TWI760294B - Thickening and stabilizing agent, and thickening and stabilizing composition using the same - Google Patents

Abstract

The present invention provides a compound for thickening or gelling a fluid organic substance to a desired viscosity or for uniformly stabilizing a composition containing a fluid organic substance, a viscosity increasing and stabilizer comprising the foregoing compound, and a viscosity increasing stabilizer comprising the foregoing A viscosity-increasing and stabilizing composition of an agent and a flowable organic substance, and a manufacturing method thereof.

The compound of the present invention is represented by the following formula (1): (R ² -HNOC) _4-n -R ¹ -(CONH-R ³ ) _n (1)

(wherein, R ¹ is a group obtained by removing 4 hydrogen atoms from the structural formula of an aromatic hydrocarbon or cyclohexane, R ² is an aliphatic hydrocarbon group with 1 to 4 carbon atoms, and R ³ is an aliphatic group with 6 or more carbon atoms family of hydrocarbon groups; n is an integer of 1 to 3).

Description

Thickening and stabilizing agent, and thickening and stabilizing composition using the same

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

The method of thickening and stabilizing the liquid is a very important technology in the industry. For example, the quasi-stable state emulsified mayonnaise and salad dressing can maintain their emulsified state stably for a long time, because the water-based component has been added. Because of the stabilization of viscosity. Therefore, various viscosity-increasing stabilizers have been developed. As the tackifier and stabilizer for aqueous media, for example, alkyl acrylate copolymers and the like are known.

On the other hand, 12-hydroxystearic acid, which is mainly used for disposal of edible oil, is known as a viscosity-increasing and stabilizer for a fluid organic substance (for example, an organic substance having fluidity such as an oily medium) (Patent Document 1 Wait). However, 12-hydroxystearic acid cannot adjust the degree of gelation, and can only be derived into either a fully solidified state or a liquid state.

[Prior Art Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 01-163111

Therefore, the objective of this invention is to provide the compound which thickens or gelatinizes a flowable organic substance to a desired viscosity, or stabilizes the composition containing a flowable organic substance uniformly.

Another object of the present invention is to provide a tackifier and stabilizer containing the aforementioned compound, a tackifier and stabilizer composition that is thickened, gelled, or stabilized by the aforementioned tackifier and stabilizer, and a method for producing the same.

In order to solve the above-mentioned problems, the inventors of the present invention have conducted intensive studies and found that a compound having a specific structure can thicken and gel a flowable organic substance, or uniformly stabilize a composition containing a flowable organic substance (=Prevention of sedimentation, local aggregation or concentration of the composition, and stable maintenance of a uniform state); by selecting and using according to the type of the flowable organic material, the viscosity of the flowable organic material can be thickened or gelatinized to the desired viscosity, or evenly stabilize the composition containing the flowable organic substance. The present invention is accomplished based on these findings.

That is, the present invention provides a compound represented by the following formula (1): (R ² -HNOC) _4-n -R ¹ -(CONH-R ³ ) _n (1)

(wherein, R ¹ is a group obtained by removing 4 hydrogen atoms from the structural formula of an aromatic hydrocarbon or cyclohexane, R ² is an aliphatic hydrocarbon group with 1 to 4 carbon atoms, and R ³ is an aliphatic group with 6 or more carbon atoms family of hydrocarbon groups; n is an integer of 1 to 3).

The present invention further provides the aforementioned compound, wherein the aromatic hydrocarbon in R ¹ is benzene, benzophenone, biphenyl or naphthalene.

The present invention further provides the aforementioned compound, wherein R ¹ is a group obtained by removing 4 hydrogen atoms from the structural formula of benzene or cyclohexane.

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

The present invention further provides a tackifying and stabilizing composition, which comprises the aforementioned tackifying and stabilizing agent and a flowable organic substance.

The present invention further provides a method for producing a viscosity-enhancing and stabilizer composition, which comprises a step of making the aforementioned viscosity-enhancing stabilizer and a flowable organic substance compatible.

That is, the present invention relates to the following.

[1] A compound represented by the following formula (1): (R ² -HNOC) _4-n -R ¹ -(CONH-R ³ ) _n (1)

(wherein, R ¹ is a group obtained by removing 4 hydrogen atoms from the structural formula of an aromatic hydrocarbon or cyclohexane, R ² is an aliphatic hydrocarbon group with 1 to 4 carbon atoms, and R ³ is an aliphatic group with 6 or more carbon atoms family of hydrocarbon groups; n is an integer of 1 to 3).

[2] The compound according to [1], wherein the aromatic hydrocarbon in R ¹ is benzene, benzophenone, biphenyl or naphthalene.

[3] The compound according to [1], wherein R ¹ is a group obtained by removing four hydrogen atoms from the structural formula of benzene or cyclohexane.

