JP2000109524A - Unsaturated carboxylic acid polymer and biodegradable builder - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an unsaturated carboxylic acid polymer having an excellent chelating ability and good biodegradability and useful as a builder for detergents by copolymerizing a specific unsaturated carboxylic acid with a specified aromatic hydrocarbon compound or the like in the presence of a polymerization initiator. SOLUTION: This polymer comprising 50-99.5 mol.% of repeating units of formula III and 0.05-50 mol.% of repeating units of formula IV and having a number-average mol.wt. of 500-1,000,000 is obtained by copolymerizing (A) an unsaturated carboxylic acid of formula I (X is H, an alkali metal or the like; Y is H or COOX; R1 is H or methyl) (for example, acrylic acid or fumaric acid) with (B) an aromatic hydrocarbon of formula II (Y is H or COOX; R2 is a 1-10C hydrocarbon; R3 is H, an alkali metal or a 1-8C hydrocarbon group; (m) is 0-4; (n) is 1 or 2; (m)+(n)<=5] (for example, 1-vinyl-4-hydroxybenzene) in the presence of a polymerization initiator (for example, hydrogen peroxide) preferably at the atmospheric pressure to 5 kg/cm2.G at 30 to 150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel unsaturated carboxylic acid polymer and a method for producing the same, a biodegradable builder using the polymer, a detergent composition and a dispersant. More specifically, a novel unsaturated carboxylic acid polymer having excellent biodegradability and excellent performance as a detergent builder, an effective production method thereof, and a biodegradable builder using the polymer and a detergent composition And dispersants.

[0002]

2. Description of the Related Art Conventionally, in detergents comprising a surfactant as a main component, the washing ability has been increased by blending a builder as an auxiliary component of the surfactant. As the builder, an inorganic compound showing alkalinity when added to water, a polymer of unsaturated aliphatic carboxylic acid, and the like are known. Examples of the former include sodium or potassium carbonates, bicarbonates, phosphates, polyphosphates, silicates and zeolites, and examples of the latter include polyacrylic acid, polymaleic acid, polyitaconic acid. And the like.

[0003] Among these builders, phosphates, polyphosphates and zeolites are used in large amounts from the viewpoints of washing effect, economy and workability. However, phosphates and polyphosphates cause eutrophication of lakes and rivers, and zeolite has various problems in terms of environmental protection, such as sedimentation. Therefore, as in the past, it has excellent builder performance, especially chelating ability (calcium ion scavenging ability), as well as excellent biodegradability, which is important in terms of environmental protection. There is a demand for the development of a so-called environmentally friendly and economically advantageous builder that does not remain for a long period.

In response to such a demand, Japanese Patent Laid-Open No.
No. 9127 discloses, as a polymer suitable for use as a builder having chelating ability and biodegradability, a water-soluble oligomer containing a biodegradable low molecular weight component, although the polymer itself has almost no chelating ability. A crosslinked polymer in which the main chains are linked to each other via a biodegradable ester group or amide group by a crosslinking agent such as polyethylene glycol, citric acid, tartaric acid or the like to increase the molecular weight has been proposed. However, this crosslinked polymer has improved biodegradability by reducing the molecular weight, but linear polyacrylic acid itself is difficult to biodegrade, and high-molecular-weight linear polyacrylic, which is difficult to biodegrade. The biodegradability is not sufficiently high because it contains a considerable amount of acid. Also, in the production process of this crosslinked polymer, it is necessary to perform in two stages of a process of polymerizing the oligomer and a process of crosslinking, and it is necessary to use a specific crosslinking agent, so that the production process is complicated. Has disadvantages.

In Japanese Patent Application Laid-Open No. 50-80377, it is proposed to use, as a builder, a copolymer obtained by copolymerizing acrylic acid with acrolein, polyoxycarboxymethylene, or polyaspartic acid. However, both the chelating ability and the biodegradability are not sufficient, and they are not satisfactory in terms of economy, so that they have not been put to practical use.

