TW201711991A - Viscosity stabilizer and viscosity stabilization composition using same which provides a compound thickening or gelling a flowing organic substance into the expected viscosity or uniformly stabilizing the composition containing the flowing organic substance - Google Patents

Abstract

The present invention provides a compound thickening or gelling a flowing organic substance into the expected viscosity or uniformly stabilizing a composition containing the flowing organic substance, a viscosity stabilizer containing the aforementioned compound, a viscosity stabilization composition containing the aforementioned viscosity stabilizer and the flowing organic substance, and manufacturing method thereof. The compound of the present invention is represented by the below-mentioned formula (1): (R 2 -HNOC)4-n-R 1 -(CONH-R 3 )n (in the formula, R1 is a group formed by deleting four hydrogen atoms from the structure formula of an aromatic hydrocarbon or a cyclic hexane, R2 is an aliphatic hydrocarbon having 1-4 carbon atoms, and R3 is an aliphatic hydrocarbon having 6 or more carbon atoms; n is an integer of 1~3).

Description

Viscosity stabilizer, and viscosity-increasing composition thereof

The present invention relates to a novel compound having an action of imparting viscosity-enhancing stability to a fluid organic substance such as oil, and an adhesion-enhancing stabilizer using the same, and a viscosity-enhancing composition containing the same.

The method of increasing the viscosity of the liquid is an important technique in the industry. For example, the beauty and the salad dressing of the quasi-stabilized state emulsion can maintain the emulsified state for a long time, because the aqueous component is given The reason for increasing viscosity is stability. Therefore, various viscosity-enhancing stabilizers have been developed. As the viscosity-enhancing stabilizer of the aqueous medium, for example, an alkyl acrylate copolymer or the like is known.

On the other hand, 12-hydroxystearic acid which is mainly used for waste treatment of edible oils is known as an viscosifying 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 be adjusted to the extent of gelation and can only be derived into either a fully cured or still liquid state.

[Previous Technical Literature] [Patent Literature]

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

Accordingly, it is an object of the present invention to provide a compound which viscosifies or gels a fluid organic substance to a desired viscosity or uniformly stabilizes a composition containing a fluid organic substance.

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

In order to solve the above problems, the present inventors have conducted intensive studies and found that a compound having a specific structure can thicken or gel a fluid organic substance or uniformly stabilize a composition containing a fluid organic substance. (=Prevent the sedimentation of the composition, local agglomeration or concentration, and maintain a uniform state in a stable manner); by using the type of the organic substance according to the fluidity, the viscosity of the fluid organic substance can be viscous or gelatinized. The desired viscosity is obtained, or the composition containing the fluid organic substance is uniformly stabilized. The present invention is based on the 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 four hydrogen atoms from a 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 a fat having 6 or more carbon atoms. a hydrocarbon group; n is an integer from 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 four hydrogen atoms from the structural formula of benzene or cyclohexane.

The present invention further provides an adhesion-enhancing stabilizer comprising the aforementioned compound.

The present invention further provides a viscosity-enhancing stabilization composition comprising the aforementioned viscosity-enhancing stabilizer and a fluid organic substance.

The present invention further provides a method of producing a viscosity-enhancing stabilization composition comprising the step of dissolving the viscosity-enhancing stabilizer with a fluid organic substance.

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 four hydrogen atoms from a 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 a fat having 6 or more carbon atoms. a hydrocarbon group; n is an integer from 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 a 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 linear or branched alkyl group, a linear or branched alkenyl group, or A linear or branched alkynyl group.

[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 carbon number 6 or more 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 chain having 6 to 20 carbon atoms or Branched alkenyl group.

[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 formulae (1-1) to (1-22). .

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

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

[10] A viscosity-enhancing 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 it is contained in two or more cases) is 0.5 weight of the total amount of the viscosity-increasing stabilizer %the above.

[12] A viscosity-enhancing stabilization composition comprising the viscosity-enhancing stabilizer and the fluid organic substance according to [10] or [11].