[4] The compound according to any one of [1] to [3], wherein the aliphatic hydrocarbon group in R ² is a straight-chain or branched-chain alkyl group, a straight-chain or branched-chain alkenyl group, or Linear or branched alkynyl.

[5] The compound according to any one of [1] to [4], wherein R ³ is a linear or branched alkyl group having 6 or more carbon atoms, or a linear or branched chain having 6 or more carbon atoms alkenyl.

[6] The compound according to any one of [1] to [4], wherein R ³ is a linear or branched alkyl group having 6 to 20 carbon atoms, or a linear or branched alkyl group having 6 to 20 carbon atoms. Branched alkenyl.

[7] The compound according to [1], wherein the compound represented by the formula (1) is at least one compound selected from the group consisting of compounds represented by the formulas (1-1) to (1-22) .

[8] The compound according to [1], wherein the compound represented by formula (1) is selected from the group consisting of formulas (1-1) to (1-4) and (1-19) to (1-22) At least one compound of the group consisting of the indicated compounds.

[9] The compound according to [1], wherein the compound represented by the formula (1) is the compound represented by the formula (1-2) and/or the formula (1-4), or the compound represented by the formula (1-20) and/ or a compound represented by formula (1-22).

[10] A viscosity-increasing stabilizer comprising the compound according to any one of [1] to [9].

[11] The viscosity-enhancing stabilizer according to [10], wherein the content of the compound represented by the formula (1) (the total amount when two or more types are contained) is 0.5 weight of the total amount of the viscosity-enhancing and stabilizer %above.

[12] A viscosity-increasing stabilizer composition comprising the viscosity-increasing stabilizer as described in [10] or [11] and a flowable organic substance.

[13] The viscosity increasing and stabilizing composition according to [12], wherein the viscosity of the flowable organic substance according to a rheometer [viscosity (η) at 25°C, shear rate 10 (1/sec)] is low at 0.1Pa·s.

[14] The viscosity increasing and stabilizing composition according to [12] or [13], wherein the flowable organic substance is selected from the group consisting of hydrocarbon oils, ethers, halogenated hydrocarbons, and petroleum components , at least one compound of the group consisting of animal and vegetable oils, silicone oils, esters, aromatic carboxylic acids and pyridine.

[15] The viscosity-enhancing and stabilizer composition according to any one of [12] to [14], wherein the content of the viscosity-enhancing and stabilizer is 0.1 to 100 parts by weight relative to 1000 parts by weight of the flowable organic substance.

[16] A method for producing a viscosity-enhancing and stabilizer composition, comprising the step of making the viscosity-enhancing stabilizer as described in [10] or [11] compatible with a flowable organic substance.

[17] A method for producing a viscosity-enhancing and stabilizer composition, which obtains the steps of [12] to [15] through the step of making the viscosity-enhancing stabilizer described in [10] or [11] compatible with a flowable organic substance The viscosity-increasing and stabilizing composition according to any one of the above.

The compound represented by the formula (1) of the present invention can easily thicken or gel the flowable organic material by making it compatible with the flowable organic material, or can uniformly stabilize the composition containing the flowable organic material change. Moreover, the viscosity-enhanced or gelled state can be stably maintained by the compound which is thickened and stabilized by the compound represented by the formula (1) of the present invention. Therefore, the compound represented by the formula (1) of the present invention can be suitably used as a viscosity-increasing and stabilizer for cosmetics, paints, foods, pharmaceuticals, etc., and by using the compound represented by the formula (1) of the present invention, the The viscosity can be adjusted to a desired range, the composition can be maintained uniformly, and the usability can be improved.

[Form of implementing the invention]

[The compound represented by the formula (1)]

The compound of the present invention is represented by the following formula (1): (R ² -HNOC) _4-n -R ¹ -(CONH-R ³ ) _n (1)

In the formula, R ¹ is a group obtained by removing 4 hydrogen atoms from the structural formula of an aromatic hydrocarbon or cyclohexane, R ² is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and R ³ is an aliphatic group having 6 or more carbon atoms. Hydrocarbyl. n is an integer from 1 to 3.

The aromatic hydrocarbon in R ¹ includes, for example, an aromatic ring having 6 to 14 carbon atoms such as a benzene ring and a naphthalene ring, and a structure in which two or more of the aforementioned aromatic rings are bonded via a single bond or a linking group.

The aforementioned linking group includes, for example, a divalent hydrocarbon group, a carbonyl group (-CO-), an ether bond (-O-), a thioether bond (-S-), an ester bond (-COO-), an amide A bond (-CONH-), a carbonate bond (-OCOO-), a group formed by connecting a plurality of these, and the like.

