JP2011132272A - Polymer builder for clothing detergent - Google Patents

Abstract

The present invention provides a polymer builder for garment detergents comprising a modified polyaspartic acid polymer exhibiting good mud dispersibility.
A specific repeating unit (I) of the aspartic acid type and a specific repeating unit (II) in which an alkylene oxide is added to aspartic acid, the mass ratio of the repeating unit (I) and the repeating unit (II) Is (I) :( II) 51:49 to 99: 1, and the total of repeating units (I) and (II) is 90% by mass or more in all repeating units, modified polyaspartic acid system A polymer builder for clothes detergent made of polymer.
[Selection figure] None

Description

  The present invention relates to a polymer builder for clothing detergents comprising a modified polyaspartic acid polymer.

  The clothes detergent is blended with a polycarboxylic acid polymer builder that has excellent mud dispersibility and improves the mud cleaning power of the detergent. In recent years, with increasing awareness of environmental problems, biodegradable polymer builders that have a low environmental impact even after disposal have been demanded.

  Patent Document 1 describes that polyaspartic acid having excellent biodegradability is produced by a specific method, and describes that the obtained polyaspartic acid can be used in a detergent.

  Patent Documents 2 and 3 propose the use of modified polyaspartic acid as an additive to detergents and cleaning agents. However, these additives could not exhibit satisfactory mud dispersibility as a clothing detergent.

JP-A-11-286546 JP-T-2004-537627 JP-T 8-507558

  An object of the present invention is to provide a polymer builder for clothing detergents comprising a modified polyaspartic acid-based polymer exhibiting good mud dispersibility.

  The present invention relates to a repeating unit selected from a repeating unit represented by general formula (1) [hereinafter referred to as repeating unit (1)] and a repeating unit represented by general formula (2) [hereinafter referred to as repeating unit (2)]. A repeating unit selected from (I) and a repeating unit represented by general formula (3) [hereinafter referred to as repeating unit (3)] and a repeating unit represented by general formula (4) [hereinafter referred to as repeating unit (4)] A unit (II) having a mass ratio of (I) to (II) of 51:49 to 99: 1 of (I) :( II), and repeating units (I) and repeating units of all repeating units The present invention relates to a polymer builder for clothing detergents comprising a modified polyaspartic acid polymer in which the total of units (II) is 90% by mass or more.

[Wherein, M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, or an alkyl-substituted ammonium group, and may be the same or different for each repeating unit. ]

[Wherein, X is NH or O, R ¹ and R ⁴ are independently a phenyl group, a hydrogen atom, or a linear or branched alkyl group having 1 to 3 carbon atoms, and R ² is a carbon number. 1 or 2 alkylene group, and R ³ is a linear or branched alkylene group having 3 to 5 carbon atoms. R ² O and R ³ O are present in a random or block form, a is 0 to 10, b is 1 to 100, and c is 0 to 100. R ¹ , R ² , R ³ , R ⁴ , a, b and c may be the same or different for each repeating unit. In the formula, “/” is a convenient symbol for separating R ² O and R ³ O. ]

  Moreover, this invention relates to the detergent for clothes containing the polymer builder for clothes detergents of the said invention.

  ADVANTAGE OF THE INVENTION According to this invention, the polymer builder for clothing detergents excellent in mud dispersibility is provided.

  In general formulas (1) and (2), M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, or an alkyl-substituted ammonium group, and may be the same for each repeating unit. May be different. From the viewpoint of good mud dispersibility, M is preferably an alkali metal.

In the general formulas (3) and (4), X is NH or O, preferably NH, and R ¹ and R ⁴ are independently phenyl, a hydrogen atom, or a straight chain having 1 to 3 carbon atoms. or a branched-chain alkyl group, preferably an alkyl group having 1 carbon atoms, R ² is an alkylene group having 1 to 2 carbon atoms, preferably ethylene group, R ³ is 3 to 5 carbon atoms A linear or branched alkylene group, preferably a propylene group. R ² O and R ³ O are present in random or block form, a is 0 to 10, preferably 1 to 3, b is 1 to 100, preferably 5 to 50, and c is 0 to 0. 100, preferably 0-50, more preferably 0-30. R ¹ , R ² , R ³ , R ⁴ , a, b and c may be the same or different for each repeating unit.

