上有し、炭化水素部位が炭素数３～６の分岐鎖状で前記炭化水素部位がアルキル基のヒドロキシアルキル基であり、全てのＲ2が水素原子であり、ｍは１の整数であることが好ましい態様の一つである。
　式（Ｉ）において、Ｒ1が、水酸基を１個有し、炭化水素部位が炭素数１～６の直鎖状で前記炭化水素部位がアルキル基のヒドロキシアルキル基であり、ｍは３の整数であることが好ましい態様の一つである。 In formula (I), R 1 is a hydroxyalkyl group having one or more hydroxyl groups, a branched hydrocarbon moiety having 3 to 6 carbon atoms, and the hydrocarbon moiety being an alkyl group; is a hydrogen atom and m is an integer of 1 in one preferred embodiment.
In formula (I), R 1 is a hydroxyalkyl group having one hydroxyl group, a linear hydrocarbon moiety having 1 to 6 carbon atoms, the hydrocarbon moiety being an alkyl group, and m being an integer of 3. It is one of preferred embodiments.
　式（Ｉ）において示した上記の好ましいそれぞれの例は、それらの少なくともいずれかの組み合わせが、より好ましい態様となり得る。 A combination of at least one of the above preferred examples shown in formula (I) can be a more preferred embodiment.
　成分（Ａ）のアミンもしくはアンモニウム化合物がアンモニウム化合物である場合、前記成分（Ａ）は、下記式（ＩＩ）で表されるアンモニウム化合物が好ましい。 When the amine or ammonium compound of component (A) is an ammonium compound, said component (A) is preferably an ammonium compound represented by the following formula (II).
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（式中、Ｒ3はそれぞれ独立に、水酸基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシ炭化水素基、カルボキシ基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいカルボキシ炭化水素基、又は水酸基及びカルボキシ基を各々１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシカルボキシ炭化水素基を示し、Ｒ4はそれぞれ独立に、水素原子又は炭素数１～２２の有機基であり、ｎは０～４の整数を示す。Ｘ-はアニオンを示す。） (In the formula, each R 3 independently has one or more hydroxyl groups, the hydrocarbon moiety is linear or branched with 1 to 22 carbon atoms, and the hydrocarbon moiety contains an oxygen atom. a hydroxy hydrocarbon group, a carboxy hydrocarbon having one or more carboxy groups, having a straight or branched hydrocarbon portion having 1 to 22 carbon atoms, and the hydrocarbon portion optionally containing an oxygen atom; or one or more each of a hydroxyl group and a carboxy group, the hydrocarbon moiety being linear or branched having 1 to 22 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom. represents a hydrogen group, each R 4 is independently a hydrogen atom or an organic group having 1 to 22 carbon atoms, n represents an integer of 0 to 4, and X − represents an anion.)
　前記式（ＩＩ）において、ｎは１～４の整数であることが好ましい。 In the above formula (II), n is preferably an integer of 1-4.
　前記式（ＩＩ）において、全てのＲ4が水素原子であることが好ましい。 In formula (II), all R 4 are preferably hydrogen atoms.
　前記式（ＩＩ）において、Ｒ3は炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状のヒドロキシ炭化水素基であることが好ましい。 In the above formula (II), R 3 is preferably a linear or branched hydroxy hydrocarbon group having 1 to 22 carbon atoms in the hydrocarbon moiety.
　前記式（ＩＩ）において、前記炭化水素部位における炭化水素が飽和脂肪族炭化水素であることが好ましい。 In the formula (II), the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon.
　前記式（ＩＩ）において、Ｒ3のうち少なくとも１つが、水酸基を１個有し、前記炭化水素部位における炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基であることが好ましい。 In formula (II), at least one of R 3 preferably has one hydroxyl group, and the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon hydroxy hydrocarbon group.
　前記式（ＩＩ）において、Ｒ3のうち少なくとも１つが、水酸基を２個以上有し、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基であることが好ましい。 In formula (II), at least one of R 3 preferably has two or more hydroxyl groups, and the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon hydroxy hydrocarbon group.
　前記式（ＩＩ）において、Ｒ3のうち少なくとも１つが、水酸基を１個以上有し、炭化水素部位が炭素数３～２２の分岐鎖状で、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基であることが好ましい。 In the formula (II), at least one of R 3 has one or more hydroxyl groups, the hydrocarbon moiety is a branched chain having 3 to 22 carbon atoms, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon. It is preferably a hydrogen hydroxy hydrocarbon group.
　前記式（ＩＩ）において、Ｘ-で表されるアニオンは、水酸化物イオンが好ましい。 In formula (II) above, the anion represented by X − is preferably a hydroxide ion.
　式（ＩＩ）において、Ｒ3が、水酸基を１個以上有し、炭化水素部位が炭素数３～６の分岐鎖状で前記炭化水素部位がアルキル基のヒドロキシアルキル基であり、全てのＲ4が水素原子であり、ｎは１の整数であることが好ましい態様の一つである。
　式（ＩＩ）において、Ｒ3が、水酸基を１個有し、炭化水素部位が炭素数１～６の直鎖状で前記炭化水素部位がアルキル基のヒドロキシアルキル基であり、ｎは３の整数であることが好ましい態様の一つである。 In formula (II), R 3 is a hydroxyalkyl group having one or more hydroxyl groups, a branched hydrocarbon moiety having 3 to 6 carbon atoms, and the hydrocarbon moiety being an alkyl group; is a hydrogen atom and n is an integer of 1 in one preferred embodiment.
In formula (II), R 3 is a hydroxyalkyl group having one hydroxyl group, a straight-chain hydrocarbon moiety having 1 to 6 carbon atoms, the hydrocarbon moiety being an alkyl group, and n being an integer of 3. It is one of preferred embodiments.
　式（ＩＩ）において示した上記の好ましいそれぞれの例は、それらの少なくともいずれかの組み合わせが、より好ましい態様となり得る。 A combination of at least one of the above preferred examples shown in formula (II) can be a more preferred embodiment.
　本発明の組成物は、成分（Ａ）と成分（Ｂ）が形成するアンモニウム塩も一つの好ましい態様である。 The ammonium salt formed by component (A) and component (B) is also one preferred embodiment of the composition of the present invention.
　好ましくは、前記成分（Ｂ）のカチオン性残基を有していてもよい前記成分（Ａ）由来のカチオンと、前記成分（Ｂ）のアニオン性残基に由来するアニオンが形成するアンモニウム塩を含有する。 Preferably, an ammonium salt formed by a cation derived from the component (A), which may have a cationic residue of the component (B), and an anion derived from the anionic residue of the component (B). contains.
　本発明において、成分（Ｂ）中の残基は電荷を有さない原子又は原子団（基）を指し、電荷を持ちカチオンとなるものをカチオン性残基、アニオンとなるものをアニオン性残基とする。 In the present invention, the residue in the component (B) refers to an uncharged atom or atomic group (group), a cationic residue having a charge that becomes a cation, and an anionic residue that becomes an anion. and
　本発明において、成分（Ｂ）の酸もしくはその塩は、カチオン性残基とアニオン性残基とを有する。カチオン性残基は、水素原子であるか又は、成分（Ａ）の窒素原子と結合して水素結合性官能基や有機基となる基（原子団）である。好ましくは、成分（Ｂ）の酸は、プロトンとなる水素とアニオン性残基から構成される化合物である。 In the present invention, the acid of component (B) or a salt thereof has a cationic residue and an anionic residue. The cationic residue is a hydrogen atom or a group (atomic group) that combines with the nitrogen atom of component (A) to form a hydrogen-bonding functional group or an organic group. Preferably, the acid of component (B) is a compound composed of protonated hydrogen and an anionic residue.
　前記カチオンは、アンモニウムカチオンが好ましい。 The cation is preferably an ammonium cation.
　本発明においてアンモニウム塩は、窒素原子をイオン中心とする有機カチオン又はＮＨ4 +、及びアニオンを含む。特に、有機カチオン及び有機アニオンを含む。ここで「有機」の用語は元素として炭素及び水素を含むことを意味する。 In the present invention, ammonium salts include organic cations or NH 4 + having a nitrogen atom as the ion center, and anions. In particular it includes organic cations and organic anions. As used herein, the term "organic" is meant to include carbon and hydrogen as elements.
　前記成分（Ａ）由来のカチオンとしては、特に限定されないが、例えば、アンモニウムカチオン（ＮＨ4 +、１級アンモニウムカチオン、２級アンモニウムカチオン、３級アンモニウムカチオン）、イミダゾリウムカチオン、ピリジニウムカチオン、ピロリジニウムカチオン、ピペリジニウムカチオン、ピロリニウムカチン、ピラジニウムカチオン、トリアゾリウムカチオン、イソキノリニウムカチオン、オキサゾリニウムカチオン、チアゾリニウムカチオン、モルホリニウムカチオン、グアニジウムカチオン、ピリミジニウムカチオン、ピペラジニウムカチオン、トリアジニウムカチオン、キノリニウムカチオン、インドリニウムカチオン、キノキサリニウムカチオン、イソオキサゾリウムカチオン等をはじめとする環状アミン由来のカチオン、カチオン性アミノ酸等が挙げられる。これらの中でもアンモニウムカチオン、イミダゾリウムカチオン、ピリジニウムカチオン、ピロリジニウムカチオン、ピペリジニウムカチオン、モルホリニウムカチオンが好ましく、アンモニウムカチオンがより好ましい。 The cations derived from the component (A) are not particularly limited, but examples include ammonium cations (NH 4 + , primary ammonium cations, secondary ammonium cations, tertiary ammonium cations), imidazolium cations, pyridinium cations, pyrrolidinium cations, cation, piperidinium cation, pyrrolinium cation, pyrazinium cation, triazolium cation, isoquinolinium cation, oxazolinium cation, thiazolinium cation, morpholinium cation, guanidinium cation, pyrimidinium cation cations derived from cyclic amines such as nium cations, piperazinium cations, triazinium cations, quinolinium cations, indolinium cations, quinoxalinium cations, isoxazolium cations, and cationic amino acids. be done. Among these, ammonium cation, imidazolium cation, pyridinium cation, pyrrolidinium cation, piperidinium cation, and morpholinium cation are preferred, and ammonium cation is more preferred.
　前記成分（Ａ）と成分（Ｂ）が形成するアンモニウム塩のカチオンは、下記式（ＩＩＩ）で表されるカチオンが好ましい。また成分（Ａ）がアンモニウム化合物である場合、そのカチオンも下記式（ＩＩＩ）で表されるカチオンが好ましい。 The cation of the ammonium salt formed by the component (A) and the component (B) is preferably a cation represented by the following formula (III). Moreover, when the component (A) is an ammonium compound, its cation is also preferably a cation represented by the following formula (III).
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
（式中、Ｒ5はそれぞれ独立に、水酸基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシ炭化水素基、カルボキシ基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいカルボキシ炭化水素基、又は水酸基及びカルボキシ基を各々１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシカルボキシ炭化水素基を示し、Ｒ6はそれぞれ独立に、水素原子又は炭素数１～２２の有機基であり、ｏは０～４の整数を示す。） (In the formula, each R 5 independently has one or more hydroxyl groups, the hydrocarbon moiety is linear or branched with 1 to 22 carbon atoms, and the hydrocarbon moiety contains an oxygen atom. a hydroxy hydrocarbon group, a carboxy hydrocarbon having one or more carboxy groups, having a straight or branched hydrocarbon portion having 1 to 22 carbon atoms, and the hydrocarbon portion optionally containing an oxygen atom; or one or more each of a hydroxyl group and a carboxy group, the hydrocarbon moiety being linear or branched having 1 to 22 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom. represents a hydrogen group, each R 6 is independently a hydrogen atom or an organic group having 1 to 22 carbon atoms, and o represents an integer of 0 to 4.)
　前記式（ＩＩＩ）において、ｏは１～４の整数であることが好ましい。 In the above formula (III), o is preferably an integer of 1-4.
　前記式（ＩＩＩ）において、全てのＲ6が水素原子であることが好ましい。 In formula (III), all R 6 are preferably hydrogen atoms.
　前記式（ＩＩＩ）において、Ｒ5がヒドロキシ炭化水素基であることが好ましい。 In formula (III) above, R 5 is preferably a hydroxy hydrocarbon group.
　前記式（ＩＩＩ）において、前記炭化水素部位における炭化水素が飽和脂肪族炭化水素であることが好ましい。 In the formula (III), the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon.
　前記式（ＩＩＩ）において、Ｒ5のうち少なくとも１つが、水酸基を１個有し、前記炭化水素部位における炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基が好ましい。 In the formula (III), at least one of R 5 has one hydroxyl group, and the hydrocarbon in the hydrocarbon moiety is preferably a hydroxy hydrocarbon group of saturated aliphatic hydrocarbon.
　前記式（ＩＩＩ）において、Ｒ5のうち少なくとも１つが、水酸基を２個以上有し、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基であることが好ましい。 In formula (III), at least one of R 5 preferably has two or more hydroxyl groups, and the hydrocarbon in the hydrocarbon moiety is preferably a saturated aliphatic hydrocarbon hydroxy hydrocarbon group.
　前記式（ＩＩＩ）において、Ｒ5のうち少なくとも１つが、水酸基を１個以上有し、炭化水素部位が炭素数３～２２の分岐鎖状で、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基であることが好ましい。 In the formula (III), at least one of R 5 has one or more hydroxyl groups, the hydrocarbon moiety is a branched chain having 3 to 22 carbon atoms, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon. It is preferably a hydrogen hydroxy hydrocarbon group.
　前記式（ＩＩＩ）で表されるカチオンのＲ6のうち少なくとも１つが水素原子の場合、その水素原子に対応するプロトンが前記成分（Ｂ）に由来することが好ましい。 When at least one of R 6 of the cation represented by the formula (III) is a hydrogen atom, the proton corresponding to the hydrogen atom is preferably derived from the component (B).
　式（ＩＩＩ）において、Ｒ5が、水酸基を１個以上有し、炭化水素部位が炭素数３～６の分岐鎖状で前記炭化水素部位がアルキル基のヒドロキシアルキル基であり、全てのＲ6が水素原子であり、ｏは１の整数であることが好ましい態様の一つである。
　式（ＩＩＩ）において、Ｒ5が、水酸基を１個有し、炭化水素部位が炭素数１～６の直鎖状で前記炭化水素部位がアルキル基のヒドロキシアルキル基であり、ｏは３の整数であることが好ましい態様の一つである。 In formula (III), R 5 is a hydroxyalkyl group having one or more hydroxyl groups, a branched hydrocarbon moiety having 3 to 6 carbon atoms, and the hydrocarbon moiety being an alkyl group; is a hydrogen atom and o is an integer of 1 in one preferred embodiment.
In the formula (III), R 5 is a hydroxyalkyl group having one hydroxyl group, a linear hydrocarbon moiety having 1 to 6 carbon atoms, the hydrocarbon moiety being an alkyl group, and o being an integer of 3. It is one of preferred embodiments.
　式（ＩＩＩ）において示した上記の好ましいそれぞれの例は、それらの少なくともいずれかの組み合わせが、より好ましい態様となり得る。 A combination of at least one of the above preferred examples shown in formula (III) can be a more preferred embodiment.
　成分（Ａ）由来のカチオン（成分（Ａ）のアンモニウム化合物のカチオン）は、本発明の効果、すなわちゲルの形成性、増粘効果、保水性、導電性、酵素をはじめとする生体材料に対する安定化効果、有効成分の溶解性と放出性、及びチクソ性の点において、１個以上の水素結合性官能基を有する炭化水素基（飽和脂肪族炭化水素基がより好ましい）を持つことが好ましい態様の一つである。 The cation derived from component (A) (the cation of the ammonium compound of component (A)) has the effects of the present invention, namely gel formation, thickening effect, water retention, electrical conductivity, and stability to biomaterials such as enzymes. From the viewpoints of synergizing effect, solubility and releasability of active ingredients, and thixotropy, it is preferable to have a hydrocarbon group having one or more hydrogen-bonding functional groups (more preferably a saturated aliphatic hydrocarbon group). one of.
　この場合、成分（Ａ）の由来のカチオン（成分（Ａ）のアンモニウム化合物のカチオン）における官能基を導入可能な部位（窒素部位や、窒素と共に環を構成する炭素部位などの、基本骨格となる化学構造に含まれる原子）が、その１つ以上が水素結合性官能基を持つ炭化水素基で置換されることが好ましく、それ以外の当該部位がある場合には、それぞれ独立に、水素原子であるか、又は炭化水素基（より好ましくは飽和脂肪族炭化水素基）等の有機基で置換されることが好ましい。また当該部位が窒素に直接結合した水素原子のみで構成されることも好ましい。 In this case, the cation derived from the component (A) (the cation of the ammonium compound of the component (A)) into which a functional group can be introduced (such as a nitrogen site or a carbon site that forms a ring together with nitrogen) becomes a basic skeleton. atoms contained in the chemical structure), one or more of which is preferably substituted with a hydrocarbon group having a hydrogen-bonding functional group. It is preferably present or substituted with an organic group such as a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group). It is also preferred that the site is composed only of hydrogen atoms directly bonded to nitrogen.
