JP2017048120A - Thickening stabilizer and thickening stabilizing composition using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound that thickens or gels a flowable organic substance to a desired viscosity, or uniformly stabilizes a composition containing a flowable organic substance.SOLUTION: The compound of the present invention is represented by the following formula (1). In the formula, Rrepresents a group obtained by removing four hydrogen atoms from the structural formula of benzene, cyclohexane, butane, benzophenone, biphenyl, or naphthalene, Rrepresents an aliphatic hydrocarbon group having 4 or more carbon atoms. n represents an integer of 1 to 3. When n is 2 or 3, 2 or 3 Rmay be the same or different.SELECTED DRAWING: None

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.

  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.

  As a compound for thickening and stabilizing an aqueous medium, for example, an alkyl acrylate copolymer is known.

  On the other hand, 12-hydroxystearic acid is known as a thickening stabilizer for organic substances having fluidity such as oily media (Patent Document 1 and the like). 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. That is, the present condition is that the compound which thickens or gelatinizes a fluid organic substance to a desired viscosity has not been found yet.

Japanese Patent Laid-Open No. 01-163111

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 studies to solve the above problems, the present inventors have found that the compound represented by the following formula (1) is a composition containing a fluid organic substance that is thickened, gelled, or contains a fluid organic substance. By being able to be uniformly stabilized (preventing sedimentation, local aggregation, or concentration of the composition and maintaining a uniform state stably), by selecting and using depending on the type of fluid organic substance, It has been found that the viscosity of the flowable organic material can be increased or gelled to the desired viscosity, or that the composition containing the flowable organic material can be uniformly stabilized. The present invention has been completed based on these findings.

（式中、Ｒ¹はベンゼン、シクロヘキサン、ブタン、ベンゾフェノン、ビフェニル、又はナフタレンの構造式から４個の水素原子を除いた基を示し、Ｒ²は炭素数４以上の脂肪族炭化水素基を示す。ｎは１〜３の整数を示す。ｎが２又は３である場合、２又は３個のＲ²はそれぞれ同一であってもよく異なっていてもよい）
で表される化合物を提供する。 That is, the present invention provides the following formula (1):

(In the formula, R ¹ represents a group obtained by removing four hydrogen atoms from the structural formula of benzene, cyclohexane, butane, benzophenone, biphenyl, or naphthalene, and R ² represents an aliphatic hydrocarbon group having 4 or more carbon atoms. N represents an integer of 1 to 3. When n is 2 or 3, 2 or 3 R ^{2 s} may be the same or different.
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 / stabilized composition, wherein a thickened / stabilized composition is obtained through a step of compatibilizing the thickened stabilizer and a fluid 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. Therefore, by using them in cosmetics, paints, foods, pharmaceuticals, etc., their viscosity can be adjusted to the desired range, their composition can be kept uniform, and their usability is improved. Can do.

[Compound represented by Formula (1)]
The compound of the present invention is represented by the following formula (1).

In the formula, R ¹ represents a group obtained by removing four hydrogen atoms from the structural formula of benzene, cyclohexane, butane, benzophenone, biphenyl, or naphthalene, and R ² represents an aliphatic hydrocarbon group having 4 or more carbon atoms. n shows the integer of 1-3. When n is 2 or 3, 2 or 3 R ^{2 s} may be the same or different.

Among the compounds represented by the formula (1), examples of the compounds in which R ¹ is a group obtained by removing four hydrogen atoms from the structural formula of benzene include, for example, the following formulas (1-1) to (1 -5) and the like. Compounds in which R ¹ in formula (1) is a group obtained by removing four hydrogen atoms from the structural formula of cyclohexane, butane, benzophenone, biphenyl, or naphthalene include the following formulas (1-1) to (1-5) ) In which the structural formula of benzene is substituted with the structural formula of cyclohexane, butane, benzophenone, biphenyl, or naphthalene. In the following formula, when 2 or 3 R ² are present, the 2 or 3 R ^{2 s} may all be the same group, and the two may be 3 different groups.