[13] The viscosity-increasing composition according to [12], wherein the fluid organic substance has a viscosity [at a viscosity (η) at 25 ° C and a shear rate of 10 (1/sec) at a shear rate of 10 (1/sec) at a low pressure of rheological meter]. At 0.1Pa‧s.

[14] The viscosity-increasing composition according to [12] or [13], wherein the fluid 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, anthrone oils, esters, aromatic carboxylic acids, and pyridine.

[15] The viscosity-enhancing composition according to any one of [12] to [14] wherein the content of the viscosity-increasing stabilizer is 0.1 to 100 parts by weight based on 1000 parts by weight of the fluid organic substance.

[16] A method for producing a viscosity-enhancing stabilization composition, comprising the step of allowing the viscosity-enhancing stabilizer according to [10] or [11] to be compatible with a fluid organic substance.

[17] A method for producing a viscosity-enhancing stabilization composition obtained by the step of allowing an adhesion-stabilizing agent as described in [10] or [11] to be compatible with a fluid organic substance, such as [12]~[15] The viscosity-enhancing composition described in any one of the above.

The compound represented by the formula (1) of the present invention can easily bind or gelatinize a fluid organic substance by being compatible with a fluid organic substance, or can uniformly stabilize a composition containing a fluid organic substance. Chemical. Further, by the compound which is thickened and stabilized by the compound represented by the formula (1) of the present invention, the state of being thickened or gelatinized can be stably maintained. 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, and by using the compound represented by the formula (1) of the present invention, The viscosity is adjusted to a desired range, the composition can be uniformly maintained, and the usability can be improved.

[Formation of the Invention]

[Compound represented by 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 four hydrogen atoms from a 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 group. 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 or a naphthalene ring, and a structure in which two or more aromatic rings are bonded through a single bond or a linking group.

Examples of the aforementioned linking group include a divalent hydrocarbon group, a carbonyl group (-CO-), an ether bond (-O-), a thioether bond (-S-), an ester bond (-COO-), and a guanamine. A bond (-CONH-), a carbonate bond (-OCOO-), and a group obtained by linking the plurality of bonds.

The divalent hydrocarbon group may, for example, be a linear chain having 1 to 18 carbon atoms such as a methylene group, a methylmethylene group, a dimethylmethylene group, an exoethyl group, a propyl group or a trimethylene group. a branched or branched alkyl group; and 1,2-cyclopentyl, 1,3-cyclopentyl, cyclopentylene, 1,2-extended cyclohexyl, 1,3-cyclohexylene, a cycloalkylene group having a carbon number of 3 to 18 such as a 1,4-cyclohexylene group or a cyclohexylene group (including a cycloalkylidene).

The aromatic hydrocarbon in R ¹ is preferably benzene, benzophenone, biphenyl or naphthalene, and particularly preferably benzene. Therefore, in the case of R ¹ of the present invention, a group in which four hydrogen atoms are removed from the structural formula of benzene or cyclohexane is preferred.

R ² is an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and examples thereof include a linear or branched group such as a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, and a tertiary butyl group. A linear alkyl group; a linear or branched alkenyl group such as a vinyl group, a propenyl group or a butenyl group; or a linear or branched alkynyl group such as an ethynyl group, a propynyl group or a butynyl group.

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

The compound represented by the formula (1) may, for example, be a compound represented by the following formula.

The compound represented by the formula (1), wherein the compound represented by the above formula (1-1) to (1-4), (1-19) to (1-22) is in a fluid organic substance It is preferable that the solubility is excellent, and when the fluid organic substance is transparent, it is preferable to impart pseudoplastic behavior and strong storage modulus while maintaining transparency, and it is particularly preferable that the above formula (1) -2) and / or (1-4), (1-20) and / or (1-22) compounds.

