TWI662016B - Viscosity-stabilizing agent, and viscosity-stabilizing composition using the same - Google Patents

Abstract

The present invention provides a compound, a viscosity-increasing stabilizer comprising the aforementioned compound, a viscosity-increasing stabilization composition comprising the aforementioned viscosity-increasing stabilizer and a fluid organic substance, and a method for manufacturing the viscosity-increasing stabilization composition; the compound is a fluid The organic substance thickens or gels to a desired viscosity, or stabilizes the composition containing the fluid organic substance uniformly.

The compound of the present invention is represented by the following formula (1). In the formula, R ¹ and R ² are different and are aliphatic hydrocarbon groups having 4 or more carbon atoms. n represents an integer from 1 to 3. The viscosity-increasing stabilizer of the present invention contains the aforementioned compound.

Description

Viscosity-stabilizing agent, and viscosity-stabilizing composition using the same

The present invention relates to a novel compound having the function of thickening and stabilizing a fluid organic substance such as oil, and a thickening stabilizer using the same, and a thickening and stabilizing composition containing the same.

The method of stabilizing liquid viscosity is a very important technology in the industry. For example, the quasi-stabilized state of emulsification such as mayonnaise and salad dressing can maintain its emulsified state stably for a long time. Stabilizing sake. Therefore, various stabilizers have been developed.

As a compound which thickens and stabilizes an aqueous medium, for example, an alkyl acrylate copolymer and the like are known.

On the other hand, as a thickening stabilizer for a fluid organic substance (for example, an organic substance having fluidity such as an oily medium), 12-hydroxystearic acid is known (Patent Document 1 and the like). 12-hydroxystearic acid is mainly used for the disposal of edible oil. However, with 12-hydroxystearic acid, it is only possible to guide a fluid organic substance to a completely solidified or liquid state.

In addition, Patent Document 2 describes 1,2,3-propanetricarboxylic acid ginseng (2-methylcyclohexylamidoamine) as a gelling agent for hydrophilic or lipophilic compounds.

Advance technical literature Patent literature

Patent Document 1 Japanese Patent Application Publication No. 01-163111

Patent Document 2 Japanese Patent Laid-Open No. 2009-155592

Summary of invention

However, it is known that 1,2,3-propanetricarboxylic acid (2-methylcyclohexylamidoamine) is difficult to dissolve in a fluid organic substance, and it is difficult to use it as a thickener for the fluid organic substance.

Therefore, an object of the present invention is to provide a compound that thickens or gels a fluid organic substance to a desired viscosity, or stabilizes a composition containing the fluid organic substance uniformly.

Another object of the present invention is to provide a viscosity-increasing stabilizer containing the aforementioned compound, a viscosity-increasing and stabilization composition which is thickened, gelled, or stabilized by the aforementioned viscosity-increasing stabilizer, and a method for producing the same.

In order to solve the above-mentioned problems, the present inventors have conducted intensive studies and found that the compound represented by the following formula (1) can be easily dissolved in a fluid organic substance to thicken, gel, or contain a fluid The composition of the organic organic substance is stabilized uniformly (prevents the precipitation of the composition, localized aggregation or concentration, and maintains a stable and uniform state); it is selected and used according to the type of the fluid organic substance, thereby enabling the flow The viscosity of the dynamic organic substance is thickened or gelled to a desired viscosity, or the composition containing the fluid organic substance is stabilized uniformly. The present invention has been completed based on this knowledge.

That is, the present invention provides a compound represented by the following formula (1).

(Wherein R ¹ and R ² are different and are aliphatic hydrocarbon groups having 4 or more carbon atoms. N represents an integer of 1 to 3)

The present invention also provides a viscosity-increasing stabilizer comprising the aforementioned compound.

The present invention also provides a viscosity-increasing and stabilizing composition, which includes the aforementioned viscosity-increasing and stabilizing agent and a fluid organic substance.

The present invention also provides a method for manufacturing a viscosity-increasing and stabilizing composition, which obtains the viscosity-increasing and stabilizing composition through a step of dissolving the viscosity-increasing and stabilizing agent with a fluid organic substance.

