JP2017039920A - Polyaspartic acid derivative and detergent composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent composition having conditioning effect and improved foam volume and foam quality.SOLUTION: There is provided a detergent using a polyaspartic acid derivative containing a unit represented by the formula (1) and a unit represented by a structure where bound carbon position of repeats of the formula (1) shifts one. (1), where Ris H or a C1 to 6 monovalent hydrocarbon group, Ris a C1 to 24 bivalent hydrocarbon group, Rto Rare monovalent hydrocarbon group having 1 to 24 H atoms or C atoms, Rto Rare each independently H or a C1 to 24 hydrocarbon group, Rto Rmay bind each other to form a ring and Xis anion of organic or inorganic acid.SELECTED DRAWING: None

Description

The present invention relates to a polyaspartic acid derivative and a detergent composition containing the same. More specifically, it is a polyaspartic acid derivative suitable for foaming properties and conditioning properties in applications such as detergents such as shampoos, body soaps, facial cleansers, and cosmetics.

Various polymers are used in detergent compositions such as shampoos, body soaps, facial cleansers, hand soaps, cleansing agents and the like in order to improve the properties of the foam and the conditioning effect.
As a polymer excellent in the conditioning effect, high molecular weight silicone and the like are known (Patent Document 1).
However, these silicone polymers have strong antifoaming properties and cannot be expected to improve foam properties.

On the other hand, nonionic surfactants such as glycerol amide (Patent Document 2) are used to improve the properties of the foams, but these nonionic surfactants cannot be expected to have a conditioning effect.

Further, in recent years, there has been a demand for a biodegradable agent that has a small environmental load with respect to this application, and a conditioning agent that replaces silicone that does not exhibit biodegradability has been demanded.
Known conditioning agents that exhibit biodegradability include cationized cellulose or cationized guar gum (Patent Document 3) and polyaspartic acid derivatives having a thiol group and an amino group (Patent Document 4).

However, the detergent composition having cationized cellulose or cationized guar gum is not at a level that satisfies the conditioning properties such as fingering of hair as compared with silicone, and the polyaspartic acid derivative having a thiol group and an amino group is not used. Although the detergent composition contained as a polymer had a conditioning effect, the foaming, the amount of foam and the foam quality required as a detergent were not satisfactory.
Therefore, there has been a demand for a detergent composition containing a polymer that not only has excellent conditioning effects but also has excellent foaming, foam amount, and foam quality.

JP 05-004907 A JP 2003-064396 A JP 2007-153791 A Japanese Patent Laid-Open No. 9-77867

An object of the present invention is to provide a cleaning composition having a conditioning effect and having improved foaming, foam amount and foam quality.

The inventors of the present invention have reached the present invention as a result of intensive studies to achieve the above object. That is, the present invention has, as an essential repeating unit, a repeating unit (A) selected from the group consisting of the repeating unit (A1) represented by the general formula (1) and the repeating unit (A2) represented by the general formula (2). A polyaspartic acid derivative (D); a detergent composition (K) containing the polyaspartic acid derivative and a surfactant (J); and a cosmetic containing the polyaspartic acid derivative.

[In the formulas (1) and (2), R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ² is a divalent saturated or unsaturated group having 1 to 24 carbon atoms. R ^{3 to} R ⁵ each independently represents a hydrogen atom or a monovalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms, and R ^{3 to} R ⁵ are bonded to each other. A ring containing a nitrogen atom may be formed. X ⁻ represents an anion of an organic or inorganic acid. ]

  The detergent composition using the polyaspartic acid derivative (D) of the present invention has a conditioning effect and is excellent in foaming, foam amount and foam quality. Therefore, it is very useful for shampoos, body soaps or facial cleansing applications. In addition, since the polyaspartic acid derivative of the present invention is excellent in the effect of smoothing hair, scalp and skin, it is also useful for cosmetics.

The polyaspartic acid derivative (D) of the present invention comprises a repeating unit (A) selected from a repeating unit (A1) represented by the following general formula (1) and a repeating unit (A2) represented by the following general formula (2). As an essential repeating unit.

[In the formulas (1) and (2), R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ² is a divalent saturated or unsaturated group having 1 to 24 carbon atoms. R ^{3 to} R ⁵ each independently represents a hydrogen atom or a monovalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms, and R ^{3 to} R ⁵ are bonded to each other. A ring containing a nitrogen atom may be formed. X ⁻ represents an anion of an organic or inorganic acid. ]

In the repeating unit (A1) represented by the general formula (1) and the repeating unit (A2) represented by the general formula (2), R ¹ in the formulas (1) and (2) is a hydrogen atom or 1 carbon atom. -6 monovalent hydrocarbon groups are shown.
Specific examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include methyl groups, ethyl groups, propyl groups, alkyl groups such as butyl, hydroxymethyl groups, hydroxyethyl groups, hydroxypropyl groups, hydroxybutyl groups, etc. And the like.
Among these, a hydrogen atom, a methyl group, and an ethyl group are preferable from the viewpoint of foaming, foam amount, and foam quality improvement, and a hydrogen atom is more preferable.

R ² in the formulas (1) and (2) represents a divalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms.
Specific examples of the divalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms include alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group, a cyclobutylene group, and a cyclopentyl group. Examples thereof include cycloalkylene groups such as a ylene group and a cyclohexylene group, hydroxyalkylene groups such as a hydroxyethylene group, a hydroxytrimethylene group, a hydroxytetramethylene group, and a hydroxypentamethylene group, and alkenylene groups such as a vinylene group and a propenylene group.
Other specific examples include, for example, an azaalkylene group such as an azatetramethylene group and an azapentamethylene group, an azaalkenylene group, an oxaalkylene group such as an oxatrimethylene group, an oxatetramethylene group, and an oxapentamethylene group; Examples include alkenylene groups, thioalkylene groups such as thiotetramethylene groups and thiopentamethylene groups, and thioalkenylene groups.
Among these, an alkylene group having 1 to 18 carbon atoms, a hydroxyalkylene group, an alkenylene group, and the like are preferable, an alkylene group having 1 to 5 carbon atoms, a hydroxyalkylene group, an alkenylene group, and the like are more preferable, and a trimethylene group is most preferable. .

R ^{3 to} R ⁵ in the formulas (1) and (2) each independently represent a hydrogen atom or a monovalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms, and R ^{3 to} R ^5. May be bonded to each other to form a ring containing a nitrogen atom.
Specific examples of the monovalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, dodecyl group, octadecyl group and the like. And an alkyl group such as a hydroxymethyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group, and an alkenyl group such as a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group.
Other specific examples include an azaalkenyl group, an oxaalkenyl group, a thioalkenyl group, and the like.
Among these, an alkyl group having 1 to 6 carbon atoms, a hydroxyalkyl group, and an alkenyl group are preferable, a methyl group and an ethyl group are more preferable, and a methyl group is most preferable.

X ⁻ in the formulas (1) and (2) represents an anion of an organic or inorganic acid.
Specific examples of organic or inorganic acid anions include aliphatic carboxylic acid carbanions, aromatic carboxylic acid carbanions, aliphatic sulfonic acid sulfoanions, and aromatic sulfonic acid sulfoanions. And anions of inorganic acids such as OH ⁻ , Cl ⁻ , Br ⁻ , F ⁻ , I ⁻ , CO ₃ ²⁻ , PO ₃ ²⁻ and SO ₄ ²⁻ .

In addition to the above repeating unit (A), the polyaspartic acid derivative (D) of the present invention has a repeating unit (B1) represented by the following general formula (3) and a repeating unit (B2 represented by the following general formula (4)). It may have a repeating unit (B) selected from.