　より具体的には、成分（Ａ）由来のカチオン（成分（Ａ）由来のアンモニウム化合物のカチオン）は、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び窒素に直接結合した水素原子のみで構成されるカチオン、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び炭化水素基（より好ましくは飽和脂肪族炭化水素基）のみで構成されるカチオン、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）のみで構成されるカチオン、水素原子のみで構成されるカチオンが好ましく、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び窒素に直接結合した水素原子のみで構成されるカチオン、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び炭化水素基（より好ましくは飽和脂肪族炭化水素基）のみで構成されるカチオン、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）のみで構成されるカチオンがより好ましく、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び窒素に直接結合した水素原子のみで構成されるカチオン、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び炭化水素基（より好ましくは飽和脂肪族炭化水素基）のみで構成されるカチオンが更に好ましく、水素結合性官能基を持つ炭化水素基（より好ましくは飽和脂肪族炭化水素基）及び窒素に直接結合した水素原子のみで構成されるカチオンが特に好ましい。
　上記水素結合性官能基は、水酸基が好ましい。 More specifically, the cation derived from component (A) (cation of the ammonium compound derived from component (A)) is a hydrocarbon group having a hydrogen-bonding functional group (more preferably a saturated aliphatic hydrocarbon group) and nitrogen A cation composed only of hydrogen atoms directly bonded to, a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) having a hydrogen-bonding functional group, and a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) only A cation composed of, a cation composed only of a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) having a hydrogen-bonding functional group, a cation composed only of hydrogen atoms is preferable, and a hydrogen-bonding functional group A hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) with a cation composed only of hydrogen atoms directly bonded to nitrogen, a hydrocarbon group with a hydrogen-bonding functional group (more preferably a saturated aliphatic hydrocarbon group) and a cation composed only of a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group), composed only of a hydrocarbon group having a hydrogen-bonding functional group (more preferably a saturated aliphatic hydrocarbon group) A cation is more preferable, and a cation composed only of a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) having a hydrogen-bonding functional group (more preferably a saturated aliphatic hydrocarbon group) and a hydrogen atom directly bonded to nitrogen, a hydrocarbon having a hydrogen-bonding functional group A cation composed only of a group (more preferably a saturated aliphatic hydrocarbon group) and a hydrocarbon group (more preferably a saturated aliphatic hydrocarbon group) is more preferable, and a hydrocarbon group having a hydrogen-bonding functional group (more preferably is a saturated aliphatic hydrocarbon group) and cations consisting only of hydrogen atoms directly bonded to nitrogen are particularly preferred.
The hydrogen-bonding functional group is preferably a hydroxyl group.
　前記式（ＩＩＩ）で表されるカチオンは、上記成分（Ａ）のアミンに水素原子等のカチオン性残基が結合したものであり、これら水素原子等のカチオン性残基は成分（Ｂ）由来が好ましい態様である。 The cation represented by the formula (III) is obtained by bonding a cationic residue such as a hydrogen atom to the amine of the component (A), and the cationic residue such as a hydrogen atom is derived from the component (B). is a preferred embodiment.
　また、ゲルの形成又は増粘特性に適する観点からは、成分（Ａ）、式（Ｉ）、（ＩＩ）、（ＩＩＩ）の炭化水素基（アルキル基等）の総炭素数は、１～１２が好ましく、１～８がより好ましく、１～６が更に好ましく、１～４が特に好ましい。 Further, from the viewpoint of suitability for gel-forming or thickening properties, the total carbon number of the hydrocarbon groups (such as alkyl groups) in component (A), formulas (I), (II), and (III) is 1 to 12. is preferred, 1 to 8 are more preferred, 1 to 6 are even more preferred, and 1 to 4 are particularly preferred.
　本発明の組成物において、成分（Ｂ）の酸もしくはその塩は、カチオン性残基とアニオン性残基とを有する。カチオン性残基は、水素原子であるか又は、成分（Ａ）の窒素原子と結合して水素結合性官能基や有機基となる基（原子団）である。 In the composition of the present invention, the acid of component (B) or a salt thereof has a cationic residue and an anionic residue. The cationic residue is a hydrogen atom or a group (atomic group) that combines with the nitrogen atom of component (A) to form a hydrogen-bonding functional group or an organic group.
　成分（Ｂ）における水素結合性官能基は、アニオン性残基に有するものであってもよく、酸におけるプロトンとなる水素であってもよい。好ましくは、水素結合性官能基を少なくともアニオン性残基に有する。 The hydrogen-bonding functional group in component (B) may be one possessed by an anionic residue, or may be hydrogen that becomes a proton in an acid. Preferably, at least the anionic residue has a hydrogen-bonding functional group.
　また本発明において成分（Ｂ）の酸は、プロトンとなる水素とアニオン性残基（例えば、下記に示すアニオン）から構成される化合物の他、成分（Ａ）との塩を形成する反応においてルイス酸的に作用する化合物を除外するものではなく、例えば、炭化水素部位に上記の置換基（好ましくは酸素含有基）を有してもよいハロゲン化炭化水素、ジアルキル硫酸、ジアルキルカーボネート、アルキルスルホン酸、リン酸アルキルエステル等を包含する。好ましくは、成分（Ｂ）の酸は、プロトンとなる水素とアニオン性残基から構成される化合物である。 In the present invention, the component (B) acid is a compound composed of protonated hydrogen and an anionic residue (e.g., the anion shown below), as well as a Lewis acid in a salt-forming reaction with component (A). Acid-acting compounds are not excluded, for example, halogenated hydrocarbons, dialkylsulfuric acids, dialkylcarbonates, alkylsulfonic acids, which may have the above substituents (preferably oxygen-containing groups) on the hydrocarbon moiety , phosphate alkyl esters, and the like. Preferably, the acid of component (B) is a compound composed of protonated hydrogen and an anionic residue.
　成分（Ｂ）のアニオン性残基由来のアニオンとしては、特に限定されるものではないが、例えば、ハロゲン系アニオン、硫黄系アニオン、リン系アニオン、シアン系アニオン、ホウ素系アニオン、フッ素系アニオン、窒素酸化物系アニオン、カルボン酸系アニオン等が挙げられる。これらは１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。これらの中でも、ハロゲン系アニオン、硫黄系アニオン、リン系アニオン、ホウ素系アニオン、フッ素系アニオン、窒素酸化物系アニオン、カルボン酸系アニオンが好ましく、ハロゲン系アニオン、ホウ素系アニオン、フッ素系アニオン、カルボン酸系アニオンがより好ましく、カルボン酸系アニオンが更に好ましい。 The anion derived from the anionic residue of component (B) is not particularly limited, but examples include halogen anions, sulfur anions, phosphorus anions, cyanide anions, boron anions, fluorine anions, Nitrogen oxide-based anions, carboxylic acid-based anions, and the like are included. These may be used individually by 1 type, and may be used in combination of 2 or more type. Among these, halogen-based anions, sulfur-based anions, phosphorus-based anions, boron-based anions, fluorine-based anions, nitrogen oxide-based anions, and carboxylic acid-based anions are preferable. Acid anions are more preferred, and carboxylate anions are even more preferred.
　成分（Ｂ）のアニオン性残基は、水素結合性官能基を有することが好ましく、水素結合性官能基としては、前記の水素結合性官能基が挙げられるが、それらの中でも水酸基、カルボキシ基、カルボキシレート基、エーテル基、アルコキシ基が好ましく、水酸基がより好ましい。 The anionic residue of component (B) preferably has a hydrogen-bonding functional group, and examples of the hydrogen-bonding functional group include the aforementioned hydrogen-bonding functional groups. A carboxylate group, an ether group and an alkoxy group are preferred, and a hydroxyl group is more preferred.
　前記ハロゲン系アニオンとしては、特に限定されないが、例えば、フッ素イオン、クロリドイオン、ブロミドイオン、ヨードイオン、フッ素系アニオン等が挙げられる。 The halogen-based anions are not particularly limited, but include, for example, fluorine ions, chloride ions, bromide ions, iodine ions, fluorine-based anions, and the like.
　前記硫黄系アニオンとしては、特に限定されないが、例えば、スルホナートアニオン、水素スルホナートアニオン、アルキルスルホナートアニオン（例えば、メタンスルホナートアニオン、エチルスルホナートアニオン、ブチルスルホナートアニオン、ベンゼンスルホナートアニオン、ｐ－トルエンスルホナートアニオン、２，４，６－トリメチルベンゼンスルホナートアニオン、スチレンスルホナートアニオン、３－スルホプロピルメタクリレートアニオン、３－スルホプロピルアクリレートアニオン等）、スルファートアニオン、水素スルファートアニオン、アルキルスルファートアニオン（例えば、メチルスルファートアニオン、エチルスルファートアニオン、ブチルスルファートアニオン、オクチルスルファートアニオン、２－(２－メトキシエトキシ)エチルスルファートアニオン等）等が挙げられる。 The sulfur-based anion is not particularly limited. p-toluenesulfonate anion, 2,4,6-trimethylbenzenesulfonate anion, styrenesulfonate anion, 3-sulfopropyl methacrylate anion, 3-sulfopropyl acrylate anion, etc.), sulfate anion, hydrogen sulfate anion, alkyl Sulfate anions (eg, methylsulfate anion, ethylsulfate anion, butylsulfate anion, octylsulfate anion, 2-(2-methoxyethoxy)ethylsulfate anion, etc.) and the like.
　前記リン系アニオンとしては、特に限定されないが、例えば、ホスファートアニオン、水素ホスファートアニオン、二水素ホスファートアニオン、ホスホナートアニオン、水素ホスホナートアニオン、二水素ホスホナートアニオン、ホスフィナートアニオン、水素ホスフィナートアニオン、アルキルホスファートアニオン（例えば、ジメチルホスファートアニオン、ジエチルホスファートアニオン、ジプロピルホスファートアニオン、ジブチルホスファートアニオン等）、アルキルホスホナートアニオン（例えば、メチルホスホナートアニオン、エチルホスホナートアニオン、プロピルホスホナートアニオン、ブチルホスホナートアニオン、メチルメチルホスホナートアニオン等）、アルキルホスフィナートアニオン、ヘキサアルキルホスファートアニオン等が挙げられる。 Examples of the phosphorus-based anion include, but are not limited to, phosphate anion, hydrogen phosphate anion, dihydrogen phosphate anion, phosphonate anion, hydrogen phosphonate anion, dihydrogen phosphonate anion, phosphinate anion, hydrogen Phosphinate anions, alkyl phosphate anions (e.g. dimethyl phosphate anion, diethyl phosphate anion, dipropyl phosphate anion, dibutyl phosphate anion, etc.), alkyl phosphonate anions (e.g. methyl phosphonate anions, ethyl phosphonate anions anion, propylphosphonate anion, butylphosphonate anion, methylmethylphosphonate anion, etc.), alkylphosphinate anion, hexaalkylphosphate anion and the like.
　前記シアン系アニオンとしては、特に限定されないが、例えば、テトラシアノボレートアニオン、ジシアナミドアニオン、チオシアネートアニオン、イソチオシアネートアニオン等が挙げられる。 The cyan anion is not particularly limited, but includes, for example, tetracyanoborate anion, dicyanamide anion, thiocyanate anion, isothiocyanate anion, and the like.
　前記ホウ素系アニオンとしては、特に限定されないが、例えば、テトラフルオロボレートアニオン、ビスオキサレートボラートアニオン、テトラフェニルボレートアニオンのようなテトラアルキルボレートアニオン等が挙げられる。 The boron-based anion is not particularly limited, but includes, for example, a tetraalkylborate anion such as a tetrafluoroborate anion, a bisoxalateborate anion, and a tetraphenylborate anion.
　前記フッ素系アニオンとしては、特に限定されないが、例えば、ビス(フルオロスルホニル)イミドアニオン、ビス(パーフルオロアルキルスルホニル)イミドアニオン（例えば、ビス(トリフルオロメチルスルホニル)イミドアニオン、ビス(ペンタフルオロエチルスルホニル)イミド、ビス（ヘプタフルオロプロパンスルホニル）イミドアニオン、ビス(ノナフルオロブチルスルホニル)イミド等）、パーフルオロアルキルスルホナートアニオン（例えば、トリフルオロメタンスルホナートアニオン、ペンタフルオロエタンスルホナートアニオン、ヘプタフルオロプロパンスルホナートアニオン、ノナフラートアニオン、パーフルオロオクタンスルホーナートアニオン等）、フルオロホスファートアニオン（例えば、ヘキサフルオロホスファートアニオン、トリ(ペンタフルオロエチル)トリフルオロホスファートアニオン等)、トリス（パーフルオロアルキルスルホニル）メチドアニオン（例えば、トリス(トリフルオロメタンスルホニル)メチドアニオン、トリス（ペンタフルオロエタンスルホニル）メチドアニオン、トリス（ヘプタフルオロプロパンスルホニル）メチドアニオン、トリス（ノナフルオロブタンスルホニル）メチドアニオン等）、フルオロハイドロジェネートアニオン、テトラフルオロボレートアニオン等が挙げられる。 The fluorine-based anion is not particularly limited. ) imide, bis(heptafluoropropanesulfonyl)imide anion, bis(nonafluorobutylsulfonyl)imide, etc.), perfluoroalkylsulfonate anion (e.g., trifluoromethanesulfonate anion, pentafluoroethanesulfonate anion, heptafluoropropanesulfonate phosphate anion, nonaflate anion, perfluorooctanesulfonate anion, etc.), fluorophosphate anion (e.g., hexafluorophosphate anion, tri(pentafluoroethyl)trifluorophosphate anion, etc.), tris (perfluoroalkylsulfonyl ) methide anion (e.g., tris(trifluoromethanesulfonyl) methide anion, tris(pentafluoroethanesulfonyl) methide anion, tris(heptafluoropropanesulfonyl) methide anion, tris(nonafluorobutanesulfonyl) methide anion, etc.), fluorohydrogenate anion, tetrafluoro borate anion and the like.
　前記窒素酸化物系アニオンとしては、特に限定されないが、例えば、硝酸アニオン、亜硝酸アニオンが挙げられる。 The nitrogen oxide anion is not particularly limited, but includes, for example, nitrate anion and nitrite anion.
　前記カルボン酸系アニオンは、分子中に、少なくとも１個以上のカルボン酸アニオン（－ＣＯＯ-）を持つ有機酸アニオンであり、酸素含有基、窒素含有基、硫黄含有基、リン含有基、炭化水素基等を有していてもよい。特に限定されないが、カルボン酸系アニオンとしては、例えば、飽和又は不飽和脂肪族炭化水素基、飽和又は不飽和脂環式炭化水素基、芳香族炭化水素基等、また、それらを組み合わせた炭化水素基とカルボン酸アニオンを有するアニオンが挙げられ、例えば、飽和脂肪族カルボン酸アニオン、不飽和脂肪族カルボン酸アニオン、飽和又は不飽和脂環式カルボン酸アニオン、芳香族カルボン酸アニオン、飽和脂肪族ヒドロキシカルボン酸アニオン、不飽和脂肪族ヒドロキシカルボン酸アニオン、飽和又は不飽和脂環式ヒドロキシカルボン酸アニオン、芳香族ヒドロキシカルボン酸アニオン、カルボニルカルボン酸アニオン、アルキルエーテルカルボン酸アニオン、ハロゲンカルボン酸アニオン、アミノ酸アニオン等が挙げられる（以下に挙げるカルボン酸アニオンの炭素数は、カルボキシ基の炭素を含む。）。 The carboxylate anion is an organic acid anion having at least one carboxylate anion (—COO − ) in the molecule, and includes an oxygen-containing group, a nitrogen-containing group, a sulfur-containing group, a phosphorus-containing group, and a hydrocarbon. You may have a group or the like. Carboxylic acid anions include, but are not limited to, saturated or unsaturated aliphatic hydrocarbon groups, saturated or unsaturated alicyclic hydrocarbon groups, aromatic hydrocarbon groups, etc., and hydrocarbons combining them. Anions having a group and a carboxylate anion include, for example, saturated aliphatic carboxylate anions, unsaturated aliphatic carboxylate anions, saturated or unsaturated alicyclic carboxylate anions, aromatic carboxylate anions, saturated aliphatic hydroxy Carboxylate anion, unsaturated aliphatic hydroxycarboxylate anion, saturated or unsaturated alicyclic hydroxycarboxylate anion, aromatic hydroxycarboxylate anion, carbonylcarboxylate anion, alkyl ether carboxylate anion, halogen carboxylate anion, amino acid anion etc. (The number of carbon atoms in the carboxylate anions listed below includes the carbon atoms in the carboxy group.).