That is, this invention relates to the following.

[1] A compound represented by the formula (1).

[2] The compound according to [1], wherein the compound represented by the formula (1) is at least one compound selected from the compounds represented by the formulae (1-1) to (1-4).

[3] The compound according to [1] or [2], wherein one of R ¹ and R ² in the formula is a branched chain alkyl group having 6 to 10 carbon atoms, and the other is 12 to 18 carbon atoms It is a linear alkyl group or a linear alkenyl group.

[4] A viscosity-increasing stabilizer comprising the compound according to any one of [1] to [3].

[5] The viscosity-increasing stabilizer according to [4], wherein the content of the compound represented by the formula (1) in the total amount of the viscosity-increasing stabilizer (100% by weight) (when it contains two or more kinds is the total amount thereof) Amount) is 60% by weight or more.

[6] A viscosity-increasing stabilizer composition comprising the viscosity-increasing stabilizer as described in [4] or [5] and a fluid organic substance.

[7] The viscosity-increasing and stabilizing composition according to [6], wherein the fluid organic substance is based on the viscosity of the rheometer [viscosity (η) at 25 ° C. and a shear rate of 10 (1 / s)] as Organic matter below 0.1Pa‧s.

[8] The viscosity-increasing and stabilizing composition according to [6] or [7], wherein the fluid organic substance is selected from hydrocarbon oil, ether, halogenated hydrocarbon, petroleum component, animal and vegetable oil, silicone oil, ester, aromatic At least one compound of carboxylic acid and pyridine.

[9] A method for producing a thickening and stabilizing composition, which comprises obtaining a thickening and stabilizing composition through a step of dissolving the thickening and stabilizing agent according to [4] or [5] with a fluid organic substance.

[10] A method for producing a viscosity-increasing and stabilizing composition, which comprises mixing the viscosity-increasing stabilizer as described in [4] or [5] and a fluid organic substance and heating it to make them compatible, and then cooling the mixture. A thickening and stabilizing composition was obtained.

The compound represented by formula (1) of the present invention is capable of easily thickening or gelling a fluid organic substance by dissolving it with a fluid organic substance, or uniformly forming a composition containing a fluid organic substance. An Definitely. Therefore, by using it in cosmetics, coatings, foods, pharmaceuticals, etc., the viscosity can be adjusted to a desired range, the composition can be maintained uniformly, and the usability can be improved.

Forms used to implement the invention

[Compound represented by formula (1)]

The compound of the present invention is represented by the following formula (1). In the formula, R ¹ and R ² are different and are aliphatic hydrocarbon groups having 4 or more carbon atoms. n represents an integer from 1 to 3.

Examples of the compound represented by the formula (1) include compounds represented by the following formulae (1-1) to (1-4).

The compound represented by the formula (1) of the present invention is preferably a compound represented by the formula (1-1) and / or (1-2) from the viewpoint of excellent solubility of a fluid organic substance. Compound. In addition, the above-mentioned compound is also capable of maintaining its transparency while the fluid organic substance is transparent, and imparting pseudoplastic behavior and strong storage modulus to the fluid organic substance. Better.

In the above formula, R ¹ and R ² are different and represent an aliphatic hydrocarbon group having 4 or more carbon atoms, and examples thereof include butyl, pentyl, isopentyl, hexyl, octyl, 2-ethylhexyl, Linear or branched alkane with a carbon number of 4 to 20 (preferably 6 to 18, particularly preferably 8 to 18) such as decyl, lauryl, myristyl, stearyl, and nonadecanyl Group; 3-butenyl, 4-pentenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 7-octenyl, 9-decenyl, 11-dodecenyl, oleyl, etc. straight or branched alkenyl with a carbon number of about 4 to 20 (preferably 6 to 18, particularly preferably 12 to 18); butynyl, pentyne Straight-chain, hexynyl, octynyl, decynyl, pentadecynyl, octadecynyl, etc. 4 to 20 carbon atoms (preferably 6 to 18, especially 12 to 18) Like or branched chain alkynyl and so on.