The compound represented by the 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 previously described) is reacted with sulfinium chloride to obtain cerium chloride carboxylic acid to give an amine (R ² -NH ₂ and R ³ -NH ₂ ; R ² , R ³ is the same as described above) method for reacting the obtained ruthenium chloride carboxylic acid

2. The amine (1) (R ² -NH ₂ or R ³ -NH ₂ ; R ² and R ^{3 are the} same as defined above) is reacted with a corresponding carboxylic acid anhydride to obtain a valine acid, and a condensing agent is used. amine (2) (when the amine (1) is an amine R _² -NH ² (2) R ³ -NH _2, when the amine (1) is an amine R ³ -NH ₂ (2) R _² -NH ² a method in which R ² and R ^{3 are the} same as described above)

The carboxylic acid used in the method of the above 1, specifically, 1,2,4,5-benzenetetracarboxylic 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 Wait.

The amine (R ² -NH ₂ ) used in the method of the above 1 may, for example, be methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, secondary butylamine or tertiary butylamine.

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

In the method of the above 1, the reaction of ruthenium carboxylate with an amine can be carried out, for example, by dropping ruthenium carboxylate into a system in which an amine has been charged.

The amount of the amine (the 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 the carboxylic acid chlorochloride. Further, by adjusting the ratio of use of R ² -NH ₂ and R ³ -NH ₂ , it is possible to control the (CONH-R ² ) group and the (CONH-R ³ ) group in the compound represented by the formula (1) obtained. Quantity.

The reaction of ruthenium carboxylate with an amine can be carried out in the presence or absence of a solvent. Examples of the solvent include a saturated or unsaturated hydrocarbon solvent such as pentane, hexane, heptane, octane or petroleum ether; an aromatic hydrocarbon solvent such as benzene, toluene or xylene; and dichloromethane; Halogenated hydrocarbon solvent such as chloroform, 1,2-dichloroethane, chlorobenzene or bromobenzene; diethyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, An ether-based solvent such as an alkane, 1,2-dimethoxyethane or cyclopentyl methyl ether; a nitrile-based solvent such as acetonitrile or benzonitrile; an anthraquinone solvent such as dimethyl hydrazine; A quinone-based solvent; a guanamine-based solvent such as dimethylformamide; a high-boiling solvent such as an oxime 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, preferably 100 to 250% by weight based on the total amount of the cerium chloride chloride and the amine. When the amount of the solvent used is outside the above range, the concentration of the reaction component becomes low, and the reaction rate tends to decrease.

The reaction of ruthenium carboxylate with an amine (= dropping) is usually carried out under normal pressure. In addition, the gas atmosphere in the above reaction (= at the time of dropping) is not particularly limited as long as it does not inhibit the reaction, and may be, for example, any of an air gas atmosphere, a nitrogen gas atmosphere, and an argon gas atmosphere. The reaction temperature (=temperature at the time of dropping) is, for example, about 30 to 60 °C. The reaction time (= dripping time) is, for example, about 0.5 to 20 hours. After the reaction (= dripping) is completed, a ripening step can also be set. When the ripening step is set, the ripening temperature is, for example, about 30 to 60 ° C, and the ripening time is, for example, about 1 to 5 hours. Further, the reaction can be carried out by any one of a batch type, a half batch type, and a continuous type.

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

In the production method of the above 2, for example, a carboxylic anhydride and an amine (1) and a solvent described below can be introduced into a system and matured to form a proline acid, and thereafter, an amine (2) and an amine (2) are charged. A compound represented by the formula (1) is produced by subjecting a condensing agent (for example, carbodiimide or a salt thereof) to aging.

The carboxylic acid anhydride used in the above method 2 may, for example, be 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, and the like.

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

The amount of the amine (1) used is, for example, 1 mol of the carboxylic anhydride. It is about 2 to 4 moles, preferably 2 to 3 moles. Further, the amount of the amine (2) to be used is, for example, about 2 to 4 moles, preferably 2 to 3 moles, per mole of the carboxylic anhydride.

The above 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 having 3 to 8 members which may have a substituent containing a hetero atom. R, R' may be the same or different. Further, R and R' may be bonded to each other and form a ring together with -N=C=N- group.