Therefore, there is a demand for the development of a builder polymer having excellent chelating ability and high biodegradability and an efficient production method thereof. In the field of inorganic pigment dispersants, sodium polyacrylate and the like are used to reduce the viscosity of the dispersion slurry and improve the viscosity stability, but since polyacrylic acid has no biodegradability,
As with the above-mentioned builders, there is a demand for the development of an economically advantageous dispersant that has biodegradability, does not remain for a long time, and is economically advantageous.

[0007]

SUMMARY OF THE INVENTION The present invention relates to an economically advantageous unsaturated carboxylic acid polymer having excellent chelating ability and biodegradability, an efficient production method thereof, and a builder comprising this polymer. It is an object of the present invention to provide a detergent composition containing the builder component and a surfactant component, and a dispersant such as an inorganic pigment.

[0008]

Means for Solving the Problems As a result of diligent studies to achieve the above object, the present inventors have found that unsaturated carboxylic acid polymers having a specific chemical structure in the molecular chain have excellent chelating ability. It has biodegradability, and is economically advantageous because it can be efficiently produced by a simple process.Furthermore, this polymer has high utility as a builder, They have found that they are highly useful as dispersants, and have completed the present invention based on such findings.

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

[0010]

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In the formula (1), X represents a hydrogen atom, an alkali metal atom or an ammonium group, Y represents a hydrogen atom or a COOX group, and R ¹ represents a hydrogen atom or a methyl group. Unit 50 to 99.5 mol%,
(B) the following general formula [2],

[0012]

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[In the formula [2], Y is a hydrogen atom or COO
An X group (where X has the same meaning as X in formula [1]); R ¹ represents a hydrogen atom or a methyl group;
² represents a hydrocarbon group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom, an alkali metal atom or a hydrocarbon group having 1 to 8 carbon atoms, m is an integer of 0 to 4, n is 1 or 2, And m + n ≦ 5. ] Is represented by a repeating unit of 0.5 to
50 mol%, having a number average molecular weight of 500 to 1,0.
An unsaturated carboxylic acid polymer which is 0.00000. (2) The following general formula [3],

[0014]

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In the formula (3), X represents a hydrogen atom, an alkali metal atom or an ammonium group, Y represents a hydrogen atom or a COOX group, and R ¹ represents a hydrogen atom or a methyl group. A saturated carboxylic acid, and the following general formula [4],

[0016]

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[In the formula [4], Y is a hydrogen atom or COO
An X group (where X has the same meaning as X in formula [1]); R ¹ represents a hydrogen atom or a methyl group;
² represents a hydrocarbon group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom, an alkali metal atom or a hydrocarbon group having 1 to 8 carbon atoms, m is an integer of 0 to 4, n is 1 or 2, And m + n ≦ 5. The method for producing an unsaturated carboxylic acid polymer according to the above (1), wherein the aromatic hydrocarbon compound represented by the formula (1) is copolymerized in the presence of a polymerization initiator. (3) As the chain transfer agent, general formula [5],

[0018]

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In the formula [5], Z represents a hydroxyl group or an amino group, and p represents an integer of 1 to 6]. The method for producing an unsaturated carboxylic acid polymer according to the above (2), wherein the copolymerization is carried out using mol%. (4) A biodegradable builder containing the unsaturated carboxylic acid polymer according to the above (1) as a constituent. (5) A detergent composition comprising the unsaturated carboxylic acid polymer according to (1) and a surfactant as constituents. (6) A dispersant comprising a polymer obtained by neutralizing the unsaturated carboxylic acid polymer according to (1) with an alkali.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION The unsaturated carboxylic acid polymer of the present invention contains the repeating units represented by the above general formulas [1] and [2] at a specific ratio and has a number average molecular weight of 500 to 500. 1,000,000 polymer. The alkali metal represented by X in the repeating unit represented by the general formula [1] includes lithium, sodium and potassium. Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by R ² in the repeating unit represented by the general formula [2] include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Group,
sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, cyclopentyl group,
Examples include a cyclohexyl group, a phenyl group, a tolyl group, a benzyl group and a phenethyl group. Among these, a methyl group, an ethyl group, an n-propyl group and an n-butyl group are preferred.