The compound represented by the formula (1) of the present invention is particularly preferably one of R ¹ and R ² from the viewpoint of excellent solubility of the fluid organic substance and exhibiting the effect of increasing the viscosity of the fluid organic substance. A branched chain alkyl group of about 4 to 20 (preferably 4 to 18, more preferably 6 to 12, especially 6 to 10, and most preferably 8 to 10), and R ¹ and R ² One is a linear alkyl group having a carbon number of about 4 to 20 (preferably 6 to 20, preferably 8 to 20, more preferably 10 to 20, particularly preferably 12 to 20, and most preferably 12 to 18) Or linear alkenyl compounds.

The compound represented by the formula (1) can be produced by, for example, the following method.

1. Cyclohexanetetracarboxylic acid is reacted with thionyl chloride to obtain cyclohexanetetracarboxylic acid tetrachloride, and amine (1) (R ¹ -NH ₂ ) and amine (2) (R ² -NH ₂ ) (R ¹ and R ² are the same as above) A method for reacting the obtained cyclohexane tetracarboxylic acid tetrachloride

2. A method of reacting amine (1) (R ¹ -NH ₂ ) with cyclohexane tetracarboxylic dianhydride to obtain amidinic acid, and further using a condensing agent to condense the amine (2) (R ² -NH ₂ )

As the cyclohexanetetracarboxylic acid in the production method of the above 1, 1,2,4,5-cyclohexanetetracarboxylic acid can be suitably used.

Examples of the amine (R ¹ -NH ₂ , R ² -NH ₂ ) in the production method of ¹ include butylamine, pentylamine, isoamylamine, hexylamine, octylamine, and 2-ethyl Hexylamine, decylamine, laurylamine, myristylamine, stearylamine, oleylamine and other aliphatic hydrocarbon groups (e.g. linear or branched) having 4 or more carbon atoms (preferably 6 to 20 carbon atoms) Chain alkyl, alkenyl or alkynyl) amines.

In the production method of the above 1, the reaction of cyclohexanetetracarboxylic acid tetrachloride and amine can be performed, for example, by dripping cyclohexanetetracarboxylic acid tetrachloride into the system in which the amine is placed.

The amount of amine used (the sum of the amounts of amine (1) and amine (2)) is 1 mole relative to cyclohexanetetracarboxylic acid tetrachloride, and is, for example, about 4 to 8 moles, preferably 4 to 6 moles.

The ratio of the amine (1) to the amine (2) (the former: the latter, and the molar ratio) can be appropriately adjusted according to the desired compound represented by the formula (1). That is, the number of (-CONHR ¹ ) groups and (-CONHR ² ) groups in the obtained compound represented by the formula (1) can be controlled by adjusting the use ratio of the amine (1) and the amine (2).

The reaction of cyclohexane tetracarboxylic acid tetrachloride and amine can be carried out in the presence or absence of a solvent. Examples of 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-dichloroethane, chlorobenzene, bromobenzene and other halogenated hydrocarbon solvents; diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, di Ether solvents such as alkane, 1,2-dimethoxyethane, cyclopentyl methyl ether; nitrile solvents such as acetonitrile, benzonitrile; fluorene solvents such as dimethylarsine; cyclobutylene such as cyclamidine Solvents; Ammonium-based solvents such as dimethylformamide; High boiling point solvents such as silicone oil. These can be used individually by 1 type or in combination of 2 or more types.

The amount of the solvent used is, for example, about 50 to 300% by weight based on the total amount of cyclohexanetetracarboxylic acid tetrachloride and amine. When the amount of the solvent used exceeds the above-mentioned range, the concentration of the reaction component becomes low, and the reaction rate tends to decrease.

The reaction (= dropping) of cyclohexane tetracarboxylic acid tetrachloride with an amine is usually carried out under normal pressure. The gas environment of the reaction (= when dripping) is not particularly limited as long as it does not hinder the reaction, and may be, for example, any of an air gas environment, a nitrogen gas environment, and an argon gas environment. The reaction temperature (= temperature at the time of dropping) is, for example, about 30 to 60 ° C. The reaction time (= dripping time) is, for example, about 0.5 to 20 hours. After the reaction (= dripping) is completed, a ripening step may be provided. When a ripening step is provided, the ripening temperature is, for example, about 30 to 60 ° C, and the ripening time is, for example, about 1 to 5 hours. The reaction can be performed by any method such as a batch method, a semi-batch method, and a continuous method.

