Compounds and compositions containing the same

Abstract

To provide a compound that has excellent thickening effect and is resistant to chelating agents. [Solution] A compound comprising α-type or β-type polyaspartic acid monomer units having a specific structure.

Description

[Technical Field]

[0001] The present invention relates to a compound containing a polyaspartic acid monomer unit, and a composition containing the same. [Background technology]

[0002] Traditionally, polyacrylic acid polymers, such as carboxyvinyl polymers, have been used as thickeners for cosmetics and other applications. While carboxyvinyl polymers can create a fresh gel in small amounts, there is a growing demand for biodegradable thickeners to replace them from an environmental perspective.

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

[0004] [Patent Document 1] Japanese Patent Publication No. 2005-344061 [Patent Document 2] Japanese Patent Publication No. 2019-089897 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, it was found that the polyaspartic acid derivatives described in Patent Documents 1 and 2 did not provide sufficient thickening effect. Furthermore, there had been little research on the compatibility of general chelating agents with polyaspartic acid derivatives.

[0006] For example, since chelating agents such as EDTA-2Na are widely used as cosmetic raw materials, it is important that the polyaspartic acid derivative has good compatibility with the chelating agent when formulating it into cosmetics. Therefore, for example, in an aqueous solution in which both the chelating agent and the polyaspartic acid derivative are dissolved, it is required to maintain the thickening effect by the polyaspartic acid derivative (hereinafter referred to as chelating agent resistance) without the aqueous solution becoming cloudy or rapidly decreasing in viscosity, etc. Therefore, an object of the present invention is to provide a compound having an excellent thickening effect and chelating agent resistance.

Means for Solving the Problems

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that a polyaspartic acid derivative containing a monomer unit having a specific structure has an excellent thickening effect and chelating agent resistance, and can solve the above problems, and have completed the invention of the present invention.

[0008] That is, the invention of the present invention is as follows. [1] A compound containing an α-type or β-type polyaspartic acid monomer unit A-U represented by the following general formula (1) and an α-type or β-type polyaspartic acid monomer unit B-U represented by the following general formula (2).

Chemical formula

Chemical formula

[0009] According to the present invention, a compound having an excellent thickening effect and chelating agent resistance can be provided. [Brief Description of the Drawings]

[0010] [Figure 1] It is a diagram showing the change over time of the viscosity when left at 40 ° C after adding EDTA-2Na to each sample in Examples 7 and 8. [Modes for Carrying Out the Invention]

[0011] Hereinafter, the invention of the present invention will be described in more detail. Note that the present invention is not limited only to the following embodiments.

[0012] Unless otherwise specified, the notation "XX or greater and YY or less" or "XX~YY" which indicates a numerical range, means a numerical range that includes the endpoints, the lower limit and the upper limit. When numerical ranges are given in stages, the upper and lower limits of each range can be combined in any way.

[0013] <Inventive compound> The compound of the present invention is a compound (also referred to as "the compound of the present invention") comprising an α-type or β-type polyaspartic acid monomer unit AU (also referred to as "monomer unit AU") represented by the following general formula (1), and an α-type or β-type polyaspartic acid monomer unit BU (also referred to as "monomer unit BU") represented by the following general formula (2). In other words, the compound of the present invention is a polyaspartic acid derivative containing monomer units AU and BU as repeating units. Polyaspartic acid includes polymers obtained by peptide condensation polymerization of aspartic acid. The monomer unit AU is a structure derived from amine A and polysuccinimide, which are used in the production of the compounds of the present invention as described later. The monomer unit BU is a structure derived from amine B and polysuccinimide, which are used in the production of the compounds of the present invention as described later.

[0014] The compound of the present invention, by containing monomer units AU and BU, provides excellent thickening effect and chelating agent resistance. The thickening effect is presumed to be due to the steric hindrance of R1 in general formula (1), which is a hydrocarbon group with a specific chain length, suppressing the bending of the polymer chain and intramolecular association, while promoting intermolecular association, and also because the intermolecular association becomes stronger due to the enhanced hydrophobic interactions. Furthermore, generally, when a chelating agent is added to an aqueous solution, the ions derived from the chelating agent and water molecules hydrate, causing hydrophobic solutes to precipitate. However, the compound of the present invention possesses a good balance of both hydrophobicity due to the monomer unit AU and hydrophilicity due to the monomer unit BU, which is believed to allow the compound to exhibit a thickening effect without precipitation even when a chelating agent is added.

[0015] [ka] (In the formula, R1 represents a hydrocarbon group with 14 to 16 carbon atoms.)

[0016] [ka] (In the formula, R 21 R represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain heteroatoms. 22 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Also, in the formula, -NR 21 -R 22 R 21 The heteroatoms or carbon atoms that make up the R 22 (It may also be a cyclic amino group covalently bonded to the carbon atoms constituting the molecule.)

[0017] In general formula (1), R1 is not particularly limited as long as it is a hydrocarbon group having 14 to 16 carbon atoms, and may be saturated or unsaturated, and may be branched or linear.

[0018] The number of carbon atoms in the hydrocarbon group R1 is 14 or more, preferably 15 or more, and more preferably 16. On the other hand, it is 16 or less, and more preferably 16.

[0019] Specifically, R1 can be defined as, for example, linear alkyl groups such as tetradecyl, pentadecyl, and hexadecyl groups; branched alkyl groups such as isotetradecyl, isopentadecyl, and isohexadecyl groups; cycloalkyl groups such as cyclotetradecyl, cyclopentadecyl, and cyclohexadecyl groups; cycloalkylalkyl groups such as cyclohexyloctyl, cyclohexylnonyl, and cyclohexyldecyl groups; and alkenyl groups such as tetradecenyl, pentadecenyl, and hexadecenyl groups. Among these, branched or linear alkyl groups are preferred, and linear alkyl groups are more preferred.

[0020] In the compound of the present invention, the monomer unit AU may consist of one type alone or two or more types.

[0021] In the compounds of the present invention, the amount of monomer unit AU is not particularly limited, but is preferably 10.0 mol% or more, more preferably 15.0 mol% or more, even more preferably 20.0 mol% or more, even more preferably 30.0 mol% or more, and most preferably 40.0 mol% or more. On the other hand, it is preferably 95.0 mol% or less, more preferably 80.0 mol% or less, even more preferably 65.0 mol% or less, even more preferably 55.0 mol% or less, and most preferably 52.0 mol% or less. For example, 10.0 mol% to 95.0 mol%, 15.0 mol% to 80.0 mol%, 20.0 mol% to 65.0 mol%, 30.0 mol% to 55.0 mol%, or 40.0 mol% to 52.0 mol%. The amount of monomer unit AU can be adjusted by the amount of amine A and other raw materials added.

[0022] In particular, when R1 in the monomer unit AU is any of tetradecyl, pentadecyl, or hexadecyl groups, the amount of monomer unit AU in the compound of the present invention is preferably 35.0 mol% or more, more preferably 38.0 mol% or more, and especially preferably 40.0 mol% or more. On the other hand, it is preferably 55.0 mol% or less, more preferably 50.0 mol% or less, and especially preferably 45.0 mol% or less. For example, 35.0 mol% to 55.0 mol%, 38.0 mol% to 50.0 mol%, and 40.0 mol% to 45.0 mol%.