Examples of the linear or branched alkyl group having 3 to 8 carbon atoms include a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, and a pentyl group. Base, isopentyl, secondary pentyl, tertiary pentyl, hexyl, isohexyl, secondary hexyl, tertiary hexyl, and the like.

Examples of the cycloalkyl group having 3 to 8 members include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

The substituent containing a hetero atom may, for example, be a substituent containing a nitrogen atom such as a di(C _1-3 )alkylamino group such as an amine group or a dimethylamino group.

As the carbodiimide, for example, diisopropylcarbodiimide, dicyclohexylcarbodiimide, N-(3-dimethylaminopropyl)-N'-B can be mentioned. Base carbon diimine and the like. Further, as the salt of the carbodiimide, for example, a hydrochloride (specifically, N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide may be mentioned. Hydrochloride, etc.).

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

As the solvent, for example, a proton-accepting solvent excellent in solubility of lysine such as pyridine, triethylamine or tributylamine is preferably used. 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 the valine acid. When the amount of the solvent used is outside the above range, the concentration of the reaction component becomes low, and the reaction rate tends to decrease.

The above reaction is usually carried out under normal pressure. In addition, the gas atmosphere of the above reaction is not particularly limited as long as it does not inhibit the reaction, and may be, for example, any of an air gas atmosphere, a nitrogen gas atmosphere, and an argon gas atmosphere. The ripening temperature (reaction temperature) is, for example, about 30 to 70 °C. The aging time of the carboxylic anhydride and the amine is, for example, about 0.5 to 5 hours, and the ripening time of the valine acid and the amine is, for example, about 0.5 to 20 hours. Further, the reaction can be carried out by any one of a batch type, a semi-batch type, and a continuous type.

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

The compound represented by the formula (1) forms a fibrous self-organizing body by self-association at the indole bond site due to hydrogen bonding. Further, since the R ² group (an aliphatic hydrocarbon group having 1 to 4 carbon atoms) exhibits strong intermolecular hydrogen bonding, and the R ³ group (aliphatic hydrocarbon group having 6 or more carbon atoms) exhibits affinity for a fluid organic substance Therefore, by being compatible with the fluid organic substance, the fluid organic substance can be thickened or gelatinized, or the composition containing the fluid organic substance can be uniformly stabilized. Further, since the side chain has two kinds of groups (R ² and R ³ groups) which are different from each other, the side chain interaction is weakened and the crystallization is suppressed as compared with the case of having one type of group. Therefore, the solubility to the fluid organic substance is excellent, and the fluidity organic substance can be made to be thickened without any particular limitation. That is, it has a wide range of viscosity-enhancing fluid organic substances (viscosified organic substances). Further, when the fluid organic substance has transparency, the viscosity-enhancing stability can be achieved while maintaining the transparency thereof, and a viscosity-stabilizing composition which is stable over time can be formed. Therefore, for example, a viscosity-enhancing stabilizer (more specifically, a tackifier, a gelling agent or a stabilizer) as a fluid organic substance is useful. 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 4 identical groups as a side chain) Or even if the R ² and R ³ groups are different from each other, and the carbon number of at least one of the R ² and R ³ groups is outside the above range, the layer is easily crystallized due to the interaction of the side chains. The fluid organic substance capable of increasing viscosity and stability is limited, and the selectivity of the viscosity-increasing organic substance is narrowed, which is not preferable. Further, since it is complicated by the fact that it is compatible with the fluid organic substance and becomes cloudy, it is difficult to maintain the appearance. Furthermore, it is easy to change the viscosity with time.

[Adhesive stabilizer]

The viscosity-enhancing 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.

The viscosity-enhancing stabilizer of the present invention may contain other thickening stabilizers as needed in addition to the compound represented by the above formula (1), but in the total amount (100% by weight) of the thickening stabilizer of the present invention, Formula (1) The content of the compound (the total amount when it is contained in two or more kinds) 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, most preferably It is preferably 60% by weight or more, and more preferably 80% by weight or more. Further, 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 outside the above range, it is difficult to make the fluid organic substance thicken or gelatinize or to uniformly stabilize the composition containing the fluid organic substance.

