Polyaspartic acid derivatives

Abstract

To provide a polyaspartic acid derivative that does not feel sticky when applied to the skin and has an excellent texture that crumbles on the skin. [Solution] A polyaspartic acid derivative characterized in that the spin-spin relaxation time (T2) obtained by solid echo method in pulsed NMR analysis at 40°C of a 1.0 wt% aqueous solution of the polyaspartic acid derivative is 1400 milliseconds to 2400 milliseconds.

Description

Technical Field

[0001] The present disclosure relates to polyaspartic acid derivatives and compositions containing the same.

Background Art

[0002] In a wide range of fields including pharmaceuticals and cosmetics, synthetic polymers such as crosslinked poly(meth)acrylic acid are used as water-soluble thickeners. As synthetic polymers with excellent usability, for example, copolymers of acrylamide alkylsulfonic acid and (meth)acrylic acid having a crosslinked structure are known (Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, polyaspartic acid derivatives are not known as synthetic polymers with excellent usability that can be used as thickeners. Therefore, an object of the present disclosure is to provide a polyaspartic acid derivative that is not sticky when applied to the skin and has an excellent feeling of collapsing on the skin.

Means for Solving the Problems

[0005] As a result of intensive studies to solve the above problems, the present inventors have found that a polyaspartic acid derivative, wherein the spin-spin relaxation time (T2) obtained by the solid echo method in the pulse NMR analysis at 40 °C of a 1.0 wt% aqueous solution of the polyaspartic acid derivative is 1400 milliseconds to 2400 milliseconds, can solve the above problems, and completed the invention of the present disclosure.

[0006] In other words, the invention of this disclosure is as follows: [1] A polyaspartic acid derivative, A polyaspartic acid derivative characterized in that the spin-spin relaxation time (T2) of a 1.0 wt% aqueous solution of the polyaspartic acid derivative, obtained by solid echo method in pulsed NMR analysis at 40°C, is 1400 milliseconds to 2400 milliseconds. [2] The polyaspartic acid derivative according to [1], wherein the shear viscosity of a 1.0% by weight aqueous solution of the polyaspartic acid derivative is 300 mPa·s to 10000 mPa·s. [3] The polyaspartic acid derivative according to [1] or [2], characterized in that the rate of variation of the spin-spin relaxation time (T2) of the aqueous solution when measured three times repeatedly, represented by the following formula (1), is 5.00% or less.

[0007]

number

[0008] According to this disclosure, it is possible to provide a polyaspartic acid derivative that does not feel sticky when applied to the skin and has an excellent texture that crumbles on the skin. [Modes for carrying out the invention]

[0009] The invention of this disclosure will be described in more detail below. However, this disclosure is not limited to the embodiments shown below.

[0010] 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.

[0011] <Spin-Spin Relaxation Time (T2)> The polyaspartic acid derivatives of this disclosure are characterized in that the spin-spin relaxation time (also referred to as "T2") obtained by solid echo method in pulsed NMR analysis at 40°C of a 1.0 wt% aqueous solution of the polyaspartic acid derivative is 1400 milliseconds to 2400 milliseconds. Having this characteristic makes it possible to obtain polyaspartic acid derivatives that do not feel sticky when applied to the skin, have a texture that crumbles on the skin, and exhibit excellent viscosity-enhancing properties. The mechanism is not clear, but the inventors speculate as follows.

[0012] T2 is a parameter that represents the mobility of water molecules in a 1.0 wt% aqueous solution of a polyaspartic acid derivative. When T2 is between 1400 and 2400 milliseconds, the side chains of the polyaspartic acid derivative form hydrophobic associations in the aqueous solution, resulting in a thickened state. Because the bonding force of this hydrophobic association is relatively weak, it easily breaks down when shear force is applied, such as during application, causing a rapid decrease in viscosity. This is thought to be the reason for the crumbling sensation when applied to the skin. Therefore, if T2 is between 1400 and 2400 milliseconds, a polyaspartic acid derivative can be obtained that does not feel sticky when applied to the skin, has a crumbling sensation on the skin, and exhibits excellent viscosity-enhancing properties. On the other hand, if T2 exceeds 2400 milliseconds, the viscosity of the aqueous solution is too low, so while there is no slippery feeling when applied to the skin, there is also no feeling of it crumbling on the skin. Also, if T2 is less than 1400 milliseconds, the viscosity of the aqueous solution is too high due to the entanglement of the polymers, resulting in a slippery feeling when applied to the skin. This entanglement is not easily broken down by the shear force of the application process, so there is no feeling of it crumbling due to a rapid decrease in viscosity.

[0013] The spin-spin relaxation time (T2) obtained by solid echo method in pulsed NMR analysis at 40°C for a 1.0 wt% aqueous solution of a polyaspartic acid derivative was 1400 milliseconds or greater, and also 1450 milliseconds or greater, 1500 milliseconds or greater, 1550 milliseconds or greater, and 1600 milliseconds or greater. 1650 milliseconds or more, 1700 milliseconds or more, 1750 milliseconds or more, 1800 milliseconds or more, 1850 milliseconds or more, 1900 milliseconds or more, 1950 milliseconds or more, 2000 milliseconds or more, 2050 milliseconds or more, 2100 milliseconds or more, 2150 milliseconds or more, 2200 milliseconds or more, 2250 milliseconds or more, or 2300 milliseconds or more, and 2400 milliseconds or less, 2350 milliseconds or less, 2300 milliseconds or less, 2 The time may be 250 milliseconds or less, 2200 milliseconds or less, 2150 milliseconds or less, 2100 milliseconds or less, 2050 milliseconds or less, 2000 milliseconds or less, 1950 milliseconds or less, 1900 milliseconds or less, 1850 milliseconds or less, 1800 milliseconds or less, 1750 milliseconds or less, 1700 milliseconds or less, 1650 milliseconds or less, 1600 milliseconds or less, 1550 milliseconds or less, or 1500 milliseconds or less, and any non-consistent combination thereof may be used. Specifically, for example, 1400-2400 milliseconds, 1450-2350 milliseconds, 1500-2300 milliseconds, 1550-2250 milliseconds, 1600-2200 milliseconds, 1650-2150 milliseconds, 1700-2100 milliseconds, 1750-2050 milliseconds, 1800-2000 milliseconds, 1850-1950 milliseconds, 1900-2400 milliseconds, 1950-2350 milliseconds, 2000-2300 milliseconds, and 2050 milliseconds. The time ranges may be ~2250 milliseconds, 2100-2200 milliseconds, 2150-2400 milliseconds, 2200-2350 milliseconds, 2250-2300 milliseconds, 2300-2400 milliseconds, 1400-1850 milliseconds, 1450-1800 milliseconds, 1500-1750 milliseconds, 1550-1700 milliseconds, 1600-1650 milliseconds, 1400-1600 milliseconds, 1450-1550 milliseconds, or 1400-1500 milliseconds. T2 can be adjusted, for example, by adjusting the balance of the ratio of hydrophilic and hydrophobic parts constituting the polyaspartic acid derivative depending on the type of amine (i.e., the amine used to modify the side chain of polyaspartic acid) which is a raw material described later, or by adjusting the molecular weight of the polyaspartic acid derivative, the molecular weight of polysuccinimide which is a raw material described later, etc.

[0014] T2 refers to the average value obtained from three measurements using the solid echo method in pulsed NMR analysis. T2 is calculated using the following method. A 1.0 wt% aqueous solution of a polyaspartic acid derivative is prepared and evaluated using pulsed NMR (e.g., Minispec mq series from Bruker). By applying a pulsed high-frequency magnetic field to the aqueous solution of the polyaspartic acid derivative placed in the NMR tube, the magnetization vector is tilted, and the mobility of the molecules constituting the aqueous solution of the polyaspartic acid derivative is evaluated from the time until the x and y components disappear (i.e., relaxation time). Detailed measurement methods and conditions are shown below.

[0015] (1)Measurement method 2 g of a 1.0 wt% aqueous solution of polyaspartic acid derivative is weighed into a 10 mm diameter NMR tube and heated for 15 minutes in a preheater adjusted to 40°C before use for measurement. The same sample used in the first measurement is used for the second and third measurements. After the first measurement, the sample is not returned to the preheater, but remains in the pulsed NMR spectrometer, and the remaining two measurements are performed immediately.

[0016] (2) Measurement conditions CPMG method ( 1 HNMR) • Scans: 8 times Recycle Delay: 5 seconds Dummy Shots: 2 • mode:magnitude • 90°-180° Pulse Separation: 1 millisecond ·Number of Data Points for Fitting:3000 ·Number of not Fitted Echoes:0 ·Desired Magnet Temperature:40℃

[0017] (3) Method for calculating spin-spin relaxation time (T2) The spin-spin relaxation time can be calculated from the decay curve obtained by the solid echo method of the pulsed NMR measurement using TDNMR-A software (manufactured by Bruker Japan). The fitting calculation formula is as shown in equation (2) below.

[0018]

number

[0019] In equation (2), W(1), W(2), and W(3) are Weibull coefficients, taking values ​​from 1 to 2. When W=1, it is an exponential function, and when W=2, it is a Gaussian function. For crystalline or glassy samples, W=2, and for solution or amorphous samples, W=1. Since the sample used in this measurement is a solution, W(1), W(2), and W(3) are each fitted as 1. Also, in equation (2), T 2(1) , T 2(2) , and T 2(3) The values ​​A(1), A(2), and A(3) represent the spin-spin relaxation times for the first, second, and third measurements, respectively, while A(1), A(2), and A(3) are constants representing the ratios of each component. In this measurement, the analysis is performed assuming a one-component system, so A(1) is set to 1, and A(2) and A(3) are set to 0 for fitting.