[0023] The "abundance of monomer units AU" referred to here is, 1 This refers to the result obtained from HNMR. 1 The detailed calculation method from 1H NMR is explained in the section "Calculation of the Composition Ratio of the Compound of the Invention" in the Examples.

[0024] In general formula (2), R 21The hydrocarbon group is not particularly limited as long as it has 1 to 20 carbon atoms and may contain heteroatoms. 21 The heteroatoms may be saturated or unsaturated, branched or linear, or have a ring structure. One or more heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur atoms are included. Examples of hydrocarbon groups having 1 to 20 carbon atoms that may contain heteroatoms include hydrophilic hydrocarbon groups containing nitrogen, oxygen, or sulfur atoms. Specifically, examples include hydrocarbon groups having 1 to 20 carbon atoms in which one or more hydrogen atoms are substituted with substituents containing heteroatoms. Examples of substituents containing heteroatoms include one or more selected from the group consisting of hydroxyl groups (-OH), amino groups (-NH2), and thiol groups (-SH). Furthermore, examples of hydrocarbon groups having 1 to 20 carbon atoms that may contain heteroatoms include those in which a structure containing one or more heteroatoms selected from the group consisting of -O-, -NH-, and -S- is interposed between the CC bonds in the above-mentioned 1 to 20 carbon-carbon groups. 21Examples include hydroxyalkyl groups such as hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, hydroxyheptyl, and hydroxyoctyl; dialkylamino groups such as dimethylamino, diethylamino, dipropylamino, and dibutylamino; azapropyl, azabutyl, azapentyl, azahexyl, N,N-dimethylaminobutyl, N,N-dimethylaminopropyl, N,N-dimethylaminoethyl, and N,N-dimethylaminomethyl groups. Azaalkyl groups such as N,N-diethylaminobutyl group, N,N-diethylaminopropyl group, N,N-diethylaminoethyl group, N,N-diethylaminomethyl group; azaalkenyl groups such as azapropenyl group, azabutenyl group, azapentenyl group, azahexenyl group, N,N-dimethylaminopropenyl group, N,N-dimethylaminobutenyl group, N,N-dimethylaminohexenyl group, N,N-diethylaminopropenyl group; oxaethyl group, oxapropyl group, oxabutyl group, oxapentyl group, oxahexyl group, oxaheptyl group, ox Oxaalkyl groups such as saoctyl group; oxaalkyl groups such as oxapropenyl group, oxabutenyl group, oxapentenyl group, oxahexenyl group, oxaheptenyl group, oxaoctenyl group; thioalkyl groups such as thiobutyl group, thiopentyl group, thiohexyl group, thioheptyl group, thiooctyl group; thioalkenyl groups such as thiopentenyl group, thiohexenyl group, thioheptenyl group, thiooctenyl group; hydroxyethoxyethyl group, hydroxyethoxypropyl group, hydroxyethoxybutyl group, hydroxypropoxyethyl group, hydroxypro Hydroxyalkoxyalkyl groups such as hydroxypropyl group and hydroxypropoxybutyl group; alkoxyalkoxyalkyl groups such as methoxyethoxyethyl group, methoxyethoxypropyl group, methoxyethoxybutyl group, methoxypropoxyethyl group, methoxypropoxypropyl group, methoxypropoxybutyl group; alkoxyalkyl groups such as methoxymethyl group, methoxyethyl group, methoxypropyl group, methoxybutyl group, methoxypentyl group, ethoxymethyl group, ethoxyethyl group, ethoxybutyl group, ethoxypentyl group;Examples include dihydroxyalkyl groups such as dihydroxyethyl, dihydroxypropyl, and dihydroxybutyl groups; and polyhydroxyalkyl groups such as the group obtained by removing the amino group (-NH2) from D-glucamine.

[0025] The number of carbon atoms in a hydrocarbon group having 1 to 20 carbon atoms, which may contain heteroatoms, is not particularly limited, but may be, for example, 1 or more, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, 10 or more, 11 or more, 12 or more, 13 or more, 14 or more, 15 or more, or 16 or more, or 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, 12 or less, 11 or less, 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less, and any non-contradictory combination of these may be used. Specifically, for example, the ranges could be 1-20, 2-19, 3-18, 4-17, 5-16, 6-15, 7-14, 8-13, 9-12, 10-11, 1-10, 2-9, 3-8, 4-7, 5-6, 4-5, 11-20, 12-19, 13-18, 14-17, 15-16, or 16-20.

[0026] R 21 From the viewpoint of viscosity and chelating agent resistance, hydroxyalkyl groups or hydroxyalkoxyalkyl groups are preferred. Examples of hydroxyalkyl groups include hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, and hydroxyhexyl group. Examples of hydroxyalkoxyalkyl groups include hydroxyethoxyethyl group, hydroxyethoxypropyl group, hydroxyethoxybutyl group, hydroxypropoxyethyl group, hydroxypropoxypropyl group, and hydroxypropoxybutyl group.

[0027] The compounds of the present invention have a thickening effect and resistance to chelating agents, but it is more preferable that the thickening effect due to the polyaspartic acid derivative persists for a long time after the addition of a chelating agent (hereinafter referred to as storage stability). From the standpoint of storage stability, R 21A hydroxyalkoxyalkyl group is preferred, a hydroxyethoxyethyl group or a hydroxyethoxypropyl group is more preferred, and a hydroxyethoxyethyl group is particularly preferred.

[0028] In general formula (2), R 22 The hydrocarbon group is not particularly limited as long as it is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. The hydrocarbon group having 1 to 6 carbon atoms may be saturated or unsaturated, branched or linear, or have a ring structure. Specific examples of hydrocarbon groups having 1 to 6 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups; branched alkyl groups such as isopropyl, isobutyl, and isopentyl groups; cycloalkyl groups such as cyclobutyl, cyclopentyl, and cyclohexyl groups; cycloalkylalkyl groups such as cyclobutylmethyl groups; and alkenyl groups such as propenyl, butenyl, pentenyl, and hexenyl groups. Among these, alkyl groups are preferred as hydrocarbon groups having 1 to 6 carbon atoms.

[0029] The number of carbon atoms in a hydrocarbon group having 1 to 6 carbon atoms is not particularly limited, but may be, for example, 1 or more, 2 or more, 3 or more, 6 or less, 5 or less, or 4 or less, and may be any non-contradictory combination of these. Specifically, for example, it may be 1 to 6, 2 to 5, or 3 to 4.

[0030] Also, general formula (2), -NR 21 -R 22 R 21 The heteroatoms or carbon atoms that make up the R 22 It may also be a cyclic amino group covalently bonded to the carbon atoms constituting it. For example, -NR 21 -R 22 R 21 One or more heteroatoms or carbon atoms that make up the R 22 It may also be a cyclic amino group covalently bonded to one or more of the carbon atoms constituting it. -NR 21 -R 22Specifically, examples include groups obtained by removing a hydrogen atom from the amino group of L-prolinol or D-prolinol. The number of carbon atoms forming the ring of the cyclic amino group is not particularly limited, but may be, for example, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, or 10 or more, or 23 or less, 22 or less, 21 or less, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, or 15 or less, and any non-contradictory combination of these may be used. Specifically, for example, it may be 2-23, 3-22, 4-21, 5-20, 6-19, 7-18, 8-17, 9-16, or 10-15.