Further, in the present invention, the "tackifying stabilizer" is a compound which dissolves into a fluid organic substance and generates viscosity, and the concept includes a tackifier which imparts viscosity to a fluid organic substance, and organicity of fluidity. A gelling agent that gels a substance and a stabilizer that enhances the viscosity of the composition containing the fluid organic substance to achieve uniform viscosity. Other thickening stabilizers include oligomers such as bases, hydroxy fatty acids, acrylic polymers, and dextrin fatty acid esters, and particles such as metal oxides.

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

The viscosity-enhancing stabilizer of the present invention can be used to thicken or gel the aforementioned fluid organic substance by being compatible with a fluid organic substance (preferably by mixing and heating to dissolve and then cooling). The fluid organic substance can be viscous or gelled to a desired viscosity for the intended use in a range of more than 30 times and 10,000 times or less (preferably more than 30 times and 5,000 times or less).

[Adhesion strengthening composition]

The viscosity-enhancing composition of the present invention comprises the above-mentioned viscosity-increasing stabilizer and a fluid organic substance, and the fluid organic substance is viscous, gelled or contains a fluid organic substance by the aforementioned viscosity-increasing stabilizer. The composition is uniformly stabilized composition.

The viscosity-enhancing composition of the present invention can be produced by a step of dissolving an adhesion-stabilizing agent with a fluid organic substance. More specifically, it can be produced by mixing a viscosity-sensitive stabilizer with a fluid organic substance (total amount), heating it, dissolving it, and then cooling it. Alternatively, it can be produced by mixing a part of a fluid organic substance with a viscosity-increasing stabilizer, heating it, dissolving it, cooling it to produce a viscosity-enhancing composition, and mixing it to the remainder. Mobility of organic matter.

The fluid organic substance as a raw material is an organic substance having a viscosity (η) at a shear rate of 10 (1/sec) at 25 ° C and a shear rate of 10 (1/sec), for example, an organic substance of less than 0.1 Pa s. : hydrocarbon oil (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.), anthrone (dimethyl group) Polyxantane, methylphenyl polyoxane, decyl ketone oil such as decamethylcyclopentanoxane, esters (octyl dodecyl oleate, cetyl octylate, cetyl ethyl hexanoate) An ester, a triisooctanoic acid glyceride, a neopentyl glycol diisooctanoate, a tricalyl tricaprate, or the like, an aromatic carboxylic acid, a pyridine or the like. These can be used alone or in combination of two or more.

The amount (or amount) of the viscosity-increasing stabilizer depends on the type of the fluid organic substance, but on the fluid organic substance. 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, most preferably 1 to 30 parts by weight. By mixing (or using) the tackifying stabilizer in the above range, a composition in which the fluid organic substance is viscosified or gelatinized, or a composition which is uniformly stabilized can be obtained.

The viscosity-enhancing composition of the present invention may contain other components in addition to the above-mentioned thickening stabilizer and the fluid organic substance, without damaging the effects of the present invention. For the other components, for example, general compounds (for example, medicinal ingredients, pigments, perfumes, and the like) contained in a composition which is desired to be thickened and stabilized, such as a cosmetic, a paint, a food, or a pharmaceutical, may be mentioned.

The temperature at the time of compatibility is suitably selected depending on the type of the viscosity-increasing stabilizer and the fluid organic substance to be used, and the temperature at which the viscosity-increasing stabilizer and the fluid organic substance are compatible is not particularly limited, but preferably not When it exceeds 100 ° C, when the boiling point of the fluid organic substance is 100 ° C or less, it is preferably about the boiling point.

The cooling after the compatibility may be cooled to 25 ° C or lower, or may be slowly cooled at room temperature, or may be rapidly cooled by ice cooling or the like.

Further, the viscosity (η) of the rheometer according to the rheological property of the viscosity-increasing composition of the present invention is preferably 0.5 to 10.0 Pa·s at 25 ° C and a shear rate of 10 (1/sec), preferably 0.5 to 10.0 Pa·s. When it is 1.0 to 8.0 Pa s, it can be adjusted in accordance with the use in the range of 30 times and 10,000 times or less (preferably more than 30 times and 5,000 times or less) of the viscosity of the fluid organic substance as a raw material.