The hydrocarbon group having 1 to 8 carbon atoms represented by R ³ in the general formula [2] includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group,
Isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, cyclopentyl group, cyclohexyl group, phenyl group, tolyl group, benzyl group and the like. Preferred among these are a methyl group, an ethyl group, an n-propyl group and an isopropyl group. further,
The alkali metal represented by R ³ is the same as in the case of X.

Next, the content ratio of the repeating units represented by the general formulas [1] and [2] is based on 50 to 99.5 mol% of the repeating units represented by the general formula [1]. The repeating unit represented by the general formula [2] is 0.5 to 5
0 mol%, and more preferably 90 to 98 mol% of the repeating unit represented by the general formula [1], and 2 to 10 mol% of the repeating unit represented by the general formula [2].

The number average molecular weight of the unsaturated carboxylic acid polymer is in the range of 500 to 1,000,000, preferably in the range of 1,000 to 100,000, and more preferably in the range of 1,000 to 50,000. When the number average molecular weight is less than 500, the chelating ability is not sufficiently obtained when the number average molecular weight is used as a builder. On the other hand, when the number exceeds 1,000,000, the biodegradable It starts to decrease.

Next, regarding the method for producing the above unsaturated carboxylic acid polymer, the unsaturated carboxylic acid represented by the general formula [3] and the aromatic hydrocarbon compound represented by the general formula [4] are used. May be copolymerized in the presence of a polymerization initiator. The specific examples of X, Y, and R ^{1 to} R ³ in these general formulas [3] and [4] are the same as the specific examples in the general formulas [1] and [2].

As the unsaturated carboxylic acid represented by the general formula [3], specifically, acrylic acid, methacrylic acid, maleic acid, fumaric acid and the like are suitably used, and these are used alone. Or a mixture of two or more. When two or more unsaturated carboxylic acids are used as a mixture, for example, maleic acid 10 to 10
Acrylic acid can be used by mixing at a ratio of 40 to 90 mol% with respect to 60 mol%. Further, these unsaturated carboxylic acids may be anhydrides thereof, and may be alkali metal salts or ammonium salts.

Next, the aromatic hydrocarbon compound represented by the general formula [4] has a monovalent group having a carbon-carbon double bond, a hydroxy group or an alkoxy group as a substituent, and further has an alkyl group. A benzene derivative which may have a substituent such as a group. Specific examples of the aromatic hydrocarbon compound having such a chemical structure include, for example, 1-
Vinyl-4-hydroxybenzene, 1- (2-carboxy) ethynyl-4-hydroxybenzene, 1- (1-methyl) vinyl-4-hydroxybenzene, 1-vinyl-
3-hydroxybenzene, 1-vinyl-2-hydroxybenzene, 1-vinyl-2-methoxy-4-hydroxylbenzene, 1-vinyl-3-methoxy-4-hydroxylbenzene, 1- (2-carboxy) ethynyl -2-hydroxybenzene, 1- (2-carboxy) ethynyl-3
-Hydroxybenzene, 1- (2-carboxy) ethynyl-2-methoxy-4-hydroxybenzene, 1- (2
-Carboxy) ethynyl-3-methoxy-4-hydroxybenzene, 1- (1-methyl) vinyl-2-hydroxybenzene, 1- (1-methyl) vinyl-3-hydroxybenzene, 1- (1-methyl) vinyl -2-methoxy-4-hydroxybenzene, 1- (1-methyl) vinyl-3-methoxy-4-hydroxybenzene, and the like.

The unsaturated carboxylic acid polymer of the present invention contains the repeating units represented by the above general formulas [1] and [2] at a specific ratio. The structural unit based on the unsaturated compound of the formula (1) may be introduced in a range not to impair the object of the present invention, for example, when the content ratio of the structural unit is in the range of 1 to 30 mol%. Such unsaturated compounds include, for example, itaconic acid, crotonic acid, α-hydroxyacrylic acid, vinyl sulfonic acid, allyl sulfonic acid, vinyl toluene sulfonic acid, and alkali metal salts, ammonium salts, or C 1 to C 12 Esters of vinyl alcohol, vinyl acetate, acrylamide, acrolein and the like.