The above-mentioned divalent hydrocarbon group includes, for example, a straight chain having 1 to 18 carbon atoms such as methylene, methylmethylene, dimethylmethylene, ethylidene, propylidene, and trimethylene. and 1,2-cyclopentylene, 1,3-cyclopentylene, cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, A cycloalkylene group (including a cycloalkylidene) having 3 to 18 carbon atoms, such as a 1,4-cyclohexylene group and a cyclohexylene group, and the like.

As for the aromatic hydrocarbon in R ¹ , among them, benzene, benzophenone, biphenyl or naphthalene are preferred, and benzene is particularly preferred. Therefore, R ¹ in the present invention is preferably a group obtained by removing four hydrogen atoms from the structural formula of benzene or cyclohexane.

R ² is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, for example, straight-chain or branched, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, tertiary butyl, and tertiary butyl group. Chain alkyl; linear or branched alkenyl such as vinyl, propenyl, butenyl; linear or branched alkynyl such as ethynyl, propynyl, butynyl, and the like.

Examples of aliphatic hydrocarbon groups having 6 or more carbon atoms in R ³ include hexyl, octyl, 2-ethylhexyl, decyl, lauryl, myristyl, stearyl, and nonadecyl. Linear or branched alkyl with carbon number of about 6 to 20 (preferably 6 to 18); 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 7-hexenyl -Octenyl, 9-decenyl, 11-dodecenyl, oleyl and other straight-chain or branched alkenyl groups with about 6 to 20 carbon atoms (preferably 6 to 18); hexynyl, Linear or branched alkynyl, etc. with carbon number of about 6 to 20 (preferably 6 to 18, particularly preferably 12 to 18) such as octynyl, decynyl, pentadecynyl, octadecynyl, etc. . In the present invention, it is preferably a linear or branched alkyl group with 6 or more carbon atoms, or a linear or branched alkenyl group with 6 or more carbon atoms, particularly preferably a linear or branched alkenyl group with 6 to 20 carbon atoms. A straight-chain or branched-chain alkyl group, or a straight-chain or branched-chain alkenyl group having 6 to 20 carbon atoms.

As a compound represented by Formula (1), the compound etc. which are represented by the following formula are mentioned, for example.

As for the compound represented by the formula (1), the compounds represented by the above-mentioned formulas (1-1) to (1-4) and (1-19) to (1-22) are in the flowable organic substance. The point of excellent solubility and the point of being able to impart pseudoplastic behavior and strong storage modulus while maintaining its transparency when the flowable organic substance is transparent are preferable, and the above-mentioned formula (1) is particularly preferable. Compounds represented by -2) and/or (1-4), (1-20) and/or (1-22).

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

1. The carboxylic acid (R ¹ -(COOH) ₄ ; R ¹ is the same as above) is reacted with thionyl chloride to obtain carboxylate chloride, and the amine (R ² -NH ₂ and R ³ -NH ₂ ; R ² , R ³ is the same as above) the method for the reaction of the obtained carboxylate chloride

2. The amine (1) (R ² -NH ₂ or R ³ -NH ₂ ; R ² and R ³ are the same as above) is reacted with the carboxylic anhydride corresponding to the aforementioned carboxylic acid to obtain an amide acid, and then a condensing agent is used to make it. Amine (2) (Amine (2) is R3- _NH2 when Amine (1) is R2- ^NH2 , Amine ( ₂ ) is R2 ^- _NH2 when Amine (1) is ^{R3 -} _NH2 ; R ² , R ³ are the same as above) the method of condensation

Specifically, 1,2,4,5-benzenetetracarboxylic acid and 3,3',4,4'-benzophenonetetracarboxylic acid are mentioned as the carboxylic acid used in the method of said 1. , 1,1'-biphenyl-2,3,3',4'-tetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid Wait.

Examples of the amine (R ² -NH ₂ ) used in the method of the above 1 include methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, secondary butylamine, tertiary butylamine, and the like.

The amine (R ³ -NH ₂ ) used in the above-mentioned method 1 includes, for example, hexylamine, octylamine, 2-ethylhexylamine, decylamine, laurylamine, myristylamine, stearylamine, oil Amines, etc., where R ³ is an aliphatic hydrocarbon group (preferably a linear or branched alkyl, alkenyl, or alkynyl group) having 6 or more carbon atoms (preferably, 6 to 20 carbon atoms), and the like.

In the method of the above-mentioned 1, the reaction of carboxylate chloride and amine can be carried out, for example, by dropping carboxylate chloride into the system containing the amine.

