JP6312669B2 - Thickening stabilizer and thickening and stabilizing composition using the same - Google Patents

Description

  The present invention relates to a novel compound having an action of thickening and stabilizing a fluid organic substance such as oil, a thickening stabilizer using the same, and a thickening and stabilizing composition containing the compound. This application claims the priority of Japanese Patent Application No. 2013-132494 and Japanese Patent Application No. 2013-132495 for which it applied to Japan on June 25, 2013, and uses the content here.

  The method of thickening and stabilizing the liquid is a very important technology in the industry. For example, 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. For this reason, various thickening stabilizers have been developed.

  For example, alkyl acrylate copolymers are known as thickening stabilizers for aqueous media.

  On the other hand, 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. However, 12-hydroxystearic acid was unable to adjust the degree of gelation and could only be induced to either solidify or remain liquid.

  In addition, as a thickening stabilizer of a fluid organic substance, compounds having an amide bond as a driving force for thickening and stabilizing (for example, compounds described in Patent Documents 2 to 5) are known. However, the compounds thickened with these compounds tend to precipitate crystals over time, and it is difficult to stabilize the composition uniformly.

Japanese Patent Laid-Open No. 01-163111 JP-A-10-231465 JP 2004-339434 A JP-A-10-273477 JP 2000-72736 A

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

  As a result of intensive investigations to solve the above problems, the present inventors have found that a compound having a specific structure thickens, gels, or uniformly stabilizes a composition containing a fluid organic substance. (= Prevents sedimentation, local aggregation, or concentration of the composition, and maintains a uniform state stably), by selecting and using depending on the type of the fluid organic material, the fluid organic material It has been found that a composition containing a flowable organic substance can be uniformly stabilized by thickening or gelling to a desired viscosity. The present invention has been completed based on these findings.

That is, the present invention provides the following formula (1):
_{^{(R 2 -HNOC) m -R 1}} - (CONH-R 3) n (1)
(In the formula, m + n is 3 or 4. When m + n is 3, n is 0, R ¹ is a group obtained by removing three hydrogen atoms from a benzene ring, and R ² is an aliphatic hydrocarbon having 6 or more carbon atoms. A group selected from a group and an aromatic hydrocarbon group, when m + n is 4, n is an integer of 1 to 3, R ¹ is a tetravalent group containing two or more benzene rings, R ² and R ³ are Different from each other, these are groups selected from aliphatic hydrocarbon groups having 6 or more carbon atoms and aromatic hydrocarbon groups)
The compound represented by these is provided.

  The present invention also provides a thickening stabilizer comprising the compound.

  The present invention also provides a thickening and stabilizing composition comprising the thickening stabilizer and a flowable organic material.

  The present invention also provides a method for producing a thickened and stabilized composition comprising the step of making the thickening stabilizer and a flowable organic material compatible.

That is, the present invention relates to the following.
[1] The following formula (1)
_{^{(R 2 -HNOC) m -R 1}} - (CONH-R 3) n (1)
(In the formula, m + n is 3 or 4. When m + n is 3, n is 0, R ¹ is a group obtained by removing three hydrogen atoms from a benzene ring, and R ² is an aliphatic hydrocarbon having 6 or more carbon atoms. A group selected from a group and an aromatic hydrocarbon group, when m + n is 4, n is an integer of 1 to 3, R ¹ is a tetravalent group containing two or more benzene rings, R ² and R ³ are Different from each other, these are groups selected from aliphatic hydrocarbon groups having 6 or more carbon atoms and aromatic hydrocarbon groups)
A compound represented by
[2] The compound according to [1], wherein the tetravalent group containing two or more benzene rings in R ¹ is a group obtained by removing four hydrogen atoms from benzophenone, biphenyl, or naphthalene.
[3] In [1] or [2], R ² and R ³ are linear or branched alkyl groups having 6 or more carbon atoms, or linear or branched alkenyl groups having 6 or more carbon atoms. The described compound.
[4] A thickening stabilizer comprising the compound according to any one of [1] to [3].
[5] A thickening / stabilizing composition comprising the thickening stabilizer according to [4] and a flowable organic substance.
[6] The fluid organic substance is at least one selected from hydrocarbon oils, ethers, halogenated hydrocarbons, petroleum components, animal and vegetable oils, silicone oils, esters, aromatic carboxylic acids, and pyridines [5] A thickening and stabilizing composition as described in 1.
[7] A method for producing a thickened / stabilized composition comprising a step of making the thickener / stabilizer according to [4] 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 material or make a composition containing the fluid organic material uniform by making it compatible with the fluid organic material. Can be stabilized. Moreover, the compound thickened and stabilized by the compound represented by the formula (1) of the present invention can stably maintain the thickened or gelled state. Therefore, the compound represented by the formula (1) of the present invention can be suitably used as a thickening stabilizer for cosmetics, paints, foods, pharmaceuticals, etc., and the compound represented by the formula (1) of the present invention. By using these, their viscosity can be adjusted to a desired range, their composition can be kept uniform, and their usability can be improved.

