JPH1192787A - Builder for detergent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a detergent builder excellent in biodegradability, chelating effect, dispersibility, and detergency by incorporating a polyaspartic acid polymer having a specific structure into the same. SOLUTION: A modified polysuccinimide obtd. by the thermal cocondensation of a monomer which gives polysuccinimide when thermally polycondensed and a compd. of formula I and/or II is hydrolyzed to give a detergent builder comprising a polyaspartic acid polymer which has a mol.wt. of 500-500,000, pref. 500-200,000, and contains at least 50 mol.% repeating units of formula III or IV (wherein M is H, an alkali or alkaline earth metal, ammonium, or an org. amine group) and 0.01-40 mol.% at least one kind of repeating units selected from among units of formulas V to VIII [wherein R<1> and R<2> are each an org. group derived from an arom. compd. having at least one benzene ring, H, or 1-2C alkyl provided at least one of them is an org. group derived from an arom. compd. having at least one benzene ring; and X is a (non)arom. heterocycle having N and bonded to carbonyl through N].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a detergent builder comprising a modified polyaspartic acid-based polymer.

[0002]

2. Description of the Related Art Since polyaspartic acid has excellent biodegradability, its use as a water treatment agent such as a detergent builder or a scale inhibitor has been studied. However, although it is superior in biodegradability to various polymers conventionally used in each application, it has not been put to practical use yet because it is inferior in various properties such as dispersing ability and metal ion chelating ability.

As an attempt to improve various properties such as surface activity of polyaspartic acid, JP-A-48-51995 and US Pat. No. 3,846,380 disclose an alkyl group having 8 to 20 carbon atoms in a side chain. And polyaspartic acid having an alkenyl group, and as a use thereof, a synthetic detergent composition and the like are disclosed. However,
Since polyaspartic acid having such an alkyl group or alkenyl group in the side chain has a weak interaction with a surfactant, a large number of modifications are required to sufficiently exert the modification effect.
As a result, the amount of the carboxylic acid is reduced, and the metal ion chelating ability and the like are reduced. As a result, there is a problem that sufficient performance cannot be obtained.

[0004]

Accordingly, an object of the present invention is to provide a polyaspartic acid polymer having a biodegradability equal to or higher than that of a conventional aspartic acid polymer, and having high chelating ability and dispersing ability. A detergent builder comprising:

[0005]

Means for Solving the Problems In order to solve the above-mentioned problems, the present invention relates to a method for producing a polymer having at least one of the repeating units represented by the following general formulas (1) and (2): 4) A detergent builder comprising a polyaspartic acid-based polymer having at least one of the repeating units represented by (5) and (6).

[0006]

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(However, in the general formulas (1) and (2), M
Represents hydrogen, an alkali metal, an alkaline earth metal, an ammonium group or an organic amine group, and may be the same or different for each repeating unit. )

[0008]

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(However, in the general formulas (3) and (4), R
¹ and R ² each represent an organic group derived from an aromatic compound having at least one benzene ring, hydrogen, or an alkyl group having 1 to 2 carbon atoms.
At least one of which is an organic group derived from an aromatic compound having one or more benzene rings. )

[0010]

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(However, in the general formulas (5) and (6), X
Is an aromatic or non-aromatic heterocycle containing a nitrogen atom, and is bonded to the carbon atom in the carbonyl group via the nitrogen atom. )

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION A polyaspartic acid-based polymer which is a feature of the present invention will be described together with a production method. Usually, polyaspartic acid, aspartic acid, ammonium maleate, ammonium fumarate, maleamic acid, polycondensed imide by thermal condensation polymerization of a monomer that can be polysuccinimide by thermal condensation polymerization such as maleimide, to obtain a polysuccinimide,
Then it is obtained by hydrolyzing it. Here, as the aspartic acid, any of DL-aspartic acid, L-aspartic acid, and D-aspartic acid can be used.

