Composition

Abstract

To provide a composition that is one or more selected from the group consisting of moisturizing, emulsifying, film-forming, gelling, and spraying. [Solution] A composition containing a polyaspartic acid derivative having a specific structure, wherein the composition is one or more selected from the group consisting of moisturizing, emulsifying, film-forming, gelling, and spraying.

Description

[Technical Field]

[0001] This disclosure relates to compositions containing polyaspartic acid derivatives. [Background technology]

[0002] In industrial fields such as cosmetics and paints, the development of biodegradable polymers is progressing from an environmental perspective. Among such biodegradable polymers, polyamino acid derivatives having specific structural units derived from amino acids are known. For example, polyamino acid derivatives with groups having carbon-carbon double bonds that can be used in paints, resists, hard coatings, resin modifiers, and compatibilizers have been reported (Patent Document 1). It has also been reported that a solution of nonionic polyaspartic acid derivatives having specific structural units can be used as a thickener or foaming agent (Patent Document 2). Furthermore, it has been reported that polyamino acid derivatives can be used in cosmetic compositions for treating keratin fibers, especially hair (Patent Document 3). Moreover, it has been reported that polyamino acid derivatives can be used as research reagents that can detect biochemical phenomena and biological activity involving sugars as fluorescence (Patent Document 4). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Application Publication No. 8-169953 [Patent Document 2] Patent No. 4546158 [Patent Document 3] Japanese Patent Publication No. 2008-088180 [Patent Document 4] Japanese Patent Publication No. 2001-139596 [Overview of the project] [Problems that the invention aims to solve]

[0004] However, it is not known that polyaspartic acid derivatives have a moisturizing effect, an emulsifying effect, a film-forming effect, and a gelling effect. Also, it is not known that when a polyaspartic acid derivative is filled in a spray container or the like, it can be discharged in a mist form. Therefore, an object of the present disclosure is to provide a composition selected from one or more of the group consisting of for moisturizing, for emulsifying, for film-forming, for gelling, and for spraying.

Means for Solving the Problems

[0005] As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by a composition containing a polyaspartic acid derivative, and have completed the invention of the present disclosure.

[0006] That is, the invention of the present disclosure is as follows. [1] A composition containing a polyaspartic acid derivative, wherein the polyaspartic acid derivative includes an α-type or β-type polyaspartic acid monomer unit A-U represented by the following general formula (1) and an α-type or β-type polyaspartic acid monomer unit B-U represented by the following general formula (2), A composition that is one or more selected from the group consisting of for moisturizing, for emulsifying, for film-forming, for gelling, and for spraying.

[0007]

Chemical formula

[0008]

Chemical formula

[0009] [ka] [4] The composition according to [3], wherein the molar ratio [(AU)+(BU)] / (CU) of the total amount of monomer unit AU and monomer unit BU to the amount of monomer unit CU in the polyaspartic acid derivative is 2.00 to 99.00. [5] The composition according to any one of [1] to [4], wherein the polyaspartic acid derivative further comprises an α-type or β-type polyaspartic acid monomer unit Crosslink-U represented by the following formula (4).

[0010] [ka] (In the formula, the dashed line indicates the bridge construction site.) [6] The composition according to [5], wherein the amount of crosslinking in the polyaspartic acid derivative is 0.1 mol% to 2.0 mol%. [7] The composition according to any one of [1] to [6], wherein the content of the polyaspartic acid derivative in the composition is 0.01% to 10.0% by weight relative to the whole composition. [8] A topical skin preparation, the composition described in any of [1] to [7]. [9] The composition described in [8] is a cosmetic.

[10] A spray product comprising filling a spray container with any of the compositions described in [1] to [9]. [Effects of the Invention]

[0011] According to this disclosure, it is possible to provide one or more compositions selected from the group consisting of moisturizing, emulsifying, film-forming, gelling, and spraying. [Modes for carrying out the invention]

[0012] The invention of this disclosure will be described in more detail below. However, this disclosure is not limited to the embodiments shown below.

[0013] 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.

[0014] <Polyaspartic acid derivative> The compositions of this disclosure are compositions containing polyaspartic acid derivatives. The polyaspartic acid derivative is a polymer containing 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 α-type or β-type polyaspartic acid monomer unit BU (also referred to as "monomer unit BU") represented by the following general formula (2). That is, the polyaspartic acid derivative contains monomer unit AU and monomer unit BU as repeating units. In this disclosure, "polyaspartic acid" includes polymers obtained by peptide condensation polymerization of aspartic acid. In the compositions of this disclosure, the polyaspartic acid derivative may be used alone or in combination of two or more.

[0015] [Chemical formula] (In the formula, R 1 represents a hydrocarbon group having 3 to 22 carbon atoms.)

[0016] [Chemical formula] (In the formula, R 21 represents a hydrocarbon group having 1 to 20 carbon atoms which may contain heteroatoms, and R 22 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Also in the formula, -NR 21 -R 22 may be a cyclic amino group in which a heteroatom or carbon atom constituting R 21 and a carbon atom constituting R 22 are covalently bonded.)

[0017] The monomer unit A-U is a structure derived from amine A and poly(succinic imide) as raw materials described later. The monomer unit B-U is a structure derived from amine B and poly(succinic imide) as raw materials described later.