[Compound represented by Formula (1)]
The compound of the present invention is represented by the following formula (1).
_{^{(R 2 -HNOC) m -R 1}} - (CONH-R 3) n (1)

In the formula, m + n is 3 or 4. When m + n is 3, n is 0, R ¹ is a group obtained by removing three hydrogen atoms from a benzene ring, and R ² is a group selected from an aliphatic hydrocarbon group having 6 or more carbon atoms and an aromatic hydrocarbon group It is. When m + n is 4, n is an integer of 1 to 3, R ¹ is a tetravalent group containing two or more benzene rings, R ² and R ³ are different from each other, an aliphatic hydrocarbon group having 6 or more carbon atoms, and It is a group selected from aromatic hydrocarbon groups.

Examples of the aliphatic hydrocarbon group having 6 or more carbon atoms in R ² and R ³ include about 6 to 20 carbon atoms such as hexyl, octyl, 2-ethylhexyl, decyl, lauryl, myristyl, stearyl, and nonadecyl groups (preferably 6-18) linear or branched alkyl group; 6-carbon such as 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 7-octenyl, 9-decenyl, 11-dodecenyl, oleyl group, etc. About 20 to 20 (preferably 6 to 18) linear or branched alkenyl group; about 6 to 20 carbon atoms such as hexynyl, octynyl, decynyl, pentadecynyl, octadecynyl group (preferably 6 to 18 and particularly preferably 12) To 18) or a linear or branched alkynyl group.

Examples of the aromatic hydrocarbon group having 6 or more carbon atoms in R ² and R ³ include aromatic hydrocarbon groups having about 6 to 20 carbon atoms (preferably 6 to 14) such as phenyl and naphthyl groups. it can.

  Examples of the compound in which m + n is 3 in the compound represented by the formula (1) include a compound represented by the following formula (1-1).

In the above formula, all three R ^{2 s} are the same group selected from an aliphatic hydrocarbon group having 6 or more carbon atoms and an aromatic hydrocarbon group, and among them, an aliphatic hydrocarbon group having 6 or more carbon atoms is Preferably, it is a linear or branched alkyl group having 6 or more carbon atoms, or a linear or branched alkenyl group having 6 or more carbon atoms, and most preferably a linear chain having 6 to 20 carbon atoms. Or it is a branched alkyl group or a C6-C20 linear or branched alkenyl group.

When m + n is 4, R ¹ represents a tetravalent group containing two or more benzene rings, for example, an aromatic hydrocarbon selected from benzophenone, biphenyl, naphthalene, etc. (preferably containing two benzene rings) A group obtained by removing four hydrogen atoms from an aromatic hydrocarbon).

  When m + n is 4, n represents an integer of 1 to 3, and preferably 2.

  Examples of the compound in which m + n in the compound represented by the formula (1) is 4 include compounds represented by the following formulas (1-2) to (1-15).

In the above formula, R ² and R ³ are groups different from each other and selected from an aliphatic hydrocarbon group having 6 or more carbon atoms and an aromatic hydrocarbon group, and in particular, an aliphatic hydrocarbon group having 6 or more carbon atoms. A linear or branched alkyl group having 6 to 20 carbon atoms (preferably 6 to 18, particularly preferably 8 to 18 carbon atoms), 6 to 20 carbon atoms (preferably 6 to 18 carbon atoms, particularly preferable). Is a linear or branched alkenyl group of 12 to 18). Preferred combinations of R ² and R ³ include a combination of a linear alkyl group and a branched alkyl group, a combination of a linear alkenyl group and a branched alkyl group, a linear alkyl group and a linear alkenyl group. It is a combination.