The polyaspartic acid-based polymer in the present invention may be prepared by, for example, (method 1) a monomer capable of forming a polysuccinimide by thermal polycondensation with the following general formula (7) and / or (8):

[0014]

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The modified polysuccinimide is hydrolyzed with the compound represented by the formula (1) to obtain a modified polysuccinimide, and the modified polysuccinimide is hydrolyzed. (Method 2) A compound represented by the above general formula (7) and / or (8) is reacted with a polysuccinimide-based polymer obtained by subjecting a monomer capable of becoming a polysuccinimide by thermal condensation polymerization to thermal condensation polymerization. After obtaining the modified polysuccinimide, the modified polysuccinimide is hydrolyzed. It can be obtained by:

Polysuccinimide repeating unit:

[0017]

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By hydrolysis of the compound represented by the general formula (1)
And / or a repeating unit of polyaspartic acid represented by (2) is obtained. The polyaspartic acid-based polymer according to the present invention contains at least one of the repeating units represented by the general formulas (1) and (2), and may be the main component. "Main component" means that the total amount of the repeating units represented by the general formulas (1) and (2) is 50 mol% or more of the whole. In order to increase the water solubility, it is preferably at least 60 mol%, more preferably at least 80 mol%. The ratio of the general formulas (1) and (2) is not particularly limited and varies depending on hydrolysis conditions and the like, but it can be generally used in a molar ratio of about 1:99 to 99: 1.
M in the general formulas (1) and (2) is hydrogen, an alkali metal, an alkaline earth metal, an ammonium group or an organic amine group, and may be the same or different for each repeating unit. Of these, alkali metals are preferred from the viewpoint that the hydrolysis rate is high. By selecting the type of hydrolyzing agent used in the hydrolysis,
Can be adjusted to which group.

The polyaspartic acid-based polymer of the present invention contains at least one of the repeating units represented by the general formulas (3), (4), (5) and (6). It is characterized by having. Since the polyaspartic acid-based polymer has high hydrophobicity by having these repeating units, a detergent builder having high chelating ability and dispersing performance and high detergency can be provided. In addition, because of its high hydrophobicity, it is excellent in compatibility with surfactants, alcohols and the like usually contained in liquid detergents, so that a one-part liquid detergent can be produced. The total amount of the repeating units represented by the general formulas (3), (4), (5) and (6) is 0.01 mol% of the whole
It is preferably at least 0.1 mol%, more preferably at least 0.1 mol%. In addition, the upper limit is 40 mo because of preventing a decrease in the amount of carboxylic acid and the detergency.
It is preferably at most 1%, more preferably at most 20 mol%.

In the above (method 1) and (method 2), a compound represented by the general formula (7) is used to form a repeating unit represented by the general formula (3) or (4) in a polymer. By using the compound represented by the general formula (8), the repeating unit represented by the general formula (5) or (6) can be formed in the polymer. Not done. Relationship between general formulas (3) and (4), (5) and (6)
Is the same as the relationship between the general formulas (1) and (2), and the ratio of the general formulas (3) and (4) and the ratio of the (5) and (6) are not particularly limited. 1: 99- in molar ratio
It can be used in a range of about 99: 1. The ratio of the total amount of the general formulas (3) and (4) to the total amount of the general formulas (5) and (6) is not particularly limited, and is usually in the range of about 1:99 to 99: 1 in molar ratio. Can be used.

In the general formulas (3) and (4), R ¹
It is important that at least one of R ² and R ² is an organic group derived from an aromatic compound having one or more benzene rings. Examples of the organic group derived from an aromatic compound having one or more benzene rings include an organic group having one benzene ring, a polycyclic ring in which two or more benzene rings such as a naphthalene ring and an anthracene ring are fused. Examples include an organic group having a benzene ring, an organic group having two or more benzene rings that are not condensed alone, and combinations thereof. Specifically, the residue (R) of the compound exemplified later as the compound represented by the general formula (7)
¹ , R ² ).

In the general formulas (3) and (4), R ¹
And only one of R ² is, if an organic radical derived from an aromatic compound having one or more benzene rings and the other is hydrogen or an alkyl group having 1 to 2 carbon atoms. In the general formulas (5) and (6), X is an aromatic or non-aromatic hetero ring containing a nitrogen atom, and it is important that X is bonded to a carbon atom in the carbonyl group via the nitrogen atom. is there. As an aromatic or non-aromatic hetero ring containing a nitrogen atom, an aziridine ring, an azetidine ring, a pyrrolidine ring, a piperidine ring, a piperazine ring, a hexamethylene imine ring, an imidazole ring, a pyrazole ring, a hydantoin ring, a pipecoline ring, a morpholine ring, Pyrrole rings,
Examples thereof include a pyrroline ring, an indazole ring, an indole ring, a carbazole ring, an iminodibenzyl ring, an iminostilbene ring, and the like, and a hydrogen-substituted derivative of these rings. Good. Specific examples include the residue (X) of the compound exemplified later as the compound represented by the general formula (8).

