WO2014061467A1 - 液体組成物 - Google Patents
液体組成物 Download PDFInfo
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- WO2014061467A1 WO2014061467A1 PCT/JP2013/077070 JP2013077070W WO2014061467A1 WO 2014061467 A1 WO2014061467 A1 WO 2014061467A1 JP 2013077070 W JP2013077070 W JP 2013077070W WO 2014061467 A1 WO2014061467 A1 WO 2014061467A1
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- Prior art keywords
- fatty acid
- formula
- acid amide
- methyl
- component
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- WOMTYMDHLQTCHY-UHFFFAOYSA-N CNCC(CO)O Chemical compound CNCC(CO)O WOMTYMDHLQTCHY-UHFFFAOYSA-N 0.000 description 2
- 0 CN(CC(COC(*)=O)O)C(*)=O Chemical compound CN(CC(COC(*)=O)O)C(*)=O 0.000 description 1
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Classifications
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- 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
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/14—Preparation of carboxylic acid amides by formation of carboxamide groups together with reactions not involving the carboxamide groups
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- 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
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- 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
- A61K2800/59—Mixtures
- A61K2800/592—Mixtures of compounds complementing their respective functions
- A61K2800/5922—At least two compounds being classified in the same subclass of A61K8/18
Definitions
- the present invention relates to a liquid composition having shear-thickening properties.
- Liquid compositions containing branched polymer compounds and water-soluble polymer compounds as materials with non-linear flow characteristics generally have non-Newtonian properties, and paints and coating agents that use pseudoplasticity, or various emulsions that use thixotropic properties Widely applied to compositions (for example, toothpaste, ink, cosmetic cream, etc.). These are compositions having a shear-thinning characteristic in which the viscosity decreases when a certain strain or more is applied.
- a composition having a shear-thinning characteristic has a problem that the composition is scattered when the production line is operated at a high speed for the purpose of improving productivity.
- Non-linear flow characteristics include the shear-thickening characteristics and the shear-thickening characteristics in which the viscosity increases or gels when a certain amount of strain is applied.
- Liquid compositions having shear-thickening properties include, for example, dental materials, coating solutions, shoe sole materials, viscoelastic polishing media, materials for silent functional devices, filling materials for display deformation suppression layers, printers It is useful in the fields of industrial inks, cosmetic base materials, impact absorbing materials, etc. (Patent Documents 1 to 12, Non-Patent Document 1).
- liquid compositions having share-thickening properties that are already known can be obtained by interaction between inorganic fine particles and polysiloxane or by interaction between microemulsion particles and water-soluble polymer compound. Or, there are cases in which the use of the inorganic fine particles, polysiloxane, ionic polymer compound, etc. is not preferable because of the shear-thickening characteristics such as rheopecy and dilatancy due to the interaction between the ionic polymer compounds. .
- a polymer compound having a thread-like structure that is entropically stable in a state without strain is stretched linearly when the solution is strained.
- the interaction with fine particles, emulsions and other polymers is induced to form a cross-linking point, thereby expressing shear-thickening properties.
- polymer compounds impart strain stress. It has been known that molecular chain scission occurs due to the degradation of the shear-thickening property due to repeated use.
- the interaction between microemulsions and ionic polymer compounds formed using ionic surfactants may vary depending on the ionic species and their concentration in the environment of use or in the product composition. It was a problem.
- the polymer compound contained in the liquid composition having these shear-thickening properties is unlikely to be biodegraded and may cause environmental pollution.
- an object of the present invention is to provide a liquid composition having a property of thickening or gelling when the environmental load is small and strain is applied.
- Another object of the present invention is to provide an N-methyl-N- (2,3-dihydroxypropyl) fatty acid amide compound and an N-methyl-N- (2-hydroxypropyl) fatty acid amide ester compound as raw materials for the liquid composition. It is in providing the manufacturing method of.
- N-methyl-N- (2,3-dihydroxypropyl) fatty acid amide compounds having one hydrophobic group and two hydrophilic groups in one molecule A liquid composition containing an N-methyl-N- (2-hydroxypropyl) fatty acid amide ester compound having two hydrophobic groups and one hydrophilic group in the molecule, an oily substance, and water is a high environmental impact polymer. Even if it does not contain a compound, it is liquid in a stationary state, and has a shear-thickening property that thickens or gels when strain is applied, which is caused by a change in the higher-order aggregation structure of a low-molecular organic compound.
- this invention provides the liquid composition containing the following component (A), (B), (C), and (D).
- the content ratio of the component (A) to the component (B) is preferably 99: 1 to 70:30.
- the component (C) is preferably a linear or branched hydrocarbon oil.
- the liquid composition of the present invention has a storage elastic modulus [G ′ (Pa)] at a shear rate of 350 rad / s and a storage elastic modulus [G ′ (Pa) at a shear rate of 1 rad / s. ]
- the difference between the loss elastic modulus [G "(Pa)] at a shear rate of 350 rad / s and the loss elastic modulus [G" (Pa)] at a shear rate of 1 rad / s is 10 Pa or more.
- the liquid composition of the present invention preferably further contains an amphiphilic substance (excluding compounds contained in components (A) and (B)) as component (E).
- the present invention also provides the following formula (3) in the presence of a basic catalyst. 0.95 mol or more and less than 1.95 mol of the following formula (4a) with respect to 1 mol of the amine compound represented by: (Wherein R a represents a linear or branched alkyl group or alkenyl group having 5 to 20 carbon atoms, and R 4 represents a hydrocarbon group) Is reacted with a fatty acid ester represented by the following formula (1a) (Wherein R a is the same as above) An N-methyl-N- (2,3-dihydroxypropyl) fatty acid amide compound represented by the formula (2a): (Wherein R a is the same as above) The N-methyl-N- (2-hydroxypropyl) fatty acid amide ester compound represented by the formula is simultaneously produced, and a method for producing the fatty acid amide ester compound is provided.
- a basic catalyst 0.95 mol or more and less than 1.95 mol of the following formula (4a) with respect to 1 mol of the
- the present invention further provides the following formula (3) in the presence of a basic catalyst.
- formula (4b) of 1.2 mol or less with respect to 1 mol of the amine compound:
- R 1 represents a linear or branched alkyl group or alkenyl group having 5 to 20 carbon atoms, and R 5 represents a hydrocarbon group
- a fatty acid ester represented by the following formula (1):
- R 1 is the same as above
- the present invention further provides a method for producing the fatty acid amide compound and the fatty acid amide ester compound represented by the following formula (1a):
- R a represents a linear or branched alkyl group or alkenyl group having 5 to 20 carbon atoms
- R a is the same as above
- a method for producing a liquid composition is provided, wherein a mixture of N-methyl-N- (2-hydroxypropyl) fatty acid amide ester compound represented by the formula (1) is obtained, and an oily substance and water are mixed with the obtained mixture. To do.
