Compound and composition containing the same

Abstract

To provide a compound having excellent thickening effect.SOLUTION: The compound comprises an α-type or β-type polyaspartic acid monomer unit having a specific structure.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to compounds comprising polyaspartic acid monomer units and compositions comprising the same. [Background technology]

[0002] Polyacrylic acid polymers, such as carboxyvinyl polymers, have traditionally been used as thickeners in cosmetics, etc. Although a small amount of carboxyvinyl polymer can produce a moist gel, from the perspective of environmental considerations, biodegradable thickeners that can replace carboxyvinyl polymers are desired.

[0003] As biodegradable polymers, polyaspartic acid derivatives having specific structural units made from aspartic acid have been reported, and it has been reported that these polyaspartic acid derivatives have thickening and foaming properties (Patent Documents 1 and 2). [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-344061 [Patent Document 2] Japanese Patent Application Publication No. 2019-089897 Summary of the Invention [Problem to be solved by the invention]

[0005] However, it has been found that a sufficient thickening effect cannot be obtained with the polyaspartic acid derivatives of Patent Documents 1 and 2. Therefore, an object of the present disclosure is to provide a compound with an excellent thickening effect. [Means for solving the problem]

[0006] As a result of intensive research to solve the above problems, the inventors discovered that polyaspartic acid derivatives containing monomer units with specific structures have excellent thickening effects and can solve the above problems, thereby completing the invention of the present disclosure.

[0007] That is, the invention of the present disclosure is as follows. [1] A compound comprising an α- or β-polyaspartic acid monomer unit represented by the following general formula (1), an α- or β-polyaspartic acid monomer unit represented by the following general formula (2), an α- or β-polyaspartic acid monomer unit represented by the following general formula (3), and an α- or β-polyaspartic acid monomer unit represented by the following formula (4). [ka] (In the formula, R1 represents a hydrocarbon group having 2 to 6 carbon atoms.) [ka] (In the formula, R2 represents a hydrocarbon group having 8 to 16 carbon atoms.) [ka] (In the formula, R3 represents a hydrocarbon group having 14 to 22 carbon atoms, provided that the number of carbon atoms in R3 is greater than the number of carbon atoms in R2.) [ka] (In the formula, the wavy lines indicate crosslinking sites.) [2] The compound according to [1], further comprising an α-type or β-type polyaspartic acid monomer unit represented by the following general formula (5): [ka] (In the formula, R4 represents a hydrocarbon group having 2 to 8 carbon atoms. The hydrocarbon group may contain a heteroatom.) [3] The compound according to [1] or [2], wherein R1 is a linear or branched alkyl group. [4] The compound according to any one of [1] to [3], wherein R2 is a linear or branched alkyl group. [5] The compound according to any one of [1] to [4], wherein R3 is a linear or branched alkyl group. [6] The compound according to any one of [1] to [5], wherein, among the constituent monomers of the compound, the molar ratio of the amount of the monomer represented by the general formula (1) to the amount of the monomer represented by the general formula (2) is 1:6 to 2:1. [7] The compound according to any one of [1] to [6], wherein, among the constituent monomers of the compound, the molar ratio of the amount of the monomer represented by the general formula (2) to the amount of the monomer represented by the general formula (3) is 10:1 to 1:2. [8] The compound according to any one of [1] to [7], wherein, among the constituent monomers of the compound, the molar ratio of the amount of the monomer represented by the general formula (1) to the amount of the monomer represented by the general formula (3) is 10:1 to 1:4. [9] A composition containing the compound according to any one of [1] to [8]. [Effects of the Invention]

[0008] According to the present disclosure, a compound having an excellent thickening effect can be provided. DETAILED DESCRIPTION OF THE INVENTION

[0009] The present disclosure will be described in more detail below. Note that the present disclosure is not limited to the following embodiments.

[0010] The expressions "XX or more and YY or less" or "XX to YY" that represent a numerical range mean a numerical range including the endpoints, that is, the lower limit and the upper limit, unless otherwise specified. When numerical ranges are stated in stages, the upper and lower limits of each numerical range can be combined in any way.

[0011] <Compounds of the Present Disclosure> The present invention relates to a polymerizable composition comprising an α- or β-polyaspartic acid monomer unit represented by the following general formula (1) (also referred to as a “monomer unit represented by the general formula (1)”), a polymerizable composition comprising an α- or β-polyaspartic acid monomer unit represented by the following general formula (2), The compound (also referred to as "compound of the present disclosure") includes an α- or β-type polyaspartic acid monomer unit represented by the following general formula (1) (also referred to as "monomer unit represented by general formula (2)"), an α- or β-type polyaspartic acid monomer unit represented by the following general formula (3) (also referred to as "monomer unit represented by general formula (3)"), and an α- or β-type polyaspartic acid monomer unit represented by the following formula (4) (also referred to as "monomer unit represented by formula (4)"). That is, the compound of the present disclosure is a polyaspartic acid derivative including, as repeating units, a monomer unit represented by general formula (1), a monomer unit represented by general formula (2), a monomer unit represented by general formula (3), and a monomer unit represented by formula (4). Polyaspartic acid includes a polymer formed by peptide condensation polymerization of aspartic acid. The monomer unit represented by general formula (1) is a structure derived from amine A and polysuccinimide used in the production of the compound of the present disclosure, which will be described later. The monomer unit represented by general formula (2) is a structure derived from amine B and polysuccinimide used in the production of the compound of the present disclosure, which will be described later. The monomer unit represented by general formula (3) is a structure derived from amine C and polysuccinimide used in the production of the compound of the present disclosure, which will be described later. The monomer unit represented by formula (4) is a structure derived from a crosslinking agent and polysuccinimide used in the production of the compound of the present disclosure, which will be described later.

[0012] The compound of the present disclosure exhibits excellent thickening effects by including a monomer unit represented by general formula (1), a monomer unit represented by general formula (2), and a monomer unit represented by general formula (3). This is presumably because the introduction of hydrocarbon groups of different chain lengths, R1 in general formula (1), R2 in general formula (2), and R3 in general formula (3), suppresses intramolecular association due to steric hindrance of the polymer chain, thereby bending the polymer chain and promoting intermolecular association. Furthermore, it is presumed that R1 in general formula (1), the shortest hydrocarbon group, fills gaps in the association, resulting in stronger associations. Furthermore, the compound of the present disclosure exhibits improved thickening effects by including a monomer unit represented by formula (4).

[0013] [ka] (In the formula, R1 represents a hydrocarbon group having 2 to 6 carbon atoms.)

[0014] [ka] (In the formula, R2 represents a hydrocarbon group having 8 to 16 carbon atoms.)

[0015] [ka] (In the formula, R3 represents a hydrocarbon group having 14 to 22 carbon atoms, provided that the number of carbon atoms in R3 is greater than the number of carbon atoms in R2.)

[0016] [ka] (In the formula, the wavy lines indicate crosslinking sites.)

[0017] In general formula (1), R1 is not particularly limited as long as it is a hydrocarbon group having 2 to 6 carbon atoms, and may be saturated or unsaturated, and may be branched or linear.

[0018] The number of carbon atoms in the hydrocarbon group of R1 is 2 or more, preferably 3 or more. or less, and preferably 5 or less. For example, 2 to 6 or 3 to 5.

[0019] Specific examples of R1 include linear alkyl groups such as an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; branched alkyl groups such as an isopropyl group, an isobutyl group, an isopentyl group, and an isohexyl group; cycloalkylalkyl groups such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopropylmethyl group, a cyclopropylethyl group, a cyclopropylpropyl group, a cyclobutylmethyl group, a cyclobutylethyl group, and a cyclopentylmethyl group; and alkenyl groups such as an ethenyl group, a propenyl group, a butenyl group, a pentenyl group, and a hexenyl group. Among these, branched or straight chain alkyl groups are preferred, and straight chain alkyl groups are more preferred.

[0020] The compound of the present disclosure may contain one type of monomer unit represented by general formula (1) alone, or may contain two or more types.