[0020] Based on the spin-spin relaxation time calculated as described above, the average value of the three spin-spin relaxation times (i.e., the sum of the first to third spin-spin relaxation times divided by 3) is calculated and defined as the "spin-spin relaxation time (T2)".

[0021] <Variability of spin-spin relaxation time (T2)> When the polyaspartic acid derivative is measured three times repeatedly using the following formula (1), the coefficient of variation of the spin-spin relaxation time (T2) of a 1.0 wt% aqueous solution may be 0% or more, 0.10% or more, 0.20% or more, 0.30% or more, 0.40% or more, 0.50% or more, 0.70% or more, or 1.00% or more, and may also be 5.00% or less, 4.00% or less, 3.00% or less, 2.00% or less, 1.00% or less, 0.70% or less, or 0.50% or less, and may be any non-contradictory combination thereof. Specifically, for example, it may be 0% to 5.00%, 0.10% to 4.00%, 0.20% to 3.00%, 0.30% to 2.00%, 0.40% to 1.00%, 0.50% to 0.70%, 0.70% to 5.00%, 1.00% to 4.00%, or 0% to 0.50%.

[0022]

Number

[0023] In formula (1), T2 represents the average value of three measurements of the spin-spin relaxation time, T 2(1) represents the spin-spin relaxation time in the first measurement, T 2(2) represents the spin-spin relaxation time in the second measurement, T 2(3) represents the spin-spin relaxation time in the third measurement.

[0024] The coefficient of variation of the spin-spin relaxation time (T2) is a parameter indicating the reliability of the measured value of T2. The smaller the coefficient of variation, the less variation there is in the measured values of T2 among the three measurements, and the larger the coefficient of variation, the more variation there is in the measured values. For example, when the polyaspartic acid derivative is uniformly dissolved in the aqueous solution of the measurement sample, the coefficient of variation becomes smaller.

[0025] A variation rate of 5.00% or less in the spin-spin relaxation time (T2) indicates high reliability of the T2 measurement. The variation rate of the spin-spin relaxation time (T2) can be adjusted, for example, by the stirring time and stirring temperature when preparing the aqueous solution of the polyaspartic acid derivative of the sample.

[0026] <Viscosity> The shear viscosity of a 1.0 wt% aqueous solution of a polyaspartic acid derivative is not particularly limited, but may be 300 mPa·s or more, 400 mPa·s or more, 500 mPa·s or more, 1000 mPa·s or more, 1500 mPa·s or more, 1600 mPa·s or more, 1900 mPa·s or more, 2000 mPa·s or more, 2500 mPa·s or more, or 3000 mPa·s or more, and may be 10000 mPa·s or less, 8000 mPa·s or less, 7000 mPa·s or less, 6000 mPa·s or less, 5000 mPa·s or less, 4000 mPa·s or less, 3000 mPa·s or less, 2500 mPa·s or less, 2000 mPa·s or less, or 1800 mPa·s or less, and may be any non-contradictory combination of these. Specifically, for example, the ranges could be 300 mPa·s to 10000 mPa·s, 400 mPa·s to 8000 mPa·s, 500 mPa·s to 7000 mPa·s, 1000 mPa·s to 6000 mPa·s, 1500 mPa·s to 5000 mPa·s, 1600 mPa·s to 4000 mPa·s, 1900 mPa·s to 3000 mPa·s, 2000 mPa·s to 2500 mPa·s, 2500 mPa·s to 10000 mPa·s, 3000 mPa·s to 8000 mPa·s, 300 mPa·s to 2000 mPa·s, or 400 mPa·s to 1800 mPa·s.

[0027] In this disclosure, shear viscosity refers to the value of the shear viscosity at a shear rate of 4.8 / s, obtained by using a rheometer (for example, a rotary rheometer MCR102 manufactured by Anton Paar) and measuring under conditions such as a cone plate CP-25, a gap of 0.106 mm, and a measurement temperature of 25°C, after pre-shearing for 15 seconds at a shear rate of 10 / s and letting it stand for 30 seconds, and then measuring the shear viscosity at shear rates from 1 / s to 1000 / s. The shear viscosity can be adjusted, for example, by the molecular weight of the polyaspartic acid derivative, the molecular weight of the raw material polysuccinimide, etc.

[0028] The weight-average molecular weight (Mw) of the polyaspartic acid derivatives of this disclosure is not particularly limited, but may be 10,000 or more, 30,000 or more, 50,000 or more, 70,000 or more, 100,000 or more, 150,000 or more, 200,000 or more, 250,000 or more, 300,000 or more, or 400,000 or more, or 1,000,000 or less, 700,000 or less, 500,000 or less, 400,000 or less, 300,000 or less, 200,000 or less, 100,000 or less, or 70,000 or less, and may be any non-consistent combination thereof. Specifically, for example, it could be 10000~1000000, 30000~700000, 50000~500000, 70000~400000, 100000~300000, 150000~200000, 200000~1000000, 250000~700000, 300000~500000, 400000~1000000, 10000~100000, or 30000~70000.

[0029] In this disclosure, the weight-average molecular weight is defined as polystyrene measured by the GPC method (differential refractometer). This refers to a converted value as a quasi-substance, specifically the weight-average molecular weight measured using, for example, 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. The weight-average molecular weight can be adjusted by the molecular weight of the polyaspartic acid derivative, the molecular weight of the raw material polysuccinimide, and so on.

[0030] <Polyaspartic acid derivative> The polyaspartic acid derivatives of this disclosure are amine-modified polyaspartic acid which may have a crosslinked structure. That is, the polyaspartic acid derivatives of this disclosure are polyaspartic acid whose side chains are modified with an amine, and which may have a crosslinked structure. Specifically, "side chains modified with an amine" means that the carboxyl group present on the side chain of the polyaspartic acid and the amino group of the amine form an amide bond. Note that "polyaspartic acid" refers to a polymer formed by peptide bonds between aspartic acid molecules. The amide bonds in the main chain of polyaspartic acid derivatives can be either α-bonds or β-bonds. Furthermore, these bonding modes may be the same or different for each structural unit.

[0031] Examples of polyaspartic acid derivatives include, for example, the following first polymer and the second polymer described later: [First polymer] A polyaspartic acid derivative containing 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, a polyaspartic acid derivative containing monomer unit AU and monomer unit BU as repeating units.

[0032] [ka] (In the formula, R 1 (This indicates a hydrocarbon group with 3 to 22 carbon atoms.)

[0033] [ka] (In the formula, R 2 (This indicates a hydrocarbon group with 1 to 20 carbon atoms, which may contain heteroatoms.)

[0034] The monomer unit AU is a structure derived from the raw materials amine A and polysuccinimide, which will be described later. The monomer unit BU is a structure derived from the raw materials amine B and polysuccinimide, which will be described later.

[0035] In general formula (1), R 1 The hydrocarbon group is not particularly limited as long as it has 3 to 22 carbon atoms. 1 The hydrocarbon group may be saturated or unsaturated, branched or linear, or have a ring structure. Specific examples of hydrocarbon groups having 3 to 22 carbon atoms include linear alkyl groups such as propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, and isohexyl groups; cycloalkyl groups such as cyclobutyl, cyclopentyl, and cyclohexyl groups; cycloalkylalkyl groups such as cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclobutylethyl, cyclopentylethyl, cyclohexylethyl, cyclobutylpropyl, cyclopentylpropyl, cyclohexylpropyl, cyclobutylbutyl, cyclopentylbutyl, and cyclohexylbutyl groups; and alkenyl groups such as propenyl, butenyl, pentenyl, and hexenyl groups. Among these, alkyl groups are preferred as hydrocarbon groups having 3 to 22 carbon atoms.

[0036] The number of carbon atoms in a hydrocarbon group having 3 to 22 carbon atoms may be 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, and may also be 22 or less, 21 or less, 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, or 9 or less, and any non-contradictory combination of these may be acceptable. Specifically, for example, 3-22, 4-21, 5-20, 6-19, 7-18, 8-17, 9-16, 10-15, 11-14, 12-13, 13-22, 14-21, 15-20, 16-19, 3-12, 4-11, 5-10, or 6-9.

[0037] The monomer unit AU contained in one molecule of polyaspartic acid derivative may consist of one type alone, or it may consist of two or more types.

[0038] In the constituent monomers of polyaspartic acid derivatives, the amount of monomer unit AU present is not particularly limited. However, the amount may be, for example, 20 mol% or more, 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, or 50 mol% or less, and any non-contradictory combination of these may be used. Specifically, for example, it may be 20 mol% to 70 mol%, 30 mol% to 65 mol%, 35 mol% to 60 mol%, 40 mol% to 55 mol%, 45 mol% to 50 mol%, or 50 mol% to 70 mol%. The amount of monomer unit AU can be adjusted by the amount of amine A and other raw materials charged.

[0039] The abundance of monomer units AU is 1 This refers to the result obtained from 1H NMR. Specifically, for example, it refers to the result obtained by measurement under the conditions described in <Calculation of Composition Ratio of Polyaspartic Acid Derivatives> below. 1 It can be calculated from the intensity ratio of peaks derived from amine A in the 1H NMR spectrum.

[0040] In general formula (2), R 2 The hydrocarbon group is not particularly limited as long as it has 1 to 20 carbon atoms and may contain heteroatoms. 2 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 atoms, oxygen atoms, sulfur atoms, etc. 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 a hydrocarbon group having 1 to 20 carbon atoms. For example, R 2Examples 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.