[0028] Examples of the polymerization initiator used in the reaction between the unsaturated carboxylic acid and the aromatic hydrocarbon compound include hydrogen peroxide, percarboxylic acid, and permaleic acid. These proportions are based on the total amount of the raw material unsaturated carboxylic acid and aromatic hydrocarbon compound.
It is 0.1 to 30% by weight, preferably 0.5 to 20% by weight. Further, as the polymerization initiator, azobisisobutyronitrile, azobis-2,4-dimethylvaleronitrile, azobiscyclohexanecarbonitrile, tetramethylthiuram disulfide, or the like may be used. These are used in an amount of 0.1 to 10% by weight, preferably 0.5 to 5% by weight, based on the total amount of the unsaturated carboxylic acid and the aromatic hydrocarbon compound as the raw materials. If the use ratio of these polymerization initiators is less than the above range, a polymer having a sufficiently high molecular weight may not be obtained, and if it exceeds the above range, an effect corresponding thereto cannot be obtained.

In the reaction between the unsaturated carboxylic acid and the aromatic hydrocarbon compound, a chain transfer agent may be used. As this chain transfer agent, a compound represented by the general formula [5] is suitably used. Examples of the compound represented by the formula [5] include mercaptoethyl alcohol, mercaptopropyl alcohol, mercaptobutyl alcohol, aminoethanethiol, and the like.
Among these compounds, mercaptoethyl alcohol is particularly preferred. The amount of the chain transfer agent to be used is generally 1 to 20% by weight, preferably 3 to 20% by weight, based on the total amount of the raw material unsaturated carboxylic acid and aromatic hydrocarbon compound.
The range is 15% by weight. If the amount is less than 1% by weight, the effect of the addition is insufficient. If the amount exceeds 20% by weight, the chelating ability of the obtained polymer may be insufficient.

In the production of the unsaturated carboxylic acid polymer, usually, no solvent or an aqueous solvent is used. A non-aqueous solvent may be used as the solvent. As this non-aqueous solvent,
Acetone, dimethylformamide, dimethylacetamide, ethyl acetate, N-methylpyrrolidone, benzene, toluene, xylene, dioxane and the like are used. In this reaction, polymerization is preferably carried out without a solvent, but when a non-aqueous solvent is used, acetone is preferred.

The reaction conditions in this case are from atmospheric pressure to atmospheric pressure.
10 kg / cm ² · G, preferably atmospheric pressure to 5 kg / c
In m ² · G, 30 to 150 ° C., preferably 50 to 150 ° C.
It can be appropriately selected from the range of 120 ° C. The polymerization time depends on the type of the raw material compound and the polymerization temperature, but is usually from 10 minutes to 20 hours, preferably from 1 to 20 hours.
4 hours.

The biodegradable builder of the present invention comprising the unsaturated carboxylic acid polymer thus obtained has excellent chelating ability, has biodegradability, and can be suitably used as a detergent builder. . Also, by using this unsaturated carboxylic acid polymer in combination with a surfactant, a detergent composition having biodegradability can be obtained.
As such a surfactant, for example, an anionic surfactant, a cationic surfactant, a nonionic surfactant, an amphoteric surfactant and the like can be used.

In the detergent composition, the mixing ratio of the builder and the surfactant is preferably 10 to 40% by weight based on the total amount of the detergent composition, and the balance is 2%.
As for 0 to 80% by weight, those obtained by appropriately blending an enzyme, a bleaching agent, an inorganic builder (for example, zeolite, sodium carbonate) and the like are suitably used. Examples of the above anionic surfactant include fatty acid soap, alkyl ether carboxylate, N-acyl amino acid salt, alkyl benzene sulfonate, alkyl naphthalene sulfonate, dialkyl sulfosuccinate, α-olefin sulfonic acid Salts, higher alcohol sulfates, alkyl ether sulfates, polyoxyethylene alkyl phenyl 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, and imidazolinium salts are preferred. Further, as nonionic surfactants, 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, Preferred are 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.