[0018] In general formula (1), R 1 is not particularly limited as long as it is a hydrocarbon group having 3 to 22 carbon atoms. R 1The 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.

[0019] 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.

[0020] A single molecule of polyaspartic acid derivative may contain one monomer unit AU, or it may contain two or more monomer units.

[0021] The amount of monomer unit AU in the constituent monomers of the polyaspartic acid derivative is not particularly limited, but may be, for example, 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-consistent combination of these may be used. Specifically, for example, it may be 35 mol% to 70 mol%, 40 mol% to 65 mol%, 45 mol% to 60 mol%, 50 mol% to 55 mol%, or 35 mol% to 50 mol%. The amount of monomer unit AU can be adjusted by the amount of amine A and other raw materials used.

[0022] The abundance of monomer units AU is 1 This refers to the value calculated from 1H NMR. Specifically, it can be calculated using the obtained NMR spectrum, for example, by the following formula. Abundance of monomer unit AU (mol%) = (peak integral of the methyl group of amine A / 3) × 100 / ((peak integral of the methyl group of amine A / 3) + (peak integral of the methylene group of amine B / 2) + (peak integral of the methine group of succinimide))

[0023] Furthermore, the amount of monomer unit AU can also be calculated from the ratio (%) of the amount of amine A charged (in moles) to the amount of polysuccinimide charged (in moles). In this disclosure, "amount of polysuccinimide charged (in moles)" means the value obtained by dividing the weight of the amount of polysuccinimide charged by the molecular weight of the repeating units of polysuccinimide.

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

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

[0026] R 21 A hydroxyalkyl group is preferred. Examples of hydroxyalkyl groups include hydroxyethyl group, hydroxypropyl group, hydroxybutyl group, hydroxypentyl group, and hydroxyhexyl group.

[0027] In general formula (2), R 22The hydrocarbon group is not particularly limited as long as it is a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. The hydrocarbon group having 1 to 6 carbon atoms may be saturated or unsaturated, branched or linear, or have a ring structure. Specific examples of hydrocarbon groups having 1 to 6 carbon atoms include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups; branched alkyl groups such as isopropyl, isobutyl, and isopentyl groups; cycloalkyl groups such as cyclobutyl, cyclopentyl, and cyclohexyl groups; cycloalkylalkyl groups such as cyclobutylmethyl groups; and alkenyl groups such as propenyl, butenyl, pentenyl, and hexenyl groups. Among these, alkyl groups are preferred as hydrocarbon groups having 1 to 6 carbon atoms.

[0028] The number of carbon atoms in a hydrocarbon group having 1 to 6 carbon atoms is not particularly limited, but may be, for example, 1 or more, 2 or more, 3 or more, 6 or less, 5 or less, or 4 or less, and may be any non-contradictory combination of these. Specifically, for example, it may be 1 to 6, 2 to 5, or 3 to 4.

[0029] Also, general formula (2), -NR 21 -R 22 R 21 The heteroatoms or carbon atoms that make up the R 22 It may also be a cyclic amino group covalently bonded to the carbon atoms constituting it. For example, -NR 21 -R 22 R 21 One or more heteroatoms or carbon atoms that make up the R 22 It may also be a cyclic amino group covalently bonded to one or more of the carbon atoms constituting it. -NR 21 -R 22 Specifically, examples include groups obtained by removing a hydrogen atom from the amino group of L-prolinol or D-prolinol. The number of carbon atoms forming the ring of the cyclic amino group is not particularly limited, but may be, for example, 2 or more, 3 or more, 4 or more, 5 or more, 6 or more, 7 or more, 8 or more, 9 or more, or 10 or more. The ranges may also be 23 or less, 22 or less, 21 or less, 20 or less, 19 or less, 18 or less, 17 or less, 16 or less, or 15 or less, and any non-contradictory combination of these is acceptable. Specifically, for example, the ranges may be 2-23, 3-22, 4-21, 5-20, 6-19, 7-18, 8-17, 9-16, or 10-15.

[0030] A single molecule of polyaspartic acid derivative may contain one monomer unit BU, or it may contain two or more monomer units.

[0031] 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.

[0032] The abundance of monomer units BU is 1 This refers to the value calculated from 1H NMR. Specifically, it can be calculated using the obtained NMR spectrum, for example, by the following formula. Abundance of monomer unit BU (mol%) = (peak integral value of the methylene group of amine B / 2) × 100 / ((peak integral value of the methyl group of amine A / 3) + (peak integral value of the methylene group of amine B / 2) + (peak integral value of the methine group of succinimide))

[0033] Furthermore, the amount of monomer unit BU can also be calculated from the ratio (%) of the amount of amine B charged (in moles) to the amount of polysuccinimide charged (in moles).

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

[0035] The ratio (AU) / (BU) can also be calculated from the amount of raw materials used. In this case, it can be calculated as (amount of amine A used (mol%)) / (amount of amine B used (mol%)).

[0036] 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.