[0041] 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.

[0042] R 2 A hydroxyalkyl group is preferred. Examples of hydroxyalkyl groups include hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, and hydroxyhexyl group.

[0043] A single molecule of polyaspartic acid derivative may contain one monomer unit BU, or it may contain two or more monomer units.

[0044] The amount of monomer unit BU in the constituent monomers of the polyaspartic acid derivative 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 BU can be adjusted by the amount of amine B and other raw materials used.

[0045] The abundance of monomer units BU is 1 This refers to the result obtained from 1H NMR. Specifically, for example, it refers to the result obtained by measurement under the conditions described in <Calculation of Composition Ratio of Polyaspartic Acid Derivatives> below. 1 It can be calculated from the intensity ratio of the peaks derived from amine B in the 1H NMR spectrum.

[0046] 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 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. The aforementioned ratio is 1This refers to the result obtained from 1H NMR. Specifically, for example, it refers to the result obtained by measurement under the conditions described in <Calculation of Composition Ratio of Polyaspartic Acid Derivatives> below. 1 HNMR spectrum It can be calculated from the ratio of the intensity of the peak derived from amine A to the intensity of the peak derived from amine B.

[0047] The polyaspartic acid derivative may further contain succinimide monomer units CU (also referred to as "monomer unit CU") represented by the following formula (3). That is, the polyaspartic acid derivative may further contain monomer unit CU as a repeating unit. The monomer unit CU is the unreacted imide ring remaining after the ring-opening reaction of polysuccinimide in the method for producing the polyaspartic acid derivative described later.

[0048] [ka]

[0049] The amount of monomer unit CU in the constituent monomers of the polyaspartic acid derivative is not particularly limited, but may be, for example, 0.01 mol% or more, 0.1 mol% or more, 0.5 mol% or more, 1 mol% or more, 3 mol% or more, 5 mol% or more, 15 mol% or less, 10 mol% or less, 5 mol% or less, or 3 mol% or less, and any non-consistent combination of these may be used. Specifically, for example, it may be 0.01 mol% to 15 mol%, 0.1 mol% to 10 mol%, 0.5 mol% to 5 mol%, 1 mol% to 3 mol%, 3 mol% to 15 mol%, or 5 mol% to 10 mol%. The amount of monomer unit CU can be adjusted by the amount of polysuccinimide and other raw materials used.

[0050] The abundance of monomeric unit CU is 1 This refers to the result obtained from 1H NMR. Specifically, for example, it refers to the result obtained by measurement under the conditions described in <Calculation of Composition Ratio of Polyaspartic Acid Derivatives> below. 1It can be calculated from the intensity ratio of peaks originating from the monomer unit CU in the 1H NMR spectrum.

[0051] The polyaspartic acid derivative 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 (4). That is, the polyaspartic acid derivative may further contain monomer units 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 units Crosslink-U in the polyaspartic acid derivative makes it easier to obtain a polyaspartic acid derivative with high viscosity.

[0052] [ka] (In the formula, the dashed line indicates the bridge construction site.)

[0053] When a polyaspartic acid derivative contains the monomer unit Crosslink-U, for example, the polyaspartic acid derivative may be a slightly crosslinked modified polyaspartic acid derivative. Here, "slightly crosslinked modified polyaspartic acid derivative" means a polyaspartic acid derivative with a crosslinking amount of 0.1 mol% to 2.0 mol%. "Slightly crosslinked" is distinguished from ordinary "crosslinking" where the crosslinking amount exceeds 2.0 mol%.

[0054] When a polyaspartic acid derivative contains the monomer unit Crosslink-U, the amount of crosslinking in the polyaspartic acid derivative (i.e., the amount of monomer unit Crosslink-U in the constituent monomers of the polyaspartic acid derivative) 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 other raw materials 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).

[0055] The bonding configurations of the monomer units AU, BU, CU, and Crosslink-U may be random, blocky, or tapered, respectively. Furthermore, the bonding configurations of each of these monomer units may be linear, macrocyclic, branched, star-shaped, or three-dimensional network-like.

[0056] The polyaspartic acid derivative may contain monomer units other than monomer units AU, BU, CU, and Crosslink-U, to the extent that it does not impair the effects of the present disclosure.

[0057] Polyaspartic acid derivatives can be obtained, for example, by opening the ring structure of polysuccinimide using amines A and B described later. Furthermore, if the polyaspartic acid derivative further contains the monomer unit Crosslink-U, it can be obtained by opening the ring structure of polysuccinimide using amines A and B, and then forming a crosslinked portion with a crosslinking agent. In addition, unreacted imide rings may remain in the ring-opening reaction of polysuccinimide; in this case, the compound of this disclosure further contains the monomer unit CU.

[0058] [Method for producing polyaspartic acid derivatives (first polymer)] One example of a method for producing polyaspartic acid derivatives is a ring-opening reaction method for polysuccinimide using polysuccinimide, amine A, and amine B. Furthermore, if the polyaspartic acid derivative contains the monomer unit Crosslink-U, in the ring-opening reaction of polysuccinimide, a crosslinking agent such as a polyfunctional amine is used in addition to polysuccinimide, amine A, and amine B. The order of addition of the crosslinking agent, amine A, and amine B is not particularly limited. Amine A and amine B may be added first, followed by the crosslinking agent; amine A, amine B, and the crosslinking agent may be added simultaneously; or the crosslinking agent may be added first, followed by amine A and amine B. 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 amine A and amine B. The order of addition of amine A and amine B is also not particularly limited. For example, amine A may be added first, followed by amine B; amine A and amine B may be added simultaneously; or amine B may be added first, followed by amine A.

[0059] A specific method for producing polyaspartic acid derivatives 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 to form a crosslinked structure, and then reacting it with amine A and amine B. 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.

[0060] The unreacted imide ring may remain, or the ring-opening reaction may be further 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.

[0061] [Polysuccinimide (PSI)] Polysuccinimide (PSI) is a polymer represented by the following formula (5).

[0062] [ka] (In the formula, n=10~10000)

[0063] There are no particular limitations on the method for producing polysuccinimide (PSI), but for example, it can be produced by heating aspartic acid in the presence of phosphoric acid in a vacuum at 170-190°C 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. There are no particular limitations on the molecular weight of polysuccinimide, but for example, it may be 20,000 or more, 50,000 or more, or 70,000 or more in weight-average molecular weight, or 500,000 or less, or 200,000 or less, or a combination thereof. Specifically, for example, it may be 20,000-500,000, 50,000-500,000, or 70,000-200,000. Note that the weight-average molecular weight here is calculated using the GPC method (differential refractometer) with polystyrene as the standard. This refers to the converted value as a substance, and specifically, it refers to the weight-average molecular weight measured using, for example, 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.

[0064] [Crosslinking agent] The crosslinking agent can be any agent capable of forming a crosslinked portion, and is not particularly limited. Specific examples of preferred crosslinking agents for forming amide bonds used in the crosslinked portion include, for example, polyfunctional amines.

[0065] A polyfunctional amine is preferably an amine having at least two amino groups selected from the group consisting of primary and 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.

[0066] 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.

[0067] 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).

[0068] 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 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), or sulfolane, 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 so that the polymer concentration is 1 to 50% by mass. When a diamine is used as a crosslinking agent, the carboxyl group present in the side chain of polyaspartic acid and the carboxyl group present in the side chain of another polyaspartic acid chain form amide bonds with the amino group of the diamine, thereby crosslinking the polyaspartic acid chains together. This crosslinking can be intramolecular or intermolecular.

[0069] The temperature of the crosslinking reaction is not particularly limited, but for example, it is between room temperature and 80°C.

[0070] In the method for producing polyaspartic acid derivatives, the amount of crosslinking agent added is not particularly limited, but may be 0.1 mol% or more, 0.3 mol% or more, or 0.5 mol% or more relative to the amount of polysuccinimide added, or it may be 2.0 mol% or less, 1.8 mol% or less, or 1.7 mol% or less, or a combination thereof. 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%.

[0071] The conditions for the crosslinking reaction (reaction time, reaction concentration, etc.) are not particularly limited.

[0072] [Amine A and Amine B] Amine A is an amine represented by the following general formula (6). R 1 -NH2(6) (In the formula, R 1 (This indicates a hydrocarbon group with 3 to 22 carbon atoms.)

[0073] Amine B is an amine represented by the following general formula (7). R 2 -NH2(7) (In the formula, R 2 (This indicates a hydrocarbon group that may contain heteroatoms.)

[0074] 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) 2 Regarding this, R in general formula (2) 2 The explanation regarding this matter will be used. Amine A and Amine B may be commercially available products or may be prepared by known methods.

[0075] Amine A and amine B may be used individually or in combination of two or more types.

[0076] In the method for producing polyaspartic acid derivatives, the amount of amine A charged may be 20 mol% or more, 30 mol% or more, 35 mol% or more, 40 mol% or more, 45 mol% or more, or 50 mol% or more relative to the amount of polysuccinimide charged, or it may be 70 mol% or less, 65 mol% or less, 60 mol% or less, 55 mol% or less, or 50 mol% or less, and any non-consistent combination of these may be used. Specifically, for example, it may be 20 mol% to 70 mol%, 30 mol% to 65 mol%, 35 mol% to 60 mol%, 40 mol% to 55 mol%, 45 mol% to 50 mol%, or 50 mol% to 70 mol%.

