JP2023043952A - Amide compound and thickener containing said amide compound - Google Patents

Abstract

To provide a novel compound that can impart thickeness with restorability to fluidity substance.SOLUTION: Provided is a compound represented by the following formula (1). In formula (1), R1 represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms. R2 and R4 are the same or different and represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms. R3 represents a divalent hydrocarbon group having 2 to 8 carbon atoms. R5 represents a group represented by (R12)(R13)NC(=O)R11-- formula (r5-1). [In formula (r5-1), R11 and R13 represent an aliphatic hydrocarbon group, and R12 represents a hydrogen atom or an aliphatic hydrocarbon group.].SELECTED DRAWING: None

Description

The present disclosure relates to novel amide compounds, thickeners comprising said amide compounds, and compositions comprising said amide compounds and flowable materials.

A low-molecular-weight compound that physically gels a fluid substance is known. Such low-molecular-weight compounds are called thickeners. The thickener causes gelation by physically forming a crosslinked structure through self-organization. Gelation by a thickener is used for adjusting fluidity in fields such as cosmetics, pharmaceuticals, agricultural chemicals, foods, adhesives, and paints.

As the thickening agent, for example, 12-hydroxystearic acid is known (Patent Document 1). 12-Hydroxystearic acid is mainly used for the disposal of edible oil for its gelling action. However, 12-hydroxystearic acid could not adjust the degree of gelation, and could only be induced to either completely solidify or remain liquid. Once solidified, it has been difficult to regain fluidity even if a shearing force is applied thereafter. Therefore, there has been a demand for a thickener capable of imparting thickening with resilience.

JP-A-01-163111

Accordingly, an object of the present disclosure is to provide a novel compound capable of imparting a restoring thickening to a fluid substance.
Another object of the present disclosure is to provide a thickening agent capable of imparting thickening with resilience to a fluid substance.
Another object of the present disclosure is to provide a composition containing a fluid substance that is thickened with resilience.

As a result of intensive studies by the present inventors in order to solve the above problems, the compound represented by the following formula (1) has a well-balanced solubility and self-organizing ability in fluid substances. , it has been found that it is possible to impart thickening with resilience to fluid substances. The present disclosure has been completed based on these findings.

［式（１）中、Ｒ¹は炭素数１～２２の１価脂肪族炭化水素基を示す。Ｒ²、Ｒ⁴は、同一又は異なって、水素原子又は炭素数１～３の１価脂肪族炭化水素基を示す。Ｒ³は炭素数２～８の２価炭化水素基を示す。Ｒ⁵は下記式（ｒ５－１）又は（ｒ５－２）で表される基を示す］

（式（ｒ５－１）中、Ｒ¹¹は炭素数２～６の２価脂肪族炭化水素基を示す。Ｒ¹²は水素原子又は炭素数１～３の１価脂肪族炭化水素基を示す。Ｒ¹³は炭素数１～２２の１価脂肪族炭化水素基を示す）
（式（ｒ５－２）中、Ｒ¹⁴は炭素数１～２２の２価脂肪族炭化水素基を示し、Ｒ¹⁵は水素原子又は炭素数１～２２の１価脂肪族炭化水素基を示す。ｎは１以上の整数を示す） That is, the present disclosure provides compounds represented by the following formula (1).

[In formula (1), R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms. R ² and R ⁴ are the same or different and represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms. R ³ represents a divalent hydrocarbon group having 2 to 8 carbon atoms. R ⁵ represents a group represented by the following formula (r5-1) or (r5-2)]

(In formula (r5-1), R ¹¹ represents a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms, and R ¹² represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms. R ¹³ represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms)
(In formula (r5-2), R ¹⁴ represents a divalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, and R ¹⁵ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms. n represents an integer of 1 or more)

The present disclosure also provides a thickening agent comprising said compound.

The disclosure also provides a composition comprising the compound and a flowable material.

The present disclosure also provides the composition, wherein the total content of the compounds is 0.1 to 10 parts by weight with respect to 100 parts by weight of the fluid material.

The present disclosure also provides that the viscosity (1) at a shear rate of 1.1 (1/s) when the shear rate is increased from 0.1 (1/s) to 100 (1/s) at 25°C is Provide the composition above 0.1 Pa·s.