[0037] [ka]

[0038] In the constituent monomers of a polyaspartic acid derivative, the ratio of the total amount of monomer units AU and BU to the amount of monomer unit CU (mol%) (also expressed as [(AU)+(BU)] / (CU)) is not particularly limited, but may be, for example, 2.00 or more, 2.50 or more, 5.00 or more, 7.00 or more, 10.00 or more, 15.00 or more, 20.00 or more, 30.00 or more, 40.00 or more, 50.00 or more, or 60.00 or more, or 99.00 or less, 90.00 or less, 80.00 or less, 70.00 or less, 60.00 or less, 50.00 or less, 40.00 or less, 30.00 or less, 20.00 or less, 15.00 or less, 10.00 or less, or 7.00 or less, and any non-contradictory combination of these may be used. Specifically, for example, the ratios may be 2.00-99.00, 2.50-90.00, 5.00-80.00, 7.00-70.00, 10.00-60.00, 15.00-50.00, 20.00-40.00, 30.00-99.00, 40.00-90.00, 50.00-80.00, 60.00-70.00, 2.00-30.00, 2.50-20.00, 5.00-15.00, 5.00-10.00, or 5.00-7.00. In this disclosure, the ratios are 1 This refers to the result obtained from HNMR. 1 The detailed calculation method from 1H NMR is explained in the section "Calculation of Composition Ratio of Polyaspartic Acid Derivatives" in the Examples.

[0039] 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.

[0040] [ka] (In the formula, the dashed line indicates the bridge construction site.)

[0041] 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%.

[0042] 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 the amount of each other raw material added. The amount of crosslinking can be calculated from the ratio (%) of the amount of crosslinking agent (in moles) to the amount of polysuccinimide (in moles).

[0043] 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.

[0044] 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.

[0045] The weight-average molecular weight (Mw) of the polyaspartic acid derivative is not particularly limited, but may be 60,000 or more, 70,000 or more, 80,000 or more, 90,000 or more, 100,000 or more, 110,000 or more, 120,000 or more, 130,000 or more, 140,000 or more, 150,000 or more, 160,000 or more, 170,000 or more, or 180,000 or more, and may be 400,000 or less, 390,000 or less, 380,000 or less, 370,000 or less, 360,000 or less, 350,000 or less, 330,000 or less, 300,000 or less, 280,000 or less, 250,000 or less, 200,000 or less, or 100,000 or less, and may be any non-contradictory combination of these. Specifically, for example, the weight-average molecular weight may be 60,000-400,000, 70,000-390,000, 80,000-380,000, 90,000-370,000, 100,000-360,000, 110,000-350,000, 120,000-330,000, 130,000-300,000, 140,000-280,000, 150,000-250,000, 160,000-200,000, 170,000-200,000, 180,000-200,000, or 60,000-100,000. The weight-average molecular weight can be adjusted by the molecular weight of the polysuccinimide used in the method for producing polyaspartic acid derivatives described later, and by the types of amine A and amine B. The weight-average molecular weight used here refers to the converted value using polystyrene as the standard substance by the GPC method (differential refractometer). Specifically, it refers to the weight-average molecular weight measured using, 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.

[0046] 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.

[0047] [Method for producing polyaspartic acid derivatives] One example of a method for producing polyaspartic acid derivatives is a ring-opening reaction method of polysuccinimide using polysuccinimide and amine A and amine B (collectively referred to as "monoamines"). Furthermore, if the polyaspartic acid derivative contains the monomer unit Crosslink-U, a crosslinking agent such as a polyfunctional amine is used in the ring-opening reaction of polysuccinimide in addition to polysuccinimide and a monoamine. The order in which the crosslinking agent and the monoamine are added is not particularly limited. The monoamine may be added first and then the crosslinking agent, the monoamine and the crosslinking agent may be added simultaneously, or the crosslinking agent may be added first and then the monoamine. From the viewpoint of easily controlling the amount of crosslinking, it is preferable to add the crosslinking agent first, allow the crosslinking reaction to proceed, and then add the monoamine. Also, the order in which amine A and amine B are added is not particularly limited. For example, amine A may be added first and then amine B may be added, amine A and amine B may be added simultaneously, or amine B may be added first and then amine A may be added.

[0048] 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 a monoamine. 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.

[0049] 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.

[0050] [Polysuccinimide (PSI)] Polysuccinimide (PSI) is a polymer represented by the following formula (5).

[0051] [ka] (In the formula, n=10~10000)

[0052] 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. The weight-average molecular weight used here refers to the converted value using polystyrene as the standard substance by the GPC method (differential refractometer). Specifically, it refers to the weight-average molecular weight measured using, 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.

[0053] [Crosslinking agent] The crosslinking agent can be any agent capable of forming a crosslinked portion, and is not particularly limited. Specifically, a preferred crosslinking agent for forming amide bonds used in the crosslinked portion is, for example, a polyfunctional amine.

[0054] 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.

[0055] 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.

[0056] 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).

[0057] 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 groups present in the side chains of polyaspartic acid and the carboxyl groups present in the side chains of other polyaspartic acid chains form amide bonds with the amino groups of the diamine, thereby crosslinking the polyaspartic acid chains together.

[0058] The temperature of the crosslinking reaction is not particularly limited, but for example, it is between room temperature and 80°C.

[0059] The conditions for the crosslinking reaction (reaction temperature, reaction time, reaction concentration, amount of crosslinking agent used, etc.) are not particularly limited.

[0060] [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.)

[0061] Amine B is an amine represented by the following general formula (7). R 21 -NH-R 22 (7) (In the formula, R 21 R represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain heteroatoms. 22 R represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Also, amines represented by general formula (7) are R 21 The heteroatoms or carbon atoms that make up the R 22 It may also be a cyclic amine covalently bonded to the carbon atoms constituting it.