[0077] In the method for producing polyaspartic acid derivatives, the amount of amine B charged may be 30 mol% or more, 35 mol% or more, 40 mol% or more, 45 mol% or more, or 50 mol% or more relative to the amount of polysuccinimide charged, or it may be 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%.

[0078] In the method for producing polyaspartic acid derivatives, monoamines other than amine A and amine B may be used. In that case, the total amount of amine A and amine B added may be 80.0 mol% or more, 90.0 mol% or more, or 95.0 mol% or more.

[0079] 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 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. Specifically, 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.

[0080] In a method for producing polyaspartic acid derivatives, the molar ratio of the amount of amine A charged to the amount of amine B charged may be 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.

[0081] [Organic solvents] In a method for producing polyaspartic acid derivatives, the organic solvent is not particularly limited as long as it substantially dissolves the polysuccinimide, the crosslinking agent, and the monoamine, and does not substantially inhibit the progress of the reaction.

[0082] Specific examples of the above-mentioned 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. The organic solvent may be used alone or in combination of two or more types.

[0083] In particular, as the solvent in the step of performing the ring-opening reaction of polysuccinimide with amine A, a solvent containing the above-mentioned organic solvent and a compound having at least one hydroxyl group can be used. By using the above-mentioned organic solvent and a compound having at least one hydroxyl group in combination, it becomes easier to obtain high molecular weight polyaspartic acid derivatives. Furthermore, in the step of performing the ring-opening reaction of polysuccinimide with amine B and the crosslinking step with a crosslinking agent, a solvent containing the above-mentioned organic solvent and a compound having at least one hydroxyl group can also be used.

[0084] Compounds having at least one hydroxyl group are not particularly limited, but examples include: 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. A single compound having at least one hydroxyl group may be used, or two or more compounds may be used in combination.

[0085] The weight ratio of the content of the organic solvent to the content of the compound having at least one hydroxyl group in the solvent in the step of carrying out the ring-opening reaction of polysuccinimide with amine A is not particularly limited, but may be, for example, 0.5 or more, 1.0 or more, 2.0 or more, 3.0 or more, or 4.0 or more, or 20.0 or less, 15.0 or less, 10.0 or less, 5.0 or less, 4.0 or less, or 3.0 or less, or any non-contradictory combination thereof. The weight ratio may be, for example, 0.5 to 20.0, 1.0 to 15.0, 2.0 to 10.0, 3.0 to 5.0, 4.0 to 10.0, 0.5 to 4.0, or 1.0 to 3.0.

[0086] [Basic catalyst] In the method for producing polyaspartic acid derivatives, 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 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. A single basic catalyst may be used, or two or more may be used in combination.

[0087] In the method for producing polyaspartic acid derivatives, 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 monoamines charged.

[0088] [Reaction temperature] In the method for producing polyaspartic acid derivatives, the reaction temperature is not particularly limited as long as 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. A method for producing a polyaspartic acid derivative preferably includes a crosslinking reaction step in which a crosslinking agent is added first and the crosslinking reaction proceeds, and an amine reaction step in which amine A and amine B are added thereafter. In this case, the temperature of the crosslinking reaction and the temperature of the amine reaction may be the same or different. It is preferable that the temperature of the crosslinking reaction is lower than the reaction temperature after the addition of the amines. In the crosslinking reaction step in which a 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. Specifically, for example, it may be 20°C to 120°C or 20°C to 100°C. Also, for example, if 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. Specifically, for example, the temperature may be 20°C to 100°C, 20°C to 80°C, 20°C to 60°C, or 20°C to 50°C. If the reaction temperature is within the above range during the crosslinking reaction process, crosslinking can proceed uniformly. The above manufacturing method makes it easier to obtain polyaspartic acid derivatives with high viscosity.

[0089] [Concentration of the reaction system] The concentration of the reaction system used in the method for producing polyaspartic acid derivatives is not particularly limited, as long as 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.

[0090] [Method for isolating polyaspartic acid derivatives] In a method for producing polyaspartic acid derivatives, 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 to the desired purity. The 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.

[0091] 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.

[0092] In the method for producing polyaspartic acid derivatives, the obtained polyaspartic acid derivative may be used as is without isolation, by using the reaction mixture directly as the polyaspartic acid derivative. Alternatively, if necessary, only some unreacted raw materials other than the solvent may be removed and included in the composition of this disclosure. Furthermore, the concentration of the mixture may be adjusted by increasing or decreasing the amount of solvent to obtain the polyaspartic acid derivative.

[0093] Furthermore, the following second polymers can be cited as polyaspartic acid derivatives: [Second Polymer] A polyaspartic acid derivative containing an α-type or β-type polyaspartic acid monomer unit DU (also referred to as "monomer unit DU") represented by the following general formula (8). That is, a polyaspartic acid derivative containing monomer unit DU as a repeating unit. The monomer unit DU has a structure derived from the raw materials amine D and polysuccinimide, which will be described later.

[0094] [ka] (In the formula, R 4 This indicates a hydrocarbon group having 1 to 20 carbon atoms in which one hydrogen atom is replaced by a carboxyl group or a salt thereof.

[0095] In general formula (8), R 4 The hydrocarbon group is not particularly limited as long as one hydrogen atom in the hydrocarbon group having 1 to 20 carbon atoms is substituted with a carboxyl group or a salt thereof. The hydrocarbon group may be saturated or unsaturated, branched or linear, or have a ring structure. Specifically, examples of hydrocarbon groups having 1 to 20 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, and isohexyl groups; cycloalkyl groups such as cyclobutyl, cyclopentyl, and cyclohexyl groups; cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclobutylethyl, cyclopentylethyl, cyclohexylethyl, and cyclobutylpropyl Examples include cycloalkylalkyl groups such as cyclopentylpropyl, cyclohexylpropyl, cyclobutylbutyl, cyclopentylbutyl, and cyclohexylbutyl groups; and alkenyl groups such as propenyl, butenyl, pentenyl, and hexenyl groups. Among these, alkyl groups are preferred as hydrocarbon groups having 1 to 20 carbon atoms.

[0096] The number of carbon atoms in a hydrocarbon group having 1 to 20 carbon atoms may be 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, or 13 or more, and may be 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less, and may be any non-contradictory combination of these. Specifically, for example, it may be 1 to 20, 2 to 19, 3 to 18, 4 to 18, 5 to 17, 6 to 16, 7 to 15, 8 to 14, 9 to 13, 10 to 12, 11 to 20, 12 to 19, 13 to 18, 1 to 20, 2 to 19, 3 to 18, 4 to 17, 5 to 16, 6 to 15, 7 to 14, 8 to 13, or 9 to 12.

[0097] Examples of carboxyl group salts include alkali metal salts of carboxyl groups, specifically lithium salts of carboxyl groups (-COOLi), sodium salts of carboxyl groups (-COONa), and potassium salts of carboxyl groups (-COOK).

[0098] The monomer unit DU contained in one molecule of polyaspartic acid derivative may consist of one type alone, or it may consist of two or more types.

[0099] The amount of monomer unit DU in the constituent monomers of the polyaspartic acid derivative is not particularly limited, but may be, for example, 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more, 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, or 70 mol% or less, and any non-consistent combination of these may be used. Specifically, for example, it may be 50 mol% to 90 mol%, 55 mol% to 85 mol%, 60 mol% to 80 mol%, 65 mol% to 75 mol%, 70 mol% to 90 mol%, or 50 mol% to 70 mol%. The amount of monomer unit DU can be adjusted by the amount of amine D and other raw materials used.

[0100] The abundance of monomer unit DU is 1This refers to the result obtained from 1H NMR. Specifically, for example, it refers to the result obtained by measurement under the conditions described in <Calculation of Composition Ratio of Polyaspartic Acid Derivatives> below. 1 It can be calculated from the intensity ratio of the peaks derived from amine D in the 1H NMR spectrum.

[0101] Polyaspartic acid derivatives may further contain α-type or β-type polyaspartic acid monomer units EU (also referred to as "monomer unit EU") represented by the following general formula (9). That is, polyaspartic acid derivatives are polyaspartic acid derivatives that contain monomer units DU and monomer units EU as repeating units. The monomer unit EU has a structure derived from the raw materials amine E and polysuccinimide, which will be described later.

[0102] [ka] (In the formula, R 5 This refers to a group in which one hydrogen atom in a hydrocarbon group having 1 to 20 carbon atoms is substituted with a carboxyl group or a salt thereof, and the other hydrogen atom in the hydrocarbon group is substituted with an amino group.

[0103] In general formula (9), R 5The hydrocarbon group is not particularly limited as long as one hydrogen atom in a hydrocarbon group having 1 to 20 carbon atoms is substituted with a carboxyl group or a salt thereof, and one hydrogen atom in the hydrocarbon group is substituted with an amino group. The hydrocarbon group may be saturated or unsaturated, branched or linear, or have a ring structure. Examples of hydrocarbon groups having 1 to 20 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, and octadecyl groups; branched alkyl groups such as isopropyl, isobutyl, isopentyl, and isohexyl groups; cycloalkyl groups such as cyclobutyl, cyclopentyl, and cyclohexyl groups; cycloalkylalkyl groups such as cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclobutylethyl, cyclopentylethyl, cyclohexylethyl, cyclobutylpropyl, cyclopentylpropyl, cyclohexylpropyl, cyclobutylbutyl, cyclopentylbutyl, and cyclohexylbutyl groups; and alkenyl groups such as propenyl, butenyl, pentenyl, and hexenyl groups. Among these, alkyl groups are preferred as hydrocarbon groups having 1 to 20 carbon atoms.