  In the modified polyaspartic acid polymer according to the present invention, the total of the repeating unit (I) and the repeating unit (II) is 90% by mass or more and preferably 95% by mass or more in all repeating units. Furthermore, the modified polyaspartic acid polymer according to the present invention is more preferably substantially composed of the repeating unit (I) and the repeating unit (II). That is, the total of the repeating unit (I) and the repeating unit (II) is preferably 100% by mass in all repeating units.

  In the modified polyaspartic acid polymer according to the present invention, the mass ratio of the repeating unit (I) to the repeating unit (II) improves the detergency against mud soil. ) 51: 49-99: 1, more preferably 54: 46-80: 20.

  The weight average molecular weight of the modified polyaspartic acid polymer according to the present invention is preferably in the range of 1000 to 100,000, more preferably 8000 to 50000, and still more preferably 10,000 to 20000, from the viewpoint of improving the detergency against mud dirt. It is. The weight average molecular weight can be measured by the method described in the examples below.

  The modified polyaspartic acid polymer according to the present invention can be obtained by, for example, the following method 1, method 2, and the like.

Method 1
A monomer that can be converted into polysuccinimide by thermal condensation polymerization and a polymer compound represented by the following general formula (5) are subjected to thermal condensation polymerization to obtain a modified polysuccinimide. A method of hydrolyzing the coalescence.

HX-CH (R ¹ ) (CH ₂ ) _a O-[(R ² O) _b / (R ³ O) _c ] -R ⁴ (5)
[Wherein X is NH or O, preferably NH, and R ¹ and R ⁴ are each independently a phenyl group, a hydrogen atom, or a linear or branched alkyl group having 1 to 3 carbon atoms. , Preferably an alkyl group having 1 carbon atom, R ² is an alkylene group having 1 to ² carbon atoms, preferably an ethylene group, and R ³ is a linear or branched alkylene group having 3 to 5 carbon atoms. And preferably a propylene group. R ² O and R ³ O is present randomly or in block form, a is 0-10, preferably 1 to 3, b is 1 to 100, preferably 10 to 50, more preferably 15 to 35 And c is 0 to 100, preferably 1 to 50, more preferably 2 to 30. R ¹ , R ² , R ³ , R ⁴ , a, b and c may be the same or different for each repeating unit. In the formula, “/” is a convenient symbol for separating R ² O and R ³ O. ]

Method 2
A polysuccinimide-based polymer, for example, a polysuccinimide-based polymer obtained by thermal condensation polymerization of a monomer that can be converted into polysuccinimide by thermal condensation polymerization, and a polymer compound represented by the above general formula (5) A method of hydrolyzing the modified polysuccinimide-based polymer after obtaining a modified polysuccinimide-based polymer.

  Of the above methods, Method 2 is preferred, and the polysuccinimide polymer that is a precursor of the modified polysuccinimide of the present invention can be synthesized by, for example, the method described in JP-A No. 11-286546.

  The monomer that can be converted into polysuccinimide by the thermal condensation polymerization can be obtained by thermal condensation polymerization of 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.

  The polymer compound represented by the general formula (5) preferably has a weight average molecular weight of 500 to 10,000, more preferably 1000 to 2500. Specific examples of commercially available compounds represented by the general formula (5) include, for example, Jeffamine (registered trademark) M series (manufactured by Huntsman Corporation).

  In addition, the modified polyaspartic acid polymer according to the present invention may use two or more different compounds represented by the general formula (5) from the viewpoint of detergency against mud dirt.

  The modified polyaspartic acid polymer according to the present invention can be used as a builder for clothing detergents, either an acid type compound or a compound neutralized to a predetermined neutralization degree. For neutralization, alkali substances such as monovalent and divalent metal hydroxides, chlorides, carbonates and bicarbonates; ammonia; organic amines can be used.

  The polymer builder for clothes detergent of the present invention is composed of a modified polyaspartic acid polymer excellent in mud dispersibility, and preferably has a transmittance of a mud dispersion test measured by the method of Examples described later. It is 75% or less, more preferably 70% or less. If the transmittance by this method is 75% or less, when used as a polymer builder for garment detergents, the effect of improving the detergency against mud stains is particularly increased, which is preferable.