[In formulas (3) and (4), R ⁶ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a represents an integer of 1 to 4. ]

When the repeating unit (B) is also contained, the content of the repeating unit (B) is preferably 0.1 to 5 mol% based on the total of all repeating units in the polyaspartic acid derivative. When it exceeds 5 mol%, foaming of the cleaning composition (K) becomes worse. It is preferable that it is 0.1-3 mol%. However, it may be preferable not to contain the repeating unit (B) depending on the use of a detergent composition such as a shampoo or body soap cleanser that requires foaming properties.

In addition to the repeating unit (A), the polyaspartic acid derivative (D) is a repeating unit (C1) represented by the general formula (5) or a repeating unit represented by the general formula (6) depending on the use of the cleaning composition. (C2), repeating unit (F1) represented by general formula (7), repeating unit (F2) represented by general formula (8), repeating unit (L1) represented by general formula (9), general formula (10) May have one or more repeating units from the group consisting of repeating units (L2).

[In the formulas (5) and (6), M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), ammonium, or an alkyl-substituted ammonium, and each repeating unit is the same or different. May be. ]

Wherein the ^{(7) (8), R} 7 is a hydrocarbon group having 1 to 32 carbon atoms. R ⁷ may be the same or different for each repeating unit. ]

[In Formulas (9) and (10), R ¹² is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹³ is a linear or branched alkylene group having 2 to 4 carbon atoms. AO is an oxyalkylene group having 2 to 4 carbon atoms, and may be used alone or in combination of two or more. b is 1-300. R ¹² and a may be the same or different for each repeating unit. ]

The repeating unit (C1) represented by the general formula (5), the repeating unit (C2) represented by the general formula (6), the repeating unit (F1) represented by the general formula (7), and the general formula (8) The repeating unit (F2) shown, the repeating unit (L1) shown by the general formula (9), and the repeating unit (L2) shown by the general formula (10) will be described below.

In the repeating unit (C) selected from the repeating unit (C1) represented by the general formula (5) and the repeating unit (C2) represented by the general formula (6), M in (5) and (6) is Represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), ammonium, or an alkyl-substituted ammonium, and may be the same or different for each repeating unit. Among these, alkali metals are preferable from the viewpoint of foaming, foam amount, and foam quality improvement.
Examples of the alkali metal include sodium, potassium, and lithium, and sodium is preferable.

In the repeating unit (F) selected from the repeating unit (F1) represented by the general formula (7) and the repeating unit (F2) represented by the general formula (8), R in the formulas (7) and (8) ⁷ is a hydrocarbon group having 1 to 32 carbon atoms. Among these, hydrocarbons having 8 to 24 carbon atoms are preferred from the viewpoint of conditioning properties, 12 to 22 are more preferred, and 12 to 18 are particularly preferred.
Specific examples include linear groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl, icosyl, tetracosyl, and dotriacontyl. Alkyl group; branched alkyl group such as isopropyl group, isobutyl group, isopentyl group, isohexyl group, isooctyl group, isooctadecyl group, decyltetradecyl group; cycloalkyl group such as cyclobutyl group, cyclopentyl group, cyclohexyl group; cyclobutylmethyl Group, cyclopentylmethyl group, cyclohexylmethyl group, cyclobutylethyl group, cyclopentylethyl group, cyclohexylethyl group, cyclobutylpropyl group, cyclopentylpropyl group, cyclohexylpropyl group, cyclobutylbutyl group, Black pentyl-butyl group, a cycloalkyl group such as cyclohexyl butyl; propenyl group, butenyl group, pentenyl group, hexenyl group, decenyl group, dodecenyl group, a hexadecenyl group, and an alkenyl group such as octadecenyl. Preferred are an octyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, an icosyl group, a tetracosyl group, an isooctyl group, an isooctadecyl group, a decyltetradecyl group, a hexadecenyl group, and an octadecenyl group, more preferably a dodecyl group and a tetradecyl group. Group, octadecyl group, isooctadecyl group and octadecenyl group, particularly preferably dodecyl group, octadecyl group, isooctadecyl group and octadecenyl group.

In the repeating unit (L) selected from the repeating unit (L1) represented by the general formula (9) and the repeating unit (L2) represented by the general formula (10), R ¹² is a hydrogen atom, or 1 to 1 carbon atoms. 20 hydrocarbon groups, which may be the same or different for each repeating unit.
Examples of the hydrocarbon group having 1 to 20 carbon atoms include methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, octadecyl and icosyl groups. Chain alkyl group; branched alkyl group such as isopropyl group, isobutyl group, isopentyl group, isohexyl group; cycloalkyl group such as cyclobutyl group, cyclopentyl group, cyclohexyl group; cyclobutylmethyl group, cyclopentylmethyl group, cyclohexylmethyl group, Cyclobutylalkyl group such as cyclobutylethyl group, cyclopentylethyl group, cyclohexylethyl group, cyclobutylpropyl group, cyclopentylpropyl group, cyclohexylpropyl group, cyclobutylbutyl group, cyclopentylbutyl group, cyclohexylbutyl group, etc. ; Propenyl group, butenyl group, pentenyl group, and an alkenyl group such as hexenyl groups. Of these, a hydrogen atom, a methyl group, and an ethyl group are preferable, and a hydrogen atom is more preferable from the viewpoints of foaming, foam amount, and foam quality of the cleaning composition (K).

R ¹³ in the formulas (9) and (10) is a linear or branched alkylene group having 2 to 4 carbon atoms. _-CH 2 _CH 2 specifically _{-, - CH 2 CH 2 CH} 2 -, - CH (CH 3) CH 2 -, or _{-CH (CH 2 CH 3) CH} 2 - and the like. Among these, —CH ₂ CH ₂ — is preferable from the viewpoints of foaming, foam amount, and foam quality of the cleaning composition (K).

AO in the formulas (9) and (10) is an oxyalkylene group having 2 to 4 carbon atoms, and may be used alone or in combination of two or more.
Examples of the oxyalkylene group having 2 to 4 carbon atoms of AO include an oxyethylene group, an oxypropylene group, and an oxybutylene group. Among these, from the viewpoint of moisture retention, oxyethylene group, combined use of oxyethylene group and oxypropylene group is preferable, and oxyethylene group is more preferable. AO may be used alone or in combination of two or more, and in the case of two or more, AO exists in a random or block form.

B in the formulas (9) and (10) is 1 to 300, preferably 1 to 100, and more preferably 1 to 50.

The cleaning composition (K) of the present invention has a cleaning effect even with the polyaspartic acid derivative and the surfactant (J) having only the repeating unit (A), but depending on the use of the cleaning agent, the repeating unit (C), The effect is further improved by using the repeating unit (F) and the repeating unit (L) together with the repeating unit (A).
When at least one of the repeating unit (C), the repeating unit (F), and the repeating unit (L) is used in addition to the repeating unit (A), it is based on the total of all the repeating units in the polyaspartic acid derivative. The repeating unit (A) is 10 to 99.6 mol%, the repeating unit (C) is 0.1 to 89.6 mol%, the repeating unit (F) is 0.1 to 89.6 mol%, the repeating unit ( L) is preferably from 0.1 to 89.6 mol%.

When the content of the repeating unit (A) is less than 10 mol%, the amount of foam of the cleaning composition (K) decreases. Preferably it is 20-70 mol%, More preferably, it is 30-50 mol%.