[0104] The number of carbon atoms in a hydrocarbon group having 1 to 20 carbon atoms may be 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, or 13 or more, and may be 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, 15 or less, 14 or less, 13 or less, or 12 or less, and may be any non-contradictory combination of these. Specifically, for example, it may be 1 to 20, 2 to 19, 3 to 18, 4 to 18, 5 to 17, 6 to 16, 7 to 15, 8 to 14, 9 to 13, 10 to 12, 11 to 20, 12 to 19, 13 to 18, 1 to 20, 2 to 19, 3 to 18, 4 to 17, 5 to 16, 6 to 15, 7 to 14, 8 to 13, or 9 to 12.

[0105] Examples of carboxyl group salts include alkali metal salts of carboxyl groups, specifically lithium salts of carboxyl groups (-COOLi), sodium salts of carboxyl groups (-COONa), and potassium salts of carboxyl groups (-COOK).

[0106] The monomer unit EU contained in one molecule of polyaspartic acid derivative is one type alone. It is acceptable for it to contain two or more types.

[0107] The amount of monomer unit EU in the constituent monomers of the polyaspartic acid derivative is not particularly limited, but may be, for example, 5 mol% or more, 10 mol% or more, or 15 mol% or more, or 30 mol% or less, 25 mol% or less, or 20 mol% or less. Specifically, for example, it may be 5 mol% to 30 mol%, 10 mol% to 25 mol%, or 15 mol% to 20 mol%. The amount of monomer unit EU can be adjusted by the amounts of amine E and other components added.

[0108] The abundance of monomeric unit EU is 1 This refers to the result obtained from 1H NMR. Specifically, for example, it refers to the result obtained by measurement under the conditions described in <Calculation of Composition Ratio of Polyaspartic Acid Derivatives> below. 1 This can be calculated from the intensity ratio of the peaks derived from amine E in the 1H NMR spectrum. For example, if the polyaspartic acid derivative further contains the monomer unit Crosslink-U (described later), and a polyfunctional epoxy compound (described later) is used as the crosslinking agent, the abundance calculated from the intensity ratio of the peaks derived from amine E includes not only the abundance of monomer unit EU but also the abundance of monomer unit Crosslink-U. In this case, the abundance of monomer unit EU can be calculated by subtracting the amount of polyfunctional epoxy compound used from the abundance calculated from the intensity ratio of the peaks derived from amine E.

[0109] The ratio of the amount of monomer unit DU (mol%) to the amount of monomer unit EU (mol%) in a polyaspartic acid derivative (also expressed as (DU) / (EU)) is not particularly limited, but may be, for example, 1.00 or more, 1.50 or more, 2.00 or more, 2.50 or more, 3.00, or 6.00 or less, 5.50 or less, 5.00 or less, 4.50 or less, or 4.00 or less. Specifically, for example, it may be 1.00 to 6.00, 1.50 to 5.50, 2.00 to 5.00, 2.50 to 4.50, or 3.00 to 4.00. The aforementioned ratio is 1 This refers to the result obtained from 1H NMR. Specifically, for example, it refers to the result obtained by measurement under the conditions described in <Calculation of Composition Ratio of Polyaspartic Acid Derivatives> below. 1 This can be calculated from the ratio of the intensity of the peak derived from amine D to the intensity of the peak derived from amine E in the 1H NMR spectrum.

[0110] The polyaspartic acid derivative may further contain monomer units CU. That is, the polyaspartic acid derivative may further contain monomer units CU as repeating units. The monomer units CU are the unreacted imide rings remaining after the ring-opening reaction of polysuccinimide in the method for producing the polyaspartic acid derivative described later.

[0111] The amount of monomer unit CU in the constituent monomers of the polyaspartic acid derivative is not particularly limited, but may be, for example, 0.01 mol% or more, 0.1 mol% or more, 0.5 mol% or more, 1 mol% or more, 3 mol% or more, 5 mol% or more, 15 mol% or less, 10 mol% or less, 5 mol% or less, or 3 mol% or less, and any non-consistent combination of these may be used. Specifically, for example, it may be 0.01 mol% to 15 mol%, 0.1 mol% to 10 mol%, 0.5 mol% to 5 mol%, 1 mol% to 3 mol%, 3 mol% to 15 mol%, or 5 mol% to 10 mol%. The amount of monomer unit CU can be adjusted by the amount of polysuccinimide and other raw materials used.

[0112] The abundance of monomeric unit CU is 1 This refers to the result obtained from 1H NMR. Specifically, for example, it refers to the result obtained by measurement under the conditions described in <Calculation of Composition Ratio of Polyaspartic Acid Derivatives> below. 1 It can be calculated from the intensity ratio of peaks originating from the monomer unit CU in the 1H NMR spectrum.

[0113] The polyaspartic acid derivative may further contain the monomer unit Crosslink-U. That is, the polyaspartic acid derivative may further contain the monomer unit Crosslink-U as a repeating unit. The monomer unit Crosslink-U is a structure derived from the crosslinking agent, amine E, and polysuccinimide of the raw materials described later. The inclusion of the monomer unit Crosslink-U in the polyaspartic acid derivative makes it easier to obtain a polyaspartic acid derivative with high viscosity.

[0114] When a polyaspartic acid derivative contains the monomer unit Crosslink-U, the amount of crosslinking in the polyaspartic acid derivative (i.e., the amount of monomer unit Crosslink-U in the constituent monomers of the polyaspartic acid derivative) may be 0.1 mol% or more, 0.5 mol% or more, or 1.0 mol% or more, and may be 10.0 mol% or less, 7.0 mol% or less, or 5.0 mol% or less. Specifically, for example, it may be 0.1 mol% to 10.0 mol%, 0.5 mol% to 7.0 mol%, or 1.0 mol% to 5.0 mol%. The amount of crosslinking can be adjusted by the amount of crosslinking agent and other raw materials 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).

[0115] The bonding configurations of the monomer units DU, EU, CU, and Crosslink-U may be random, blocky, or tapered, respectively. Furthermore, the bonding configurations of each of these monomer units may be linear, macrocyclic, branched, star-shaped, or three-dimensional network-like.

[0116] The polyaspartic acid derivative may contain monomer units other than DU, EU, CU, and Crosslink-U, to the extent that it does not impair the effects of the present disclosure.

[0117] [Method for producing polyaspartic acid derivatives (second polymer)] One example of a method for producing polyaspartic acid derivatives is a ring-opening reaction method of polysuccinimide using polysuccinimide, amine D, and optionally amine E. Furthermore, if the polyaspartic acid derivative contains the monomer unit Crosslink-U, in the ring-opening reaction of polysuccinimide, a crosslinking agent such as a polyfunctional epoxy compound is used in addition to polysuccinimide and amine D (and amine E if necessary). The order of addition of the crosslinking agent, amine D, and amine E is not particularly limited. Amine D (and amine E if necessary) may be added first, followed by the crosslinking agent; amine D (and amine E if necessary) and the crosslinking agent may be added simultaneously; or the crosslinking agent may be added first, followed by amine D (and amine E if necessary). 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 amine D (and amine E if necessary). The order of addition of amine D and amine E is also not particularly limited. For example, amine D may be added first, followed by amine E; amine D and amine E may be added simultaneously; or amine E may be added first, followed by amine D.

[0118] [Polysuccinimide (PSI)] With regard to polysuccinimide (PSI), refer to the explanation of [Polysuccinimide (PSI)] in [First Polymer] above.

[0119] [Crosslinking agent] The crosslinking agent can be any agent capable of forming a crosslinked portion, and is not particularly limited, but examples include polyfunctional epoxy compounds.

[0120] Examples of polyfunctional epoxy compounds include ethylene glycol diglycidyl ether, Polyglycidyl ethers of (C2-C6) alkane polyols and poly(alkylene glycols), such as diethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, glycerin diglycidyl ether, glycerin triglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, propylene glycol diglycidyl ether, and butanediol diglycidyl ether; sorbitol polyglycidyl ether, pentaerythritol polyglycidyl ether, erythritol polyglycidyl ether, trimethylol Examples include (C4-C8) diepoxyalkanes and diepoxyalalkanes such as ruethane polyglycidyl ether, trimethylolpropane polyglycidyl ether, 1,2,3,4-diepoxybutane, 1,2,4,5-diepoxypentane, 1,2,5,6-diepoxyhexane, 1,2,7,8-diepoxyoctane, and 1,4- and 1,3-divinylbenzene epoxide; and (C6-C15) polyphenol polyglycidyl ethers such as 4,4'-isopropylidene diphenol diglycidyl ether (bisphenol A diglycidyl ether) and hydroquinone diglycidyl ether. Commercially available examples include Denacol EX-810, Denacol EX-861, Denacol EX-313, Denacol EX-614B, and Denacol EX-512, which are polyfunctional epoxy compounds manufactured by Nagase ChemteX.

[0121] The following methods can be used to produce polyaspartic acid derivatives that contain monomer units DU, EU, and Crosslink-U. First, PSI is reacted with amine D and amine E, and then the ester is hydrolyzed with an alkaline aqueous solution or water to obtain a polyaspartic acid derivative containing monomer units DU and EU. Subsequently, the obtained reaction product is reacted with a crosslinking agent in water or an aqueous solvent to form a crosslinked product, thereby obtaining a polyaspartic acid derivative further containing monomer unit Crosslink-U.

