WO2014123110A1 - 増粘安定剤、及びそれを用いた増粘安定化組成物 - Google Patents
増粘安定剤、及びそれを用いた増粘安定化組成物 Download PDFInfo
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- WO2014123110A1 WO2014123110A1 PCT/JP2014/052534 JP2014052534W WO2014123110A1 WO 2014123110 A1 WO2014123110 A1 WO 2014123110A1 JP 2014052534 W JP2014052534 W JP 2014052534W WO 2014123110 A1 WO2014123110 A1 WO 2014123110A1
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- WIPO (PCT)
- Prior art keywords
- thickening
- organic substance
- thickening stabilizer
- stabilizer
- composition
- Prior art date
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- 230000008719 thickening Effects 0.000 title claims abstract description 60
- 239000003381 stabilizer Substances 0.000 title claims abstract description 45
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- 230000000087 stabilizing effect Effects 0.000 title claims description 16
- 239000000126 substance Substances 0.000 claims abstract description 59
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 11
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- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
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- 239000012965 benzophenone Substances 0.000 claims abstract description 6
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- XJNUECKWDBNFJV-UHFFFAOYSA-N hexadecyl 2-ethylhexanoate Chemical compound CCCCCCCCCCCCCCCCOC(=O)C(CC)CCCC XJNUECKWDBNFJV-UHFFFAOYSA-N 0.000 description 2
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- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000005070 decynyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C#C* 0.000 description 1
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- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
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- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
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- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
- C07C235/70—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton
- C07C235/84—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups and doubly-bound oxygen atoms bound to the same carbon skeleton with the carbon atom of at least one of the carboxamide groups bound to a carbon atom of a six-membered aromatic ring
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
- A23L29/00—Foods or foodstuffs containing additives; Preparation or treatment thereof
- A23L29/20—Foods or foodstuffs containing additives; Preparation or treatment thereof containing gelling or thickening agents
-
- 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
- A61K47/44—Oils, fats or waxes according to two or more groups of A61K47/02-A61K47/42; Natural or modified natural oils, fats or waxes, e.g. castor oil, polyethoxylated castor oil, montan wax, lignite, shellac, rosin, beeswax or lanolin
-
- 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
- A61K8/42—Amides
-
- 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
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/43—Thickening agents
-
- 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
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23V—INDEXING SCHEME RELATING TO FOODS, FOODSTUFFS OR NON-ALCOHOLIC BEVERAGES AND LACTIC OR PROPIONIC ACID BACTERIA USED IN FOODSTUFFS OR FOOD PREPARATION
- A23V2002/00—Food compositions, function of food ingredients or processes for food or foodstuffs
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/10—General cosmetic use
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K2800/00—Properties of cosmetic compositions or active ingredients thereof or formulation aids used therein and process related aspects
- A61K2800/40—Chemical, physico-chemical or functional or structural properties of particular ingredients
- A61K2800/48—Thickener, Thickening system
-
- 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
-
- 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
- C08K5/20—Carboxylic acid amides
Definitions
- the present invention relates to a novel compound having an action of thickening and stabilizing fluid organic substances such as oil, a thickening stabilizer using the same, and a thickening and stabilizing composition containing the same.
- the method of thickening and stabilizing the liquid is a very important technology in the industry.
- a metastable emulsion of mayonnaise or salad dressing can stably maintain the emulsion for a long period of time. This is because the aqueous component is thickened and stabilized.
- a hydrophilic thickening stabilizer is a compound that thickens and stabilizes an aqueous medium, and for example, an alkyl acrylate copolymer is known.
- 12-hydroxystearic acid is known as a thickening stabilizer for fluid organic substances (for example, organic substances having fluidity such as oily media) (Patent Document 1, etc.).
- 12-Hydroxystearic acid is mainly used for its gelling action for disposal of edible oil.
- 12-hydroxystearic acid cannot adjust the degree of gelation, it can only be induced to either solidify completely or remain liquid. That is, the present condition is that the compound which thickens or gelatinizes a fluid organic substance to a desired viscosity has not been found yet.
- an object of the present invention is to provide a compound that thickens or gels a flowable organic substance to a desired viscosity or uniformly stabilizes the composition of a composition containing the flowable organic substance.
- Another object of the present invention is to provide a thickening stabilizer containing the compound, a thickening and stabilizing composition thickened, gelled or stabilized by the thickening stabilizer, and a method for producing the same. It is in.