　前記飽和脂肪族カルボン酸アニオンは、直鎖状又は分岐鎖状の飽和脂肪族炭化水素基と１個以上のカルボン酸アニオンからなり、カルボキシ基、カルボキシレート基を含んでも良く、炭素数１～２２が好ましい。具体的には、特に限定されないが、例えば、蟻酸、酢酸、プロピオン酸、酪酸、吉草酸、カプロン酸、エナント酸、カプリル酸、ペラルゴン酸、カプリン酸、ラウリン酸、ミリスチン酸、ペンタデシル酸、パルミチン酸、マルガリン酸、ステアリン酸、アラキジン酸、ヘンイコシル酸、ベヘン酸、イソ酪酸、２－メチル酪酸、イソ吉草酸、２－エチルヘキサン酸、イソノナン酸、イソパルミチン酸、イソステアリン酸、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、ピメリン酸、スベリン酸、アゼライン酸、セバシン酸等からプロトンが解離したアニオンが挙げられる。 The saturated aliphatic carboxylate anion consists of a linear or branched saturated aliphatic hydrocarbon group and one or more carboxylate anions, may contain a carboxy group or a carboxylate group, and has 1 to 22 carbon atoms. is preferred. Specifically, but not limited to, formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, pentadecyl acid, palmitic acid , margaric acid, stearic acid, arachidic acid, henicosyl acid, behenic acid, isobutyric acid, 2-methylbutyric acid, isovaleric acid, 2-ethylhexanoic acid, isononanoic acid, isopalmitic acid, isostearic acid, oxalic acid, malonic acid, Examples include anions obtained by dissociating protons from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, and the like.
　前記不飽和脂肪族カルボン酸アニオンは、直鎖状又は分岐鎖状の不飽和脂肪族炭化水素基と１個以上のカルボン酸アニオンからなり、カルボキシ基、カルボキシレート基を含んでも良く、炭素数３～２２が好ましい。具体的には、特に限定されないが、例えば、アクリル酸、メタクリル酸、クロトン酸、パルミトレイン酸、オレイン酸、バクセン酸、リノール酸、リノレン酸、エレオステアリン酸、アラキドン酸、マレイン酸、フマル酸等からプロトンが解離したアニオンが挙げられる。 The unsaturated aliphatic carboxylate anion consists of a linear or branched unsaturated aliphatic hydrocarbon group and one or more carboxylate anions, may contain a carboxy group or a carboxylate group, and has 3 carbon atoms. ~22 is preferred. Specifically, but not limited to, acrylic acid, methacrylic acid, crotonic acid, palmitoleic acid, oleic acid, vaccenic acid, linoleic acid, linolenic acid, eleostearic acid, arachidonic acid, maleic acid, fumaric acid, etc. Anions in which protons are dissociated from are exemplified.
　前記飽和又は不飽和脂環式カルボン酸アニオンは、芳香族性を持たない飽和もしくは不飽和の炭素環と１個以上のカルボン酸アニオンからなり、カルボキシ基、カルボキシレート基を含んでもよく、炭素数６～２０が好ましい。中でも、シクロヘキサン環骨格を有する飽和脂環式カルボン酸アニオンが好ましく、具体的には、特に限定されないが、例えば、シクロヘキサンカルボン酸、シクロヘキサンジカルボン酸からプロトンが解離したアニオンが挙げられる。 The saturated or unsaturated alicyclic carboxylate anion consists of a saturated or unsaturated carbocyclic ring having no aromaticity and one or more carboxylate anions, may contain a carboxy group or a carboxylate group, and has a carbon number of 6 to 20 are preferred. Among them, a saturated alicyclic carboxylic acid anion having a cyclohexane ring skeleton is preferable, and specific examples include, but are not particularly limited to, anions in which protons are dissociated from cyclohexanecarboxylic acid and cyclohexanedicarboxylic acid.
　前記芳香族カルボン酸アニオンは、芳香族性を持つ単環又は複数の環と１個以上のカルボン酸アニオンからなり、カルボキシ基、カルボキシレート基を含んでもよく、炭素数６～２０が好ましい。中でも、ベンゼン環骨格を有する芳香族カルボン酸アニオンが好ましく、具体的には、特に限定されないが、例えば、安息香酸、ケイヒ酸、フタル酸、イソフタル酸、テレフタル酸等からプロトンが解離したアニオンが挙げられる。 The aromatic carboxylate anion consists of a single ring or a plurality of aromatic rings and one or more carboxylate anions, may contain a carboxy group or a carboxylate group, and preferably has 6 to 20 carbon atoms. Among them, aromatic carboxylate anions having a benzene ring skeleton are preferred, and specific examples thereof include, but are not limited to, anions in which protons are dissociated from benzoic acid, cinnamic acid, phthalic acid, isophthalic acid, terephthalic acid, and the like. be done.
　前記飽和脂肪族ヒドロキシカルボン酸アニオンは、直鎖状又は分岐鎖状の飽和脂肪族炭化水素基、１個以上のカルボン酸アニオン及び１個以上の水酸基からなり、カルボキシ基、カルボキシレート基を含んでも良く、炭素数２～２４が好ましい。中でも、１～４個の水酸基を有する炭素数２～７の飽和脂肪族ヒドロキシカルボン酸アニオンが好ましい。具体的には、特に限定されないが、例えば、グリコール酸、乳酸、タルトロン酸、グリセリン酸、ヒドロキシ酢酸、ヒドロキシ酪酸、２－ヒドロキシデカン酸、３－ヒドロキシデカン酸、１２－ヒドロキシステアリン酸、ジヒドロキシステアリン酸、セレブロン酸、リンゴ酸、酒石酸、シトラマル酸、クエン酸、イソクエン酸、ロイシン酸、メバロン酸、パントイン酸等からプロトンが解離したアニオンが挙げられる。 The saturated aliphatic hydroxycarboxylic acid anion consists of a linear or branched saturated aliphatic hydrocarbon group, one or more carboxylic acid anions and one or more hydroxyl groups, and may include a carboxy group and a carboxylate group. Well, preferably 2 to 24 carbon atoms. Among them, saturated aliphatic hydroxycarboxylic acid anions having 2 to 7 carbon atoms and 1 to 4 hydroxyl groups are preferred. Specific examples include, but are not limited to, glycolic acid, lactic acid, tartronic acid, glyceric acid, hydroxyacetic acid, hydroxybutyric acid, 2-hydroxydecanoic acid, 3-hydroxydecanoic acid, 12-hydroxystearic acid, and dihydroxystearic acid. , cerebronic acid, malic acid, tartaric acid, citramaric acid, citric acid, isocitric acid, leucic acid, mevalonic acid, pantoic acid, and the like.
　前記不飽和脂肪族ヒドロキシカルボン酸アニオンは、直鎖状又は分岐鎖状の不飽和脂肪族和炭化水素基、１個以上のカルボン酸アニオン及び１個以上の水酸基からなり、カルボキシ基、カルボキシレート基を含んでもよく、炭素数３～２２が好ましい。具体的には、特に限定されないが、例えば、リシノール酸、リシノレイン酸、リシネライジン酸等からプロトンが解離したアニオンが挙げられる。 The unsaturated aliphatic hydroxycarboxylate anion consists of a linear or branched unsaturated aliphatic sum hydrocarbon group, one or more carboxylate anions and one or more hydroxyl groups, a carboxy group, a carboxylate group and preferably has 3 to 22 carbon atoms. Specific examples include, but are not particularly limited to, anions obtained by dissociating protons from ricinoleic acid, ricinoleic acid, ricineraidic acid, and the like.
　前記飽和又は不飽和の脂環式ヒドロキシカルボン酸アニオンは、芳香族性を持たない飽和もしくは不飽和の炭素環、１個以上のカルボン酸アニオン及び１個以上の水酸基からなり、カルボキシ基、カルボキシレート基を含んでもよく、炭素数４～２０が好ましい。中でも、１～４個の水酸基を有する６員環骨格の飽和脂環式ヒドロキシカルボン酸アニオンが好ましく、具体的には、特に限定されないが、例えば、ヒドロキシシクロヘキサンカルボン酸、ジヒドロキシシクロヘキサンカルボン酸、キナ酸（１，３，４，５－テトラヒドロキシシクロヘキサンカルボン酸）、シキミ酸等からプロトンが解離したアニオンが挙げられる。また、水酸基を有する環状ラクトンからプロトンが解離したアニオンも好ましく使用でき、具体的には、特に限定されないが、例えば、アスコルビン酸、エリソルビン酸等からプロトン解離したアニオンが挙げられる。 The saturated or unsaturated alicyclic hydroxycarboxylate anion is composed of a saturated or unsaturated carbocyclic ring having no aromaticity, one or more carboxylate anions and one or more hydroxyl groups, and includes a carboxy group, a carboxylate It may contain a group, and preferably has 4 to 20 carbon atoms. Among them, a saturated alicyclic hydroxycarboxylic acid anion having a 6-membered ring skeleton having 1 to 4 hydroxyl groups is preferable. Specifically, although not particularly limited, examples include hydroxycyclohexanecarboxylic acid, dihydroxycyclohexanecarboxylic acid, and quinic acid. (1,3,4,5-tetrahydroxycyclohexanecarboxylic acid), anions dissociated from protons from shikimic acid, and the like. In addition, an anion obtained by proton dissociation from a cyclic lactone having a hydroxyl group can also be preferably used. Specific examples include, but are not limited to, anions obtained by proton dissociation from ascorbic acid, erythorbic acid, and the like.
　前記芳香族ヒドロキシカルボン酸アニオンは、芳香族性を持つ単環あるいは複数の環、１個以上のカルボン酸アニオン及び１個以上の水酸基からなり、カルボキシ基、カルボキシレート基を含んでもよく、炭素数６～２０が好ましい。中でも、１～３個の水酸基を有するベンゼン環骨格の芳香族カルボン酸アニオンが好ましく、具体的には、特に限定されないが、例えば、サリチル酸、ヒドロキシ安息香酸、ジヒドロキシ安息香酸、トリヒドロキシ安息香酸、ヒドロキシメチル安息香酸、バニリン酸、シリング酸、ピロトカテク酸、ゲンチジン酸、オルセリン酸、マンデル酸、ベンジル酸、アトロラクチン酸、フロレト酸、クマル酸、ウンベル酸、コーヒー酸、フェルラ酸、シナピン酸等からプロトンが解離したアニオンが挙げられる。 The aromatic hydroxycarboxylic acid anion consists of a single ring or a plurality of rings having aromaticity, one or more carboxylic acid anions and one or more hydroxyl groups, and may contain a carboxy group and a carboxylate group. 6 to 20 are preferred. Among them, an aromatic carboxylic acid anion having a benzene ring skeleton having 1 to 3 hydroxyl groups is preferable, and specific examples thereof include, but are not limited to, salicylic acid, hydroxybenzoic acid, dihydroxybenzoic acid, trihydroxybenzoic acid, hydroxy Protons are released from methylbenzoic acid, vanillic acid, syringic acid, pyrotocatechuic acid, gentisic acid, orceric acid, mandelic acid, benzilic acid, atrolactinic acid, phloretic acid, coumaric acid, umberic acid, caffeic acid, ferulic acid, sinapic acid, etc. Dissociated anions are included.
　前記カルボニルカルボン酸アニオンは、分子内にカルボニル基を有する炭素数３～２２のカルボン酸アニオンであり、カルボキシ基、カルボキシレート基を含んでもよく、１～２個のカルボニル基を有する炭素数３～７のカルボニルカルボン酸アニオンが好ましい。中でも、ＣＨ3（（ＣＨ2）pＣＯ（ＣＨ2）q）ＣＯＯ-（ｐ及びｑは０～２の整数を示す。）で表わされるカルボニルカルボン酸アニオンが好ましい。具体的には、特に限定されないが、例えば、ピルビン酸等からプロトンが解離したアニオンが挙げられる。 The carbonyl carboxylate anion is a carboxylate anion having 3 to 22 carbon atoms having a carbonyl group in the molecule, may contain a carboxy group and a carboxylate group, and has 1 to 2 carbonyl groups and has 3 to 2 carbon atoms. A carbonyl carboxylate anion of 7 is preferred. Among them, a carbonyl carboxylate anion represented by CH 3 ((CH 2 ) p CO(CH 2 ) q )COO - (p and q are integers of 0 to 2) is preferred. Specific examples thereof include, but are not particularly limited to, anions in which protons are dissociated from pyruvic acid or the like.
　前記アルキルエーテルカルボン酸アニオンは、ポリオキシアルキレンアルキルエーテル カルボン酸アニオンを含む、分子内にエーテル基を有する炭素数２～２２のカルボン酸アニオンであり、カルボキシ基、カルボキシレート基を含んでもよく、１～２個のエーテル基を有する炭素数２～１２のアルキルカルボン酸アニオンが好ましく、中でも、ＣＨ3（ＣＨ2）rＯ（ＣＨ2）sＣＯＯ-（ｒ及びｓは０～４の整数を示す。）で表わされるアルキルエーテルカルボン酸アニオン、更には、ポリオキシエチレンアルキルエーテルカルボン酸アニオンが好ましい。アルキルエーテルカルボン酸アニオンは、具体的には、特に限定されないが、例えば、メトキシ酢酸、エトキシ酢酸、メトキシ酪酸、エトキシ酪酸等からプロトンが解離したアニオンが挙げられる。 The alkyl ether carboxylate anion is a carboxylate anion having 2 to 22 carbon atoms having an ether group in the molecule, including a polyoxyalkylene alkyl ether carboxylate anion, and may contain a carboxy group and a carboxylate group. C2-C12 alkyl carboxylate anions with ~2 ether groups are preferred, especially CH3 ( CH2 ) rO ( CH2 ) sCOO- ( r and s are integers from 0 to 4 ), and more preferably polyoxyethylene alkyl ether carboxylate anions. Alkyl ether carboxylate anions are not particularly limited, but include, for example, anions in which protons are dissociated from methoxyacetic acid, ethoxyacetic acid, methoxybutyric acid, ethoxybutyric acid, and the like.
　前記ハロゲンカルボン酸アニオンは、分子内にハロゲン原子を有する炭素数２～２２のカルボン酸アニオンであり、カルボキシ基、カルボキシレート基を含んでもよく、炭素数２～２２のハロゲンカルボン酸アニオンが好ましい。具体的には、特に限定されないが、例えば、トリフルオロ酢酸、トリクロロ酢酸、トリブロモ酢酸、ペンタフルオロプロピオン酸、ペンタクロロプロピオン酸、ペンタブロモプロピオン酸、パーフルオロノナン酸、パークロロノナン酸、パーブロモノナン酸等のフッ素置換のハロゲンカルボン酸等からプロトンが解離したアニオンが挙げられる。 The halogen carboxylate anion is a carboxylate anion having 2 to 22 carbon atoms having a halogen atom in the molecule, and may contain a carboxy group or a carboxylate group, preferably a halogen carboxylate anion having 2 to 22 carbon atoms. Specifically, but not particularly limited, for example, trifluoroacetic acid, trichloroacetic acid, tribromoacetic acid, pentafluoropropionic acid, pentachloropropionic acid, pentabromopropionic acid, perfluorononanoic acid, perchlorononanoic acid, perbromonanoic acid, etc. and an anion obtained by dissociating a proton from a fluorine-substituted halogen carboxylic acid.
　前記アミノ酸アニオンは、分子内にアミノ基を有する炭素数２～２２のカルボン酸アニオンであり、カルボキシ基、カルボキシレート基を含んでもよく、１～３個のアミノ基を有する炭素数２～７のアミノ酸アニオンが好ましい。具体的には、特に限定されないが、例えば、グリシン、アラニン、グルタミン酸、アルギニン、アスパラギン、アスパラギン酸、イソロイシン、グルタミン、ヒスチジン、システイン、ロイシン、リシン、プロリン、フェニルアラニン、トレオニン、セリン、トリプトファン、チロシン、メチオニン、バリン、サルコシン、アミノ酪酸、メチルロイシン、アミノカプリル酸、アミノヘキサン酸、アミノカプリン酸、アミノラウリン酸、アミノミリスチン酸、アミノパルミチン酸、アミノステアリン酸、ノルバリン、アミノ吉草酸、アミノイソ酪酸、チロキシン、クレアチン、オルニチン、オパイン、テアニン、トリコロミン、カイニン酸、ドウモイ酸、イボテン酸、アクロメリン酸、シスチン、ヒドロキシプロリン、ヒドロキシリシン、サイロキシン、ホスホセリン、デスモシン、βアラニン、シトルリン、クレアチン、トリメチルグリシン、シスタチオニン、メチルヒスチジン、アンセリン、カルノシン、アミノアジピン酸、オミチン等からプロトンが解離したアニオンが挙げられる。 The amino acid anion is a carboxylate anion having 2 to 22 carbon atoms and having an amino group in the molecule, and may contain a carboxy group or a carboxylate group. Amino acid anions are preferred. Specifically, but not limited to, for example, glycine, alanine, glutamic acid, arginine, asparagine, aspartic acid, isoleucine, glutamine, histidine, cysteine, leucine, lysine, proline, phenylalanine, threonine, serine, tryptophan, tyrosine, methionine , valine, sarcosine, aminobutyric acid, methylleucine, aminocaprylic acid, aminohexanoic acid, aminocapric acid, aminolauric acid, aminomyristic acid, aminopalmitic acid, aminostearic acid, norvaline, aminovaleric acid, aminoisobutyric acid, thyroxine, Creatine, ornithine, opine, theanine, tricolamine, kainate, domoic acid, ibotenic acid, acromelic acid, cystine, hydroxyproline, hydroxylysine, thyroxine, phosphoserine, desmosine, beta-alanine, citrulline, creatine, trimethylglycine, cystathionine, methylhistidine , anserine, carnosine, aminoadipic acid, omitin, and the like.