  The polymer builder for garment detergents comprising the modified polyaspartic acid polymer according to the present invention is not particularly limited to the form of the detergent, and can be blended in, for example, a powder detergent or a liquid detergent. The polymer builder for clothes detergent of the present invention is blended in a clothes detergent containing a surfactant, preferably a liquid detergent for clothes.

  The surfactant used together with the polymer builder for clothes detergent of the present invention may be any of an anionic surfactant, a cationic surfactant, a nonionic surfactant, and an amphoteric surfactant.

  Examples of the anionic surfactant include fatty acid soap, alkyl ether carboxylate, N-acyl amino acid salt, alkylbenzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, α-olefin sulfonate. Higher alcohol sulfates, alkyl ether sulfates, polyoxyethylene alkylphenyl ether sulfates, fatty acid alkylolamide sulfates, alkyl ether phosphates, alkyl phosphates and the like are preferably used.

  As the cationic surfactant, aliphatic amine salts, aliphatic quaternary ammonium salts, benzalkonium salts, benzethonium chloride, pyridinium salts, imidazolinium salts and the like are preferably used.

  Nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene polyoxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene Castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyethylene glycol fatty acid ester, fatty acid monoglyceride, polyglycerin fatty acid ester, sorbitan fatty acid ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, Alkylamine oxide and the like are preferably used.

  As the amphoteric surfactant, for example, carboxybetaine type compounds, aminocarboxylates, imidazolinium betaines and the like are preferably used.

  As an example of the clothing detergent containing the polymer builder for clothes detergent of the present invention, 0.1-10% by weight of the polymer builder for clothes detergent of the present invention, 20-70% by weight of nonionic surfactant, A liquid detergent for clothing containing 5 to 20% by mass of an ionic surfactant and 5 to 50% by mass of water is exemplified.

  In producing the detergent composition of the present invention, various detergent components used in ordinary detergent compositions can be blended in addition to the polymer builder for detergents and surfactants of the present invention. . These detergent components include, for example, bleach (percarbonate, perborate, etc.), bleach activator, recontamination inhibitor (carboxymethylcellulose, etc.), softener, reducing agent (sulfite, etc.), fluorescence Examples include brighteners, antifoaming agents (silicone, etc.), enzymes such as cellulase and protease, dyes, and fragrances.

The weight average molecular weights of various polymers (synthetic polymers A to E and comparative synthetic polymers F to H) obtained in the following synthesis examples and comparative synthesis examples were measured by GPC (gel permeation chromatography) under the following conditions. The mass ratio (I) :( II) was measured and calculated by the proton nuclear magnetic resonance method ( ¹ H NMR measurement) under the following conditions.

<Weight average molecular weight measurement (GPC analysis)>
Column: TSKgel G400PWXL, G2500PWXL made by TOSO
Detector: RI
Column temperature: 40 ° C
Eluent: 0.2M phosphate buffer / CH ₃ CN = 9/1 (mass ratio)
Reference material: Pullulan

<Proton nuclear magnetic resonance method ⁽¹ H NMR determination)>
Apparatus: Mercury 400 (400 MHz) manufactured by Varian
Integration count: 64 times Solvent: heavy water

<Synthesis Example 1 (Synthesis of polysuccinimide)>
Polysuccinimide was obtained by the method described in Example 1 of JP-A-11-286546. In a glass reactor (500 mL) equipped with a thermometer, stirrer, nitrogen inlet tube, and reflux condenser, 39.9 g of L-aspartic acid (manufactured by Kishida Chemical Co., Ltd.), 85% phosphoric acid (manufactured by Kishida Chemical Co., Ltd.) ) 80 g was charged, and stirring was continued at 155 ° C. for 3 hours while distilling off the water produced by the reaction under a reduced pressure of 8 kPa (60 torr). The mixture was returned to room temperature and washed with water and ethanol to obtain 28.2 g of polysuccinimide.

<Synthesis Example 2 (Synthesis of Synthetic Polymer A)>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 3.0 g of polysuccinimide obtained in Synthesis Example 1 and 120 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was mixed in a nitrogen atmosphere, and the temperature was raised to 100 ° C. Then, Jeffamine (registered trademark) M-1000 (polyetheramine, EO average addition mole number 19, PO average addition mole number 3, Huntsman Corporation) 0.6 g was added to dimethylformamide (Wako Pure Chemical Industries, Ltd.) (Made) It was made to melt | dissolve in 10g and it was dripped. After completion of the dropwise addition, stirring was continued at 100 ° C. for 4 hours. After returning to room temperature, the residue was concentrated and washed with diethyl ether to obtain 4.6 g of a modified polysuccinimide. Note that EO is an abbreviation for ethylene oxide and PO is an abbreviation for propylene oxide (the same applies hereinafter).