The molecular weight of the polyaspartic acid polymer in the present invention is preferably 500 or more and 500,000 or less.
0 or more and 200,000 or less are more preferable. It can be controlled by adjusting reaction conditions such as reaction temperature, reaction time, presence or absence and amount of an acid catalyst. The method for producing a polyaspartic acid-based polymer in the present invention will be described in more detail. In the following description, these items are common to the method 1 and the method 2 unless otherwise specified.

At the time of thermal condensation polymerization, amino acids or polyfunctional monomers having two or more functional groups may be copolymerized. Examples of such amino acids include glycine, alanine, phenylalanine, leucine, isoleucine, valine, methionine, cysten, cysteine, serine, threonine, glutamic acid, α-amino-adipic acid, aminomalonic acid, α-amino-sebacic acid , Α-methylglutamic acid, β, β-dimethylaspartic acid, ornithine,
Lysine, arginine, histidine, β-alanine, β-
Phenylalanine, β-aminobutyric acid, α-methyl-β-
Aminopropionic acid, isoserine, β-tyrosine, taurine and the like.Examples of polyfunctional monomers include diamines such as ethylenediamine and hexamethylenediamine, polyamines such as diethylenetriamine, dicarboxylic acids such as succinic acid, and polycarboxylic acids. Is mentioned. These may be used alone or in combination of two or more. In this case, the amount of the amino acid or the polyfunctional monomer having two or more functional groups is preferably less than 50% by weight of the whole. If it is more than this, the water solubility will decrease,
It may not be dissolved in water.

In the thermal polycondensation reaction, the mixture of the raw materials is preferably heated to 110 to 300 ° C, more preferably 150 to 270 ° C.
By heating to a temperature of The time of the thermal polycondensation reaction varies depending on conditions such as the reaction temperature, the reaction pressure, and the type of the apparatus, but usually requires 1 minute to 12 hours. The apparatus for heating is not particularly limited, and examples thereof include a batch mixer and a continuous mixer capable of uniformly heating a mixture of raw materials.

The thermal polycondensation reaction can be carried out at normal pressure without any problem as long as the generated water can be removed from the reaction system. Is also good. In the heat condensation polymerization reaction, a heat condensation polymerization catalyst may be used as necessary. As the thermal condensation polymerization catalyst, phosphoric acid, phosphorus pentoxide, polyphosphoric acid, alkyl phosphonic acid,
Arylphosphonic acid, phosphorous acid, hypophosphorous acid / nitric acid, nitrous acid / sulfuric acid, sulfurous acid, alkylsulfonic acid, arylsulfonic acid / hydrochloric acid, chloric acid, chlorous acid, hypochlorous acid / bromic acid,
Hypobromous acid, hypobromous acid / iodic acid / molybdic acid, tungstic acid, hydrogen sulfide, hydrogen bromide, sodium bisulfate,
Examples thereof include potassium bisulfate and ammonium bisulfate.

The heat condensation polymerization may be carried out without a solvent.
It may be performed in a solvent. Examples of the solvent include solvents such as ethylene glycol, glycerin, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, tetralin, dodecyl alcohol, dimethylformamide, and dimethyl sulfoxide.