　成分（Ｂ）の塩としては、上記のアニオンとカチオン（アルカリ金属カチオン、アルカリ土類金属カチオン又はアンモニウムカチオン等）との塩が挙げられる。 Salts of component (B) include salts of the above anions and cations (alkali metal cations, alkaline earth metal cations, ammonium cations, etc.).
　成分（Ａ）であるアミンもしくはアンモニウム化合物、成分（Ｂ）である酸もしくはその塩、及び成分（Ａ）と成分（Ｂ）が形成するアンモニウム塩は、１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。 The amine or ammonium compound as component (A), the acid or its salt as component (B), and the ammonium salt formed by component (A) and component (B) may be used singly. More than one species may be used in combination.
　成分（Ｂ）が多塩基酸の場合には、成分（Ａ）と成分（Ｂ）の配合は、成分（Ｂ）の価数に対して成分（Ａ）の価数が等価であってもよく、もしくは等価未満の配合であってもよく、等価以上の配合であってもよい（成分（Ｂ）が多塩基酸の場合には、部分中和塩又は完全中和塩でもよい。）。 When component (B) is a polybasic acid, component (A) and component (B) may be blended so that the valence of component (A) is equivalent to that of component (B). Alternatively, the composition may be less than equivalent, or more than equivalent (when component (B) is a polybasic acid, it may be a partially neutralized salt or a completely neutralized salt).
　例えば、成分（Ｂ）が２塩基酸で、成分（Ａ）の価数が１の場合、成分（Ａ）と成分（Ｂ）の配合モル比は１：１モル～２：１モルとすることができる。また、成分（Ａ）は２種以上を使用してもよい。水素結合性官能基が成分（Ａ）に有する場合、それらの水素結合性官能基の効果を高めることができる。成分（Ａ）と成分（Ｂ）がアンモニウム塩を形成する場合、成分（Ａ）由来のカチオンを１分子の塩中に２分子導入することができるため、成分（Ａ）に導入した水素結合性官能基の効果をより高めることができる。 For example, when component (B) is a dibasic acid and component (A) has a valence of 1, the blending molar ratio of component (A) and component (B) should be 1:1 mol to 2:1 mol. can be done. Two or more kinds of components (A) may be used. When component (A) has hydrogen-bonding functional groups, the effects of those hydrogen-bonding functional groups can be enhanced. When component (A) and component (B) form an ammonium salt, two molecules of cations derived from component (A) can be introduced into one molecule of salt. The effect of the functional group can be further enhanced.
　ゲルの形成性、増粘効果、保水性、導電性、酵素をはじめとする生体材料に対する安定化効果、有効成分の溶解性と放出性、及びチクソ性を高めるためには、成分（Ａ）と成分（Ｂ）の混合物又は成分（Ａ）と成分（Ｂ）との塩の場合、成分（Ａ）と成分（Ｂ）又は成分（Ａ）と成分（Ｂ）との塩のカチオンとアニオンのどちらか一方に、水素結合性官能基を有することが好ましく、両方に水素結合性官能基を有することがより好ましい。成分（Ａ）の好ましい水素結合性官能基は前記に挙げたものであり、成分（Ｂ）の水素結合性官能基としては、酸素含有基、窒素含有基、硫黄含有基、リン含有基等が挙げられる。これらの各元素含有基の中でも、水酸基、カルボキシ基、カルボキシレート基、エステル基、エーテル基、アルコキシ基、カルボニル基、アミノ基、スルホニル基、硫酸エステル基、リン酸基、リン酸エステル基が好ましく、水酸基、カルボキシ基、カルボキシレート基、エステル基、エーテル基、アルコキシ基、カルボニル基がより好ましく、水酸基、カルボキシ基、カルボキシレート基、エステル基、エーテル基、アルコキシ基が更に好ましく、水酸基が特に好ましい。 In order to improve gel formability, thickening effect, water retention, electrical conductivity, stabilizing effect on biomaterials such as enzymes, solubility and release of active ingredients, and thixotropy, component (A) and In the case of a mixture of component (B) or a salt of component (A) and component (B), either the cation or the anion of the salt of component (A) and component (B) or component (A) and component (B) One of them preferably has a hydrogen-bonding functional group, and both preferably have a hydrogen-bonding functional group. Preferred hydrogen-bonding functional groups for component (A) are those listed above, and hydrogen-bonding functional groups for component (B) include oxygen-containing groups, nitrogen-containing groups, sulfur-containing groups, phosphorus-containing groups, and the like. mentioned. Among these element-containing groups, a hydroxyl group, a carboxy group, a carboxylate group, an ester group, an ether group, an alkoxy group, a carbonyl group, an amino group, a sulfonyl group, a sulfate ester group, a phosphate group, and a phosphate ester group are preferred. , more preferably a hydroxyl group, a carboxyl group, a carboxylate group, an ester group, an ether group, an alkoxy group, or a carbonyl group, more preferably a hydroxyl group, a carboxyl group, a carboxylate group, an ester group, an ether group, or an alkoxy group, and particularly preferably a hydroxyl group .
　本発明の組成物は、成分（Ａ）と成分（Ｂ）の少なくともいずれかにおける水素結合性官能基を有するが、この水素結合性官能基が水酸基であることは好ましい態様の一つである。 The composition of the present invention has a hydrogen-bonding functional group in at least one of component (A) and component (B), and it is one of preferred embodiments that this hydrogen-bonding functional group is a hydroxyl group.
　また、用途によっては、安全性、使用上の観点から、成分（Ｂ）は、医薬部外品原料規格（外原規）、医薬部外品添加物規格、日本薬局方（日局）、日本薬局方外医薬部外品規格（局外規）、医薬品添加物規格（薬添規）、食品添加物公定書（食添）に記載された化合物を原料に用いることが好ましく、特に限定されないが、例えば、酢酸、カプリル酸、カプリン酸、ラウリン酸、ミリスチン酸、パルミチン酸、ステアリン酸、オレイン酸、リノール酸、乳酸、グリコール酸、コハク酸、クエン酸、塩酸、フマル酸、リン酸、アスコルビン酸等が挙げられる。また、成分（Ａ）及び成分（Ｂ）に用いることができるアミノ酸としては、グリシン、アラニン、アルギニン、アスパラギン酸、ヒスチジン、システイン、プロリン、セリン、トリプトファン、チロシン、メチオニン、アミノ酪酸、アミノヘキサン酸、シスチン、グルタミン酸、イソロイシン、フェニルアラニン、トレオニン、トリプトファン、メチオニン、バリン、テアニン等が挙げられる。 In addition, depending on the application, from the viewpoint of safety and use, component (B) may be Compounds listed in the Pharmacopoeial Standards for Quasi-Drugs (Regulations), Pharmaceutical Additives Standards (Medicine Additives), and Food Additives Standards (Food Additives) are preferably used as raw materials, but are not particularly limited. For example, acetic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic acid, lactic acid, glycolic acid, succinic acid, citric acid, hydrochloric acid, fumaric acid, phosphoric acid, ascorbic acid, etc. is mentioned. Amino acids that can be used for component (A) and component (B) include glycine, alanine, arginine, aspartic acid, histidine, cysteine, proline, serine, tryptophan, tyrosine, methionine, aminobutyric acid, aminohexanoic acid, Cystine, glutamic acid, isoleucine, phenylalanine, threonine, tryptophan, methionine, valine, theanine and the like.
　ゲルの形成性、増粘特性、保水性、導電性、酵素をはじめとする生体材料に対する安定化効果、有効成分の溶解性及び放出性、及びチクソ性を付与する点では、本発明の組成物における、成分（Ａ）と成分（Ｂ）の配合モル比は、特に限定されず、１：９９から９９：１とすることができ、好ましくは１：９から９：１であり、より好ましくは１：５から５：１であり、更に好ましくは１：２から２：１である。 The composition of the present invention provides gel formability, thickening properties, water retention, electrical conductivity, stabilizing effect on biomaterials such as enzymes, solubility and release of active ingredients, and thixotropy. is not particularly limited, and can be from 1:99 to 99:1, preferably from 1:9 to 9:1, more preferably 1:5 to 5:1, more preferably 1:2 to 2:1.
　本発明の組成物は、成分（Ａ）と成分（Ｂ）の混合物又は成分（Ａ）と成分（Ｂ）との塩が、無水状態（無水物）であってもよく、空気中の水分を吸収した水和物であってもよい。水和物とは、化合物を空気中２５℃で放置した時、吸水し、その水分率が飽和状態となった化合物をいう。空気中２５℃で放置した時、吸水しない化合物は、水和物が無く、無水物である。 In the composition of the present invention, the mixture of component (A) and component (B) or the salt of component (A) and component (B) may be in an anhydrous state (anhydrous), and the moisture in the air may be It may be an absorbed hydrate. A hydrate refers to a compound that, when left in the air at 25°C, absorbs water and has a saturated moisture content. Compounds that do not absorb water when left in air at 25° C. are non-hydrated and anhydrous.
　本発明の組成物において、成分（Ａ）と（Ｂ）との混合物又は（Ａ）と（Ｂ）との塩は、無水物及び／又は水和物が２５℃で液体、固体のいずれであってもよいが、ゲルを形成させる点、増粘効果を付与する点で、２５℃で液体が好ましく、無水物及び／又は水和物の凝固点は２５℃未満が好ましく、－５℃未満がより好ましく、－１０℃未満が更に好ましい。 In the composition of the present invention, the mixture of components (A) and (B) or the salt of (A) and (B) is an anhydride and/or hydrate that is liquid or solid at 25°C. However, in terms of forming a gel and imparting a thickening effect, it is preferably liquid at 25 ° C. The freezing point of the anhydride and / or hydrate is preferably less than 25 ° C., more preferably less than -5 ° C. It is preferred, and less than -10°C is more preferred.
　本発明の組成物は、目的とする組成物を製造する際に、その任意の工程で配合される組成物を主な対象としている。本発明の組成物は、成分（Ａ）、（Ｂ）、高分子化合物及び水を添加したものである。本発明において成分（Ａ）、（Ｂ）、高分子化合物及び水を「添加した」とは、最終的に組成物を調製するまでに成分（Ａ）、（Ｂ）、高分子化合物及び水を添加したことを包含し、成分（Ａ）、（Ｂ）又はこれらと水を出発原料として成分（Ａ）、（Ｂ）又は成分（Ａ）、（Ｂ）、及び水で形成される塩又は塩水溶液を合成し、当該塩又は塩水溶液を添加剤とした場合、及び当該塩又は塩水溶液を必要に応じて水及び／又は高分子化合物等の成分と混合して組成物とした場合を包含する。本発明の組成物は、成分（Ａ）、（Ｂ）、高分子化合物及び水のみからなる混合物（これらの塩である場合を含む。）であってもよく、（Ａ）、（Ｂ）（又は（Ａ）と（Ｂ）の塩）、高分子化合物及び水以外の成分を含む組成物であってもよい。 The composition of the present invention is mainly intended for a composition that is blended in an arbitrary step when manufacturing a desired composition. The composition of the present invention contains components (A) and (B), a polymer compound and water. In the present invention, "adding" components (A), (B), a polymer compound, and water means that components (A), (B), a polymer compound, and water are added until the final composition is prepared. Salts or salts formed with components (A), (B) or components (A), (B) or components (A), (B) and water using these and water as starting materials It includes the case where an aqueous solution is synthesized and the salt or salt solution is used as an additive, and the case where the salt or salt solution is optionally mixed with water and/or components such as a polymer compound to form a composition. . The composition of the present invention may be a mixture (including a salt thereof) consisting only of components (A), (B), a polymer compound and water, and (A), (B) ( Alternatively, it may be a composition containing components other than (A) and (B)), a polymer compound and water.
　本発明の組成物は、目的とする最終組成物も主な対象としている。本発明の組成物は、成分（Ａ）、成分（Ｂ）、高分子化合物及び水を、その任意の工程で添加して製造した最終組成物を包含し、本発明の組成物を使用するのみではなく、成分（Ａ）、（Ｂ）、高分子化合物及び水を含んでいればよく、例えば、成分（Ａ）、成分（Ｂ）、高分子化合物、水を別々に配合して目的とする最終組成物を製造した組成物、予め、成分（Ａ）と（Ｂ）、又は成分（Ａ）と成分（Ｂ）と水を配合し、高分子化合物と、必要に応じて水を配合する組成物も包含する。すなわち、成分（Ａ）と、成分（Ｂ）と、高分子化合物と水との混合順は限定されず、本発明の組成物は、最終的に組成物を調製するまでに成分（Ａ）、（Ｂ）、高分子化合物及び水を添加したものであり、その他の添加剤を添加してもよい。 The composition of the present invention also primarily targets the desired final composition. The composition of the present invention includes the final composition produced by adding the component (A), the component (B), the polymer compound and water in any step thereof, and only using the composition of the present invention Instead, it may contain components (A), (B), a polymer compound, and water. A composition from which the final composition is produced, a composition in which components (A) and (B), or components (A) and (B), and water are blended in advance, and a polymer compound and, if necessary, water are blended. It also includes objects. That is, the order of mixing the component (A), the component (B), the polymer compound, and the water is not limited, and the composition of the present invention contains the components (A), (B), a polymer compound and water are added, and other additives may be added.
　本発明のゲル組成物は、上記のゲルの形成又は増粘特性に適した組成物の中でもゲル状の組成物である。 The gel composition of the present invention is a gel-like composition among the compositions suitable for the above gel-forming or thickening properties.
　本発明の増粘された、あるいは増粘するための組成物は、上記のゲルの形成又は増粘特性に適した組成物の中でも、成分（Ａ）、成分（Ｂ）、及び高分子化合物の作用によって、増粘された組成物、あるいは、目的とする増粘された組成物を調製する際に添加される、成分（Ａ）、成分（Ｂ）、及び高分子化合物の作用によって増粘が可能な組成物である。 The thickened or to-be-thickened compositions of the present invention contain, among other compositions suitable for gel-forming or thickening properties as described above, components (A), (B) and polymeric compounds. Thickening is caused by the action of the component (A), the component (B), and the polymer compound added when preparing the composition thickened by the action or the intended thickened composition. possible compositions.
　効率よくゲル組成物を得るためには、成分（Ａ）、成分（Ｂ）、高分子化合物及び水を例えば５０℃以上で加熱溶解した後、室温まで徐冷した方が良く、その冷却時間は、１５分以上が好ましく、３０分以上がより好ましい。 In order to efficiently obtain a gel composition, it is preferable to heat and dissolve the component (A), the component (B), the polymer compound and water at, for example, 50° C. or higher, and then slowly cool to room temperature. , preferably 15 minutes or more, more preferably 30 minutes or more.
　本発明の組成物に使用される高分子化合物としては、特に限定されないが、合成高分子化合物、半合成高分子化合物、天然系高分子化合物等が挙げられる。それらの中でも、高分子化合物に水素結合性官能基を有すると、水、成分（Ａ）及び／又は成分（Ｂ）と相互作用でき、親和性が高くなるため、水素結合性官能基を有する化合物が好ましく、特に水酸基、カルボニル基、カルボキシ基、カルボキシレート基から選ばれる少なくともいずれかを含む高分子化合物が好ましい。特に、安全性の点からは半合成高分子化合物、天然系高分子化合物が好ましく、天然系高分子化合物がより好ましい。これらは１種単独で使用してもよく、２種以上を組み合わせて使用してもよい。 The polymer compound used in the composition of the present invention is not particularly limited, but includes synthetic polymer compounds, semi-synthetic polymer compounds, natural polymer compounds, and the like. Among them, when the polymer compound has a hydrogen-bonding functional group, it can interact with water, the component (A) and/or the component (B), and the affinity increases, so the compound having a hydrogen-bonding functional group is preferred, and polymer compounds containing at least one selected from a hydroxyl group, a carbonyl group, a carboxy group, and a carboxylate group are particularly preferred. In particular, from the viewpoint of safety, semi-synthetic polymer compounds and natural polymer compounds are preferred, and natural polymer compounds are more preferred. These may be used individually by 1 type, and may be used in combination of 2 or more type.
　合成高分子化合物としては、特に限定されないが、例えば、ポリアクリル酸系、酢酸ビニル共重合体系、無水マレイン酸共重合体系、ポリビニルアルコール系、ポリビニルピロリドン系、ポリエチレングリコール系、ポリエチレンオキシド系、ポリエステル系、ポリアクリロニトリル系、ポリアミド系、ポリイミド系、ポリアミドイミド系、ポリマレイミド系、ポリウレタン系、ポリカーボネート系、ポリアリレート系の高分子化合物等が挙げられる。 Examples of synthetic polymer compounds include, but are not limited to, polyacrylic acid, vinyl acetate copolymer, maleic anhydride copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyethylene glycol, polyethylene oxide, and polyester. , polyacrylonitrile-based, polyamide-based, polyimide-based, polyamideimide-based, polymaleimide-based, polyurethane-based, polycarbonate-based, and polyarylate-based high molecular compounds.