The present disclosure also provides viscosity (1) at a shear rate of 1.1 (1/s) when the shear rate is increased from 0.1 (1/s) to 100 (1/s) at 25°C and , The ratio of viscosity (2) at a shear rate of 1.1 (1/s) when the shear rate is lowered from 100 (1/s) to 0.1 (1/s) (former/latter) is 15 or less The composition is provided.

The present disclosure also provides the composition having a haze value of 80% or less.

The compound represented by the following formula (1) has excellent solubility in fluid substances (particularly medium-polarity oils) and high self-organizing power. Therefore, by using the compound represented by the following formula (1) as a thickening agent, it is possible to impart a restoring thickening property to the fluid substance. The fluid substance imparted with resilience and thickening in this manner can be suitably used as a base material in the fields of cosmetics, pharmaceuticals, agricultural chemicals, foods, adhesives, paints, and the like.

¹ H-NMR data of compound (1-1c) obtained in Example. ¹ H-NMR data of compound (1-2a) obtained in Example.

［式（１）中、Ｒ¹は炭素数１～２２の１価脂肪族炭化水素基を示す。Ｒ²、Ｒ⁴は、同一又は異なって、水素原子又は炭素数１～３の１価脂肪族炭化水素基を示す。Ｒ³は炭素数２～８の２価炭化水素基を示す。Ｒ⁵は下記式（ｒ５－１）又は（ｒ５－２）で表される基を示す］

（式（ｒ５－１）中、Ｒ¹¹は炭素数２～６の２価脂肪族炭化水素基を示す。Ｒ¹²は水素原子又は炭素数１～３の１価脂肪族炭化水素基を示す。Ｒ¹³は炭素数１～２２の１価脂肪族炭化水素基を示す）
（式（ｒ５－２）中、Ｒ¹⁴は炭素数１～２２の２価脂肪族炭化水素基を示し、Ｒ¹⁵は水素原子又は炭素数１～２２の１価脂肪族炭化水素基を示す。ｎは１以上の整数を示す） [Compound (1)]
Compound (1) of the present disclosure is a compound represented by the following formula (1).

[In formula (1), R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms. R ² and R ⁴ are the same or different and represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms. R ³ represents a divalent hydrocarbon group having 2 to 8 carbon atoms. R ⁵ represents a group represented by the following formula (r5-1) or (r5-2)]

(In formula (r5-1), R ¹¹ represents a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms, and R ¹² represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms. R ¹³ represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms)
(In formula (r5-2), R ¹⁴ represents a divalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, and R ¹⁵ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms. n represents an integer of 1 or more)

Therefore, the compound (1) of the present disclosure includes a compound represented by the following formula (1-1) (hereinafter sometimes referred to as "compound (1-1)") and a compound represented by the following formula (1-2) The represented compound (hereinafter sometimes referred to as "compound (1-2)") is included. R ¹ to R ⁴ , R ¹¹ to R ¹⁵ and n in the following formula are the same as above.

The monovalent aliphatic hydrocarbon groups having 1 to 22 carbon atoms include saturated aliphatic hydrocarbon groups and unsaturated aliphatic hydrocarbon groups. Examples of the saturated aliphatic hydrocarbon group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, hexyl group, decyl group and dodecyl. and linear or branched alkyl groups such as groups. Examples of the unsaturated aliphatic hydrocarbon group include linear or branched alkenyl groups such as vinyl group, allyl group and 1-butenyl group; linear or branched alkynyl groups such as ethynyl group and propynyl group; groups.

The divalent aliphatic hydrocarbon group having 1 to 22 carbon atoms includes a linear or branched alkylene group, a linear or branched alkenylene group, and a linear or branched alkynylene group. Specific examples thereof include groups obtained by removing one hydrogen atom from the structural formula of the monovalent aliphatic hydrocarbon group.

Examples of the monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms include linear or branched alkyl groups.