The compound represented by Formula (1) can be manufactured by the following method etc., for example.
1. An aromatic carboxylic acid is reacted with thionyl chloride to obtain an aromatic carboxylic acid chloride, and an amine [when m + n in the compound represented by the formula (1) is 3 is produced in the compound represented by formula (1)] method 2, R ² -NH _2, if m + n in the compound represented by formula (1) to produce a compound which is 4, is reacted with R ² -NH ₂ and R ³ -NH _2]. The aromatic carboxylic acid anhydride corresponding to the aromatic carboxylic acid is reacted with amine (1) (R ² —NH ₂ ) to obtain an amic acid, and further amine (2) [compound represented by formula (1) In the case of producing a compound in which m + n is 3, R ² —NH ₂ , and in the case of producing a compound in which m + n in the compound represented by formula (1) is 4, R ³ —NH ₂ ] is used as a condensing agent. Condensation method using

  When producing a compound in which m + n in the compound represented by formula (1) is 3, 1,2,4-benzenetricarboxylic acid (= trimellitic acid) can be used as the aromatic carboxylic acid. .

In the case of producing a compound in which m + n in the compound represented by the formula (1) is 4, the aromatic carboxylic acid may be represented by the following formula R ^1- (COOH) ₄
(R ¹ represents a tetravalent group containing two or more benzene rings)
The compound represented by these can be used. Specifically, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid, 1,1′-biphenyl-2,3,3 ′, 4′-tetracarboxylic acid, 1,4,5,8-naphthalene Examples include compounds in which four carboxyl groups are bonded to an aromatic hydrocarbon group containing two or more benzene rings such as tetracarboxylic acid.

Examples of the amine (R ² —NH ₂ , R ³ —NH ₂ ; R ² and R ³ are the same as above) include, for example, hexylamine, octylamine, 2-ethylhexylamine, decylamine, laurylamine, myristylamine, stearylamine. An amine that is an aliphatic hydrocarbon group having 6 or more carbon atoms (preferably 6 to 20 carbon atoms) (preferably a linear or branched alkyl group, alkenyl group, or alkynyl group), such as oleylamine Can be mentioned.

  In the above method 1, the reaction between the aromatic carboxylic acid chloride and the amine can be carried out, for example, by dropping the aromatic carboxylic acid chloride into a system charged with the amine.

The amount of amine used (the total amount when R ² —NH ₂ and R ³ —NH ₂ are used in combination) is, for example, about 3 to 8 mol, preferably 3 to 6 mol, per 1 mol of aromatic carboxylic acid chloride. It is.

When R ² —NH ₂ and R ³ —NH ₂ are used in combination, the (CONH—R ² ) group in the compound represented by the formula (1) and ( The number of CONH-R ³ ) groups can be controlled.

  The reaction between the aromatic carboxylic acid chloride and the 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 -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; sulfoxide solvents such as dimethyl sulfoxide; sulfolane solvents such as sulfolane; amide solvents such as dimethylformamide; high-boiling solvents such as silicone oil. These can be used individually by 1 type or in mixture of 2 or more types.

  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 aromatic carboxylic acid chloride and amine. 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 rate to fall.

  The reaction (= dropping) of the aromatic carboxylic acid chloride and the amine is usually performed under normal pressure. Further, the atmosphere of the above reaction (= drip) is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. Reaction temperature (= temperature at the time of dripping) is about 30-60 degreeC, for example. The reaction time (= dropping time) is, for example, about 0.5 to 20 hours. After completion of the reaction (= dropping), 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.

  After completion of the reaction, 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 separation means combining these.

  In the above production method 2, for example, an aromatic carboxylic acid anhydride, an amine (1) and the following solvent are charged into the system and aged to form an amic acid, and then the amine (2) and a condensing agent (for example, , Carbodiimide or a salt thereof) and aging, the compound represented by the formula (1) can be produced.

  As the aromatic carboxylic acid anhydride, an anhydride corresponding to the aromatic carboxylic acid can be used, and in the case of producing a compound in which m + n in the compound represented by the formula (1) is 3, for example, Mention may be made of trimellitic anhydride.