- a compound having a specific structure thickens, gels, or makes the composition of the composition containing the fluid organic substance uniform.
- a composition containing a fluid organic substance which can be stabilized, thickened or gelled to a desired viscosity by using the fluid organic substance selected according to the type of the fluid organic substance, or used. It was found that the composition of can be uniformly stabilized.
- the present invention has been completed based on these findings.
- R 1- CONH-R 2 ) n (1) (Wherein R 1 is an n-valent aromatic hydrocarbon group containing two or more benzene rings, R 2 is an aliphatic hydrocarbon group having 6 or more carbon atoms, and n is an integer of 4 or more)
- R 1 is an n-valent aromatic hydrocarbon group containing two or more benzene rings
- R 2 is an aliphatic hydrocarbon group having 6 or more carbon atoms
- n is an integer of 4 or more
- R 1 in formula (1) is a group obtained by removing n hydrogen atoms from an aromatic hydrocarbon selected from benzophenone, biphenyl, and naphthalene.
- the present invention also provides a thickening stabilizer containing the compound.
- the present invention also provides a thickening and stabilizing composition comprising the thickening stabilizer and a flowable organic substance.
- the present invention also provides a method for producing a thickened and stabilized composition comprising a step of making the thickening stabilizer and a flowable organic material compatible.
- R 1- (CONH-R 2 ) n (1) (Wherein R 1 is an n-valent aromatic hydrocarbon group containing two or more benzene rings, R 2 is an aliphatic hydrocarbon group having 6 or more carbon atoms, and n is an integer of 4 or more)
- R 1 in Formula (1) is a group obtained by removing n hydrogen atoms from an aromatic hydrocarbon selected from benzophenone, biphenyl, and naphthalene.
- a thickening / stabilizing composition comprising the thickening stabilizer according to [3] and a flowable organic substance.
- a method for producing a thickened / stabilized composition comprising the step of making the thickener / stabilizer according to [3] compatible with a flowable organic substance.
- the compound represented by the formula (1) of the present invention can easily thicken or gel a fluid organic substance by being compatible with the fluid organic substance, or a composition containing a fluid organic substance. Can be uniformly stabilized. Therefore, by using them in cosmetics, paints, foods, pharmaceuticals, etc., their viscosity can be adjusted to the desired range, their composition can be kept uniform, and their usability is improved. Can do.
- R 1 represents an n-valent aromatic hydrocarbon group containing two or more benzene rings, for example, an aromatic hydrocarbon selected from benzophenone, biphenyl, naphthalene, etc. (preferably a benzene ring A group obtained by removing n hydrogen atoms from an aromatic hydrocarbon containing 2).
- R 2 represents an aliphatic hydrocarbon group having 6 or more carbon atoms, such as hexyl, octyl, 2-ethylhexyl, decyl, dodecyl, tetradecyl, octadecyl, nonadecyl group, etc.
- linear or branched alkyl group (Preferably 6 to 18, particularly preferably 8 to 18) linear or branched alkyl group; 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 7-octenyl, 9-decenyl, 11 A linear or branched alkenyl group having about 6 to 20 carbon atoms (preferably 6 to 18, particularly preferably 12 to 18) such as dodecenyl and 9-octadecenyl group; hexynyl, octynyl, decynyl, pentadecenyl, octadecenyl group A linear or branched alkynyl group having about 6 to 20 carbon atoms (preferably 6 to 18 and particularly preferably 12 to 18). It can be mentioned.
- n represents an integer of 4 or more, preferably 4 to 8, particularly preferably 4 to 6.
- the compound represented by the formula (1) include 3,3 ′, 4,4′-benzophenone tetracarboxylic acid tetrahexylamide, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid tetra Octylamide, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetradecylamide, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetradodecylamide, 3,3 ′, 4,4′-benzophenone 3,3 ′, 4 such as tetracarboxylic acid tetramyristylamide, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetrastearylamide, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetraoleylamide , 4'-benzophenone tetracarboxylic acid
- the compound represented by the formula (1) includes, for example, (1) an aromatic carboxylic acid [R 1- (COOH) n : R 1 , n is the same as R 1 in the formula (1), n]] thionyl chloride is reacted with to give the carboxylic acid chloride, carboxylic acid chloride obtained in the aliphatic amine: and methods (R 2 -NH 2 R 2 is the same as R 2 in the formula (1)) are reacted, (2)
- the aromatic carboxylic acid anhydride corresponding to the aromatic carboxylic acid can be reacted with the aliphatic amine to obtain an amic acid, and the aliphatic amine can be further condensed using carbodiimide.