The divalent aliphatic hydrocarbon group having 2 to 8 carbon atoms includes a divalent aliphatic hydrocarbon group, a divalent alicyclic hydrocarbon group, a divalent aromatic hydrocarbon group, and two selected from these A divalent group in which the above are bonded via a single bond is included. Examples of the divalent aliphatic hydrocarbon group include alkylene groups having 2 to 8 carbon atoms such as methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, tetramethylene group and hexamethylene group. is mentioned. Examples of the divalent alicyclic hydrocarbon group include cycloalkylene groups having 3 to 8 carbon atoms such as 1,2-cyclohexylene group, 1,3-cyclohexylene group and 1,4-cyclohexylene group. be done. Examples of the divalent aromatic hydrocarbon group include arylene groups such as o-phenylene, m-phenylene and p-phenylene.

R ¹ is preferably a branched-chain aliphatic hydrocarbon group, particularly preferably a branched-chain alkyl group, because of its excellent solubility in fluid substances. The branched-chain aliphatic hydrocarbon group (particularly, branched-chain alkyl group) is a group having at least one branch point. The number of branch points is, for example, 1 to 4, preferably 2 to 4, particularly preferably 3 to 4, in terms of excellent solubility in fluid substances.

In addition, the branched-chain aliphatic hydrocarbon group (particularly, the branched-chain alkyl group) has excellent solubility in a fluid substance, so the α-position (more specifically, the α-position of the adjacent carbonyl group) A group having a branch point at is preferred. In other words, the branched-chain aliphatic hydrocarbon group (particularly the branched-chain alkyl group) is preferably a group in which the α-position carbon is a tertiary carbon.

The number of carbon atoms in R ¹ is 1 to 22, and the lower limit of the number of carbon atoms is preferably 5, particularly preferably 9, most preferably 12, and most preferably 15 from the viewpoint of excellent solubility in fluid substances. be. The upper limit of the number of carbon atoms is preferably 20, particularly preferably 19, most preferably 18.

Hydrogen atoms are particularly preferred as R ² , R ⁴ and R ¹² in terms of having high self-organizing ability.

As R ³ , a divalent aliphatic hydrocarbon group or a divalent group in which an aliphatic hydrocarbon group and an aromatic hydrocarbon group are bonded via a single bond is preferable in terms of having high self-organizing ability. As the divalent aliphatic hydrocarbon group, an alkylene group is particularly preferred, and a linear alkylene group is particularly preferred.

The number of carbon atoms in R ³ is 2 to 8, and even numbers (2, 4, 6, or 8) are preferred, and 4 is particularly preferred, in terms of high self-organizing ability. Further, when R ³ has an odd number of carbon atoms (for example, 3), R ⁵ represents a group represented by formula (r5-1) in terms of high self-organizing power, and in the above formula preferably represents a linear saturated aliphatic hydrocarbon group having ¹⁶ to 24 carbon atoms.

In compound (1), when the number of carbon atoms in R ³ is an even number, the directions of the amide groups are aligned, so that the compounds (1) can form close hydrogen bonds with each other, resulting in high self-organizing ability. can be demonstrated.

As R ¹¹ , an alkylene group having 2 to 6 carbon atoms is preferable, an alkylene group having 2 to 4 carbon atoms is particularly preferable, and an alkylene group having 2 to 3 carbon atoms is particularly preferable.

R ¹³ is preferably a straight-chain aliphatic hydrocarbon group, particularly preferably a straight-chain unsaturated aliphatic hydrocarbon group, especially a straight-chain alkenyl group, in terms of excellent solubility in fluid substances. is preferred.

The number of carbon atoms in the monovalent aliphatic hydrocarbon group for R ¹³ is 1 to 22, and the lower limit of the number of carbon atoms is preferably 5, particularly preferably 9, most preferably 9, from the viewpoint of excellent solubility in fluid substances. is 12, particularly preferably 15. The upper limit of the number of carbon atoms is preferably 20, particularly preferably 19, most preferably 18.

（式中、ｓ、ｔは同一又は異なって、５～１０の整数を示す） As R ¹³ , a group represented by the following formula (r13-1) is preferable from the viewpoint of particularly excellent solubility in fluid substances.

(Wherein, s and t are the same or different and represent an integer of 5 to 10)

R ¹⁴ is preferably a divalent saturated aliphatic hydrocarbon group, more preferably a linear alkylene group.