When the repeating unit (C) is used in combination, the performance as a cleaning agent such as shampoo, body soap and face wash is improved. The content of the repeating unit (C) is preferably 30 to 80 mol%, particularly preferably 50 to 70 mol%.

When the repeating unit (F) is used in combination, the conditioning effect for cosmetics is improved. The content of the repeating unit (F) is preferably 30 to 80 mol%, particularly preferably 50 to 70 mol%.

When the repeating unit (L) is used in combination, the performance as a cleaning agent such as shampoo, body soap and face wash is improved. The content of the repeating unit (L) is preferably 10 to 80 mol%, particularly preferably 30 to 70 mol%.

The polyaspartic acid derivative (D) is a range other than the above-mentioned repeating units (A), (B), (C), (F), and (L) as long as foaming, foam amount, and foam quality improvement are not lowered. You may have a repeating unit further.
For example, it contains a repeating unit (E) represented by the following general formula (11), a repeating unit (G1) represented by the general formula (12), a repeating unit (G2) represented by the general formula (13), and the like. May be.

[R ^{8 in} Formulas (12) and (13) represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms. R ⁹ represents a divalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms. R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a monovalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms, and R ¹⁰ and R ¹¹ are bonded to each other to form a ring containing a nitrogen atom. It may be formed. ]

In the formulas (12) and (13) of the repeating units (G1) and (G2), R ⁸ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms.
Specific examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms include methyl groups, ethyl groups, propyl groups, alkyl groups such as butyl, hydroxymethyl groups, hydroxyethyl groups, hydroxypropyl groups, hydroxybutyl groups, etc. And the like.

R ⁹ represents a divalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms.
Specific examples of the divalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms include alkylene groups such as a methylene group, an ethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group, a cyclobutylene group, and a cyclopentyl group. Examples thereof include cycloalkylene groups such as a ylene group and a cyclohexylene group, hydroxyalkylene groups such as a hydroxyethylene group, a hydroxytrimethylene group, a hydroxytetramethylene group, and a hydroxypentamethylene group, and alkenylene groups such as a vinylene group and a propenylene group.
Other specific examples include, for example, an azaalkylene group such as an azatetramethylene group and an azapentamethylene group, an azaalkenylene group, an oxaalkylene group such as an oxatrimethylene group, an oxatetramethylene group, and an oxapentamethylene group; Examples include alkenylene groups, thioalkylene groups such as thiotetramethylene groups and thiopentamethylene groups, and thioalkenylene groups.

R ¹⁰ and R ¹¹ each independently represents a hydrogen atom or a monovalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms, and R ¹⁰ and R ¹¹ are bonded to each other to form a ring containing a nitrogen atom. It may be formed.
Specific examples of the monovalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms include a hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, dodecyl group, octadecyl group and the like. And an alkyl group such as a hydroxymethyl group, a hydroxymethyl group, a hydroxyethyl group, a hydroxypropyl group, and a hydroxybutyl group, and an alkenyl group such as a propenyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group. Other specific examples include an azaalkenyl group, an oxaalkenyl group, a thioalkenyl group, and the like.

The method for producing the polyaspartic acid derivative (D) of the present invention is not particularly limited, and examples thereof include the following production methods.
First, PSI obtained by thermal condensation polymerization of a monomer that can be converted into polysuccinimide (hereinafter also abbreviated as PSI) by thermal condensation polymerization, diamine (H) and, if necessary, monoamine (M ), A polyetheramine (N) is reacted to obtain a PSI derivative, and then a quaternizing agent is reacted to perform quaternization and hydrolyze.

Examples of the monomer that can be converted to PSI by the thermal condensation polymerization include aspartic acid, ammonium maleate, ammonium fumarate, maleamic acid, maleimide, and the like. Here, as aspartic acid, any of DL-aspartic acid, L-aspartic acid, and D-aspartic acid can be used.

  Specific examples of the diamine (H) include N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-diisopropylethylenediamine, N, N-diallylethylenediamine, N, N-benzylmethylethylenediamine, N, N- Dibenzylethylenediamine, N, N-cyclohexylmethylethylenediamine, N, N-dicyclohexylethylenediamine, N- (2-aminoethyl) pyrrolidine, N- (2-aminoethyl) piperidine, N- (2-aminoethyl) ) Morpholine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) -N′-methylpiperazine, N, N, N′-trimethylethylenediamine, N, N-dimethyl-N′-methylethylenediamine, N, N-dimethyl-N'-ethylethylene Amines, N, N-diethyl-N′-methylethylenediamine, N, N, N′-triethylethylenediamine, N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N, N-diisopropyl-1,3-propanediamine, N, N-diallyl-1,3-propanediamine, N, N-benzylmethyl-1,3- Propanediamine, N, N-dibenzyl-1,3-propanediamine, N, N-cyclohexylmethyl-1,3-propanediamine, N, N-dicyclohexyl-1,3-propanediamine, N- (3-aminopropyl ) Pyrrolidine, N- (3-aminopropyl) piperidine, N- (3-aminopropyl) morpholine, N- (3-aminopropyl) ) Piperazine, N- (3-aminopropyl) -N'-methylpiperidine, 4- (N, N-dimethylamino) benzylamine, 4- (N, N-diethylamino) benzylamine, 4- (N, N- Diisopropylamino) benzylamine, N, N, -dimethylisophoronediamine, N, N-dimethylbisaminocyclohexane, N, N-dimethyl-N′-methyl-1,3-propanediamine, N, N-dimethyl-N ′ -Ethyl-1,3-propanediamine, N, N-diethyl-N'-methyl-1,3-propanediamine, N, N-dimethylaminobutylamine, N, N-diethylaminobutylamine, N, N-dimethylaminoamyl Amine, N, N-diethylaminoamylamine, N, N-dimethyl-1,6-hexanediamine, N, N-diiso Tyl-1,6-hexanediamine, N, N- (bisaminopropyl) -N-methylamine, N, N-bisaminopropylethylamine, N, N-bisaminopropylpropylamine, N, N-bisaminopropyl Butylamine, N, N-bisaminopropylpentylamine, N, N-bisaminopropylhexylamine, N, N-bisaminopropyl-2-ethylhexylamine, N, N-bisaminopropylcyclohexylamine, N, N-bis Aminopropylbenzylamine, N, N-bisaminopropylallylamine, bis [3- (N, N-dimethylaminopropyl)] amine, bis [3- (N, N-diethylaminopropyl)] amine, bis [3- ( N, N-diisopropylaminopropyl)] amine, bis [3- (N, N-dibu Le aminopropyl)] amine.

Specific examples of monoamine (M) include ethylamine, propylamine, butylamine, pentylamine, hexylamine, octylamine, decylamine, dodecylamine, tetradecylamine, octadecylamine, icosylamine, tetracosylamine, dotriacontylamine and the like. Linear alkylamines; branched alkylamines such as isopropylamine, isobutylamine, isopentylamine, isohexylamine, isooctylamine, isooctadecylamine, decyltetradecylamine; cyclobutylamine, cyclopentylamine, cyclohexylamine, etc. Alkylamine; cyclobutylmethylamine, cyclopentylmethylamine, cyclohexylmethylamine, cyclobutylethylamine, cyclopentyl ester Cycloalkylalkylamines such as ruamine, cyclohexylethylamine, cyclobutylpropylamine, cyclopentylpropylamine, cyclohexylpropylamine, cyclobutylbutylamine, cyclopentylbutylamine, cyclohexylbutylamine; propenylamine, butenylamine, pentenylamine, hexenylamine, decenylamine, dodecenylamine, hexa Examples include alkenylamines such as decenylamine and octadecenylamine.