Put 4.2 g of the synthesized modified polysuccinimide and 60 g of ion-exchanged water in a glass reactor equipped with a stirrer, and adjust the pH of the reaction solution using a 1 N aqueous sodium hydroxide solution (manufactured by Kishida Chemical Co., Ltd.). Adjusted to 9. After dropping, stirring was continued at room temperature for 3 hours. The insoluble part of the reaction residue was filtered off, followed by dialysis and subsequent lyophilization to obtain 2.6 g of synthetic polymer A. In the synthetic polymer A, the total of the repeating units (I) and (II) is 100% by mass in the total repeating units, and the mass ratio of the repeating units (I) and (II) is (I) :( II) = 76. : 24 (mass ratio). As a result of GPC measurement of the obtained synthetic polymer A, the weight average molecular weight was 12,000. In the obtained synthetic polymer A, M in the general formulas (1) and (2) in the repeating unit (I) is a Na atom, and in the general formulas (3) and (4) in the repeating unit (II) X in the formula is NH, R ¹ and R ⁴ are methyl groups, R ² is an ethylene group, and R ³ is a branched propylene group. R ² O and R ³ O existed in a random form, a was 1, b was 19, and c was 2.

<Synthesis Example 3 (Synthesis of Synthetic Polymer B)>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 1.1 g of polysuccinimide obtained in Synthesis Example 1 and 45 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was mixed in a nitrogen atmosphere, and the temperature was raised to 100 ° C. Thereto, 1.5 g of Jeffamine (registered trademark) M-1000 (polyetheramine, EO average addition mole number 19, PO average addition mole number 3, manufactured by Huntsman Corporation) and dimethylformamide (Wako Pure Chemical Industries, Ltd.) (Manufactured) dissolved in 30 g and added dropwise. After completion of the dropping, stirring was continued at 70 ° C. for 8 hours. After returning to room temperature, the residue was concentrated and washed with diethyl ether to obtain 2.1 g of a modified polysuccinimide.

Put 1.5 g of the synthesized modified polysuccinimide and 60 g of ion-exchanged water in a glass reactor equipped with a stirrer, and adjust the pH of the reaction solution using a 1 N aqueous sodium hydroxide solution (manufactured by Kishida Chemical Co., Ltd.). Adjusted to 10. After dropping, stirring was continued at room temperature for 3 hours. The insoluble part of the reaction residue was filtered off and dialysis followed by lyophilization was performed to obtain 0.7 g of synthetic polymer B. In the synthetic polymer B, the total of the repeating units (I) and (II) is 100% by mass in all repeating units, and the mass ratio of the repeating units (I) and (II) is (I) :( II) = 58 : 42 (mass ratio). As a result of GPC measurement of the obtained synthetic polymer B, the weight average molecular weight was 13,000. In the obtained synthetic polymer B, M in the general formulas (1) and (2) in the repeating unit (I) is a Na atom, and in the general formulas (3) and (4) in the repeating unit (II) X in the formula is NH, R ¹ and R ⁴ are methyl groups, R ² is an ethylene group, and R ³ is a branched propylene group. R ² O and R ³ O existed in random form, a was 1, b was 19, and c was 2.

<Synthesis Example 4 (Synthesis of Synthetic Polymer C)>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux condenser was charged with 2.0 g of polysuccinimide obtained in Synthesis Example 1 and 90 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was mixed in a nitrogen atmosphere, and the temperature was raised to 100 ° C. There, 0.8 g of Jeffamine (registered trademark) M-2070 (polyetheramine, EO average addition mole number 31, PO average addition mole number 10, Huntsman Corporation) was added to dimethylformamide (Wako Pure Chemical Industries, Ltd.) (Made) was dissolved in 20 g and added dropwise. After completion of the dropwise addition, stirring was continued at 100 ° C. for 4 hours. After returning to room temperature, the residue was concentrated and then washed with diethyl ether to obtain 2.8 g of a modified polysuccinimide.