As the amphoteric surfactant, for example, a carboxybetaine type compound, an aminocarboxylate, imidazolinium betaine and the like are suitable. Further, the unsaturated carboxylic acid polymer of the present invention is an alkali,
For example, by neutralizing with an aqueous solution of sodium hydroxide or potassium hydroxide, a hydrophilic polymer having an unsaturated carboxylic acid monomer as a main chain and having a number average molecular weight of 1,000 to 100,000 can be obtained. Since this polymer is also excellent in biodegradability due to its chemical structure, it is highly useful as a dispersant for inorganic pigments such as calcium carbonate and clay used in coating agents such as paper.

In preparing such a coating agent, an inorganic pigment such as calcium carbonate or clay may be used.
It can be obtained by adding the dispersant in an amount of 0.05 to 2.0 parts by weight to 0 parts by weight and dispersing the same in water. By using this dispersant, the coating agent can have low viscosity and high fluidity. In this case, the dispersant may be used alone, or another compounding agent such as polyvinyl alcohol may be used in combination.

Further, the unsaturated carboxylic acid polymer of the present invention is excellent in chelating ability and therefore has high utility as a scale adhesion inhibitor in cooling water systems, boiler water systems and the like.

[0038]

[Example 1]

(1) Production of unsaturated carboxylic acid polymer In a separable flask having a capacity of 100 ml and equipped with a stirrer and a thermocouple, 2.4 g of maleic anhydride, 0.96 g of sodium hydroxide and 3 g of water were placed. 1
Heated to 10 ° C.

Then, 9.4 g of maleic anhydride was added thereto.
And a permaleic acid solution synthesized from 6.8 g of a hydrogen peroxide solution having a concentration of 60% by weight, 8.6 g of acrylic acid and 0.48 g of 1-vinyl-4-hydroxybenzene (5 mol% based on the total amount of monomers). And an aqueous solution obtained by adding 2.6 g of 2-mercaptoethyl alcohol to 17.3 g of a 50% by weight aqueous sodium hydroxide solution was added dropwise over 50 minutes while stirring. After completion of the dropwise addition of each of these solutions, at 110 ° C. for another hour,
The reaction continued under stirring.

After the completion of the reaction, the obtained reaction product was freeze-dried to obtain 33.8 g (yield: 91%) of a solid polymer. The number average molecular weight of the obtained polymer measured by gel permeation chromatography (GPC) using polyacrylic acid as a standard substance was 5,600. The weight average molecular weight of this polymer was 22,800.

From the results of ¹ H-NMR measurement of this polymer, the absorption based on the main chain of the polymer was found at 1.2 to 3.0 ppm, and the absorption derived from the benzene ring was found at 6.7 to 6.8 ppm. From these results and the raw material charge ratio, it was confirmed that the chemical structure of this polymer was as follows.

[0042]

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(2) Evaluation of Calcium Capturing Ability 20 mg of the polymer obtained in the above (1) was added to an inner volume of 200 mg.
Put into a milliliter beaker, and then add calcium chloride 0.1N, potassium chloride 0.1N, ammonia 0.4N, calcium ion concentration 40N.
100 g of an aqueous solution of ppm was added and dissolved. Next, the divalent calcium ion concentration in the aqueous solution was measured using a calcium ion electrode, and calcium carbonate (unit: m) captured by 1 g of the polymer was measured.
g) and this value was taken as the calcium ion trapping ability. As a result of the measurement, the calcium ion-capturing ability of the polymer obtained in the above (1) was 190 mg / g.

(3) Evaluation of biodegradability The polymer obtained in the above (1) was subjected to JIS K69.
The biodegradation rate was measured according to 50. The biodegradation rate is T
It was calculated from OC (total organic carbon content). As a result of this measurement,
The biodegradation rate of the polymer obtained in the above (1) was 85%. Table 1 summarizes these results.

Example 2 (1) Production of unsaturated carboxylic acid polymer 1- (2-carboxy) ethynyl- was used in place of 1-vinyl-4-hydroxybenzene used in (1) of Example 1. Except that 0.66 g of 4-hydroxybenzene (5 mol% based on the total amount of monomers) was used, (1) of Example 1 was used.
In the same manner as in the above, an unsaturated carboxylic acid polymer was obtained.