[0122] When a polyfunctional epoxy compound is used as a crosslinking agent, an addition reaction occurs between the -NH2 group of the monomer unit EU and the epoxy group of the polyfunctional epoxy compound, and the carbon atom constituting the epoxy group bonds with the N atom of the -NH2 group to form a bond represented by -NH-CH2-CH(OH)-. In addition, a similar bond is formed between the -NH2 group of another monomer unit EU and the epoxy group at the other end of the polyfunctional epoxy compound, thereby crosslinking the polyaspartic acid chains. The crosslinking can be intramolecular or intermolecular.

[0123] The temperature of the crosslinking reaction is not particularly limited, but for example, it is between room temperature and 80°C.

[0124] In the method for producing polyaspartic acid derivatives, the amount of crosslinking agent added is not particularly limited, but may be 0.1 mol% or more, 0.5 mol% or more, or 1.0 mol% or more relative to the amount of polysuccinimide added, or it may be 10.0 mol% or less, 7.0 mol% or less, or 5.0 mol% or less, or a combination thereof. Specifically, for example, it may be 0.1 mol% to 10.0 mol%, 0.5 mol% to 7.0 mol%, or 1.0 mol% to 5.0 mol%.

[0125] The conditions for the crosslinking reaction (reaction time, reaction concentration, etc.) are not particularly limited.

[0126] [Amine D] Amine D is an amine represented by the following general formula (10) or its acidic salt. R 4‘ -NH2(10)

[0127] R in general formula (8) 4 R is defined as "a group in which one hydrogen atom in a hydrocarbon group having 1 to 20 carbon atoms is replaced by a carboxyl group or a salt thereof," but the R in general formula (10) 4‘ R 4 This refers to a group in which a hydrogen atom of the carboxyl group or an atom of the salt of the carboxyl group is substituted with a hydrocarbon group having 1 to 5 carbon atoms. For example, R 4 If it is "-C2H4COOH" or "-C2H4COONa", R 4‘ is "-C2H4COOC n H (2n+1) (n=1~5)

[0128] Hydrocarbon groups having 1 to 5 carbon atoms may be saturated or unsaturated, branched or linear, or have a ring structure. Specific examples of hydrocarbon groups having 1 to 5 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, and pentyl groups; branched alkyl groups such as isopropyl, isobutyl, and isopentyl groups; cycloalkyl groups such as cyclobutyl and cyclopentyl groups; cycloalkylalkyl groups such as cyclobutylmethyl groups; and alkenyl groups such as propenyl, butenyl, and pentenyl groups. Among these, alkyl groups are preferred as hydrocarbon groups having 1 to 5 carbon atoms.

[0129] Examples of amine D include alkyl esters and cycloalkyl esters of amino acids such as alanine, or their acidic salts (such as hydrochlorides of lysine hydrochloride, ornithine hydrochloride, arginine hydrochloride, etc., and similar sulfates), and more specifically, β-alanine ethyl ester hydrochloride.

[0130] [Amine E] Amine E is an amine represented by the following general formula (11). R 5‘ -NH2(11)

[0131] R in general formula (9)5 R is defined as "a group in which one hydrogen atom in a hydrocarbon group having 1 to 20 carbon atoms is substituted with a carboxyl group or a salt thereof, and one hydrogen atom in the hydrocarbon group is substituted with an amino group," but the R in general formula (11) 5‘ R 5 This refers to a group in which a hydrogen atom of the carboxyl group or an atom of the salt of the carboxyl group is substituted with a hydrocarbon group having 1 to 5 carbon atoms. For example, R 5 If it is "-C5H9(NH2)COOH" or "-C5H9(NH2)COONa", R 5‘ is "-C5H9(NH2)COOC n H (2n+1) (n=1~5)

[0132] Hydrocarbon groups having 1 to 5 carbon atoms may be saturated or unsaturated, branched or linear, or have a ring structure. Specific examples of hydrocarbon groups having 1 to 5 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, and pentyl groups; branched alkyl groups such as isopropyl, isobutyl, and isopentyl groups; cycloalkyl groups such as cyclobutyl and cyclopentyl groups; cycloalkylalkyl groups such as cyclobutylmethyl groups; and alkenyl groups such as propenyl, butenyl, and pentenyl groups. Among these, alkyl groups are preferred as hydrocarbon groups having 1 to 5 carbon atoms.

[0133] Examples of amine E include alkyl esters and cycloalkyl esters of amino acids such as lysine, or their acidic salts (such as hydrochlorides of lysine hydrochloride, ornithine hydrochloride, arginine hydrochloride, etc., and similar sulfates), and more specifically, L-lysine methyl ester dihydrochloride.

[0134] Amine D and amine E may be commercially available products or prepared by known methods. Amine D and amine E may be used individually or in combination of two or more. That's good too.

[0135] In the method for producing polyaspartic acid derivatives, the amount of amine D charged may be 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more relative to the amount of polysuccinimide charged, or 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, or 70 mol% or less, and any non-consistent combination of these may be used. Specifically, for example, it may be 50 mol% to 90 mol%, 55 mol% to 85 mol%, 60 mol% to 80 mol%, 65 mol% to 75 mol%, 70 mol% to 90 mol%, or 50 mol% to 70 mol%.

[0136] In the method for producing polyaspartic acid derivatives, the amount of amine E charged may be 50 mol% or more, 55 mol% or more, 60 mol% or more, 65 mol% or more, 70 mol% or more relative to the amount of polysuccinimide charged, or 90 mol% or less, 85 mol% or less, 80 mol% or less, 75 mol% or less, or 70 mol% or less, and any non-consistent combination of these may be used. Specifically, for example, it may be 50 mol% to 90 mol%, 55 mol% to 85 mol%, 60 mol% to 80 mol%, 65 mol% to 75 mol%, 70 mol% to 90 mol%, or 50 mol% to 70 mol%.

[0137] In the method for producing polyaspartic acid derivatives, monoamines other than amine D and amine E may be used. In that case, the total amount of amine D and amine E added may be 80.0 mol% or more, 90.0 mol% or more, or 95.0 mol% or more.

[0138] The total amount of amine D, amine E, and other monoamines used in the charge is not particularly limited, as long as they are substantially soluble in the organic solvent and 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 1.2 times or less the molar equivalent. Specifically, 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.

[0139] In the method for producing polyaspartic acid derivatives, the molar ratio of the amount of amine D charged to the amount of amine E charged may be 0.50 or more, 1.00 or more, 1.50 or more, 2.00 or more, 2.50 or more, 5.00 or less, 4.00 or less, 3.00 or less, 2.50 or less, 2.00 or less, or 1.50 or less, and any non-contradictory combination of these may be used. Specifically, for example, it may be 0.50 to 5.00, 1.00 to 4.00, 1.50 to 3.00, 2.00 to 2.50, 2.50 to 5.00, 0.50 to 2.00, or 1.00 to 1.50.

[0140] [Organic solvents] In a method for producing polyaspartic acid derivatives, the organic solvent is not particularly limited as long as it substantially dissolves the polysuccinimide, the crosslinking agent, and the monoamine, and does not substantially inhibit the progress of the reaction.

[0141] Specific examples of the above-mentioned 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. The organic solvent may be used alone or in combination of two or more types.

[0142] [Basic catalyst] Regarding basic catalysts, refer to the explanation of [basic catalysts] in [First Polymer] above. do.

[0143] [Reaction temperature] Regarding the reaction temperature, refer to the explanation of [reaction temperature] in [First Polymer] above.

[0144] [Concentration of the reaction system] Regarding the concentration of the reaction system, refer to the explanation of [concentration of the reaction system] in [first polymer] above.

[0145] [Method for isolating polyaspartic acid derivatives] Regarding the method for isolating polyaspartic acid derivatives, refer to the explanation of [Method for Isolating Polyaspartic Acid Derivatives] in [First Polymer] above.

[0146] <Composition containing polyaspartic acid derivatives> The compositions of this disclosure are compositions containing the polyaspartic acid derivatives of this disclosure. The content of the polyaspartic acid derivative in the compositions of this disclosure is not particularly limited and can be adjusted as appropriate depending on the purpose, but for example it may be 0.1% by weight or more, 0.15% by weight or more, 0.2% by weight or more, 0.5% by weight or more, or 1.0% by weight or more, or 2.0% by weight or less, 1.8% by weight or less, or 1.5% by weight or less, or a combination thereof. Specifically, for example it may be 0.1% to 2.0% by weight, 0.15% to 2.0% by weight, 0.2% to 1.8% by weight, 0.5% to 1.5% by weight, or 1.0% to 1.5% by weight.

[0147] The compositions of this disclosure preferably further contain water. The water content in the compositions of this disclosure is not particularly limited and can be adjusted as appropriate depending on the purpose, but may be, for example, 10.0% by weight or more, 20.0% by weight or more, 30.0% by weight or more, 40.0% by weight or more, 50.0% by weight or more, 60.0% by weight or more, 70.0% by weight or more, 80.0% by weight or more, or 90.0% by weight or more relative to the whole composition, or 99.9% by weight or less, 99.5% by weight or less, 99.0% by weight or less, 90.0% by weight or less, 80.0% by weight or less, 70.0% by weight or less, 60.0% by weight or less, 50.0% by weight or less, 40.0% by weight or less, 30.0% by weight or less, or 20.0% by weight or less, and may be any non-consistent combination thereof. Specifically, for example, it could be 10.0% to 99.9% by weight, 20.0% to 99.5% by weight, 30.0% to 99.0% by weight, 40.0% to 90.0% by weight, 50.0% to 80.0% by weight, 60.0% to 70.0% by weight, 70.0% to 99.9% by weight, 80.0% to 99.5% by weight, 90.0% to 99.9% by weight, 10.0% to 60.0% by weight, 20.0% to 50.0% by weight, 30.0% to 40.0% by weight, 10.0% to 30.0% by weight, or 10.0% to 20.0% by weight.