The amount of amine used (total amount of R ² -NH ₂ and R ³ -NH ₂ ) is, for example, about 3 to 8 moles, preferably 3 to 6 moles, relative to 1 mole of carboxylic acid acyl chloride. Furthermore, by adjusting the use ratio of R ² -NH ₂ and R ³ -NH ₂ , it is possible to control the difference between the (CONH-R ² ) group and the (CONH-R ³ ) group in the obtained compound represented by the formula (1). quantity.

烷、1,2-二甲氧基乙烷、環戊基甲基醚等醚系溶媒；乙腈、苯甲腈等腈系溶媒；二甲亞碸等亞碸系溶媒；環丁碸等環丁碸系溶媒；二甲基甲醯胺等醯胺系溶媒；矽酮油等高沸點溶媒等。該等能以單獨1種，或組合2種以上來使用。 The reaction of carboxylate chloride and amine can be carried out in the presence or absence of a solvent. Examples of the aforementioned solvent include saturated or unsaturated hydrocarbon-based solvents such as pentane, hexane, heptane, octane, and petroleum ether; aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene; dichloromethane, Halogenated hydrocarbon solvents such as chloroform, 1,2-dichloroethane, chlorobenzene, and bromobenzene; diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, diethyl ether

Ether-based solvents such as alkane, 1,2-dimethoxyethane, and cyclopentyl methyl ether; nitrile-based solvents such as acetonitrile and benzonitrile; sulfite-based solvents such as dimethylsulfoxide; cyclobutanes such as cyclobutane Sulfur-based solvents; amide-based solvents such as dimethylformamide; high-boiling point solvents such as silicone oil, etc. 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, preferably 100 to 250% by weight, based on the total amount of 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 a reaction rate to fall.

The reaction (=dropping) of carboxylate chloride and amine is usually carried out under normal pressure. Moreover, the gas atmosphere of the above-mentioned reaction (= at the time of dropping) is not particularly limited as long as the reaction is not inhibited. The reaction temperature (= temperature at the time of dropping) is, for example, about 30 to 60°C. 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. In addition, the reaction can be carried out by any method such as a batch method, a semi-batch method, and a continuous method.

After the reaction is completed, the obtained reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination of these separation means.

In the production method of the above 2, for example, carboxylic acid anhydride, amine (1), and the following solvent can be charged into the system and aged to form amide acid, and then amine (2) and amine (2) can be charged. A condensing agent (for example, carbodiimide or its salt) is matured to produce the compound represented by the formula (1).

As the carboxylic acid anhydride used in the method of the above 2, for example, 1,2,4,5-benzenetetracarboxylic acid-1,2:4,5-dianhydride, 3,3',4,4' - Benzophenone tetracarboxylic 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, etc.

As the amines (1) and (2) used in the above-mentioned method 2, the same compounds as those used in the above-mentioned production method in the above-mentioned 1 can be used.

The amount of the amine (1) used is, for example, based on 1 mole of the carboxylic acid anhydride. It is about 2-4 mol, preferably 2-3 mol. Moreover, the usage-amount of amine (2) is about 2-4 mol, for example, Preferably it is 2-3 mol with respect to 1 mol of carboxylic anhydride.

The aforementioned carbodiimide is represented by the following formula: R-N=C=N-R'

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

Examples of linear or branched alkyl groups having 3 to 8 carbon atoms include propyl, isopropyl, butyl, isobutyl, tertiary butyl, tertiary butyl, pentyl base, isopentyl, secondary pentyl, tertiary pentyl, hexyl, isohexyl, secondary hexyl, tertiary hexyl, etc.

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

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

Examples of carbodiimide include diisopropylcarbodiimide, dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)-N'-ethyl Carbodiimide, etc. Moreover, as the salt of carbodiimide, for example, hydrochloride (specifically, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide) can be mentioned. hydrochloride, etc.) etc.

The amount of carbodiimide used is, for example, about 2 to 6 moles, preferably 2 to 4 moles, relative to 1 mole of the carboxylic acid anhydride.

As the aforementioned solvent, for example, a proton-accepting solvent excellent in solubility of amide acids such as pyridine, triethylamine, and tributylamine is preferably used. 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 amide 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 a reaction rate to fall.

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

After the reaction is completed, the obtained reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, or a combination of these separation means.