  In the case of producing a compound in which m + n in the compound represented by the formula (1) is 4, as the aromatic carboxylic acid anhydride, for example, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride 1,1′-biphenyl-2,3,3 ′, 4′-tetracarboxylic acid-2,3: 3 ′, 4′-dianhydride, naphthalene-1,4,5,8-tetracarboxylic acid— 1,8: 4,5-dianhydride and the like.

  As said amine (1) and (2), the compound similar to the amine used with said 1 manufacturing method can be used.

  The amount of the amine (1) used is, for example, about 2 to 4 mol, preferably 2 to 3 mol, per 1 mol of the aromatic carboxylic acid anhydride. Moreover, as the usage-amount of amine (2), it is about 2-4 mol with respect to 1 mol of aromatic carboxylic anhydrides, Preferably it is 2-3 mol.

The carbodiimide is represented by the following formula.
RN = C = NR ′
In the above formula, as R and R ′, for example, a linear or branched alkyl group having 3 to 8 carbon atoms which may have a heteroatom-containing substituent, or 3 to 8 membered cyclo It is an alkyl group. 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.

  Examples of the linear or branched alkyl group having 3 to 8 carbon atoms include propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, t-pentyl, Examples include hexyl, isohexyl, s-hexyl, and t-hexyl groups.

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

Examples of the heteroatom-containing substituent include nitrogen atom-containing substituents such as di (C _1-3 ) alkylamino groups such as amino groups and dimethylamino groups.

  Examples of the carbodiimide include diisopropylcarbodiimide, dicyclohexylcarbodiimide, N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide and the like. Examples of the carbodiimide salt include hydrochloride (specifically, N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide hydrochloride) and the like.

  The amount of carbodiimide used is, for example, about 2 to 6 mol, preferably 2 to 4 mol, per 1 mol of the aromatic carboxylic acid anhydride.

  As the solvent, for example, it is preferable to use a proton-accepting solvent excellent in solubility of amic acid such as pyridine, triethylamine, tributylamine and the like. These can be used individually by 1 type or in mixture of 2 or more types.

  As the usage-amount of the said solvent, it is about 50 to 300 weight% with respect to the total amount of amic acid, Preferably it is 100 to 250 weight%. 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 rate to fall.

  The above reaction is usually performed under normal pressure. Further, the atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The aging temperature (reaction temperature) is, for example, about 30 to 70 ° C. The aging time of the aromatic carboxylic acid anhydride and the amine is, for example, about 0.5 to 5 hours, and the aging time of the amic acid and the amine is, for example, about 0.5 to 20 hours. The reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  After completion of the reaction, 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 separation means combining these.

The compound represented by the formula (1) can self-associate by hydrogen bonding at the amide bond site to form a fibrous self-assembly. Furthermore, since the R ² group (in the case where m + n in the compound represented by the formula (1) is 4), the R ² and R ³ groups have affinity for the fluid organic substance, the fluid organic By compatibilizing with the substance, the fluid organic substance can be thickened, gelled, or the composition containing the fluid organic substance can be uniformly stabilized. Furthermore, since the compound represented by the formula (1) where m + n is 4 has two different groups (R ² and R ³ groups), it has moderate crystallinity. Therefore, if it is a fluid organic substance, it can be thickened and stabilized without particular limitation. When the fluid organic material has transparency, it can be thickened and stabilized while maintaining its transparency, and a thickened and stabilized composition that is stable over time can be formed. Therefore, for example, it is useful as a thickening stabilizer (more specifically, a thickening agent, a gelling agent, or a stabilizer) of a fluid organic substance.

[Thickening 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.

  In the present invention, the thickening stabilizer is a compound that dissolves in a flowable organic substance to generate viscosity, and the “thickening stabilizer” is a thickening agent that imparts viscosity to the flowable organic substance. It is a concept including a gelling agent that gels a substance and a stabilizer that increases the viscosity for the purpose of uniformly stabilizing a composition containing a flowable organic substance.