The number of carbon atoms in R ¹⁴ is 1 to 22, and the lower limit of the number of carbon atoms is preferably 4, more preferably 6, and particularly preferably 8 from the viewpoint of excellent solubility in fluid substances. The upper limit of the number of carbon atoms is preferably 20, more preferably 18, particularly preferably 16, most preferably 14, particularly preferably 12.

R ¹⁵ is preferably a monovalent saturated aliphatic hydrocarbon group, particularly preferably a linear alkyl group.

The carbon number of R ¹⁵ is, for example, 1-22. The lower limit of the number of carbon atoms is preferably 2, more preferably 4 from the viewpoint of excellent solubility in fluid substances. The upper limit of the number of carbon atoms is preferably 16, more preferably 14, particularly preferably 12, most preferably 10, most preferably 8.

n is the number of repeating structural units shown in parentheses, preferably an integer of 1 to 3, particularly preferably 1 or 2, most preferably 1.

In the compound (1-1), the total number of carbon atoms of R ¹ and R ¹³ is preferably 16 or more, more preferably 20 or more, particularly preferably 27 or more, and most preferably, from the viewpoint of excellent solubility in fluid substances. is 30 or more.

In the compound (1-2), the total number of carbon atoms of R ¹⁴ and R ¹⁵ is preferably 10 or more, more preferably 12 or more, and particularly preferably 14 or more, from the viewpoint of excellent solubility in fluid substances. The upper limit of the total number of carbon atoms of R ¹⁴ and R ¹⁵ is, for example, 26, preferably 22, and particularly preferably 18.

Since the compound (1) of the present disclosure has the above structure, it has excellent solubility in fluid substances and excellent self-organizing ability. Therefore, by dissolving the compound (1) in a heated fluid material and cooling, the fluid material can be imparted with a thickening property having resilience. Therefore, the compound (1) can be suitably used as a thickening agent or a thickening agent.

The compound (1-1) in which R ¹² is a hydrogen atom can be produced, for example, through the following steps [1] to [3]. R ¹ to R ⁴ , R ¹¹ and R ¹³ in the following formula are the same as above. X represents a halogen atom.

The step [1] is a step of reacting the compound represented by the above formula (2) with the compound represented by the above formula (3) to produce the compound represented by the above formula (4).

The reaction is preferably carried out in the presence of a base. Examples of the base include organic bases such as triethylamine, pyridine and 4-dimethylaminopyridine. The amount of the base to be used is about 0.5 to 2.0 mol per 1 mol of the compound represented by the above formula (2) and the compound represented by the above formula (3).

Water is produced as the reaction proceeds. Therefore, it is preferable to carry out the reaction while removing water using a dehydrating agent (eg, acetic anhydride) in order to promote the progress of the reaction.

The reaction is preferably carried out in the presence of a solvent. Examples of solvents include pentafluorophenol, N,N-dimethylformamide, dimethylacetamide, o-dichlorobenzene and the like. These can also be used individually by 1 type, and can also be used in combination of 2 or more type.

The step [2] is a step of reacting the compound represented by the above formula (4) with the compound represented by the above formula (5) to produce the compound represented by the above formula (6).

The reaction is preferably carried out in the presence of a solvent. Solvents include, for example, nitrile solvents such as acetonitrile and propionitrile. These can also be used individually by 1 type, and can also be used in combination of 2 or more type.

The step [3] is a step of reacting the compound represented by the above formula (6) with the compound represented by the above formula (7) to produce the compound (1-1).

The reaction is preferably carried out in the presence of a base. Examples of the base include the same examples as the base used in step [1]. The amount of the base to be used is about 0.5 to 2.0 mol per 1 mol of the compound represented by the above formula (6) and the compound represented by the above formula (7).

The reaction is preferably carried out in the presence of a solvent. Examples of solvents include alcohol solvents such as methanol, ethanol, propanol and butanol. These can also be used individually by 1 type, and can also be used in combination of 2 or more type.

The compound (1-2) can be produced, for example, through the following steps [1'], [2'] and [3']. R ¹ to R ⁴ , R ¹⁴ , R ¹⁵ and n in the following formula are the same as above. X represents a halogen atom. In the formula below, R' represents an alkyl group having 1 to 5 carbon atoms.

