JP2002194026A - Unsaturated carboxylic copolymer, its production method and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a biodegradative unsaturated carboxylic copolymer which does not bring about the adverse effects on the nature environment, to provide its production method, and to obtain a detergent builder, a detergent composition and a dispersant which use the copolymer. SOLUTION: The copolymer obtained by reacting a copolymer of an unsaturated carboxylic acid such as acrylic acid and a halogenated vinylidene with a bifunctional compound such as p-aminophenol and its production method are provided. The builder, the composition and the dispersant contain the copolymer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an unsaturated carboxylic acid copolymer, a method for producing the same and its use. More specifically, the present invention relates to a biodegradable unsaturated carboxylic acid copolymer and a method for producing the same, and a detergent builder, a detergent composition, and a dispersant using the unsaturated carboxylic acid copolymer.

[0002]

2. Description of the Related Art A synthetic detergent for fibers mainly comprises a surfactant, but a detergent builder is incorporated as an auxiliary component of the surfactant in order to enhance the cleaning ability. Sodium carbonate, phosphates, polyphosphates, zeolites, acrylic polymers and the like have hitherto been used as the detergent builder. Thereafter, sodium tripolyphosphate, which does not produce insoluble precipitates even when hard water is used as the washing water, has been actively used.

However, zeolite A is currently used in sodium tripolyphosphate because its used wastewater flows into lakes and rivers and causes eutrophication in lakes and rivers. . This zeolite A
Has insufficient performance as a builder, and a high molecular weight polycarboxylic acid is used to supplement the performance of zeolite A.

[0004] By the way, this high molecular weight polycarboxylic acid is excellent in performance as a builder,
Since there is no biodegradability, the effect of washing wastewater on the environment is great, and the mixing ratio is greatly restricted. Therefore, a method has been proposed in which this high-molecular-weight polycarboxylic acid exhibits biodegradability. For example, proposals have been made of a method of increasing the molecular weight by bonding an acrylic acid oligomer with an ester, and a method of using polyaspartic acid. However, even in these methods, the performance as a builder is insufficient or the production process is complicated,
There was a problem that it was not an economically advantageous method.

[0005] Accordingly, a polymer suitable for a material of a detergent builder which does not adversely affect the natural environment due to biodegradation of builder components contained in washing wastewater, and a detergent builder using the same. The development of detergent compositions and dispersants has been desired.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a biodegradable unsaturated carboxylic acid copolymer which does not adversely affect the natural environment, a method for producing the same, a detergent builder, a detergent composition and a detergent composition using the same. It is intended to provide a dispersant.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, a specific compound is reacted with a copolymer of unsaturated carboxylic acids and vinylidene halide. The inventors have found that the obtained unsaturated carboxylic acid copolymer has biodegradability, and has excellent calcium ion trapping ability and dispersibility, and based on these findings, has completed the present invention. .

That is, the gist of the present invention is as follows. (1) The following general formula [1]

[0009]

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[In the formula [1], R represents a hydrogen atom or a methyl group, X represents a hydrogen atom, an alkali metal atom or an ammonium group, and Y represents a hydrogen atom or -COOX. And a repeating unit (1) represented by the following general formula [2]

[0011]

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[In the formula [2], V ¹ represents -O-, -S- or -NH-, and Z represents an aromatic hydrocarbon group having 1 to 3 rings or-(CH ₂ ) _k- ( k is an integer of 1 to 12)
And P represents a hydrogen atom, a hydroxyl group, an amino group or a thiol group. And / or the following general formula [3]:

[0013]

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[0014] [In the formula (3), W ¹ represents a hydrogen atom, a halogen atom or a hydroxyl group, V ^1, Z, P has a V ^1, Z, same meaning as P in formula (2). ] The unsaturated carboxylic acid copolymer containing the repeating unit (3) represented by these. (2) When the content ratio of each repeating unit is represented by a molar ratio,
The unsaturated carboxylic acid copolymer according to the above (1), wherein the repeating unit (1): [the repeating unit (2) + the repeating unit (3)] = 50 to 99: 1 to 50. (3) The repeating unit (1) represented by the general formula [1] in the above (1) and the following general formula [4]

[0015]

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[W ² in the formula [4] represents a halogen atom. ] To the unsaturated carboxylic acid copolymer comprising a repeating unit (4) represented by the following general formula [5]

[0017]

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[V ² in the formula [5] represents -OH, -SH or -NH ₂ , and Z and P have the same meanings as Z and P in the general formula [2]. The method for producing an unsaturated carboxylic acid copolymer according to the above (1), wherein the compound represented by the formula (1) is reacted in the presence of a base. (4) A detergent builder containing the unsaturated carboxylic acid copolymer according to (1) as a constituent. (5) A detergent composition containing the unsaturated carboxylic acid copolymer according to (1) as a constituent. (6) A dispersant comprising a copolymer obtained by neutralizing the unsaturated carboxylic acid copolymer according to (1).