[0021] The amount of the monomer unit represented by general formula (1) present in the constituent monomers of the compound of the present disclosure is preferably 1.0 mol% or more, more preferably 3.0 mol% or more, even more preferably 5.0 mol% or more, even more preferably 8.0 mol% or more, and most preferably 9.0 mol% or more. On the other hand, it is preferably 30.0 mol% or less, more preferably 27.0 mol% or less, even more preferably 25.0 mol% or less, even more preferably 23.0 mol% or less, and most preferably 20.0 mol% or less. For example, it is 1.0 mol% to 30.0 mol%, 3.0 mol% to 27.0 mol%, 5.0 mol% to 25.0 mol%, 8.0 mol% to 23.0 mol%, or 9.0 mol% to 20.0 mol%. Here, the term "constituent monomer of the compound of the present disclosure" refers to, among the monomers contained in the compound of the present disclosure, a monomer derived from polysuccinimide used in the production of the compound of the present disclosure, which will be described later (specifically, for example, a monomer unit represented by general formula (1), a monomer unit represented by general formula (2), a monomer unit represented by general formula (3), a monomer unit represented by formula (4), a monomer unit represented by general formula (5), and a monomer unit represented by formula (6), as well as a monomer unit derived from polysuccinimide that does not fall under these monomer units). The amount of the monomer unit represented by general formula (1) present can be calculated from the ratio (%) of the number of moles of amine A used in the production of the compound of the present disclosure to the number of moles of polysuccinimide used in the production of the compound of the present disclosure, which will be described later.

[0022] In general formula (2), R2 is not particularly limited as long as it is a hydrocarbon group having 8 to 16 carbon atoms. R2 may be saturated or unsaturated, and may be branched or linear. In addition, when the compound of the present disclosure contains three or more types of monomer units corresponding to both the monomer unit represented by general formula (2) and the monomer unit represented by general formula (3), among such monomer units, among the amines corresponding to both the amine B and the amine C used in the production of the compound of the present disclosure described below, the monomer units derived from the two amines with the largest charged amounts (mol %) are referred to as the "monomer unit represented by general formula (2)" and the "monomer unit represented by general formula (3)." However, of the two monomer units, the one with the larger number of carbon atoms in the hydrocarbon group corresponding to R2 and R3 is referred to as the "monomer unit represented by general formula (3)," and the one with the smaller number of carbon atoms is referred to as the "monomer unit represented by general formula (2)." That is, for example, when 1.0 mol % of an amine having 14 carbon atoms, 30.0 mol % of an amine having 15 carbon atoms, and 20.0 mol % of an amine having 16 carbon atoms are used in the production of a compound of the present disclosure, the monomer unit having 15 carbon atoms is defined as a "monomer unit represented by general formula (2)" and the monomer unit having 16 carbon atoms is defined as a "monomer unit represented by general formula (3)." The compound of the present disclosure may also be a compound having a monomer unit represented by general formula (2) and a monomer unit represented by general formula (3). In the case where a monomer unit contains three or more types of monomer units corresponding to all of the monomer units represented by general formula (1) and the three or more amines corresponding to all of amines B and amine C used in the production of the compound of the present disclosure that are charged in equal amounts (mol %), the monomer unit having the smallest number of carbon atoms in the hydrocarbon group corresponding to R2 and R3 among such monomer units is defined as the "monomer unit represented by general formula (2)," and the monomer unit having the hydrocarbon group with the next largest number of carbon atoms after the number of carbon atoms in R2 of the "monomer unit represented by general formula (2)" is defined as the "monomer unit represented by general formula (3)." That is, for example, when an amine having 14 carbon atoms, an amine having 15 carbon atoms, and an amine having 16 carbon atoms are used in the production of the compound of the present disclosure at 20.0 mol % each, the monomer unit having 14 carbon atoms is defined as the "monomer unit represented by general formula (2)," and the monomer unit having 15 carbon atoms is defined as the "monomer unit represented by general formula (3)."

[0023] The number of carbon atoms in the hydrocarbon group of R2 is 8 or more, preferably 9 or more, more preferably 10 or more, and even more preferably 11 or more. On the other hand, it is 16 or less, preferably 15 or less, more preferably 14 or less, and even more preferably 13 or less. For example, it is 8 to 16, 9 to 15, 10 to 14, or 11 to 13.

[0024] Specific examples of R2 include linear alkyl groups such as octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, and hexadecyl groups; branched alkyl groups such as isooctyl, isononyl, isodecyl, isoundecyl, isododecyl, isotridecyl, isotetradecyl, isopentadecyl, and isohexadecyl groups; cyclooctyl, cyclononyl, cyclodecyl, and cycloundecyl groups; Examples of such cycloalkyl groups include cyclododecyl, cyclotridecyl, cyclotetradecyl, cyclopentadecyl, and cyclohexadecyl groups; cycloalkylalkyl groups such as cyclohexylethyl, cyclohexylpropyl, cyclobutylbutyl, cyclopentylbutyl, and cyclohexylbutyl groups; and alkenyl groups such as octenyl, nonenyl, decenyl, undecenyl, tridecenyl, tetradecenyl, pentadecenyl, and hexadecenyl groups. Among these, branched or straight chain alkyl groups are preferred, and straight chain alkyl groups are more preferred.

[0025] The compound of the present disclosure may contain one or more types of monomer units represented by general formula (2), provided that when two or more types are contained, the number of carbon atoms in R2 is the same.

[0026] In the constituent monomers of the compounds of the present disclosure, the abundance of the monomer unit represented by the general formula (2) is preferably 5.0 mol% or more, more preferably 10.0 mol% or more, still more preferably 15.0 mol% or more, and even more preferably 20.0 mol% or more. On the other hand, it is preferably 60.0 mol% or less, more preferably 50.0 mol% or less, still more preferably 40.0 mol% or less, and even more preferably 30.0 mol% or less. For example, it is 5.0 mol% to 60.0 mol%, 10.0 mol% to 50.0 mol%, 15.0 mol% to 40.0 mol%, or 20.0 mol% to 30.0 mol%. Here, the "constituent monomers of the compounds of the present disclosure" refers to the monomers contained in the compounds of the present disclosure, among which are the monomers derived from poly(succinimide) used in the production of the compounds of the present disclosure described later (specifically, for example, the monomer unit represented by the general formula (1), the monomer unit represented by the general formula (2), the monomer unit represented by the general formula (3), the monomer unit represented by the formula (4), the monomer unit represented by the general formula (5), and the monomer unit represented by the formula (6), as well as the monomer units derived from poly(succinimide) that do not correspond to these monomer units). The abundance of the monomer unit represented by the general formula (2) can be calculated from the ratio (%) of the number of moles of the amine B used in the production of the compounds of the present disclosure to the number of moles of poly(succinimide) used in the production of the compounds of the present disclosure described later.

[0027] In the general formula (3), R3 is a hydrocarbon group having 14 to 22 carbon atoms, and is not particularly limited as long as the number of carbon atoms of R3 is larger than the number of carbon atoms of R2. R3 may be saturated or unsaturated, and may be branched or linear. In the present disclosure, "the number of carbon atoms of R3 is larger than the number of carbon atoms of R2" means that when the number of carbon atoms of R2 is x (x is an integer of 8 to 16) and the number of carbon atoms of R3 is y (y is an integer of 14 to 22), the relationship x < y is satisfied.

[0028] The number of carbon atoms in the hydrocarbon group of R3 is 14 or more, preferably 15 or more, more preferably 16 or more, and even more preferably 17 or more. On the other hand, it is 22 or less, preferably 21 or less, more preferably 20 or less, and even more preferably 19 or less. For example, it is 14 to 22, 15 to 21, 16 to 20, or 17 to 19.

[0029] Specific examples of R3 include linear alkyl groups such as tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, and docosyl groups; branched alkyl groups such as isotetradecyl, isopentadecyl, isohexadecyl, isoheptadecyl, isooctadecyl, isononadecyl, isoeicosyl, isoheneicosyl, and isodocosyl groups; cyclotetradecyl, cyclopentadecyl, and cyclohexyl groups; Examples of the cycloalkyl group include a cyclooctadecyl group, a cycloheptadecyl group, a cyclooctadecyl group, a cyclononadecyl group, a cycloeicosyl group, a cycloheneicosyl group, and a cyclodocosyl group; a cycloalkylalkyl group such as a cyclooctylhexyl group, a cyclononylpentyl group, and a cyclododecylbutyl group; and an alkenyl group such as a tetradecenyl group, a pentadecenyl group, a hexadecenyl group, a heptadecenyl group, an octadecenyl group, a nonadecenyl group, an eicosenyl group, a heneicosenyl group, and a docosenyl group. Among these, branched or straight chain alkyl groups are preferred, and straight chain alkyl groups are more preferred.

[0030] The compound of the present disclosure may contain one or more types of monomer units represented by general formula (3), provided that when two or more types are contained, the number of carbon atoms in R3 is the same.