[0031] In the compound of the present invention, the monomer unit BU may consist of one type alone or two or more types.

[0032] In the compounds of the present invention, the amount of monomer unit BU is not particularly limited, but may be, for example, 30 mol% or more, 35 mol% or more, 40 mol% or more, 45 mol% or more, or 50 mol% or more, or 70 mol% or less, 65 mol% or less, 60 mol% or less, 55 mol% or less, 50 mol% or less, or 45 mol% or less, and any non-consistent combination of these may be used. Specifically, for example, it may be 30 mol% to 70 mol%, 35 mol% to 65 mol%, 40 mol% to 60 mol%, 45 mol% to 55 mol%, 50 mol% to 70 mol%, 30 mol% to 50 mol%, or 35 mol% to 45 mol%. The amount of monomer unit represented by general formula (2) can be adjusted by the amount of amine B and other raw materials added.

[0033] The "abundance of monomer units BU" referred to here is, 1 This refers to the result obtained from HNMR. 1 The detailed calculation method from 1H NMR is explained in the section "Calculation of the Composition Ratio of the Compound of the Invention" in the Examples.

[0034] In polyaspartic acid derivatives, the ratio of the amount of monomer unit AU (mol%) to the amount of monomer unit BU (mol%) (also expressed as (AU) / (BU)) is not particularly limited, but may be, for example, 0.50 or more, 0.60 or more, 0.70 or more, 0.80 or more, 0.90 or more, 1.00 or more, 1.10 or more, 1.20 or more, 1.30 or more, or 1.40 or more, and may also be 3.00 or less, 2.70 or less, 2.50 or less, 2.30 or less, 2.00 or less, 1.90 or less, 1.80 or less, 1.70 or less, 1.60 or less, or 1.50 or less. Specifically, for example, the ratios may be 0.50-3.00, 0.60-2.70, 0.70-2.50, 0.80-2.30, 0.90-2.00, 1.00-1.90, 1.10-1.80, 1.20-1.70, 1.30-1.60, or 1.40-1.50. In the present invention, the above ratios are 1 This refers to the result obtained from HNMR. 1 The detailed calculation method from 1H NMR is explained in the section "Calculation of the Composition Ratio of the Compound of the Invention" in the Examples.

[0035] The compounds of the present invention may further contain α-type or β-type polyaspartic acid monomer units Crosslink-U (also referred to as "monomer unit Crosslink-U") represented by the following formula (3). That is, the compounds of the present invention may further contain monomer unit Crosslink-U as repeating units. The monomer unit Crosslink-U has a structure derived from the crosslinking agent and polysuccinimide of the raw materials described later. The inclusion of monomer unit Crosslink-U in the compounds of the present invention makes it easier to obtain polyaspartic acid derivatives with high viscosity.

[0036] [ka] (In the formula, the dashed line indicates the bridge construction site.)

[0037] When the compound of the present invention contains the monomer unit Crosslink-U, for example, the compound of the present invention may be a slightly crosslinked modified polyaspartic acid derivative. Here, "slightly crosslinked modified polyaspartic acid derivative" means a polyaspartic acid derivative in which the amount of crosslinking is 0.1 mol% to 2.0 mol%. "Slightly crosslinked" is distinguished from ordinary "crosslinking" in which the amount of crosslinking exceeds 2.0 mol%.

[0038] When the compound of the present invention contains the monomer unit Crosslink-U, the amount of crosslinking in the polyaspartic acid derivative (i.e., the amount of monomer unit Crosslink-U present in the compound of the present invention) may be 0.1 mol% or more, 0.3 mol% or more, or 0.5 mol% or more, and may be 2.0 mol% or less, 1.8 mol% or less, or 1.7 mol% or less. Specifically, for example, it may be 0.1 mol% to 2.0 mol%, 0.3 mol% to 1.8 mol%, or 0.5 mol% to 1.7 mol%. The amount of crosslinking can be adjusted by the amount of crosslinking agent and the amount of each other raw material added. The amount of crosslinking can be calculated from the ratio (%) of the amount of crosslinking agent (in moles) to the amount of polysuccinimide (in moles).

[0039] The compounds of the present invention may further contain succinimide monomer units CU (also referred to as "monomer unit CU") represented by the following formula (4). That is, the compounds of the present invention may further contain monomer unit CU as repeating units. Monomer unit CU is the unreacted imide ring remaining after the ring-opening reaction of polysuccinimide in the method for producing the compounds of the present invention described later.

[0040] [ka]

[0041] In the compounds of the present invention, the ratio of the total amount of monomer unit AU and monomer unit BU to the amount of monomer unit CU (mol%) (also expressed as [(AU)+(BU)] / (CU)) is not particularly limited, but may be, for example, 2.00 or more, 2.50 or more, 5.00 or more, 7.00 or more, 10.00 or more, 15.00 or more, 20.00 or more, 30.00 or more, 40.00 or more, 50.00 or more, or 60.00 or more, or 99.00 or less, 90.00 or less, 80.00 or less, 70.00 or less, 60.00 or less, 50.00 or less, 40.00 or less, 30.00 or less, 20.00 or less, 15.00 or less, 10.00 or less, or 7.00 or less, and may be any non-contradictory combination of these. Specifically, for example, the ratios may be 2.00-99.00, 2.50-90.00, 5.00-80.00, 7.00-70.00, 10.00-60.00, 15.00-50.00, 20.00-40.00, 30.00-99.00, 40.00-90.00, 50.00-80.00, 60.00-70.00, 2.00-30.00, 2.50-20.00, 5.00-15.00, 5.00-10.00, or 5.00-7.00. In the present invention, the above ratios are 1 This refers to the result obtained from HNMR. 1 The detailed calculation method from 1H NMR is explained in the section "Calculation of the Composition Ratio of the Compound of the Invention" in the Examples.

[0042] The bonding configuration of the monomer units AU, BU, CU, and Crosslink-U may be random, blocky, or tapered, respectively. Furthermore, the bonding configuration of each of these monomer units may be linear, macrocyclic, branched, star-shaped, or three-dimensional network, but linear is preferred.

[0043] The compounds of the present invention may contain monomer units other than monomer units AU, BU, CU, and Crosslink-U, to the extent that they do not impair the effects of the present invention.

[0044] In the compound of the present invention, either α-type polyaspartic acid monomer units or β-type aspartic acid monomer units may be present alone, or both may coexist. When both coexist, the ratio of α-type polyaspartic acid monomer units to β-type aspartic acid monomer units is not particularly limited.

[0045] The viscosity of an aqueous solution (concentration 1.0 wt%) of the compound of the present invention is preferably 5000 mPa·s or more, more preferably 6000 mPa·s or more, even more preferably 7000 mPa·s or more, even more preferably 8000 mPa·s or more, and most preferably 10000 mPa·s or more. On the other hand, it is preferably 30000 mPa·s or less, more preferably 28000 mPa·s or less, even more preferably 26000 mPa·s or less, and even more preferably 25000 mPa·s or less. For example, 5000 mPa·s to 30000 mPa·s, 6000 mPa·s to 28000 mPa·s, 7000 mPa·s to 26000 mPa·s, 8000 mPa·s to 25000 mPa·s, or 10000 mPa·s to 25000 mPa·s. Note that viscosity here refers to the measured value obtained using a B-type viscometer under a rotational speed of 12 rpm.