The step [1'] is a step of reacting the compound represented by the formula (8) with an alcohol (R'OH; for example, methanol) to produce the compound represented by the formula (9).

Water is produced as the reaction proceeds. Therefore, it is preferable to carry out the reaction while removing water using a dehydrating agent (eg, sulfuric acid) in order to promote the progress of the reaction.

The step [2'] is a step of reacting the compound represented by the above formula (9) with the compound represented by the above formula (5) to produce the compound represented by the above formula (10).

The step [3'] is a step of reacting the compound represented by the above formula (10) with the compound represented by the above formula (7) to produce the compound (1-2).

The reaction is preferably carried out in the presence of a base. Examples of the base include organic bases such as triethylamine, pyridine and 4-dimethylaminopyridine. The amount of the base to be used is about 0.5 to 2.0 mol per 1 mol of the compound represented by the above formula (10) and the compound represented by the above formula (7).

After completion of the reaction in each step, the obtained reaction product can be separated and purified by general precipitation, washing, and filtration.

[Thickener]
The thickener of the present disclosure includes compound (1) above. The above compound (1) may contain one type alone, or may contain two or more types in combination.

The thickening agent is a compound having the action of increasing the viscosity of a fluid substance and imparting a thickening effect to the fluid substance. The thickening agent may be a thickening agent.

The thickener may contain other components in addition to the compound (1), but the proportion of the compound (1) in the total amount of the thickener is, for example, 60% by weight or more, preferably 70% by weight. Above, particularly preferably 80% by weight or more, most preferably 90% by weight or more, particularly preferably 99% by weight or more.

[Composition]
The composition of the present disclosure is a composition containing the compound (1) and a fluid substance, preferably a thick composition in which the fluid substance is thickened by the compound (1).

The fluid substance is not particularly limited, but is, for example, an organic substance having a rheometer viscosity [viscosity (η) at 25° C. and a shear rate of 10 (1/s)] of 0.1 Pa·s or less.

Examples of the fluid substance include alcohols (monohydric alcohols such as methanol, ethanol, propanol and butanol; dihydric alcohols such as ethylene glycol; polyhydric alcohols such as glycerin), hydrocarbon oils (hexane, cyclohexane, isododecane, Benzene, toluene, poly-α-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, castor oil, beef tallow, jojoba oil, sesame oil, squalane, etc.), silicone oil (dimethylpolysiloxane, methylphenylpolysiloxane, decamethylcyclopentasiloxane, etc.), esters (octyl oleate) dodecyl, cetyl octanoate, cetyl ethylhexanoate, glyceryl triisooctanate, neopentyl glycol diisooctanate, etc.), aromatic carboxylic acids, pyridine and the like. These can be used individually by 1 type or in combination of 2 or more types.

The fluid substance is preferably a medium or high polar fluid organic substance, for example, an IOB (Inorganic/Organic Balance) of 0.05 or more (IOB The upper limit of is preferably 1.0) for the fluid organic substance.

Among them, the fluid substance preferably contains at least animal and vegetable oils and/or alcohol, and more than 50% by weight (preferably 60% by weight or more, particularly preferably 70% by weight or more, most preferably 80% by weight or more, particularly preferably 90% by weight or more).

The compound (1) may contain one type alone, or may contain two or more types in combination. Preferred combinations when the compound (1) contains two kinds of compounds include, for example, the following combinations.
1. a compound (1-1) in which R ³ has an even number of carbon atoms (for example, 2) and R ¹ has 1 to 12 carbon atoms; 2. a combination of compounds in which R ³ has an even number of carbon atoms (for example, 2) and R ¹ has 13 to 22 carbon atoms; A compound (1-1) in which R ³ has an odd number of carbon atoms (eg, 3), R ¹ has 1 to 12 carbon atoms, and R ¹³ has 1 to 17 carbon atoms (preferably is an aliphatic hydrocarbon group of 7 to 17) and a compound (1-1) in which the number of carbon atoms in R ³ is an odd number (for example, 3) and the number of carbon atoms in R ¹ is 1 to 12, and R ¹³ is an aliphatic hydrocarbon group having 18 to 22 carbon atoms.