  In addition to the compound represented by the above formula (1), 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. Ester, particles of metal oxides, etc.) may be contained, but the content of the other components is that of the compound represented by the above formula (1) in the total amount of the thickening stabilizer (100% by weight). The content (the total amount when two or more are contained) is, for example, 0.5% by weight or more, preferably 1% by weight or more, more preferably 10% by weight or more, particularly preferably 30% by weight or more, and most preferably 60%. It is within the range of at least 80% by weight, more preferably at least 80% by weight. The upper limit of the content of the compound represented by the above formula (1) is 100% by weight. When the content of the compound represented by the above formula (1) is out of the above range, it is difficult to thicken the fluid organic substance, gelate it, or to uniformly stabilize the composition containing the fluid organic substance. Tend to be.

  As the 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 flowable organic substance can be thickened or gelled to a desired viscosity according to the application within a range of more than 1 to 600 times.

[Thickening and stabilizing composition]
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. It is a composition in which the product is uniformly stabilized.

  The thickening / stabilizing composition of the present invention can be produced through a step of making the thickening stabilizer and the flowable organic material compatible. More specifically, it can be produced by mixing a thickening stabilizer with a fluid organic substance (total amount), heating and dissolving them, and then cooling. In addition, a thickening stabilizer is mixed with a part of the fluid organic material, heated, compatible, and then cooled to produce a thickened and stabilized composition, which is then used as the remaining fluid organic material. It can also be produced by a method of mixing the two.

  The flowable organic material as the raw material is an organic material having a viscosity [η at 25 ° C., shear rate 10 (1 / s)] of less than 0.1 Pa · s by a rheometer, for example, hydrocarbon oil ( Hexane, cyclohexane, isododecane, benzene, toluene, poly-alpha olefin, liquid paraffin, etc., ethers (tetrahydrofuran, etc.), halogenated hydrocarbons (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 (silicone oils such as dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane) , Esters (octyldodecyl oleate, cetyl octoate, Cetyl ethylhexanoate, glyceryl triisooctanoate, neopentyl glycol diisooctanoate, etc.), aromatic carboxylic acids, pyridine and the like. These can be used alone or in combination of two or more.

  The mixing amount (or use amount) of the thickening stabilizer is, for example, 0.1 to 100 parts by weight, preferably 0.1 to 100 parts by weight with respect to 1000 parts by weight of the fluid organic substance, although it depends on the type of the fluid organic substance. 5 to 90 parts by weight, particularly preferably 1 to 80 parts by weight. By mixing (or using) the thickening 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 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. Examples of the other components include general compounds (for example, medicinal ingredients, pigments, fragrances, etc.) contained in a composition desired to be thickened and stabilized such as cosmetics, paints, foods, and pharmaceuticals. it can.

  The temperature at the time of compatibilization is appropriately selected depending on the type of thickening stabilizer used and the flowable organic substance, and is not particularly limited as long as the thickening stabilizer and the flowable 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 rapidly by ice cooling or the like.

  And the viscosity [viscosity (η) at 25 ° C., shear rate 10 (1 / s)] of the thickening and stabilizing composition of the present invention exceeds 1 times the viscosity of the fluid organic material as a raw material. Within the range of 600 times or less, it can be appropriately adjusted according to the application.

  The thickening / stabilizing composition of the present invention is not particularly limited as long as it contains a fluid organic substance and thickening / stabilization is desired. For example, cosmetics, paints, foods, pharmaceuticals Etc.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Example 1 (Preparation Example) [Thickening Stabilizer (1) (Synthesis of 1,2,4-trimellitic acid tri-n-hexylamide)]
Chloroform 20 mL and n-hexylamine 9.56 g (0.0945 mol) were charged into a 100 mL four-neck separable flask equipped with a Dimroth condenser, a nitrogen inlet, a dropping funnel, and a thermocouple. The system temperature was set to 40 ° C., 4.18 g (0.0158 mol) of 1,2,4-trimellitic acid trichloride was added dropwise over 2.5 hours, and aging was further performed for 2 hours. Thereafter, the low boiling content of the obtained crude liquid was removed by an evaporator, and the solvent was washed to obtain 4.1 g of 1,2,4-trimellitic acid tri-n-hexylamide as a white solid (yield: 56 %). The structure of the product was confirmed by ¹ H-NMR.
¹ H-NMR (270MHz, CDCl ₃ ): δ 0.89 (t, J = 7.0Hz, 9H), 1.21-1.40 (m, 18H), 1.45-1.72 (m, 6H), 3.33-3.47 (m, 6H) , 6.79 (t, J = 5.9Hz, 1H), 7.40 (d, J = 6.2Hz, 1H), 7.57-7.73 (m, 3H), 7.74 (s, 1H)