[0046] The viscosity of an aqueous solution of the compound of the present invention (concentration 1.0 wt%) with a chelating agent (concentration 0.1 wt%) added is preferably 1000 mPa·s or more, more preferably 2000 mPa·s or more, and even more preferably 3000 mPa·s or more. On the other hand, it is preferably 30000 mPa·s or less, more preferably 28000 mPa·s or less, and even more preferably 26000 mPa·s or less. For example, 1000 mPa·s to 30000 mPa·s, 2000 mPa·s to 28000 mPa·s, and 3000 mPa·s to 26000 mPa·s. Here, viscosity refers to the measurement value under a rotational speed of 12 rpm using a B-type viscometer.

[0047] The weight-average molecular weight (Mw) of the compound of the present invention is not particularly limited, but is preferably 60,000 or more, more preferably 70,000 or more, and even more preferably 80,000 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 may be 60,000 to 700,000, 70,000 to 600,000, or 80,000 to 500,000. 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 invention, as described later, and by the types of amine A, amine B, and amine C. The weight-average molecular weight used here refers to the converted value using polystyrene as the standard substance by the GPC method (differential refractometer). Specifically, it refers to the weight-average molecular weight measured using a G1000HHR column (TSKgel®, manufactured by Tosoh Corporation), a G4000HHR column (TSKgel®, manufactured by Tosoh Corporation), or a GMHHR-H column (TSKgel®, manufactured by Tosoh Corporation), with dimethylformamide containing 10 mM lithium bromide as the eluent.

[0048] The compounds of the present invention are obtained by ring-opening polysuccinimide using amines A and B, described later. If the compounds of the present invention further contain the monomer unit Crosslink-U, they can be obtained by further forming a crosslinked portion with a crosslinking agent. In addition, unreacted imide rings may remain in the ring-opening reaction of polysuccinimide, in which case the compounds of the present invention further contain the monomer unit CU.

[0049] [Polysuccinimide] Polysuccinimide (PSI) is a polymer represented by the following formula (5).

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

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

[0052] [Amine A, Amine B] As amine A, we use an amine represented by the following general formula (7). R1-NH2(7) (In the formula, R1 represents a hydrocarbon group with 14 to 16 carbon atoms.)

[0053] Amine B is an amine represented by the following general formula (7). R 21 -NH-R 22 (7) (In the formula, R 21 R represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain heteroatoms. 22 R represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Also, amines represented by general formula (7) are R 21 The heteroatoms or carbon atoms that make up the R22 It may also be a cyclic amine covalently bonded to the carbon atoms constituting it.

[0054] R in general formula (6) 1 Regarding this, R in general formula (1) 1 We will use the explanation regarding this. Also, R in general formula (7) 21 and R 22 Regarding this, R in general formula (2) 21 Explanation and R 22 The explanation regarding this matter will be used. Amine A and amine B (hereinafter sometimes referred to as monoamines) may be commercially available products or prepared by known methods.

[0055] Amine A and amine B may be used individually or in combination of two or more types.

[0056] [Crosslinking agent] The crosslinking agent is not particularly limited as long as it can form a crosslinked portion. Specifically, a preferred crosslinking agent for forming amide bonds used in the crosslinked portion is, for example, a polyfunctional amine.

[0057] A 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 aromatic rings such as xylenediamine; alicyclic diamines such as norbornenediamine; 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), polyoxyethylenediamine, and polyoxypropylenediamine; amino acids with amino groups in their side chains, such as lysine and ornithine, and their derivatives; monoamino compounds linked by disulfide bonds, such as cystine and cystamine, and their derivatives. It is preferable that the polyfunctional amine does not contain the above amino acids and their derivatives. From the viewpoint of having a flexible structure that makes it less likely for insoluble matter to be generated during the crosslinking reaction and easier to control the crosslinking reaction, it is preferable that the polyfunctional amine be one of the above ether-based diamines.

[0058] Examples of polyfunctional amines other than diamines include tris(2-aminoethyl)amine (TREN), tris(3-aminopropyl)amine, and other tris(2-aminoalkyl)amines (preferably with 1 to 5 alkyl carbonates, and more preferably 2 to 4); diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like.

[0059] 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).

[0060] One method for reacting polysuccinimide with a polyfunctional amine is to carry out the reaction in an organic solvent. We will explain this using an example where the polyfunctional amine is a diamine. In a method for reacting polysuccinimide with diamine in an organic solvent, the polysuccinimide is dissolved in the organic solvent, and then the diamine, or a solution of the diamine in the organic solvent, is added dropwise. At this time, the amount of organic solvent used to dissolve the polysuccinimide is not particularly limited, but it is usually adjusted to achieve a polymer concentration of 1 to 50% by mass.

[0061] The temperature at which polysuccinimide reacts with diamine is not particularly limited, but is, for example, room temperature to 80°C.

[0062] The conditions for the above reaction (reaction temperature, reaction time, reaction concentration, amount of diamine used, etc.) are not particularly limited, but it is desirable to use conditions that prevent the entire reaction solution from gelling.

[0063] [Method for producing the compound of the present invention] One example of a method for producing the compound of the present invention is a ring-opening reaction method for polysuccinimide using polysuccinimide and a monoamine. The order in which amine A and amine B are added is not particularly limited. From the viewpoint of easily controlling the hydrophobicity of the compound of the present invention, it is more preferable to add amine A first. Furthermore, in the ring-opening reaction of polysuccinimide, in addition to polysuccinimide and monoamines, crosslinking agents such as polyfunctional amines can also be used. The order of addition of the crosslinking agent and monoamine is not particularly limited. The monoamine may be added first, followed by the crosslinking agent, the monoamine and crosslinking agent may be added simultaneously, or the crosslinking agent may be added first, followed by the monoamine. From the viewpoint of easily controlling the amount of crosslinking, it is preferable to add the crosslinking agent first, allow the crosslinking reaction to proceed, and then add the monoamine.

[0064] A specific method for producing the compound of the present invention is, for example, when a polyfunctional amine is used as a crosslinking agent, a method of ring-opening the imide ring of polysuccinimide by reacting polysuccinimide with the crosslinking agent and then reacting it with a monoamine. By reacting polysuccinimide with a monoamine, the imide ring of polysuccinimide opens. Furthermore, by using a crosslinking agent, the resulting compound of the present invention has a crosslinked structure. The total amount of crosslinking agent and monoamine used may be less than 1 molar equivalent relative to the molar equivalent of the monomer unit of polysuccinimide, in which case unreacted imide rings may remain, or it may be 1 molar equivalent or more, in which case no unreacted imide rings may remain.

[0065] The unreacted imide ring may remain, or further ring-opening reactions may be carried out using monoamines other than amine A and amine B. Alternatively, the unreacted imide ring may be opened with a substituted amine such as ethanolamine, cysteamine, or dibutylamine, if desired.