- aromatic carboxylic acid [R 1- (COOH) n ] include 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 1,1′-biphenyl-2,3,3 ′, 4 ′.
- Examples of the aliphatic amine include those having 6 or more carbon atoms (preferably 6 to 20 carbon atoms) such as hexylamine, octylamine, decylamine, dodecylamine, myristylamine, stearylamine, and oleylamine.
- An amine having an aliphatic hydrocarbon group preferably a linear or branched alkyl group, alkenyl group, or alkynyl group) can be given.
- the reaction between the carboxylic acid chloride and the aliphatic amine can be carried out, for example, by dropping the carboxylic acid chloride into the system charged with the aliphatic amine.
- the reaction between the carboxylic acid chloride and the aliphatic amine can be carried out in the presence or absence of a solvent.
- the solvent include saturated or unsaturated hydrocarbon solvents such as pentane, hexane, heptane, octane and petroleum ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; methylene chloride, chloroform, 1, 2 -Halogenated hydrocarbon solvents such as dichloroethane, chlorobenzene, bromobenzene; ether solvents such as diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane, cyclopentyl methyl ether; acetonitrile, benzonitrile, etc.
- Nitrile solvents such as dimethyl sulfoxide
- sulfolane solvents such as sulfolane
- amide solvents such as dimethylformamide
- high-boiling solvents such as silicone oil.
- a halogenated hydrocarbon solvent in terms of excellent solubility of the reaction components (carboxylic acid chloride and aliphatic amine).
- the amount of the solvent used is, for example, about 50 to 300% by weight, preferably 100 to 250% by weight, based on the total amount of carboxylic acid chloride and aliphatic amine.
- concentration of a reaction component will become low and there exists a tendency for reaction rate to fall.
- an aging step may be provided. When the aging step is provided, the aging temperature is, for example, about 30 to 60 ° C., and the aging time is, for example, about 1 to 5 hours.
- the reaction can be carried out by any method such as batch, semi-batch and continuous methods.
- the obtained reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, etc., or a combination means combining these.
- the compound represented by the formula (1) self-assembles by hydrogen bonding at the amide bond site to form a fiber-like self-assembly, and the side chain (R 2 in the formula (1)) is a fluid organic substance. Since it has an affinity for the liquid, it is possible to thicken the fluid organic substance, gelate it, or stabilize the composition of the composition containing the fluid organic substance uniformly by making it compatible with the fluid organic substance. Can do. Therefore, for example, it is useful as a thickening stabilizer (more specifically, a thickener, a gelling agent, or a stabilizer).
- the thickening stabilizer of this invention is characterized by including the compound represented by the said Formula (1) individually by 1 type or in combination of 2 or more types.
- the thickening stabilizer is a compound that dissolves in a flowable organic substance to generate viscosity
- the “thickening stabilizer” is a thickening agent that imparts viscosity to the flowable organic substance. It is a concept that includes a gelling agent that gels a substance and a stabilizer that increases its viscosity for the purpose of uniformly stabilizing the composition of a composition containing a flowable organic substance.
- the thickening stabilizer of the present invention may contain other components (for example, bases, hydroxy fatty acids, acrylic polymers, dextrin fatty acid esters, etc.) as necessary. And particles of esters, metal oxides, etc.).
- the content of the other components the content of the compound represented by the above formula (1) in the total amount (100% by weight) of the thickening stabilizer (the total amount when containing two or more kinds) is, for example, 0.5 It is within a range of at least 1% by weight, preferably at least 1% by weight.
- the upper limit of the content of the compound represented by the above formula (1) is 100% by weight.
- dosage form of the thickening stabilizer of the present invention various dosage forms such as powder, granule, liquid, and emulsion can be employed.
- the thickening stabilizer of the present invention thickens the flowable organic substance by making it compatible with the flowable organic substance (preferably by mixing, heating, making it compatible, and cooling). Alternatively, it can be gelled, and the viscosity of the flowable organic substance can be increased or gelled to a desired viscosity according to the use within the range of more than 1 and not more than 600 times.
- the thickening and stabilizing composition of the present invention comprises the above thickening stabilizer and a flowable organic substance, and the thickening stabilizer causes the flowable organic substance to thicken, gel, or contain the flowable organic substance.