[0062] R in general formula (6) 1 Regarding this, R in general formula (1) 1 We will use the explanation regarding this. Also, R in general formula (7) 21 and R 22 Regarding this, R in general formula (2) 21 Explanation and R 22 The explanation regarding this matter will be used. Amine A and Amine B may be commercially available products or may be prepared by known methods.

[0063] Amine A and amine B may be used individually or in combination of two or more types.

[0064] In the method for producing polyaspartic acid derivatives, the amount of amine A charged is not particularly limited, but for example, it may be 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 35 mol% to 70 mol%, 40 mol% to 65 mol%, 45 mol% to 60 mol%, 50 mol% to 55 mol%, or 35 mol% to 50 mol%.

[0065] In the method for producing polyaspartic acid derivatives, the amount of amine B charged is not particularly limited, but for example, it 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%, or 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%.

[0066] 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%.

[0067] 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.

[0068] The total amount of amine A, amine B, and other monoamines used in the charge is not particularly limited, as long as they are substantially soluble in the organic solvent and / or do not substantially inhibit the progress of the reaction. Generally, the amount used is a molar equivalent of 0.1 times or more the molar equivalent of the monomer unit of polysuccinimide. On the other hand, generally, the amount used is a molar equivalent of 10 times or less the molar equivalent of the monomer unit of polysuccinimide, and preferably 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.

[0069] 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.

[0070] [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.

[0071] Specific examples of the above organic solvents include, for example, aprotic polar solvents such as dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethylimidazolidinone (DMI), dimethyl sulfoxide (DMSO), and sulfolane. Examples include organic solvents, and organic solvents may be used individually or in combination of two or more.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] [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.

[0076] 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.

[0077] [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. The method for producing polyaspartic acid derivatives involves first adding a crosslinking agent and allowing the crosslinking reaction to proceed. Preferably, the process includes a crosslinking step and a subsequent monoamine reaction step in which a monoamine is added. In this case, the temperature of the crosslinking reaction and the temperature of the monoamine reaction may be the same or different. Preferably, the temperature of the crosslinking reaction is lower than the reaction temperature after the addition of the monoamine. In the crosslinking reaction step in which a crosslinking agent is added to polysuccinimide and 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, or 50°C or lower. It may also be 20°C or higher. Specifically, for example, it may be 20°C to 100°C, 20°C to 80°C, 20°C to 60°C, or 20°C to 50°C. In the crosslinking reaction process, if the reaction temperature is within the above range, crosslinking can proceed uniformly. The above manufacturing method makes it easier to obtain polyaspartic acid derivatives with a large molecular weight and high viscosity when an aqueous solution is prepared.

[0078] [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.

[0079] [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.

[0080] 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.

[0081] 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.

[0082] <Composition containing polyaspartic acid derivatives> The compositions of this disclosure are compositions containing a polyaspartic acid derivative. The polyaspartic acid derivative has moisturizing, emulsifying, film-forming, and gelling properties. Furthermore, when filled into a spray container or the like, the polyaspartic acid derivative can be dispensed in a mist. Therefore, the compositions of this disclosure are one or more compositions selected from the group consisting of moisturizing, emulsifying, film-forming, gelling, and spraying. Alternatively, the compositions of this disclosure may be two or more compositions selected from the group consisting of moisturizing, emulsifying, film-forming, gelling, and spraying.

[0083] [For moisturizing] Since polyaspartic acid derivatives have the ability to suppress moisture evaporation, applying the composition of this disclosure to the skin or other areas can suppress moisture evaporation and prevent dryness. Therefore, the composition of this disclosure can be used for moisturizing purposes. In other words, the composition of this disclosure can be used as a humectant.

[0084] [For emulsification] Because polyaspartic acid derivatives have excellent emulsifying properties, the compositions of this disclosure can be used for emulsification. In other words, the compositions of this disclosure can be used as emulsifiers. The emulsifying effect can be confirmed by stirring the oily component, aqueous component, and polyaspartic acid derivative in the presence of an oily component, an aqueous component, and a polyaspartic acid derivative, and confirming the formation of an emulsion in which the oily component and aqueous component are uniformly or nearly uniformly dispersed in fine particles (usually 0.1 to several tens of μm) during or after stirring (preferably after stirring). The emulsion may be oil-in-water (O / W) type, water-in-oil (W / O) type, or a composite type such as W / O / W or O / W / O type.

[0085] When the compositions of this disclosure are used for emulsification, the content of oily components in the compositions of this disclosure is not particularly limited and can be adjusted as appropriate depending on the purpose. For example, it may be 1% by weight or more, 5% by weight or more, 10% by weight or more, 20% by weight or more, or 30% by weight or more relative to the whole composition, or 90% by weight or less, 70% by weight or less, 50% by weight or less, 30% by weight or less, 20% by weight or less, or 15% by weight or less, and any non-inconsistent combination thereof is acceptable. Specifically, for example, it may be 1% to 90% by weight, 5% to 70% by weight, 10% to 50% by weight, 20% to 30% by weight, 30% to 90% by weight, 1% to 20% by weight, or 5% to 15% by weight. In this disclosure, "oily components" refers to so-called oils or oil-soluble components, and specifically refers to components that separate from water after being suspended in water at 25 to 65°C and left to stand for 1 hour. Oily components typically consist of oils, and may also include essential oils and oily fragrances. Components that do not phase-separate with water (usually excluding emulsifiers) are defined as "aqueous components."