Example 2 (Preparation Example) [Thickening Stabilizer (2) (Synthesis of 1,2,4-trimellitic acid tri-n-octylamide)]
1,2,4-trimellitic acid as a white solid in the same manner as in Example 1 except that 9.56 g (0.0945 mol) of n-hexylamine was changed to 12.22 g (0.0945 mol) of n-octylamine. 4.1 g of tri-n-octylamide was obtained (yield: 48%).
¹ H-NMR (270MHz, CDCl ₃ ): δ 0.87 (t, J = 7.0Hz, 9H), 1.18-1.34 (m, 30H), 1.45-1.81 (m, 6H), 3.35-3.46 (m, 6H) , 6.76 (t, J = 5.4Hz, 1H), 7.40 (d, J = 8.1Hz, 1H), 7.59-7.74 (m, 3H), 7.75 (s, 1H)

Example 3 (Preparation Example) [Thickening Stabilizer (3) (Synthesis of 1,2,4-trimellitic acid tri-2-ethylhexylamide)]
1,2,4-trimellitic acid as a white solid in the same manner as in Example 1 except that 9.56 g (0.0945 mol) of n-hexylamine was changed to 12.22 g (0.0945 mol) of 2-ethylhexylamine. 5.1 g of tri-2-ethylhexylamide was obtained (yield: 54%).
¹ H-NMR (270MHz, CDCl ₃ ): δ 0.89 (t, J = 7.0Hz, 18H), 1.33-1.46 (m, 24H), 1.50-1.75 (m, 3H), 3.28-3.47 (m, 6H) , 6.73 (t, J = 5.8Hz, 1H), 7.38 (d, J = 7.8Hz, 1H), 7.59 (dd, J = 7.8,1.6Hz, 1H), 7.74 (d, J = 1.6Hz, 1H) , 7.78-7.85 (m, 2H)

Example 4 (Preparation Example) [Thickening Stabilizer (4) (Synthesis of 1,2,4-trimellitic acid trilaurylamide)]
Except that 9.56 g (0.0945 mol) of n-hexylamine was changed to 17.52 g (0.0945 mol) of laurylamine, it was the same as in Example 1 except that trilauryl 1,2,4-trimellitic acid was used as a white solid. 8.0 g of amide was obtained (yield: 62%).
¹ H-NMR (270MHz, CDCl ₃ ): δ 0.88 (t, J = 6.8Hz, 9H), 1.18-1.34 (m, 54H), 1.45-1.85 (m, 6H), 3.33-3.47 (m, 6H) , 6.74 (t, J = 5.7Hz, 1H), 7.40 (d, J = 7.8Hz, 1H), 7.59-7.65 (m, 3H), 7.75 (s, 1H)

Example 5 (Preparation Example) [Thickening Stabilizer (5) (Synthesis of 1,2,4-trimellitic acid trimyristylamide)]
Trimyristyl 1,2,4-trimellitic acid as a white solid in the same manner as in Example 1 except that 9.56 g (0.0945 mol) of n-hexylamine was changed to 20.16 g (0.0945 mol) of myristylamine. 7.4 g of amide was obtained (yield: 59%).
¹ H-NMR (270MHz, CDCl ₃ ): δ 0.89 (t, J = 6.8Hz, 9H), 1.18-1.41 (m, 66H), 1.46-1.85 (m, 6H), 3.34-3.50 (m, 6H) , 6.74 (t, J = 5.1Hz, 1H), 7.47 (d, J = 8.1Hz, 1H), 7.69-7.72 (m, 3H), 7.81 (s, 1H)