After completion of the reaction, the reaction products obtained can be separated by, for example, filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography and other separation means, or a combination of these separation means. refined.

In the production method of 2 described above, for example, cyclohexanetetracarboxylic dianhydride, amine (1) (R ¹ -NH ₂ ), and the following solvent can be placed in the system and matured to form amidin. Then, an amine (2) (R ² -NH ₂ ) and a condensing agent (for example, carbodiimide or a salt thereof) are placed in the amine (2), and then matured to produce a compound represented by the formula (1).

As the aforementioned cyclohexanetetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-dianhydride can be suitably used.

Examples of the amines (1) and (2) include the same examples as those that can be used in the production method of the above 1.

The use amount of the amine (1) is 1 mole relative to cyclohexanetetracarboxylic dianhydride, and is, for example, about 2 to 4 moles, and preferably 2 to 3 moles. The amount of amine (2) used is 1 mole relative to cyclohexanetetracarboxylic dianhydride, and is, for example, about 2 to 4 moles, and preferably 2 to 3 moles.

The carbodiimide is represented by the following formula.

R-N = C = N-R ’

In the above formula, R and R ′ include, for example, a linear or branched alkyl group having 3 to 8 carbon atoms and a 3 to 8-membered alkyl group which may have a substituent containing a hetero atom. Cycloalkyl. R and R 'may be the same or different. R and R 'may be bonded to each other to form a ring together with the (-N = C = N-) group in the above formula.

Examples of the straight-chain or branched-chain alkyl group having 3 to 8 carbon atoms include propyl, isopropyl, butyl, isobutyl, secondary butyl, and tertiary butyl. , Pentyl, isopentyl, secondary pentyl, tertiary pentyl, hexyl, isohexyl, secondary hexyl, tertiary hexyl, etc.

Examples of the 3 to 8-membered cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl.

Examples of the hetero atom-containing substituent include a nitrogen atom-containing substituent such as a di (C _1-3 ) alkylamino group such as an amine group and a dimethylamino group.

Examples of the carbodiimide include diisopropylcarbodiimide, dicyclohexylcarbodiimide, and N- (3-dimethylaminopropyl) -N'- Ethylcarbodiimide and the like. Examples of the carbodiimide salt include a hydrochloride (specifically, N- (3-dimethylaminopropyl) -N'-ethylcarbodiimide). Hydrochloride, etc.). These can be used individually by 1 type or in combination of 2 or more types.

The amount of carbodiimide used is 1 mole relative to cyclohexanetetracarboxylic dianhydride, and is, for example, about 2 to 6 moles, preferably 2 to 4 moles.

As the solvent, it is preferred to use a proton-accepting solvent (eg, pyridine, triethylamine, tributylamine, etc.) which is excellent in solubility of the amino acid. These can be used individually by 1 type or in mixture of 2 or more types.

The use amount of the aforementioned solvent is, for example, about 50 to 300% by weight, and preferably 100 to 250% by weight, with respect to the total amount of the amino acid. When the usage-amount of a solvent exceeds the said range, the density | concentration of a reaction component will become low and there exists a tendency for reaction speed to fall.

The above reaction is usually carried out under normal pressure. The gas environment of the reaction is not particularly limited as long as it does not hinder the reaction, and may be, for example, any of an air gas environment, a nitrogen gas environment, and an argon gas environment. The ripening temperature (reaction temperature) is, for example, about 30 to 70 ° C. right. The maturation time of cyclohexanetetracarboxylic dianhydride and amine is, for example, about 0.5 to 5 hours, and the maturation time of sulfamic acid and amine is, for example, about 0.5 to 20 hours. The reaction can be performed by any method such as a batch method, a semi-batch method, and a continuous method.