A glass reactor equipped with a stirrer is charged with 2.2 g of the synthesized modified polysuccinimide and 80 g of ion-exchanged water, and the pH of the reaction solution is adjusted using a 1 N aqueous sodium hydroxide solution (manufactured by Kishida Chemical Co., Ltd.). Adjusted to 10. After dropping, stirring was continued at room temperature for 3 hours. The insoluble part of the reaction residue was filtered off, followed by dialysis and lyophilization to obtain 2.1 g of synthetic polymer C. In the synthetic polymer C, the total of the repeating units (I) and (II) is 100% by mass, and the mass ratio of the repeating units (I) and (II) is (I) :( II) = 73. : 27 (mass ratio). As a result of GPC measurement of the obtained synthetic polymer C, the weight average molecular weight was 16000. In the obtained synthetic polymer C, M in the general formulas (1) and (2) in the repeating unit (I) is a Na atom, and in the general formulas (3) and (4) in the repeating unit (II) X in the formula is NH, R ¹ and R ⁴ are methyl groups, R ² is an ethylene group, and R ³ is a branched propylene group. R ² O and R ³ O existed in random form, a was 1, b was 31, and c was 9.

<Synthesis Example 5 (Synthesis of Synthetic Polymer D)>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 1.1 g of polysuccinimide obtained in Synthesis Example 1 and 45 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was mixed in a nitrogen atmosphere, and the temperature was raised to 70 ° C. Then, Jeffamine (registered trademark) M-2005 (polyetheramine, EO average addition mole number 6, PO average addition mole number 29, manufactured by Huntsman Corporation) 3.0 g dimethylformamide (Wako Pure Chemical Industries, Ltd.) (Manufactured) dissolved in 30 g and added dropwise. After completion of the dropwise addition, stirring was continued at 70 ° C. for 4 hours. After returning to room temperature, the residue was concentrated and washed with diethyl ether to obtain 1.7 g of a modified polysuccinimide.

A glass reactor equipped with a stirrer is charged with 1.0 g of the synthesized modified polysuccinimide and 35 g of ion-exchanged water, and the pH of the reaction solution is adjusted using a 1N aqueous sodium hydroxide solution (manufactured by Kishida Chemical Co., Ltd.). Adjusted to 10. After dropping, stirring was continued at room temperature for 3 hours. The insoluble part of the reaction residue was filtered off and dialysis followed by lyophilization to obtain 0.4 g of synthetic polymer D. In the synthetic polymer D, the total of the repeating units (I) and (II) is 100% by mass, and the mass ratio of the repeating units (I) and (II) is (I) :( II) = 54. : 46 (mass ratio). As a result of GPC measurement of the obtained synthetic polymer D, the weight average molecular weight was 16000. In the obtained synthetic polymer D, M in the general formulas (1) and (2) in the repeating unit (I) is a Na atom, and in the general formulas (3) and (4) in the repeating unit (II) X in the formula is NH, R ¹ and R ⁴ are methyl groups, R ² is an ethylene group, and R ³ is a branched propylene group. R ² O and R ³ O existed in random form, a was 1, b was 6, and c was 28.

<Synthesis Example 6 (Synthesis of Synthetic Polymer E)>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 2.5 g of polysuccinimide obtained in Synthesis Example 1 and 90 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was mixed in a nitrogen atmosphere, and the temperature was raised to 100 ° C. Then, 1.0 g of Sunbright (registered trademark) MEPA-20H [aminopropyl polyethylene glycol, EO average added mole number 48, manufactured by NOF Corporation] into 20 g of dimethylformamide (Wako Pure Chemical Industries, Ltd.) It was dissolved and added dropwise. After completion of the dropwise addition, stirring was continued at 100 ° C. for 4 hours. After returning to room temperature, the residue was concentrated and washed with diethyl ether to obtain 3.7 g of a modified polysuccinimide.