The polyetheramine (N) is represented by the following general formula (14).

Wherein (14), R ¹² is a hydrocarbon group of a hydrogen atom, or a C 1 to ^{20, R 13} is a straight-chain or branched alkylene group having 2 to 4 carbon atoms. AO is an oxyalkylene group having 2 to 4 carbon atoms, and may be used alone or in combination of two or more. c is 1-300. R ¹³ and a may be the same or different for each repeating unit. ]

The polyetheramine (N) has a weight average molecular weight of preferably 61 to 10,000, and more preferably 200 to 2500.

Specific examples of the polyetheramine (N) include adducts of 1 to 225 mol of ethylene oxide such as 2-aminoethanol and 3-amino-1-propanol.

Specific examples of commercially available polyetheramine (N) include, for example, Jeffamine (registered trademark) M series (manufactured by Huntsman Corporation).

  Although it does not specifically limit as a quaternizing agent, Usually, aliphatic monohalogenated alkyls, aromatic monohalogenated alkyls, dialkyl carbonates, dialkyl sulfates, etc. are mentioned. Specific examples of aliphatic monohalogenated alkyls (linear or branched alkyl groups having 1 to 24 carbon atoms) include methyl chloride, ethyl chloride, butyl bromide, methyl iodide, lauryl bromide, stearyl chloride, iodine And isopropyl chloride. Of these, methyl chloride and ethyl chloride are preferred.

Specific examples of aromatic monohalogenated alkyls (straight or branched alkyl groups having 1 to 24 carbon atoms) include benzyl chloride, benzyl bromide, benzyl iodide and the like. Of these, benzyl chloride is preferred.

  Specific examples of dialkyl carbonates (linear or branched alkyl groups having 1 to 24 carbon atoms) include diethyl carbonate, dimethyl carbonate, dibutyl carbonate, diisopropyl carbonate, dilauryl carbonate, distearyl carbonate and the like. Of these, dimethyl carbonate and diethyl carbonate are preferred.

Specific examples of dialkyl sulfates (linear or branched alkyl groups having 1 to 24 carbon atoms) include dimethyl sulfate, diethyl sulfate, dibutyl sulfate, diisopropyl sulfate, dilauryl sulfate, distearyl sulfate, dibehenyl sulfate, and the like. Can be mentioned. Of these, dimethyl sulfate and diethyl sulfate are preferable.

Examples of the polyaspartic acid derivative (D) include a homopolymer (D0) composed only of the repeating unit (A), a copolymer (D1) composed of the repeating unit (A) and the repeating unit (C), and a repeating unit (A ) And a repeating unit (F), a copolymer (D3) composed of a repeating unit (A) and a repeating unit (L), and the like. The

  The homopolymer (D0) is produced by reacting PSI with diamine (H) equimolar to the number of moles of the monomer that forms PSI, and performing quaternization.

  Copolymer (D1) is prepared by reacting PSI with equimolar or less of diamine (H) and PSI with respect to the number of moles of the monomer forming PSI, and performing the quaternization. Manufactured by hydrolysis.

The copolymer (D2) is produced by reacting PSI with equimolar amounts of diamine (H) and monoamine (M) with respect to the number of moles of monomers that form PSI, and performing quaternization.

The copolymer (D3) is produced by reacting PSI with equimolar amounts of diamine (H) and polyetheramine (N) with respect to the number of moles of the monomer forming PSI, and performing quaternization. The

  The weight average molecular weight of the polyaspartic acid derivative (D) is preferably 1,000 to 200,000, more preferably 8,000 to 100,000, from the viewpoints of foaming, foam amount, and foam quality improvement, and 10,000 to 100,000 is preferable. 50,000 is more preferable.

The polyaspartic acid derivative (D) of the present invention can be used as it is for cosmetics that do not require foaming, such as conditioners and lotions, but a detergent composition that requires foaming, such as shampoo, body soap, and facial cleanser. In the use of the product (K), a surfactant (J) may be used in combination as necessary.

The cleaning composition (K) of the present invention contains the polyaspartic acid derivative (D) and the surfactant (J).

The content of the polyaspartic acid derivative (D) is preferably 0.05 to 10% by weight, more preferably 0.1 to 5% by weight, based on the weight of the cleaning composition (K) and the cosmetic.

The surfactant (J) that is an essential component of the cleaning composition (K) of the present invention includes an anionic surfactant (J1), an amphoteric surfactant (J2), a nonionic surfactant (J3), and a cationic interface. There is an activator (J4).

  Examples of the anionic surfactant (J1) include alkyl sulfate esters, alkyl ether sulfates, fatty acid soaps, ether carboxylic acids and salts thereof, alkane sulfonates, α-olefin sulfonates, and sulfonates of higher fatty acid esters. , Dialkylsulfosuccinate, monoalkylsulfosuccinate, polyoxyethylene monoalkylsulfosuccinate, sulfonate of higher fatty acid amide, sulfate ester of glycerin fatty acid ester, alkyl ether phosphate ester salt, sulfuric acid of higher fatty acid alkanolamide Examples thereof include ester salts and acylated amino acid salts.

Examples of the amphoteric surfactant (J2) include imidazoline type, amide amino acid salt, carbobetaine type, alkylbetaine type, alkylamide betaine type, and alkylsulfobetaine type.

Nonionic surfactant (J3) includes, for example, monoglyceride, sorbitan fatty acid ester, sugar sugar fatty acid ester, polyglycerin fatty acid ester, alkanolamide, amine oxide, polyoxyethylene alkyl ether, polyethylene glycol fatty acid ester, polyoxyethylene polyoxypropylene Examples include block polymers, polyoxyethylene glycerin monofatty acid esters, polyoxyethylene propylene glycol monofatty acid esters, polyoxyethylene hydrogenated castor oil, polyoxyethylene fatty acid amides, polyoxyethylene alkylamines, and alkyl saccharides.

Examples of the cationic surfactant (J4) include alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, dipolyoxyethylene oleyl methyl ammonium chloride, dipolyoxyethylene stearyl oleyl methyl ammonium chloride, polyoxyethylene dioleyl methyl ammonium chloride, and alkyl. Examples thereof include dimethylbenzylammonium chloride, N-coconut oil fatty acid acyl-L-arginine ethyl salt, pyridinium salt type, imidazoline salt type, alkylamidoguanidine salt, and alkylguanidine salt.

Furthermore, in addition to the surfactant, a known auxiliary component can be blended as necessary.
Such components include humectants [ethanol, glycerin, propylene glycol, 1
, 3-butylene glycol, dipropylene glycol, sodium lactate, sodium hyaluronate, sodium pyrrolidone carboxylate, etc.], conditioning agents [cationized cellulose having a weight average molecular weight in the range of 5 to 5 million, cationized guar gum, silicones, esters Linear or branched carbon atoms such as polyethylene glycol, sodium polyacrylate, hydroxyethyl cellulose, protein derivatives, ceramides, pseudoceramides, higher alcohols having 12 to 24 carbon atoms, 18-methyleicosane, etc. 16-40 fatty acids, hydroxy acids, panthenol, etc.], thickeners [cellulose derivatives, polyvinyl alcohol, polyacrylic acid soda, etc.], preservatives [alkyl parabenzoate (carbon atoms 1-5) ester, benzoic acid] And Dehydroacetic acid etc.], antioxidants [2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, triphenyl phosphite and octylated diphenylamine etc.], UV absorbers [2- (2′-hydroxy -5'-methylphenyl) benzotriazole and 2-hydroxy-4-methoxybenzophenone], chelating agents [sodium ethylenediaminetetraacetate, 1-hydroxyethane-1, sodium 1-diphosphonate, sodium polyphosphate and sodium metaphosphate, etc. ], Bactericides [benzalkonium chloride, etc.], pH adjusters [mono and diethanolamine, caustic soda, lactic acid, citric acid, etc.], coloring agents [food additive blue No. 1, food additive red No. 2, food additive yellow No. 4, etc. ], Fragrance [limonene, phenylethyl alcohol and hexyl cinnamic Dehydrogenase, etc.], and the like.