[0148] The compositions disclosed herein can take the form of external skin preparations such as cosmetics, quasi-drugs, and pharmaceuticals. Examples of cosmetics include cleansers, lotions, toners, serums, makeup bases, hair care products, foundations, sunscreens, shaving creams, facial cleansing foams, and facial cleansing creams.

[0149] Examples of topical skin preparations include, but are not limited to, lotions, emulsifiers such as emulsions and creams, oils, gels, packs, and cleansers. Furthermore, the topical skin preparation may be either a leave-on type or a leave-off type.

[0150] [Optional ingredients] The compositions disclosed herein may optionally contain other components, provided that they do not impair the effects of the invention disclosed herein. Such optional components may be those commonly used in topical skin preparations such as cosmetics, quasi-drugs, and pharmaceuticals, and include, for example, the following:

[0151] Examples of surfactants include anionic surfactants such as sulfosuccinate esters and sodium polyoxyethylene alkyl sulfate, amphoteric surfactants such as alkyl betaine salts, lecithin, and lecithin derivatives, cationic surfactants such as dialkylammonium salts, and nonionic surfactants such as sorbitan fatty acid esters, fatty acid monoglycerides, polyoxyethylene adducts thereof, fatty acid triglycerides, polyoxyethylene alkyl ethers, polyoxyethylene fatty acid esters, and polyoxyethylene hydrogenated castor oil.

[0152] Oily components include hydrocarbons such as petrolatum, mineral oil, and squalane; higher fatty acids such as lauric acid, stearic acid, oleic acid, and retinoic acid; higher alcohols such as stearyl alcohol, behenyl alcohol, oleidodecanol, and octyldodecanol; oils and fats such as olive fruit oil, coconut oil, and horse oil; waxes such as candelilla wax, jojoba seed oil, and beeswax; esters such as triethylhexanoin, isopropyl myristate, and caprylic / capric triglyceride; and silicone oils such as dimethicone and cyclopentasiloxane.

[0153] Examples of thickening agents 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.

[0154] Powders may 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.

[0155] 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.

[0156] Other ingredients include alcohols (e.g., lower alcohols such as methanol, ethanol, and propanol; polyhydric alcohols such as glycerin, propylene glycol, butylene glycol, and dipropylene glycol), fragrances, preservatives (e.g., phenoxyethanol), antibacterial agents (e.g., ethylhexylglycerin, glyceryl caprylate), pH adjusters, and colorants. Fees and other charges are listed.

[0157] <Composition for increasing viscosity> The compositions of this disclosure are preferably used for thickening purposes, that is, they are preferably thickeners (viscosity-enhancing compositions) containing the polyaspartic acid derivative of this disclosure. The viscosity-enhancing compositions are not particularly limited, but are preferably topical skin preparations, and may contain the above-mentioned optional components in addition to the polyaspartic acid derivative of this disclosure, to an extent that does not impair the effects of this disclosure. The content of the polyaspartic acid derivative of this disclosure in the viscosity-enhancing compositions is not particularly limited and can be adjusted as appropriate depending on the purpose.

[0158] 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 disclosure. 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]

[0159] The invention of this disclosure will be described in detail below with reference to examples, but this disclosure is not limited thereto.

[0160] [Synthesis Example 1] 160 parts of aspartic acid (manufactured by YIXING QIANCHENG BIO-ENGINEERING, 99.97% purity) and 83 parts of 85% phosphoric acid 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, the filtrate was washed with distilled water until it became neutral, and then vacuum-dried at 80°C to obtain 115 parts of polysuccinimide (PSI) with a weight-average molecular weight of 81,000.

[0161] [Example 1] 10 g of PSI obtained in Synthesis Example 1 was mixed with 40 g of dimethylformamide (DMF) and dissolved by stirring at 60°C for 5 hours. While warming the solution to 40°C, 12.7 g of β-alanine ethyl ester hydrochloride and 10 g of triethylamine were added as amine D, and the reaction was carried out at 40°C for 8 hours. 14.4 g of L-lysine methyl ester dihydrochloride and 13.1 g of triethylamine were added as amine E, and the reaction was carried out at 40°C for 8 hours. After filtering off the triethylamine hydrochloride from the reaction solution, it was added to 1300 g of isopropanol, and the precipitate was collected. The precipitate was washed with 600 g of isopropanol for 1 hour, and the filtered precipitate was vacuum-dried at 60°C to obtain 14.1 g of the β-alanine ethyl ester / L-lysine methyl ester modified product. Ten g of the obtained β-alanine ethyl ester / L-lysine methyl ester modified product was dispersed in 15 g of deionized water. Nine and a half g of 20% sodium hydroxide were added dropwise over two hours, followed by a 15-hour reaction. The mixture was then added to 600 g of isopropanol, and the precipitate was collected by filtration. The mixture was then washed with another 350 g of isopropanol. The precipitate was collected by vacuum drying at 60°C to obtain ten and a half g of β-alanine sodium / lysine sodium modified product. 2.0 g of the obtained β-alanine sodium / L-lysine sodium modified compound was dissolved in 3.0 g of deionized water. 0.16 g of a 20% aqueous solution of Denacol EX-810 (ethylene glycol diglycidyl ether, manufactured by Nagase ChemteX) as a polyfunctional epoxy compound was mixed in and reacted at 60°C for 2 hours. The resulting gel composition was vacuum-dried at 60°C. It was then added to a mixture of 50 g of ethanol and 20 g of deionized water, and a 20% aqueous solution of methanesulfonic acid was added dropwise until the pH reached 5.0. After adding to 350 g of ethanol and filtering out the precipitate, it was washed with 200 g of ethanol. Vacuum drying at 60°C yielded 2.0 g of the polyaspartic acid derivative of Example 1.

[0162] [Example 2] 3.0 g of PSI obtained in Synthesis Example 1 and 17.0 g of DMF were placed in a reaction vessel and completely dissolved under heating at 60°C. After lowering the temperature to 40°C, 1.94 g of n-dodecylamine (35.0 mol%) per mole of polysuccinimide units) and 1.61 g of octadecylamine (10.0 mol%) per mole of polysuccinimide units) were added as amine A, and the mixture was reacted for 30 minutes. Furthermore, 1.80 g of 3-amino-1-propanol (80.0 mol%) per mole of polysuccinimide units) was added as amine B, and the mixture was reacted for 7 hours while maintaining the temperature in the reaction vessel at 60°C. The reaction vessel was then cooled and allowed to stand overnight at room temperature. Subsequently, the reaction mixture was discharged into 1200 mL of ethyl acetate with stirring to precipitate the reaction products, and the solid was recovered by filtration. The solid was then washed with stirring in 600 mL 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 6.5 g of the polyaspartic acid derivative of Example 2.

[0163] [Examples 3, 5, 7, and 8, and Comparative Example 2] Except for using the raw materials shown in Table 1 in the amounts shown in Table 1, the polyaspartic acid derivatives of Examples 3, 5, 7, and 8, and Comparative Example 2 were obtained using the same procedure as in Example 2.

[0164] [Example 4] 3.0 g of PSI and 17.0 g of DMF were placed in a reaction vessel and completely dissolved under heating at 60°C. After lowering the temperature to 40°C, a mixture of 0.044 g of 1,2-bis(2-aminoethoxy)ethane (AEE) (1.0 mol% per mole of polysuccinimide units) and 0.40 g of DMF was added as a crosslinking agent and the mixture was reacted for 7 hours. Next, 2.42 g of octadecylamine (30.0 mol% per mole of polysuccinimide units) was added as amine A and the mixture was reacted for 30 minutes. Furthermore, 1.78 g of 3-amino-1-propanol (79.0 mol% per mole of polysuccinimide units) was added as amine B and the mixture was reacted for 7 hours while maintaining the temperature in the reaction vessel at 60°C. The reaction vessel was then cooled and allowed to stand overnight at room temperature. Subsequently, the reaction mixture was discharged into 1200 mL of ethyl acetate with stirring to precipitate the reaction products, and the solid was recovered by filtration. The mixture was further washed with stirring in 600 mL 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 6.2 g of the polyaspartic acid derivative of Example 4.

[0165] [Examples 6 and 10, and Comparative Example 1] Except for using the raw materials shown in Table 1 in the amounts shown in Table 1, the polyaspartic acid derivatives of Examples 6 and 10, and Comparative Example 1 were obtained using the same procedure as in Example 4.

[0166] [Example 9] 3.0 g of PSI and 16.8 g of N-methyl-2-pyrrolidinone (NMP) were placed in a reaction vessel and completely dissolved under heating at 130°C. 1.68 g of ethanol (EtOH) was added dropwise over 15 minutes while stirring at 80°C. Then, a mixture of 0.044 g of 1,2-bis(2-aminoethoxy)ethane (AEE) (1.0 mol% per mole of succinimide units) and 0.4 g of NMP was added as a crosslinking agent, and the mixture was reacted for 7 hours. Next, a mixture of 2.84 g of dodecylamine (51 mol% per mole of succinimide units) and 2.84 g of 99.5% by weight EtOH was added dropwise as amine A, and the mixture was reacted at 40°C for 1 hour. Furthermore, 1.40 g of 3-amino-1-propanol (PA) (62 mol%) per 1 mole of succinimide units) was added as amine B, and the reaction was carried out for 7 hours while maintaining the temperature in the reaction vessel at 40°C. Then the reaction vessel was cooled to room temperature, and the reaction mixture was added to 1020 g of ethyl acetate with stirring to precipitate the reaction product, and the solid was recovered by filtration. The recovered solid was further washed with stirring in 600 mL 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 6.0 g of the polyaspartic acid derivative of Example 9.