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention relates to a repeating unit (1) represented by the general formula [1] and a repeating unit (2) represented by the general formula [2] and / or a compound represented by the general formula [3]. Is an unsaturated carboxylic acid copolymer containing a repeating unit (3). Here, in the general formula [1], examples of the alkali metal represented by X include a lithium atom, a sodium atom, and a potassium atom. Also, the general formula [2]
In the above, examples of the 1 to 3 ring aromatic hydrocarbon group represented by Z include a phenylene group, a naphthylene group and an anthranylene group. Further, in the general formulas [3] and [4], examples of the halogen atom represented by W ¹ and W ² include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Some are preferred.

The content ratio of each repeating unit in the unsaturated carboxylic acid copolymer is, in terms of molar ratio, repeating unit (1): [repeat unit (2) + repeat unit (3)] = 50 to 99: Those having a value of 1 to 50 are preferable because they are more suitable for properties required when they are used as detergent builders, detergent compositions and dispersants. That is, if the content of the repeating unit (1) is less than 50% in molar ratio, the calcium ion-capturing ability may decrease, and the molar ratio may be 99%.
This is because if it exceeds 300, the biodegradability may decrease.
If the total content of the repeating unit (2) and the repeating unit (3) is less than 1%, the biodegradability will decrease, and if the total exceeds 50%, the calcium ion-capturing ability will decrease. This is because it causes a decrease. The content ratio of each repeating unit in the unsaturated carboxylic acid copolymer is represented by a molar ratio of repeating unit (1):
[Repeat unit (2) + Repeat unit (3)] = 50-9
A ratio of 0:10 to 50 is more preferable.

Further, the unsaturated carboxylic acid copolymer may contain only these repeating units (1) to (3), or may contain, in addition to these repeating units, acrolein, vinyl acetate, acrylic Structural units composed of residues derived from acid alkyl esters, maleic acid half esters and the like may be contained at a content of 30 mol% or less. When the content ratio of these structural units exceeds 30 mol%, the water solubility thereof is reduced.

Next, in producing the unsaturated carboxylic acid copolymer, first, as a first step, a base polymer is produced. As a raw material monomer used in the production of the base polymer, the following general formula [6]

[0023]

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[R, X and Y in the formula [6] have the same meanings as R, X and Y in the general formula [1]. ] Is used. Preferable examples of the unsaturated carboxylic acid represented by the general formula [6] include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and alkali metal salts and ammonium salts thereof. .

Further, as a monomer of the raw material, the following general formula [7]

[0026]

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[W ² in the formula [7] has the same meaning as W ² in the general formula [4]. ] Is used. Examples of the vinylidene halide represented by the general formula [4] include vinylidene fluoride, vinylidene chloride, vinylidene bromide, and vinylidene iodide. Then, the copolymerization reaction between the unsaturated carboxylic acid and the vinylidene halide as the raw materials is preferably performed in the presence of a polymerization initiator. As the polymerization initiator, an azo initiator such as azobisisobutyronitrile, benzoyl peroxide and the like are suitably used. The usage ratio of these polymerization initiators is 0.5 to 10% by mass, and preferably 1 to 5% by mass, based on the amount of the raw material monomer. In addition, during the copolymerization reaction, the molecular weight of the unsaturated carboxylic acid copolymer can be adjusted by using a chain transfer agent. As this chain transfer agent, for example, mercaptans such as mercaptoethanol and ethanethiol are suitably used. Further, the use ratio of this chain transfer agent may be usually about 0.5 to 5% by mass based on the raw material compound. And
Although the molecular weight of the unsaturated carboxylic acid copolymer is not particularly limited, the weight average molecular weight is 500 to 1,000.
It may be adjusted within the range of 0000 according to the use.