[0031] The amount of the monomer unit represented by general formula (3) present in the constituent monomers of the compound of the present disclosure is preferably 0.5 mol% or more, more preferably 1.0 mol% or more, even more preferably 3.0 mol% or more, and even more preferably 6.0 mol% or more. On the other hand, it is preferably 30.0 mol% or less, more preferably 25.0 mol% or less, even more preferably 20.0 mol% or less, and even more preferably 18.0 mol% or less. For example, it is 0.5 mol% to 30.0 mol%, 1.0 mol% to 25.0 mol%, 3.0 mol% to 20.0 mol%, or 6.0 mol% to 18.0 mol%. Here, the term "constituent monomer of the compound of the present disclosure" refers to, among the monomers contained in the compound of the present disclosure, a monomer derived from polysuccinimide used in the production of the compound of the present disclosure, which will be described later (specifically, for example, a monomer unit represented by general formula (1), a monomer unit represented by general formula (2), a monomer unit represented by general formula (3), a monomer unit represented by formula (4), a monomer unit represented by general formula (5), and a monomer unit represented by formula (6), as well as a monomer unit derived from polysuccinimide that does not fall under these monomer units). The amount of the monomer unit represented by general formula (3) present can be calculated from the ratio (%) of the number of moles of amine C used in the production of the compound of the present disclosure to the number of moles of polysuccinimide used in the production of the compound of the present disclosure, which will be described later.

[0032] The amount of the monomer unit represented by formula (4) present in the constituent monomers of the compound of the present disclosure is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, and even more preferably 0.5 mol% or more. On the other hand, it is preferably 2.0 mol% or less, more preferably 1.8 mol% or less, and even more preferably 1.7 mol% or less. For example, it is 0.1 mol% to 2.0 mol%, 0.3 mol% to 1.8 mol%, or 0.5 mol% to 1.7 mol%. Here, the term "constituent monomer of the compound of the present disclosure" refers to, among the monomers contained in the compound of the present disclosure, a monomer derived from polysuccinimide used in the production of the compound of the present disclosure, which will be described later (specifically, for example, a monomer unit represented by general formula (1), a monomer unit represented by general formula (2), a monomer unit represented by general formula (3), a monomer unit represented by formula (4), a monomer unit represented by general formula (5), and a monomer unit represented by formula (6), as well as a monomer unit derived from polysuccinimide that does not fall under these monomer units). When the amount of the monomer unit represented by formula (4) present is within the above range, the compound of the present disclosure has an appropriate amount of crosslinking, and therefore does not gel even when dissolved in a solution, and it becomes easy to obtain a more excellent thickening effect while maintaining a certain level of fluidity. The amount of the monomer unit represented by formula (4) present can be calculated from the ratio (%) of the number of moles of the crosslinking agent used in the production of the compound of the present disclosure to the number of moles of the polysuccinimide used in the production of the compound of the present disclosure, which will be described later.

[0033] The compound of the present disclosure preferably further contains an α- or β-type polyaspartic acid monomer unit represented by the following general formula (5) (also referred to as a "monomer unit represented by general formula (5)"). The monomer unit represented by general formula (5) has a structure derived from amine D and polysuccinimide, which are used in the production of the compound of the present disclosure, which will be described later. [ka] (In the formula, R4 represents a hydrocarbon group having 2 to 8 carbon atoms. The hydrocarbon group may contain a heteroatom.)

[0034] In general formula (5), R4 is not particularly limited as long as it is a hydrocarbon group having 2 to 4 carbon atoms, and may be saturated or unsaturated, and may be branched or linear. The number of carbon atoms in the hydrocarbon group of R4 is 2 or more, or may be 3 or more, or 4 or more. On the other hand, it may be 8 or less, 7 or less, or 6 or less. For example, it may be 2 to 4, 3 to 7, or 4 to 6.

[0035] Specific examples of hydrocarbon groups having 2 to 8 carbon atoms include linear alkylene groups such as an ethylene group (-CH2CH2-), a trimethylene group (-CH2CH2CH2-), and a tetramethylene group (-CH2CH2CH2CH2-); a propylene group (-CH(CH3)CH branched alkylene groups such as 2-, -CH2CH(CH3)-, and 1,2-dimethylethylene group (-(CH3)CHCH(CH3)-); and alkenyl groups such as propenylene group (-CH2CH=CH-, -CH=CHCH2-). Among these, branched or straight chain alkylene groups are preferred, and straight chain alkyl groups are more preferred.

[0036] Furthermore, the hydrocarbon group having 2 to 8 carbon atoms in R4 may contain a heteroatom, such as one or more selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom. Examples of hydrocarbon groups having 2 to 8 carbon atoms and containing a heteroatom include those in which one or more hydrogen atoms of the aforementioned hydrocarbon groups having 2 to 8 carbon atoms are substituted with a substituent containing a heteroatom. Examples of the substituent containing a heteroatom include one or more selected from the group consisting of a hydroxy group (-OH), an amino group (-NH), and a thiol group (-SH). Specific examples of hydrocarbon groups having 2 to 8 carbon atoms and substituted with a substituent containing a heteroatom include hydroxyalkylene groups such as a hydroxyethylene group (-CH(OH)CH-), a hydroxypropylene group (-CHCH(OH)CH-), and a hydroxybutylene group (-CHCHCH(OH)CH-); and polyhydroxyalkylene groups such as the group obtained by removing the amino group (-NH-) and the terminal hydroxy group (-OH) from D-glucamine. Furthermore, examples of hydrocarbon groups having 2 to 8 carbon atoms and containing a heteroatom include those in which a heteroatom interrupts the aforementioned hydrocarbon groups having 2 to 8 carbon atoms. The interrupting heteroatom may be one or more selected from the group consisting of -O-, -N-, and -S-. Specific examples of hydrocarbon groups having 2 to 8 carbon atoms interrupted by a heteroatom include hydroxyalkoxyalkyl groups such as an ethoxyethylene group (-CH2CHOCH2CH2-), an ethoxytrimethylene group (-CH2CH2CHOCH2CH2-), an ethoxytetramethylene group (-CH2CH2CH2CH2CH2CHOCH2CH2-), a propoxyethylene group (-CH2CHOCH2CH2CH2-), a propoxytrimethylene group (-CH2CH2CHOCH2CH2CH2-), and a propoxytetramethylene group (-CH2CH2CH2CHOCH2CH2CH2-).

[0037] The compound of the present disclosure may contain one type of monomer unit represented by general formula (5) alone, or may contain two or more types.

[0038] The amount of the monomer unit represented by general formula (5) present in the constituent monomers of the compound of the present disclosure is preferably 20.0 mol% or more, more preferably 30.0 mol% or more, even more preferably 35.0 mol% or more, and even more preferably 40.0 mol% or more. On the other hand, it is preferably 70.0 mol% or less, more preferably 60.0 mol% or less, even more preferably 55.0 mol% or less, and even more preferably 50.0 mol% or less. For example, it is 20.0 mol% to 70.0 mol%, 30.0 mol% to 60.0 mol%, 35.0 mol% to 55.0 mol%, or 40.0 mol% to 50.0 mol%. Here, the term "constituent monomer of the compound of the present disclosure" refers to, among the monomers contained in the compound of the present disclosure, a monomer derived from polysuccinimide used in the production of the compound of the present disclosure, which will be described later (specifically, for example, a monomer unit represented by general formula (1), a monomer unit represented by general formula (2), a monomer unit represented by general formula (3), a monomer unit represented by formula (4), a monomer unit represented by general formula (5), and a monomer unit represented by formula (6), as well as a monomer unit derived from polysuccinimide that does not fall under these monomer units). The amount of the monomer unit represented by general formula (5) present can be calculated from the ratio (%) of the number of moles of amine D used in the production of the compound of the present disclosure to the number of moles of polysuccinimide used in the production of the compound of the present disclosure, which will be described later.

[0039] In the compounds of the present disclosure, α-type polyaspartic acid monomer units and β-type aspartic acid The monomer units may be either one or both. When both are present, the ratio of the α-type polyaspartic acid monomer units to the β-type aspartic acid monomer units is not particularly limited.

[0040] The compound of the present disclosure may further contain a succinimide monomer unit represented by the following formula (6) (also referred to as a "monomer unit represented by formula (6)"). The monomer unit represented by formula (6) is an unreacted imide ring remaining in the ring-opening reaction of polysuccinimide in the production of the compound of the present disclosure, which will be described later. [ka]

[0041] The compound of the present disclosure may contain a monomer unit other than the monomer unit represented by general formula (1), the monomer unit represented by general formula (2), the monomer unit represented by general formula (3), the monomer unit represented by formula (4), the monomer unit represented by general formula (5), and the monomer unit represented by formula (6), within a range that does not impair the effects of the present disclosure.