After completion of the reaction, the reaction product obtained can be separated and purified by, for example, filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or other separation means, or a combination of these separation means.

The compound represented by the formula (1) is capable of forming a fibrous self-organization by self-association at the amido bond site through hydrogen bonding. Furthermore, since the R ¹ and R ² groups have an affinity for the fluid organic substance, the fluid organic substance can be made thicker, gelatinized, or fluidized by being compatible with the fluid organic substance. The composition of organic matter is stabilized uniformly. Further, the compounds represented by formula (1) have different crystallinity because the R ¹ and R ² groups are different. Therefore, as long as it is a fluid organic substance, the viscosity can be increased and stabilized without any particular limitation. On the other hand, when a fluid organic substance is transparent, it can maintain its transparency and stabilize the viscosity, and can form a stable viscosity-increasing and stable composition over time. Therefore, for example, it is useful as a viscosity-increasing stabilizer (more specifically, a thickener, a gelling agent, or a stabilizer) of a fluid organic substance. On the other hand, since the R ¹ and R ² groups in the compound represented by the formula (1) represent the same group together (that is, the compound system represented by the formula (1) has 4 identical groups as side chains (Case) Because the crystallinity becomes too high, there is a tendency that the flowable organic substance capable of increasing viscosity and stabilization is limited. In addition, the turbidity is often caused by the stabilization of the viscosity, and the appearance tends to be damaged. Furthermore, the viscosity tends to decrease over time.

[Viscosity stabilizer]

The viscosity-increasing stabilizer of the present invention is characterized in that the compound represented by the formula (1) is contained singly or in combination of two or more kinds.

In addition, in the present invention, the so-called "viscosifying stabilizer" refers to a compound that is dissolved in a fluid organic substance to produce viscosity, and includes a thickener that imparts viscosity to the fluid organic substance, and gelatinizes the fluid organic substance. A gelling agent for substances and a stabilizer for improving the viscosity of a composition containing a fluid organic substance for the purpose of uniformly stabilizing the composition.

In the viscosity-increasing stabilizer of the present invention, in addition to the compound represented by the formula (1), other components (for example, a base agent, a hydroxy fatty acid, an acrylic polymer, and a dextrin fatty acid ester) may be contained as needed Particles such as esters, metal oxides, etc.). As for the content of other ingredients, the content of the compound represented by the above formula (1) (the total amount when two or more kinds are contained) in the total amount of the thickening stabilizer (100% by weight) is, for example, 0.5% by weight or more, preferably 1% by weight or more, more preferably 10% by weight or more, still more preferably 30% by weight or more, particularly preferably 60% by weight or more, and most preferably 85% by weight or more. The upper limit of the content of the compound represented by the formula (1) is 100% by weight. If the content of the compound represented by the formula (1) is out of the above range, it tends to become difficult to thicken and gel the fluid organic substance, or stabilize the composition containing the fluid organic substance uniformly. .

As for the dosage form of the viscosity-increasing stabilizer of the present invention, various dosage forms such as powder, granule, liquid, and emulsion can be used.

The viscosity-increasing stabilizer of the present invention is capable of thickening the above-mentioned fluid organic substance by making it compatible with the fluid organic substance (preferably by mixing and warming, and after the miscibility is achieved by cooling). Gelatinization, the viscosity of the above-mentioned fluid organic substance can be thickened or gelled to the corresponding application within the range of more than 1 to 10,000 times (preferably 5 to 1000 times, particularly preferably 10 to 1000 times). Desired viscosity.

[Viscosity-stabilizing composition]

The viscosity-increasing and stabilizing composition of the present invention comprises the above-mentioned viscosity-increasing stabilizer and a fluid organic substance, and the fluid-organic substance is thickened and gelled by the aforementioned viscosity-increasing stabilizer, or contains a fluid organic substance. A composition in which objects are uniformly stabilized.