The compound represented by the formula (1) can form a fibrous self-organizing body by self-association at the amide bond site due to hydrogen bonding. Further, since the R ² group (aliphatic hydrocarbon group with 1 to 4 carbon atoms) exhibits strong intermolecular hydrogen bonding, and the R ³ group (aliphatic hydrocarbon group with 6 or more carbon atoms) exhibits affinity for fluid organic substances Therefore, by making it compatible with the fluid organic matter, the fluid organic matter can be thickened and gelled, or the composition containing the fluid organic matter can be uniformly stabilized. Furthermore, since the side chain has two types of groups (R ² and R ³ groups) different from each other, the interaction of the side chains is weakened and crystallization is suppressed compared with the case of having one type of group. Therefore, it is excellent in solubility to a flowable organic substance, and can be stabilized in viscosity without particular limitation as long as it is a flowable organic substance. That is, there is a wide range of viscosified flowable organic matter (viscosified flowable organic matter) selectivity. Furthermore, when the flowable organic substance has transparency, it is possible to increase and stabilize the viscosity while maintaining the transparency, and to form a viscosity-enhancing and stabilized composition that is stable over time. Therefore, for example, it is useful as a viscosity-increasing stabilizer (more specifically, a viscosity-increasing agent, a gelling agent, or a stabilizer) of a flowable organic substance. On the other hand, when the R ² and R ³ groups together represent the same group in the compound represented by the formula (1) (that is, when the compound represented by the formula (1) has four identical groups as side chains) , or even if the R ² and R ³ groups are different groups from each other, when the carbon number of at least one of the R ² and R ³ groups is outside the above range, crystallization becomes easy due to the interaction of the side chains, so The flowable organic substances that can be thickened and stabilized are limited, and the selectivity of the thickened and flowable organic substances is narrowed, which is not good. In addition, there are many cases of cloudiness due to compatibility with a flowable organic substance, which makes it difficult to maintain the appearance. Furthermore, it is easy to reduce viscosity over time.

[viscosity stabilizer]

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

In addition to the compound represented by the above formula (1), the viscosity-enhancing and stabilizer of the present invention may also contain other viscosity-enhancing and stabilizers as required. Formula (1) shows The content of the compound (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 Preferably it is 60 weight% or more, More preferably, it is 80 weight% or more. In addition, the upper limit of the content of the compound represented by the said formula (1) is 100 weight%. If the content of the compound represented by the above formula (1) is outside the above range, it tends to be difficult to thicken and gel the flowable organic substance or to uniformly stabilize the composition containing the flowable organic substance.

Furthermore, in the present invention, the so-called "viscosity stabilizer" refers to a compound that dissolves into a fluid organic substance and generates viscosity, and the concept includes: a viscosity increaser that imparts viscosity to a fluid organic substance, and a fluid organic substance. A gelling agent that gels a substance, and a stabilizer that improves the viscosity of a composition containing a fluid organic substance for the purpose of uniformly stabilizing it. Other viscosity-increasing stabilizers include: bases, hydroxy fatty acids, acrylic polymers, oligomer esters such as dextrin fatty acid esters, particles such as metal oxides, etc.

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

The viscosity-increasing stabilizer of the present invention can increase the viscosity or gel the above-mentioned flowable organic material by making it compatible with the flowable organic material (preferably by mixing and heating, making it compatible and then cooling), The above-mentioned flowable organic substance can be thickened or gelled to the desired viscosity according to the application in the range of more than 30 times and 10000 times or less (preferably more than 30 times and 5000 times or less).

[Tackifier and stabilizer composition]

The viscosity-enhancing and stabilizing composition of the present invention comprises the above-mentioned viscosity-enhancing and stabilizer and a flowable organic substance, and the flowable organic substance is thickened or gelled by the aforesaid viscosity-enhancing and stabilizer, or the liquid containing the flowable organic substance is viscous and gelled. The composition is stabilized uniformly.

The viscosity-enhancing and stabilizer composition of the present invention can be produced by the step of making the viscosity-enhancing stabilizer and the flowable organic substance compatible. In more detail, it can manufacture by mixing a viscosity increasing and stabilizer with a flowable organic substance (total amount), heating it, making it compatible, and cooling it. In addition, it can also be produced by the following method: a part of the fluid organic substance is mixed with a viscosity-enhancing and stabilizer, heated, made to dissolve, and then cooled to produce a viscosity-enhancing and stabilizer composition, and mixed until the remainder of mobile organic matter.

The flowable organic substance used as a raw material is an organic substance whose viscosity is lower than 0.1 Pa·s according to the viscosity of a rheometer [viscosity (η) at 25° C., shear rate 10 (1/sec)], for example. : Hydrocarbon oils (hexane, cyclohexane, isododecane, benzene, toluene, polyalphaolefin, mobile 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.), silicones (dimethyl Polysiloxane, methylphenyl polysiloxane, decamethylcyclopentasiloxane and other silicone oils), esters (octyldodecyl oleate, cetyl caprylate, cetyl ethylhexanoate) esters, glyceryl triisocaprylate, neopentyl glycol diisocaprylate, glyceryl tricaprylin (tricaprylin, etc.), aromatic carboxylic acids, pyridine, and the like. These can be used alone or in combination of two or more.