For the viscosity-enhancing composition of the present invention, as long as it contains The fluid organic substance is not particularly limited as long as it is a composition which is desired to be thickened and stabilized, and examples thereof include cosmetics, paints, foods, and pharmaceuticals.

[Examples]

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

Synthesis Example 1 [Synthesis of Anti-adhesive Stability Agent (1) (1,2,4,5-Phenylenetetracarboxylic Acid Di(butylguanamine) Di(oleylguanamine)]

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

Thereafter, 2.1 g (0.028 mol) of butylamine and 7.0 g (0.056 mol) of diisopropylcarbodiimide were charged, followed by further aging for 8 hours.

Thereafter, the low boiling portion 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 di(butyl decylamine) 1,2,4,5-benzenetetracarboxylic acid. (oleyl decylamine) [1,2,4,5-benzenetetracarboxylic acid-1,4-bis(butyl decylamine)-2,5-di(oleyl decylamine) and 1,2,4, A mixture of 5-benzenetetracarboxylic acid-1,5-di(butylammonium)-2,4-di(oleylguanamine)] 7.3 g (yield: 61%). The structure of the reaction product was confirmed by ¹ H-NMR.

^{1 H-NMR (270MHz, 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 [Adhesive stabilizer (2) (1,2,4,5-cyclohexanetetracarboxylic acid) Synthesis of di(butyl decylamine) bis(oleyl decylamine))

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

Thereafter, 2.9 g (0.02 mol) of butylamine and 5.5 g (0.044 mol) of diisopropylcarbodiimide were charged, followed by further aging for 8 hours.

Thereafter, the low boiling portion 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-cyclohexanetetracarboxylic acid di(butyl decylamine). Di(oleyl decylamine) [1,2,4,5-cyclohexanetetracarboxylic acid-1,4-bis(butylguanamine)-2,5-di(oleyl decylamine) and 1, A mixture of 2,4,5-cyclohexanetetracarboxylic acid-1,5-di(butylammonium)-2,4-di(oleyl decylamine)] 11.6 g (yield: 67%). The structure of the reaction product was confirmed by ¹ H-NMR.

^{1 H-NMR (270MHz, 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 a viscosity-enhancing stabilizer (3) (1,2,4,5-benzenetetracarboxylic acid di(2-ethylhexylguanamine) bis(oleyl decylamine)]

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

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

Thereafter, the low boiling portion 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 di(2-ethylhexylfluorene). Amine) bis(oleyl decylamine) [1,2,4,5-benzenetetracarboxylic acid-1,4-bis(2-ethylhexyl decylamine)-2,5-di(oleyl decylamine) and a mixture of 1,2,4,5-benzenetetracarboxylic acid-1,5-di(2-ethylhexyldecylamine)-2,4-di(oleylguanamine)]5.9 g (yield: 51%) ). The structure of the reaction product was confirmed by ¹ H-NMR.

^{1 H-NMR (270MHz, 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 viscosity-increasing stabilizer (4) (1,2,4,5-benzenetetracarboxylic acid bis(hexyl decylamine) bis(oleyl decylamine)]

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

Thereafter, 2.8 g (0.028 mol) of hexylamine and 7.0 g (0.056 mol) of diisopropylcarbodiimide were charged, followed by further aging for 8 hours.

Thereafter, the low boiling portion 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(hexyl decylamine) II ( Oil-based decylamine) [1,2,4,5-benzenetetracarboxylic acid-1,4-bis(hexyl decylamine)-2,5-di(oleyl decylamine) and 1,2,4,5- A mixture of benzenetetracarboxylic acid-1,5-di(hexyldecylamine)-2,4-di(oleyl decylamine)] 8.1 g (yield: 64%). The structure of the reaction product was confirmed by ¹ H-NMR.