The detergent composition (K) of the present invention can be used as a shampoo, body soap, facial cleanser, hand soap, cleansing agent, dish detergent, clothing detergent and the like.
The dosage form is not particularly limited, and can be any dosage form such as liquid, paste, gel, solid, foam, and powder.

The cleaning composition (K) of the present invention can be prepared by blending the polyaspartic acid derivative (D), the surfactant (J), and other components.
The order of blending is not particularly limited, but when water (and optionally a hydrophilic organic solvent) is used, polyaspartic acid derivative (D), surfactant (J) and other components are added to water. The order is preferable because it is easily dissolved. The preferred temperature of the blending step is from room temperature to 80 ° C., and when blending solid components, heating is preferable because dissolution increases. As a stirring blade that can be used for blending, a vertical stirring blade or a helical stirring blade can be used.

Cosmetics of the present invention are hair cosmetics such as conditioners, foundations, lotions, creams, emulsions, skin lotions, skin softening cosmetics, nutritional cosmetics, astringent cosmetics, whitening cosmetics, wrinkle improving cosmetics, anti-aging It can be used as skin cosmetics such as cosmetics, antiperspirants, deodorants, perfumes, eau de cologne, eau de toilette and the like.
The dosage form is not particularly limited, and can be any dosage form such as liquid, paste, gel, solid, foam, and powder.

The cosmetic of the present invention can be produced by blending the polyaspartic acid derivative (D) and, if necessary, the surfactant (J) and other components.
The order of blending is not particularly limited, but when water (and optionally a hydrophilic organic solvent) is used, polyaspartic acid derivative (D), surfactant (J) and other components are added to water. The order is preferable because it is easily dissolved. The preferred temperature of the blending step is from room temperature to 80 ° C., and when blending solid components, heating is preferable because dissolution increases. As a stirring blade that can be used for blending, a vertical stirring blade or a helical stirring blade can be used.

EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to this.

The weight average molecular weights of various polyaspartic acid derivatives obtained in the following examples and comparative examples were measured by GPC (gel permeation chromatography) under the following conditions.
<Weight average molecular weight measurement (GPC analysis)>
Equipment: HLC-8320GPC EcoSEC manufactured by Tosoh Corporation
Column: Guardcolumn PWXL, TSKgel G6000 PWXL,
TSKgel G3000 PWXL
Detector: RI
Column temperature: 40 ° C
Eluent: Water / methanol = 7/3 (volume ratio)
Reference material: Polyethylene oxide

<Production Example 1>
In a glass reactor (500 mL) equipped with a thermometer, stirrer, nitrogen inlet tube, and reflux condenser, 60.0 g of L-aspartic acid (manufactured by Kanto Chemical Co., Ltd.), 85% phosphoric acid (manufactured by Kanto Chemical Co., Ltd.) 33.8 g was charged, and stirring was continued at 160 ° C. for 2 hours while distilling off the water produced by the reaction under a reduced pressure of 50 torr. The mixture was returned to room temperature, washed with water, and dried under reduced pressure at 80 ° C. for 6 hours to obtain 41.0 g of polysuccinimide (PSI-1).

<Production Example 1>
In a glass reactor (500 mL) equipped with a thermometer, stirrer, nitrogen inlet tube, and reflux condenser, 60.0 g of L-aspartic acid (manufactured by Kanto Chemical Co., Ltd.), 85% phosphoric acid (manufactured by Kanto Chemical Co., Ltd.) 33.8 g was charged, and stirring was continued at 160 ° C. for 2 hours while distilling off the water produced by the reaction under a reduced pressure of 50 torr. The mixture was returned to room temperature, washed with water, and dried under reduced pressure at 80 ° C. for 6 hours to obtain 41.0 g of polysuccinimide (PSI-1).

In a glass reactor equipped with a thermometer and a stirrer, (PSI-1), 5.00 g, N 2, N-dimethylformamide (DMF) 25 g were added, and N, N-dimethyl-1,3-propanediamine was added. 27g was dripped and it heated up to 90 degreeC. After the temperature increase, stirring was continued at 90 ° C. for 5 hours. Thereafter, the reaction product was charged into a glass autoclave and purged with nitrogen. Then, the temperature was raised to 60 ° C., 3.19 g of methyl chloride was added dropwise, and quaternization was performed for 3 hours at the same temperature. Got. De-DMF was performed at 95 ° C. for 2 hours with an evaporator to obtain a polyaspartic acid derivative (D-1). The resulting polyaspartic acid derivative (D-1) had a weight average molecular weight of 25,000.
In the polyaspartic acid derivative (D-1), the content of the repeating unit (A) is 100 mol%, and R ¹ in the general formulas (1) and (2) in the repeating unit (A) is a hydrogen atom. R ² is a trimethylene group, R ^{3 to} R ⁵ are methyl groups, and X ⁻ is Cl ⁻ .

<Production Example 2>
A glass reactor equipped with a thermometer and a stirrer was charged with polysuccinimide ((PSI-1), 2.00 g, DMF 10 g obtained in the first half of Production Example 1, and N, N-dimethyl-1,3- Propanediamine (1.06 g) was added dropwise and the temperature was raised to 90 ° C. After the temperature rise, stirring was continued for 5 hours at 90 ° C. Thereafter, the reaction product was charged into a glass autoclave and purged with nitrogen. The temperature was raised to 0 ° C., 3.31 g of methyl chloride was added dropwise, and quaternization was performed at the same temperature for 3 hours to obtain a quaternized product.

A glass reactor equipped with a stirrer was charged with 1.50 g of a quaternized product and 7.50 g of ion-exchanged water, and the pH of the reaction solution was adjusted to 13 using 0.64 g of 48% aqueous sodium hydroxide. After the dropwise addition, stirring was continued at room temperature for 4 hours. Thereafter, dehydration was performed at 95 ° C. for 2 hours with an evaporator to obtain a polyaspartic acid derivative (D-2). The resulting polyaspartic acid derivative (D-2) had a weight average molecular weight of 26,500.
In the polyaspartic acid derivative (D-2), the content of the repeating unit (A) is 50 mol%, the content of (C) is 50 mol%, the general formula (1) in the repeating unit (A) and R ^{1 in} (2) is a hydrogen atom, R ² is a trimethylene group, R ^{3 to} R ⁵ are methyl groups, and X ⁻ is Cl ⁻ . M in the general formulas (5) and (6) in the repeating unit (C) is a Na atom.

<Production Example 3>
A glass reactor equipped with a thermometer and a stirrer was charged with PSI-12.00 g and DMF 10 g obtained in the first half of Production Example 1, and 0.63 g of N, N-dimethyl-1,3-propanediamine was added dropwise. The reaction product was obtained in the same manner as in Production Example 1. Thereafter, the reaction product was charged into a glass autoclave and operated in the same manner as in Production Example 1 using 3.31 g of methyl chloride to obtain a quaternized product.