Example 6 (Preparation Example) [Thickening Stabilizer (6) (Synthesis of 1,2,4-trimellitic acid tristearylamide)]
Tristearyl 1,2,4-trimellitic acid as a white solid in the same manner as in Example 1 except that 9.56 g (0.0945 mol) of n-hexylamine was changed to 25.47 g (0.0945 mol) of stearylamine. 7.2 g of amide was obtained (yield: 47%).
¹ H-NMR (270MHz, CDCl ₃ ): δ 0.88 (t, J = 7.0Hz, 9H), 1.10-1.45 (m, 90H), 1.51-1.65 (m, 6H), 3.34-3.45 (m, 6H) , 6.75 (t, J = 5.4Hz, 1H), 7.52 (d, J = 7.8Hz, 1H), 7.72-7.75 (m, 3H), 7.84 (s, 1H)

Example 7 (Preparation Example) [Synthesis of thickening stabilizer (7) (1,2,4-trimellitic acid trioleylamide)]
9.56 g (0.0945 mol) of n-hexylamine was changed to 14.07 g (0.0526 mol) of oleylamine, and the dropping amount of 1,2,4-trimellitic acid trichloride was changed from 4.18 g (0.0158 mol) to 2. Except for changing to .33 g (0.0088 mol), 4.1 g of 1,2,4-trimellitic acid trioleylamide was obtained as a white paste in the same manner as in Example 1 (yield: 48%).
¹ H-NMR (270MHz, CDCl ₃ ): δ 0.88 (t, J = 7.0Hz, 9H), 1.10-1.45 (m, 66H), 1.50-1.65 (m, 6H), 1.96-2.05 (m, 12H) , 3.33-3.46 (m, 6H), 5.29-5.40 (m, 6H), 6.76 (m, 1H), 7.43 (d, J = 8.1Hz, 1H), 7.50-7.67 (m, 3H), 7.75 (s , 1H)

Example 8 [Synthesis of thickening stabilizer (8) (3,3 ′, 4,4′-benzophenonetetracarboxylic acid di2-ethylhexylamide dioleylamide)]
Into a 100 mL 4-neck separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, and thermocouple, 20 mL of pyridine, 3.0 g of 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (0. 012 mol) and 6.47 g (0.024 mol) of oleylamine were charged. The system temperature was set to 50 ° C. and aged for 3 hours.
Thereafter, 3.1 g (0.024 mol) of 2-ethylhexylamine and 6.1 g (0.048 mol) of diisopropylcarbodiimide were added, followed by further aging for 8 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)), and 3,3 ′, 4,4′-benzophenone tetracarboxylic acid di-2-ethylhexylamide dioleyl was obtained. 5.3 g of amide was obtained (yield: 41%).
¹ H-NMR (270 MHz, CDCl ₃ ): δ 0.83-0.96 (m, 18H), 1.35-1.45 (m, 60H), 1.55-1.72 (m, 6H), 1.90-2.08 (m, 8H), 3.31- 3.43 (m, 8H), 5.40-5.49 (m, 4H), 7.45-7.54 (m, 4H), 7.65-7.73 (m, 6H)

Example 9 [Synthesis of thickening stabilizer (9) (3,3 ′, 4,4′-benzophenone tetracarboxylic acid di2-ethylhexylamide distearylamide)]
Into a 100 mL four-necked separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, and thermocouple, 20 mL of pyridine, 3.0 g (0.012 mol) of 3,3 ′, 4,4′benzophenone tetracarboxylic dianhydride ), 6.52 g (0.024 mol) of stearylamine was charged. The system temperature was set to 70 ° C. and aged for 3 hours.
Thereafter, 3.1 g (0.024 mol) of 2-ethylhexylamine and 6.1 g (0.048 mol) of diisopropylcarbodiimide were added, followed by further aging for 8 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)), and 3,3 ′, 4,4′-benzophenone tetracarboxylic acid di-2-ethylhexylamide distearyl was obtained. 5.8 g of amide was obtained (yield: 44%).
¹ H-NMR (270 MHz, CDCl ₃ ): δ 0.83-0.96 (m, 18H), 1.28-1.51 (m, 76H), 1.55-1.72 (m, 6H), 3.31-3.45 (m, 8H), 7.45- 7.54 (m, 4H), 7.65-7.92 (m, 6H)