- the liquid composition of the present invention has the above-described configuration, it has the characteristic of expressing the shear-thickening characteristic with high sensitivity, and can maintain the characteristic for a long period of time. Moreover, it is not necessary to use a polymer compound with a large environmental load, and it is environmentally friendly.
- the liquid composition of the present invention is a material that requires shear-thickening characteristics as a rheology control material (for example, shock absorbing material filler, shoe sole material, viscoelastic polishing medium, material for silent functional device, display deformation suppression layer filling) Materials, printer inks, coating liquids, cosmetic base materials, dental materials, etc.).
- the liquid composition of the present invention contains the following components (A), (B), (C), and (D).
- Component (A) N-methyl-N- (2,3-dihydroxypropyl) fatty acid amide compound represented by formula (1)
- Component (B) N-methyl-N- (formula represented by formula (2) 2-Hydroxypropyl) fatty acid amide ester compound
- Component (C) Oily substance
- Component (A) of the present invention is an N-methyl-N- (2,3-dihydroxypropyl) fatty acid amide compound represented by the above formula (1).
- R 1 represents a linear or branched alkyl group or alkenyl group having 5 to 20 carbon atoms.
- R 1 C ( ⁇ O) group examples include n-pentanoyl, isopentanoyl, n-hexanoyl, n-octanoyl, isooctanoyl, 2-ethylhexanoyl, 3-ethylhexanoyl, n-nonanoyl, isononyl, n -Decanoyl, isodecanoyl, n-undecanoyl, n-dodecanoyl, n-tetradecanoyl, n-hexadecanoyl, n-eicosanoyl, n-pentenoyl, isopentenoyl, n-hexenoyl, n-octenoyl, isooctenoyl, 2-e
- a linear alkyl group having 9 to 15 carbon atoms is preferable in view of excellent fluidity and temperature stability.
- the number of carbon atoms is below the above range, it is difficult to form a high-order ordered aggregate structure, and thus there is a tendency that the shear-thickening characteristic is hardly exhibited.
- the interaction between hydrophobic chains becomes stronger, so the higher-order structure becomes too hard, and even if strain is applied, recombination from the unit structure to the crosslinked structure accompanying the deformation of the higher-order structure Since the shear-thickening characteristic is difficult to appear, it may cause crystallization and separation at low temperatures in some cases.
- the content of component (A) in the liquid composition of the present invention is, for example, about 1 to 70% by weight, preferably 2 to 50% by weight, particularly preferably 3 to 30% by weight, and most preferably 5 to 15% by weight. It is.
- the content of the component (A) is below the above range, even if strain is applied, the viscosity does not increase sufficiently, or the composition itself tends to separate and become non-uniform.
- the content of the component (A) exceeds the above range, the viscosity becomes remarkably high without imparting strain, and the practical value of the thickening effect when imparting strain is impaired, or the premise of function expression It tends to be difficult to form a higher order structure.
- the N-methyl-N- (2,3-dihydroxypropyl) fatty acid amide compound represented by the formula (1) can be produced, for example, by a known method such as the following method. 1) A method in which a fatty acid ester and an alkanolamine are reacted in the presence of a basic catalyst (see US Pat. No. 2,844,609). 2) A method of reacting a fatty acid with a large excess of alkanolamine in the absence of a solvent (Oil Chemistry, Vol. 24, No. 12, 869-873, 1975).
- the above method 1 is preferable, and in the presence of a basic catalyst, the following formula (3) is particularly preferable.
- formula (4b) of 1.2 mol or less with respect to 1 mol of the amine compound: (Wherein R 1 represents a linear or branched alkyl group or alkenyl group having 5 to 20 carbon atoms, and R 5 represents a hydrocarbon group) Is reacted with a fatty acid ester represented by the formula (1) (Wherein R 1 is the same as above)
- R 1 is the same as above
- R 1 in formula (4b) corresponds to R 1 in formula (1).
- R 5 in the formula (4b) represents a hydrocarbon group, for example, methyl group, ethyl group, propyl group, allyl group, isopropyl group, butyl group, amyl group, hexyl group, cyclohexyl group, octyl group, ethylhexyl group, Examples thereof include linear, branched or cyclic saturated or unsaturated alkyl groups having 1 to 20 carbon atoms such as decyl group, dodecyl group, cetyl group, stearyl group and eicosyl group.
- the alcohol produced as a by-product in the reaction has a low molecular weight, and the alcohol can be removed under mild conditions.
- the alkyl group of number 1 or 2 is preferable.
- fatty acid ester represented by the formula (4b) include methyl laurate, ethyl laurate, 2-ethylhexyl laurate and the like.
- the amount of the fatty acid ester represented by the formula (4b) is about 1.2 mol or less (for example, 0.95 to 1.20 mol), preferably 1 mol of the amine compound represented by the formula (3). Is 0.96 to 1.05 mol, particularly preferably 0.96 mol or more and less than 1.03 mol.
- amount of the fatty acid ester represented by the formula (4b) exceeds the above range, a side reaction proceeds and an N-methyl-N- (2,3-dihydroxypropyl) fatty acid amide represented by the formula (1) There is a tendency for the yield of the compound to decrease.
- Examples of the basic catalyst include sodium hydroxide, potassium hydroxide, sodium methoxide and methanol solution thereof, potassium t-butoxide, lithium hydroxide and the like.
- the amount of the basic catalyst used is, for example, about 0.001 mol to 0.1 mol, preferably 0.003 to 0.05 mol, per 1 mol of the amine compound represented by the formula (3).
- the reaction temperature is, for example, about 60 ° C. to 150 ° C., preferably 70 ° C. to 130 ° C., particularly preferably 80 ° C. to 100 ° C.
- the reaction time is, for example, about 1 to 60 hours, preferably 10 to 50 hours.
- the reaction is preferably performed under reduced pressure (for example, about 0.1 to 600 mmHg, preferably 1.0 to 400 mmHg).
- the reaction atmosphere is not particularly limited as long as it does not inhibit the reaction. For example, when the reaction is carried out in a low pressure state at the beginning of the reaction, the inside of the reactor is charged with an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere after the raw materials are charged. From the viewpoint of improving the hue and catalytic activity, it is preferable to perform the reaction.