A glass reactor equipped with a stirrer was charged with 1.50 g of a quaternized product and 7.50 g of ion-exchanged water, and the pH of the reaction solution was adjusted to 13 with 0.90 g of a 48% aqueous sodium hydroxide solution. After the dropwise addition, stirring was continued at room temperature for 4 hours. Thereafter, dehydration was performed at 95 ° C. for 2 hours with an evaporator to obtain a polyaspartic acid derivative (D-3). The obtained polyaspartic acid derivative (D-3) had a weight average molecular weight of 27,000.
The polyaspartic acid derivative (D-3) has a repeating unit (A) content of 30 mol% and a repeating unit (C) content of 70 mol%, and the general formula (1) in the repeating unit (A) (1) ) and (2) R ¹ in is a hydrogen atom, ^{R 2} is a trimethylene ^group, R 3 to R ⁵ is a methyl group, X ^- is Cl ^- is. M in the general formulas (5) and (6) in the repeating unit (C) is a Na atom.

<Production Example 4>
A glass reactor equipped with a thermometer and a stirrer was charged with PSI-12.00 g of Production Example 1 and 10 g of DMF, and 0.21 g of N, N-dimethyl-1,3-propanediamine was added dropwise thereto. By operating in the same manner, a reaction product was obtained. Thereafter, the reaction product was charged into a glass autoclave and operated in the same manner as in Production Example 1 using 3.31 g of methyl chloride to obtain a quaternized product.

A glass reactor equipped with a stirrer was charged with 1.50 g of quaternized product and 7.50 g of ion-exchanged water, and the pH of the reaction solution was adjusted to 13 using 1.55 g of 48% aqueous sodium hydroxide. After the dropwise addition, stirring was continued at room temperature for 4 hours. Thereafter, dehydration was performed at 95 ° C. for 2 hours with an evaporator to obtain a polyaspartic acid derivative (D-4). As a result of GPC measurement of the obtained polyaspartic acid derivative (D-4), the weight average molecular weight was 27,500.
The polyaspartic acid derivative (D-4) has a repeating unit (A) content of 10 mol% and a repeating unit (C) content of 90 mol%, and the general formula (1) in the repeating unit (A) (1) ) and (2) R ¹ in is a hydrogen atom, ^{R 2} is a trimethylene ^group, R 3 to R ⁵ is a methyl group, X ^- is Cl ^- is. M in the general formulas (5) and (6) in the repeating unit (C) is a Na atom.

<Production Example 5>
A glass reactor equipped with a thermometer and a stirrer was charged with PSI-15.00 g and DMF (manufactured by Kanto Chemical Co., Inc.) 25 g, and N, N-dimethylethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) 2 .27 g was added dropwise and operated in the same manner as in Production Example 1 to obtain a reaction product. Thereafter, the reaction product was charged into a glass autoclave and operated in the same manner as in Production Example 1 using 3.31 g of methyl chloride to obtain a quaternized product.

A glass reactor equipped with a stirrer was charged with 2.00 g of quaternized product and 10.00 g of ion exchange water, and the pH of the reaction solution was adjusted to 13 using 0.86 g of 48% aqueous sodium hydroxide. After the dropwise addition, stirring was continued at room temperature for 4 hours. Thereafter, dehydration was performed at 95 ° C. for 2 hours with an evaporator to obtain a polyaspartic acid derivative (D-5). The resulting polyaspartic acid derivative (D-5) had a weight average molecular weight of 26,500.
The polyaspartic acid derivative (D-5) has a repeating unit (A) content of 50 mol% and a repeating unit (C) content of 50 mol%. The general formula (1) in the repeating unit (A) ) and (2) R ¹ in is a hydrogen atom, ^{R 2} is a dimethylene ^group, R 3 to R ⁵ is a methyl group, X ^- is Cl ^- is. M in the general formulas (5) and (6) in the repeating unit (C) is a Na atom.

<Production Example 6>
A glass reactor equipped with a thermometer and a stirrer was charged with PSI-15.00 g and DMF (manufactured by Kanto Chemical Co., Inc.) 25 g, and N, N, N′-trimethylethylenediamine (Tokyo Chemical Industry Co., Ltd.) (Manufactured) 2.63 g was added dropwise and operated in the same manner as in Production Example 1 to obtain a reaction product. Thereafter, the reaction product was charged into a glass autoclave and operated in the same manner as in Production Example 1 using 3.31 g of methyl chloride to obtain a quaternized product.

A glass reactor equipped with a stirrer was charged with 2.00 g of quaternized product and 10.00 g of ion exchange water, and the pH of the reaction solution was adjusted to 13 using 0.86 g of 48% aqueous sodium hydroxide. After the dropwise addition, stirring was continued at room temperature for 4 hours. Thereafter, dehydration was performed at 95 ° C. for 2 hours with an evaporator to obtain a polyaspartic acid derivative (D-6). As a result of measurement of GPC of the obtained polyaspartic acid derivative (D-6), the weight average molecular weight was 26,500.
The polyaspartic acid derivative (D-6) has a repeating unit (A) content of 50 mol% and a repeating unit (C) content of 50 mol%. The general formula (1) in the repeating unit (A) ) and (2) R ¹ in is a methyl group, ^{R 2} is a dimethylene ^group, R 3 to R ⁵ is a methyl group, X ^- is Cl ^- is. M in the general formulas (5) and (6) in the repeating unit (C) is a Na atom.

<Production Example 7>
A glass reactor equipped with a thermometer and a stirrer was charged with PSI-15.00 g, DMF 25 g, oleylamine (M-1) (trade name “Farmin O”, manufactured by Kao Corp.) 6.90 g, N, N -2.64 g of dimethyl-1,3-propanediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) was added dropwise, and the temperature was raised to 90 ° C. After the temperature increase, stirring was continued at 90 ° C. for 5 hours. Thereafter, the reaction product was charged into a glass autoclave and purged with nitrogen. Then, the temperature was raised to 60 ° C., 3.31 g of methyl chloride was added dropwise, and quaternization was performed for 3 hours at the same temperature. Got.
De-DMF was performed at 95 ° C. for 2 hours with an evaporator to obtain the polyaspartic acid derivative (D-7) of the present invention. The weight average molecular weight (Mw) of the obtained polyaspartic acid derivative (D-7) was 27,500.
The polyaspartic acid derivative (D-7) has a repeating unit (A) content of 50 mol% and a repeating unit (F) content of 50 mol%, and the general formula (1) in the repeating unit (A) (1) R ¹ in) and (2) is a hydrogen atom, ^{R 2} is a trimethylene ^group, R 3 to R ⁵ is a methyl group, X ^- is Cl ^- in is generally in the repeating unit (F) R ⁷ in the formulas (7) and (8) is an oleyl group.

<Production Example 8>
A glass reactor equipped with a thermometer, stirrer, nitrogen inlet tube and reflux condenser was charged with 150.0 g of 2-aminoethanol and 368.9 g of methyl isobutyl ketone (MIBK) and stirred at 110 ° C. for 6 hours under normal pressure. Thereafter, stirring was continued at 90 ° C. for 4 hours while distilling off the water produced by the reaction and unreacted MIBK under a reduced pressure of 360 Torr to obtain a ketimine product of 2-aminoethanol.