[0066] In the method for producing the compound of the present invention, the amount of amine A charged is preferably 10.0 mol% or more, more preferably 13.0 mol% or more, even more preferably 15.0 mol% or more, even more preferably 20.0 mol% or more, and most preferably 45.0 mol% or more, relative to the amount of polysuccinimide charged. On the other hand, it is preferably 95.0 mol% or less, more preferably 80.0 mol% or less, even more preferably 70.0 mol% or less, even more preferably 60.0 mol% or less, and most preferably 55.0 mol% or less. For example, 10.0 mol% to 95.0 mol%, 13.0 mol% to 80.0 mol%, 15.0 mol% to 70.0 mol%, 20.0 mol% to 60.0 mol%, or 45.0 mol% to 55.0 mol%.

[0067] In the method for producing the compound of the present invention, the amount of amine B charged is preferably 20.0 mol% or more, more preferably 30.0 mol% or more, even more preferably 40.0 mol% or more, and even more preferably 45.0 mol% or more, relative to the amount of polysuccinimide charged. On the other hand, it is preferably 90.0 mol% or less, more preferably 80.0 mol% or less, even more preferably 70.0 mol% or less, and even more preferably 65.0 mol% or less. For example, 20.0 mol% to 90.0 mol%, 30.0 mol% to 80.0 mol%, 40.0 mol% to 70.0 mol%, or 45.0 mol% to 65.0 mol%.

[0068] In the method for producing the compound of the present invention, 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, 0.1 mol% to 2.0 mol%, 0.3 mol% to 1.8 mol%, or 0.5 mol% to 1.7 mol%.

[0069] In the method for producing the compound of the present invention, the ratio of the amount of amine A charged (mol%) to the amount of amine B charged (mol%) (also expressed as (amine A) / (amine B)) is not particularly limited, but may be, for example, 0.50 or more, 0.60 or more, 0.70 or more, 0.80 or more, 0.90 or more, 1.00 or more, 1.10 or more, 1.20 or more, 1.30 or more, or 1.40 or more, and may also be 3.00 or less, 2.70 or less, 2.50 or less, 2.30 or less, 2.00 or less, 1.90 or less, 1.80 or less, 1.70 or less, 1.60 or less, or 1.50 or less. Specifically, for example, the ranges may be 0.50-3.00, 0.60-2.70, 0.70-2.50, 0.80-2.30, 0.90-2.00, 1.00-1.90, 1.10-1.80, 1.20-1.70, 1.30-1.60, or 1.40-1.50.

[0070] In the method for producing the compound of the present invention, monoamines other than amine A and amine B may be used. In that case, the total amount of amine A and amine B added is preferably 80.0 mol% or more, more preferably 90.0 mol% or more, and even more preferably 95.0 mol% or more.

[0071] The total amount of amine A, amine B, and other monoamines used in the charge 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. Generally, the amount used is a molar equivalent of 0.1 times or more the molar equivalent of the monomer unit of polysuccinimide. On the other hand, generally, the amount used is a molar equivalent of 10 times or less the molar equivalent of the monomer unit of polysuccinimide, and preferably a molar equivalent of 1.2 times or less. For example, a molar equivalent of 0.1 to 10 times is used, and a molar equivalent of 0.1 to 1.2 times is preferred.

[0072] [Organic solvents] In the method for producing the compound of the present invention, the organic solvent is not particularly limited as long as it substantially dissolves the polysuccinimide and the monoamine and / or does not substantially inhibit the progress of the reaction.

[0073] Specific examples of organic solvents include, for example, aprotic polar organic solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethyl sulfoxide (DMSO), and sulfolane; lower alcohols with 1 to 5 carbon atoms such as methanol, ethanol, n-propanol, and isopropanol; polyhydric alcohols with 1 to 8 carbon atoms such as dihydric alcohols such as butylene glycol, propylene glycol, ethylene glycol, and dibutylene glycol, and trihydric alcohols such as glycerin; sterols such as cholesterol, sitosterol, phytosterol, and lanosterol; monosaccharides such as pentoses such as ribose, arabinose, and xylose, and hexoses such as glucose, galactose, and fructose; and sugar alcohols such as sorbitol, xylitol, and maltitol. These can be used individually or in combination.

[0074] [Basic catalyst] In the method for producing the compound of the present invention, a catalyst may be used or not. A catalyst such as a basic catalyst may be used. The basic catalyst used is not particularly limited as long as it substantially accelerates the reaction rate. Specific examples of basic catalysts include, for example, aliphatic tertiary amines such as trimethylamine, triethylamine, tripropylamine, tributylamine, diisopropylethylamine (DIEA), triethanolamine, and triethylenediamine (DABCO), alicyclic tertiary amines such as N-methylmorpholine, aromatic tertiary amines such as dimethylaniline and diethylaniline, and tetramethylguanidine, which can be used alone or in combination.

[0075] In the method for producing the compound of the present invention, the amount of basic catalyst used is not particularly limited, as long as it substantially accelerates the reaction rate. Generally, the amount of basic catalyst used is 0 to 2 times the molar equivalent of the total amount of monoamine charged.

[0076] [Reaction temperature] In the method for producing the compound of the present invention, the reaction temperature is not particularly limited as long as the progress of the reaction can be substantially maintained. Generally, the reaction temperature is selected from a temperature range of 5 to 150°C. The reaction temperature can also be selected to be optimal from the viewpoint of the monoamine used, shortening the reaction time, and improving the reaction rate. The method for producing the compound of the present invention preferably includes an amine A reaction step in which amine A is added, and an amine B reaction step in which amine B is added. In this case, the temperatures of the amine A reaction step and the amine B reaction step may be the same or different. Furthermore, when a crosslinking agent is used, it is preferable to include a crosslinking reaction step in which the crosslinking agent is added first and the crosslinking reaction proceeds, and a monoamine reaction step in which a monoamine is added thereafter. In this case, the temperature of the crosslinking reaction and the temperature of the monoamine reaction may be the same or different. In the crosslinking reaction step in which the crosslinking agent is added to polysuccinimide and the crosslinking reaction proceeds, the reaction temperature may be 120°C or lower, 100°C or lower, or 20°C or higher. For example, it may be 20°C to 120°C or 20°C to 100°C. Also, for example, when the crosslinking agent is an ether-based diamine or tris(2-aminoalkyl)amine, in the crosslinking reaction step, the reaction temperature is preferably 100°C or lower, more preferably 80°C or lower, even more preferably 60°C or lower, and may be 50°C or lower. It may also be 20°C or higher. For example, it 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, if the reaction temperature is within the above range, crosslinking can proceed uniformly. The above manufacturing method yields the compound of the present invention with high viscosity.

[0077] [Concentration of the reaction system] The concentration of the reaction system used in the method for producing the compound of the present invention is not particularly limited, as long as the progress of the reaction can be substantially maintained. The concentration of the reaction system is selected based on the concentration of polysuccinimide, and generally, the polysuccinimide concentration is selected from a range of 1 to 50% by weight. The concentration of the reaction system can also be selected from a polysuccinimide concentration of 1 to 50% by weight to be the optimal concentration for the monoamine used.