　半合成高分子化合物としては、特に限定されないが、例えば、セルロース誘導体（カルボキシメチルセルロースナトリウム、ヒドロキシエチルセルロース、メチルセルロース、エチルセロース、ニトロセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、結晶セルロース）、アルギン酸ナトリウム、エステルガム、可溶性デンプン等が挙げられる。天然系高分子化合物としては、特に限定されないが、例えば、多糖類、セルロース、核酸又はその塩類、リボ核酸又はその塩類、水溶性タンパク質（カゼイン、コラーゲン、ゼラチン、アルブミン、フィブロイン、エラスチン、ケラチン、セリシン等）、ヒアルロン酸又はその塩、ムコ多糖類（コンドロイチン硫酸等）等が挙げられ、特に多糖類が好ましい。 Examples of semisynthetic polymer compounds include, but are not limited to, cellulose derivatives (sodium carboxymethylcellulose, hydroxyethylcellulose, methylcellulose, ethylcellulose, nitrocellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, crystalline cellulose), sodium alginate, ester gum, Soluble starch etc. are mentioned. Examples of natural polymer compounds include, but are not limited to, polysaccharides, cellulose, nucleic acids or salts thereof, ribonucleic acids or salts thereof, water-soluble proteins (casein, collagen, gelatin, albumin, fibroin, elastin, keratin, sericin, etc.), hyaluronic acid or its salts, mucopolysaccharides (such as chondroitin sulfate), etc., and polysaccharides are particularly preferred.
　多糖類としては、特に限定されないが、例えば、キサンタンガム、カラギーナン、タマリンドシーガム、ジェランガム、グアーガム、ペクチン、アラビアガム、カラヤガム、ローカストビーンガム、ダイユータンガム、アルギン酸ソーダ、アガロース、ヒアルロン酸、ポリガラクチュロン酸などの天然多糖類、カルボキシメチルプルラン、カルボキシメチルキチン、カルボキシメチルキトサン、カルボキシメチルマンナン、カルボキシメチルスターチ、カルボキシメチルデキストラン、カルボキシエチルセルロース、カルボキシメチルプルランなどのカルボキシアルキル多糖類、酸化セルロースや酸化でんぷんなどの酸化多糖類、コンドロイチン硫酸、デルマタン硫酸、ヘパリンやヘパラン硫酸など硫酸基を含む多糖類等が挙げられる。 Examples of polysaccharides include, but are not limited to, xanthan gum, carrageenan, tamarind sea gum, gellan gum, guar gum, pectin, gum arabic, karaya gum, locust bean gum, daiutang gum, sodium alginate, agarose, hyaluronic acid, polygalactose. Natural polysaccharides such as uronic acid, carboxymethyl pullulan, carboxymethyl chitin, carboxymethyl chitosan, carboxymethyl mannan, carboxymethyl starch, carboxymethyl dextran, carboxyethyl cellulose, carboxy alkyl polysaccharides such as carboxymethyl pullulan, oxidized cellulose and oxidized starch and polysaccharides containing sulfate groups such as chondroitin sulfate, dermatan sulfate, heparin and heparan sulfate.
　これらの中でも、水素結合性官能基を有する高分子化合物が好ましく、水溶性の高分子化合物がより好ましい。そのような高分子化合物としては、キサンタンガム、カラギーナン、ジェランガム、グアーガム、ダイユータンガム、アルギン酸ソーダが好ましく、キサンタンガム、カラギーナン、ジェランガム、グアーガム、ダイユータンガムがより好ましく、キサンタンガム、グアーガムが更に好ましい。 Among these, polymer compounds having hydrogen-bonding functional groups are preferred, and water-soluble polymer compounds are more preferred. Such polymer compounds are preferably xanthan gum, carrageenan, gellan gum, guar gum, diutane gum and sodium alginate, more preferably xanthan gum, carrageenan, gellan gum, guar gum and diutane gum, and still more preferably xanthan gum and guar gum.
（組成物、ゲル組成物、及び増粘された、あるいは増粘するための組成物）
　本発明の組成物において、成分（Ａ）、成分（Ｂ）、高分子化合物、及び水は任意の割合で配合される。その配合量は特に限定されないが、例えば、ゲルの形成又は増粘特性に適する点から、組成物中の成分（Ａ）と成分（Ｂ）の合計は９０質量％以下が好ましく、５０質量％以下がより好ましく、３０質量％以下が更に好ましく、１０質量％以下が特に好ましい。一方で、組成物中の高分子化合物は、０．０１質量％以上が好ましく、０．１質量％以上がより好ましく、１質量％以上が更に好ましい。 (Compositions, Gel Compositions, and Thickened or To Thicken Compositions)
In the composition of the present invention, component (A), component (B), polymer compound, and water are blended in any ratio. Although the amount thereof is not particularly limited, for example, the total amount of component (A) and component (B) in the composition is preferably 90% by mass or less, and 50% by mass or less, from the viewpoint of being suitable for gel formation or thickening properties. is more preferable, 30% by mass or less is even more preferable, and 10% by mass or less is particularly preferable. On the other hand, the polymer compound in the composition is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and even more preferably 1% by mass or more.
　本発明の組成物は、水素結合性官能基を持つ成分（Ａ）、成分（Ｂ）、水、及び高分子化合物の相互作用によりゲルを形成、増粘効果を有し、特に、水素結合性官能基を有する高分子化合物、例えば、多糖類とは、更にゲル組成物を形成しやすく、増粘効果とチクソ性の付与に適している。 The composition of the present invention forms a gel through the interaction of component (A), component (B), water, and a polymer compound having hydrogen-bonding functional groups, and has a thickening effect. A polymer compound having a functional group, such as a polysaccharide, is more likely to form a gel composition and is suitable for imparting a thickening effect and thixotropy.
　本発明の組成物は、水素結合性官能基を持つ成分（Ａ）又は成分（Ａ）と成分（Ｂ）、更には高分子化合物を用いることで、水と水素結合を形成し、保水性を高めることができる。また、成分（Ａ）と成分（Ｂ）との相互作用や、更に成分（Ａ）と成分（Ｂ）が密に配列することによって、導電性を発現する。 The composition of the present invention forms a hydrogen bond with water by using the component (A) or the component (A) and the component (B) having a hydrogen-bonding functional group, and further by using a polymer compound. can be enhanced. Also, the interaction between the component (A) and the component (B) and the dense arrangement of the component (A) and the component (B) result in the development of electrical conductivity.
　本発明の組成物は、成分（Ａ）又は成分（Ａ）と成分（Ｂ）中の水素結合性官能基が、更には、高分子化合物に水素結合性官能基を有する場合には当該官能基が、酵素をはじめとする生体材料と相互作用し、生体材料を安定化する。 In the composition of the present invention, the hydrogen-bonding functional group in component (A) or component (A) and component (B) further includes a hydrogen-bonding functional group when the polymer compound has a hydrogen-bonding functional group. interacts with enzymes and other biomaterials to stabilize them.
　本発明の組成物は、組成物と水との親和性が良好となり、ゲルの形成に適し、増粘効果に優れるため、成分（Ａ）、成分（Ｂ）のいずれかに水素結合性官能基を有し、成分（Ａ）、成分（Ｂ）のいずれも水素結合性官能基を有することが好ましい。一方で高分子化合物に水素結合性官能基を有することが好ましい。ゲルを形成する組成物は、増粘効果に優れる。 The composition of the present invention has good affinity between the composition and water, is suitable for gel formation, and has an excellent thickening effect. and both component (A) and component (B) preferably have a hydrogen-bonding functional group. On the other hand, it is preferable that the polymer compound has a hydrogen-bonding functional group. A composition that forms a gel has an excellent thickening effect.
　本発明の組成物は、せん断力をかけたときに粘度が下がり、対象物への塗布がしやすく、その後せん断力がかからない状態では粘度が増加し塗布面の液だれが起こりにくい点で優れるチクソ性を発現する点から、同様に、成分（Ａ）、成分（Ｂ）のいずれかに水素結合性官能基を有し、成分（Ａ）、成分（Ｂ）のいずれも水素結合性官能基を有することが好ましい。一方で高分子化合物に水素結合性官能基を有することが好ましい。 The composition of the present invention is excellent in that the viscosity decreases when a shearing force is applied, making it easy to apply to an object, and then the viscosity increases when the shearing force is not applied, making it difficult for dripping to occur on the application surface. From the point of view of exhibiting properties, similarly, either component (A) or component (B) has a hydrogen-bonding functional group, and both component (A) and component (B) have a hydrogen-bonding functional group. It is preferable to have On the other hand, it is preferable that the polymer compound has a hydrogen-bonding functional group.
　本発明の組成物は、成分（Ａ）、又は成分（Ａ）と成分（Ｂ）、更には高分子化合物にある水素結合性官能基により、有機材料又は無機材料からなる有効成分、特に、水素結合性官能基（水酸基、カルボニル基、カルボキシ基、カルボキシレート基、アミノ基、水素原子等）を持つ有機材料又は無機材料からなる有効成分との親和性に優れ、それらの溶解性、分散性に優れ、更に、それらの有効成分の放出性、徐放性にも優れる。 The composition of the present invention comprises an active ingredient made of an organic material or an inorganic material, in particular, hydrogen Excellent compatibility with active ingredients consisting of organic or inorganic materials with bonding functional groups (hydroxyl, carbonyl, carboxyl, carboxylate, amino, hydrogen atoms, etc.), and their solubility and dispersibility Furthermore, they are excellent in release properties and sustained release properties of their active ingredients.
　本発明の組成物は、様々な用途へ優位な展開が期待される。特に限定されないが、例えば、保水性、導電性、生体及び酵素をはじめとする生体材料（特に限定されないが、一例としては、タンパク、酵素、アミノ酸及びそれらの塩、核酸、抗体・抗原、細胞、動物、植物、臓器等の生体組織、セルロース等の生体・天然材料）に対する親和性及び安定化効果、無機材料及び有機材料の溶解性、分散性、放出性及び徐放性、増粘性、チクソ性、高比熱、高熱伝導性、潤滑性、凝固点降下、沸点上昇、蒸気圧降下、浸透性、親水性、吸着性、反応性、保湿性、安全性等の効果を要求される分野に適用できる。 The composition of the present invention is expected to have superior development in various uses. Although not particularly limited, for example, biomaterials such as water retention, conductivity, living organisms and enzymes (although not particularly limited, examples include proteins, enzymes, amino acids and salts thereof, nucleic acids, antibodies / antigens, cells, (animals, plants, living tissues such as organs, biological and natural materials such as cellulose), solubility, dispersibility, release and sustained release, thickening and thixotropic properties of inorganic and organic materials , High specific heat, high thermal conductivity, lubricity, freezing point depression, boiling point elevation, vapor pressure depression, permeability, hydrophilicity, adsorptivity, reactivity, moisture retention, safety, etc.
　具体的には、特に限定されないが、例えば、保水・保湿剤、導電材料、電解質材料、帯電防止剤、生体材料の溶解溶媒、分散溶媒、保存溶媒及び培地、増粘剤、有機材料又は無機材料（特に限定されないが、金属、金属酸化物（特に限定されないが、例えば、シリカ、酸化アルミニウム（アルミナ）、ジルコニア、酸化チタン、酸化マグネシウム、酸化インジウムスズ（ＩＴＯ）、コバルトブルー（ＣｏＯ・Ａｌ2Ｏ3）、酸化アンチモン、酸化亜鉛、酸化セシウム、酸化ジルコニウム、酸化イットリウム、酸化タングステン、酸化バナジウム、酸化カドミウム、酸化タンタル、酸化ニオブ、酸化スズ、酸化ビスマス、酸化セリウム、酸化銅、酸化鉄、酸化インジウム、酸化ホウ素、酸化カルシウム、酸化バリウム、酸化トリウム、酸化インジウムスズ、フェライト等）、炭素材料）の溶解溶媒、分散溶媒、表面処理剤、化粧品、香粧品、衛生・整理用品、医薬品、外用剤、経皮吸収剤、土壌改良剤、緑化用資材、食品包装材、シート、コンクリート混和・改質剤、シーリング材、浸水防止剤、衝撃吸収材、吸着剤、抽出剤、医療用センサー、ドラックデリバリーシステム、潤滑剤、反応溶媒、熱媒体、冷媒、食品、農薬、肥料、殺虫剤顔料、染料、粘着剤として用いることができる。 Specifically, but not particularly limited, for example, water retention / moisturizing agents, conductive materials, electrolyte materials, antistatic agents, biomaterial dissolution solvents, dispersion solvents, storage solvents and culture media, thickeners, organic materials or inorganic materials (Although not particularly limited, metals, metal oxides (but not particularly limited, for example, silica, aluminum oxide (alumina), zirconia, titanium oxide, magnesium oxide, indium tin oxide (ITO), cobalt blue (CoO Al 2 O 3 ), antimony oxide, zinc oxide, cesium oxide, zirconium oxide, yttrium oxide, tungsten oxide, vanadium oxide, cadmium oxide, tantalum oxide, niobium oxide, tin oxide, bismuth oxide, cerium oxide, copper oxide, iron oxide, indium oxide , boron oxide, calcium oxide, barium oxide, thorium oxide, indium tin oxide, ferrite, etc.), carbon materials), dissolution solvents, dispersion solvents, surface treatment agents, cosmetics, cosmetics, hygiene products, pharmaceuticals, external agents, Transdermal absorbents, soil conditioners, greening materials, food packaging materials, sheets, concrete admixtures/modifiers, sealants, flood prevention agents, shock absorbers, adsorbents, extractants, medical sensors, drug delivery systems , lubricants, reaction solvents, heat carriers, refrigerants, foods, pesticides, fertilizers, insecticide pigments, dyes, and adhesives.
　以上に本発明の実施形態について説明したが、本発明はこれらの実施形態に限定されるものではなく、その要旨を逸脱しない範囲内において各種の変更が可能である。また、式（Ｉ）において示した上記の好ましいそれぞれの例、式（ＩＩ）において示した上記の好ましいそれぞれの例、式（ＩＩＩ）において示した上記の好ましいそれぞれの例は、それらのうち少なくともいずれかの組み合わせが、実施例の結果に基づきより好ましい態様となり得る。式（Ｉ）～式（ＩＩＩ）において示した上記の好ましいそれぞれの例は、それら全てのうち少なくともいずれかの組み合わせが、実施例の結果に基づきより好ましい態様となり得る。また、それらとアニオンにおいて示した上記の好ましいそれぞれの例との組み合わせや、更にはそれらと成分（Ａ）と（Ｂ）との混合物又は（Ａ）と（Ｂ）との塩の特性との組み合わせや、更にはそれらと高分子化合物の好ましいそれぞれの例との組み合わせが、実施例の結果に基づきより好ましい態様となり得る。 Although the embodiments of the present invention have been described above, the present invention is not limited to these embodiments, and various modifications are possible without departing from the scope of the invention. In addition, each of the above preferred examples shown in formula (I), each of the above preferred examples shown in formula (II), and each of the above preferred examples shown in formula (III) are at least any of them. Any combination can be a more preferable embodiment based on the results of the examples. At least one combination of all of the above preferred examples shown in formulas (I) to (III) can be a more preferred embodiment based on the results of the examples. Also, combinations of them with the respective preferred examples shown above for anions, and further combinations thereof with the properties of mixtures of components (A) and (B) or salts of (A) and (B) Or, furthermore, a combination of each of them and preferable examples of the polymer compound can be a more preferable embodiment based on the results of the examples.
　以下に、実施例により本発明を更に詳しく説明するが、本発明はこれらの実施例に限定されるものではない。 The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.
　成分（Ａ）のアミン化合物として、２－アミノ－２－ヒドロキシメチル－１,３－プロパンジオール（富士フィルム和光純薬株式会社）、トリエタノールアミン（関東化学株式会社）を、成分（Ｂ）の酸として、乳酸、リンゴ酸、クエン酸（関東化学株式会社）を、高分子化合物として、キサンタンガム（エコーガムＴ：ＤＳＰ五協フード＆ケミカル製）、カラギーナン（シーピーガムＦＡ：ＤＳＰ五協フード＆ケミカル製）、ジェランガム（ケルコゲル：三栄源エフ・エフ・アイ製）、グアーガム（ＳＵＰＥＲＧＥＬ ＣＳＡ ２００／５０：三晶製）、ダイユータンガム（ＫＥＬＣＯ－ＶＩＳ ＤＧ：三晶製）を、成分（Ａ）のアンモニウム化合物として水酸化コリン（東京化成工業株式会社）を用いた。また、比較例の１－ブチル－３－メチルイミダゾリウムクロリド（ＢＭＩ－Ｃｌ）は東京化成工業株式会社製、グリセリンは富士フィルム和光純薬株式会社製を用いた。 2-Amino-2-hydroxymethyl-1,3-propanediol (Fuji Film Wako Pure Chemical Industries, Ltd.) and triethanolamine (Kanto Chemical Co., Ltd.) are used as the amine compound of component (A). Lactic acid, malic acid, and citric acid (Kanto Kagaku Co., Ltd.) are used as acids, and xanthan gum (Echo Gum T: manufactured by DSP Gokyo Food & Chemical) and carrageenan (Ceepigum FA: manufactured by DSP Gokyo Food & Chemical) are used as polymer compounds. , gellan gum (Kelcogel: manufactured by Saneigen FFI), guar gum (SUPERGEL CSA 200/50: manufactured by Sankei), diutan gum (KELCO-VIS DG: manufactured by Sankei), the ammonium compound of component (A) Choline hydroxide (Tokyo Chemical Industry Co., Ltd.) was used as the solvent. In addition, 1-butyl-3-methylimidazolium chloride (BMI-Cl) in Comparative Examples was manufactured by Tokyo Chemical Industry Co., Ltd., and glycerin was manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.