The compound represented by the general formula (7) includes
For example, 1-naphthylamine-2-sulfonic acid, 1-naphthylamine-3-sulfonic acid, 1-naphthylamine-
4-sulfonic acid, 1-naphthylamine-5-sulfonic acid, 1-naphthylamine-6-sulfonic acid, 1-naphthylamine-7-sulfonic acid, 1-naphthylamine-8-
Sulfonic acid, 2-naphthylamine-1-sulfonic acid, 2
Naphthylaminesulfonic acids such as -naphthylamine-4-sulfonic acid, 2-naphthylamine-5-sulfonic acid, 2-naphthylamine-6-sulfonic acid, 2-naphthylamine-7-sulfonic acid, 2-naphthylamine-8-sulfonic acid; 1 -Naphthylamine-2,4-disulfonic acid, 1
-Naphthylamine-2,5-disulfonic acid, 1-naphthylamine-2,7-disulfonic acid, 1-naphthylamine-2,8-disulfonic acid, 1-naphthylamine-3,5
-Disulfonic acid, 1-naphthylamine-3,6-disulfonic acid, 1-naphthylamine-3,7-disulfonic acid,
1-naphthylamine-3,8-disulfonic acid, 1-naphthylamine-4,6-disulfonic acid, 1-naphthylamine-4,7-disulfonic acid, 1-naphthylamine-4,
8-disulfonic acid, 1-naphthylamine-5,7-disulfonic acid, 1-naphthylamine-5,8-disulfonic acid, 2-naphthylamine-1,5-disulfonic acid, 2-
Naphthylamine-1,6-disulfonic acid, 2-naphthylamine-1,7-disulfonic acid, 2-naphthylamine-
3,6-disulfonic acid, 2-naphthylamine-3,7-
Disulfonic acid, 2-naphthylamine-4,7-disulfonic acid, 2-naphthylamine-4,8-disulfonic acid, 2
Naphthylamine disulfonic acid such as -naphthylamine-5,7-disulfonic acid, 2-naphthylamine-6,8-disulfonic acid; 1-naphthylamine-2,4,6-trisulfonic acid, 1-naphthylamine-2,4,7- Trisulfonic acid, 1-naphthylamine-2,5,7-trisulfonic acid, 1-naphthylamine-3,5,7-trisulfonic acid, 1-naphthylamine-3,6,8-trisulfonic acid, 1-naphthylamine- Naphthylamine trisulfonic acid such as 4,6,8-trisulfonic acid; 1-amino-2-
Naphthol-4-sulfonic acid, 1-amino-2-naphthol-6-sulfonic acid, 5-amino-1-naphthol-
2-sulfonic acid, 1-amino-7-naphthol-3-sulfonic acid, 1-amino-8-naphthol-4-sulfonic acid, 8-amino-1-naphthol-4-sulfonic acid, 2
-Amino-3-naphthol-6-sulfonic acid, 2-amino-5-naphthol-7-sulfonic acid, 2-amino-8
Aminonaphtholsulfonic acid such as -naphthol-6-sulfonic acid; 1-amino-2-naphthol-3,6-disulfonic acid, 1-amino-8-naphthol-2,4-disulfonic acid, 1-amino-8- Naphthol-3,5-disulfonic acid, 1-amino-8-naphthol-3,6-disulfonic acid, 1-amino-8-naphthol-4,6-disulfonic acid, 1-amino-8-naphthol-5,7 Aminonaphthol disulfonic acid such as -disulfonic acid, 2-amino-1-naphthol-4,8-disulfonic acid, 2-amino-8-naphthol-3,6-disulfonic acid; 1-amino-2-ethoxynaphthalene-6 -Aminoethoxynaphthalenesulfonic acid such as sulfonic acid; 2-amino-1-naphthol, 4-amino-1-naphthol, 5-amino-
1-naphthol, 8-amino-1-naphthol, 1-amino-2-naphthol, 5-amino-2-naphthol,
Aminonaphthols such as 7-amino-2-naphthol and 8-amino-2-naphthol; 1-naphthylamine, 2-
Naphthylamines such as naphthylamine, 1-naphthylmethylamine, and 2-naphthylmethylamine; and in the following, aminoazonaphthalene: naphthylethylamine; Aminoacridone; aminoacridone; aminoquinoline; aminoisoquinoline; aminophenanthrene; aminofluorene; aminoanthracene; aminofluorenone; aminopyrene; aminofluoranthene; aminofluoroscein; aminocoumarin; Diaminonaphthalenedisulfonic acid; aminoanthraquinone; aminohydroxyanthraquinone; aminochloroanthraquinone; Rakinon; amino bromine anthraquinone acid; aminomethyl anthraquinone; amino bromine hydroxy anthraquinone; C. I. Aci
d Blue 25, C.I. I. Acid Yellow
Anthraquinone dyes having an amino group such as 7; and aniline, anisidine, (o, m,
p-) aminophenol, 4-aminobenzonitrile,
Chloroaniline, 2-aminothiophenol, aminobenzaldehyde, anthranilic acid, xylidine, (o,
p-) cresidine, metanilic acid, p-aminobenzoic acid,
Phenylhydrazine, benzylamine, α-methylbenzylamine, 2-amino-4-chlorophenol, m-
Xylylenediamine, sulfanilic acid, toluidine, toluylenediamine, nitroaniline, m-nitro-p-
Toluidine, (o, m, p-) phenylenediamine, phenetidine, phenethylamine, mesidine and the like.