  As the compound represented by the formula (1) of the present invention, among them, the compound represented by the above formula (1-4) and / or (1-5), or the above formula (1-4) and / or ( A compound obtained by substituting the structural formula of benzene in the compound represented by 1-5) with a structural formula of cyclohexane, butane, benzophenone, biphenyl, or naphthalene is preferable in terms of excellent solubility of the fluid organic substance. Moreover, the said compound is preferable also in the point which can provide a pseudoplastic behavior and a strong storage elastic modulus to the said fluid organic substance, maintaining the transparency, when a fluid organic substance is transparent.

In the formula (1), R ² represents an aliphatic hydrocarbon group having 4 or more carbon atoms, such as butyl, hexyl, octyl, 2-ethylhexyl, decyl, lauryl, myristyl, stearyl, nonadecyl group, etc. About 20 (preferably 4 to 10, particularly preferably 6 to 10) linear or branched alkyl group; butenyl, pentenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 7-octenyl , 9-decenyl, 11-dodecenyl, oleyl group and the like having about 4 to 20 carbon atoms (preferably 8 to 20, particularly preferably 12 to 20, most preferably 12 to 18) linear or branched alkenyl groups About 4 to 20 carbon atoms such as butynyl, pentynyl, hexynyl, octynyl, decynyl, pentadecynyl, octadecynyl group (preferably 6 to 8, particularly preferable examples thereof include such linear or branched alkynyl group having 12 to 18).

  n represents an integer of 1 to 3, and is preferably 2 or 3.

Especially, the compound whose R < ² > in Formula (1) is a C4-C20 branched alkyl group and / or a linear alkenyl group is excellent in the solubility of fluid organic substance, and fluid organic It is preferable at the point which can exhibit the effect of thickening a substance.

In particular, among the n R ^{2 in} the formula (1), at least one (preferably two) is a linear or branched alkenyl group having about 4 to 20 carbon atoms. It is preferable in that it is excellent in solubility of a substance and can exert an effect of thickening a fluid organic substance. When n is 2 or 3, 2 or 3 R ² has about 4 to 20 carbon atoms. It is a linear or branched alkenyl group alone, or a combination of a linear or branched alkenyl group having about 4 to 20 carbon atoms and a linear or branched alkyl group having about 4 to 20 carbon atoms. It is preferable.

The compound represented by Formula (1) can be manufactured by the following method etc., for example.
1, the carboxylic acid (R ¹ - (COOH) _4: R ¹ corresponds to R ¹ in the formula (1)) to give the carboxylic acid tetrachloride is reacted with thionyl chloride, the resulting carboxylic acid tetrachloride aliphatic amines (R ² -NH _2: R ² corresponds to R ² in the formula (1), hereinafter, simply referred to as "aliphatic amine") and cysteamine _{(NH 2 CH 2 CH 2 SH} ) 2. Reaction of carboxylic dianhydride corresponding to the carboxylic acid (R ^1- (COOH) ₄ ) with an amine selected from an aliphatic amine and cysteamine to obtain an amic acid, and further an aliphatic amine A method of condensing an amine selected from cysteamine (including amines not used in the amic acid formation step) with carbodiimide

  Examples of the carboxylic acid used in the production method 1 include 1,2,4,5-benzenetetracarboxylic acid (= pyromellitic acid), 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 1 , 1′-biphenyl-2,3,3 ′, 4′-tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2, 3,4-butanetetracarboxylic acid and the like can be mentioned.

Examples of the aliphatic amines, for example, n- butylamine, hexylamine s- butylamine to, octylamine, 2-ethylhexylamine, decylamine, dodecylamine, myristyl amine, stearyl amine, oleylamine, etc., R in R ² -NH ₂ ² Are compounds having an aliphatic hydrocarbon group having 4 or more carbon atoms (preferably 4 to 20 carbon atoms) (preferably a linear or branched alkyl group, alkenyl group, or alkynyl group). it can. These can be used alone or in combination of two or more.