１．組成物の調製
　下記方法で、各組成物を調製した（表１Ａ、Ｂ～表４Ａ、Ｂ、表５）。
　なお、表１Ａ、Ｂ～表４Ａ、Ｂ、表５の記載の成分（Ａ）と成分（Ｂ）を水中で混合した後、水を留去し、得られた混合物又は塩は水和物であり、２５℃で液体であった。 1. Preparation of Composition Each composition was prepared by the following method (Tables 1A, B to 4A, B, Table 5).
In addition, after mixing the component (A) and the component (B) described in Tables 1A, B to 4A, B, and Table 5 in water, the water is distilled off, and the resulting mixture or salt is a hydrate. and was liquid at 25°C.
＜実施例１＞組成物１
　アミン化合物（成分（Ａ））の２－アミノ－２－ヒドロキシメチル－１,３－プロパンジオール０．０５７ｇ、酸（成分（Ｂ））の９０％乳酸０．０４８ｇ（成分（Ａ）：成分（Ｂ）のモル比＝１：１、組成物中の（成分（Ａ）＋成分（Ｂ））濃度：１質量％）、高分子化合物のキサンタンガム０．１ｇ（組成物中の高分子化合物濃度：１質量％）及び水９．７９５ｇを混合し、５０℃で３０分間加熱撹拌、溶解させた後、６０分間かけて室温まで冷却し、ゲル状の組成物１を得た。 <Example 1> Composition 1
0.057 g of 2-amino-2-hydroxymethyl-1,3-propanediol as an amine compound (component (A)) and 0.048 g of 90% lactic acid as an acid (component (B)) (component (A): component ( B) molar ratio = 1: 1, (component (A) + component (B)) concentration in the composition: 1% by mass), 0.1 g of polymer compound xanthan gum (polymer compound concentration in the composition: 1% by mass) and 9.795 g of water were mixed, heated and stirred at 50° C. for 30 minutes to dissolve, and then cooled to room temperature over 60 minutes to obtain a gel composition 1.
＜実施例２～１００＞組成物２～１００
　同様に、表１Ａ、Ｂ～表４Ａ、Ｂに記載した所定量のアミン化合物（成分（Ａ））と酸（成分（Ｂ））、高分子化合物を、実施例１と同条件で調製し、ゲル状の組成物２～１００を得た。
　また、実施例１～１００記載の各アミン化合物（成分（Ａ））、酸（成分（Ｂ））及び水を上記と同仕込み量で予め混合し、アンモニウム塩を合成した後に、高分子化合物を添加し、実施例１と同条件で加熱攪拌、溶解、冷却することで、同様にゲル状の組成物が得られることを確認した。 <Examples 2 to 100> Compositions 2 to 100
Similarly, predetermined amounts of an amine compound (component (A)), an acid (component (B)), and a polymer compound listed in Tables 1A and B to Table 4A and B were prepared under the same conditions as in Example 1, Gel compositions 2 to 100 were obtained.
In addition, each amine compound (component (A)), acid (component (B)) and water described in Examples 1 to 100 were premixed in the same amount as above to synthesize an ammonium salt, and then a polymer compound was added. It was confirmed that a gel composition was similarly obtained by adding, heating, stirring, dissolving, and cooling under the same conditions as in Example 1.
＜実施例１０１＞組成物１０１
　アンモニウム化合物（成分（Ａ））の４８％水酸化コリン１．３１ｇ、酸（成分（Ｂ））の９０％乳酸０．５２ｇ（成分（Ａ）：成分（Ｂ）のモル比＝１：１、組成物中の（成分（Ａ）＋成分（Ｂ））濃度：１０質量％）、高分子化合物のキサンタンガム０．１ｇ（組成物中の高分子化合物濃度：１質量％）及び水８．１７ｇを混合し、５０℃で３０分間加熱撹拌、溶解させた後、６０分間かけて室温まで冷却し、ゲル状の組成物１０１を得た。 <Example 101> Composition 101
1.31 g of 48% choline hydroxide as an ammonium compound (component (A)), 0.52 g of 90% lactic acid as an acid (component (B)) (molar ratio of component (A):component (B) = 1:1, (Concentration of component (A) + component (B)) in the composition: 10% by mass), 0.1 g of xanthan gum as a polymer compound (concentration of polymer compound in the composition: 1% by mass) and 8.17 g of water After mixing and dissolving by heating and stirring at 50° C. for 30 minutes, the mixture was cooled to room temperature over 60 minutes to obtain a gel composition 101 .
＜実施例１０２～１０６＞組成物１０２～１０６
　同様に、表５に記載した所定量のアンモニウム化合物と酸、高分子化合物を、実施例１０１と同条件で調製し、ゲル状の組成物１０２～１０６を得た。
　また、実施例１０１～１０６記載の各アンモニウム化合物、酸及び水を上記と同仕込み量で予め混合し、高分子化合物を添加し、実施例１０１と同条件で加熱攪拌、溶解、冷却することで、同様にゲル状の組成物が得られることを確認した。 <Examples 102-106> Compositions 102-106
Similarly, predetermined amounts of ammonium compound, acid, and polymer compound shown in Table 5 were prepared under the same conditions as in Example 101 to obtain gel compositions 102-106.
Further, each ammonium compound, acid and water described in Examples 101 to 106 are premixed in the same charge amount as above, the polymer compound is added, and the mixture is heated and stirred under the same conditions as in Example 101, dissolved, and cooled. , confirmed that a gel-like composition was similarly obtained.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000014
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000015
Figure JPOXMLDOC01-appb-T000016
Figure JPOXMLDOC01-appb-T000016
２．保水性の評価
　上記で得られたゲル状の組成物２０～２４、４２、６６、９３（実施例１０７～１１１、１１６～１１８）、１０７～１０９（比較例１～３）の保水性を評価した（表６）。 2. Evaluation of water retention Evaluation of the water retention of the gel compositions 20 to 24, 42, 66, 93 (Examples 107 to 111, 116 to 118) and 107 to 109 (Comparative Examples 1 to 3) obtained above. (Table 6).
＜比較例１＞組成物１０７
　１－ブチル－３－メチルイミダゾリウムクロリド１．０ｇ（組成物中の濃度：１０質量％）、高分子化合物のキサンタンガム０．１ｇ（組成物中の高分子化合物濃度：１質量％）及び水８．９ｇを混合し、５０℃で３０分間加熱撹拌、溶解させた後、６０分間かけて室温まで冷却し、ゲル状の組成物１０７を得た。 <Comparative Example 1> Composition 107
1-butyl-3-methylimidazolium chloride 1.0 g (concentration in composition: 10% by mass), polymer compound xanthan gum 0.1 g (polymer compound concentration in composition: 1% by mass) and water 8 9 g was mixed, heated and stirred at 50° C. for 30 minutes to dissolve, and then cooled to room temperature over 60 minutes to obtain a gel composition 107 .
＜比較例２＞組成物１０８
　グリセリン１．０ｇ（組成物中の濃度：１０質量％）、高分子化合物のキサンタンガム０．１ｇ（組成物中の高分子化合物濃度：１質量％）及び水８．９ｇを混合し、５０℃で３０分間加熱撹拌、溶解させた後、６０分間かけて室温まで冷却し、ゲル状の組成物１０８を得た。 <Comparative Example 2> Composition 108
1.0 g of glycerin (concentration in the composition: 10% by mass), 0.1 g of high molecular compound xanthan gum (concentration of high molecular compound in the composition: 1% by mass) and 8.9 g of water were mixed and heated at 50°C. After heating and stirring for 30 minutes for dissolution, the mixture was cooled to room temperature over 60 minutes to obtain a gel composition 108 .
＜比較例３＞組成物１０９
　高分子化合物のキサンタンガム０．１ｇ（組成物中の高分子化合物濃度：１質量％）及び水９．９ｇを混合し、５０℃で３０分間加熱撹拌、溶解させた後、６０分間かけて室温まで冷却し、ゲル状の組成物１０９を得た。 <Comparative Example 3> Composition 109
0.1 g of xanthan gum, which is a polymer compound (concentration of polymer compound in the composition: 1% by mass) and 9.9 g of water are mixed, heated and stirred at 50° C. for 30 minutes to dissolve, and then cooled to room temperature over 60 minutes. After cooling, a gel composition 109 was obtained.
　カールフィッシャー水分計でゲル状の組成物の水分率（試験前水分率）を測定し、それらのサンプル１．０ｇをスクリュー管に加え蓋しない状態で、４０℃４０％ＲＨに設定した恒温恒湿器（東京理化器械株式会社製ＫＣＬ－２０００Ｗ）中に、２４時間静置した。２４時間後の水分率を測定し（試験後水分率）、下記式を用いて、水分減少率を算出し、保水性を評価した（表６）。
　Ａ：試験前水分率（％）
　Ｂ：試験後水分率（％）
　水分減少率（％）＝[（Ａ（％）－Ｂ（％））／Ａ（％）]×１００ The moisture content of the gel composition (pre-test moisture content) was measured with a Karl Fischer moisture meter, and 1.0 g of the sample was added to the screw tube without a lid, and the temperature and humidity were set to 40 ° C. and 40% RH. It was allowed to stand in a vessel (KCL-2000W manufactured by Tokyo Rikakikai Co., Ltd.) for 24 hours. The moisture content after 24 hours was measured (moisture content after test), and the water retention rate was calculated using the following formula to evaluate water retention (Table 6).
A: Moisture content before test (%)
B: Moisture content after test (%)
Moisture reduction rate (%) = [(A (%) - B (%)) / A (%)] × 100
　表６に水分減少率を示す。組成物２０～２４、４２、６６、９３（実施例１０７～１１１、１１６～１１８）は、組成物１０７～１０９（比較例１～３）より水分減少率が小さく保水性に優れていた。組成物２０（実施例１０７）は、組成物１０７（比較例１）より保湿性が高く、本発明に係る組成物中の成分（Ａ）及び／又は成分（Ｂ）にある水素結合性官能基が保水性に寄与することが示唆された。また、水素結合性官能基（水酸基）を有するグリセリンを含む組成物１０８（比較例２）より組成物２０（実施例１０７）は保水性が良好であり、本発明に係る組成物中に成分（Ａ）と成分（Ｂ）（成分（Ａ）と成分（Ｂ）から形成されるアンモニウム塩）が、保水性に有効であることを確認した。 Table 6 shows the moisture reduction rate. Compositions 20 to 24, 42, 66 and 93 (Examples 107 to 111 and 116 to 118) had a smaller water loss rate and better water retention than Compositions 107 to 109 (Comparative Examples 1 to 3). Composition 20 (Example 107) has higher moisturizing properties than Composition 107 (Comparative Example 1), and the hydrogen-bonding functional groups present in component (A) and/or component (B) in the composition according to the present invention was suggested to contribute to water retention. Composition 20 (Example 107) has better water retention than Composition 108 (Comparative Example 2) containing glycerin having a hydrogen-bonding functional group (hydroxyl group). It was confirmed that A) and component (B) (the ammonium salt formed from component (A) and component (B)) are effective in retaining water.
３．酵素安定化の評価
　各ゲル状の組成物２０～２４（実施例１０７～１１１）、１０７～１０９、（比較例１～３）にウレアーゼを３０ｍｇ/ｇの酵素濃度で溶解し、４０℃の条件に設定した恒温器に放置した。１４日間放置した後、各サンプルを採取して、下記方法を用いて、それぞれの組成物に溶解したウレアーゼの活性を測定、活性保持率を算出して、ゲル状の組成物の酵素安定化効果を評価した（表６）。 3. Evaluation of enzyme stabilization Urease was dissolved in each gel composition 20 to 24 (Examples 107 to 111), 107 to 109, (Comparative Examples 1 to 3) at an enzyme concentration of 30 mg / g, and the conditions were 40 ° C. It was left in a thermostat set to After allowing to stand for 14 days, each sample was collected, the activity of urease dissolved in each composition was measured using the following method, and the activity retention rate was calculated to determine the enzyme stabilizing effect of the gel composition. was evaluated (Table 6).
＜加水分解酵素：ウレアーゼの活性測定＞
　ウレアーゼの活性は、ウレアーゼの酵素反応によって尿素から分解生成するアンモニウムイオンをインドフェノール法によって定量して測定した。 <Hydrolytic enzyme: activity measurement of urease>
Urease activity was measured by quantifying the amount of ammonium ions produced from urea by the enzymatic reaction of urease by the indophenol method.
　まず、三角フラスコに１ｍＭの基質溶液（ｐＨ７．５の１０ｍＭリン酸緩衝液に基質となる尿素を溶解して調製）を１００ｍＬ取り、３０℃で約３０分間予備加温した。次に、酵素０．５ｍｇを含む上記サンプルを、上記の基質溶液に加え、３０℃で６０分間反応させた。 First, 100 mL of a 1 mM substrate solution (prepared by dissolving urea as a substrate in a pH 7.5 10 mM phosphate buffer) was placed in an Erlenmeyer flask and preheated at 30°C for about 30 minutes. Next, the sample containing 0.5 mg of enzyme was added to the substrate solution and allowed to react at 30° C. for 60 minutes.
　反応後、反応溶液を０．１ｍＬ採取し、直ちにフェノール溶液（イオン交換水にフェノール１０ｇとペンタシアノニトロシル鉄(III)酸ナトリウム５０ｍｇを溶解した後、イオン交換水で１０００ｍＬにメスアップして調製）２ｍＬと、次亜塩素酸ナトリウム溶液（イオン交換水に水酸化ナトリウム５ｇと５％の次亜塩素酸ナトリウム溶液８．４ｍＬを溶解した後、イオン交換水で１０００ｍＬにメスアップして調製）２ｍＬを加え、３７℃の恒温槽中で２０分間反応させた。この反応液の波長６３５ｎｍの吸光度（Ｖ－５５０：日本分光（株））を測定して得られたインドフェノール量からアンモニウムイオンの生成量（放置後のアンモニウムイオン量）を求めて、ウレアーゼ活性を算出した。アンモニウムイオンの定量は、０．１～３．０ｍＭの濃度範囲でアンモニウムイオン溶液を調製して、上記と同様にインドフェノール法で定量して得られた検量線を用いた。 After the reaction, 0.1 mL of the reaction solution was collected, and immediately a phenol solution (10 g of phenol and 50 mg of sodium pentacyanonitrosylferrate(III) were dissolved in ion-exchanged water, and then diluted to 1000 mL with ion-exchanged water to prepare). 2 mL and sodium hypochlorite solution (prepared by dissolving 5 g of sodium hydroxide and 8.4 mL of 5% sodium hypochlorite solution in ion-exchanged water, and then diluting to 1000 mL with ion-exchanged water). In addition, they were reacted for 20 minutes in a constant temperature bath at 37°C. The amount of ammonium ions produced (the amount of ammonium ions after standing) was determined from the amount of indophenol obtained by measuring the absorbance at a wavelength of 635 nm (V-550: JASCO Corporation) of the reaction solution, and the urease activity was measured. Calculated. Ammonium ion was quantified using a calibration curve obtained by preparing an ammonium ion solution in the concentration range of 0.1 to 3.0 mM and quantifying by the indophenol method in the same manner as described above.
　なお、酵素活性保持率の基準となる酵素活性の値は、次のように算出した。適正温度で保存したウレアーゼ粉末をバッファー（ｐＨ７．５の１０ｍＭリン酸緩衝液）に溶解して酵素濃度５０ｍｇ／ｍＬの酵素溶液を調製した。調製後、直ちにその溶液を、上記と同様に、酵素０．５ｍｇを基質溶液に加え、酵素反応を行った後、インドフェノール法で定量したアンモニウムイオン量（調整直後のアンモニウムイオン量）を基準として、下記の式により酵素活性保持率を算出した。
　Ｃ：放置後のアンモニウムイオン量（ｍｍｏｌ／Ｌ）
　Ｄ：調整直後のアンモニウムイオン量（ｍｍｏｌ／Ｌ）
　酸素活性保持率（％）＝[ Ｃ（ｍｍｏｌ／Ｌ）／Ｄ（ｍｍｏｌ／Ｌ ]×１００ The enzymatic activity value, which serves as a reference for the enzymatic activity retention rate, was calculated as follows. Urease powder stored at an appropriate temperature was dissolved in a buffer (10 mM phosphate buffer of pH 7.5) to prepare an enzyme solution with an enzyme concentration of 50 mg/mL. Immediately after preparation, 0.5 mg of the enzyme was added to the substrate solution in the same manner as above, and the enzyme reaction was performed. , the enzymatic activity retention rate was calculated by the following formula.