When the compound (1) contains two compounds, the mixing ratio (weight ratio) of the two compounds is, for example, 90/10 to 10/90, preferably 80/20 to 20/80, particularly preferably is 70/30 to 30/70, most preferably 60/40 to 40/60.

The compounding amount of the compound (1) (the total amount when two or more are contained) depends on the type of the fluid material, but for 100 parts by weight of the fluid material, for example, 0.1 to 10 parts by weight, It is preferably 0.5 to 5 parts by weight.

In addition to the compound (1) and the fluid substance, the composition may contain one or two or more other components within a range that does not impair the effects of the present disclosure. Other ingredients include, for example, general compounds (e.g., medicinal ingredients, pigments, fragrances, etc.) contained in compositions that desire to impart thickening, such as cosmetics, pharmaceuticals, agricultural chemicals, foods, adhesives, and paints. mentioned.

The compound (1) can be dissolved in the fluid material by mixing the compound (1) and the fluid material and stirring the mixture while heating at, for example, 60 to 100°C. After the above compound (1) is dissolved in the fluid material, it can be cooled to develop a thickening, thereby obtaining the thickening composition of the present disclosure. Cooling may be carried out as long as it can be cooled to 25° C. or lower, and it may be gradually cooled at room temperature, or rapidly cooled by ice cooling or the like.

As the fluid substance, if a fluid substance having excellent solubility of compound (1) is selected and used, excellent transparency (haze value is, for example, 80% or less, preferably 40% or less, particularly preferably is 20% or less) can produce a thick composition.

The viscosity (1) at a shear rate of 1.1 (1/s) when the shear rate of the composition is increased from 0.1 (1/s) to 100 (1/s) at 25°C is , for example, more than 0.1 Pa·s, preferably 1.0 Pa·s or more, particularly preferably 5.0 Pa·s or more, and most preferably 10.0 Pa·s or more. The upper limit of viscosity (1) is, for example, 100 Pa·s, preferably 80 Pa·s, particularly preferably 70 Pa·s.

The viscosity (2) at a shear rate of 1.1 (1/s) when the shear rate of the composition is lowered from 100 (1/s) to 0.1 (1/s) at 25°C is For example, it is 0.08 Pa·s or more, preferably 0.1 Pa·s or more, particularly preferably 1.0 Pa·s or more, and most preferably 2.0 Pa·s or more. The upper limit of viscosity (2) is, for example, 50 Pa·s, preferably 40 Pa·s, and particularly preferably 30 Pa·s.

The ratio of the viscosity (1) to the viscosity (2) [viscosity (1)/viscosity (2); rate of change] is preferably low in terms of excellent restorability, for example 15 or less, preferably 12 or less, more preferably is 10 or less, particularly preferably 7 or less, most preferably 5 or less.

Said viscosity can be measured using a rheometer.

The composition has a configuration in which the fluid substance is thickened by the compound (1). The thickening has resilience, and when a shearing force is applied, the fluidity increases and the thickness decreases.

Since the composition has the properties described above, it can be suitably used for cosmetics, pharmaceuticals, agricultural chemicals, foods, adhesives, and paints.

As described above, each configuration and combination thereof of the present disclosure are examples, and addition, omission, replacement, and modification of the configuration are possible as appropriate without departing from the gist of the present disclosure.

Hereinafter, the present disclosure will be described more specifically with reference to examples, but the present disclosure is not limited by these examples, but only by the description of the claims.

Example 1
Oleylamine (compound represented by formula (2a) below, 47.0 g, 175 mmol) and triethylamine (26.7 g, 363 mmol) were dissolved in DMF (50 mL). A DMF (100 mL) solution of succinic anhydride (compound represented by the following formula (3a), 19.3 g, 199 mmol) was added dropwise to this solution at 50° C. over 10 minutes. After stirring for 10 minutes, acetic anhydride (23.3 g, 228 mmol) was added and stirred at 50°C for 20 minutes. The dissolved reaction mixture was poured into 300 mL of 2N HCl, extracted with ethyl acetate (150 mL x 3), the extract was concentrated and dried under reduced pressure. As a result, compound (4a) (compound represented by formula (4a) below, 53.5 g, 153 mmol) was obtained with a yield of 87%.