The viscosity-increasing and stabilizing composition can be produced through a step of dissolving the viscosity-increasing stabilizer with a fluid organic substance. More specifically, it can be produced by mixing the total amount of the fluid organic substance and the viscosity-increasing stabilizer and heating it to make them compatible, and then cooling. In addition, it can also be manufactured by mixing a part of a fluid organic substance with a viscosity-increasing stabilizer and heating it to make them compatible, and then cooling to produce a viscosity-increasing and stabilizing composition, and mixing the remaining fluidity organic matters.

The flowing organic substance as the raw material is an organic substance whose viscosity [viscosity (η) at 25 ° C. and shear rate 10 (1 / s) at 25 ° C.] is lower than 0.1 Pa · s, and examples thereof include, for example, : Hydrocarbon oil (hexane, cyclohexane, isododecane, benzene, toluene, polyalphaolefin, flowing paraffin, etc.), ethers (tetrahydrofuran, etc.), halogenated hydrocarbons (carbon tetrachloride, chlorobenzene, etc.), petroleum Ingredients (kerosene, gasoline, light oil, heavy oil, etc.), animal and vegetable oils (sunflower oil, olive oil, soybean oil, corn oil, castor oil, tallow, jojoba oil, squalane, etc.), Silicone oil (dimethyl polysiloxane, methyl phenyl polysiloxane, etc.), esters (octyldodecyl oleate, cetyl octoate, cetyl ethylhexanoate, triisocaprylic acid Glyceryl triisooctanate, neopentyl glycol diisooctanate, etc.), aromatic carboxylic acids, pyridine and the like. These can be used individually by 1 type or in combination of 2 or more types.

The mixing amount (or usage amount) of the viscosity-increasing stabilizer also depends on the type of the fluid organic substance, but it is preferably 0.1 to 100 parts by weight with respect to 1,000 parts by weight of the fluid organic substance, for example. 0.5 to 90 parts by weight, particularly preferably 1 to 80 parts by weight, and most preferably 1 to 30 parts by weight. By mixing (or using) the viscosity-increasing stabilizer in the above range, a composition in which the fluid organic substance is thickened or gelled, or a composition in which the composition is uniformly stabilized can be obtained.

The viscosity-increasing and stabilizing composition of the present invention may contain other components in addition to the above-mentioned viscosity-increasing stabilizer and fluid organic substance, as long as the effect of the present invention is not impaired. Other components include, for example, general compounds (for example, medicinal ingredients, pigments, and fragrances) contained in a composition that is desired to be stabilized and thickened, such as cosmetics, coatings, foods, and pharmaceuticals.

The temperature at the time of compatibility is appropriately selected according to the type of the viscosity-increasing stabilizer and the fluid organic substance. The temperature at which the viscosity-increasing stabilizer and the fluid organic substance are compatible is not particularly limited. However, it is preferably not more than 100 ° C, and when the boiling point of the fluid organic substance is 100 ° C or less, it is preferably about the boiling point.

The cooling after the miscibility is sufficient as long as it can be cooled to room temperature (for example, 25 ° C.) or less, and it may be cooled slowly at room temperature, or it may be rapidly cooled by ice cooling or the like.

In addition, the viscosity of the viscosity-increasing and stabilizing composition of the present invention based on a rheometer [viscosity (η) at 25 ° C. and a shear rate of 10 (1 / s)] can exceed the flowability of the raw material. The viscosity of the organic substance is within a range of 1 to 10,000 times (preferably 5 to 1000 times, particularly preferably 10 to 1000 times), and is appropriately adjusted according to the application.

The viscosity-increasing and stabilizing composition of the present invention is not particularly limited as long as it is a composition containing a fluid organic substance and the viscosity-stabilizing is desired, and examples thereof include cosmetics, coatings, foods, Medicines, etc.

Examples

Hereinafter, the present invention will be described more specifically with reference to the examples, but the present invention is not limited by these examples.

Example 1 [Synthesis of viscosity increasing stabilizer (1) (1,2,4,5-cyclohexanetetracarboxylic acid bis (2-ethylhexylamidine) bis (oleylamidine))]

A 100 mL four-neck separable flask equipped with a dimroth condenser, a nitrogen inlet, a dropping funnel, and a thermocouple was charged with 20 mL of pyridine, 1,2,4,5-cyclohexane tetra Carboxylic acid-1,2: 4,5-dianhydride 4.5 g (0.02 mol) and oleylamine 10.6 g (0.04 mol), the internal temperature was set to 50 ° C., and ripening was performed for 3 hours.