The reaction temperature for performing the copolymerization reaction between the unsaturated carboxylic acid and the vinylidene halide in the presence of these polymerization initiators is preferably in the range of 50 to 100 ° C., and the reaction time is preferably 1 to 10 hours. It should be time. As the reaction solvent, acetone, tetrahydrofuran, N-methylpyrrolidone and the like are suitably used. Next, the repeating unit (1) thus obtained represented by the general formula [1] and the repeating unit (4) represented by the general formula [4] are obtained.
The unsaturated carboxylic acid copolymer of the present invention is obtained by reacting an unsaturated carboxylic acid copolymer containing a compound represented by the general formula [5] in the presence of a base. Polymers can be produced.

Here, as the compound represented by the general formula [5], for example, p-aminophenol, m-aminophenol, o-aminophenol, hydroquinone,
Resorcinol, catechol, p-hydroxythiophenol, m-hydroxythiophenol, o-hydroxythiophenol, 1,2-dihydroxynaphthalene, 1,
3-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,3-
Dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 1-hydroxy-2-aminonaphthalene, 1-hydroxy-3-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-6 Aminonaphthalene, 2-hydroxy-3-aminonaphthalene, 2-hydroxy-6
Aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 1-hydroxy-2-thionaphthalene, 1-hydroxy-3-thionaphthalene, 1-hydroxy-5-thionaphthalene, 1-hydroxy-6-thionaphthalene,
2-hydroxy-3-thionaphthalene, 2-hydroxy-6-thionaphthalene, 2-hydroxy-7-thiononaphthalene, 1,8-dihydroxyanthracene, 1-hydroxy-8-aminoanthracene, 1-hydroxy-
8-thioanthracene, 1,8-dihydroxyanthraquinone, methanediol, ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, aminomethanol, 2-aminoethanol, 3-amino-1-propanol, 4-amino- 1-
Butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, mercaptomethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 4-mercapto-1-butanol, 5-mercapto-1-pen Suitable examples include tanol and 6-mercapto-1-hexanol.

As the base used in this reaction, sodium hydroxide, potassium hydroxide, lithium hydroxide and the like are used, and sodium hydroxide is preferred. The reaction temperature in this case is 30 to 150.
C. is preferable, and the reaction time may be 0.5 to 12 hours. Further, as a solvent used for performing this reaction, N-methylpyrrolidone, N-methylpyrrolidinone, dimethylformamide, dimethylacetamide, acetone, tetrahydrofuran, water, methyl alcohol,
Preferred examples include ethyl alcohol and isopropyl alcohol.

The unsaturated carboxylic acid copolymer thus obtained is excellent in calcium ion trapping ability and biodegradable, so that it is highly useful as a builder component for detergents. Further, the neutralized product of the unsaturated carboxylic acid copolymer with a base is excellent in dispersibility of inorganic particles such as pigments, and therefore, is highly useful as a dispersant.

When the unsaturated carboxylic acid copolymer is used as a builder for detergents, the unsaturated carboxylic acid copolymer may be used alone as a builder for detergents, or may be used as a builder for detergents. It may be used in combination with an inorganic detergent builder such as sodium or sodium sulfate. The surfactant used together with the detergent builder 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 salts, alkyl benzene sulfonates,
Alkyl naphthalene sulfonate, dialkyl sulfosuccinate, α-olefin sulfonate, higher alcohol sulfate, alkyl ether sulfate,
Polyoxyethylene alkyl phenyl ether sulfate,
Sulfate, alkyl ether phosphate, alkyl phosphate, and the like of fatty acid alkylolamide are preferably used. Further, as the cationic surfactant, an aliphatic amine salt, an aliphatic quaternary ammonium salt, a benzalkonium salt, a benzethonium chloride, a pyridinium salt, an imidazolinium salt and the like are preferable.

Further, as the nonionic surfactant,
Polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl 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, etc. are preferably used. . As the amphoteric surfactant, for example, a carboxybetaine-type compound, an aminocarboxylate, imidazolinium betaine and the like are suitably used.

When a detergent composition containing the unsaturated carboxylic acid copolymer and a surfactant as main components is produced, in addition to the unsaturated carboxylic acid copolymer and the surfactant component, In addition, enzymes, fluorescent brighteners, antifoaming agents, and the like used in ordinary detergent compositions can be blended.

[0036]

[Example 1]

(1) Production of backbone polymer In a separable flask having an internal volume of 100 ml equipped with a stirrer and a thermocouple, 7.2 g of acrylic acid as an unsaturated carboxylic acid, 9.4 g of vinylidene chloride, and azobisiso as a polymerization initiator. 0.48 g of butyronitrile and 30 ml of acetone as a solvent were added, and this was immersed in an oil bath maintained at 70 ° C., and polymerized for 5 hours with stirring. After the reaction, the product is reprecipitated with hexane,
Drying under reduced pressure gave an acrylic acid-vinylidene chloride copolymer.