[0078] [Method for isolating the compound of the present invention] In the method for producing the compound of the present invention, the method for isolating the resulting polymer from the reaction solution after the reaction is complete is not particularly limited, as long as it substantially allows for the isolation of the reaction product with a desired purity. The above isolation method may be any known or publicly used method. Generally, known or publicly used isolation operations such as concentration, recrystallization, or reprecipitation are employed.

[0079] Specific examples of the above isolation method include, for example, adding an excess of a poor solvent (e.g., ethyl acetate, methyl alcohol, ethyl alcohol, isopropyl alcohol, etc.) to the reaction solution in which the reaction product is dissolved at a suitable temperature after the reaction is complete, isolating the precipitated reaction product by decantation, filtration, or suction filtration, thoroughly washing the crystals with a poor solvent that does not dissolve them, and then drying them. Another specific example is adding the same excess of a poor solvent as above to the reaction solution in which the reaction product is dissolved at a suitable temperature after the reaction is complete, isolating the precipitated reaction product in the same manner as above, washing it, and drying it.

[0080] In the method for producing the compound of the present invention, the resulting compound may be used as is without isolation, using the reaction mixture as the compound of the present invention. Alternatively, if necessary, only some unreacted raw materials other than the solvent may be removed to obtain the compound of the present invention. Furthermore, the concentration of the solvent in the mixture may be adjusted to obtain the compound of the present invention.

[0081] <Inventive Composition> The composition of the present invention contains the compound of the present invention. Because the compounds of the present invention have excellent thickening effects and chelating agent resistance, the compositions of the present invention are preferably in the form of topical skin preparations, and specifically in the form of cosmetics, quasi-drugs, and pharmaceuticals. When applied as topical skin preparations, the dosage form can be any of the commonly known forms such as lotion, emulsion, essence, cream, or powder-containing formulations.

[0082] The content of the compound of the present invention in the composition of the present invention is not particularly limited and can be adjusted as appropriate depending on the purpose, but is preferably 0.1% by weight or more, more preferably 0.3% by weight or more, even more preferably 0.5% by weight or more, even more preferably 0.7% by weight or more, and even more preferably 0.9% by weight or more, relative to the whole composition. On the other hand, is preferably 20.0% by weight or less, more preferably 15.0% by weight or less, even more preferably 10.0% by weight or less, even more preferably 5.0% by weight or less, and even more preferably 2.0% by weight or less, relative to the whole composition. For example, 0.1% to 20.0% by weight, 0.3% to 15.0% by weight, 0.5% to 10.0% by weight, 0.7% to 5.0% by weight, or 0.9% to 2.0% by weight. The compounds of the present invention contained in the composition of the present invention may be used individually or in combination of two or more.

[0083] Since the compounds of the present invention are chelating agent resistant, the compositions of the present invention may further contain chelating agents.

[0084] Examples of chelating agents include EDTA, EDTA-2Na, EDTA-3Na, EDTA-4Na, HEDTA-3Na, etidronic acid, etidronic acid 4Na, ethylenediaminedisuccinate 3Na, edetic acid, sodium citrate, sodium gluconate, glutamic acid diacetate 4Na, phytic acid, sodium phytate, sodium hexametaphosphate, pentasodium pentetate, and sodium metaphosphate. Sodium and potassium salts of EDTA are more preferred, and EDTA-2Na is the most preferred. In the examples, EDTA-2Na was used as a typical evaluation agent, but the chelating agent resistance effect of the compounds of the present invention is not limited to EDTA-2Na. Furthermore, the chelating agent included in the compositions of the present invention is not limited to EDTA-2Na. Chelating agents can be used individually or in combination of two or more types.

[0085] The content of the chelating agent in the composition of the present invention is not particularly limited and can be adjusted as appropriate depending on the purpose, but is preferably 0.0001% by weight or more, more preferably 0.001% by weight or more, and still more preferably 0.01% by weight or more, relative to the whole composition. Furthermore, is preferably 3% by weight or less, more preferably 1% by weight or less, and still more preferably 0.5% by weight or less. For example, it is 0.0001 to 3% by weight, 0.001 to 1% by weight, or 0.01 to 0.5% by weight.

[0086] [Optional ingredients] In manufacturing the composition of the present invention, any ingredients commonly used in the formulation of cosmetics, quasi-drugs, pharmaceuticals, etc., can be arbitrarily added, and the composition can be manufactured by conventional methods. Furthermore, since the compounds of the present invention are resistant to chelating agents, it is conceivable that they are also resistant to cosmetic quality preservatives other than chelating agents. Examples of cosmetic quality preservatives include preservatives, preservative aids, antioxidants, pH adjusters, colorfastness inhibitors, thickeners / solidifying agents, emulsifying stabilizers, and dispersants. Although these quality preservatives have different purposes than chelating agents, some of these compounds are salts and share similarities with chelating agents in terms of molecular weight, so it is conceivable that some of these compounds are compatible with the compounds of the present invention. Therefore, the compositions of the present invention may contain these cosmetic quality preservatives.

[0087] More specifically, optional ingredients can be any ingredients commonly used in topical skin preparations such as cosmetics, for example, the following: Examples of oily components include polar oils, volatile hydrocarbon oils, hydrocarbon oils, higher fatty acids, oils and fats, higher alcohols, waxes, ester oils, and silicone oils. As polar oils, synthetic ester oils include 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-hydroxystearylate, and ethylene glycol di-2-ethylhexylate. Examples include dipentaerythritol fatty acid ester, N-alkyl glycol monoisostearate, neopentyl glycol dicaprate, diisostearyl malate, glyceryl di-2-heptylundecanoate, trimethylolpropane tri-2-ethylhexylate, trimethylolpropane triisostearate, pentaneerythritol tetra-2-ethylhexylate, glyceryl tri-2-ethylhexylate, and trimethylolpropane triisostearate. Furthermore, other examples include cetyl 2-ethylhexanoate, 2-ethylhexyl palmitate, glyceryl trimyristate, glyceride tri-2-heptylundecanoate, methyl castor oil fatty acid ester, oleic acid oil, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, 2-octyldodecyl N-lauroyl-L-glutamate, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebatate, 2-hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebatate, 2-ethylhexyl succinate, triethyl citrate, octyl methoxycinnamate, and the like. Other natural oils include avocado oil, camellia oil, turtle oil, macadamia nut oil, corn oil, mink oil, olive oil, rapeseed oil, egg yolk oil, sesame oil, peach oil, wheat germ oil, sasanqua oil, castor oil, linseed oil, safflower oil, cottonseed oil, elm oil, soybean oil, peanut oil, tea seed oil, kaya oil, rice bran oil, cinnamon oil, Japanese tung oil, jojoba oil, wheat germ oil, triglycerin, glyceryl trioctanoate, glyceryl triisopalmitate, and shea butter.

[0088] Examples of volatile hydrocarbon oils include isododecane and isohexadecane. Examples of hydrocarbon oils include petrolatum, mineral oil, and squalane. Examples of high-grade fatty acids include lauric acid, stearic acid, and oleic acid. Examples of higher alcohols include stearyl alcohol, cetanol, and behenyl alcohol. Examples of oils and fats include olive fruit 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.