Although the mixing amount (or usage amount) of the viscosity increasing stabilizer also depends on the type of the flowable organic substances, it is relatively 1000 parts by weight, for example, 0.1 to 100 parts by weight, preferably 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-mentioned range, a composition in which a fluid organic substance is thickened or gelled, or a composition in which the composition is uniformly stabilized can be obtained.

The viscosity-enhancing and stabilizing composition of the present invention may contain, in addition to the above-mentioned viscosity-enhancing and stabilizer and the flowable organic substance, other components within the scope of not impairing the effect of the present invention. Examples of other components include general compounds (eg, medicinal ingredients, pigments, fragrances, etc.) contained in compositions that are desired to be thickened and stabilized, such as cosmetics, paints, foods, and pharmaceuticals.

The temperature at the time of compatibility is appropriately selected according to the type of the viscosity-enhancing stabilizer and the flowable organic substance. The temperature at which the viscosity-enhancing stabilizer and the flowable organic substance are compatible is not particularly limited, but it is preferably not. When it exceeds 100°C, when the boiling point of the flowable organic substance is 100°C or lower, it is preferably about the boiling point.

The cooling after compatibility may be cooled to 25° C. or lower, and may be cooled slowly at room temperature, or 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 according to a rheometer [viscosity (η) at 25° C. and shear rate 10 (1/sec)] is, for example, 0.5 to 10.0 Pa·s, preferably It is 1.0 to 8.0 Pa·s, and can be appropriately adjusted according to the application within the range of more than 30 times and 10,000 times or less (preferably more than 30 times and 5,000 times or less) of the viscosity of the flowable organic substance used as the raw material.

As far as the viscosity increasing and stabilizing composition of the present invention is concerned, as long as it contains The flowable organic substance is a composition desirably thickened and stabilized, and is not particularly limited, and examples thereof include cosmetics, paints, foods, and pharmaceuticals.

[Example]

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

Synthesis Example 1 [Synthesis of Thickening Stabilizer (1) (1,2,4,5-benzenetetracarboxylic acid bis(butylamide)bis(oleylamide))]

A 100 mL four-neck separable flask equipped with a dimroth condenser, nitrogen inlet, dropping funnel and thermocouple was charged with 20 mL of pyridine, 1,2,4,5-benzenetetracarboxylic acid-1, 2: 3.0 g (0.014 mol) of 4,5-dianhydride, and 7.4 g (0.028 mol) of oleylamine. The temperature in the system was set to 50°C, and it was aged for 3 hours.

Then, 2.1 g (0.028 mol) of butylamine and 7.0 g (0.056 mol) of diisopropylcarbodiimide were charged, and aging was further performed for 8 hours.

Then, the low boiling part of the obtained crude liquid was removed by the evaporator, and it wash|cleaned with methanol, and obtained the pale yellow wet powder. The obtained wet powder was further recrystallized with CHCl ₃ /CH ₃ OH (70/30(v/v)) to obtain 1,2,4,5-benzenetetracarboxylic acid bis(butylamide)bis (Oleylamide)[1,2,4,5-benzenetetracarboxylic acid-1,4-bis(butylamide)-2,5-bis(oleylamide) and 1,2,4, 5-benzenetetracarboxylic acid-1,5-bis(butylamide)-2,4-bis(oleylamide) mixture] 7.3 g (yield: 61%). The structure of the reaction product was confirmed by ¹ H-NMR.

¹ H-NMR (270 MHz, CDCl ₃ ): δ 0.75-1.1 (m, 12H), 1.01-1.86 (m, 64H), 1.96-2.04 (m, 8H), 5.25-5.55 (m, 4H), 8.5- 9.5(m, 2H)

Synthesis Example 2 [Tackifier Stabilizer (2) (1,2,4,5-cyclohexanetetracarboxyl) Synthesis of acid bis(butyl amide) bis(oleyl amide)]

20 mL of pyridine, 1,2,4,5-cyclohexanecarboxylic acid-1,2:4 were placed in a 100 mL four-neck separable flask equipped with a Day's condenser, nitrogen inlet, dropping funnel, and thermocouple. , 4.5g (0.02mol) of 5-dianhydride, and 10.7g (0.04mol) of oleylamine. The temperature in the system was set to 50°C, and it was aged for 3 hours.

Then, 2.9 g (0.02 mol) of butylamine and 5.5 g (0.044 mol) of diisopropylcarbodiimide were charged, and aging was further performed for 8 hours.

Then, the low boiling part of the obtained crude liquid was removed by the evaporator, and it wash|cleaned with methanol, and obtained the pale yellow wet powder. 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 di(butylamide) ) bis(oleylamide)[1,2,4,5-cyclohexanetetracarboxylic acid-1,4-bis(butylamide)-2,5-bis(oleylamide) with 1, 2,4,5-cyclohexanetetracarboxylic acid-1,5-bis(butylamide)-2,4-bis(oleylamide) mixture] 11.6 g (yield: 67%). The structure of the reaction product was confirmed by ¹ H-NMR.