[0042] In the compounds of the present disclosure, the bonding form of the monomer units represented by general formula (1), (2), (3), (4), (5), and (6) may be random, block, or tapered. The bonding form of each of these monomer units may be linear, macrocyclic, branched, star-shaped, or three-dimensional network-shaped, but is preferably linear.

[0043] Among the constituent monomers of the compound of the present disclosure, the molar ratio of the amount of the monomer unit represented by general formula (1) to the amount of the monomer unit represented by general formula (2) is preferably 1:6 to 2:1, more preferably 1:5 to 3:2, even more preferably 1:4 to 4:3, and even more preferably 1:3 to 1:1. Here, "constituent monomers of the compound of the present disclosure" refers to, among the monomers contained in the compound of the present disclosure, monomers derived from polysuccinimide used in the production of the compound of the present disclosure described below (specifically, for example, monomer units represented by general formula (1), monomer units represented by general formula (2), monomer units represented by general formula (3), monomer units represented by formula (4), monomer units represented by general formula (5), and monomer units represented by formula (6), as well as monomer units derived from polysuccinimide that do not fall into these monomer units). Within the above range, the thickening effect of the compound of the present disclosure is further improved. The molar ratio can be calculated from the blending amounts of the raw materials, and can be calculated from (molar number of amine A):(molar number of amine B) used in the production of the compound of the present disclosure described below.

[0044] In the constituent monomers of the compound of the present disclosure, the molar ratio of the amount of the monomer unit represented by general formula (2) to the amount of the monomer unit represented by general formula (3) is preferably 10:1 to 1:2, more preferably 8:1 to 2:3, even more preferably 6:1 to 3:4, and even more preferably 4:1 to 1:1. " refers to, among the monomers contained in the compound of the present disclosure, monomers derived from polysuccinimide used in the production of the compound of the present disclosure described below (specifically, for example, a monomer unit represented by general formula (1), a monomer unit represented by general formula (2), a monomer unit represented by general formula (3), a monomer unit represented by formula (4), a monomer unit represented by general formula (5), and a monomer unit represented by formula (6), as well as monomer units derived from polysuccinimide that do not fall under these monomer units). Within the above range, the thickening effect of the compound of the present disclosure is further improved. The molar ratio can be calculated from the blending amounts of the raw materials, and can be calculated from (the number of moles of amine B):(the number of moles of amine C) used in the production of the compound of the present disclosure described below.

[0045] Among the constituent monomers of the compound of the present disclosure, the molar ratio of the amount of the monomer unit represented by general formula (1) to the amount of the monomer unit represented by general formula (3) is preferably 10:1 to 1:4, more preferably 8:1 to 1:3, even more preferably 6:1 to 1:2, and even more preferably 3:1 to 1:2. Here, "constituent monomers of the compound of the present disclosure" refers to, among the monomers contained in the compound of the present disclosure, monomers derived from polysuccinimide used in the production of the compound of the present disclosure described below (specifically, for example, monomer units represented by general formula (1), monomer units represented by general formula (2), monomer units represented by general formula (3), monomer units represented by formula (4), monomer units represented by general formula (5), and monomer units represented by formula (6), as well as monomer units derived from polysuccinimide that do not fall into these monomer units). Within the above range, the thickening effect of the compound of the present disclosure is further improved. The molar ratio can be calculated from the blending amounts of the raw materials, and can be calculated from (the number of moles of amine A):(the number of moles of amine C) used in the production of the compound of the present disclosure described below.

[0046] The shear viscosity of an aqueous solution of the compound of the present disclosure (concentration 1.0 wt%) is preferably 3,000 mPa·s or more, more preferably 4,000 mPa·s or more, even more preferably 10,000 mPa·s or more, even more preferably 20,000 mPa·s or more, and most preferably 50,000 mPa·s or more. On the other hand, it is preferably 120,000 mPa·s or less, more preferably 110,000 mPa·s or less, even more preferably 100,000 mPa·s or less, and even more preferably 90,000 mPa·s or less. For example, it is 3,000 mPa·s to 120,000 mPa·s, 4,000 mPa·s to 110,000 mPa·s, 10,000 mPa·s to 100,000 mPa·s, 20,000 mPa·s to 90,000 mPa·s, or 50,000 mPa·s to 90,000 mPa·s. The shear viscosity here refers to the shear viscosity value at a shear rate of 0.02 / s measured using a rotational rheometer (R / Splus manufactured by Brookfield) under the conditions of Measuring System C25-2, Con Truncation 0.046 mm, and a measurement temperature of 25°C, after pre-shearing for 15 seconds at a shear rate of 10 / s and leaving it to stand for 30 seconds, while increasing the shear rate from 0 / s to 1000 / s.

[0047] The weight-average molecular weight (Mw) of the compound of the present disclosure is not particularly limited, but is preferably 80,000 or more, more preferably 150,000 or more, and even more preferably 200,000 or more. It is also preferably 700,000 or less, more preferably 600,000 or less, and even more preferably 500,000 or less. For example, it is 80,000 or more and 700,000 or less, 150,000 or more and 600,000 or less, or 200,000 or more and 500,000 or less. The weight-average molecular weight can be adjusted by the molecular weight of the polysuccinimide used in the production of the compound of the present disclosure, as described below, and the types of amine A, amine B, amine C, and amine D. The weight-average molecular weight here refers to a converted value measured by the GPC method (differential refractometer) using polystyrene as a standard substance. Specifically, a G1000HHR column (TSKgel (registered trademark), manufactured by Tosoh Corporation), a G4000HHR column (TSKgel (registered trademark), manufactured by Tosoh Corporation), or a GMHHR-H column (TSKgel (registered trademark), manufactured by Tosoh Corporation) was used, and dimethylformamide containing 10 mM lithium bromide was used as the eluent. The weight average molecular weight is measured by

[0048] The compound of the present disclosure can be obtained by ring-opening polysuccinimide using amine A, amine B, and amine C described below, and then forming a crosslinked moiety with a crosslinking agent. When the compound of the present disclosure further contains a monomer unit represented by general formula (5), the compound of the present disclosure can be obtained by ring-opening polysuccinimide using amine A, amine B, and amine C, and also amine D, and then forming a crosslinked moiety with a crosslinking agent. In addition, unreacted imide rings may remain in the ring-opening reaction of polysuccinimide. In this case, the compound of the present disclosure further contains a monomer unit represented by formula (6).

[0049] [Polysuccinimide] Polysuccinimide (PSI) is a polymer represented by the following formula (7).

[0050] [ka] (In the formula, n=10~10000)

[0051] The method for producing polysuccinimide is not particularly limited. For example, it can be produced by heating aspartic acid in the presence of phosphoric acid in a vacuum at 170 to 190°C and dehydrating and condensing it. To obtain a polysuccinimide with a higher molecular weight, the polysuccinimide obtained as described above can be treated with a condensing agent such as dicyclohexylcarbodiimide. The molecular weight of the polysuccinimide is not particularly limited. For example, the weight-average molecular weight is preferably 20,000 or more, more preferably 50,000 or more, and even more preferably 70,000 or more. The molecular weight of the polysuccinimide is preferably 500,000 or less, and more preferably 200,000 or less. For example, the weight-average molecular weight is 20,000 to 500,000, 50,000 to 200,000, or 70,000 to 200,000. The weight-average molecular weight here refers to a converted value measured by the GPC method (differential refractometer) using polystyrene as a standard substance, and specifically refers to the weight-average molecular weight measured using a G1000HHR column (TSKgel (registered trademark), manufactured by Tosoh Corporation), a G4000HHR column (TSKgel (registered trademark), manufactured by Tosoh Corporation), or a GMHHR-H column (TSKgel (registered trademark), manufactured by Tosoh Corporation) using dimethylformamide containing 10 mM lithium bromide as an eluent.

[0052] [Crosslinking agent] The cross-linking agent is not particularly limited as long as it can form a cross-linked moiety. Specific examples of cross-linking agents preferred for forming an amide bond used in the cross-linked moiety include polyfunctional amines.

[0053] The polyfunctional amine is preferably an amine having at least two primary and / or secondary amino groups. Examples of diamines include aliphatic diamines such as ethylenediamine and hexamethylenediamine, aliphatic diamines containing an aromatic ring such as xylenediamine, and norbornenediamine. Examples of suitable polyfunctional amines include alicyclic diamines; ether-based diamines such as 1,2-bis(2-aminoethoxy)ethane (AEE), diethylene glycol bis(3-aminopropyl)ether (bis[2-(3-aminopropoxy)ethyl ether (APEE)), polyoxyethylene diamine, and polyoxypropylene diamine; amino acids and derivatives thereof having an amino group in the side chain, such as lysine and ornithine; and monoamino compounds linked by disulfide bonds, such as cystine and cystamine, and derivatives thereof. The polyfunctional amine preferably does not contain the above amino acids and derivatives thereof. The polyfunctional amine is preferably an ether-based diamine, as its flexible structure makes it less likely that insoluble matter will be generated during the crosslinking reaction and the crosslinking reaction is easier to control.