The number average molecular weight of the polymer obtained here is:
4,800. The weight average molecular weight of this polymer was 26,700. Also, the ¹ H
From the measurement results by -NMR, absorption based on the main chain of the polymer was confirmed at 1.2 to 3.0 ppm, and absorption derived from the benzene ring was confirmed at 6.7 to 6.8 ppm. From these results and the raw material charging ratio, The chemical structure of this polymer was found to be as follows:

[0047]

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(2) Evaluation of Calcium-Capturing Ability The calcium ion-capturing ability of the polymer obtained in (1) above was measured in the same manner as in (2) of Example 1, and as a result, 1
It was 80 mg / g. (3) Evaluation of biodegradability As a result of measuring the biodegradability of the polymer obtained in (1) in the same manner as in (3) of Example 1, it was 75%. The results are shown in Table 1.

Example 3 (1) Production of unsaturated carboxylic acid polymer In place of 1-vinyl-4-hydroxybenzene used in (1) of Example 1, 1- (1-methyl) vinyl-
An unsaturated carboxylic acid polymer was obtained in the same manner as in (1) of Example 1, except that 0.66 g (5 mol% based on the total amount of the monomers) of 4-hydroxybenzene was used.

The number average molecular weight of the polymer obtained here is:
4,300. The weight average molecular weight of this polymer was 21,100. Also, the ¹ H
From the measurement results by -NMR, absorption based on the main chain of the polymer was confirmed at 1.2 to 3.0 ppm, and absorption derived from the benzene ring was confirmed at 6.7 to 6.8 ppm. From these results and the raw material charging ratio, The chemical structure of this polymer was found to be as follows:

[0051]

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(2) Evaluation of Calcium Capturing Ability The polymer obtained in the above (1) was measured for calcium ion capturing ability in the same manner as in Example 1 (2).
It was 75 mg / g. (3) Evaluation of biodegradability The biodegradation rate of the polymer obtained in (1) was measured in the same manner as in (3) of Example 1, and as a result, it was 80%. The results are shown in Table 1.

Comparative Example 1 (1) Production of Unsaturated Carboxylic Acid Polymer 1.96 g of maleic anhydride and 0.8 g of sodium hydroxide were placed in a separable flask having a capacity of 100 ml and equipped with a stirrer and a thermocouple. And 2 g of water.
Heated to 00 ° C.

Then, 13.7 parts of maleic anhydride were added.
g and a solution consisting of 6.35 g of a hydrogen peroxide solution having a concentration of 60% by weight and 11.52 g of acrylic acid, and a solution consisting of 12 g of sodium hydroxide and 12 g of water were simultaneously dropped over 30 minutes while stirring. After completion of the dropwise addition of these solutions, the resulting reaction product was freeze-dried to give 37.5 g of a copolymer of maleic acid and acrylic acid.
(94% yield). The number average molecular weight of the copolymer obtained here was 8,360. The weight average molecular weight of this copolymer was 49,100.

(2) Evaluation of Calcium Capturing Ability Calcium ion capturing capacity of the copolymer obtained in the above (1) was measured in the same manner as in Example 1 (2).
It was 251 mg / g.

(3) Evaluation of biodegradability The biodegradability of the copolymer obtained in the above (1) was measured in the same manner as in (3) of Example 1, and the result was 5%. The results are shown in Table 1.

[0057]

[Table 1]

Example 4 (1) Preparation of Detergent Composition After the polymer obtained in (1) of Example 1 was converted into an aqueous solution, sodium hydroxide was added to adjust the liquid property to pH 10. This was used as a builder. Then, as a surfactant, sodium linear alkylbenzene sulfonate [L in Table 2 was added to 20 parts by weight of this builder.
AS) 25 parts by weight, sodium alkyl sulfate [abbreviated as AS in Table 2] 10 parts by weight, other additives such as sodium silicate 10 parts by weight, polyethylene glycol [abbreviated as PEG in Table 2] 2 parts by weight, 20 parts by weight of sodium carbonate and 13 parts by weight 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.

Organic dirt component 69.7 parts by weight Baking viscosity 29.8 parts by weight Carbon black 0.5 part by weight As the organic dirt component, one containing the following substances in a predetermined ratio is used. Using.