[0086] When the compositions of this disclosure are used for emulsification, the weight ratio of the aqueous component to the oily component (aqueous component content / oily component content) is not particularly limited and can be adjusted as appropriate depending on the purpose. For example, it may be 0.1 or more, 0.3 or more, 0.5 or more, 1 or more, 2 or more, 3 or more, 4 or more, or 5 or more, or 10 or less, 9 or less, 8 or less, 7 or less, 6 or less, or 5 or less, and any non-contradictory combination thereof is acceptable. Specifically, for example, it may be 0.1 to 10, 0.3 to 9, 0.5 to 8, 1 to 7, 2 to 6, 3 to 5, 4 to 10, 5 to 9, or 0.1 to 5.

[0087] [For film formation] Since polyaspartic acid derivatives have film-forming properties, the compositions of this disclosure can be used for film formation on coated surfaces such as skin. In other words, the compositions of this disclosure can be used as film-forming agents. In particular, since polyaspartic acid derivatives can form films with excellent water resistance, the compositions of this disclosure can be used for water-resistant film formation.

[0088] [For gelling] Because polyaspartic acid derivatives have excellent gelling properties, the compositions of this disclosure can be used for gelling. In other words, the compositions of this disclosure can be used as gelling agents. For example, when the monomer unit BU has a hydroxyl group, a physical gel is formed by intermolecular crosslinking through hydrogen bonding. Also, for example, when the monomer unit BU has If a carboxyl group is present, a physical gel is formed by ionic crosslinking through the addition of divalent metal ions such as zinc ions to an aqueous solution of the polyaspartic acid derivative. Even if the monomer unit BU does not have a hydroxyl group or a carboxyl group, a physical gel is formed by crosslinking using polymer entanglement. Alternatively, a chemical gel can be formed by crosslinking with the monomer unit Crosslink-U. In this disclosure, gelation refers to a state in which a fluid liquid loses its fluidity.

[0089] [For spraying] The compositions of this disclosure have excellent spray discharge properties. Therefore, the compositions of this disclosure can be suitably used for spraying. The disclosure also includes spray products, which are obtained by filling a spray container with the compositions of this disclosure. In this disclosure, "spraying" means, for example, filling a spray container with a composition and dispensing it in the form of fine droplets, or mist.

[0090] When the compositions of this disclosure are used for spraying, the spray container used to fill the compositions of this disclosure may be a non-gas type spray container or a spray container that is filled with a propellant gas (for example, an aerosol spray container). Examples of propellant gases include hydrocarbons such as ethane, propane, n-butane, isobutane, n-pentane, isopentane, and neopentane, as well as ethers such as dimethyl ether and diethyl ether, and compressed gases such as carbon dioxide, nitrogen gas, and oxygen.

[0091] [For viscosity enhancement] Furthermore, polyaspartic acid derivatives possess excellent moisturizing, emulsifying, film-forming, gelling, and spray-dispensing properties, while also exhibiting high viscosity. Therefore, the compositions of this disclosure can be suitably used for viscosity enhancement. In other words, the compositions of this disclosure can also be used as thickeners.

[0092] 〔viscosity〕 Furthermore, for example, when an aqueous solution containing 1% by weight of a polyaspartic acid derivative is prepared, the shear viscosity of the aqueous solution is not particularly limited, but may be 1000 mPa·s or more, 1500 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, or 4000 mPa·s or less. Specifically, for example, the shear viscosity may be 1000 mPa·s to 10000 mPa·s, 1500 mPa·s to 8000 mPa·s, 2000 mPa·s to 7000 mPa·s, 2500 mPa·s to 6000 mPa·s, 3000 mPa·s to 5000 mPa·s, or 1000 mPa·s to 4000 mPa·s. The shear viscosity can be adjusted by the molecular weight of the polymer containing monomer units derived from succinimide, the types of amine A and amine B, the type of solvent in step (a), etc. In this disclosure, shear viscosity refers to the value of the shear viscosity at a shear rate of 5 / s, measured using a rotary rheometer (Brookfield R / Splus), under the conditions of Measuring System C50-2, measurement temperature 25°C, after pre-shearing for 15 seconds at a shear rate of 10 / s and standing for 30 seconds, while increasing the shear rate from 1 / s to 1000 / s.

[0093] The content of the polyaspartic acid derivative in the composition of this disclosure is not particularly limited and can be adjusted as appropriate depending on the purpose. For example, it may be 0.01% by weight or more, 0.05% by weight or more, 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 relative to the whole composition, or 10.0% by weight or less, 5.0% by weight or less, 2.0% by weight or less, 1.8% by weight or less, or 1.5% by weight or less, and combinations thereof are also possible. Specifically, for example, it may be 0.01% to 10.0% by weight, 0.05% to 5.0% by weight, 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.

[0094] 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.

[0095] 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.

[0096] 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.

[0097] Furthermore, the compositions disclosed herein can be used for purposes other than topical skin preparations, such as in food and beverages, chemicals, pesticides, toiletries, paints, and the like. In particular, when the composition of this disclosure is used for film formation, it can be used in any field where film formation is required, especially where the film needs to have a water-repellent effect (water resistance). Specifically, it can be used, for example, in paint compositions, water-repellent agents for fibers, and treatment agents for inorganic and organic materials.