¹ H-NMR (270 MHz, CDCl ₃ ): δ 0.81-0.97 (m, 12H), 0.97-1.61 (m, 64H), 1.82-2.04 (m, 8H), 2.50-3.10 (m, 4H), 3.30- 3.45(m,4H),5.25-5.45(m,4H),6.25-6.30(m,4H)

Synthesis Example 3 [Synthesis of thickening stabilizer (3) (1,2,4,5-benzenetetracarboxylic acid bis(2-ethylhexylamide)bis(oleylamide))]

20 mL of pyridine, 1,2,4,5-benzenetetracarboxylic acid 1,2:4,5 was placed in a 100 mL four-neck separable flask equipped with a Day's condenser, nitrogen inlet, dropping funnel, and thermocouple. -3.0 g (0.014 mol) of dianhydride, and 7.4 g (0.028 mol) of oleylamine. The temperature in the system was set to 50°C, and it was aged for 3 hours.

Then, 3.6 g (0.028 mol) of 2-ethylhexylamine and diisopropyl were charged 7.0 g (0.056 mol) of carbodiimide was further aged for 8 hours.

Then, the low boiling part of the obtained crude liquid was removed by the evaporator, and it wash|cleaned with methanol, and obtained the 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(2-ethylhexyl) amine) bis(oleylamide)[1,2,4,5-benzenetetracarboxylic acid-1,4-bis(2-ethylhexylamide)-2,5-bis(oleylamide) with Mixture of 1,2,4,5-benzenetetracarboxylic acid-1,5-bis(2-ethylhexylamide)-2,4-bis(oleylamide)] 5.9g (yield: 51% ). The structure of the reaction product was confirmed by ¹ H-NMR.

¹ H-NMR (270 MHz, CDCl ₃ ): δ 0.81-1.02 (m, 18H), 1.03-1.85 (m, 74H), 1.96-2.04 (m, 8H), 5.35-5.56 (m, 4H), 8.5- 9.5(m, 2H)

Synthesis Example 4 [Synthesis of Thickening Stabilizer (4) (1,2,4,5-benzenetetracarboxylic acid bis(hexylamide)bis(oleylamide))]

20 mL of pyridine, 1,2,4,5-benzenetetracarboxylic acid 1,2:4,5 was placed in a 100 mL four-neck separable flask equipped with a Day's condenser, nitrogen inlet, dropping funnel, and thermocouple. -3.0 g (0.014 mol) of dianhydride, and 7.4 g (0.028 mol) of oleylamine. The temperature in the system was set to 50°C, and it was aged for 3 hours.

Then, 2.8 g (0.028 mol) of hexylamine and 7.0 g (0.056 mol) of diisopropylcarbodiimide were charged, and aging was further performed for 8 hours.

Then, the low boiling part of the obtained crude liquid was removed by the evaporator, and it wash|cleaned with methanol, and obtained the 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(hexylamide)bis( Oleylamide)[1,2,4,5-benzenetetracarboxylic acid-1,4-bis(hexylamide)-2,5-bis(oleylamide) and 1,2,4,5- Mixture of benzenetetracarboxylic acid-1,5-bis(hexylamide)-2,4-bis(oleylamide)] 8.1 g (yield: 64%). The structure of the reaction product was confirmed by ¹ H-NMR.

¹ H-NMR (270 MHz, CDCl ₃ ): δ 0.80-1.01 (m, 12H), 1.0-1.82 (m, 72H), 1.96-2.04 (m, 8H), 5.31-5.61 (m, 4H), 8.5- 9.5(m, 2H)

Example 1

The various flowable organic substances shown in the table [flowable paraffin (viscosity: 0.14Pa·s), isododecane (viscosity: 0.001Pa·s), cetyl caprylate (viscosity: 0.012Pa·s), three Caprylic acid glyceride (viscosity: 0.023Pa·s); the boiling point of any one is above 100°C] Weigh 1cm ³ of each into a test tube, add 10mg of the viscosity-enhancing stabilizer (1) obtained in the above synthesis example to each, and mix , heated and stirred at 100° C. to make the flowable organic substance and the viscosity-enhancing stabilizer (1) compatible, and cooled to 25° C. to obtain a viscosity-enhancing and stabilized composition.

The viscosity of the obtained thickening and stabilizing composition is as follows.