Thereafter, 5.2 g (0.04 mol) of 2-ethylhexylamine and 5.5 g (0.044 mol) of diisopropylcarbodiimide were charged, and the mixture was further aged for 8 hours.

Then, the low-boiling-point component of the obtained crude liquid was removed with an evaporator, and it washed with methanol, and the pale yellow wet powder was obtained. The obtained wet powder was further recrystallized with CHCl ₃ / CH ₃ OH (70/30 (v / v)) to obtain 1,2,4,5-cyclohexanetetracarboxylic acid bis (2-ethyl). Hexylamidoamine) bis (oleylamidoamine) [1,2,4,5-cyclohexanetetracarboxylic acid-1,4-bis (2-ethylhexylamidoamine) -2,5-bis (oleyl Amidoamine) and 1,2,4,5-cyclohexanetetracarboxylic acid-1,5-bis (2-ethylhexylamidoamine) -2,4-bis (oleylamidoamine) 11.9g (Yield: 61%). The structure of the reaction product was confirmed by ¹ H-NMR.

¹ H-NMR (270MHz, CDCl ₃ ): δ 0.81-0.88 (m, 18H), 1.0-1.4 (m, 68H), 1.40-1.45 (m, 2H), 1.76-1.99 (m, 8H), 2.50 -3.10 (m, 8H), 3.30-3.45 (m, 4H), 5.21-5.40 (m, 4H), 6.31 (s, 4H)

Example 2 [Synthesis of Viscosity Stabilizing Agent (2) (1,2,4,5-cyclohexanetetracarboxylic acid bis (2-ethylhexylamidoamine) bis (stearylamidoamine))]

A 100 mL four-neck separable flask equipped with a Dessert condenser, a nitrogen inlet, a dropping funnel, and a thermocouple was charged with 20 mL of pyridine, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2 : 4.5 g (0.02 mol) of 4,5-dianhydride and 10.7 g (0.04 mol) of stearylamine. The internal temperature of the system was set to 50 ° C, and it was matured for 3 hours.

Then, 5.2 g (0.04 mol) of 2-ethylhexylamine and 5.5 g (0.044 mol) of diisopropylcarbodiimide were charged, and the mixture was further aged for 8 hours.

Then, the low-boiling-point component of the obtained crude liquid was removed with an evaporator, and it washed with methanol, and the pale yellow wet powder was obtained. The obtained wet powder was further recrystallized with CHCl ₃ / CH ₃ OH (70/30 (v / v)) to obtain 1,2,4,5-cyclohexanetetracarboxylic acid bis (2-ethyl). Hexylamidoamine) bis (stearylamidoamine) [1,2,4,5-cyclohexanetetracarboxylic acid-1,4-bis (2-ethylhexylamidoamine) -2,5-bis (hard Mixture of stearylamine) and 1,2,4,5-cyclohexanetetracarboxylic acid-1,5-bis (2-ethylhexylamidoamine) -2,4-bis (stearylamidoamine) ] 11.2 g (yield: 57%). The structure of the reaction product was confirmed by ¹ H-NMR.

¹ H-NMR (270MHz, CDCl ₃ ): δ 0.81-0.88 (m, 18H), 1.0-1.4 (m, 84H), 1.40-1.45 (m, 2H), 2.57-2.77 (m, 8H), 2.85- 3.12 (m, 4H), 6.31 (s, 4H)

Comparative Example 1 [Synthesis of Viscosity Stabilizer (3) (1,2,3-propanetricarboxylic acid (2-methylcyclohexylamidoamine))]

A 100 mL four-neck separable flask equipped with a Dessert condenser, a nitrogen inlet, a dropping funnel, and a thermocouple was charged with 20 mL of pyridine, 2.97 g (0.017 mol) of 1,2,3-propanetricarboxylic acid, and diisocyanate. 7.0 g (0.056 mol) of propylcarbodiimide, and the internal temperature of the system was set to 50 ° C., and matured for 3 hours.