Examples of the cyclic compound giving the cyclic amide represented by the general formula (8) include, for example, ethyleneimine, pyrrolidine, piperidine, piperazine, hexamethyleneimine, imidazole, pyrazole, hydantoin, pipecoline, morpholine, pyrrole, pyrroline, indazole , Indole, carbazole, iminodibenzyl, iminostilbene, derivatives of these cyclic compounds in which cyclic hydrogen is substituted, etc., and one or more of these can be used.

The amounts of the compounds represented by the general formulas (7) and / or (8) are represented by the general formulas (3), (4), (5) and (6) in one molecule of the polymer. It suffices that at least one of the repeating units is designed to be at least one. Preferably, a monomer which can be converted into a polysuccinimide by thermal condensation polymerization or a polysuccinimide-based polymer obtained by thermal condensation polymerization of these monomers For 0.
1% by weight or more.

In the method 1, after a monomer capable of forming a polysuccinimide by thermal polycondensation, a compound represented by the general formula (7) and / or (8) and other raw materials are mixed as necessary, Polymerized. In particular, when aspartic acid is used as a monomer and no solvent is used, a compound represented by the following general formula (9) (a naphthylamine (mono, di, tri) sulfonic acid) may be used as the compound represented by the general formula (7). )

[0032]

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It is preferable to use aminonaphthol (mono, di) sulfonic acid whose salt shows water solubility. In this case, the salt of aspartic acid and the general formula (9)
It is preferable to perform a heat-condensation polymerization after performing a pretreatment step of adding an acid to an aqueous solution containing a salt of the compound represented by the formula to precipitate crystals. By performing such a pretreatment step, aspartic acid and the compound represented by the general formula (7) are uniformly mixed in the crystal. In this case, as the base of the salt,
Sodium, potassium, ammonium and the like,
As the acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, maleic acid, fumaric acid, aspartic acid and the like can be used.
The compound represented by the general formula (8) is not particularly limited. However, when a compound having a 5- to 7-membered ring such as pyrrolidine, piperidine, hexamethyleneimine, or imidazole is used, interaction with a surfactant is strongly preferred. .

In the method 2, a polysuccinimide-based polymer is obtained by subjecting a monomer capable of being converted to a polysuccinimide by thermal condensation polymerization and, if necessary, a raw material to other monomers to obtain a polysuccinimide-based polymer. The system polymer is reacted with a compound represented by the general formula (7) and / or (8). The reaction between the polysuccinimide-based polymer and the compound represented by the general formula (7) and / or (8) is preferably performed in a solvent. As the solvent, the same solvent as the solvent used in the above-mentioned thermal condensation polymerization, such as ethylene glycol, is used. The reaction is preferably carried out at 20
It is carried out by heating to a temperature of ３００300 ° C., more preferably 40-270 ° C. When a solvent having an OH group such as ethylene glycol or propylene glycol is used as the solvent, the compound represented by the general formulas (7) and / or (8) is not particularly limited in terms of reactivity, but is not cost-effective. From the viewpoint, benzene, naphthalene and anthraquinone compounds of the general formula (7) are preferred.
When a solvent other than the above, such as dimethylformamide, is used, it is preferable to use a highly reactive amine, such as naphthalenemethylamine. Also,
The compound represented by the general formula (8) is not particularly limited, but when a 5- to 7-membered ring compound such as pyrrolidine, piperidine, hexamethyleneimine, imidazole is used,
Interaction with surfactants is strongly preferred.