Compound (4a) (compound represented by formula (4a) below, 50.0 g, 143 mmol) and ethylenediamine (compound represented by formula (5a) below, 34.4 g, 572 mmol) were dissolved in 30 mL of acetonitrile. Refluxed for hours. The reaction solution was poured into 300 mL of acetonitrile, cooled to 0° C., and the solid produced was collected by filtration. The resulting solid was dissolved in 2-propanol at 80° C. and filtered. 2-Propanol was removed under reduced pressure and purified by recrystallization with acetonitrile. As a result, compound (6a) (compound represented by formula (6a) below, 42.2 g, 103 mmol) was obtained as a white crystalline powder with a yield of 72%.

Compound (6a) (compound represented by formula (6a) below, 8.7 g, 21.2 mmol) and triethylamine (3.44 g, 34.0 mmol) were dissolved in 50 mL of 2-propanol. To this solution, isostearoyl chloride (8.36 g, 21.2 mmol of the compound represented by the following formula (7a)) was added dropwise at room temperature over 15 minutes. The reaction solution was poured into 500 mL of 1N HCl at 50° C. and stirred. The mixed solution was cooled to 0° C. and the obtained solid was washed with distilled water. The solid was purified by recrystallization with ethyl acetate to give compound (1-1a) (compound represented by the following formula (1-1a), 12.4 g, 18.3 mmol) as a white crystalline powder, yield 86%. I got it in FIG. 1 shows the results of ¹ H-NMR (400 MHz, CDCl ₃ ) measurement of the obtained compound (1-1a).

Example 2
Compound (6a) was obtained in the same manner as in Example 1.

The obtained compound (6a) (10.8 g, 26.4 mmol) and triethylamine (4.26 g, 42.2 mmol) were dissolved in 50 mL of 2-propanol. 2-Ethylhexanoyl chloride (5.57 g, 34.3 mmol) of the compound represented by the following formula (7b) was added dropwise to this solution at room temperature over 15 minutes. The reaction solution was poured into 500 mL of 1N HCl at 50° C. and stirred. The mixed solution was cooled to 0° C. and the obtained solid was washed with distilled water. The solid was purified by recrystallization with ethyl acetate to give compound (1-1b) (compound represented by the following formula (1-1b), 12.7 g, 23.7 mmol) as a white crystalline powder with a yield of 90%. Obtained.

Examples 3-10
The following compounds (1-1c) to (1-1j) were obtained in the same manner as in Examples 1 and 2. FIG. 1 shows the results of ¹ H-NMR (400 MHz, CDCl ₃ ) measurement of the following compound (1-1c).

Example 11
12-Hydroxystearic acid (40.0 g, 166 mmol) was dissolved in methanol (150 mL) by heating. A solution of sulfuric acid (10.0 g, 102 mmol) in methanol (100 mL) was added dropwise to this solution and refluxed for 24 hours. This reaction solution was poured into 1 L of water cooled to 0° C. with stirring, and the solid produced was collected by filtration. The resulting solid was dried and purified by recrystallization with n-hexane. As a result, a white crystalline powder of the methyl ester was obtained with a yield of 85% (44.4 g, 141 mmol).

12-Hydroxystearic acid methyl ester (20.0 g, 63.6 mmol) was dissolved in ethylenediamine (38.2 g, 636 mmol) and refluxed for 30 hours. After dissolving the reaction solution in 2-propanol (100 mL), the insoluble matter was filtered. Unreacted ethylenediamine and 2-propanol were removed from the filtrate using an evaporator, and the filtrate was purified by recrystallization with acetonitrile. The amine was obtained as a white crystalline powder with a yield of 90% (19.6 g, 57.2 mmol).

Amine form (5.00 g, 14.6 mmol) and triethylamine (2.95 g, 29.2 mmol) were dissolved in 50 mL of 2-propanol:water (5:1). To this solution was added isostearoyl chloride (8.36 g, 21.2 mmol) dropwise over 15 minutes at room temperature. The reaction solution was poured into 100 mL of water and stirred. The mixed solution was cooled to 0° C. and the resulting solid was filtered. The solid was purified by recrystallization with acetone to give a compound (1-2a) (compound represented by the following formula (1-2a)) as a white crystalline powder with a yield of 79% (7.02 g, 11.5 mmol). I got it in FIG. 2 shows the results of ¹ H-NMR (400 MHz, CDCl ₃ ) measurement of the obtained compound (1-2a).