(2) Production of unsaturated carboxylic acid copolymer Next, 2.5 g of the base polymer obtained in the above (1) was
A 100 ml separable flask equipped with a stirrer and a thermocouple was placed in a separable flask, and 50 ml of N-methylpyrrolidinone was added as a solvent and dissolved therein.

Next, 1.63 g of p-aminophenol was added to the flask, and the mixture was heated to 80 ° C. and reacted for 5 hours with stirring. After the completion of the reaction, the reaction product was poured into acetone, and a 1N aqueous solution of sodium hydroxide was added thereto to adjust the pH to 7, followed by filtration. The filtrate was dissolved in water and freeze-dried to obtain 3.5 g (yield: 72%) of the desired unsaturated carboxylic acid copolymer.

The unsaturated carboxylic acid copolymer obtained here had a number average molecular weight of 8,900 and a weight average molecular weight of 28,400. The ¹ H-NMR spectrum of the unsaturated carboxylic acid copolymer was as shown in FIG. 1, and an absorption peak derived from a benzene skeleton was confirmed at around 6.2 to 7.8 ppm. The ¹ H-
From the measurement results of NMR and ¹³ C-NMR, it was confirmed that the chemical structure of the unsaturated carboxylic acid copolymer was as follows.

[0040]

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The composition of each of these structural units is such that the molar ratio of the repeating unit represented by the formula [8] is 0.76,

The total molar ratio of the repeating units represented by [9] and [10] was 0.24. (3) Evaluation of biodegradability of unsaturated carboxylic acid copolymer The unsaturated carboxylic acid copolymer obtained in the above (2) was evaluated for biodegradability in accordance with JIS K 6950. The biodegradation rate was calculated from TOC (total organic carbon content). As a result, the biodegradability of the unsaturated carboxylic acid copolymer obtained in the above (2) was 60%.

(4) Evaluation of Calcium Ion Capturing Ability of Unsaturated Carboxylic Acid Copolymer In a beaker having an internal volume of 200 ml, 20 mg of the unsaturated carboxylic acid copolymer obtained in the above (1) was added. To 100 g of an aqueous solution having a calcium ion concentration of 40 ppm containing 0.1 N of calcium chloride, 0.1 N of potassium chloride, and 0.4 N of ammonia,
These were dissolved. Next, the concentration of divalent calcium ions in the aqueous solution was measured using a calcium ion electrode, converted to calcium carbonate (unit: mg) captured by 1 g of the copolymer, and this value was calculated as calcium ion capture. Ability. As a result, the calcium ion trapping ability of this product was 115 mg / g. The properties and evaluation results of the unsaturated carboxylic acid copolymer obtained here are shown in Tables 1 and 2.

Example 2 (1) Production of unsaturated carboxylic acid copolymer Hydroquinone was used in place of p-aminophenol in the amount of 1.5.
Except for using g, an unsaturated carboxylic acid copolymer was obtained in the same manner as in (2) of Example 1. The properties of the unsaturated carboxylic acid copolymer obtained here are as shown in Table 1, and the ¹ H-NMR spectrum of this unsaturated carboxylic acid copolymer is as shown in FIG. The chemical structure was found to be:

[0044]

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The composition of each of these structural units is represented by the formula [1]
1] the molar ratio of the repeating unit is 0.93,
The molar ratio of the total of the repeating units represented by the formulas [12] and [13] was 0.07. (2) Evaluation of unsaturated carboxylic acid copolymer For the unsaturated carboxylic acid copolymer obtained in the above (1), the biodegradability and the biodegradability of the unsaturated carboxylic acid copolymer were obtained in the same manner as in (3) and (4) of Example 1. The calcium ion scavenging ability was evaluated.
The results are shown in Table 2.

Example 3 (1) Production of Unsaturated Carboxylic Acid Copolymer In Example 1, (2) except that 1.77 g of p-hydroxythiophenol was used instead of p-aminophenol.
In the same manner as in the above, an unsaturated carboxylic acid copolymer was obtained.