The hydrolysis of the modified polysuccinimide can be carried out in the same manner as in the known hydrolysis of polysuccinimide. As a hydrolyzing agent used for hydrolysis,
Acid compounds and alkali compounds can be mentioned. As the acid compound, inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid are preferable, and as the alkali compound, hydroxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide and lithium hydroxide are preferable. Or alkali metal or alkaline earth metal carbonates such as sodium carbonate, calcium carbonate and lithium carbonate; and organic amines such as ammonia, monoethanolamine, diethanolamine and triethanolamine.

According to the present invention, there is provided a detergent builder comprising the above polyaspartic acid-based polymer. The above polyaspartic acid-based polymer can be used alone as a builder for detergents, and other builder (polycarboxylic acid polymers such as sodium polyacrylate, acrylic acid / maleic acid copolymer, tripolyphosphoric acid) sodium,
Sodium metasilicate, sodium aluminosilicate, nitrolyl triacetate, citrate, laurate, triethanolamine hydrochloride, etc.) can also be used in combination. In addition, inorganic compounds (eg, sodium nitrate, urea), alkaline agents (eg, sodium hydroxide, sodium carbonate, sodium silicate, triethanolamine, etc.), acids (eg, hydrochloric acid, citric acid), and solvents (eg, ethanol, isopropyl alcohol, butyl alcohol, and ethylene glycol) , Propylene glycol, etc.), oxidizing agents (hydrogen peroxide, sodium percarbonate, etc.), reducing agents (sodium bisulfite, etc.), chelating agents (sodium diglycolate, ethylenediaminetetraacetate, diethylenetriaminepentaacetate, hydroxyiminodisuccinate) Acid, iminodisuccinic acid, citric acid, etc.), anti-staining agent (carboxymethylcellulose, etc.), abrasive (talc, fine powdered silica, etc.), fragrance, colorant, preservative, foaming agent, foam stabilizer, polishing agent, Ingredients such as enzymes, fluorescent dyes, antibacterial agents, and hydrotopes can be added. That. The above-mentioned other builders and various agents may be mixed in advance with the polyaspartic acid-based copolymer, or may be mixed when producing a detergent composition.

The preparation of the detergent composition using the detergent builder of the present invention may be carried out according to a known method, and may be carried out by mixing a surfactant and an appropriate solvent such as water or alcohol with the various agents described above. Good. The detergent builder of the present invention can be used for both liquid detergents and powder detergents. The amount of the polyaspartic acid-based polymer is usually 0.05 to 50%, preferably 0.5 to 50%, based on the weight of the detergent composition.
20%. If it is less than this range, the effect of improving performance (such as detergency) will be insufficient, and if it is more than this range, it is uneconomical.

As the surfactant used in the detergent composition, any of an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant can be used. Examples of the anionic surfactant include alkyl benzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α
-Olefin sulfonates, α-sulfofatty acids or ester salts, alkane sulfonates, saturated or unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid surfactants, N-acyl amino acid surfactants, alkyl Or alkenyl phosphate or a salt thereof can be mentioned.

Examples of the nonionic surfactant include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycooxide,
Fatty acid glycerin monoester, alkylamine oxide and the like can be mentioned.

Examples of the cationic surfactant include a quaternary ammonium salt. Examples of the amphoteric surfactant include a carboxyl-type or sulfobetaine-type amphoteric surfactant.

[0041]