Examples 12-17
The following compounds (1-2b) to (1-2g) were obtained in the same manner as in Example 11.

Comparative Examples 1 and 2
The following compounds (x1) and (x2) were obtained in the same manner as in Example 11.

Example 18
As a thickener, 0.2 g of the compound (1-1a) obtained in Example 1 was dissolved in 20 g of olive oil (IOB=0.16) at 80° C. and cooled to room temperature to obtain a composition.

Examples 19-34, Comparative Examples 3, 4, 5
A composition was obtained in the same manner as in Example 18, except that the compound shown in Table 1 below was used as the thickener instead of compound (1-1a). In Comparative Example 5, a composition was obtained in the same manner as in Example 18, except that no thickening agent was used.

Examples 35 and 36
Two types of compounds listed in Table 1 below were used as thickeners. For these two compounds, 0.2 g of each compound was dissolved in 20 g of olive oil (IOB=0.16) at 80° C. to obtain a melt, the resulting melts were mixed 1:1, and then The composition was obtained by cooling to room temperature.

The obtained composition was evaluated for transparency, shear viscosity and restorability. The results are summarized in the table below.

Evaluation of transparency was made according to the following criteria. The haze value was measured by placing the composition in a quartz cell using a haze meter (trade name: "NDH4000", manufactured by Nippon Denshoku Industries Co., Ltd.).
<Evaluation criteria>
◎: haze value is less than 20% ○: haze value is 20% or more and less than 40% △: haze value is 40% or more and less than 80% ×: haze value is 80% or more

The shear viscosity is measured using a rheometer at 25°C at a shear rate of 1.1 (1/s) when the shear rate is increased from 0.1 (1/s) to 100 (1/s). Viscosity (1) and viscosity (2) at a shear rate of 1.1 (1/s) when the shear rate was lowered from 100 (1/s) to 0.1 (1/s) were measured.

Using the viscosities (1) and (2) obtained using a rheometer, the rate of change was calculated from the following formula to evaluate the restorability. In addition, the one where the value of change rate is low is excellent in restorability.
Rate of Change = Shear Viscosity (1)/Shear Viscosity (2)

Claims (7)

A compound represented by the following formula (1).

[In formula (1), R ¹ represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms. R ² and R ⁴ are the same or different and represent a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms. R ³ represents a divalent hydrocarbon group having 2 to 8 carbon atoms. R ⁵ represents a group represented by the following formula (r5-1) or (r5-2)]

(In formula (r5-1), R ¹¹ represents a divalent aliphatic hydrocarbon group having 2 to 6 carbon atoms, and R ¹² represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms. R ¹³ represents a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms)
(In formula (r5-2), R ¹⁴ represents a divalent aliphatic hydrocarbon group having 1 to 22 carbon atoms, and R ¹⁵ represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 22 carbon atoms. n represents an integer of 1 or more) A thickening agent comprising the compound of claim 1 . A composition comprising a compound of claim 1 and a flowable material. The composition according to claim 3, wherein the total content of the compound according to claim 1 is 0.1-10 parts by weight with respect to 100 parts by weight of the fluid material. At 25 ° C., the viscosity (1) at a shear rate of 1.1 (1 / s) when the shear rate is increased from 0.1 (1 / s) to 100 (1 / s) is more than 0.1 Pa s 5. The composition of claim 3 or 4, wherein At 25 ° C., viscosity (1) at a shear rate of 1.1 (1 / s) when the shear rate is increased from 0.1 (1 / s) to 100 (1 / s), and a shear rate of 100 ( 1/s) to 0.1 (1/s), the ratio (former/latter) of viscosity (2) at a shear rate of 1.1 (1/s) is 15 or less. 6. The composition according to any one of 1 to 5. The composition according to any one of claims 3 to 6, which has a haze value of 80% or less.

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