  In the production method of 1 above, the reaction of carboxylic acid tetrachloride and amine (aliphatic amine and cysteamine) can be carried out, for example, by dropping carboxylic acid tetrachloride into a system charged with amine.

  The amount of amine used (the amount of aliphatic amine and cysteamine used (total amount)) is, for example, about 4 to 8 mol, preferably 4 to 6 mol, per 1 mol of carboxylic acid tetrachloride.

And the usage-amount (former: latter, molar ratio) of an aliphatic amine and a cysteamine can be suitably adjusted according to the compound represented by desired Formula (1). That is, by adjusting the use ratio of the aliphatic amine and cysteamine, the aliphatic amide group (CONH-R ² group) and the cysteamide group (CONHCH ₂ CH ₂ SH group) in the compound represented by the formula (1) to be obtained ) Can be controlled.

  The reaction of carboxylic acid tetrachloride and amine (aliphatic amine and cysteamine) 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 alone or in combination of two or more.

  The amount of the solvent used is, for example, about 50 to 300% by weight with respect to the total amount of carboxylic acid tetrachloride and amine (aliphatic amine and cysteamine). 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 carboxylic acid tetrachloride and amine (aliphatic amine and cysteamine) is usually carried out 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 amic dianhydride, an amine selected from an aliphatic amine and cysteamine, and the following solvent are charged into the system and aged to form an amic acid. A compound represented by the formula (1) is prepared by charging and aging an amine selected from amine and cysteamine (including an amine that was not used in the amic acid formation step) and a condensing agent (carbodiimide or a salt thereof). Can be manufactured.

  Examples of the carboxylic dianhydride include 1,2,4,5-benzenetetracarboxylic acid-1,2: 4,5-dianhydride, 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, 1,2,4,5-cyclohexanetetracarboxylic acid-1,2: 4,5-dianhydride, meso-butane-1,2,3,4 Tetracarboxylic dianhydride etc. can be used conveniently.

  As said aliphatic amine, the same example as the aliphatic amine which can be used with said manufacturing method of 1 can be mentioned. An aliphatic amine can be used individually by 1 type or in combination of 2 or more types.

  For example, when producing a compound in which n in formula (1) is 1, the amount of the aliphatic amine used is, for example, about 1 mole with respect to 1 mole of carboxylic dianhydride. The amount of cysteamine used is, for example, about 3 moles per 1 mole of carboxylic dianhydride.

  For example, when producing a compound in which n in formula (1) is 2, the amount of aliphatic amine used (the total amount when two or more are used) is, for example, 1 mol of carboxylic dianhydride, About 2 to 4 mol, preferably 2 to 3 mol. Moreover, as the usage-amount of a cysteamine, it is about 2-4 mol with respect to 1 mol of carboxylic dianhydrides, Preferably it is 2-3 mol.

  For example, when producing a compound in which n in formula (1) is 3, the amount of aliphatic amine used (the total amount when two or more are used) is, for example, 1 mol of carboxylic dianhydride, About 3 moles. Moreover, the usage-amount of cysteamine is about 1 mol with respect to 1 mol of carboxylic dianhydrides.

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 a (—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. These can be used alone or in combination of two or more.