- the reaction product can adsorb, for example, a catalyst-derived metal component remaining in the reaction crude liquid or an amine compound represented by the formula (3) as a solid adsorbent (both metal and amine).
- a catalyst-derived metal component remaining in the reaction crude liquid or an amine compound represented by the formula (3) as a solid adsorbent (both metal and amine).
- those that can be separated by means such as filtration after the adsorption operation are preferable.
- various ion exchange resins, various inorganic solid adsorbents in the form of powder or particles can be suitably used), and thereafter It can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these.
- Component (B) of the present invention is an N-methyl-N- (2-hydroxypropyl) fatty acid amide ester compound represented by the above formula (2).
- R 2 and R 3 are the same or different and each represents a linear or branched alkyl group or alkenyl group having 5 to 20 carbon atoms, and examples similar to those in R 1 are given. be able to.
- the content of component (B) in the liquid composition of the present invention is, for example, about 0.01 to 10% by weight, preferably 0.02 to 5% by weight, particularly preferably 0.03 to 3% by weight.
- content of a component (B) is less than the said range, even if distortion is provided, there exists a tendency for thickening or gelatinization to become difficult to occur.
- content of the component (B) exceeds the above range, the initial viscosity and elastic modulus of the blend are remarkably increased and may be gelled to impair the properties as a practical shear-thickening material.
- the content ratio of the component (A) to the component (B) is, for example, about 99: 1 to 70:30, preferably 99: 1 to 80:20, more preferably 98. : 2 to 80:20, particularly preferably 97: 3 to 90:10, and most preferably 96: 4 to 91: 9.
- N-methyl-N- (2-hydroxypropyl) fatty acid amide ester compound represented by the formula (2) for example, in the presence of a basic catalyst, the following formula (3) And the following formula (4a) of 1.95 mol or more (for example, 1.95 to 2.95 mol, preferably 1.97 to 2.10 mol) with respect to 1 mol of the amine compound: (Wherein R a represents a linear or branched alkyl group or alkenyl group having 5 to 20 carbon atoms, and R 4 represents a hydrocarbon group) Is reacted with a fatty acid ester represented by the following formula (2a) (Wherein R a is the same as above) And a method for producing an N-methyl-N- (2-hydroxypropyl) fatty acid amide ester compound represented by the formula:
- R a in formula (4a) represents a linear or branched alkyl group or alkenyl group having 5 to 20 carbon atoms, and examples similar to those in R 1 in formula (1) can be given. .
- R 4 in the formula (4a) represents a hydrocarbon group, and examples similar to R 5 in the formula (4b) can be given.
- Specific examples of the fatty acid ester represented by the formula (4a) include methyl laurate, ethyl laurate, 2-ethylhexyl laurate and the like.
- Examples of the basic catalyst include the same examples as described above.
- the amount of the basic catalyst used is, for example, about 0.001 to 0.1 mol, preferably 0.005 to 0.1 mol, with respect to 1 mol of the amine compound represented by the formula (3).
- the reaction temperature is, for example, 90 ° C. to 150 ° C., more preferably 100 ° C. to 140 ° C., particularly preferably 110 ° C. to 130 ° C.
- the reaction time is not particularly limited, but if it is attempted to be too short, it is necessary to use a large amount of an alkali catalyst. On the other hand, if it is too long, the hue of the product tends to deteriorate, for example, 10 to 100 hours. Degree, preferably 20 to 70 hours.
- the reaction is preferably performed under reduced pressure (for example, about 0.1 to 600 mmHg, preferably 1.0 to 400 mmHg).
- the reaction atmosphere is not particularly limited as long as it does not inhibit the reaction.
- the reactor is filled with a nitrogen atmosphere, an argon atmosphere, or the like after the raw materials are charged. It is preferable to perform the reaction after substituting with an active gas atmosphere from the viewpoint of improving the hue and catalytic activity.
- reaction product After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these, as described above.
- separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these, as described above.
- the ester compound can also be produced simultaneously by the following method.
- the amount of the fatty acid ester represented by the formula (4a) to be used is, for example, about 0.95 mol or more and less than 1.95 mol, preferably about 1.5 mol with respect to 1 mol of the amine compound represented by the formula (3).
- the amount is from 0 to 1.5 mol, particularly preferably from 1.03 to 1.2 mol.
- Examples of the basic catalyst include the same examples as described above.
- the amount of the basic catalyst used is, for example, about 0.001 to 0.1 mol, preferably 0.003 to 0.05 mol, per 1 mol of the amine compound represented by the formula (3).
- the reaction temperature is, for example, 90 ° C. to 150 ° C., more preferably 100 ° C. to 140 ° C., particularly preferably 110 ° C. to 130 ° C.
- the reaction time is not particularly limited, but if it is too short, it is necessary to use a large amount of an alkali catalyst. Conversely, if it is too long, the hue of the product tends to deteriorate. For example, 1 to 60 hours. Degree, preferably 3 to 40 hours.
- the reaction is preferably performed under reduced pressure (for example, about 0.1 to 600 mmHg, preferably 1.0 to 400 mmHg).
- the reaction atmosphere is not particularly limited as long as it does not inhibit the reaction.
- the inside of the reactor is charged after the raw materials are charged.
- Substitution with an inert gas atmosphere such as a nitrogen atmosphere or an argon atmosphere, and then performing the reaction is preferable from the viewpoint of improving the hue and catalytic activity.
- reaction product After completion of the reaction, the reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these, as described above.
- separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, etc., or a separation means combining these, as described above.
- the N-methyl-N- (2,3-dihydroxypropyl) fatty acid amide compound represented by the formula (1) and the N-methyl-N- (2-hydroxy) represented by the formula (2) (Propyl) fatty acid amide ester compound, the former: latter (weight ratio) is about 99: 1 to 70:30, preferably 99: 1 to 80:20, more preferably 98: 2 to 80:20, particularly preferably 97. : 3 to 90:10, most preferably a mixture containing 96: 4 to 91: 9.
- N-methyl-N- (2-hydroxypropyl) fatty acid amide ester compound represented by the formula (2) may be used as a mixture of those obtained by independent production equipment and production process. Is an amphiphilic compound having two hydrophobic groups and one hydrophilic group in one molecule, and thus has a strong tendency to self-assemble such as forming a gel by itself, and handling properties may be reduced during production. is there.
- an N-methyl-N- (2,3-dihydroxypropyl) fatty acid amide compound represented by the above formula (1) and an N-methyl-N- (2-hydroxypropyl) fatty acid represented by the formula (2) It is preferable to employ a method capable of producing an amide ester compound at the same time because the production process is simple and the target compound can be obtained efficiently.