¹ H-NMR (270MHz, 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

Various liquid organic substances as shown in the table [mobile paraffin (viscosity: 0.14Pa‧s), isododecane (viscosity: 0.001Pa‧s), cetyl octanoate (viscosity: 0.012Pa‧s), three Triglyceride (viscosity: 0.023Pa‧s); either of them has a boiling point of 100 ° C or more. Each scale is taken from 1 cm ³ to a test tube, and 10 mg of the viscosity-increasing stabilizer obtained in the above synthesis example is added (1) The mixture was mixed and heated and stirred at 100 ° C to dissolve the fluid organic substance with the viscosity-increasing stabilizer (1), and cooled to 25 ° C to obtain a viscosity-increasing composition.

The viscosity of the obtained viscosity-increasing composition is as follows.

Viscosity-stabilizing composition of mobile paraffin: 4.84Pa‧s

Viscosity-stabilizing composition of isododecane: 1.98Pa‧s

Viscosity-stabilizing composition of cetyl octanoate: 2.48Pa‧s

Viscosity-stabilizing composition of triglyceride trihexanoate: 7.78 Pa‧s

The viscosity-increasing ratio was calculated from the following formula, and the viscosity-increasing property was evaluated according to the following evaluation criteria, and the evaluation of obtaining 5 or more of all the fluid organic substances was made to have a good viscosity-increasing effect (○), and other than The condition is that the viscosity-increasing effect is poor (×).

Viscosity increase ratio = viscosity of the viscosity-enhancing composition/viscosity of the fluid organic substance before the viscosity is stabilized

<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

The viscosity of the organic substance and the viscosity-increasing composition before the viscosity-enhancing stabilization is carried out using a cone-and-plate sensor (1° in the diameter of 60 mm and 35 mm in diameter). Using a cone angle of 1°, 2°, 4°) and a Peltier temperature controller, a viscoelasticity measuring device (rheometer) (trade name "RheoStress 600", manufactured by HAAKE), The viscosity curve was obtained by measuring the viscosity at a logarithmic scale from 0.001 to 100 (1/sec) in a steady-flow viscosity measurement mode at 25 ° C to obtain a viscosity curve. The viscosity curve was found to have a viscosity at a shear rate of 10 (1/sec), which was used as the viscosity of the present invention. Further, each plot is a value obtained by controlling the variation of the torque value of the device to be in the range of 5% and the time at which the data is stabilized.

Example 2, Comparative Example 1~2

The same procedure as in Example 1 was carried out except that the tackifier (1) was changed to the tackifier described in the following table.

The above results are summarized and shown in the following table.

Compared with the viscosity-enhancing stabilizer of the comparative example, the viscosity-enhancing stabilizer of the present invention can exert an excellent viscosity-increasing effect on a wide range of fluid organic substances. That is, it has a wide range of viscosity-enhancing organic matter selectivity.

[Industrial availability]

When the compound represented by the formula (1) of the present invention is compatible with a fluid organic substance, the fluid organic substance can be easily viscous or gelled or the composition containing the fluid organic substance can be uniformly stabilized. And can maintain a stable or gelatinized 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 (6)

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 self-aromatic hydrocarbon or cyclohexane The structural formula is a group in which four hydrogen atoms are removed; R ² is an aliphatic hydrocarbon group having 1 to 4 carbon atoms; and R ³ is an aliphatic hydrocarbon group having 6 or more carbon atoms; n is an integer of 1 to 3). The compound of claim 1, wherein the aromatic hydrocarbon in R ¹ is benzene, benzophenone, biphenyl, or naphthalene. The compound of claim 1, wherein R ¹ is a group derived from the structural formula of benzene or cyclohexane to remove four hydrogen atoms. An viscosifying stabilizer comprising the compound of any one of claims 1 to 3. An adhesion-enhancing composition comprising the viscosity-enhancing stabilizer of claim 4 and a fluid organic substance. A method of producing a viscosity-enhancing stabilization composition comprising the step of dissolving the viscosity stabilizer of claim 4 with a fluid organic material.