The present invention will be described in more detail with reference to the following Examples, but it should not be construed that the invention is limited thereto. <Example 1> (Aspartic acid raw material benzylamine-modified polyaspartic acid) 40 g of dimethylformamide was added to 10 g of polysuccinimide obtained by heating DL-aspartic acid at 250 ° C for 1 hour and dissolved. Thereto was added 0.552 g of benzylamine, and the mixture was heated and stirred at 100 ° C. for 3 hours. Next, it was poured into a large amount of methanol. The resulting precipitate was separated by filtration, dried in a vacuum dryer at 50 ° C., dispersed in water, and hydrolyzed with a 48% aqueous sodium hydroxide solution to obtain polymer A. Example 2 Ammonium Maleate Raw Material Benzylamine-Modified Polyaspartic Acid To 10 g of polysuccinimide obtained by heating ammonium maleate at 250 ° C. for 1 hour, 40 g of dimethylformamide was added and dissolved. Thereto was added 0.552 g of benzylamine, and the mixture was heated and stirred at 100 ° C. for 3 hours. Next, it was poured into a large amount of methanol. The resulting precipitate was separated by filtration, dried in a vacuum dryer at 50 ° C., dispersed in water, and hydrolyzed with a 48% aqueous sodium hydroxide solution to obtain polymer B. <Example 3> (Aspartic acid raw material naphthylmethylamine-modified polyaspartic acid) 40 g of dimethylformamide was added to and dissolved in 10 g of polysuccinimide obtained by heating DL-aspartic acid at 250 ° C for 1 hour. 0.647 g of 1-naphthylmethylamine was added thereto, and
The mixture was heated and stirred for hours. Next, it was poured into a large amount of methanol. The resulting precipitate was separated by filtration, dried in a vacuum dryer at 50 ° C., dispersed in water, and hydrolyzed with a 48% aqueous sodium hydroxide solution to obtain Polymer C. <Example 4> (Aspartic acid raw material hexamethylene imine-modified polyaspartic acid) 40 g of dimethylformamide was added to 10 g of polysuccinimide obtained by heating DL-aspartic acid at 250 ° C for 1 hour, and dissolved. Thereto, 0.511 g of hexamethyleneimine was added, and the mixture was heated and stirred at 100 ° C. for 3 hours. Next, it was poured into a large amount of methanol.
The resulting precipitate was separated by filtration, dried in a vacuum drier at 50 ° C., dispersed in water, and hydrolyzed with a 48% aqueous sodium hydroxide solution to obtain polymer D. <Comparative Example 1> (Aspartic acid raw material polyaspartic acid) 13.3 g of DL-aspartic acid was heated at 250 ° C for 1 hour. The obtained powder was dispersed in water and hydrolyzed with a 48% aqueous sodium hydroxide solution to obtain Polymer E. <Comparative Example 2> (Aspartic acid raw material laurylamine-modified polyaspartic acid) 80 g of dimethylformamide was added to and dissolved in 20 g of polysuccinimide obtained by heating DL-aspartic acid at 250 ° C for 1 hour. Thereto, 3.8 g of laurylamine was added, and the mixture was heated and stirred at 80 ° C. for 3 hours. Next, it was poured into a large amount of methanol. The precipitate formed was separated by filtration and dried in a vacuum drier at 50 ° C.
The resultant was dispersed in water and hydrolyzed with a 48% aqueous sodium hydroxide solution to obtain a polymer F. <Comparative Example 3> (Aspartic acid raw material monoethanolamine-modified polyaspartic acid) To 20 g of polysuccinimide obtained by heating DL-aspartic acid at 250 ° C for 1 hour, 80 g of dimethylformamide was added and dissolved. Thereto was added 1.26 g of monoethanolamine, and the mixture was heated and stirred at 80 ° C. for 3 hours. Next, it was poured into a large amount of methanol. The resulting precipitate was separated by filtration, dried in a vacuum dryer at 50 ° C., dispersed in water, and hydrolyzed with a 48% aqueous sodium hydroxide solution to obtain polymer G.

Polymers A to D obtained in Examples 1 to 4
And, for the polymers EG obtained in Comparative Examples 1 to 3,
In order to evaluate the performance as a detergent builder, the following (1) compatibility test with detergent composition, (2) detergency test, (3) calcium ion trapping ability (calcium chelating ability) test, (4) clay dispersion A performance test was performed. Table 1 shows the results. (1) Compatibility test for detergent composition Using each of polymers A to G, 5 parts by weight of polymer, 10 parts by weight of sodium polyoxyethylene lauryl sulfate, 10 parts by weight of sophthanol 70H (manufactured by Nippon Shokubai Co., Ltd.), dodecylbenzene A detergent aqueous solution comprising 20 parts by weight of sodium sulfonate, 10 parts by weight of ethanol and 45 parts by weight of water was prepared, and the compatibility at each temperature of 25 ° C. and 0 ° C. was evaluated. (Evaluation criteria) ：: Uniform and transparent liquid ×: Precipitation, turbidity, and separation occurred (2) Detergency test 5 cm × in 1000 ml of each aqueous detergent solution using each of polymers A to G prepared in (1) above Ten pieces of 5 cm artificially stained cloth (wet artificially stained cloth manufactured by Washing Science Association) were put in and washed with a tergotometer at 100 rpm under the following conditions. (Washing conditions) Detergent concentration: 0.05% by weight Washing temperature: 25 ° C Washing time: 10 minutes Water hardness: 3DH Rinsing: 2 minutes with tap water Washing power is determined by measuring the reflectance of contaminated cloth before and after washing with a color difference meter. The cleaning rate (%) was calculated from the following equation. However, Table 1 shows the average value of 10 sheets.