- Component (C) of the present invention is an oily substance, and a known and commonly used oily substance can be used.
- hydrocarbon oils such as liquid paraffin, squalane, n-octane, n-heptane, cyclohexane and isododecane
- ether oils such as dioctyl ether, ethylene glycol monolauryl ether, ethylene glycol dioctyl ether and glycerol monooleyl ether
- octyl myristate Ester oil such as dodecyl, isopropyl palmitate, butyl stearate, myristyl myristate, isopropyl myristate, di-2-ethylhexyl adipate, diisopropyl sebacate, neopentyl glycol dicaprate, tricaproine; isostearyl alcohol, octyldodecan
- the number of carbons is about the same as R 1 to R 3 in the compound represented by the above formula (1) or the above formula (2) (that is, Use of a straight or branched hydrocarbon oil having 5 to 20 carbon atoms, preferably 9 to 15 carbon atoms, is a highly fluid precursor higher order in a state where no strain is applied. It is preferable in that it is excellent in formability of the structure, easily changes to a crosslinked higher order structure when imparted with strain, and can be quickly thickened or gelled.
- the content of the component (C) in the liquid composition of the present invention is, for example, about 1 to 50% by weight, preferably 2 to 30% by weight, particularly preferably 3 to 20% by weight.
- the content of the component (C) is out of the above range, the composition tends to be separated without being uniform.
- Component (D) of the present invention is water. Any of hard water and soft water may be used. For example, pure water, industrial water, tap water, ion exchange water, distilled water, and the like can be used.
- the content of component (D) in the liquid composition of the present invention is, for example, about 50 to 98% by weight, preferably 70 to 97% by weight, particularly preferably 75 to 95% by weight.
- content of the component (D) exceeds the above range, even if the liquid is separated without being maintained in a uniform state, or even when distortion is applied, it tends to be difficult to thicken or gel.
- the liquid composition of the present invention may contain other components (E) in addition to the components (A) to (D) as long as they do not inhibit the expression of the rheology control function of the present invention.
- other components (E) include various amphipathic substances, oil-soluble additives, solvents such as alcohol and polyhydric alcohol, antioxidants, humectants, pigment powders, fragrances, dyes, organic or inorganic ultraviolet rays.
- absorbents, preservatives, whitening agents, plant extracts, and the like can be used alone or in combination of two or more.
- amphiphilic substance examples include an anionic surfactant [for example, alkyl sulfate salts such as sodium lauryl sulfate and potassium lauryl sulfate; alkyl ether sulfate salts such as polyoxyethylene lauryl sulfate triethanolamine salt; N -N-acyl sarcosine salts such as sodium lauroyl sarcosine; higher fatty acid amide sulfonates such as sodium N-myristoyl-N-methyltaurine and sodium N-stearoyl-N-methyltaurine; sodium monostearyl phosphate, polyoxyethylene oleyl Phosphate esters such as sodium ether phosphate and sodium polyoxyethylene stearyl ether; sulfosuccinates such as sodium di-2-ethylhexyl sulfosuccinate; linear dodecylbenzenes Alkylbenzene sulfonates such as sodium a
- oil-soluble additive examples include sphingosine, dihydrosphingosine, phytosphingosine, dehydrosphingosine, dehydrophytosphingosine, sphingadienin, and sphingosines such as N-methyl or N, N-dimethyl thereof; cholesterol And sterols such as cholesterol sulfate, polyoxyethylene cholesterol, stigmasterol and ergosterol; 1- (2-hydroxyethylamino) -3-isostearyloxy-2-propanol and the like.
- Examples of the alcohol and polyhydric alcohol include ethanol, isopropanol, ethylene glycol, 1,2-propanediol, propylene glycol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, and glycerin. , Trimethylolpropane, pentaerythritol and the like.
- antioxidants examples include trade names “HP-136”, “Irganox 1010”, “Irganox 1076”, “Irganox 1330”, “Irganox 3114”, “Irganox 3125” (trade name, manufactured by Ciba Specialty Chemicals Co., Ltd.).
- ADK STAB AO-20 “ADK STAB AO-50”, “ADK STAB AO-60”, “ADK STAB AO-80”, “ADK STAB AO-30”, “ADK STAB AO-40” (above, ADEKA CORPORATION) (Trademark), “BHT” (trademark, manufactured by Takeda Pharmaceutical Co., Ltd.), “Cyanox 1790” (trademark, manufactured by Cyanamid Co., Ltd.), “Sumizer GP”, “Sumizer GM”, “Sumizer GS”, “Sumizer GA-80” As described above, hindered phenolic antioxidants such as Sumitomo Chemical Co., Ltd., and the like; “IRAGAFOS168”, “IRAGAFOS12”, “IRAGAFOS38”, “IRAGAFOS P-EPQ”, “IRAGAFOS126” (above, Ciba Specialty Chemicals Co., Ltd., Trademark), “ADKSTAB 329K”, “ADKSTAB PEP-36”, “ADKST
- the liquid composition of the present invention may contain a water-soluble or oil-soluble polymer compound depending on the application.
- the water-soluble polymer compound include polyvinyl alcohol, polyacrylamide, polyvinyl methyl ether, polyisopropyl acrylamide, polyethylene oxide, and cellulose derivatives (for example, methyl cellulose, ethyl cellulose, methyl hydroxypropyl cellulose, hydroxypropyl cellulose, hydroxyethyl cellulose, and the like).
- Starch-based modified polymer propylene glycol alginate, guar gum, locust bean gum, tragacanth gum, gelatin, casein, dextrin, xanthan gum, pullulan, starch and the like.
- oil-soluble polymer compound examples include cyclopentasiloxane, dimethicone, alkyl dimethicone, highly polymerized methyl polysiloxane, polybutene, hydrogenated polyisobutene, and polybutyl acrylate.
- the addition amount of the water-soluble or oil-soluble polymer compound (the total amount when two or more are used) is 10% by weight or less, preferably 5% by weight or less of the total amount of the liquid composition. When the addition amount of the water-soluble or oil-soluble polymer compound exceeds the above range, the environmental load becomes large, which may cause environmental pollution.
- liquid composition of the present invention the above components (A) to (D) and other components (E) as necessary are mixed, and heated as necessary (for example, about 40 ° C. to 80 ° C.)
- a general-purpose stirrer such as a single-axis or multi-axis extruder, kneader, dissolver, homogenizer, or rotor mixer to stir and mix until uniform, or use an ultrasonic emulsifier or high-pressure emulsifier Can be prepared.