Example 10 [Synthesis of thickening stabilizer (10) (3,3 ′, 4,4′-benzophenonetetracarboxylic acid distearylamide dioleylamide)]
Into a 100 mL 4-neck separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, and thermocouple, 20 mL of pyridine, 3.0 g of 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride (0. 012 mol) and 6.47 g (0.024 mol) of oleylamine were charged. The system temperature was set to 50 ° C. and aged for 3 hours.
Thereafter, 6.5 g (0.024 mol) of stearylamine and 6.1 g (0.048 mol) of diisopropylcarbodiimide were added, followed by further aging for 8 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 3,3 ′, 4,4′-benzophenonetetracarboxylic acid distearylamide dioleylamide. 7.1 g (yield: 43%) was obtained.
¹ H-NMR (270MHz, CDCl ₃ ): δ 0.82-0.93 (m, 12H), 1.21-1.35 (m, 104H), 1.55-1.71 (m, 8H), 1.90-2.08 (m, 8H), 3.35- 3.42 (m, 8H), 5.33-5.37 (m, 4H), 7.45-7.54 (m, 4H), 7.65-7.73 (m, 6H)

Examples 11-20
Each flowable organic substance shown in the table was weighed in a test tube by 1 cm ^3, and 10 mg of the thickening stabilizers (1) to (10) obtained in Examples 1 to 10 were added and mixed. Appropriate temperature for fluid organic materials (boiling temperature for boiling organic materials with a boiling point of less than 100 ° C. or lower (40-80 ° C.), 80-100 ° C. for fluid organic materials with a boiling point of 100 ° C. or higher) Specifically, when liquid paraffin is used as a fluid organic substance: 80 ° C., when isododecane is used: 80 ° C., when sunflower oil is used: 100 ° C., when cetyl octanoate is used: 100 ° C, when dimethylpolysiloxane is used: 100 ° C, when decamethylcyclopentasiloxane is used: 80 ° C) It is allowed to obtain a thickening stabilizer composition was cooled to 25 ° C..
The viscosity of the resulting thickened and stabilized composition was measured to confirm how many times the viscosity of various fluid organic substances was increased, and the thickened stability was evaluated according to the following criteria.
<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: Over 50 times, 100 times or less 6: Over 100 times, 600 times or less 7: Over 600 times

  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. Using a measured viscosity / viscoelasticity measuring device (rheometer) (trade name “Rheo Stress 600”, manufactured by HAAKE Co., Ltd.) at 25 ° C. in a normal flow viscosity measurement mode, 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. In addition, each plot used the value when the torque value fluctuation | variation of an apparatus was settled in the 5% range, and the data became stable.

The above results are summarized in the following table.

  The compound represented by the formula (1) of the present invention can easily thicken or gel a fluid organic material or make a composition containing the fluid organic material uniform by making it compatible with the fluid organic material. Can be stabilized. Moreover, the composition thickened and stabilized by the compound represented by the formula (1) of the present invention can stably maintain the thickened or gelled state. Therefore, the compound represented by the formula (1) of the present invention can be suitably used as a thickening stabilizer for cosmetics, paints, foods, pharmaceuticals and the like.

Claims (4)

Following formula (1)
_{^{(R 2 -HNOC) m -R 1}} - (CONH-R 3) n (1)
(Wherein m + n is 4, n is 2 , R ¹ is a group obtained by removing four hydrogen atoms from benzophenone, biphenyl, or naphthalene , R ² and R ³ are different from each other, and aliphatic carbonization having 6 or more carbon atoms. Is a hydrogen group )
A compound represented by Following formula (1 ')
_{^{(R 2 -HNOC) m -R 1}} - (CONH-R 3) n (1 ')
(In the formula, m + n is 3 or 4. When m + n is 3, n is 0, R ¹ is a group obtained by removing three hydrogen atoms from a benzene ring, and R ² is an aliphatic hydrocarbon having 6 or more carbon atoms. When m + n is 4, n is 2, R ¹ is a group obtained by removing 4 hydrogen atoms from benzophenone, biphenyl, or naphthalene, R ² and R ³ are different from each other, and are fatty acids having 6 or more carbon atoms. Group hydrocarbon group)
A thickening stabilizer containing a compound represented by:   A thickening and stabilizing composition comprising the thickening stabilizer according to claim 2 and a flowable organic substance.   A method for producing a thickened / stabilized composition comprising a step of making the thickener / stabilizer according to claim 2 compatible with a fluid organic substance.