[0054] Examples of polyfunctional amines other than diamines include tris(2-aminoalkyl)amines (where the alkyl preferably has 1 to 5 carbon atoms, more preferably 2 to 4 carbon atoms), such as tris(2-aminoethyl)amine (TREN) and tris(3-aminopropyl)amine; diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.

[0055] Among these, preferred examples of polyfunctional amines include 1,2-bis(2-aminoethoxy)ethane (AEE), bis[2-(3-aminopropoxy)ethyl ether (APEE), and tris(2-aminoethyl)amine (TREN).

[0056] The reaction of polysuccinimide with a polyfunctional amine can be carried out in an organic solvent, for example. This will be explained using an example in which the polyfunctional amine is a diamine. In the method of reacting polysuccinimide with diamine in an organic solvent, polysuccinimide is dissolved in an aprotic polar organic solvent such as dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethyl sulfoxide (DMSO), sulfolane, etc., and then diamine or a solution of diamine in the organic solvent is added dropwise. At this time, the amount of organic solvent used to dissolve polysuccinimide is not particularly limited, but is usually adjusted so that the polymer concentration is 1 to 50 mass%.

[0057] The temperature at which the polysuccinimide and diamine are reacted is not particularly limited, but is, for example, room temperature to 80°C.

[0058] The reaction conditions (reaction temperature, reaction time, reaction concentration, amount of diamine used, etc.) are not particularly limited, but it is desirable to set the conditions such that the entire reaction solution does not gel.

[0059] [Amine A, Amine B, Amine C, and Amine D] As the amine A, an amine represented by the following general formula (8) is used. R1-NH2(8) (In the formula, R1 represents a hydrocarbon group having 2 to 6 carbon atoms.)

[0060] As the amine B, an amine represented by the following general formula (9) is used. R2-NH2(9) (In the formula, R2 represents a hydrocarbon group having 8 to 16 carbon atoms.)

[0061] As the amine C, an amine represented by the following general formula (10) is used. R3-NH2(10) (In the formula, R3 represents a hydrocarbon group having 14 to 22 carbon atoms, provided that the number of carbon atoms in R3 is greater than the number of carbon atoms in R2.)

[0062] As the amine D, an amine represented by the following general formula (11) is used. OH-R4-NH2(11) (In the formula, R4 represents a hydrocarbon group having 2 to 4 carbon atoms.)

[0063] For R1 in general formula (8), the explanation for R1 in general formula (1) is used. For R2 in general formula (9), the explanation for R2 in general formula (2) is used. For R3 in general formula (10), the explanation for R3 in general formula (3) is used. For R4 in general formula (11), the explanation for R4 in general formula (5) is used.

[0064] In the method for producing a compound of the present disclosure, when three or more amines corresponding to both the amine represented by general formula (9) and the amine represented by general formula (10) are included, the two amines with the largest charged amounts (mol %) among these amines are designated "amine B" and "amine C." However, of the two amines with the largest number of carbon atoms in the hydrocarbon group corresponding to R2 and R3, the amine with the largest number of carbon atoms is designated "amine C," and the amine with the smallest number is designated "amine B." That is, for example, when 1.0 mol % of an amine having 14 carbon atoms, 30.0 mol % of an amine having 15 carbon atoms, and 20.0 mol % of an amine having 16 carbon atoms are used, the amine with 15 carbon atoms is designated "amine B," and the amine with 16 carbon atoms is designated "amine C." Furthermore, when a compound of the present disclosure contains three or more amines that correspond to both the amine represented by general formula (9) and the amine represented by general formula (10), and the three or more amines that are charged in the highest amounts (mol %) among these amines are charged in the same amount, the amine with the smallest number of carbon atoms in the hydrocarbon group corresponding to R2 and R3 among these amines is designated "amine B," and the amine with the hydrocarbon group with the next highest number of carbon atoms after the carbon atom number of R2 of "amine B" is designated "amine C." That is, for example, when an amine with 14 carbon atoms, an amine with 15 carbon atoms, and an amine with 16 carbon atoms are used at 20.0 mol % each in a production method of a compound of the present disclosure, the amine with 14 carbon atoms is designated "amine B," and the amine with 15 carbon atoms is designated "amine C."

[0065] In the compounds of the present disclosure, amine A, amine B, amine C, and amine D may each be used alone or in combination of two or more. However, when two or more types of amine B are included, the number of carbon atoms in R2 must be the same. Furthermore, when two or more types of amine C are included, the number of carbon atoms in R3 must be the same.

[0066] Amine A, amine B, amine C, and amine D (collectively referred to as "monoamines") may be commercially available products, or may be prepared by a known method.

[0067] [Method for producing compounds of the present disclosure] Examples of methods for producing the compounds of the present disclosure include a method of ring-opening reaction of polysuccinimide using polysuccinimide and a monoamine. In addition, in the ring-opening reaction of polysuccinimide, in addition to polysuccinimide and monoamine, a crosslinking agent such as a polyfunctional amine is used. The order of addition of the crosslinking agent and monoamine is not particularly limited. The monoamine may be added first and then the crosslinking agent, or the monoamine and crosslinking agent may be added simultaneously, or the crosslinking agent may be added first and then the monoamine. From the viewpoint of easy control of the amount of crosslinking, it is preferable to add the crosslinking agent first and then add the monoamine after the crosslinking reaction has progressed. The order of addition of amine A, amine B, amine C, and amine D is also not particularly limited. For example, one to three of amine A, amine B, amine C, and amine D may be added first and then the remaining three to one may be added simultaneously, or amine A, amine B, amine C, and amine D may be added simultaneously.

[0068] Specific examples of the method for producing the compound of the present disclosure include, for example, when a polyfunctional amine is used as a crosslinking agent, a method for ring-opening the imide ring of polysuccinimide by reacting the polysuccinimide with the crosslinking agent and then reacting with a monoamine. By reacting the polysuccinimide with the monoamine, the imide ring of polysuccinimide is opened. Furthermore, by using a crosslinking agent, the resulting polyamino acid derivative has a crosslinked structure. The total amount of the crosslinking agent and monoamine used may be less than 1 molar equivalent relative to the molar equivalent of the monomer unit of polysuccinimide, allowing unreacted imide rings to remain, or may be 1 molar equivalent or more, allowing no unreacted imide rings to remain.

[0069] The unreacted imide ring may be left as it is, or may be further subjected to a ring-opening reaction using a monoamine other than amine A, amine B, amine C, and amine D. If desired, the unreacted imide ring may be opened with a substituted amine such as ethanolamine, cysteamine, or dibutylamine.

[0070] In the method for producing a compound of the present disclosure, the amount of amine A relative to the amount of polysuccinimide charged is preferably 1.0 mol% or more, more preferably 3.0 mol% or more, even more preferably 5.0 mol% or more, even more preferably 8.0 mol% or more, and most preferably 9.0 mol% or more. On the other hand, it is preferably 30.0 mol% or less, more preferably 27.0 mol% or less, even more preferably 25.0 mol% or less, even more preferably 23.0 mol% or less, and most preferably 20.0 mol% or less. For example, it is 1.0 mol% to 30.0 mol%, 3.0 mol% to 27.0 mol%, 5.0 mol% to 25.0 mol%, 8.0 mol% to 23.0 mol%, or 9.0 mol% to 20.0 mol%.

[0071] In the method for producing a compound of the present disclosure, the amount of amine B relative to the amount of polysuccinimide charged is preferably 5.0 mol% or more, more preferably 10.0 mol% or more, even more preferably 15.0 mol% or more, and even more preferably 20.0 mol% or more. On the other hand, it is preferably 60.0 mol% or less, more preferably 50.0 mol% or less, even more preferably 40.0 mol% or less, and even more preferably 30.0 mol% or less. For example, it is 5.0 mol% to 60.0 mol%, 10.0 mol% to 50.0 mol%, 15.0 mol% to 40.0 mol%, or 20.0 mol% to 30.0 mol%.