A glass reactor equipped with a stirrer is charged with 2.0 g of the synthesized modified polysuccinimide and 60 g of ion-exchanged water, and the pH of the reaction solution is adjusted using a 1 N aqueous sodium hydroxide solution (manufactured by Kishida Chemical Co., Ltd.). Adjusted to 9. After dropping, stirring was continued at room temperature for 3 hours. The insoluble part of the reaction residue was filtered off and dialysis followed by lyophilization was performed to obtain 1.9 g of a synthetic polymer E. In the synthetic polymer E, the total of the repeating units (I) and (II) is 100% by mass in all the repeating units, and the mass ratio of the repeating units (I) and (II) is (I) :( II) = 74. : 26 (mass ratio). As a result of GPC measurement of the obtained synthetic polymer E, the weight average molecular weight was 16000. In the obtained synthetic polymer E, M in the general formulas (1) and (2) in the repeating unit (I) is a Na atom, and in the general formulas (3) and (4) in the repeating unit (II) X in the formula is NH, R ¹ is a hydrogen atom, R ⁴ is a methyl group, and R ² is an ethylene group. a was 2, b was 48, and c was 0.

<Comparative Synthesis Example 1 (Synthesis of Comparative Synthetic Polymer F)>
A glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 1.0 g of polysuccinimide obtained in Synthesis Example 1 and 45 g of dimethylformamide (manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was mixed in a nitrogen atmosphere, and the temperature was raised to 100 ° C. Then, 2.1 g of Jeffamine (registered trademark) M-1000 (polyetheramine, EO average addition mole number 19, PO average addition mole number 3, Huntsman Corporation) was added to dimethylformamide (Wako Pure Chemical Industries, Ltd.) And then added dropwise. After completion of the dropwise addition, stirring was continued at 100 ° C. for 4 hours. After returning to room temperature and concentrating the residue, the residue was washed with diethyl ether to obtain 2.0 g of a modified polysuccinimide.

Into a glass reactor equipped with a stirrer, 1.7 g of the synthesized modified polysuccinimide and 40 g of ion-exchanged water are added, and the pH of the reaction solution is adjusted using a 1 N aqueous sodium hydroxide solution (manufactured by Kishida Chemical Co., Ltd.). Adjusted to 10. After dropping, stirring was continued at room temperature for 3 hours. The insoluble part of the reaction residue was filtered off and dialysis followed by lyophilization was performed to obtain 0.7 g of comparative synthetic polymer F. In the comparative synthetic polymer F, the total of the repeating units (I) and (II) is 100% by mass in all the repeating units, and the mass ratio of the repeating units (I) and (II) is (I) :( II) = It was 50:50 (mass ratio). As a result of GPC measurement of the obtained comparative synthetic polymer F, the weight average molecular weight was 5,800. In the obtained synthetic polymer F, M in the general formulas (1) and (2) in the repeating unit (I) is a Na atom, and in the general formulas (3) and (4) in the repeating unit (II) X in the formula is NH, R ¹ and R ⁴ are methyl groups, R ² is an ethylene group, and R ³ is a branched propylene group. R ² O and R ³ O existed in random form, a was 1, b was 31, and c was 9.

<Comparative Synthesis Example 2 (Comparative Synthesis Polymer G: Synthesis of Unmodified Polyaspartic Acid)>
A glass reactor equipped with a stirrer was charged with 10.1 g of polysuccinimide obtained in Synthesis Example 1 and 300 g of ion-exchanged water, and a 1N aqueous sodium hydroxide solution (manufactured by Kishida Chemical Co., Ltd.) was used for the reaction. The pH of the solution was adjusted to 11. After dropping, stirring was continued at room temperature for 3 hours. The residue was concentrated and washed with methanol to obtain 14.7 g of a comparative synthetic polymer G. ^{From 1} H NMR measurement, it was confirmed that the hydrolysis was completely progressing. The comparative synthetic polymer G obtained was unmodified polyaspartic acid, and the repeating unit (I) was 100% by mass in all repeating units. As a result of GPC measurement of the obtained comparative synthetic polymer G, the weight average molecular weight was 5,800. In the obtained comparative synthetic polymer G, M in the general formulas (1) and (2) in the repeating unit (I) was a Na atom.