[0089] Surfactants include fatty acid soaps (sodium laurate, sodium palmitate, etc.), anionic surfactants such as potassium lauryl sulfate and alkyl sulfate triethanolamine ether, cationic surfactants such as stearyltrimethylammonium chloride, benzalkonium chloride and laurylamine oxide, betaine surfactants (alkyl betaine, amide betaine, sulfobetaine, etc.), imidazoline amphoteric surfactants (2-cocoyl-2-imidazolinium hydroxide-1-carboxyethyloxy disodium salt, etc.), amphoteric surfactants such as acylmethyl taurine, sorbitan fatty acid esters (sorbitan monostearate, sorbitan sesquioleate, etc.), glycerin fatty acids (glyceryl monostearate, etc.), polyglycerin fatty acids (polyglyceryl-10 laurate, etc.), propylene glycol fatty acid esters (propylene glycol monostearate, etc.), and hydrogenated castor oil. Examples include castor oil derivatives, glycerin alkyl ethers, POE sorbitan fatty acid esters (POE sorbitan monooleate, polyoxyethylene sorbitan monostearate, etc.), POE sorbitol fatty acid esters (POE-sorbitol monolaurate, etc.), POE glycerin fatty acid esters (POE-glycerin monoisostearate, etc.), POE fatty acid esters (polyethylene glycol monooleate, POE distearate, etc.), POE alkyl ethers (POE 2-octyldodecyl ether, etc.), POE alkylphenyl ethers (POE nonylphenyl ether, etc.), Pluronic® type surfactants, POE·POP alkyl ethers (POE·POP 2-decyltetradecyl ether, etc.), Tetronic surfactants, POE castor oil and hydrogenated castor oil derivatives (POE castor oil, POE hydrogenated castor oil, etc.), sucrose fatty acid esters, and nonionic surfactants such as alkyl glucosides.

[0090] The composition of the present invention may contain, in addition to the compound of the present invention, known thickeners, to an extent that does not impair the effects of the present invention. Known thickeners include guar gum, quince seed, carrageenan, galactan, gum arabic, pectin, mannan, starch, xanthan gum, curdlan, methylcellulose, hydroxyethylcellulose, carboxymethylcellulose, methylhydroxypropylcellulose, 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, kerato sulfate, locust bean gum, succinoglycan, carotenoid acid, chitin, chitosan, carboxymethyl chitin, agar, polyvinyl alcohol, polyvinylpyrrolidone, carboxyvinyl polymer, alkyl-modified carboxyvinyl polymer, sodium polyacrylate, polyethylene glycol, and bentonite.

[0091] 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 have surface treatments; inorganic pigments such as red iron oxide, yellow iron oxide, black iron oxide, cobalt oxide, ultramarine, Prussian blue, titanium dioxide, and zinc oxide, which may have surface treatments; pearlescent agents such as titanium mica, fish scale foil, and bismuth oxychloride, which may have surface treatments; and Examples include organic dyes such as Red 202, Red 228, Red 226, Yellow 4, Blue 404, Yellow 5, Red 505, Red 230, Red 223, Orange 201, Red 213, Yellow 204, Yellow 203, Blue 1, Green 201, Violet 201, and Red 204, which may be carboxylated; organic powders such as polyethylene powder, polymethyl methacrylate, nylon powder, and organopolysiloxane elastomers.

[0092] Examples of 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, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 4-methoxy-4'-t-butyldibenzoylmethane, and other UV absorbers.

[0093] The composition of the present invention may also contain water, ethanol, fragrance, coloring agents, and the like.

[0094] <Composition for increasing viscosity> Compositions containing the compound of the present invention are preferably used for thickening purposes, that is, they are preferably thickeners (viscosity-enhancing compositions) containing the compound of the present invention. The viscosity-enhancing composition is not particularly limited, but is preferably a topical skin preparation, and may contain, in addition to the compound of the present invention, any of the above-mentioned optional components in an amount that does not impair the effects of the present invention. The content of the compound of the present invention in the viscosity-enhancing composition is not particularly limited and can be appropriately adjusted depending on the purpose.

[0095] The composition whose viscosity is to be enhanced is not particularly limited, but it is preferably a topical skin preparation, and any of the above-mentioned optional components can be incorporated to the extent that they do not impair the effects of the present invention. Furthermore, it is preferable that at least one of the viscosity-enhancing composition and the composition whose viscosity is to be enhanced contains water. The viscosity-enhancing composition and the composition whose viscosity is to be enhanced can each be manufactured by conventional methods. [Examples]

[0096] The present invention will be described in detail below with reference to examples, but the present invention is not limited thereto.

[0097] [Synthesis Example 1] <Synthesis of polysuccinimide> 160 parts of aspartic acid and 83 parts of 85% phosphoric acid from YIXING QIANCHENG BIO-ENGINEERING were mixed in a mortar and pestle, transferred to a tray, and reacted at 190°C, 1.3 kPa for 6 hours. After grinding the reaction mixture, it was washed with distilled water until the filtrate was neutral, and then vacuum-dried at 80°C to obtain 115 parts of polysuccinimide (PSI) with a weight-average molecular weight of 80,000.

[0098] [Example 1] 3.0 g of PSI obtained in Synthesis Example 1 and 16.8 g of N-methyl-2-pyrrolidone (NMP) were placed in a reaction vessel and heated at 130°C for 2 hours until completely dissolved. After lowering the temperature to 80°C, 1.68 g of ethanol was added dropwise over 30 minutes while stirring, and the reaction vessel was then cooled and allowed to stand overnight at room temperature. Next, 6.7 g of a 50 wt% ethanol solution of tetradecylamine (3.35 g of tetradecylamine, 52.0 mol% per unit of succinimide) was added as amine A, and the reaction was carried out at 40°C for 4 hours. Furthermore, 1.383 g of 3-amino-1-propanol (61.0 mol% per unit of succinimide) was added as amine B, and the reaction was carried out at 40°C for 4 hours, and the reaction vessel was then cooled and allowed to stand overnight at room temperature. After that, the reaction mixture was discharged into 300 g of ethyl acetate while stirring to precipitate the reactants, and the solid was recovered by filtration. The mixture was then washed with stirring in 150 g of ethyl acetate, and the solid was recovered by filtration. The recovered solid was dried under reduced pressure at 60°C for 12 hours to obtain 6.69 g of the compound from Example 1.

[0099] [Examples 2-4, Comparative Examples 1-5] The compounds of Example 2-4 and Comparative Examples 1-5 were obtained using the same procedure as in Example 1, except that the types of amine A and amine B, and the amounts of amine A and amine B used were changed as shown in Tables 1 and 2.