A SUS autoclave was charged with 132.7 g of the ketimine product of 2-aminoethanol and 0.1 g of potassium hydroxide (manufactured by Toagosei Co., Ltd.), purged with nitrogen, heated to 180 ° C., The reaction product and potassium hydroxide were mixed uniformly. Thereafter, 365.1 g of EO was reacted dropwise over a period of 3 hours at 180 ° C. and a reaction pressure of 0.4 MPa or less, and aged at the same temperature for 3 hours.
5.0 g of Kyoward 600 (manufactured by Kyowa Chemical Co., Ltd .; synthetic magnesium silicate) and 5.0 g of ion-exchanged water were added and treated at 70 ° C. for 1 hour. After taking out from an autoclave, it filtered using Kyoward 700 (made by Kyowa Chemical Co., Ltd .; synthetic aluminum silicate), and obtained EO9 mol adduct of the ketimine product of 2-aminoethanol.

  A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 451.1 g of 2-aminoethanol ketimine compound and 15.6 g of ion-exchanged water, and 100 ° C. for 3 hours under normal pressure. And the ketimine decomposition was carried out. Thereafter, under reduced pressure of 10 Torr, stirring was continued at 100 ° C. for 2 hours while distilling off the MIBK produced by the reaction and the remaining water to obtain polyetheramine (N-1).

A glass reactor equipped with a thermometer and a stirrer was charged with 5.00 g of PSI-1, 25 g of DMF, and 11.8 g of polyetheramine (N-1), and N, N-dimethyl-1,3-propanediamine 2 .64 g was added dropwise and the temperature was raised to 90 ° C. After the temperature increase, stirring was continued at 90 ° C. for 5 hours. Thereafter, the reaction product was charged into a glass autoclave and purged with nitrogen. Then, the temperature was raised to 60 ° C., 3.31 g of methyl chloride was added dropwise, and quaternization was performed for 3 hours at the same temperature. Got.
De-DMF was performed at 95 ° C. for 2 hours with an evaporator to obtain the polyaspartic acid derivative (D-8) of the present invention. The obtained polyaspartic acid derivative (D-8) had a weight average molecular weight (Mw) of 27,500.
The polyaspartic acid derivative (D-8) has a repeating unit (A) content of 50 mol% and a repeating unit (L) content of 50 mol%. The general formula (1) in the repeating unit (A) R ¹ in) and (2) is a hydrogen atom, ^{R 2} is a trimethylene ^group, R 3 to R ⁵ is a methyl group, X ^- is Cl ^- in is generally in the repeating unit (L) R ¹² in the formulas (9) and (10) is a hydrogen atom, X and A are —CH ₂ CH ₂ —, and a is 9.

<Comparative Production Example 1>
In a glass reactor equipped with a stirrer, PSI-1, 1.50 g of Production Example 1 and 7.50 g of ion-exchanged water were added, and 1.30 g of 48% sodium hydroxide aqueous solution was used in the same manner as in Production Example 2. Operation was performed to obtain sodium polyaspartate (D′-1). As a result of GPC measurement of the obtained sodium polyaspartate (D′-1), the weight average molecular weight was 30000.
Sodium polyaspartate (D′-1) does not contain the repeating unit (A) essential in the present invention, the content of the repeating unit (C) is 100 mol%, and the general formula in the repeating unit (C) M in (5) and (6) is a Na atom.

<Comparative Production Example 2>
A glass reactor equipped with a thermometer and a stirrer was charged with 5.00 g of PSI-1 and 25 g of DMF, 0.32 g of cysteamine (manufactured by Tokyo Chemical Industry Co., Ltd.), N, N-dimethyl-1,3-propane. 0.53 g of diamine was added dropwise and operated in the same manner as in Production Example 1 to obtain a reaction product.

A glass reactor equipped with a stirrer was charged with 2.00 g of the reaction product and 10.00 g of ion-exchanged water, and the pH of the reaction solution was adjusted to 13 using 1.41 g of 48% aqueous sodium hydroxide. After the dropwise addition, stirring was continued at room temperature for 4 hours. Thereafter, dehydration was performed at 95 ° C. for 2 hours with an evaporator to obtain a polyaspartic acid derivative (D′-2). The weight average molecular weight of the obtained polyaspartic acid derivative (D′-2) was 27,000.
The polyaspartic acid derivative (D′-2) does not contain the repeating unit (A) essential in the present invention, the content of the repeating unit (B) is 8 mol%, and the content of the repeating unit (C) is 82 mol. %, The content of the repeating unit (G) is 10 mol%, R ⁶ in the general formulas (3) and (4) in the repeating unit (B) is a hydrogen atom, a is 2, M in the general formulas (5) and (6) in the unit (C) is a Na atom, R ⁸ in the general formulas (12) and (13) in the repeating unit (G) is a hydrogen atom, R ⁹ is a trimethylene group, and R ¹⁰ and R ¹¹ are methyl groups.

<Comparative Production Example 3>
In a glass reactor equipped with a thermometer and a stirrer, 5.00 g of PSI-1 and 25 g of DMF were added, 13.8 g of oleylamine (M-1) was dropped, and the same operation as in Production Example 1 was carried out. Obtained.

Into a glass reactor equipped with a stirrer, 2.00 g of the reaction product was added, and the solvent was removed by an evaporator at 95 ° C. for 2 hours to obtain a polyaspartic acid derivative (D′-3). The weight average molecular weight of the obtained polyaspartic acid derivative (D′-3) was 30,000.
The polyaspartic acid derivative (D′-3) does not contain the repeating unit (A) essential in the present invention, the content of the repeating unit (F) is 100 mol%, and the general formula in the repeating unit (F) R ^{7 in} (7) and (8) is an oleyl group.

<Comparative Production Example 4>
A glass reactor equipped with a thermometer and a stirrer was charged with 5.00 g of PSI-1 and 25 g of DMF, 23.6 g of polyetheramine (N-1) was added, and the same operation as in Production Example 1 was carried out. Got.

Into a glass reactor equipped with a stirrer, 2.00 g of the obtained reaction product was put, and the solvent was removed by an evaporator at 95 ° C. for 2 hours to obtain a polyaspartic acid derivative (D′-4). The obtained polyaspartic acid derivative (D′-4) had a weight average molecular weight of 30,000. The polyaspartic acid derivative (D′-4) does not contain the repeating unit (A) essential in the present invention, the content of the repeating unit (L) is 100 mol%, and the general formula in the repeating unit (L) R ^{12 in} (9) and (10) is a hydrogen atom, X and A are —CH ₂ CH ₂ —, and a is 9.

Table 1 below collectively shows polyaspartic acid derivatives (D) of Production Examples 1 to 8 and Comparative Production Examples 1 to 4.

Examples 1-13, Comparative Examples 1-5
Each component was mix | blended with the compounding quantity described in Table 2, and cleaning composition (K-1)-(K-13), (K'-1)-(K'-5) was produced.

In Table 2, the following components were used.
Anionic surfactant (1): Polyoxyethylene (average added mole number = 2) Sodium lauryl ether sulfate Anionic surfactant (2): Polyoxyethylene (average added mole number = 3) Sodium lauryl ether acetate amphoteric interface Activator (1): Palm oil fatty acid amidopropyldimethylaminoacetic acid betaine amphoteric surfactant (2): 2-alkyl-N-carboxymethyl-N-hydroxyethylimidazolinium betaine nonionic surfactant (1): coconut Oil fatty acid monoethanolamide nonionic surfactant (2): polyoxyethylene (average number of added moles = 1) dodecylene glycol Conventional conditioning agent: cationized hydroxyethyl cellulose, manufactured by Lion Corporation, “Leogard GP”

<Various performance evaluation and methods>
After thoroughly wetting the hair with hot water of 40 ° C, shampooing with 5 g of each cleaning composition, rinsing with hot water of 40 ° C, and blending the hair with 5 g of the standard conditioner prepared according to the following formulation. Rinse and dry with a dryer. The foaming, foam amount, foam quality, fingering during hair washing, familiarity of conditioner, and fingering after drying were evaluated.
Each evaluation was performed according to the following criteria, and the results were shown as an average value of 10 professional panelists. 3.8 or higher.
Table 2 summarizes the evaluation results.