[0043]

(Equation 1)

(3) Calcium ion capturing ability test Each of the polymers A to G was added to the aqueous solution of calcium carbonate prepared under the following conditions and stirred under the following conditions, and the calcium ions in the aqueous solution of calcium carbonate before and after the stirring were added. The concentration was measured using an ion analyzer manufactured by Orion (EA92).
0) using Orion calcium electrode (93-20)
The amount of calcium ions captured by the polymer was determined in terms of mg of calcium carbonate from the difference in concentration before and after stirring, and the value was used as the calcium ion capturing ability of each polymer. (Calcium ion trapping ability measurement conditions) Container: 100 cc beaker Liquid: Ca ²⁺ 1.0 × 10 ⁻³ mol / L aqueous solution 50 c
c Polymer: 10 mg (in terms of solid content) Temperature: 25 ° C. Stirring time: 10 minutes (using a stirrer) (4) Clay dispersibility test Clay was added to a polymer aqueous solution prepared using each of polymers A to G under the following conditions. , Agitation, and standing, the absorbance obtained was used as the clay dispersing ability of each polymer. The higher the value, the higher the clay dispersing ability. (Conditions for measuring clay dispersibility) Container: 100 cc graduated cylinder Polymer solution: 0.5% by weight (in terms of solid content) 1 cc of aqueous polymer solution + 100 g of tap water (Himeji-shi water) Clay: Amazon clay 1.0 g Stirring time: 10 minutes ( Static stirrer) Static time: 18 hours Measurement method: Absorbance (ABS) at UV 380 nm was measured using a 1 cm cell by sampling the top 10 cc of the measuring cylinder, and the numerical value was used as the clay dispersing ability.

[0045]

[Table 1]

Each of the polymers A to D of Examples 1 to 4 has high chelating ability and dispersing ability, excellent detergency, and excellent compatibility. On the other hand, since the polymer E of Comparative Example 1 is unmodified polyaspartic acid, it does not have a hydrophobic portion and is not compatible with a liquid detergent. Also,
Polymers F and G of Comparative Examples 2 and 3 are modified polyaspartic acids but are modified with a group having low hydrophobicity, so that they have poor compatibility and low cleaning performance.

[0047]

As described above, the polyaspartic acid polymer contained in the detergent builder of the present invention exhibits high hydrophobicity, so that it is possible to provide a detergent builder having high chelating ability and dispersing ability and excellent detergency. In addition, because of its high hydrophobicity, it has excellent compatibility with alcohols and the like usually contained in liquid detergents, so that a one-part liquid detergent can be produced. Furthermore, it shows biodegradability equal to or higher than that of a conventional aspartic acid polymer.

Claims (1)

[Claims] 1. A repeating unit represented by the following general formulas (3), (4), (5) and (6) and at least one of the repeating units represented by the following general formulas (1) and (2): Detergent builder comprising a polyaspartic acid-based polymer having at least one of the foregoing. Embedded image (However, in the general formulas (1) and (2), M represents hydrogen, an alkali metal, an alkaline earth metal, an ammonium group or an organic amine group, and may be the same or different for each repeating unit. ) (However, in the general formulas (3) and (4), R ¹ and R ² each represent an organic group derived from an aromatic compound having at least one benzene ring, hydrogen or an alkyl group having 1 to 2 carbon atoms. And at least one is an organic group derived from an aromatic compound having one or more benzene rings.) (However, in the general formulas (5) and (6), X is an aromatic or non-aromatic hetero ring containing a nitrogen atom, and is bonded to the carbon atom in the carbonyl group via the nitrogen atom. )