[0072] In the method for producing a compound of the present disclosure, the amount of amine C added relative to the amount of polysuccinimide added is preferably 0.5 mol% or more, more preferably 1.0 mol% or more, even more preferably 3.0 mol% or more, and even more preferably 6.0 mol% or more. On the other hand, it is preferably 30.0 mol% or less, more preferably 25.0 mol% or less, even more preferably 20.0 mol% or less, and even more preferably 18.0 mol% or less. For example, it is 0.5 mol% to 30.0 mol%, 1.0 mol% to 25.0 mol%, 3.0 mol% to 20.0 mol%, or 6.0 mol% to 18.0 mol%.

[0073] When amine D is used in the method for producing a compound of the present disclosure, the amount of amine D relative to the amount of polysuccinimide charged is preferably 20.0 mol% or more, more preferably 30.0 mol% or more, even more preferably 35.0 mol% or more, and even more preferably 40.0 mol% or more. On the other hand, it is preferably 70.0 mol% or less, more preferably 60.0 mol% or less, even more preferably 55.0 mol% or less, and even more preferably 50.0 mol% or less. For example, it is 20.0 mol% to 70.0 mol%, 30.0 mol% to 60.0 mol%, 35.0 mol% to 55.0 mol%, or 40.0 mol% to 50.0 mol%.

[0074] In the method for producing a compound of the present disclosure, the amount of crosslinking agent added is preferably 0.1 mol% or more, more preferably 0.3 mol% or more, and even more preferably 0.5 mol% or more, relative to the amount of polysuccinimide added. On the other hand, it is preferably 2.0 mol% or less, more preferably 1.8 mol% or less, and even more preferably 1.7 mol% or less. For example, it is 0.1 mol% to 2.0 mol%, 0.3 mol% to 1.8 mol%, or 0.5 mol% to 1.7 mol%.

[0075] In the method for producing a compound of the present disclosure, the molar ratio of the amount of amine A charged to the amount of amine B charged is preferably 1:6 to 2:1, more preferably 1:5 to 3:2, even more preferably 1:4 to 4:3, and still more preferably 1:3 to 1:1.

[0076] In the method for producing a compound of the present disclosure, the molar ratio of the amount of amine B charged to the amount of amine C charged is preferably 10:1 to 1:2, more preferably 8:1 to 2:3, even more preferably 6:1 to 3:4, and even more preferably 4:1 to 1:1.

[0077] In the method for producing a compound of the present disclosure, the molar ratio of the amount of amine A charged to the amount of amine C charged is preferably 10:1 to 1:4, more preferably 8:1 to 1:3, even more preferably 6:1 to 1:2, and still more preferably 3:1 to 1:2.

[0078] In the method for producing a compound of the present disclosure, a monoamine other than amine A, amine B, amine C, and amine D may be used. In this case, the total amount of amine A, amine B, amine C, and amine D charged is preferably 80.0 mol % or more, more preferably 90.0 mol % or more, and even more preferably 95.0 mol % or more.

[0079] The total amount of amine A, amine B, amine C, and amine D, as well as other monoamines, is not particularly limited as long as they are substantially soluble in the organic solvent and / or do not substantially inhibit the progress of the reaction. The amount is generally 0.1 or more molar equivalents relative to the molar equivalents of the monomer units of polysuccinimide. On the other hand, the amount is generally 10 or less molar equivalents relative to the molar equivalents of the monomer units of polysuccinimide, preferably 1.2 or less molar equivalents. For example, 0.1 to 10 molar equivalents are used, preferably 0.1 to 1.2 molar equivalents.

[0080] [Organic solvent] In the method for producing a compound of the present disclosure, the organic solvent is not particularly limited as long as it can substantially dissolve the polysuccinimide, the crosslinking agent, and the monoamine and / or does not substantially inhibit the progress of the reaction.

[0081] Specific examples of organic solvents include aprotic polar organic solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethyl sulfoxide (DMSO), and sulfolane, which can be used alone or in combination.

[0082] [Basic catalyst] In the method for producing the compound of the present disclosure, a catalyst may not be used, or a catalyst such as a basic catalyst may be used. The optionally used basic catalyst is not particularly limited as long as it substantially accelerates the reaction rate. Specific examples of basic catalysts include aliphatic tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine (DIEA), triethanolamine, and triethylenediamine (DABCO), alicyclic tertiary amines such as N-methylmorpholine, dimethylaniline, and diethylaniline. and tetramethylguanidine, which may be used alone or in combination.

[0083] In the method for producing the compound of the present disclosure, the amount of the basic catalyst used is not particularly limited as long as it substantially accelerates the reaction rate. The amount of the basic catalyst used is generally 0 to 2 molar equivalents relative to the molar equivalents of the total amount of monoamines charged.

[0084] [Reaction temperature] In the method for producing a compound of the present disclosure, the reaction temperature is not particularly limited as long as the reaction progress can be substantially maintained. The reaction temperature is generally selected from a temperature range of 5 to 150°C. The reaction temperature can also be selected optimally from the viewpoints of the monoamine used, shortening the reaction time, improving the reaction rate, etc. The method for producing a compound of the present disclosure preferably includes a crosslinking reaction step in which a crosslinking agent is first added and a crosslinking reaction proceeds, followed by a monoamine reaction step in which a monoamine is added. In this case, the temperature of the crosslinking reaction and the temperature of the monoamine reaction may be the same or different. The temperature of the crosslinking reaction is preferably lower than the reaction temperature after the addition of the monoamine. In the crosslinking reaction step in which a crosslinking agent is added to polysuccinimide and a crosslinking reaction proceeds, the reaction temperature may be 120°C or lower, or 100°C or lower. It may also be 20°C or higher. For example, it may be 20°C to 120°C or 20°C to 100°C. Furthermore, for example, when the crosslinking agent is an ether-based diamine or tris(2-aminoalkyl)amine, the reaction temperature in the crosslinking reaction step is preferably 100°C or lower, more preferably 80°C or lower, even more preferably 60°C or lower, and may also be 50°C or lower. It may also be 20°C or higher. For example, the reaction temperature may be 20°C to 100°C, 20°C to 80°C, 20°C to 60°C, or 20°C to 50°C. In the crosslinking reaction step, crosslinking can proceed uniformly as long as the reaction temperature is within the above range. The above production method provides a compound of the present disclosure having high viscosity.

[0085] [Concentration of reaction system] The concentration of the reaction system employed in the method for producing the compound of the present disclosure is not particularly limited as long as it can substantially maintain the progress of the reaction. The concentration of the reaction system is selected based on the concentration of polysuccinimide, and generally, the polysuccinimide concentration is selected from a concentration range of 1 to 50 wt %. The concentration of the reaction system can also be selected from a polysuccinimide concentration range of 1 to 50 wt % to be optimal for the monoamine used.

[0086] Methods for isolating compounds of the present disclosure In the method for producing a compound of the present disclosure, the method for isolating the produced polymer from the reaction solution after completion of the reaction is not particularly limited as long as it can isolate the reaction product with the desired purity. The isolation method may be any known or commonly used method. Generally, known or commonly used isolation procedures such as concentration, recrystallization, or reprecipitation are used.

[0087] A specific example of the isolation method is a method in which, after completion of the reaction, an excess of a poor solvent (e.g., ethyl acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, etc.) is added to the reaction solution in which the reaction product is dissolved at an appropriate temperature, the precipitated reaction product is isolated by decantation, filtration, suction filtration, etc., and the crystals are thoroughly washed with a poor solvent that does not dissolve the crystals, followed by drying. Another specific example is a method in which, after completion of the reaction, the reaction solution in which the reaction product is dissolved is added to an excess of the same poor solvent as above at an appropriate temperature, and the precipitated reaction product is isolated, washed, and dried in the same manner as above.

[0088] In the method for producing the compound of the present disclosure, the obtained compound may not be isolated, and the mixture after the reaction may be used as the compound of the present disclosure as it is. The compound of the present disclosure may be obtained by removing only the raw material, or by adjusting the concentration by increasing or decreasing the amount of solvent in the mixed solution.

[0089] <Composition of the present disclosure> The compositions of the present disclosure contain the compounds of the present disclosure. Since the compound of the present disclosure has an excellent thickening effect, the composition of the present disclosure is preferably used as an external preparation for skin, specifically as a cosmetic, quasi-drug, or pharmaceutical.When used as an external preparation for skin, the formulation can be any of the commonly known lotion, emulsion, essence, cream, powder-containing formulations, etc.