[0167] [Example 11] The polyaspartic acid derivative of Example 11 was obtained using the same procedure as in Example 9, except that the raw materials shown in Table 1 were used in the amounts shown in Table 1.

[0168] [Comparative Example 3] Xanthan gum (KELTROL CG, manufactured by CP Kelco Inc.) was used as Comparative Example 3.

[0169] (Measurement of weight-average molecular weight of PSI and polyaspartic acid derivatives) For the measurement of the weight-average molecular weight of PSI in Synthesis Example 1, the polystyrene equivalent value was determined by the GPC method (differential refractometer). 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) was used for the measurement. Dimethylformamide containing 10 mM lithium bromide was used as the eluent. The weight-average molecular weights of Examples 2-11 and the polyaspartic acid derivatives were also measured using the same method. However, since the polyaspartic acid derivative in Example 1 was in gel form, it was impossible to measure its weight-average molecular weight.

[0170] <Calculation of the composition ratio of polyaspartic acid derivatives> The amount of each monomer unit present (composition ratio) (mol%) in the polyaspartic acid derivatives of each example and Comparative Examples 1-2 is as follows: 1 It was calculated from the intensity ratio of each peak in the HNMR spectrum. 1 HNMR measurement conditions: A sample was prepared by dissolving 0.1 g of polyaspartic acid derivative in 0.6 mL of deuterated dimethyl sulfoxide, and measured using a JNM-ECZ400S (manufactured by JEOL Ltd.) under the following conditions. Observation frequency: 400MHz Chemical shift standard: TMS (tetramethylsilane) (0 ppm) Pulse delay: 6.8 seconds Number of scans: 16 Pulse width: 45° (3.2μs) Measurement temperature: 60℃

[0171] At this time, the abundance of each monomer unit was calculated from the intensity ratio of the following peaks. Monomer unit AU: 0.8 ppm (Peak derived from amine A (n-dodecylamine or octadecylamine)) Monomer unit BU: 1.6 ppm (peak derived from amine B (3-amino-1-propanol)) or 2.1 ppm (peak derived from amine B (N,N-dimethylethylenediamine)) Monomer unit DU: 3.2 ppm (peak derived from amine D (β-alanine ethyl ester hydrochloride)) Monomer unit EU: 3.0 ppm (peak derived from amine E (L-lysine methyl ester dihydrochloride)) Monomer unit CU: 5.0 ppm Furthermore, taking advantage of the fact that the intensity ratio of the 1.2 ppm and 1.4 ppm peaks is 18:2 for n-dodecylamine and 30:2 for octadecylamine, examples of using both n-dodecylamine and octadecylamine together are presented. Therefore, the abundance of monomer units (AU) was calculated from the intensity ratio of the peaks at 1.2 ppm and 1.4 ppm. Furthermore, since the abundance calculated from the intensity ratio of the peaks derived from amine E includes not only the abundance of monomer unit EU but also the abundance of monomer unit Crosslink-U, the abundance of monomer unit EU was calculated by subtracting the amount of crosslinking agent (ethylene glycol diglycidyl ether) listed in Table 1 from the abundance calculated from the intensity ratio of the peaks derived from amine E.

[0172] [Table 1]

[0173] <Viscosity Measurement> A 1.0 wt% aqueous solution of each obtained example and comparative example was prepared, and the viscosity of the aqueous solution was measured. For viscosity measurement, a rotary rheometer MCR102 (Anton Paar) was used, with a cone plate CP-25, a gap of 0.106 mm, and a measurement temperature of 25°C. A pre-shear was performed for 15 seconds at a shear rate of 10 / s, followed by 30 seconds of standing. The shear viscosity was then measured at shear rates from 1 / s to 1000 / s, and the shear viscosity at a shear rate of 4.8 / s was adopted.

[0174] <Calculation of spin-spin relaxation time (T2)> (1) Measurement of spin-spin relaxation time (T2) The spin-spin relaxation time (T2) was determined using the CPMG method (Carr-PurcellMeiboom-Gill method) in pulsed NMR analysis. Two g of a 1.0 wt% aqueous solution of each example and comparative example was weighed into a 10 mm diameter NMR tube and heated for 15 minutes in a preheater adjusted to 40°C before being used for measurement. The same sample used in the first measurement was used for the second and third measurements. After the first measurement, the sample was not returned to the preheater but remained in the pulsed NMR spectrometer (Bruker Minispec mq series) while the remaining two measurements were performed.

[0175] (2) Measurement conditions CPMG method ( 1 HNMR) • Scans: 8 times Recycle Delay: 5 seconds Dummy Shots: 2 • mode:magnitude • 90°-180° Pulse Separation: 1 millisecond ·Number of Data Points for Fitting:3000 ·Number of not Fitted Echoes:0 ·Desired Magnet Temperature:40℃

[0176] (3) Calculation of spin-spin relaxation time (T2) The spin-spin relaxation time was calculated from the decay curve obtained by the CPMG method of the pulsed NMR measurement using TDNMR-A software (Bruker Japan). The fitting calculation formula is shown in equation (2) below.

[0177]

number

[0178] In equation (2), W(1), W(2), and W(3) are Weibull coefficients, taking values ​​from 1 to 2. When W=1, it is an exponential function, and when W=2, it is a Gaussian function. For crystalline or glassy samples, W=2, and for solution or amorphous samples, W=1. Since the sample used in this measurement is a solution, W(1), W(2), and W(3) were each fitted as 1. Also, in equation (2), T 2(1) , T 2(2) , and T 2(3) The values ​​A(1), A(2), and A(3) represent the spin-spin relaxation times for the first, second, and third measurements, respectively, while A(1), A(2), and A(3) are constants representing the ratios of each component. In this measurement, the analysis was performed assuming a one-component system, so A(1) was set to 1, and A(2) and A(3) were set to 0 for fitting.

[0179] Furthermore, based on the spin-spin relaxation time calculated as described above, the average value of the three spin-spin relaxation time measurements (i.e., the sum of the first to third spin-spin relaxation times divided by 3) was calculated.

[0180] <Calculation of the variability of spin-spin relaxation time (T2)> The variability of the spin-spin relaxation time (T2) was calculated using the following formula (1).

[0181]

number

[0182] In equation (1), T2 represents the average of three measurements of the spin-spin relaxation time, and T 2(1) represents the spin-spin relaxation time in the first measurement, T 2(2) represents the spin-spin relaxation time in the second measurement, T 2(3) This represents the spin-spin relaxation time in the third measurement.

[0183] <Evaluation of feel> Ten expert panelists applied 1.0% by weight aqueous solutions of the polyaspartic acid derivatives of each example and comparative example to their faces and evaluated the sensation of rapid breakdown on the skin, as if dissolving, according to the following criteria. A rating of C or higher was considered good. "A sensation that is not sticky and breaks down on the skin" refers to a sensation where the viscosity is high when applied to the skin, but it rapidly decreases to a low viscosity and spreads like water during the application process. A: More than 8 out of 10 panelists responded that it did not feel sticky and had a texture that seemed to crumble on the skin. B: Between 5 and 8 out of 10 panelists responded that the product was not sticky and had a texture that seemed to crumble on the skin. C: Between 1 and 5 out of 10 panelists responded that the product was not sticky and had a texture that seemed to crumble on the skin. D: Out of 10 panelists, 0 responded that it did not feel sticky and had a texture that seemed to crumble on the skin.

[0184] The results are shown in Table 1. The polyaspartic acid derivatives of Examples 1-11 were shown to be superior to the polyaspartic acid derivatives of Comparative Examples 1-2 in that they were not sticky and had a texture that crumbled on the skin. From these results, it was shown that a spin-spin relaxation time (T2) of 1400 milliseconds to 2400 milliseconds in the polyaspartic acid derivatives resulted in a superior texture.

Claims

1. A polyaspartic acid derivative, The spin-spin relaxation time (T) obtained by the solid echo method in pulsed NMR analysis at 40°C of a 1.0 wt% aqueous solution of the polyaspartic acid derivative is ２ A polyaspartic acid derivative characterized by having a time interval of 1400 milliseconds to 2400 milliseconds.

2. The polyaspartic acid derivative according to claim 1, wherein the shear viscosity of a 1.0% by weight aqueous solution of the polyaspartic acid derivative is 300 mPa·s to 10,000 mPa·s.

3. The spin-spin relaxation time (T) of the aqueous solution when measured repeatedly three times is represented by the following formula (1). ２ The polyaspartic acid derivative according to claim 1, characterized in that the rate of change of ) is 5.00% or less. [Math 1] (In the above formula (1), T ２ This represents the average of three measurements of spin-spin relaxation time, and T ２（１） represents the spin-spin relaxation time in the first measurement, T ２（２） This represents the spin-spin relaxation time in the second measurement, T ２（３） (This represents the spin-spin relaxation time in the third measurement.)

4. The polyaspartic acid derivative according to claim 1, wherein the polyaspartic acid derivative is an amine-modified polyaspartic acid which may have a crosslinked structure.

5. A composition containing the polyaspartic acid derivative described in any one of claims 1 to 4.

6. The composition according to claim 5, for the purpose of increasing viscosity.

7. The composition according to claim 5, further containing water.

8. The composition according to claim 7, which is a topical skin preparation.

9. The composition according to claim 8, which is a cosmetic.

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