[0098] [Optional ingredients] The compositions disclosed herein may optionally contain other components, provided that the effects of the inventions disclosed herein are not impaired. Such optional components may be those commonly used in topical skin preparations such as cosmetics, quasi-drugs, and pharmaceuticals, as well as in food and beverages, chemicals, pesticides, toiletries, paints, etc., and examples include the following:

[0099] As surfactants, anionic surfactants such as sulfosuccinates and sodium polyoxyethylene alkyl sulfates, amphoteric surfactants such as alkyl betaine salts, lecithin, and lecithin derivatives, cationic surfactants such as dialkylammonium salts, sorbitan fatty acid esters, fatty acid monoglycerides, polyoxyethylene adducts thereof, fatty acid triglycerides, polyoxyethylene alkyl ethers, and polyoxyethylene fatty acid esters are examples of surfactants. Examples include nonionic surfactants such as polyoxyethylene hydrogenated castor oil.

[0100] 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.

[0101] 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.

[0102] 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.

[0103] 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.

[0104] Other ingredients include alcohols (for example, lower alcohols such as methanol, ethanol, and propanol, and polyhydric alcohols such as glycerin, propylene glycol, butylene glycol, and dipropylene glycol), fragrances, preservatives (for example, phenoxyethanol), antibacterial agents (for example, ethylhexylglycerin and glyceryl caprylate), pH adjusters, and colorants. [Examples]

[0105] The invention of this disclosure will be described in detail below with reference to examples, but this disclosure is not limited thereto.

[0106] [Synthesis Example 1] <Synthesis of polysuccinimide (PSI)> Mix 160 parts of aspartic acid (manufactured by YIXING QIANCHENG BIO-ENGINEERING, 99.97% purity) and 83 parts of 85% phosphoric acid in a mortar and transfer to a tray. The mixture was then reacted at 190°C, 1.3 kPa, and for 6 hours. After grinding the reaction mixture, it was washed with distilled water until the filtrate was neutral, and then vacuum-dried at 80°C to obtain 115 parts of polysuccinimide (PSI) with a weight-average molecular weight of 80,000.

[0107] [Example 1] 10.0 g of PSI obtained in Synthesis Example 1 and 95.3 g of dimethylformamide (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 0.229 g of 1,2-bis(2-aminoethoxy)ethane (AEE) (1.5 mol%) per unit of succinimide and 2.06 g of DMF was added as a crosslinking agent and the mixture was reacted for 7 hours. Next, 10.51 g of Farmin 20D (a mixture of 1% decylamine, 96% dodecylamine, and 3% tetradecylamine, manufactured by Kao Corporation) (55.0 mol%) per unit of succinimide) was added as amine A and the mixture was reacted for 30 minutes. Furthermore, 3.37 g of 3-amino-1-propanol (43.5 mol%) per unit of succinimide was added as amine B, and the reaction was carried out for 7 hours while maintaining the temperature in the reaction vessel at 60°C. Then the reaction vessel was cooled and left to stand overnight at room temperature. After that, 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 recovered by filtration. The recovered solid was dried under reduced pressure at 60°C for 12 hours to obtain 18 g of the polyaspartic acid derivative of Example 1.

[0108] [Example 2] 10.0 g of PSI obtained in Synthesis Example 1 and 60.0 g of dimethylformamide (DMF) were placed in a reaction vessel and completely dissolved under heating at 60°C. While stirring at 60°C, 10.0 g of ethanol (EtOH) was added dropwise over 30 minutes. Then, a mixture of 0.228 g of 1,2-bis(2-aminoethoxy)ethane (AEE) (1.5 mol% per mole of succinimide units) and 2.06 g of DMF was added as a crosslinking agent, and the mixture was reacted for 2 hours. Next, 10.3 g of Farmin 20D (a mixture of 1% decylamine, 96% dodecylamine, and 3% tetradecylamine, manufactured by Kao Corporation) (54 mol% per mole of succinimide units) and 10.3 g of 99.5% by weight pure EtOH was added dropwise as amine A, and the mixture was reacted at 60°C for 30 minutes. Furthermore, 3.45 g of 3-amino-1-propanol (PA) (44.5 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 60°C. Then the reaction vessel was cooled to room temperature, and the reaction mixture was added to 1080 g of ethyl acetate (EA) with stirring to precipitate the reaction product, and the solid was recovered by filtration. The recovered solid was further washed with stirring in 540 g of ethyl acetate (EA), and the solid was recovered by filtration. The recovered solid was dried under reduced pressure at 60°C for 12 hours to obtain 22.2 g of the polyaspartic acid derivative of Example 2.

[0109] [Examples 3, 6] Polyaspartic acid derivatives of Examples 3 and 6 were obtained using the same procedure as in Example 1, except that the types of amine A and amine B, and the amounts of amine A, amine B, and crosslinking agent were changed as shown in Table 1.

[0110] [Examples 4, 5, 7] Polyaspartic acid derivatives of Examples 4, 5, and 7 were obtained using the same procedure as in Example 2, except that the types of amine A and amine B, and the amounts of amine A, amine B, and crosslinking agent were changed as shown in Table 1.