[0090] The content of the compound of the present disclosure in the composition of the present disclosure is not particularly limited and can be adjusted appropriately depending on the purpose, but is preferably 0.1 wt% or more, more preferably 0.3 wt% or more, even more preferably 0.5 wt% or more, even more preferably 0.7 wt% or more, and even more preferably 0.9 wt% or more, based on the total composition. On the other hand, it is preferably 20.0 wt% or less, more preferably 15.0 wt% or less, even more preferably 10.0 wt% or less, even more preferably 5.0 wt% or less, and even more preferably 2.0 wt% or less, based on the total composition. For example, it is 0.1 wt% to 20.0 wt%, 0.3 wt% to 15.0 wt%, 0.5 wt% to 10.0 wt%, 0.7 wt% to 5.0 wt%, or 0.9 wt% to 2.0 wt%. The compound of the present disclosure contained in the composition of the present disclosure may be used alone or in combination of two or more types.

[0091] [Optional ingredients] When producing the composition of the present disclosure, any ingredients that are normally used in the formulation of cosmetics, quasi-drugs, pharmaceuticals, etc. can be blended, and the composition can be produced by a conventional method. Such optional ingredients may be any ingredients that are commonly used in external skin preparations such as cosmetics, and examples thereof include the following: Examples of oily components include polar oils, volatile hydrocarbon oils, hydrocarbon oils, higher fatty acids, fats and oils, higher alcohols, waxes, ester oils, and silicone oils. Polar oils include synthetic ester oils such as isopropyl myristate, cetyl octanoate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanoate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2-ethylhexylate, dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glycerin di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, pentaneerythritol tetra-2-ethylhexylate, glycerin tri-2-ethylhexylate, triisostearate, and tetraisostearate. Mention may be made of trimethylolpropane tearate. Also contains cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glycerin trimyristate, tri-2-heptylundecanoic acid glyceride, and methyl castor oil fatty acid. Ester, oleyl oleate, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamine Phosphate-2-octyldodecyl ester, Di-2-heptylundecyl adipate, Ethyl laurate, Di-2-ethylhexyl sebacate, 2-hexyldecyl myristate, Palmitic acid 2-hexyldecyl, 2-hexyldecyl adipate, diisopropyl sebacate, 2-ethylhexyl succinate, triethyl citrate, octyl methoxycinnamate, and the like. In addition, natural oils such as avocado oil, camellia oil, turtle oil, macadamia nut oil, and tallow oil are also used. Examples of suitable oils include sorghum oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, persic oil, wheat germ oil, camellia oil, castor oil, linseed oil, safflower oil, cottonseed oil, perilla oil, soybean oil, peanut oil, tea seed oil, Japanese kaya oil, rice bran oil, Chinese tung oil, Japanese tung oil, jojoba oil, germ oil, triglycerin, glycerin trioctanoate, glycerin triisopalmitate, and shea butter.

[0092] Examples of volatile hydrocarbon oils include isododecane and isohexadecane. Examples of hydrocarbon oils include petrolatum, mineral oil, and squalane. Examples of higher fatty acids include lauric acid, stearic acid, and oleic acid. Examples of higher alcohols include stearyl alcohol, cetanol, and behenyl alcohol. Examples of oils include olive oil, coconut oil, and horse oil. Examples of waxes include candelilla wax, jojoba seed oil, and beeswax. Examples of ester oils include triethylhexanoin and isopropyl myristate. Examples of silicone oils include dimethicone and cyclopentasiloxane.

[0093] Examples of surfactants include anionic surfactants such as fatty acid soaps (sodium laurate, sodium palmitate, etc.), potassium lauryl sulfate, and alkyl sulfate triethanolamine ether; cationic surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride, and laurylamine oxide; betaine surfactants (alkylbetaine, amidobetaine, sulfobetaine, etc.); imidazoline amphoteric surfactants (2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.); Amphoteric surfactants such as silmethyl taurine, sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, etc.), glycerin fatty acids (glycerin monostearate, etc.), polyglycerin fatty acids (polyglyceryl-10 laurate, etc.), propylene glycol fatty acid esters (propylene glycol monostearate, etc.), hydrogenated castor oil derivatives, glycerin alkyl ether, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbit fatty acid esters (POE-sorbit monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisostearate, etc.), POE fatty acid esters (poly ethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE 2-octyldodecyl ether, etc.), POE alkyl phenyl ethers (POE nonylphenyl ether, etc.), Pluronic types, POE·POP alkyl ethers (POE·POP 2-decyltetradecyl ether, etc.), Tetronics, POE castor oil / hydrogenated castor oil derivatives (POE castor oil, POE hydrogenated castor oil, etc.), sucrose fatty acid esters, non-ionic surfactants such as alkyl glucosides surfactants, etc.

[0094] The composition of the present disclosure may contain a known thickener in addition to the compound of the present disclosure, to the extent that the effect of the present disclosure is not impaired. Known thickeners include guar gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum, curdlan, methylcellulose, hydroxyethyl cellulose, carboxymethyl cellulose, methylhydroxypropyl cellulose, chondroitin sulfate, dermatan sulfate, glycogen, heparan sulfate, hyaluronic acid, sodium hyaluronate, tragacanth gum, keratan sulfate, chondroitin, mucoitin sulfate, hydroxyethyl guar gum, carboxymethyl guar gum, dextran, keratosulfuric acid, locust bean gum, succinoglucan, caronic acid, chitin, chitosan, carboxymethyl chitin, agar, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, sodium polyacrylate, polyethylene glycol, and bentonite.

[0095] Examples of powders include powders such as mica, talc, kaolin, synthetic mica, calcium carbonate, magnesium carbonate, anhydrous silicic acid (silica), aluminum oxide, and barium sulfate, which may be surface-treated; inorganic pigments such as red iron oxide, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, iron blue, titanium oxide, and zinc oxide, which may be surface-treated; pearling agents such as titanium dioxide, fish phosphate foil, and bismuth oxychloride, which may be surface-treated; and Red No. 202, Red No. 228, Red No. 226, Yellow No. 4, Blue No. 404, Yellow No. 5, Red No. 505, which may be laked. Examples of suitable organic pigments include organic pigments such as Color No. 230, Red No. 223, Orange No. 201, Red No. 213, Yellow No. 204, Yellow No. 203, Blue No. 1, Green No. 201, Purple No. 201, and Red No. 204; and organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, and organopolysiloxane elastomer.

[0096] UV absorbers include para-aminobenzoic acid-based UV absorbers, anthranilic acid-based UV absorbers, salicylic acid-based UV absorbers, cinnamic acid-based UV absorbers, benzophenone-based UV absorbers, sugar-based UV absorbers, and 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazo. and ultraviolet absorbers such as benzoyl methyl ether, 4-methoxy-4'-t-butyldibenzoylmethane, etc.

[0097] The composition of the present disclosure may also contain other ingredients such as water, ethanol, fragrances, preservatives, pH adjusters, and coloring agents.

[0098] <Viscosity-enhancing composition> The composition containing the compound of the present disclosure is preferably used for thickening purposes, that is, it is preferably a thickener (viscosity enhancing composition) containing the compound of the present disclosure. The viscosity enhancing composition is not particularly limited, but is preferably a skin topical preparation, and may contain, in addition to the compound of the present disclosure, the above-mentioned optional components to the extent that the effect of the present disclosure is not impaired. The content of the compound of the present disclosure in the viscosity enhancing composition is not particularly limited and can be appropriately adjusted depending on the purpose.

[0099] The composition to be enhanced in viscosity is not particularly limited, but is preferably a topical skin preparation, and the optional components described above can be blended to an extent that does not impair the effects of the present disclosure. In addition, it is preferable that at least one of the viscosity-enhancing composition and the composition to be enhanced in viscosity contains water. The viscosity-enhancing composition and the composition to be viscosity-enhanced can each be produced by a conventional method. [Example]

[0100] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited thereto.

[0101] The compounds of Test Examples 1 to 9 were prepared according to the following procedure.

[0102] <Synthesis of Polysuccinimide> 160 parts of aspartic acid (manufactured by YIXING QIANCHENG BIO-ENGINEERING Co., Ltd.) and 83 parts of 85% phosphoric acid were mixed in a mortar, transferred to a tray, and reacted at 190°C and 1.3 kPa for 6 hours. The reaction mixture was pulverized, washed with distilled water until the filtrate became neutral, and then vacuum dried at 80°C to obtain 115 parts of polysuccinimide (PSI) with a weight-average molecular weight of 80,000.