5.7 g (0.051 mol) of 2-methylcyclohexylamine was further charged, and the mixture was aged for 8 hours.

Then, the low-boiling-point component of the obtained crude liquid was removed with an evaporator, and it washed with methanol, and the pale yellow wet powder was obtained. The obtained wet powder was further washed with acetone to obtain 4.7 g of 1,2,3-propanetricarboxylic acid (2-methylcyclohexylamidoamine) (yield: 61%).

Examples 3 to 4, Comparative Example 2

Various fluid organic substances (flow paraffin, isododecane, and cetyl octanoate: each of which also has a boiling point of 100 ° C. or more) shown in Table 1 were weighed into a test tube of 1 cm ³ , and the above Examples 1 and 2 And 10 mg of the viscosity-increasing stabilizer obtained in Comparative Example 1 were added and mixed separately, and heated and stirred at 100 ° C to dissolve the fluid organic substance and the viscosity-increasing stabilizer, and cooled to 25 ° C to obtain a viscosity-increasing stabilizer.组合 物。 Composition.

The viscosity of the obtained viscosity-stabilizing composition was measured, and it was confirmed that the viscosity of various fluid organic substances was increased to several times, and the viscosity was evaluated according to the following criteria. Valuation and thickening properties. The results of the evaluation of the thickening properties of these solvents are all 4 or more as a good thickening effect. "○", the results of the thickening evaluation of these solvents include 3 or less. The condition is regarded as a poor thickening effect "×".

<Evaluation Criteria>

1: more than 1.0 times and less than 2.0 times

2: more than 2.0 times and less than 4.8 times

3: more than 4.8 times and less than 10 times

4: more than 10 times and less than 50 times

5: more than 50 times and less than 100 times

6: more than 100 times and less than 10,000 times

In addition, the viscosity of various fluid organic substances and viscosity-increasing and stabilizing compositions is based on the use of a cone plate sensor (a cone angle of 1 ° for a diameter of 60mm, and a cone angle of 1 ° and 2 ° for a diameter of 35mm , 4 °) and Peltier temperature controller (viscosity and viscoelasticity measuring device (rheometer) (trade name "RheoStress600", manufactured by HAAKE)) at 25 ° C under constant flow Viscosity measurement mode (normal flow viscosity measurement mode), the shear rate is changed from 0.001 to 100 (1 / s) on a logarithmic scale, the viscosity is measured to obtain a viscosity curve, and the obtained viscosity curve is obtained at a shear rate of 10 The viscosity of (1 / s) is regarded as the viscosity of the invention. In addition, for each drawing, the value at the time point when the torque value variation of the device is within 5% and the data has stabilized is used.

The results are summarized and shown in the following table.

From the above, it can be seen that the viscosity-increasing stabilizer of the present invention is excellent in the effect of thickening fluid organic substances.

Industrial availability

The compound represented by formula (1) of the present invention is capable of easily thickening or gelling a fluid organic substance by dissolving it with a fluid organic substance, or uniformly forming a composition containing a fluid organic substance. Stabilization. Therefore, by using it in cosmetics, coatings, foods, pharmaceuticals, etc., the viscosity can be adjusted to a desired range, the composition can be maintained uniformly, and the usability can be improved.

Claims (4)

A compound represented by the following formula (1): (In the formula, R ¹ is a branched chain alkyl group having 6 to 20 carbon atoms, R ² is a linear alkyl group or linear alkenyl group having 6 to 20 carbon atoms, and n represents an integer of 1 to 3). A viscosity-increasing stabilizer comprising the compound as claimed in claim 1. A viscosity-increasing and stabilizing composition comprising the viscosity-increasing and stabilizing agent according to claim 2 and a fluid organic substance. A method for producing a viscosity-increasing and stabilizing composition, which comprises obtaining a viscosity-increasing and stabilizing composition through a step of dissolving a viscosity-increasing stabilizing agent as described in claim 2 with a fluid organic substance.