- This is a composition in which the composition of the product is uniformly stabilized.
- the fluid organic substance is an organic substance having a rheometer viscosity [viscosity ( ⁇ ) at 25 ° C., shear rate 10 (1 / s)] of less than 0.1 Pa ⁇ s, for example, hydrocarbon oil (for example, Hexane, cyclohexane, isododecane, benzene, toluene, polyalphaolefin, liquid paraffin, etc., ethers (eg, tetrahydrofuran), halogenated hydrocarbons (eg, carbon tetrachloride, chlorobenzene, etc.), petroleum components (kerosene, gasoline, Light oil, heavy oil, etc.), animal and vegetable oils (sunflower oil, olive oil, soybean oil, corn oil, sunflower oil, beef tallow, jojoba oil, squalane, etc.), silicones (dimethylpolysiloxane, methylphenylpolysiloxane, etc.), esters (olein
- the thickening / stabilizing composition of the present invention may contain other components in addition to the thickening stabilizer and the flowable organic substance as long as the effects of the present invention are not impaired.
- Other components include, for example, general compounds (for example, medicinal ingredients, pigments) contained in addition to the above-described fluid organic substances in a composition desired to be thickened and stabilized, such as cosmetics, paints, foods, and pharmaceuticals. , Fragrances, etc.).
- the thickening / stabilizing composition can be manufactured through a step of compatibilizing the thickening stabilizer and the flowable organic substance. More specifically, the total amount of the thickening stabilizer and the flowable organic substance can be mixed and heated to be compatible with each other and then cooled. In addition, a thickening stabilizer is mixed with a part of the fluid organic substance, heated and mixed, and then cooled to produce a thickened and stabilized composition, which is then used as the remaining fluid organic substance. It can also be produced by a method of mixing the two.
- the mixing amount (or use amount) of the thickening stabilizer is, for example, 0.1 to 100 parts by weight, preferably 0. The amount is 5 to 90 parts by weight, particularly preferably 1 to 80 parts by weight.
- the temperature at the time of heating is appropriately selected depending on the type of the thickening stabilizer and the fluid organic substance to be used, and is not particularly limited as long as the thickening stabilizer and the fluid organic substance are compatible with each other. However, it is preferable not to exceed 100 ° C., and when the boiling point of the fluid organic substance is 100 ° C. or lower, the boiling point is preferable.
- the cooling after the compatibilization is not limited as long as it can be cooled to 25 ° C. or lower, and may be gradually cooled at room temperature, or may be forcedly cooled by ice cooling or the like.
- the viscosity [25 degreeC, the viscosity ((eta)) in shear rate 10 (1 / s)] by the rheometer of the thickening stabilization composition of this invention exceeds 1 time of the viscosity of the fluid organic substance to contain, and is 600 Within the range of double or less, it can be appropriately adjusted according to the application.
- the thickening and stabilizing composition of the present invention is not particularly limited as long as it contains a flowable organic substance and its thickening and stabilization are desired.
- cosmetics, paints, foods, Examples include pharmaceuticals.
- Synthesis Example 1 Synthesis of thickening stabilizer (BTDA-C 6 : 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetrahexylamide)
- BDA-C 6 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetrahexylamide
- the system temperature was set to 50 ° C., and 6.59 g (0.141 mol) of 3,3 ′, 4,4′-benzofetontetracarboxytetrachloride (hereinafter sometimes referred to as “BTDA-Cl”)
- BTDA-Cl 3,3 ′, 4,4′-benzofetontetracarboxytetrachloride
- the solution was added dropwise over 5 hours, and further aged for 4 hours. Thereafter, the low boiling content of the obtained crude liquid was removed by an evaporator and washed with methanol to obtain a pale yellow wet powder. Further, the obtained wet powder was recrystallized with CHCl 3 / CH 3 OH (70/30 (v / v)) to obtain 5.0 g of BTDA-C 6 (yield: 42%).
- Synthesis Example 2 Synthesis of thickening stabilizer (BTDA-C 8 : 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetraoctylamide)
- a 100 mL four-neck separable flask equipped with a Dimroth condenser, nitrogen inlet and dropping funnel, and thermocouple was charged with 20 mL of CHCl 3 and 13.77 g (0.106 mol) of n-octylamine.
- the system temperature was set to 40 ° C., 6.23 g (0.133 mol) of “BTDA-Cl” was added dropwise over 2.5 hours, and aging was further performed for 4 hours.