[0103] <Test Example 1> 10.0 g of PSI and 50.0 g of N-methylpyrrolidone (NMP) were placed in a reaction vessel and completely dissolved by heating at 90°C for 4 hours. After lowering the temperature to 40°C, A mixture of 0.23 g of 1,2-bis(2-aminoethoxy)ethane (AEE) and 2.07 g of N-methylpyrrolidone (NMP) as an organic solvent was added and reacted for 7 hours. Furthermore, 10.0 g of n-dodecylamine was added as amine B and reacted for 60 minutes at 40°C. Next, 3.58 g of 3-amino-1-propanol was added as amine D and reacted for 6 hours. The reaction vessel was then cooled and allowed to stand overnight at room temperature. The reaction mixture was then poured into 1200 mL of ethyl acetate with stirring to precipitate the reaction product, and the solid was collected by filtration. The reaction mixture was then washed with 600 mL of ethyl acetate with stirring, and the solid was collected by filtration. The collected solid was dried under reduced pressure at 60°C for 12 hours to obtain 19.0 g of the compound of Test Example 1.

[0104] <Test Example 2> 10.0 g of PSI and 50.0 g of N-methylpyrrolidone (NMP) were placed in a reaction vessel and heated to 90°C for 4 hours to completely dissolve. After lowering the temperature to 40°C, a mixture of 0.23 g of AEE as a crosslinker and 2.07 g of N-methylpyrrolidone (NMP) as an organic solvent was added and allowed to react for 7 hours. Furthermore, 1.64 g of n-butylamine as amine A, 5.01 g of n-dodecylamine as amine B, and 1.25 g of n-octadecylamine as amine C were added and allowed to react for 60 minutes at 40°C. Next, 3.57 g of 3-amino-1-propanol as amine D was added and allowed to react for 6 hours. Subsequently, 17.4 g of the compound of Test Example 2 was obtained by the same procedure as Test Example 1.

[0105] <Test Example 3> 17.8 g of the compound of Test Example 3 was obtained in the same manner as in Test Example 2, except that the amount of n-butylamine added was 1.43 g and the amount of n-octadecylamine added was 2.00 g.

[0106] <Test Example 4> The same procedure as in Test Example 2 was followed except that the amount of n-butylamine added was 1.30 g and the amount of n-octadecylamine added was 2.50 g, to obtain 18.1 g of the compound of Test Example 4.

[0107] <Test Example 5> The same procedure as in Test Example 2 was followed except that the amount of n-butylamine added was 1.03 g and the amount of n-octadecylamine added was 3.50 g, to obtain 18.7 g of the compound of Test Example 5.

[0108] <Test Example 6> The same procedure as in Test Example 2 was followed except that the amount of n-butylamine added was 0.75 g and the amount of n-octadecylamine added was 4.50 g, to obtain 19.2 g of the compound of Test Example 6.

[0109] <Test Example 7> 10.0 g of PSI and 50.0 g of N-methylpyrrolidone (NMP) were placed in a reaction vessel and heated to 90°C for 4 hours to completely dissolve. After lowering the temperature to 40°C, 11.5 g of n-dodecylamine (amine B) was added and the mixture was allowed to react at 40°C for 60 minutes. Next, 3.10 g of 3-amino-1-propanol (amine D) was added and the mixture was allowed to react for 6 hours. Then, 19.7 g of the compound of Test Example 7 was obtained by the same procedure as in Test Example 1.

[0110] <Test Example 8> 10.0 g of PSI and 50.0 g of N-methylpyrrolidone (NMP) were placed in a reaction vessel and completely dissolved by heating at 90°C for 4 hours. After lowering the temperature to 40°C, amine D and Then, 7.74 g of 3-amino-1-propanol was added and reacted for 6 hours. Thereafter, the same procedure as in Test Example 1 was carried out to obtain 14.2 g of the compound of Test Example 8.

[0111] <Test Example 9> 19.1 g of the compound of Test Example 9 was obtained in the same manner as in Test Example 1, except that the amount of n-dodecylamine added was 10.2 g and the amount of 3-amino-1-propanol added was 3.48 g.

[0112] <Calculation of the abundance of each monomer unit> The amount (mol %) of the monomer unit represented by general formula (1) present in the compound of each test example was calculated from the ratio (%) of the number of moles of amine A used in the production of the compound to the number of moles of polysuccinimide used in the production of the compound. The amount (mol %) of the monomer unit represented by general formula (2) present in the compound of each test example was calculated from the ratio (%) of the number of moles of amine B used in the production of the compound to the number of moles of polysuccinimide used in the production of the compound. The amount (mol %) of the monomer unit represented by general formula (3) present in the compound of each test example was calculated from the ratio (%) of the number of moles of amine C used in the production of the compound to the number of moles of polysuccinimide used in the production of the compound. The amount (mol %) of the monomer unit represented by formula (4) present in the compound of each test example was calculated from the ratio (%) of the number of moles of the crosslinking agent used in the production of the compound to the number of moles of the polysuccinimide used in the production of the compound. The amount (mol %) of the monomer unit represented by general formula (5) present in the compound of each test example was calculated from the ratio (%) of the number of moles of amine D used in the production of the compound to the number of moles of polysuccinimide used in the production of the compound. The calculated abundance of each monomer unit is shown in Tables 1 and 2.

[0113] In addition, the rational formulas of R1 of the monomer unit represented by general formula (1), R2 of the monomer unit represented by general formula (2), R3 of the monomer unit represented by general formula (3), and R4 of the monomer unit represented by general formula (5) in each test example are shown in Tables 1 and 2.

[0114] <Evaluation of shear viscosity> The shear viscosity of the compounds of Test Examples 1 to 6 was measured according to the following procedure. Using a rotational rheometer (Brookfield R / Splus) with Measuring System C25-2, Con Truncation 0.046 mm, and a measurement temperature of 25°C, the sample was presheared for 15 seconds at a shear rate of 10 / s, allowed to stand for 30 seconds, and then measured while increasing the shear rate from 0 / s to 1000 / s. The shear viscosity at a shear rate of 0.02 / s was used. The results are shown in Table 1.

[0115] The shear viscosities of the compounds in Test Examples 7 to 9 were measured in the same manner as in Test Examples 1 to 6, except that the shear viscosities were measured at a shear rate of 5 / s. The results are shown in Table 2.

[0116] As shown in Table 2, either no thickening effect or viscosity could not be measured for the compounds of Test Examples 7 and 8. On the other hand, as shown in Table 1, excellent thickening effects were observed for the compounds of Test Examples 2 to 6, and in particular, the compounds of Test Examples 3 to 6 exhibited a thickening effect superior to that of the compound of Test Example 1.

[0117]

Table 1

[0118]

Table 2

Claims

1. A compound comprising an α- or β-type polyaspartic acid monomer unit represented by the following general formula (1), an α- or β-type polyaspartic acid monomer unit represented by the following general formula (2), an α- or β-type polyaspartic acid monomer unit represented by the following general formula (3), and an α- or β-type polyaspartic acid monomer unit represented by the following formula (4): 【Chemical 1】 (In the formula, R １ represents a hydrocarbon group having 2 to 6 carbon atoms.) 【Chemistry 2】 (In the formula, R ２ represents a hydrocarbon group having 8 to 16 carbon atoms. 【Chemistry 3】 (In the formula, R ３ represents a hydrocarbon group having 14 to 22 carbon atoms. ３ The number of carbon atoms in R ２ (The number of carbon atoms is greater than that of 【Chemistry 4】 (In the formula, the wavy lines indicate crosslinking sites.)

2. The compound according to claim 1, further comprising an α-type or β-type polyaspartic acid monomer unit represented by the following general formula (5): 【Chemistry 5】 (In the formula, R ４ represents a hydrocarbon group having 2 to 8 carbon atoms. The hydrocarbon group may contain a heteroatom.

3. The R １ The compound according to claim 1 or 2, wherein is a straight or branched chain alkyl group.

4. The R ２ The compound according to claim 1 or 2, wherein is a straight or branched chain alkyl group.

5. The R ３ The compound according to claim 1 or 2, wherein is a straight or branched chain alkyl group.

6. The compound according to claim 1 or 2, wherein, among the constituent monomers of the compound, a molar ratio of the amount of the monomer represented by general formula (1) to the amount of the monomer represented by general formula (2) is 1:6 to 2:

1.

7. The compound according to claim 1 or 2, wherein, among the constituent monomers of the compound, a molar ratio of the amount of the monomer represented by the general formula (2) to the amount of the monomer represented by the general formula (3) is 10:1 to 1:

2.

8. The compound according to claim 1 or 2, wherein, among the constituent monomers of the compound, the molar ratio of the amount of the monomer represented by the general formula (1) to the amount of the monomer represented by the general formula (3) is 10:1 to 1:

4.

9. A composition comprising the compound of claim 1 or 2.

Images