<Comparative Synthesis Example 3 (Synthesis of Comparative Synthetic Polymer H)>
Modified polyaspartic acid (comparative synthetic polymer H) was synthesized by the method described in “a.” Of paragraph 0027 “II.” Of JP-T-2004-537627. As a result of the GPC measurement of the obtained comparative synthetic polymer H, the weight average molecular weight was 22,000. The obtained synthetic polymer H is composed of a repeating unit (I), a repeating unit (II), and a repeating unit having a benzylamide moiety, and the mass ratio of the repeating units (I) and (II) is (I): (II) = 49: 51 (mass ratio), M in the general formulas (1) and (2) in the repeating unit (I) is a Na atom, and the general formula (3 in the repeating unit (II) (3) ) And (4) are NH, R ¹ and R ⁴ are methyl groups, R ² is an ethylene group, and R ³ is a branched propylene group. R ² O and R ³ O existed in random form, a was 1, b was 31, and c was 9.

<Mud dispersibility test>
Using the synthetic polymers A to E and comparative synthetic polymers F to H obtained above, a mud dispersibility test was conducted as follows.

[I] Mud dispersion test (I-1)
4.845 g of tris (hydroxymethyl) aminomethane (manufactured by Wako Pure Chemical Industries, Ltd.) was placed in a 2 L volumetric flask, and about 1 L of ion exchange water was added and dissolved. 1N-HCl (manufactured by Wako Pure Chemical Industries, Ltd.) 35 mL, 0.1 N-HCl (manufactured by Wako Pure Chemical Industries, Ltd.) 2 mL are added, and 0.1583 g of calcium chloride (manufactured by Wako Pure Chemical Industries, Ltd.) is added and dissolved. Then, ion exchange water was added to make 2 L (referred to as “4 ° dH / pH 7-buffer solution”).

(I-2)
To a 100 mL volumetric flask, 0.05 g of synthetic polymers A to E and comparative synthetic polymers F to H were added as effective polymer components, and a 4 ° dH / pH 7-buffer solution was added to make a total volume of 100 mL (referred to as “polymer solution”).

(I-3)
A colorimetric tube (IWAKI diameter 24 mm × length 200 mm) was charged with 50 mL of 4 ° dH / pH 7-buffer solution. Thereto, 0.5 mL of the polymer solution prepared in (I-2) was added and mixed. Thereafter, 0.05 g of Kanuma red soil for horticulture was placed in a colorimetric tube and stoppered. Thereafter, the colorimetric tube was shaken to uniformly disperse it and allowed to stand for 2 hours. After standing for 2 hours, 4 mL of the supernatant of the dispersion was sampled, and the transmittance was measured with a UV measuring device (Shimadzu Corporation UV-2550 1 cm cell, wavelength 575 nm). In this test, the transmittance is preferably 75% or less.

  Synthetic polymers A to E all exhibit good dispersion performance. A polymer having a mass ratio of (I) :( II) of 50:50, such as the comparative synthetic polymer F, cannot provide sufficient mud dispersibility. In addition, the synthetic polymers A to E have improved mud dispersibility as compared with the comparative synthetic polymer G which is unmodified polyaspartic acid and the comparative synthetic polymer H which is an existing modified polymer.

Claims (3)

The repeating unit (I) selected from the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2), and the repeating unit represented by the general formula (3) and the general formula (4). Having a repeating unit (II) selected from repeating units, the mass ratio of the repeating unit (I) to the repeating unit (II) is 51:49 to 99: 1 (I) :( II), and all repeating A polymer builder for garment detergents comprising a modified polyaspartic acid polymer in which the total of repeating units (I) and (II) is 90% by mass or more.

[Wherein, M represents a hydrogen atom, an alkali metal, an alkaline earth metal (1/2 atom), an ammonium group, or an alkyl-substituted ammonium group, and may be the same or different for each repeating unit. ]

[Wherein, X is NH or O, R ¹ and R ⁴ are independently a phenyl group, a hydrogen atom, or a linear or branched alkyl group having 1 to 3 carbon atoms, and R ² is a carbon number. 1 or 2 alkylene group, and R ³ is a linear or branched alkylene group having 3 to 5 carbon atoms. R ² O and R ³ O are present in a random or block form, a is 0 to 10, b is 1 to 100, and c is 0 to 100. R ¹ , R ² , R ³ , R ⁴ , a, b and c may be the same or different for each repeating unit. In the formula, “/” is a convenient symbol for separating R ² O and R ³ O. ]   The polymer builder for clothes detergents of Claim 1 whose weight average molecular weights are 1000-100000.   A detergent for clothing containing the polymer builder for clothes detergent according to claim 1 or 2.