[0100] [Example 5] 3.0 g of PSI obtained in Synthesis Example 1 and 1.68 g of N-methyl-2-pyrrolidone (NMP) were placed in a reaction vessel and heated at 130°C for 2 hours until completely dissolved. After lowering the temperature to 80°C, 1.68 g of ethanol was added dropwise over 30 minutes while stirring. The reaction vessel was then cooled, and when it reached 40°C, a mixture of 0.447 g of a 10 wt% NMP solution of 1,2-bis(2-aminoethoxy)ethane (AEE) (1.0 mol / 0.0447 g as AEE, per 1 mole of succinimide units) and 0.403 g of NMP was added as a crosslinking agent, and the mixture was allowed to react for 6 hours. The reaction vessel was then cooled and left to stand overnight at room temperature. Next, 6.7 g of a 50 wt% ethanol solution of tetradecylamine (3.35 g of tetradecylamine, 52.0 mol% per unit of succinimide) was added as amine A, and the mixture was reacted at 40°C for 4 hours. Furthermore, 1.383 g of 3-amino-1-propanol (61.0 mol% per unit of succinimide) was added as amine B, and the mixture was reacted at 40°C for 4 hours. The reaction vessel was then cooled and allowed to stand overnight at room temperature. Subsequently, the reaction mixture was discharged into 300 g of ethyl acetate while stirring to precipitate the reaction products, and the solid was recovered by filtration. The mixture was then washed in 150 g of ethyl acetate while stirring, and the solid was recovered by filtration. The recovered solid was dried under reduced pressure at 60°C for 12 hours to obtain 6.71 g of the compound of Example 5.

[0101] [Examples 6-8, Comparative Example 6] The compounds of Example 6 and Comparative Example 6 were obtained using the same procedure as in Example 5, except that the types of amine A and amine B, and the amounts of amine A and amine B used were changed as shown in Tables 1 to 3.

[0102] <Calculation of the composition ratio of the compound of the present invention> 1 The composition ratio (mol%) of the compounds obtained in each example and comparative example was calculated using 1H NMR. 1Measurement conditions for \(^1H\) NMR: 0.1 g of the compound was dissolved in 0.6 mL of dimethyl sulfoxide-d6 to prepare a measurement sample, and measurement was performed using a JNM-ECZ400S (manufactured by JEOL Ltd.) under the following conditions. Observation frequency: 400 MHz Chemical shift reference: TMS (tetramethylsilane) (0 ppm) Pulse delay: 6.8 seconds Number of scans: 16 times Pulse width: 45° (3.2 μs) Measurement temperature: 60 °C

[0103] The composition ratio (mol%) of the compound of the present invention was calculated using the obtained NMR spectrum by the following formula. Mol% of monomer unit A-U = (peak integral value of methyl group of amine A / 3) × 100 / ((peak integral value of methyl group of amine A / 3) + (peak integral value of methylene group of amine B / 2) + (peak integral value of methine group of succinimide)) Mol% of monomer unit B-U = (peak integral value of methylene group of amine B / 2) × 100 / ((peak integral value of methyl group of amine A / 3) + (peak integral value of methylene group of amine B / 2) + (peak integral value of methine group of succinimide)) Ratio of mol% of monomer unit A-U to mol% of monomer unit B-U (A-U) / (B-U) = (peak integral value of methyl group of amine A / 3) / (peak integral value of methylene group of amine B / 2) Ratio of the total mol% of monomer units A-U and B-U to mol% of monomer unit C-U [(A-U) + (B-U)] / (C-U) = [(peak integral value of methyl group of amine A / 3) + (peak integral value of methylene group of amine B / 2)] / (peak integral value of methine group of succinimide) The composition ratios calculated by the above method are shown in Tables 1 to 3.

[0104] <Measurement of the weight average molecular weight of PSI and the compound of the present invention> In the measurement of the weight-average molecular weight of the PSI of Synthesis Example 1, the polystyrene-equivalent value was determined by the GPC method (differential refractometer). For the measurement, 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. As the eluent, dimethylformamide containing 10 mM lithium bromide was used. Also, the weight-average molecular weights of the compounds obtained in Examples 1 to 8 and Comparative Examples 1 to 6 were measured in the same manner and are shown in Tables 1 to 3.

[0105] <Evaluation of Viscosity> The viscosity was measured according to the following procedure. Samples were prepared by dissolving the compounds obtained in Examples 1 to 6 and Comparative Examples 1 to 6 in ion-exchanged water under the condition of 60 °C so that the concentration became 1.0% by weight. Using a B-type viscometer (Brookfield "Viscometer DV2T"), the values measured for each sample at a rotational speed of 12 rpm, a measurement time of 1 minute, and using a spindle LV3 or LV4 under the condition of a temperature of 25 °C are shown in Tables 1 and 2.

[0106] <Evaluation of Viscosity after Adding EDTA-2Na> For each sample prepared in the above <Evaluation of Viscosity>, evaluation was carried out in the same manner as in the above <Evaluation of Viscosity>, except that disodium ethylenediamine-N,N,N',N'-tetraacetate dihydrate was added so that the EDTA-2Na concentration became 0.1% by weight, and the results are shown in Tables 1 to 3.

[0107] <Evaluation of Storage Stability> Each sample of Examples 7 and 8 prepared in the above <Evaluation of Viscosity after Adding EDTA-2Na> was left standing under the condition of 40 °C, and the viscosity at each elapsed number of days was measured by the method described in the above <Evaluation of Viscosity>, and the results are shown in Table 3 and Figure 1.

[0108] As shown in Tables 1-3, the compounds in Examples 1-8, which contained monomer units AU and BU, exhibited excellent thickening effects and chelating agent resistance. On the other hand, the compounds in Comparative Examples 1-6, which did not contain monomer unit AU, were found to be inferior in either thickening effect or chelating agent resistance, or both. Furthermore, as shown in Figure 1, the viscosity was maintained for a certain period after the addition of the chelating agent. This confirms that the compound of the present invention exhibits storage stability.

[0109] [Table 1]

[0110] [Table 2] *Unmeasurable 1: Viscosity was below the measurement limit. *Unmeasurable 2: The solution did not separate and become homogeneous, or its viscosity was below the measurement limit.

[0111] [Table 3]

Claims

1. A compound comprising an α- or β-polyaspartic acid monomer unit A-U represented by the following general formula (1), and an α- or β-polyaspartic acid monomer unit B-U represented by the following general formula (2). 【Chemistry 1】 (In the formula, R １ (This indicates a hydrocarbon group with 14 to 16 carbon atoms.) 【Chemistry 2】 (In the formula, R ２１ R represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain heteroatoms. ２２ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Also, in the formula, -NR ２１ -R ２２ R ２１ The heteroatoms or carbon atoms that make up the R ２２ (It may also be a cyclic amino group covalently bonded to the carbon atoms constituting the molecule.)

2. The compound according to claim 1, wherein the molar ratio (A-U) / (B-U) of the amount of monomer unit A-U to the amount of monomer unit B-U is in the range of 0.50 to 3.

00.

3. The compound according to claim 1 or 2, further comprising an α-type or β-type polyaspartic acid monomer unit Crosslink-U represented by the following formula (3). 【Transformation 3】 (In the formula, the dashed line indicates the bridge construction site.)

4. The compound according to claim 3, wherein the crosslinking amount is 0.1 mol% to 2.0 mol%.

5. The monomer unit B-U is R in the general formula (2). ２１ where R is a hydroalkoxyalkyl group and R ２２ is a hydrogen atom, and the compound according to claim 1.

6. A composition containing the compound described in claim 1 or 2.

7. The composition according to claim 6, further comprising a chelating agent.

8. The composition according to claim 7, wherein the chelating agent is EDTA-2Na.

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