<Standard conditioner prescription>
Polydimethylsiloxane 2.0 parts Cetyl alcohol 2.5 parts Stearyl alcohol 2.5 parts Behenyltrimethylammonium chloride 1.5 parts Glycerin 4.0 parts Water 87.5 parts

<Bubbling>
5; I felt that foaming was very good.
4; I felt that foaming was good.
3; I felt that foaming was normal.
2; I felt that foaming was a little bad.
1; I felt that foaming was bad.

<Amount of foam>
5; I felt that the amount of foam was very large.
4; I felt that the amount of foam was large.
3; I felt that the amount of foam was normal.
2; I felt that the amount of foam was slightly small.
1; I felt that the amount of foam was small.

<Foam quality (creamy)>
5; felt fine and very creamy with good foam quality.
4: Feeled creamy and good foam quality.
3; I felt a slightly creamy foam.
2; felt slightly light and pale.
1; It felt light and rough foam quality.

<Fingering during hair washing>
5; It was very smooth and felt that there was no squeaky feeling.
4; I felt that it was a little smooth and squeaky.
3; I felt it was normal.
2; Slightly bad and felt squeaky.
1; I felt bad and squeaky.

<Familiar with conditioner>
5; I felt very familiar.
4; I felt familiar.
3; I felt familiar.
2; I felt that familiarity was a little bad.
1; I felt unfamiliar.

<Fingering after drying>
5; It was very smooth and felt that there was no squeaky feeling.
4; I felt that it was a little smooth and squeaky.
3; I felt it was normal.
2; Slightly bad and felt squeaky.
1; I felt bad and squeaky.

As is clear from Table 2, the detergent compositions (K-1) to (K-13) containing the polyaspartic acid derivative (D) of the present invention have a conditioning effect, and are foamed, foamed, foamed. Excellent quality.
On the other hand, in the present invention, it is understood that all of (K′-1) to (K′-5) not containing the essential repeating unit (A) are inferior in terms of foaming, foam amount, and foam quality. Furthermore, (K′-1), (K′-4), and (K′-5) are inferior in the fingering condition during hair washing, the familiarity of the conditioner, and the conditioning effect on the fingering after drying.

Examples 14-22, Comparative Examples 6-8
Each component was blended in the blending amounts shown in Table 3 to prepare a hair conditioner.

Wet your hair thoroughly with 40 ° C hot water, then shampoo with 5g of standard shampoo prepared according to the following formula, rinse with 40 ° C hot water, rinse each hair conditioner 5g by hand, and rinse. Dry with a dryer. The fingering of the hair after drying at that time was evaluated.

(Standard shampoo prescription)
25% polyoxyethylene (2.5) sodium lauryl ether sulfate 62.0% by mass
Lauric acid diethanolamide 2.3% by mass
Edetate disodium 0.15% by mass
Sodium benzoate 0.5% by mass
Sodium chloride 0.8 mass%
75% phosphoric acid appropriate amount perfume, methyl paraben appropriate amount purified water remaining

Evaluation was performed according to the following criteria, and the results were shown as the average value of 10 professional panelists. Pass at 4.0 or higher. Table 3 shows the evaluation results.

<As per finger of hair after drying>
5; It was very smooth and felt that there was no squeaky feeling.
4; I felt that it was a little smooth and squeaky.
3; I felt it was normal.
2; Slightly bad and felt squeaky.
1; I felt bad and squeaky.

As is apparent from Table 3, the conditioner formulated with the polyaspartic acid derivative (D) of the present invention is excellent in fingering of the hair after drying.
On the other hand, it turns out that the comparative examples 6-8 which do not contain a repeating unit (A) have bad fingering of hair.

The polyaspartic acid derivative (D) of the present invention has a conditioning effect and has a role of improving foaming, foam amount, and foam quality. The cleaning of the present invention containing such a polyaspartic acid derivative (D) The agent composition (K) is excellent in foaming, foam amount and foam quality and can be applied to shampoos, body soaps, facial cleansers, hand soaps, cleansing agents, dish detergents, clothing detergents and the like. Cosmetics of the present invention are hair cosmetics such as conditioners, foundations, lotions, creams, emulsions, skin lotions, skin softening cosmetics, nutritional cosmetics, astringent cosmetics, whitening cosmetics, wrinkle improving cosmetics, anti-aging It can be used as skin cosmetics such as cosmetics, antiperspirants, deodorants, perfumes, eau de cologne, eau de toilette and the like.

Claims (8)

A polyaspartic acid derivative having, as an essential repeating unit, a repeating unit (A) selected from the group consisting of the repeating unit (A1) represented by the general formula (1) and the repeating unit (A2) represented by the general formula (2) ( D).
[In the formulas (1) and (2), R ¹ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and R ² is a divalent saturated or unsaturated group having 1 to 24 carbon atoms. R ^{3 to} R ⁵ each independently represents a hydrogen atom or a monovalent saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms, and R ^{3 to} R ⁵ are bonded to each other. A ring containing a nitrogen atom may be formed. X ⁻ represents an anion of an organic or inorganic acid. ] Furthermore, it has a repeating unit (B) selected from the group consisting of the repeating unit (B1) represented by the general formula (3) and the repeating unit (B1) represented by the general formula (4), and contains the repeating unit (B) The polyaspartic acid derivative according to claim 1, wherein the amount is 0.1 to 5 mol%.
[In formulas (3) and (4), R ⁶ represents a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and a represents an integer of 1 to 4. ] Furthermore, the repeating unit (C1) represented by the general formula (5), the repeating unit (C2) represented by the general formula (6), the repeating unit (F1) represented by the general formula (7), and the general formula (8) 1 or 2 comprising at least one repeating unit from the group consisting of the repeating unit (F2), the repeating unit (L1) represented by the general formula (9), and the repeating unit (L2) represented by the general formula (10). The polyaspartic acid derivative according to 1.
[In the formulas (5) and (6), M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), ammonium, or an alkyl-substituted ammonium, and each repeating unit is the same or different. May be. ]
Wherein the ^{(7) (8), R} 7 is a hydrocarbon group having 1 to 32 carbon atoms. R ⁷ may be the same or different for each repeating unit. ]
[In Formulas (9) and (10), R ¹² is a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ¹³ is a linear or branched alkylene group having 2 to 4 carbon atoms. AO is an oxyalkylene group having 2 to 4 carbon atoms, and may be used alone or in combination of two or more. b is 1-300. R ¹² and a may be the same or different for each repeating unit. ] Based on the total of all repeating units in the polyaspartic acid derivative, the repeating unit (A) is 10 to 99.6 mol%, and the total of the repeating units (C1) and (C2) is 0.1 to 89.6 mol. %, The total of repeating units (F1) and (F2) is 0.1 to 89.6 mol%, and the total of repeating units (L1) and (L2) is 0.1 to 89.6 mol%. 3. The polyaspartic acid derivative according to 3. The polyaspartic acid derivative according to any one of claims 1 to 4, which has a weight average molecular weight of 1,000 to 200,000. A cleaning composition (K) comprising the polyaspartic acid derivative (D) according to any one of claims 1 to 5 and a surfactant (J). The detergent composition according to claim 6, which is used for shampoo, body soap or facial cleanser. Cosmetics containing the polyaspartic acid derivative (D) according to any one of claims 1 to 5.