- the liquid composition of the present invention has a shear-thickening property of thickening or gelling by imparting strain, and has a storage modulus [G ′ at a shear rate of 350 rad / s in a temperature range of 10 ° C. to 50 ° C. (Pa)] and the storage elastic modulus [G ′ (Pa)] at a shear rate of 1 rad / s is, for example, 20 Pa or more (preferably 30 or more, particularly preferably 40 or more).
- the difference between the loss elastic modulus [G ′′ (Pa)] at a shear rate of 350 rad / s and the loss elastic modulus [G ′′ (Pa)] at a shear rate of 1 rad / s is, for example, 10 Pa or more (preferably 15 Pa or more). , Particularly preferably 20 Pa or more).
- the liquid composition of the present invention has reversible rheological properties, and once it thickens or gels, for example, it is heated to about 50 ° C. and then cooled in a stationary state, or it is allowed to stand at room temperature for about 1 month. By placing it, the viscosity is lowered and high fluidity can be recovered. In addition, when strain is imparted to the liquid composition whose fluidity has been restored, it can be thickened or gelled again with high sensitivity.
- the liquid composition of the present invention has the above-described shear-thickening characteristics, the liquid composition does not scatter even when the production line is operated at a high speed for the purpose of improving productivity. In addition, even if printing is performed at high speed, printing can be performed with high accuracy.
- a cosmetic base material for example, it is liquid and highly fluid in the container, but it is distorted by shaking it immediately before use or by discharging from a container having a nozzle mechanism such as a pump former.
- the user can change the state by himself.
- the liquid composition of the present invention is used as a rheology control material, for example, a shock absorbing material filler, a shoe sole material, a viscoelastic polishing medium, a material for a silent functional device, a filling material for a display deformation suppressing layer, a printer ink, It can be suitably used as a coating liquid, cosmetic base material, dental material and the like.
- Example 1 (Production of 3-lauroylmethylamide-1,2-propanediol) To a 1 L four-necked flask with a reflux pipe equipped with a nitrogen inlet line with three-way cock switching, a thermometer with a sheath pipe, and a three-way cock for switching between a vent line and a vacuum pump vacuum line, 300.10 g of methyl laurate ( 1.40 mol) and 151.62 g (1.44 mol) of 3- (N-methylamino) -1,2-propanediol (manufactured by Daicel Corporation) were added, and the internal temperature was increased to 70 ° C. The inside of the reactor was purged with nitrogen while stirring.
- Example 2 (Production of 1- (3-lauroylmethylamido-2-hydroxypropyl) laurate) 342.97 g of methyl laurate in a 1 L four-necked flask with a reflux pipe equipped with a nitrogen inlet line with a three-way cock switch, a thermometer with a sheath pipe, and a three-way cock for switching between the vent line and the vacuum pump vacuum line ( 1.60 mol) and 85.38 g (0.81 mol) of 3- (N-methylamino) -1,2-propanediol (manufactured by Daicel Corporation) were added and the internal temperature was raised to 70 ° C. The inside of the reactor was purged with nitrogen while stirring.
- Example 3 (Preparation of a mixture of 3-lauroylmethylamido-1,2-propanediol and 1- (3-lauroylmethylamido-2-hydroxypropyl) laurate) 331.17 g of methyl laurate was added to a 1 L four-necked flask having a reflux pipe equipped with a nitrogen introduction line with a three-way cock switching, a thermometer with a sheath pipe, and a three-way cock for switching between a vent line and a vacuum pump vacuum line ( 1.55 mol), 3- (N-methylamino) -1,2-propanediol (manufactured by Daicel Corporation) 157.71 g (1.50 mol) was added, and the internal temperature was raised to 70 ° C.
- the inside of the reactor was purged with nitrogen while stirring. To this was added 3.377 g (0.015 mol) of a 28% sodium methoxide methanol solution, the internal temperature was raised to 110 ° C., and the pressure was gradually reduced to 600 mmHg while observing the distillation state so that methanol would not bump. did. Thereafter, the pressure was gradually reduced to 150 mmHg while maintaining 110 ° C., and after 28 hours, it was confirmed by GC analysis that the amount of residual methyl laurate was 0.1% or less, and then cooled to 80 ° C.
- Example 4 (Preparation of a mixture of 3-lauroylmethylamido-1,2-propanediol and 1- (3-lauroylmethylamido-2-hydroxypropyl) laurate)
- a reflux pipe equipped with a nitrogen introduction line with a three-way cock switching, a thermometer with a sheath pipe, and a three-way cock for switching between a vent line and a vacuum pump vacuum line
- 3- (N-methylamino) -1,2-propanediol manufactured by Daicel Corporation 157.70 g (1.50 mol) was added, and the internal temperature was increased to 70 ° C.
- the inside of the reactor was purged with nitrogen while stirring. To this was added 3.377 g (0.015 mol) of a 28% sodium methoxide methanol solution, and the internal temperature was raised to 110 ° C., and the distillate state was monitored so that methanol would not suddenly boil up to 600 mmHg. The pressure was reduced. Thereafter, while maintaining 110 ° C., the pressure was gradually reduced to 150 mmHg, and when 40 hours had elapsed, it was confirmed by GC analysis that the amount of residual methyl laurate was 0.1% or less, and then cooled to 80 ° C.
- compositions obtained in Examples 5 to 11 are composed only of low molecular weight organic compounds, and are manually formed at room temperature (20 ° C. to 30 ° C.) despite the fact that over 70% of the composition is water. It was found that when the internal composition was distorted by shaking, the viscosity rapidly increased and gelled, resulting in gelation. In addition, the compositions obtained in Examples 5 to 7 were once gelled and then cooled by heating to 50 ° C. or standing at room temperature for about 1 month to restore high fluidity. It was also clarified that when the liquid was shaken by hand at room temperature, it re-gelled again.
- the dynamic viscoelasticity at 10 ° C., 30 ° C., and 50 ° C. was measured using a MCR301 type rheometer (manufactured by Anton-Paar) at a shear rate ( ⁇ ) of 0.1 to It measured in the range of 500 rad / s (refer FIG. 1, 2).
- ⁇ shear rate
- the liquid composition of the present invention has a rheology control function that imparts various physical properties from a liquid state to a gel state depending on the application, and maintains the function even when various additives are added depending on the application. be able to. Therefore, it is a rheology control material with a wide range of applications.
- the liquid composition of the present invention has the property of expressing the shear-thickening property with high sensitivity, and can maintain the property over a long period of time. Moreover, it is not necessary to use a polymer compound with a large environmental load, and it is environmentally friendly.