- Synthesis Example 3 Synthesis of thickening stabilizer (BTDA-C 12 : 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetradodecylamide)
- a 100 mL four-neck separable flask equipped with a Dimroth condenser, nitrogen inlet and dropping funnel, and thermocouple was charged with 20 mL of CHCl 3 and 11.4 g (0.062 mol) of dodecylamine.
- the system temperature was set to 50 ° C., 4.97 g (0.011 mol) of “BTDA-Cl” was added dropwise over 0.5 hours, and aging was further performed for 4 hours.
- Synthesis Example 4 Synthesis of thickening stabilizer (BTDA-C 14 : 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetramyristylamide)
- a 100 mL four-neck separable flask equipped with a Dimroth condenser, a nitrogen inlet and a dropping funnel, and a thermocouple was charged with 20 mL of CHCl 3 and 13.2 g (0.062 mol) of myristylamine.
- the system temperature was set to 50 ° C., 4.97 g (0.011 mol) of “BTDA-Cl” was added dropwise over 0.5 hours, and aging was further performed for 4 hours.
- the low boiling content of the obtained crude liquid was removed by an evaporator and washed with methanol to obtain a pale yellow wet powder. Further, the obtained wet powder was recrystallized with CHCl 3 / CH 3 OH (70/30 (v / v)) to obtain 3.1 g (yield 31%) of BTDA-C 14 .
- Synthesis Example 5 Synthesis of thickening stabilizer (BTDA-C 18 : 3,3 ′, 4,4′-benzophenonetetracarboxylic acid tetrastearylamide)
- the system temperature was set to 50 ° C., 5.35 g (0.011 mol) of “BTDA-Cl” was added dropwise over 2.5 hours, and aging was further performed for 4 hours.
- the low boiling content of the obtained crude liquid was removed by an evaporator and washed with methanol to obtain a pale yellow wet powder. Further, the obtained wet powder was recrystallized with CHCl 3 / CH 3 OH (70/30 (v / v)) to obtain 3.4 g of BTDA-oleyl (yield: 39%).
- Viscosity of various flowable organic substances and thickening and stabilizing compositions is equipped with a cone plate sensor (60 mm diameter, cone angle 1 °, 35 mm diameter cone angles 1 °, 2 °, 4 °) and Peltier temperature controller.
- a cone plate sensor 60 mm diameter, cone angle 1 °, 35 mm diameter cone angles 1 °, 2 °, 4 °
- Peltier temperature controller Using a measured viscosity / viscoelasticity measuring device (rheometer) (trade name “Rheo Stress 600”, manufactured by HAAKE) under a normal viscosity measurement mode under a 25 ° C.
- the shear rate is 0.001 to 100 (1 / s)
- the viscosity was measured to obtain a viscosity curve
- the viscosity at a shear rate of 10 (1 / s) was determined from the obtained viscosity curve, and this was used as the viscosity of the present invention.
- each plot used the value when the torque value fluctuation
- the compound represented by the formula (1) of the present invention can easily thicken or gel a fluid organic substance by being compatible with the fluid organic substance, or a composition containing a fluid organic substance. Can be uniformly stabilized. Therefore, by using them in cosmetics, paints, foods, pharmaceuticals, etc., their viscosity can be adjusted to the desired range, their composition can be kept uniform, and their usability is improved. Can do.