C: amount of ammonium ions after standing (mmol/L)
D: amount of ammonium ions immediately after adjustment (mmol/L)
Oxygen activity retention rate (%) = [C (mmol/L)/D (mmol/L)] x 100
　表６に酵素活性保持率を示す。組成物２０～２４（実施例１０７～１１１）は、組成物１０７～１０９（比較例１～３）より酵素活性保持率が大きく酵素安定化効果に優れていた。組成物２０（実施例１０７）は、組成物１０７（比較例１）より酵素活性保持率が高く、本発明に係る組成物中の成分（Ａ）及び／又は成分（Ｂ）の水素結合性官能基が酵素安定化効果に寄与することが示唆された。また、水素結合性官能基（水酸基）を有するグリセリンを含む組成物１０８（比較例２）より組成物２０（実施例１０７）は保水性が良好であり、本発明に係る組成物中に成分（Ａ）と成分（Ｂ）（成分（Ａ）と成分（Ｂ）から形成されるアンモニウム塩）が、酵素安定化効果に有効であることを確認した。 Table 6 shows the enzyme activity retention rate. Compositions 20 to 24 (Examples 107 to 111) had a higher enzymatic activity retention rate and were superior in enzyme stabilizing effect than Compositions 107 to 109 (Comparative Examples 1 to 3). Composition 20 (Example 107) has a higher enzymatic activity retention rate than Composition 107 (Comparative Example 1), and the hydrogen-bonding functionality of component (A) and/or component (B) in the composition according to the present invention It was suggested that the groups contributed to the enzyme stabilizing effect. Composition 20 (Example 107) has better water retention than Composition 108 (Comparative Example 2) containing glycerin having a hydrogen-bonding functional group (hydroxyl group). It was confirmed that A) and component (B) (the ammonium salt formed from component (A) and component (B)) are effective in stabilizing the enzyme.
４．導電性（帯電防止能）、コーティング効果の評価
　ゲル状の組成物の導電性、コーティング効果を評価した（表６）。表６のゲル状の組成物２０～２４（実施例１０７～１１１）、１０７（比較例１）をガラス板上に塗布し、減圧下で３時間乾燥し、得られたサンプルを四探針法（ロレスタＧＰ　ＭＣＰ－Ｔ６１０　三菱化学アナリテック製）を用いて表面抵抗率を測定した。 4. Evaluation of conductivity (antistatic ability) and coating effect The gel composition was evaluated for conductivity and coating effect (Table 6). Gel compositions 20 to 24 (Examples 107 to 111) and 107 (Comparative Example 1) in Table 6 were applied to a glass plate and dried under reduced pressure for 3 hours, and the resulting sample was subjected to a four-probe method. (Loresta GP MCP-T610 manufactured by Mitsubishi Chemical Analytic Tech) was used to measure the surface resistivity.
　その結果、ゲル状の組成物２０～２４（実施例１０７～１１１）のサンプルは、いずれも粘稠状であり、組成物１０７（比較例１）より導電性が高く（表面抵抗率が小さく）、帯電防止効果に優れていることを確認した。つまり、本発明に係る組成物中の成分（Ａ）及び／又は成分（Ｂ）にある水素結合性官能基、また、成分（Ａ）と成分（Ｂ）（成分（Ａ）と成分（Ｂ）から形成されるアンモニウム塩）が２５℃で液体であることが有効と示唆された。 As a result, the samples of gel compositions 20 to 24 (Examples 107 to 111) are all viscous and have higher conductivity (lower surface resistivity) than composition 107 (Comparative Example 1). , it was confirmed that the antistatic effect is excellent. That is, the hydrogen-bonding functional groups in component (A) and/or component (B) in the composition according to the present invention, component (A) and component (B) (component (A) and component (B) It was suggested that the ammonium salt formed from ) is liquid at 25°C.
　また、本発明に係る組成物が比較例組成物より導電性が高いことから、塗布対象物の表面に均一にコーティングしていることが示唆され、導電性、帯電防止効果以外の他の効果も対象物に効率よく発揮できる。 In addition, since the composition according to the present invention has higher conductivity than the comparative example composition, it is suggested that the surface of the application object is uniformly coated, and other effects other than conductivity and antistatic effects It can be effectively applied to the target object.
Figure JPOXMLDOC01-appb-T000017
Figure JPOXMLDOC01-appb-T000017
５．有効成分放出性（有効成分皮膚透過性）の評価
　有効成分の一例としてアスコルビン酸を採用し、組成物からの有効成分の皮膚透過性を評価した（表７Ａ、Ｂ）。 5. Evaluation of Active Ingredient Releasability (Active Ingredient Skin Permeability) Using ascorbic acid as an example of an active ingredient, the skin permeability of the active ingredient from the composition was evaluated (Table 7A, B).
組成物１１０（実施例１１２）の調製
　アミン化合物（成分（Ａ））の２－アミノ－２－ヒドロキシメチル－１,３－プロパンジオール０．５７ｇ、酸（成分（Ｂ））の９０％乳酸０．４８ｇ（成分（Ａ）：成分（Ｂ）のモル比＝１：１、組成物（成分（Ａ）、成分（Ｂ）、高分子化合物、水）中の（成分（Ａ）＋成分（Ｂ））濃度：１０質量％）、高分子化合物のキサンタンガム０．１ｇ（組成物中の高分子化合物濃度：１質量％）、水８．８５ｇ、有効成分としてアスコルビン酸０．１ｇ（組成物に対して１質量％）を混合し、５０℃で３０分間加熱撹拌、溶解させた後、６０分間かけて室温まで冷却し、本発明に係る組成物に有効成分を含有したゲル状の組成物１１０を得た。 Preparation of Composition 110 (Example 112) 0.57 g of 2-amino-2-hydroxymethyl-1,3-propanediol as the amine compound (component (A)), 0.57 g of 90% lactic acid as the acid (component (B)) .48 g (component (A): component (B) molar ratio = 1: 1, composition (component (A), component (B), polymer compound, water) in (component (A) + component (B )) concentration: 10% by mass), 0.1 g of polymer compound xanthan gum (polymer compound concentration in the composition: 1% by mass), 8.85 g of water, 0.1 g of ascorbic acid as an active ingredient (relative to the composition 1% by mass) is mixed, heated and stirred at 50 ° C. for 30 minutes to dissolve, and then cooled to room temperature over 60 minutes to obtain a gel composition 110 containing the active ingredient in the composition according to the present invention. Obtained.
組成物１１１（比較例４）の調製
　１－ブチル－３－メチルイミダゾリウムクロリド（ＢＭＩ－Ｃｌ）１．０ｇ、高分子化合物のキサンタンガム０．１ｇ（組成物（ＢＭＩ－Ｃｌ、高分子化合物、水）中の高分子化合物濃度：１質量％）、水８．９ｇ、有効成分としてアスコルビン酸０．１ｇ（組成物（ＢＭＩ－Ｃｌ、高分子化合物、水）に対して１質量％）を混合し、５０℃で３０分間加熱撹拌、溶解させた後、６０分間かけて室温まで冷却し、組成物に有効成分を含有したゲル状の組成物１１１を得た。 Preparation of composition 111 (Comparative Example 4) 1-butyl-3-methylimidazolium chloride (BMI-Cl) 1.0 g, polymer compound xanthan gum 0.1 g (composition (BMI-Cl, polymer compound, water ), 8.9 g of water, and 0.1 g of ascorbic acid as an active ingredient (1% by mass of the composition (BMI-Cl, polymer compound, water)) were mixed. , at 50° C. for 30 minutes to dissolve the mixture, and then cooled to room temperature over 60 minutes to obtain a gel composition 111 containing an active ingredient.
　次に、ピアースバイアル（２ｍＬ）にバッファー（リン酸緩衝生理食塩水（ＰＢＳ）溶液）を満たし、ラボスキン（株式会社星野試験動物飼育所）をピアースバイアルにセットし３２℃に保持した。ラボスキンの表面上に、それぞれ、上記のゲル状の組成物１１０、１１１を０．１ｇ添加し（添加したゲル状の組成物中のアスコルビン酸量：１．０ｍｇ）、３２℃、２４～４８～７２時間撹拌し、ＨＰＬＣを用いて２４、４８、７２時間後のバッファー中におけるアスコルビン酸を定量し（バッファー中のアスコルビン酸量（ｍｇ）、単位時間（０～２４時間、２４～４８時間、４８～７２時間）あたりのゲル状の組成物中からのアスコルビン酸（有効成分）放出率（皮膚透過率）を下記式を用いて算出した。
　Ｅ：バッファー中のアスコルビン酸量（ｍｇ）
　Ｆ：添加したゲル状の組成物中のアスコルビン酸量：１．０ｍｇ
　有効成分放出率の式＝[Ｅ（ｍｇ）／Ｆ（ｍｇ）]×１００ Next, a Pierce vial (2 mL) was filled with a buffer (phosphate-buffered saline (PBS) solution), Lab Skin (Hoshino Laboratory Animal Breeding Co., Ltd.) was placed in the Pierce vial, and maintained at 32°C. 0.1 g of each of the gel compositions 110 and 111 described above was added to the surface of the lab skin (the amount of ascorbic acid in the added gel composition: 1.0 mg), and the mixture was heated at 32° C. from 24 to 48 to Stir for 72 hours and quantify ascorbic acid in the buffer after 24, 48 and 72 hours using HPLC (amount of ascorbic acid in buffer (mg), unit time (0-24 hours, 24-48 hours, 48 hours) The ascorbic acid (active ingredient) release rate (skin permeation rate) from the gel composition per 72 hours) was calculated using the following formula.
E: Amount of ascorbic acid in buffer (mg)
F: Amount of ascorbic acid in gel composition added: 1.0 mg
Active ingredient release rate formula = [E (mg) / F (mg)] × 100
　組成物１１０（実施例１１２）中の有効成分は組成物１１１（比較例４）より、長時間にわたり、良好に放出し（皮膚透過し）、徐放性に優れていることを確認した。 It was confirmed that the active ingredient in Composition 110 (Example 112) was better released (permeated through the skin) over a longer period of time than in Composition 111 (Comparative Example 4) and had excellent sustained release properties.
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000019
Figure JPOXMLDOC01-appb-T000019
６．増粘効果、チクソ性の評価
　組成物の増粘効果、チクソ性を評価した（表８）。ゲル状の組成物２０～２３（実施例１１３～１１５）、１０９、１１２、１１３（比較例５～７）を、粘度計（ＤＶ－２ｐｒｏ ブルックフィールド社製）を用いて、回転速度を１、１０、１００、２００ｒｐｍにて測定した。 6. Evaluation of thickening effect and thixotropic property The thickening effect and thixotropic property of the composition were evaluated (Table 8). Gel compositions 20 to 23 (Examples 113 to 115), 109, 112, 113 (Comparative Examples 5 to 7) were measured using a viscometer (DV-2pro, manufactured by Brookfield) at a rotation speed of 1, Measured at 10, 100 and 200 rpm.
　ゲル状の組成物２０～２３（実施例１１３～１１５）のサンプルは、いずれも増粘効果を示した。比較例５の多糖類単独の１質量％水溶液よりも増粘効果に優れることが確認された。成分（Ａ）と成分（Ｂ）の１：１モル混合物１０質量％水溶液では水の増粘は確認されなかった。また、回転速度が速くなるにつれ粘度が低下し、シュウドプラスチック性も認められ、更に、測定後のサンプルを６０分間放置したところ、測定前のゲル状となり、本組成物はチクソ性を有することが確認された。また、成分（Ａ）、成分（Ｂ）、高分子化合物の添加順を変えて得られた組成物も同様の増粘効果、チクソ性を有することを確認した。つまり、目的物に成分（Ａ）、成分（Ｂ）、高分子化合物、水が含まれると、増粘効果、チクソ性を有することが示唆された。一方、ゲル状の組成物１１２（比較例５）は、粘度測定後６０分間放置してもゲル状とならず、チクソ性を示さなかった。また、比較例６、７の組成物１１３、１１４はいずれもゲル化せず、ゲル状の組成物が得られなかった。 All samples of gel compositions 20 to 23 (Examples 113 to 115) exhibited a thickening effect. It was confirmed that the thickening effect was superior to that of the 1% by mass aqueous solution of the polysaccharide alone of Comparative Example 5. No thickening of water was observed in a 10% by mass aqueous solution of a 1:1 molar mixture of component (A) and component (B). In addition, as the rotation speed increased, the viscosity decreased, and pseudoplasticity was also observed. Furthermore, when the sample after measurement was left for 60 minutes, it became gel-like before measurement, and the composition had thixotropic properties. was confirmed. It was also confirmed that compositions obtained by changing the order of addition of component (A), component (B), and polymer compound have the same thickening effect and thixotropy. In other words, it was suggested that when the target product contained component (A), component (B), a polymer compound, and water, it had a thickening effect and thixotropy. On the other hand, the gel composition 112 (Comparative Example 5) did not become a gel even after standing for 60 minutes after the viscosity measurement, and did not exhibit thixotropy. Moreover, none of the compositions 113 and 114 of Comparative Examples 6 and 7 were gelled, and a gel composition was not obtained.
Figure JPOXMLDOC01-appb-T000020
Figure JPOXMLDOC01-appb-T000020
７．有効成分徐放性（蒸発率）の評価
　有効成分の一例としてメチルエチルケトンとイソプロパノールを採用し、組成物からの有効成分の徐放性（蒸発率）を評価した（表９Ａ、Ｂ、表１０Ａ、Ｂ）。 7. Evaluation of sustained release of active ingredient (evaporation rate) Methyl ethyl ketone and isopropanol were employed as examples of active ingredients, and the sustained release (evaporation rate) of the active ingredient from the composition was evaluated (Tables 9A, B, Table 10A, B ).
　実施例として組成物２０、６６、９３、比較例として組成物１１４、１１５、１１６、１１７を１８ｇ、有効成分としてメチルエチルケトン及びイソプロパノール２ｇを混合し、温度２５℃、湿度６０％ＲＨの恒温槽に静置した。２．５時間後、６時間後、８時間後、２４時間時間後、有効成分を溶解した組成物の重量を測定し、下記式より蒸発率を算出した。 Compositions 20, 66, and 93 as examples, 18 g of compositions 114, 115, 116, and 117 as comparative examples, and methyl ethyl ketone and 2 g of isopropanol as active ingredients were mixed and placed in a constant temperature bath at a temperature of 25°C and a humidity of 60% RH. placed. After 2.5 hours, 6 hours, 8 hours, and 24 hours, the weight of the composition in which the active ingredient was dissolved was measured, and the evaporation rate was calculated from the following formula.
蒸発率の式＝[（Ｇ－Ｈ）／Ｉ×１００]－Ｊ
　Ｇ：有効成分を溶解した組成物の試験前の重量（ｇ）
　Ｈ：有効成分を溶解した組成物の各時間後の重量（ｇ）
　Ｉ：有効成分の仕込み量：２ｇ
　Ｊ：有効成分を水とした際の組成物の各時間後の蒸発率 Evaporation rate formula = [(G - H) / I x 100] - J
G: Weight (g) of the composition in which the active ingredient is dissolved before the test
H: Weight (g) of the composition in which the active ingredient was dissolved after each hour
I: Charged amount of active ingredient: 2 g
J: Evaporation rate of the composition after each time when the active ingredient is water
　表９Ａ、Ｂより実施例１１９～１２１は比較例８～１２よりも２．５時間後、６時間後、８時間後、２４時間時間後の蒸発率が低くなったことから、実施例の組成物の徐放性を確認した。
　また、表１０Ａ、Ｂより実施例１２２～１２４は比較例１３～１７よりも２．５時間後、６時間後、８時間後、２４時間時間後の蒸発率が低くなったことから、実施例の組成物の徐放性を確認した。 From Tables 9A and B, Examples 119 to 121 had lower evaporation rates after 2.5 hours, 6 hours, 8 hours, and 24 hours than Comparative Examples 8 to 12. The sustained release of the substance was confirmed.
Also, from Tables 10A and B, Examples 122 to 124 had lower evaporation rates after 2.5 hours, 6 hours, 8 hours, and 24 hours than Comparative Examples 13 to 17. confirmed the sustained release properties of the composition.
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000021
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000022
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000023
Figure JPOXMLDOC01-appb-T000024
Figure JPOXMLDOC01-appb-T000024

Claims (32)

  1. 　次の成分（Ａ）、（Ｂ）、高分子化合物及び水を添加成分として含み、
    　成分（Ａ）と成分（Ｂ）の少なくともいずれかに水素結合性官能基を有する組成物。
    （Ａ）アミンもしくはアンモニウム化合物
    （Ｂ）酸もしくはその塩     Including the following components (A) and (B), a polymer compound and water as additive components,
    A composition having a hydrogen-bonding functional group in at least one of component (A) and component (B).