- the liquid composition of the present invention is a material that requires shear-thickening characteristics as a rheology control material (for example, shock absorbing material filler, shoe sole material, viscoelastic polishing medium, material for silent functional device, display deformation suppression layer filling) Materials, printer inks, coating liquids, cosmetic base materials, dental materials, etc.).
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Abstract
Description
本発明の他の目的は前記液体組成物の原料であるN-メチル-N-(2,3-ジヒドロキシプロピル)脂肪酸アミド化合物と、N-メチル-N-(2-ヒドロキシプロピル)脂肪酸アミドエステル化合物の製造方法を提供することにある。
成分(A):下記式(1)
で表されるN-メチル-N-(2,3-ジヒドロキシプロピル)脂肪酸アミド化合物
成分(B):下記式(2)
で表されるN-メチル-N-(2-ヒドロキシプロピル)脂肪酸アミドエステル化合物
成分(C):油性物質
成分(D):水
で表される脂肪酸エステルを反応させて、下記式(1a)
で表されるN-メチル-N-(2,3-ジヒドロキシプロピル)脂肪酸アミド化合物と、下記式(2a)
で表されるN-メチル-N-(2-ヒドロキシプロピル)脂肪酸アミドエステル化合物を同時に生成することを特徴とする脂肪酸アミド化合物及び脂肪酸アミドエステル化合物の製造方法を提供する。
で表される脂肪酸エステルを反応させて、下記式(1)
で表されるN-メチル-N-(2,3-ジヒドロキシプロピル)脂肪酸アミド化合物を生成することを特徴とする脂肪酸アミド化合物の製造方法を提供する。
成分(A):式(1)で表されるN-メチル-N-(2,3-ジヒドロキシプロピル)脂肪酸アミド化合物
成分(B):式(2)で表されるN-メチル-N-(2-ヒドロキシプロピル)脂肪酸アミドエステル化合物
成分(C):油性物質
成分(D):水
本発明の成分(A)は、上記式(1)で表されるN-メチル-N-(2,3-ジヒドロキシプロピル)脂肪酸アミド化合物である。
1)脂肪酸エステルとアルカノールアミンを塩基性触媒の存在下で反応させる方法(米国特許第284609号参照)。
2)脂肪酸と、それに対して大過剰量のアルカノールアミンとを無溶媒下で反応させる方法(油化学、第24巻、第12号、869~873、1975)。
3)脂肪酸とアルカノールアミンを反応させてアミドエステルを生成させ、その後、この反応系に塩基性触媒を溶解又は分散させたアルカノールアミンを添加する方法(特開昭53-44513号公報)。
4)アルカノールアミン中に、脂肪酸を間欠的に又は連続して添加する方法(特開平8-301827)。
5)冷却下にて、アルカノールアミンに脂肪酸ハライドとアルカリ水溶液を滴下することにより反応させる方法(ショッテン・バウマン反応)
で表される脂肪酸エステルを反応させて式(1)
で表されるN-メチル-N-(2,3-ジヒドロキシプロピル)脂肪酸アミド化合物を生成することが、安全性に優れた原料から、温和な反応条件下で選択的に目的化合物を製造することができる点で好ましい。
本発明の成分(B)は、上記式(2)で表されるN-メチル-N-(2-ヒドロキシプロピル)脂肪酸アミドエステル化合物である。
で表される脂肪酸エステルを反応させて、下記式(2a)
で表されるN-メチル-N-(2-ヒドロキシプロピル)脂肪酸アミドエステル化合物を製造する方法を挙げることができる。
で表される脂肪酸エステルを反応させて、下記式(1a)
で表されるN-メチル-N-(2,3-ジヒドロキシプロピル)脂肪酸アミド化合物と、下記式(2a)
で表されるN-メチル-N-(2-ヒドロキシプロピル)脂肪酸アミドエステル化合物を同時に生成することができる。この方法によれば、シェア-シックニング特性を有する液体組成物に好適な重量分率で脂肪酸アミド化合物及び脂肪酸アミドエステル化合物を一度に得ることができる。
本発明の成分(C)は油性物質であり公知慣用の油性物質を使用することができる。例えば、流動パラフィン、スクワラン、n-オクタン、n-ヘプタン、シクロヘキサン、イソドデカン等の炭化水素油;ジオクチルエーテル、エチレングリコールモノラウリルエーテル、エチレングリコールジオクチルエーテル、グリセロールモノオレイルエーテル等のエーテル油;ミリスチン酸オクチルドデシル、パルミチン酸イソプロピル、ステアリン酸ブチル、ミリスチン酸ミリスチル、ミリスチン酸イソプロピル、アジピン酸ジ-2-エチルヘキシル、セバシン酸ジイソプロピル、ジカプリン酸ネオペンチルグリコール、トリカプロイン等のエステル油;イソステアリルアルコール、オクチルドデカノール等の飽和分岐鎖高級(炭素数10~22)アルコール;ラウリン酸ラウリルアミド、ラウリン酸ブチルアミド等の高級(炭素数10~22)脂肪酸アミド;オリーブ油、大豆油、綿実油等の植物油;ジメチルポリシロキサン、環状ジメチルポリシロキサン、メチルフェニルポリシロキサン、アミノ変性シリコーン、エポキシ変性シリコーン、カルボキシ変性シリコーン、アルコール変性シリコーン、アルキル変性シリコーン、ポリエーテル変性シリコーン、フッ素変性シリコーン等のシリコーン油;パーフルオロアルキルエチルリン酸、パーフルオロアルキルポリオキシエチレンリン酸、パーフルオロポリエーテル、ポリテトラフルオロエチレン等のフッ素系油等を挙げることができる。これらは1種を単独で、又は2種以上を組み合わせて使用することができる。
本発明の成分(D)は水である。硬水、軟水の何れでもよく、例えば、純水、工業用水、水道水、イオン交換水、蒸留水等を使用することができる。