[0111] In Examples 6 and 7, the farming CS used as Amine A is coconut amine (a mixture of 7% octylamine, 7% decylamine, 51% dodecylamine, 19% tetradecylamine, 8% cetylamine, 2% stearylamine, and 6% oleylamine, manufactured by Kao Corporation).

[0112] [Comparative Examples 1 - 2] As Comparative Example 1, xanthan gum (KELTOROL CG, manufactured by CP Kelco Inc.) was used, and as Comparative Example 2, carbomer (NTC - CARBOMER 381, manufactured by Nippon Surfactant Industry Co., Ltd.) was used.

[0113] [Measurement of the Weight - Average Molecular Weight of PSI and Polyamino Acid Derivatives] In the measurement of the above - mentioned weight - average molecular weight of PSI in Synthesis Example 1, the value in terms of polystyrene conversion by the GPC method (differential refractometer) was obtained. For the measurement, a G1000HHR column (TSKgel (registered trademark), manufactured by Tosoh Corporation), a G4000HHR column (TSKgel (registered trademark), manufactured by Tosoh Corporation), or a GMHHR - H column (TSKgel (registered trademark), manufactured by Tosoh Corporation) was used. As the eluent, dimethylformamide containing 10 mM lithium bromide was used. Also, the weight - average molecular weights of the polyaspartic acid derivatives in Examples 1 - 7 were measured by the same method.

[0114] [Calculation of the Composition Ratio of Polyaspartic Acid Derivatives] 1 The composition ratio (mol%) of the polyaspartic acid derivatives in each example was calculated using HNMR. 1 Measurement conditions for HNMR: 0.1 g of the polyaspartic acid derivative was dissolved in 0.6 mL of deuterated dimethyl sulfoxide to prepare a measurement sample, and it was measured using JNM - ECZ400S (manufactured by JEOL Ltd.) under the following conditions. Observation frequency: 400 MHz Chemical shift standard: TMS (tetramethylsilane) (0 ppm) Pulse delay: 6.8 seconds ​Number of scans: 16 Pulse width: 45° (3.2μs) Measurement temperature: 60℃

[0115] The composition ratio (mol%) of the polyaspartic acid derivative was calculated using the obtained NMR spectrum with the following formula. The ratio of the amount of monomer unit AU (mol%) to the amount of monomer unit BU (mol%) is (AU) / (BU) = (peak integral value of the methyl group of amine A / 3) / (peak integral value of the methylene group of amine B / 2) The ratio of the total amount of monomer units AU and BU to the amount of monomer unit CU (mol%) is [(AU) + (BU)] / (CU) = [(peak integral value of the methyl group of amine A / 3) + (peak integral value of the methylene group of amine B / 2)] / (peak integral value of the methine group of succinimide)

[0116] [Table 1]

[0117] <Viscosity Measurement (Initial Viscosity)> A 1% by weight aqueous solution of the polymers from Examples 1-7 and Comparative Example 1, and a 0.2% by weight aqueous solution of Comparative Example 2 were prepared. Using a rotary rheometer (Brookfield R / Splus), under the conditions of Measuring System C50-2 and a measurement temperature of 25°C, a pre-shear was performed for 15 seconds at a shear rate of 100 / s, followed by a 30-second standing period. The shear viscosity at a shear rate of 5 / s was then adopted when measurements were taken while increasing the shear rate from 1 / s to 1000 / s.

[0118] <Evaluation of water evaporation suppression ability> A quantitative filter paper (Advantec, filter paper No. 5A) was placed and secured over the mouth of a 70ml mayonnaise bottle (Tokyo Glass Instruments Co., Ltd., product code 0323058301). The aqueous solutions of the polymers in the examples and comparative examples were then applied to the filter paper to a solid content of 20mg each. The bottles were then dried overnight in a drying oven at 40°C. After that, the filter paper was removed, 25g of distilled water was placed inside the bottle, and the removed filter paper was placed back over the mouth of the bottle and sealed with vinyl tape to form the test specimen. The initial weight [g] of the test specimen was measured, and after being left to stand in a drying oven at 40°C for one week, the weight [g] (weight over time) of the test specimen was measured.

[0119] The amount of distilled water lost was calculated using the following formula, and the water evaporation suppression ability was evaluated according to the following evaluation criteria: Distilled water loss [%] = {(Initial weight - Weight over time) / 25g} × 100 (Evaluation Criteria) A: The decrease in distilled water is between 0% and less than 40%. B: Distilled water reduction of 40% or more but less than 60% C: Distilled water reduction of 60% or more but less than 80% D: Distilled water reduction of 80% or more but less than 100%

[0120] <Evaluation of water-resistant film formation ability> 25 g each of a 0.2 wt% aqueous solution of the polymer from each example and comparative example was poured into a 3 cm square polystyrene cup. The polystyrene cups were arranged in a tray, covered with perforated aluminum foil, and heated in an oven at 40°C until all the water evaporated, forming a film on the polystyrene cups. After that, the tray and polystyrene cups were removed from the oven, a portion of the film with less unevenness was cut, and it was fixed to a glass slide to be used as a sample. 1 μl of deionized water was dropped onto the sample, and the contact angle with respect to the water was measured over time using a contact angle meter OCA40 (DataPhysics) immediately after dropping. Images were acquired every 8 ms. The contact angle was evaluated from the obtained image data by circlefitting.