Abstract
Description
本発明の他の目的は、前記化合物を含有する増粘安定剤、前記増粘安定剤により増粘、ゲル化、又は安定化された増粘安定化組成物、及びその製造方法を提供することにある。
R1-(CONH-R2)n (1)
(式中、R1はベンゼン環を2個以上含むn価の芳香族炭化水素基、R2は炭素数6以上の脂肪族炭化水素基、nは4以上の整数を示す)
で表される化合物を提供する。
[1] 下記式(1)で表される化合物。
R1-(CONH-R2)n (1)
(式中、R1はベンゼン環を2個以上含むn価の芳香族炭化水素基、R2は炭素数6以上の脂肪族炭化水素基、nは4以上の整数を示す)
[2] 式(1)中のR1が、ベンゾフェノン、ビフェニル、及びナフタレンから選択される芳香族炭化水素からn個の水素原子を除いた基である[1]に記載の化合物。
[3] [1]又は[2]に記載の化合物を含む増粘安定剤。
[4] [3]に記載の増粘安定剤と流動性有機物質を含む増粘安定化組成物。
[5] [3]に記載の増粘安定剤と流動性有機物質を相溶させる工程を含む増粘安定化組成物の製造方法。
本発明の化合物は、下記式(1)で表される。
R1-(CONH-R2)n (1)
本発明の増粘安定剤は、上記式(1)で表される化合物を1種単独で、又は2種以上を組み合わせて含むことを特徴とする。
本発明の増粘安定化組成物は、上記増粘安定剤と流動性有機物質を含み、前記増粘安定剤により流動性有機物質が増粘、ゲル化、又は流動性有機物質を含有する組成物の組成が均一に安定化されてなる組成物である。
ジムロート冷却管、窒素導入口および滴下ロート、熱伝対を備えた100mL4つ口セパラブルフラスコにCHCl320mL、ヘキシルアミン11.41g(0.113mol)を仕込んだ。系内温度を50℃に設定し、3,3’,4,4’-ベンゾフェトンテトラカルボキシテトラクロリド(以下、「BTDA-Cl」と称する場合がある)6.59g(0.141mol)を2.5時間かけて滴下し、更に4時間熟成を行った。その後、得られた粗液の低沸分をエバポレータにて除去し、メタノールで洗浄し、淡黄色の湿粉を得た。更に得られた湿粉についてCHCl3/CH3OH(70/30(v/v))で再結晶を行い、BTDA-C6を5.0g得た(収率:42%)。
1H-NMR (270 MHz, CDCl3): δ 0.91 (t, 12H, J=4.9Hz), 1.35-1.45 (m, 24H), 1.57-1.72 (m, 8H), 3.38 (q, 8H, J=6.8Hz), 7.45-7.54 (m, 4H), 7.65-7.73 (m, 6H)
ジムロート冷却管、窒素導入口および滴下ロート、熱伝対を備えた100mL4つ口セパラブルフラスコにCHCl320mL、n-オクチルアミン13.77g(0.106mol)を仕込んだ。系内温度を40℃に設定し、「BTDA-Cl」6.23g(0.133mol)を2.5時間かけて滴下し、更に4時間熟成を行った。その後、得られた粗液の低沸分をエバポレータにて除去し、メタノールで洗浄し、淡黄色の湿粉を得た。更に得られた湿粉についてCHCl3/CH3OH(70/30(v/v))で再結晶を行い、BTDA-C8を5.4g得た(収率:43%)。
1H-NMR (270 MHz, CDCl3): δ 0.88 (t, 12H, J=6.2Hz), 1.18-1.40 (m, 40H), 1.59-1.61 (m, 8H), 3.35-3.42 (m, 8H), 7.28-7.53 (m, 4H), 7.69-8.14 (m, 6H)
ジムロート冷却管、窒素導入口および滴下ロート、熱伝対を備えた100mL4つ口セパラブルフラスコにCHCl320mL、ドデシルアミン11.4g(0.062mol)を仕込んだ。系内温度を50℃に設定し、「BTDA-Cl」4.97g(0.011mol)を0.5時間かけて滴下し、更に4時間熟成を行った。その後、得られた粗液の低沸分をエバポレータにて除去し、メタノールで洗浄し、淡黄色の湿粉を得た。更に得られた湿粉についてCHCl3/CH3OH(70/30(v/v))で再結晶を行い、BTDA-C12を2.4g得た(収率:27%)。
1H-NMR (270 MHz, CDCl3): δ 0.88 (t, 12H, J=7.3Hz), 1.05-1.44 (m, 72H), 1.59-1.61 (m, 8H), 3.38 (m, 8H), 7.34-7.52 (m, 2H), 7.67-7.70 (m, 2H), 7.77 (s, 2H)