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

  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 carboxylic dianhydride and amine is, for example, about 0.5 to 5 hours, and the aging time of amic acid and 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) has a total of four aliphatic amide groups and cysteamide groups as substituents, and self-associates at the amide bond site of the aliphatic amide group to form a fibrous self-assembly. can do. Further, the R ² group of the aliphatic amide group and the SH group of the cysteamide group both have an affinity for the fluid organic substance, and in particular, the SH group of the cysteamide group is the R ² group of the aliphatic amide group. Rather than the case where all four substituents are aliphatic amide groups, the hydrogen bond interaction can exert a stronger affinity for the fluid organic material. Highly thickening and stabilizing effect can be achieved, and by compatibilizing with fluid organic material, fluid organic material can be thickened, gelled, or composition containing fluid organic material can be uniformly stabilized. Can be Furthermore, since the compound represented by Formula (1) has an aliphatic amide group and a cysteamide group as substituents, it has moderate crystallinity. Therefore, thickening and stabilizing curing can be exerted on a wider range of fluid organic substances than when all four substituents are aliphatic amide groups. 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, a thickener that imparts viscosity to the flowable organic substance, and a gel that gels the flowable organic substance. It is a concept that includes a stabilizer 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. And particles of esters, metal oxides, etc.). As the content of the other components, the content of the compound represented by the above formula (1) in the total amount (100% by weight) of the thickening stabilizer (the total amount when containing two or more kinds) is, for example, 0.5 % By weight, preferably 1% by weight or more, more preferably 10% by weight or more, further preferably 30% by weight or more, particularly preferably 50% by weight or more, most preferably 60% by weight or more, and particularly preferably 85% by weight or more. Within the range. 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 formula (1) is out of the above range, the effect of the present invention tends to be difficult to obtain.

  The dosage form of the thickening stabilizer of the present invention is not particularly limited. For example, 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, the viscosity of the fluid organic substance can be more than 1 time (for example, more than 1 time and 100000 times or less), preferably 5 times or more (for example, 5 to 10000 times), particularly preferably 10 times. It can be adjusted according to the application within the above range (for example, 10 to 10,000 times), most preferably within the range of more than 30 times (for example, more than 30 times and 10000 times or less).

[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. A composition in which the product is uniformly stabilized.

  The thickening and stabilizing composition can be manufactured through a step of making the thickening stabilizer and the flowable organic material compatible. More specifically, the total amount of the fluid organic substance and the thickening stabilizer can be mixed and heated to be compatible with each other, followed by 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 fluid organic material as a raw material is an organic material having a viscosity [η at a shear rate of 10 (1 / s)] of less than 0.1 Pa · s measured 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 (dimethylpolysiloxane, methylphenylpolysiloxane, etc.), esters (octyldodecyl oleate, Cetyl octanoate, cetyl ethylhexanoate, glyceryl triisoocta Acid, tricaprylin, neopentyl glycol diisooctanoate, etc.), aromatic carboxylic acid, 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, most preferably 1 to 30 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 room temperature or lower (for example, 25 ° C. or lower), and may be gradually cooled at room temperature or rapidly by ice cooling or the like.

  The viscosity of the thickened and stabilized composition of the present invention by the rheometer [viscosity (η) at 25 ° C., shear rate 10 (1 / s)] is more than 1 times the viscosity of the fluid organic material as a raw material ( For example, more than 1 time and less than 100,000 times, preferably 5 times or more (for example, 5 to 10,000 times), particularly preferably 10 times or more (for example, 10 to 10000 times), most preferably more than 30 times (for example, more than 30 times) Within the range of 10,000 times or less, it can be appropriately adjusted according to the application.

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

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

Synthesis Example 1 [Synthesis of thickening stabilizer (1)]
20 mL of pyridine, 1,2,4,5-benzenetetracarboxylic acid-1,2: 4,5-dianhydride in a 100 mL four-necked separable flask equipped with a Dimroth condenser, nitrogen inlet, dropping funnel, thermocouple 3.0 g (0.014 mol) and 7.4 g (0.028 mol) of oleylamine were charged. The system temperature was set to 50 ° C. and aged for 3 hours.
Thereafter, 2.2 g (0.028 mol) of cysteamine and 7.0 g (0.056 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 1,2,4,5-benzenetetracarboxylic acid bis (cysteamide) bis (oleylamide). ) [1,2,4,5-benzenetetracarboxylic acid-1,4-bis (cysteamide) -2,5-bis (oleylamide) and 1,2,4,5-benzenetetracarboxylic acid-1,5 -9.5 g of bis (cysteamide) -2,4-bis (oleylamide) mixture] (yield: 79%). The structure of the reaction product was confirmed by ¹ H-NMR.