[0121] The rate of decrease in contact angle was calculated using the following formula. Contact angle decrease rate [%] = {(Contact angle immediately after dropping) - (Contact angle 10 seconds after dropping)} / (Contact angle immediately after dropping) × 100

[0122] Furthermore, if the contact angle reduction rate was less than 5%, the film was gently pulled with a finger or tweezers to observe whether the film easily broke. Based on the contact angle reduction rate and the observations above, the water-resistant film formation ability and the brittleness of the film were evaluated according to the following evaluation criteria. A smaller contact angle reduction rate indicates higher water resistance. (Evaluation Criteria) A: The contact angle reduction rate is less than 5%, and the coating does not easily break when lightly pulled with a finger or tweezers. B: The contact angle reduction rate is less than 5%, but the coating easily breaks when lightly pulled with a finger or tweezers. C: The contact angle reduction rate is 5% or more. D: No film is formed.

[0123] <Evaluation of emulsifying ability> 90 g of a 2 wt% aqueous solution of the polymer from each example and comparative example was added to a 200 ml beaker and heated to 80°C. 10 g of squalane was then added little by little while stirring as the oily component. The mixture was then heated to 140°C on a hot plate and stirred at 6000 rpm for 5 minutes using a homomixer. After that, it was cooled to room temperature while stirring with a stirrer to obtain the composition. The average particle size of the emulsion in the obtained composition was measured using a particle size analyzer SALD-7000 (Shimadzu Corporation) and evaluated according to the following criteria. (Evaluation Criteria) A: The median diameter (by volume) of the emulsion is 50 μm or less. B: The median diameter (by volume) of the emulsion is greater than 50 μm and less than or equal to 100 μm. C: Does not emulsify

[0124] <Evaluation of spray discharge performance> The aqueous solutions of each example and comparative example were adjusted to have a viscosity of 3000 mPa·s. The viscosity was measured using the same method as described in "<Measurement of Viscosity (Initial Viscosity)>" above. The adjusted aqueous solutions were placed in spray vials (manufactured by Maruemu Co., Ltd.), and the solutions were dispensed from the spray vials. Visual inspection was performed to determine whether or not the solution was sprayed from the spray vials (i.e., whether or not it was dispensed in a mist form), and the results were evaluated according to the following criteria. (Evaluation Criteria) A: Easily sprayed from a spray bottle. B: Sprayed from a spray bottle C: Discharged from the spray bottle in a mixture of spray and jet (i.e., a mixture of mist and liquid). D: It is not sprayed from the spray bottle, but is dispensed as a liquid.

[0125] The results are shown in Table 1. The aqueous solutions of the polyaspartic acid derivatives of Examples 1-7 were shown to have high viscosity. In particular, the aqueous solutions of the polyaspartic acid derivatives of Examples 1-2 and 4-7 obtained using a crosslinking agent were shown to have higher viscosity compared to the aqueous solution of the polyaspartic acid derivative of Example 3, which did not use a crosslinking agent. This suggests that the thickening effect of the polyaspartic acid derivative is further improved by having a crosslinked structure. Furthermore, the polyaspartic acid derivatives of Examples 1-7 showed improved water evaporation suppression ability and water-resistant film compared to Comparative Examples 1-2. It was demonstrated to be excellent in terms of formation, emulsification ability, and spray discharge properties.

Claims

1. A composition containing a polyaspartic acid derivative, The polyaspartic acid derivative comprises an α- or β-type polyaspartic acid monomer unit A-U represented by the following general formula (1), and an α- or β-type polyaspartic acid monomer unit B-U represented by the following general formula (2). A composition that is one or more selected from the group consisting of moisturizing, emulsifying, film-forming, gelling, and spraying. 【Chemistry 1】 (In the formula, R １ (This indicates a hydrocarbon group with 3 to 22 carbon atoms.) 【Chemistry 2】 (In the formula, R ２１ R represents a hydrocarbon group having 1 to 20 carbon atoms, which may contain heteroatoms. ２２ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Also, in the formula, -NR ２１ -R ２２ R ２１ The heteroatoms or carbon atoms that make up the R ２２ (It may also be a cyclic amino group covalently bonded to the carbon atoms constituting the molecule.)

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

00.

3. The polyaspartic acid derivative is further expressed in succinimide monomers represented by the following formula (3) The composition according to claim 1 or 2, comprising the unit C-U. 【Transformation 3】

4. The composition according to claim 3, wherein the molar ratio [(A-U) + (B-U)] / (C-U) of the total amount of monomer unit A-U and monomer unit B-U to the amount of monomer unit C-U in the polyaspartic acid derivative is 2.00 to 99.

00.

5. The composition according to claim 1 or 2, wherein the polyaspartic acid derivative further comprises an α-type or β-type polyaspartic acid monomer unit Crosslink-U represented by the following formula (4). 【Chemistry 4】 (In the formula, the dashed line indicates the bridge construction site.)

6. The composition according to claim 5, wherein the amount of crosslinking in the polyaspartic acid derivative is 0.1 mol% to 2.0 mol%.

7. The composition according to claim 1 or 2, wherein the content of the polyaspartic acid derivative in the composition is 0.01% by weight to 10.0% by weight relative to the entire composition.

8. The composition according to claim 1 or 2, which is a topical skin preparation.

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

10. A spray product comprising filling a spray container with the composition according to claim 1 or 2.

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