3方コック切り替え付き窒素導入ラインを備えた還流管、さや管入り温度計、ベントラインと真空ポンプ減圧ラインの切替用3方コックを有する1Lの4つ口フラスコに、ラウリン酸メチル300.10g(1.40モル)、3-(N-メチルアミノ)-1,2-プロパンジオール((株)ダイセル製)151.62g(1.44モル)を入れ、内部温度を70℃に加温して撹拌しつつ反応器内を窒素置換した。これに28%ナトリウムメトキシドのメタノール溶液6.30g(0.028モル)を添加し、内部温度を90℃に昇温してメタノールが突沸しないように留出状態を見ながら徐々に500mmHgまで減圧した。その後、90℃を維持しつつ徐々に100mmHgまで減圧し40時間経過時点で、GC分析にて残留ラウリン酸メチル量が0.1%以下であることを確認してから70℃に冷却した。
無機合成吸着剤(商品名「キョーワード700」、協和化学工業(株)製)を80.48g添加して5時間撹拌した後、温水ジャケット付き加圧濾過器を用いてセライト濾紙で濾過し、濾液とエタノール洗浄液を合一してロータリーエバポレーターで濃縮、減圧乾燥して380.93gの淡黄白色ワックス状生成物を得た。
得られた生成物をアセトンより再結晶して、白色針状結晶粉末として、3-ラウロイルメチルアミド-1,2-プロパンジオール297.13g(収率:78.3%)を得た(生成物1)。1H-NMRおよびIRにより目的とする分子構造を有することを確認した。
3方コック切り替え付き窒素導入ラインを備えた還流管、さや管入り温度計、ベントラインと真空ポンプ減圧ラインの切替用3方コックを有する1Lの4つ口フラスコに、ラウリン酸メチル342.97g(1.60モル)、3-(N-メチルアミノ)-1,2-プロパンジオール((株)ダイセル製)85.38g(0.81モル)を入れ、内部温度を70℃に加温して撹拌しつつ反応器内を窒素置換した。これに28%ナトリウムメトキシドのメタノール溶液1.55g(0.008モル)を添加し、内部温度を110℃に昇温してメタノールが突沸しないように留出状態を見ながら徐々に600mmHgまで減圧した。その後、110℃を維持しつつ徐々に150mmHgまで減圧し65時間経過時点で、GC分析にて残留ラウリン酸メチル量が0.1%以下であることを確認してから80℃に冷却した。エタノール380gを添加し、均一になるまで撹拌して-10℃の冷蔵庫中で結晶を析出させ、濾過、洗浄、乾燥して白色結晶粉末として、1-(3-ラウロイルメチルアミド-2-ヒドロキシプロピル)ラウレート88.55g(収率:23.6%)を得た(生成物2)。1H-NMRにより目的とする分子構造を有することを確認した。
3方コック切り替え付き窒素導入ラインを備えた還流管、さや管入り温度計、ベントラインと真空ポンプ減圧ラインの切替用3方コックを有する1Lの4つ口フラスコに、ラウリン酸メチル331.17g(1.55モル)、3-(N-メチルアミノ)-1,2-プロパンジオール((株)ダイセル製)157.71g(1.50モル)を入れ、内部温度を70℃に加温して撹拌しつつ反応器内を窒素置換した。これに28%ナトリウムメトキシドのメタノール溶液3.377g(0.015モル)を添加し、内部温度を110℃に昇温してメタノールが突沸しないように留出状態を見ながら徐々に600mmHgまで減圧した。その後、110℃を維持しつつ徐々に150mmHgまで減圧し28時間経過時点で、GC分析にて残留ラウリン酸メチル量が0.1%以下であることを確認してから80℃に冷却した。
無機合成吸着剤(商品名「キョーワード700」、協和化学工業(株)製)を80.48g添加し、5時間撹拌した後、温水ジャケット付き加圧濾過器を用いてセライト濾紙で濾過し、濾液とエタノール洗浄液を合一してロータリーエバポレーターで濃縮、減圧乾燥して408.85gの淡黄白色ワックス状生成物を得た(生成物3)。
1H-NMRにより当該生成物3には、3-ラウロイルメチルアミド-1,2-プロパンジオール及び1-(3-ラウロイルメチルアミド-2-ヒドロキシプロピル)]ラウレートが重量比91.2:8.8で含まれていることを確認した。
3方コック切り替え付き窒素導入ラインを備えた還流管、さや管入り温度計、ベントラインと真空ポンプ減圧ラインの切替用3方コックを有する1Lの4つ口フラスコに、ラウリン酸メチル321.52g(1.50モル)、3-(N-メチルアミノ)-1,2-プロパンジオール((株)ダイセル製)157.70g(1.50モル)を入れ、内部温度を70℃に加温して撹拌しつつ反応器内を窒素置換した。これに28%ナトリウムメトキシドのメタノール溶液3.377g(0.015モル)を添加し、内部温度を110℃に昇温してメタノールが突沸しないように留出状態を監視しつつ徐々に600mmHgまで減圧した。その後、110℃を維持しつつ徐々に150mmHgまで減圧し40時間経過時点で、GC分析にて残留ラウリン酸メチル量が0.1%以下であることを確認してから80℃に冷却した。
無機合成吸着剤(商品名「キョーワード700」、協和化学工業(株)製)を43.2g添加し、5時間撹拌した後、温水ジャケット付き加圧濾過器を用いてセライト濾紙で濾過し、濾液とエタノール洗浄液を合一してロータリーエバポレーターで濃縮、減圧乾燥して413.12gの淡黄白色ワックス状生成物を得た(生成物4)。
1H-NMRにより当該生成物4には、3-ラウロイルメチルアミド-1,2-プロパンジオール及び1-(3-ラウロイルメチルアミド-2-ヒドロキシプロピル)ラウレートが重量比95.4:4.6で含まれていることを確認した。
エタノールアミン8.325g(300mmol)とエタノール14.885gの混合液を70℃に加熱し、これにヘキサデシルグリシジルエーテル7.443g(24.6mmol)を1時間かけて滴下し、さらに3時間、70℃で撹拌した後、ロータリーエバポレーターで濃縮乾燥後、メタノールで再沈殿してN-(2-ヒドロキシ-3-ヘキサデシロキシプロピル)エタノールアミン5.615g(14.44mmol)を得た(収率62.8%)。これにカリウム-t-ブトキシド87mg(0.77mmol)を添加し、80℃に加熱して液状とした。この混合物にパルミチン酸メチル1.392g(5.15mmol)を添加して300mmHg~20mmHgで2時間減圧脱低沸する操作を3回くり返した後、n-ヘプタンに反応粗液を加えて固形分を濾取して乾燥して粗生成物7.557gを得た。このうち7.000gをヘプタン-酢酸エチル混合溶媒を用いたシリカゲルクロマトグラフによる精製に付し、N-(2-ヒドロキシ-3-ヘキサデシロキシプロピル)-N-ヒドロキシエチルヘキサデカナミド6.290g(10.45mmol)を得た(収率73.0%)(生成物5)。構造は、CDCl3とDMSO-d6の混合溶媒を用いた1H-NMRおよび13C-NMRにより確認し、同溶媒中、室温においてN元素中心に結合した置換基の立体配置の異なる2種類の回転異性体からなる混合物であることを確認した。