The properties of the unsaturated carboxylic acid copolymer obtained here are as shown in Table 1, and the ¹ H-NMR spectrum of this unsaturated carboxylic acid copolymer is shown in FIG. As shown, the chemical structure was found to be:

[0048]

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The composition of each of these structural units is represented by the formula [1]
4] the molar ratio of the repeating unit is 0.90,
The molar ratio of the total of the repeating units represented by the formulas [15] and [16] was 0.10. (2) Evaluation of unsaturated carboxylic acid copolymer For the unsaturated carboxylic acid copolymer obtained in (1) above, the biodegradability and the biodegradability of the unsaturated carboxylic acid copolymer were determined in the same manner as in (3) and (4) of Example 1. The calcium ion scavenging ability was evaluated.
The results are shown in Table 2.

Example 4 (1) Production of Unsaturated Carboxylic Acid Copolymer 7.2 g of acrylic acid as an unsaturated carboxylic acid was placed in a separable flask having an internal volume of 100 ml and equipped with a stirrer and a thermocouple. 9.7 g of vinylidene, 0.5 g of azobisisobutyronitrile as a polymerization initiator, and 30 ml of acetone as a solvent were added, and this was immersed in an oil bath maintained at 60 ° C., and polymerized for 3 hours with stirring. Then, 1.65 g of p-aminophenol, 1.5 g of sodium hydroxide and N
Then, 20 ml of -methylpyrrolidinone was added and reacted at 60 ° C for 3 hours with stirring. After the reaction,
50 g of an aqueous solution containing 3.0 g of sodium hydroxide in the product
And lyophilized to yield an unsaturated carboxylic acid copolymer.
9 g (yield 76%) was obtained. Table 1 shows the properties of this unsaturated carboxylic acid copolymer.

(2) Evaluation of unsaturated carboxylic acid copolymer The unsaturated carboxylic acid copolymer obtained in the above (1) was produced in the same manner as in (3) and (4) of Example 1. Degradability and calcium ion scavenging ability were evaluated.
The results are shown in Table 2.

Example 5 (1) Production of unsaturated carboxylic acid copolymer Hydroquinone was replaced with 1.1 in place of p-aminophenol.
Except for using g, an unsaturated carboxylic acid copolymer was obtained in the same manner as in (2) of Example 1. Table 1 shows the properties of this unsaturated carboxylic acid copolymer. (2) Evaluation of unsaturated carboxylic acid copolymer For the unsaturated carboxylic acid copolymer obtained in the above (1), the biodegradability and the biodegradability of the unsaturated carboxylic acid copolymer were obtained in the same manner as in (3) and (4) of Example 1. The calcium ion scavenging ability was evaluated.
The results are shown in Table 2.

[0053]

[Table 1]

[0054]

[Table 2]

Examples 6 to 10 (1) Preparation of detergent compositions The unsaturated carboxylic acid copolymers obtained in (2) of Example 1 and (1) of Examples 2 to 5 were each dissolved in an aqueous solution. After that, sodium hydroxide was added to adjust the pH of the solution to pH 10.
This was used as a builder. Then, with respect to 20 parts by mass of this builder, as a surfactant, sodium linear alkyl benzene sulfonate [L in Table 6,
AS; 25 parts by mass; sodium alkyl sulfate [abbreviated as AS in Table 6] 10 parts by mass; sodium silicate 10 parts by mass as other additives; polyethylene glycol [abbreviated as PEG in Table 6] 2 parts by mass, 20 parts by mass of sodium carbonate and 13 parts by mass of water were blended to prepare a detergent composition.

(2) Evaluation of Detergency of Detergent Composition Next, an evaluation test of the detergency of the detergent composition obtained in the above (1) was performed. As the artificial soil used here, one having the following composition was prepared.

[0057]

[Table 3]

As the organic dirt component, those containing the following substances at predetermined ratios were used.

[0059]

[Table 4]

Then, using this artificial soil, a contaminated cloth was prepared from a clean cloth by a water-solvent-based wet method, and 5 cm × 5 cm.
cm, the surface was measured to measure the surface reflectance before cleaning, and then a cleaning test was performed under the following conditions.

[0061]

[Table 5]

Next, the surface reflectance of the washed cloth (cleaning cloth) was measured, and the detergency was determined from the following equation.

[0063]

(Equation 1)

[Where K / S = (1-R) ²
/ 2R (Kubelka-Munk equation), where R represents the surface reflectance of the cloth. As a result of evaluating the detergency of the detergent composition as described above, the detergency of the detergent composition obtained in the above (1) was 60%.
%Met. Table 6 shows the compositions of these detergent compositions and the results of the evaluation of detergency.