    (A) amine or ammonium compound (B) acid or salt thereof
  2. 　前記成分（Ａ）は、下記式（Ｉ）又は（ＩＩ）：
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ1はそれぞれ独立に、水酸基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシ炭化水素基、カルボキシ基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいカルボキシ炭化水素基、又は水酸基及びカルボキシ基を各々１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシカルボキシ炭化水素基を示し、Ｒ2はそれぞれ独立に、水素原子又は炭素数１～２２の有機基であり、ｍは０～３の整数を示す。）
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ3はそれぞれ独立に、水酸基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシ炭化水素基、カルボキシ基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいカルボキシ炭化水素基、又は水酸基及びカルボキシ基を各々１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシカルボキシ炭化水素基を示し、Ｒ4はそれぞれ独立に、水素原子又は炭素数１～２２の有機基であり、ｎは０～４の整数を示す。Ｘ-はアニオンを示す。）
    で表される請求項１に記載の組成物。     The component (A) has the following formula (I) or (II):
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, each R 1 independently has one or more hydroxyl groups, the hydrocarbon moiety is linear or branched with 1 to 22 carbon atoms, and the hydrocarbon moiety contains an oxygen atom. a hydroxy hydrocarbon group, a carboxy hydrocarbon having one or more carboxy groups, having a straight or branched hydrocarbon portion having 1 to 22 carbon atoms, and the hydrocarbon portion optionally containing an oxygen atom; or one or more each of a hydroxyl group and a carboxy group, the hydrocarbon moiety being linear or branched having 1 to 22 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom. represents a hydrogen group, each R 2 is independently a hydrogen atom or an organic group having 1 to 22 carbon atoms, and m represents an integer of 0 to 3.)
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, each R 3 independently has one or more hydroxyl groups, the hydrocarbon moiety is linear or branched with 1 to 22 carbon atoms, and the hydrocarbon moiety contains an oxygen atom. a hydroxy hydrocarbon group, a carboxy hydrocarbon having one or more carboxy groups, having a straight or branched hydrocarbon portion having 1 to 22 carbon atoms, and the hydrocarbon portion optionally containing an oxygen atom; or one or more each of a hydroxyl group and a carboxy group, the hydrocarbon moiety being linear or branched having 1 to 22 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom. represents a hydrogen group, each R 4 is independently a hydrogen atom or an organic group having 1 to 22 carbon atoms, n represents an integer of 0 to 4, and X − represents an anion.)
    2. The composition of claim 1, represented by:
  3. 　前記式（Ｉ）において、ｍは１～３の整数であり、前記式（ＩＩ）において、ｎは１～４の整数である請求項２に記載の組成物。 The composition according to claim 2, wherein m is an integer of 1 to 3 in the formula (I), and n is an integer of 1 to 4 in the formula (II).
  4. 　前記式（Ｉ）において、全てのＲ2が水素原子であり、前記式（ＩＩ）において、全てのＲ4が水素原子である請求項２又は３に記載の組成物。 4. The composition according to claim 2 or 3, wherein in formula (I) all R2 are hydrogen atoms and in formula (II) all R4 are hydrogen atoms.
  5. 　前記式（Ｉ）において、Ｒ1は炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状のヒドロキシ炭化水素基であり、前記式（ＩＩ）において、Ｒ3は炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状のヒドロキシ炭化水素基である請求項２～４のいずれか一項に記載の組成物。 In the above formula (I), R 1 is a linear or branched hydroxy hydrocarbon group having a hydrocarbon moiety of 1 to 22 carbon atoms, and in the above formula (II), R 3 is a hydrocarbon moiety having carbon atoms. The composition according to any one of claims 2 to 4, which is a linear or branched hydroxy hydrocarbon group of numbers 1 to 22.
  6. 　前記式（Ｉ）及び式（ＩＩ）において、前記炭化水素部位における炭化水素が飽和脂肪族炭化水素である請求項２～５のいずれか一項に記載の組成物。 The composition according to any one of claims 2 to 5, wherein in the formulas (I) and (II), the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon.
  7. 　前記式（Ｉ）において、Ｒ1のうち少なくとも１つが、水酸基を１個有し、前記炭化水素部位における炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基であり、
    　前記式（ＩＩ）において、Ｒ3のうち少なくとも１つが、水酸基を１個有し、前記炭化水素部位における炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基である請求項２～６のいずれか一項に記載の組成物。     In the formula (I), at least one of R 1 has one hydroxyl group, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon hydroxy hydrocarbon group,
    7. Any one of claims 2 to 6, wherein in the formula (II), at least one of R 3 has one hydroxyl group, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon hydroxy hydrocarbon group. A composition according to claim 1.
  8. 　前記式（Ｉ）において、Ｒ1のうち少なくとも１つが、水酸基を２個以上有し、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基であり、
    　前記式（ＩＩ）において、Ｒ3のうち少なくとも１つが、水酸基を２個以上有し、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基である請求項２～６のいずれか一項に記載の組成物。     In the formula (I), at least one of R 1 has two or more hydroxyl groups, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon hydroxy hydrocarbon group,
    7. Any one of claims 2 to 6, wherein in the formula (II), at least one of R 3 has two or more hydroxyl groups, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon hydroxy hydrocarbon group. or the composition according to claim 1.
  9. 　前記式（Ｉ）において、Ｒ1のうち少なくとも１つが、水酸基を１個以上有し、炭化水素部位が炭素数３～２２の分岐鎖状で、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基であり、
    　前記式（ＩＩ）において、Ｒ3のうち少なくとも１つが、水酸基を１個以上有し、炭化水素部位が炭素数３～２２の分岐鎖状で、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基である請求項２～６のいずれか一項に記載の組成物。     In the formula (I), at least one of R 1 has one or more hydroxyl groups, the hydrocarbon moiety is a branched chain having 3 to 22 carbon atoms, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon. is a hydroxy hydrocarbon group of hydrogen,
    In the formula (II), at least one of R 3 has one or more hydroxyl groups, the hydrocarbon moiety is a branched chain having 3 to 22 carbon atoms, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon. A composition according to any one of claims 2 to 6 which is a hydroxyhydrocarbon group of hydrogen.
  10. 　前記式（ＩＩ）において、Ｘ-が水酸化物イオンである請求項２～９のいずれか一項に記載の組成物。 A composition according to any one of claims 2 to 9, wherein in formula (II), X - is a hydroxide ion.
  11. 　前記成分（Ａ）は、前記式（Ｉ）で表される請求項２～１０のいずれか一項に記載の組成物。 The composition according to any one of claims 2 to 10, wherein the component (A) is represented by the formula (I).
  12. 　請求項１～１１のいずれか一項に記載の成分（Ｂ）のカチオン性残基を有していてもよい請求項１～１１のいずれか一項に記載の成分（Ａ）由来のカチオンと、前記成分（Ｂ）のアニオン性残基に由来するアニオンが形成するアンモニウム塩を含有する組成物。 With a cation derived from the component (A) according to any one of claims 1 to 11, which may have a cationic residue of the component (B) according to any one of claims 1 to 11 , a composition containing an ammonium salt formed by an anion derived from the anionic residue of component (B).
  13. 　前記カチオンがアンモニウムカチオンである請求項１２に記載の組成物。 The composition according to claim 12, wherein the cation is an ammonium cation.
  14. 　前記成分（Ａ）と成分（Ｂ）が形成するアンモニウム塩のカチオンが、下記式（ＩＩＩ）：
    Figure JPOXMLDOC01-appb-C000003
     （式中、Ｒ5はそれぞれ独立に、水酸基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシ炭化水素基、カルボキシ基を１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいカルボキシ炭化水素基、又は水酸基及びカルボキシ基を各々１個以上有し、炭化水素部位が炭素数１～２２の直鎖状もしくは分岐鎖状で、該炭化水素部位が酸素原子を含んでいてもよいヒドロキシカルボキシ炭化水素基を示し、Ｒ6はそれぞれ独立に、水素原子又は炭素数１～２２の有機基であり、ｏは０～４の整数を示す。）で表される請求項１２又は１３に記載の組成物。     The cation of the ammonium salt formed by the component (A) and the component (B) is represented by the following formula (III):
    Figure JPOXMLDOC01-appb-C000003
     (In the formula, each R 5 independently has one or more hydroxyl groups, the hydrocarbon moiety is linear or branched with 1 to 22 carbon atoms, and the hydrocarbon moiety contains an oxygen atom. a hydroxy hydrocarbon group, a carboxy hydrocarbon having one or more carboxy groups, having a straight or branched hydrocarbon portion having 1 to 22 carbon atoms, and the hydrocarbon portion optionally containing an oxygen atom; or one or more each of a hydroxyl group and a carboxy group, the hydrocarbon moiety being linear or branched having 1 to 22 carbon atoms, and the hydrocarbon moiety may contain an oxygen atom. represents a hydrogen group, each R 6 is independently a hydrogen atom or an organic group having 1 to 22 carbon atoms, and o represents an integer of 0 to 4.). thing.
  15. 　前記式（ＩＩＩ）において、ｏは１～４の整数である請求項１４に記載の組成物。 The composition according to claim 14, wherein o is an integer of 1 to 4 in the formula (III).
  16. 　前記式（ＩＩＩ）において、全てのＲ6が水素原子である請求項１４又は１５に記載の組成物。 16. The composition according to claim 14 or 15, wherein in formula (III) all R6 are hydrogen atoms.
  17. 　前記式（ＩＩＩ）において、Ｒ5がヒドロキシ炭化水素基である請求項１４～１６のいずれか一項に記載の組成物。 A composition according to any one of claims 14 to 16, wherein in said formula (III), R 5 is a hydroxy hydrocarbon group.
  18. 　前記式（ＩＩＩ）において、前記炭化水素部位における炭化水素が飽和脂肪族炭化水素である請求項１４～１７のいずれか一項に記載の組成物。 The composition according to any one of claims 14 to 17, wherein in the formula (III), the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon.
  19. 　前記式（ＩＩＩ）において、Ｒ5のうち少なくとも１つが、水酸基を１個有し、前記炭化水素部位における炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基である請求項１４～１８のいずれか一項に記載の組成物。 Any one of claims 14 to 18, wherein in the formula (III), at least one of R 5 has one hydroxyl group, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon hydroxy hydrocarbon group. A composition according to claim 1.
  20. 　前記式（ＩＩＩ）において、Ｒ5のうち少なくとも１つが、水酸基を２個以上有し、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基である請求項１４～１８のいずれか一項に記載の組成物。 Any one of claims 14 to 18, wherein at least one of R 5 in the formula (III) has two or more hydroxyl groups, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon hydroxy hydrocarbon group. or the composition according to claim 1.
  21. 　前記式（ＩＩＩ）において、Ｒ5のうち少なくとも１つが、水酸基を１個以上有し、炭化水素部位が炭素数３～２２の分岐鎖状で、前記炭化水素部位の炭化水素が飽和脂肪族炭化水素のヒドロキシ炭化水素基である請求項１４～１８のいずれか一項に記載の組成物。 In the formula (III), at least one of R 5 has one or more hydroxyl groups, the hydrocarbon moiety is a branched chain having 3 to 22 carbon atoms, and the hydrocarbon in the hydrocarbon moiety is a saturated aliphatic hydrocarbon. A composition according to any one of claims 14 to 18 which is a hydroxyhydrocarbon group of hydrogen.
  22. 　前記式（ＩＩＩ）で表されるカチオンのＲ6のうち少なくとも１つが水素原子の場合、その水素原子に対応するプロトンが前記成分（Ｂ）に由来する請求項１４～２１のいずれか一項に記載の組成物。 When at least one of R 6 of the cation represented by the formula (III) is a hydrogen atom, the proton corresponding to the hydrogen atom is derived from the component (B). The described composition.
  23. 　前記成分（Ｂ）のアニオン性残基に前記水素結合性官能基を有する請求項１～２２のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 22, wherein the anionic residue of component (B) has the hydrogen-bonding functional group.
  24. 　前記水素結合性官能基が、水酸基、カルボキシ基、カルボキシレート基、エーテル基、及びアルコキシ基から選ばれるいずれかである請求項２１記載の組成物。 The composition according to claim 21, wherein the hydrogen-bonding functional group is any one selected from a hydroxyl group, a carboxy group, a carboxylate group, an ether group, and an alkoxy group.
  25. 　前記成分（Ｂ）のアニオン性残基に由来するアニオンがカルボン酸系アニオンである請求項１～２４のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 24, wherein the anion derived from the anionic residue of component (B) is a carboxylic anion.
  26. 　前記水素結合性官能基が水酸基である請求項１～２５のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 25, wherein the hydrogen-bonding functional group is a hydroxyl group.
  27. 　前記成分（Ａ）と（Ｂ）との混合物又は（Ａ）と（Ｂ）との塩は、無水物及び／又は水和物が２５℃で液体である請求項１～２６のいずれか一項に記載の組成物。 27. Any one of claims 1 to 26, wherein the mixture of components (A) and (B) or the salt of (A) and (B) is an anhydride and/or hydrate liquid at 25°C. The composition according to .
  28. 　前記高分子化合物が水素結合性官能基を有する、請求項１～２７のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 27, wherein the polymer compound has a hydrogen-bonding functional group.
  29. 　前記高分子化合物が多糖類である請求項１～２８のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 28, wherein the polymer compound is a polysaccharide.
  30. 　前記多糖類が、キサンタンガム、カラギーナン、ジェランガム、グアーガム、及びダイユータンガムから選ばれる請求項２９に記載の組成物。 The composition according to claim 29, wherein said polysaccharide is selected from xanthan gum, carrageenan, gellan gum, guar gum, and diutan gum.
  31. 　ゲル組成物である請求項１～３０のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 30, which is a gel composition.
  32. 　増粘された、あるいは増粘するための組成物である請求項１～３１のいずれか一項に記載の組成物。 The composition according to any one of claims 1 to 31, which is a thickened composition or a composition for thickening.
PCT/JP2022/018554 2021-04-23 2022-04-22 Composition suitable for gel formation and thickening characteristics WO2022225046A1 (en)

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Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000053552A (en) * 1998-08-07 2000-02-22 Nisshin Oil Mills Ltd:The Cosmetic material
US20030206936A1 (en) * 2002-04-22 2003-11-06 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Cosmetic composition and method of treating skin and hair
JP2005534639A (en) * 2002-05-29 2005-11-17 ユニリーバー・ナームローゼ・ベンノートシヤープ Suppression of odors in cosmetic compositions containing amine salts
JP2010174145A (en) * 2009-01-29 2010-08-12 Kagoshima Univ Method for producing xanthan gel and xanthan hydrogel
JP2013100305A (en) * 2011-12-28 2013-05-23 Neige Corporation:Kk Gel and semi-solid detergent
JP2014131974A (en) * 2012-12-05 2014-07-17 Miyoshi Oil & Fat Co Ltd Hydrophilic room-temperature ionic liquid and use thereof
JP2014131975A (en) * 2012-12-05 2014-07-17 Miyoshi Oil & Fat Co Ltd Hydrophilic room-temperature ionic liquid and use thereof
JP2016185933A (en) * 2015-03-27 2016-10-27 株式会社キレートジャパン Hydrogel-containing cosmetic
JP2019023185A (en) * 2017-07-21 2019-02-14 ミヨシ油脂株式会社 Water-and-moisture-retentive agent
WO2020166674A1 (en) * 2019-02-13 2020-08-20 ミヨシ油脂株式会社 Composition containing organic ammonium salt
WO2020166678A1 (en) * 2019-02-13 2020-08-20 ミヨシ油脂株式会社 Cosmetic ingredient, cosmetic, and production method for cosmetic

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000053552A (en) * 1998-08-07 2000-02-22 Nisshin Oil Mills Ltd:The Cosmetic material
US20030206936A1 (en) * 2002-04-22 2003-11-06 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Cosmetic composition and method of treating skin and hair
JP2005534639A (en) * 2002-05-29 2005-11-17 ユニリーバー・ナームローゼ・ベンノートシヤープ Suppression of odors in cosmetic compositions containing amine salts
JP2010174145A (en) * 2009-01-29 2010-08-12 Kagoshima Univ Method for producing xanthan gel and xanthan hydrogel
JP2013100305A (en) * 2011-12-28 2013-05-23 Neige Corporation:Kk Gel and semi-solid detergent
JP2014131974A (en) * 2012-12-05 2014-07-17 Miyoshi Oil & Fat Co Ltd Hydrophilic room-temperature ionic liquid and use thereof
JP2014131975A (en) * 2012-12-05 2014-07-17 Miyoshi Oil & Fat Co Ltd Hydrophilic room-temperature ionic liquid and use thereof
JP2016185933A (en) * 2015-03-27 2016-10-27 株式会社キレートジャパン Hydrogel-containing cosmetic
JP2019023185A (en) * 2017-07-21 2019-02-14 ミヨシ油脂株式会社 Water-and-moisture-retentive agent
WO2020166674A1 (en) * 2019-02-13 2020-08-20 ミヨシ油脂株式会社 Composition containing organic ammonium salt
WO2020166678A1 (en) * 2019-02-13 2020-08-20 ミヨシ油脂株式会社 Cosmetic ingredient, cosmetic, and production method for cosmetic

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