ジムロート冷却管、窒素導入口および滴下ロート、熱伝対を備えた100mL4つ口セパラブルフラスコにCHCl320mL、ミリスチルアミン13.2g(0.062mol)を仕込んだ。系内温度を50℃に設定し、「BTDA-Cl」4.97g(0.011mol)を0.5時間かけて滴下し、更に4時間熟成を行った。その後、得られた粗液の低沸分をエバポレータにて除去し、メタノールで洗浄し、淡黄色の湿粉を得た。更に得られた湿粉についてCHCl3/CH3OH(70/30(v/v))で再結晶を行い、BTDA-C14を3.1g(収率31%)で得た。
1H-NMR (270 MHz, CDCl3): δ 0.88 (t, 12H, J=6.8Hz), 1.12-1.41 (m, 88H), 1.45-1.65 (m, 8H), 3.38 (dd, 8H, J=13.2Hz, 6.5Hz), 7.26-7.68 (m, 6H) , 7.69-7.72 (m, 2H) , 7.79 (s, 2H)
ジムロート冷却管、窒素導入口および滴下ロート、熱伝対を備えた100mL4つ口セパラブルフラスコにCHCl320mL、ステアリルアミン24.65g(0.091mol)を仕込んだ。系内温度を50℃に設定し、「BTDA-Cl」5.35g(0.011mol)を2.5時間かけて滴下し、更に4時間熟成を行った。その後、得られた粗液の低沸分をエバポレータにて除去し、メタノールで洗浄し、淡黄色の湿粉を得た。更に得られた湿粉についてCHCl3/CH3OH(80/20(v/v))で再結晶を行い、BTDA-C18を5.4g得た(収率:31%)。
1H-NMR (270 MHz, CDCl3): δ 0.88 (t, 12H, J=6.8Hz), 1.12-1.41 (m, 120H), 1.45-1.65 (m, 8H), 3.35-3.40(m, 8H), 7.37-7.58 (m, 6H) , 7.65-7.81 (m, 4H)
ジムロート冷却管、窒素導入口および滴下ロート、熱伝対を備えた100mL4つ口セパラブルフラスコにCHCl320mL、オレイルアミン12.31g(0.046mol)を仕込んだ。系内温度を50℃に設定し、「BTDA-Cl」2.69g(0.0058mol)を2.5時間かけて滴下し、更に4時間熟成を行った。その後、得られた粗液の低沸分をエバポレータにて除去し、メタノールで洗浄し、淡黄色の湿粉を得た。更に得られた湿粉についてCHCl3/CH3OH(70/30(v/v))で再結晶を行い、BTDA-oleylを3.4g得た(収率:39%)。
1H-NMR (270 MHz, CDCl3): δ 0.84-0.87 (m, 12H), 1.06-1.41 (m, 88H), 1.42-1.57 (m, 8H),1.75-2.11 (m, 16H), 3.21-3.48 (m, 8H), 5.31-5.52 (m, 8H), 7.43-8.10 (m, 10H)
表1に示す各種流動性有機物質を試験管に1cm3ずつ秤りとり、これに上記合成例1~6で得られた増粘安定剤をそれぞれ10mg加えて混合し、各流動性有機物質についての適温(沸点が100℃未満の流動性有機物質については沸点又はそれ以下の温度(40~80℃)、沸点が100℃以上の流動性有機物質については80~100℃で加熱した。具体的には、流動性有機物質としてヘキサンを使用した場合:40℃、シクロヘキサンを使用した場合:40℃、ヒマワリ油を使用した場合:100℃、イソドデカンを使用した場合:80℃、流動パラフィンを使用した場合:80℃、エチルヘキサン酸セチルを使用した場合:80℃、ポリαオレフィンを使用した場合:80℃)で加熱撹拌して流動性有機物質と増粘安定剤を相溶させることにより増粘安定化組成物を得た。
得られた増粘安定化組成物を25℃まで冷却してその粘度を測定し、各種流動性有機物質の粘度が何倍に増粘されたかを確認し、下記基準に従って増粘安定性を評価した。
<評価基準>
1: 1.0倍を超え、2.0倍以下
2: 2.0倍を超え、4.8倍以下
3: 4.8倍を超え、10倍以下
4: 10倍を超え、50倍以下
5: 50倍を超え、100倍以下
6: 100倍を超え、600倍以下
Claims (5)
- 下記式(1)
R1-(CONH-R2)n (1)
(式中、R1はベンゼン環を2個以上含むn価の芳香族炭化水素基、R2は炭素数6以上の脂肪族炭化水素基、nは4以上の整数を示す)
で表される化合物。 - 式(1)中のR1が、ベンゾフェノン、ビフェニル、及びナフタレンから選択される芳香族炭化水素からn個の水素原子を除いた基である請求項1に記載の化合物。
- 請求項1又は2に記載の化合物を含む増粘安定剤。
- 請求項3に記載の増粘安定剤と流動性有機物質を含む増粘安定化組成物。
- 請求項3に記載の増粘安定剤と流動性有機物質を相溶させる工程を含む増粘安定化組成物の製造方法。
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