The viscosity-increasing and stabilizing composition of flowing paraffin: 4.84Pa‧s

Viscosity-stabilizing composition of isododecane: 1.98Pa‧s

The thickening and stabilizing composition of cetyl caprylate: 2.48Pa‧s

Viscosity-stabilizing composition of glyceryl tricaprylate: 7.87Pa‧s

The thickening ratio was calculated from the following formula, and the thickening property was evaluated according to the following evaluation criteria, and the situation where an evaluation of 5 or more was obtained for all the flowable organic substances was regarded as a good thickening effect (○), and the other The condition of , is called poor viscosity increase effect (×).

Viscosity increase ratio = viscosity of the viscosity increase and stabilization composition / viscosity of the flowable organic substance before viscosity increase and stabilization

<Evaluation Criteria>

1: 2.0 times or less

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: More than 30 times and less than 200 times

6: More than 200 times and less than 500 times

7: More than 500 times and less than 3000 times

8: More than 3000 times

A cone-and-plate sensor (cone angle of 1° is used for the 60mm diameter system, and 1° for the 35mm diameter system) is used for the viscosity of the flowable organic substance before the viscosity increase and stabilization and the viscosity of the viscosity increase and stabilization composition. A viscosity and viscoelasticity measuring device (rheometer) (trade name "RheoStress 600", manufactured by HAAKE Corporation) using a taper angle of 1°, 2°, and 4°) and a Peltier temperature controller was used in the Under the condition of 25°C, by the steady-flow viscosity measurement mode, the viscosity is measured by changing the shear rate from 0.001 to 100 (1/sec) on a logarithmic scale to obtain a viscosity curve. The viscosity at a shear rate of 10 (1/sec) was obtained from the viscosity curve, which was referred to as the viscosity of the present invention. In addition, each graph (plot) adopts the value at the time point when the torque value fluctuation of the apparatus was controlled within 5% and the data was stable.

Example 2, Comparative Examples 1~2

It carried out similarly to Example 1 except having changed the viscosity-enhancing stabilizer (1) to the viscosity-enhancing stabilizer described in the following table.

The above-mentioned results are put together and shown in the following table.

Compared with the viscosity-increasing stabilizer of the comparative example, the viscosity-increasing and stabilizer of the present invention can exert an excellent viscosity-increasing effect on a wide range of flowable organic substances. That is, there is a wide range of selectivity for viscosified flowable organic matter.

[Industrial Availability]

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

Claims (7)

A compound represented by the following formula (1), (R ² -HNOC) _4-n -R ¹ -(CONH-R ³ ) _n (1) (wherein, R ¹ is to remove 4 from the structural formula of benzene A base made of hydrogen atoms; n is an integer of 1 to 3; R ² is a linear or branched alkyl group with 1 to 4 carbon atoms, and R ³ is a linear or branched chain with 6 to 20 carbon atoms. alkenyl). A viscosity-increasing stabilizer comprising a compound represented by the following formula (1'), (R ² -HNOC) _4-n -R ¹ -(CONH-R ³ ) _n (1') (in the formula, R ¹ is A base obtained by removing 4 hydrogen atoms from the structural formula of cyclohexane; R ² is an aliphatic hydrocarbon group with 1 to 4 carbon atoms; R ³ is an aliphatic hydrocarbon group with a carbon number of 6 or more; n is an integer of 1 to 3) . A viscosity-enhancing stabilizer comprising the compound of claim 1. A tackifying and stabilizing composition comprising the tackifying and stabilizing agent as claimed in item 2 or 3 and a viscosity (η) of less than 0.1Pa according to a rheometer at a shear rate of 10 (1/sec) at 25°C. The flowable organic substance of s, wherein relative to 1000 parts by weight of the flowable organic substance, the amount of the tackifier and stabilizer is 0.1 to 100 parts by weight. A method for producing a viscosity-increasing stabilizer composition, comprising making the viscosity-increasing stabilizer as claimed in item 2 or 3 and the viscosity (η) at a shear rate of 10 (1/sec) at 25°C according to a rheometer lower than 0.1Pa. S, the step of dissolving the flowable organic substances, wherein relative to 1000 parts by weight of the flowable organic substances, the amount of the viscosity increasing and stabilizer is 0.1-100 parts by weight. A kind of compound comprising 1,2,4,5-benzenetetracarboxylic acid-1,4-bis(butylamide)-2,5-bis(oleylamide) and 1,2,4,5-benzenetetracarboxylic acid Acid-1,5-bis(butylamide)-2,4- Synthetic mixture of bis(oleylamide). A compound comprising 1,2,4,5-cyclohexanetetracarboxylic acid-1,4-bis(butylamide)-2,5-bis(oleylamide) and 1,2,4,5-cyclohexane Synthetic mixture of hexanetetracarboxylic acid-1,5-bis(butylamide)-2,4-bis(oleylamide).