[Comparative Examples 1 and 2] Detergent compositions were prepared and evaluated in the same manner as in Examples 6 to 10 except that a conventionally used A-type zeolite was used as a builder. Table 6 shows the compositions and evaluation results of these detergent compositions.

[0066]

[Table 6]

Examples 11 to 15 (1) Preparation of Dispersion The polymer obtained in (2) of Example 1 and (1) of Examples 2 to 5 was prepared so that the concentration of the polymer was 10 ppm. A dispersion was prepared by dissolving it in water and further dissolving activated clay in water such that the concentration thereof was 1% by mass.

(2) Evaluation of Dispersion Performance After stirring 100 ml of this dispersion for 10 minutes,
It was placed in a 100 ml graduated cylinder and allowed to stand for 14 hours. Next, 5 ml of the supernatant of the dispersion was sampled, the absorbance was measured using a light source having a wavelength of 400 nm, and the dispersion performance of the polymer was evaluated based on the measured absorbance. The absorbance when only this polymer was used as a dispersant was 0.100, and in the blank test, the absorbance was 0.000. Table 7 shows the evaluation results of the dispersion performance of these polymers.

[0069]

[Table 7]

[0070]

According to the present invention, there are provided a detergent builder, a detergent composition, a dispersant, an unsaturated carboxylic acid copolymer as a raw material thereof, and a method for producing the same, which do not adversely affect the natural environment. be able to.

[Brief description of the drawings]

FIG. 1 is a ¹ H-NMR spectrum of the unsaturated carboxylic acid copolymer obtained in Example 1.

FIG. 2 is a ¹ H-NMR spectrum of the unsaturated carboxylic acid copolymer obtained in Example 2.

FIG. 3 is a ¹ H-NMR spectrum of the unsaturated carboxylic acid copolymer obtained in Example 3.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 214/00 C08F 214/00 222/02 222/02 C11D 3/37 C11D 3/37 // (C08F 220 / 06 (C08F 220/06 216: 14 216: 14 228: 02 228: 02 226: 02) 226: 02) F term (reference) 4D077 AB10 AC05 CA12 CA13 DC20X DC26X DC26Y DC42X DC52X DC71X 4H003 AB19 AB27 DA01 EA16 EB15 EB30 EB32 EB36 ED02 FA03 FA04 FA37 4J100 AC04Q AC11Q AC24Q AJ02P AJ09P AK32P AN02Q AN02R BA03Q BA03R BB01R BC43Q BC43R CA04 CA05 HC09 HC43 HC70 JA60

Claims (6)

[Claims] [Claim 1] The following general formula [1] [In the formula (1), R represents a hydrogen atom or a methyl group;
Represents a hydrogen atom, an alkali metal atom or an ammonium group, and Y represents a hydrogen atom or -COOX. And a repeating unit (1) represented by the following general formula [2]: [In the formula [2], V ¹ represents -O-, -S- or -NH-, and Z represents an aromatic hydrocarbon group having 1 to 3 rings or-(CH
₂ ) _k- (where k is an integer of 1 to 12), and P represents a hydrogen atom, a hydroxyl group, an amino group or a thiol group. And / or the following general formula [3]: [In Formula [3], W ¹ represents a hydrogen atom, a halogen atom or a hydroxyl group, and V ¹ , Z, and P represent V ¹ ,
It has the same meaning as Z and P. ] The unsaturated carboxylic acid copolymer containing the repeating unit (3) represented by these. 2. The composition according to claim 1, wherein the content ratio of each repeating unit is, in molar ratio, repeating unit (1): [repeat unit (2) + repeat unit (3)] = 50 to 99: 1 to 50. The unsaturated carboxylic acid copolymer according to the above. 3. The repeating unit (1) represented by the general formula [1] in claim 1, and the following general formula [4]: [W ² in the formula [4] represents a halogen atom. To the unsaturated carboxylic acid copolymer comprising a repeating unit (4) represented by the following general formula [5]: [V ² in the formula [5] is -OH, -SH or -NH ₂
And Z and P have the same meaning as Z and P in the general formula [2]. The method for producing an unsaturated carboxylic acid copolymer according to claim 1, wherein the compound represented by the formula (1) is reacted in the presence of a base. 4. A detergent builder comprising the unsaturated carboxylic acid copolymer according to claim 1 as a constituent. 5. A detergent composition comprising the unsaturated carboxylic acid copolymer according to claim 1 as a constituent. 6. A dispersant comprising a copolymer obtained by neutralizing the unsaturated carboxylic acid copolymer according to claim 1.