Synthesis Example 2 [Synthesis of thickening stabilizer (2)]
The same procedure as in Synthesis Example 1 was conducted except that 1.8 g (0.014 mol) of 2-ethylhexylamine and 1.1 g (0.014 mol) of cysteamine were used instead of 2.2 g (0.028 mol) of cysteamine. , 2,4,5-benzenetetracarboxylic acid 2-ethylhexylamide cysteamide bis (oleylamide) was obtained in an amount of 11.0 g (yield: 85%).

Synthesis Example 3 [Synthesis of thickening stabilizer (3)]
The same procedure as in Synthesis Example 1 was conducted except that 2.7 g (0.021 mol) of 2-ethylhexylamine and 0.54 g (0.007 mol) of cysteamine were used instead of 2.2 g (0.028 mol) of cysteamine. , 2,4,5-Benzenetetracarboxylic acid 2-ethylhexylamide cysteamide bis (oleylamide) and 1,2,4,5-benzenetetracarboxylic acid bis (2-ethylhexylamide) bis (oleylamide) 11.7 g was obtained (yield: 88%).

Synthesis Example 4 [Synthesis of thickening stabilizer (4)]
1,2,4,5-benzenetetracarboxylic was carried out in the same manner as in Synthesis Example 1 except that 3.6 g (0.028 mol) of 2-ethylhexylamine was used instead of 2.2 g (0.028 mol) of cysteamine. 5.9 g of acid bis (2-ethylhexylamide) bis (oleylamide) was obtained (yield: 51%).

Examples 1-3, Comparative Example 1
Various fluid organic substances (liquid paraffin, isododecane, cetyl octoate, tricaprylin: boiling points of 100 ° C. or more) shown in Table 1 were weighed in a test tube by 1 cm ³ , and the increase obtained in the above synthesis example was obtained. 10 mg of each of the viscosity stabilizers (1) to (4) is added and mixed, heated and stirred at 100 ° C. to dissolve the fluid organic substance and the thickening stabilizer, and then cooled to 25 ° C. to stabilize the viscosity. A composition was obtained.
Measure the viscosity of the resulting thickened and stabilized composition, confirm how many times the viscosity of various fluid organic substances has been increased, evaluate the thickening and stabilizing effect according to the following criteria, The case where a thickening and stabilizing effect of 5 or more was exhibited with respect to the organic substance was marked as ◯.
<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 30 times 5: Over 30 times, 200 times or less 6: Over 200 times, 500 times or less 7: Over 500 times, 3000 times or less 8: Over 3000 times, 10,000 times or less

  In addition, the viscosity of various fluid organic substances and thickening and stabilizing compositions is a cone plate sensor (cone angle of 1 ° at a diameter of 60 mm, cone angles of 1 °, 2 ° and 4 ° at a diameter of 35 mm) and a Peltier temperature controller. Using a viscosity / viscoelasticity measuring device (rheometer) (trade name “RheoStress600”, manufactured by HAAKE Co., Ltd.) and a normal viscosity measurement mode under a 25 ° C. condition and a shear rate of 0.001 to 100 (logarithmically) 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.

  From Table 1, it was found that the thickening stabilizer of the present invention has an excellent thickening and stabilizing effect for a wide range of flowable organic substances. On the other hand, the thickening stabilizer obtained in the comparative example may not have a sufficient thickening and stabilizing effect depending on the type of the fluid organic substance.

Claims (4)

Following formula (1)

(In the formula, R ¹ represents a group obtained by removing four hydrogen atoms from the structural formula of benzene, cyclohexane, butane, benzophenone, biphenyl, or naphthalene, and R ² represents an aliphatic hydrocarbon group having 4 or more carbon atoms. N represents an integer of 1 to 3. When n is 2 or 3, 2 or 3 R ^{2 s} may be the same or different.
A compound represented by   A thickening stabilizer comprising the compound according to claim 1.   A thickening and stabilizing composition comprising the thickening stabilizer according to claim 2 and a flowable organic substance.   The manufacturing method of the thickening stabilization composition which obtains a thickening stabilization composition through the process of making the thickening stabilizer and fluid organic substance of Claim 2 compatible.