3-(N-メチルアミノ)-1,2-プロパンジオール((株)ダイセル製)2.835g(26.97mmol)にエタノール5.670gを加え混合して氷浴冷却した。これにドデシルイソシアネート5.533g(26.18mmol)を1時間かけて滴下し、さらに室温下で1時間、加熱還流下に1時間撹拌した後、トリエチルアミン2.649g(26.18mmol)を添加して氷浴にて冷却し、ラウリン酸クロリド6.095g(26.18g)を1時間かけて滴下し、さらに氷浴冷却下に2時間、室温で5時間撹拌した後、減圧脱低沸、乾燥して固形物11.15gを得た。
全量をヘプタン-酢酸エチル混合溶媒を用いたシリカゲルクロマトグラフによる精製に付し、TLC 1スポットの位置異性体混合物として、1-[3-(N-ラウリルカルバモイルメチルアミノ)-2-ヒドロキシプロピル]ラウレートと2-[3-(N-ラウリルカルバモイルメチルアミノ)-1-ヒドロキシプロピル]ラウレートの混合物4.590g(10.45mmol)を得た(収率36.5%)(生成物6)。なお、両成分は、再結晶および条件を変更してのTLCにおいても混合物として確認されたことから、溶液中、室温下では速やかに相互に構造が交換しており通常の精製法では単離困難な平衡混合物となる性質を持つ物質であると考えられる。
3方コック切り替え付き窒素導入ラインを備えた還流管、さや管入り温度計、ベントラインと真空ポンプ減圧ラインの切替用3方コックを有する1Lの4つ口フラスコに、ラウリン酸メチル85.739g(400mmol)、2-(メチルアミノ)エタノール30.945g(0.412mmol)を入れ、内部温度を70℃に加温して撹拌しつつ反応器内を窒素置換した。これに28%ナトリウムメトキシドのメタノール溶液0.772g(4mmol)を添加し、内部温度を90℃に昇温してメタノールが突沸しないように留出状態を見ながら徐々に500mmHgまで減圧した。その後、90℃を維持しつつ徐々に100mmHgまで減圧し10時間経過時点で、GC分析にて残留ラウリン酸メチル量が0.1%以下であることを確認してから70℃に冷却した。
無機合成吸着剤(商品名「キョーワード700」、協和化学工業(株)製)を20.6g添加し、5時間撹拌した後、温水ジャケット付き加圧濾過器を用いてセライト濾紙で濾過し、濾液とエタノール洗浄液を合一してロータリーエバポレーターで濃縮、減圧乾燥して94.503gの淡黄白色ワックス状生成物を得た。これをアセトンより再結晶して、白色針状結晶粉末として、N-メチル-N-(2-ヒドロキシエチル)ラウロイルアミド68.436gを得た(収率:66.5%)(生成物7)。1H-NMRにより目的とする分子構造を有することを確認した。
実施例1~4及び比較例1~3で得られた生成物を使用して、表1に示した所定量(単位:g)の原料を[操作-1]に示した操作に従って混合することにより組成物を得た。得られた組成物について[操作-2]~[操作-3]に示した操作によりその特性を確認した。
[操作-1]
表1に示した組成に従い、純水-2を除く各成分を10mL目盛り付ねじ口試験管に秤量し、ボルテックスミキサーで撹拌・分散後、ローターミキサー(商品名「MIX ROTOR VMRC-5」、アズワン(株)製)を用いて45℃で1時間撹拌して目視で均一になるまで混合し、ボルテックスミキサーで撹拌しつつ、純水-2を所定量滴下混合して組成物を得た。得られた組成物を40℃の恒温槽中に10時間以上保存し、更に25℃恒温槽中で約3時間程度保存した後で状態を目視確認した。
[操作-2]
各組成物の入ったねじ口試験管を室温(20℃~30℃)下に手で強く振とうすることにより組成物に歪みを与えた直後に状態を目視確認した。
[操作-3]
各組成物の入ったねじ口試験管を50℃の恒温水槽に浸漬して1時間加温した後、25℃恒温槽に約3時間程度保存した後で状態を目視確認した。
また、実施例5~7で得られた組成物のように別個に製造された成分(A)と成分(B)を混合した場合であっても、実施例8、9で得られた組成物のように成分(A)と成分(B)の混合物を1ポット合成した場合であっても、さらには実施例10、11で得られた組成物のように、成分(A)と成分(B)以外の他の両親媒性物質を添加した場合であっても、シェア-シックニング特性を有することがわかった。
一方、表2に示したごとく、比較例4~11で得られた組成物は、何れも歪みを付与することによってゲル化するシェア-シックニング特性を有しなかった。
その結果、貯蔵弾性率(G’)および損失弾性率(G”)共に剪断速度が大きくなるに従って顕著に増大し、ゲル化する(=組成物が変形しにくくなる)傾向を示すことが明らかになった。
Claims (8)
- 成分(A)と成分(B)の含有割合[前者:後者(重量比)]が、99:1~70:30である請求項1に記載の液体組成物。
- 成分(C)が直鎖状若しくは分岐鎖状の炭化水素油である請求項1又は2に記載の液体組成物。
- 10℃~50℃の温度範囲において、剪断速度350rad/sにおける貯蔵弾性率[G’(Pa)]と剪断速度1rad/sにおける貯蔵弾性率[G’(Pa)]の差が20Pa以上であり、且つ、剪断速度350rad/sにおける損失弾性率[G”(Pa)]と剪断速度1rad/sにおける損失弾性率[G”(Pa)]の差が10Pa以上である請求項1~3の何れか1項に記載の液体組成物。
- 更に、成分(E)として両親媒性物質(成分(A)及び(B)に含まれる化合物を除く)を含有する請求項1~4の何れか1項に記載の液体組成物。
- 塩基性触媒の存在下、下記式(3)
で表される脂肪酸エステルを反応させて、下記式(1a)
で表されるN-メチル-N-(2,3-ジヒドロキシプロピル)脂肪酸アミド化合物と、下記式(2a)
で表されるN-メチル-N-(2-ヒドロキシプロピル)脂肪酸アミドエステル化合物を同時に生成することを特徴とする脂肪酸アミド化合物及び脂肪酸アミドエステル化合物の製造方法。
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JP2016124786A (ja) * | 2014-12-26 | 2016-07-11 | 川研ファインケミカル株式会社 | 油ゲル化剤、該油ゲル化剤を含有する油ゲル組成物 |
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