Oleic acid 28.3 parts by weight Triolein 15.6 parts by weight Cholesterol olein 12.2 parts by weight Liquid paraffin 2.5 parts by weight Squalene 2.5 parts by weight Cholesterol 1.6 parts by weight Gelatin 7.0 parts by weight 69.7 parts by weight Next, using this artificial soil, a contaminated cloth is prepared from a clean cloth by a water solvent-based wet method, and cut into 5 cm × 5 cm to obtain a cloth having a reflectance of 38 to 43%. After preparing and measuring the surface reflectance before cleaning, a cleaning test was performed under the following conditions.

Tester Terg-O-Tometer Number of revolutions 120 rpm Water hardness 90 ppm (CaCO ₃ equivalent) Wash amount 900 ml Wash temperature 30 ° C. Detergent concentration 0.067% Bath ratio 30 times Wash time 10 minutes Rinse time 3 minutes Dry twice Iron on the filter paper, then measure the surface reflectance of the washed cloth (wash cloth)
The detergency was determined from the following equation.

Detergency (%) = [(K / S of dirty cloth−K / S of cleaning cloth) / (K / S of dirty cloth−K / S of cleaning cloth)]
× 100 [where K / S = (1−R) ² / 2R (Kub
Elka-Munk equation), and 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 65.
%Met. Table 2 summarizes the results of the evaluation of the detergency of these detergent compositions.

Example 5 (1) Preparation of Detergent Composition After converting the polymer obtained in (1) of Example 2 into an aqueous solution, sodium hydroxide was added to adjust the liquid property to pH 10. This was used as a builder. Then, 20 parts by weight of this builder, 20 parts by weight of sodium linear alkylbenzene sulfonate, 10 parts by weight of sodium alkylsulfate and 5 parts by weight of a linionic surfactant were used as surfactants. 10 parts by weight of sodium silicate, 2 parts by weight of polyethylene glycol,
A detergent composition was prepared by mixing 15 parts by weight of sodium carbonate, 5 parts by weight of sodium sulfate and 13 parts by weight of water. (2) Evaluation of Detergency of Detergent Composition Next, with respect to the detergent composition obtained in the above (1), an evaluation test of the detergency was performed in the same manner as in (2) of Example 4. Table 2 shows the evaluation results.

Example 6 (1) Preparation of Detergent Composition After converting the polymer obtained in (1) of Example 3 into an aqueous solution, sodium hydroxide was added to adjust the liquid property to pH 10. This was used as a builder. Then, based on 20 parts by weight of this builder, 25 parts by weight of sodium linear alkyl benzene sulfonate and 10 parts by weight of sodium alkyl sulfate were used as surfactants, and 10 parts by weight of sodium silicate and polyethylene glycol 2 were used as other additives. Parts by weight, 20 parts by weight of sodium carbonate and 1 part of water
3 parts by weight were blended to prepare a detergent composition. (2) Evaluation of Detergency of Detergent Composition Next, the detergent composition obtained in the above (1) was subjected to an evaluation test of its detergency in the same manner as in (2) of Example 4. Table 2 shows the evaluation results.

Comparative Example 2 (1) Preparation of Detergent Composition As a builder, 20 parts by weight of A-type zeorant was used, and as a surfactant, 25 parts by weight of sodium linear alkylbenzene sulfonate and alkyl sulfate were used. Using 10 parts by weight of sodium, as other additives, 10 parts by weight of sodium silicate, 2 parts by weight of polyethylene glycol,
20 parts by weight of sodium carbonate and 13 parts by weight of water were blended to prepare a detergent composition. (2) Evaluation of Detergency of Detergent Composition Next, the detergent composition obtained in the above (1) was subjected to an evaluation test of its detergency in the same manner as in (2) of Example 4. Table 2 shows the evaluation results.

Comparative Example 3 (1) Preparation of Detergent Composition As a builder, 20 parts by weight of A-type zeorant was used, and as surfactants, 25 parts by weight of sodium linear alkylbenzene sulfonate and alkyl sulfate were used. 10 parts by weight of sodium and 5 parts by weight of a nonionic surfactant were used. As other additives, 10 parts by weight of sodium silicate, 2 parts by weight of polyethylene glycol, 15 parts by weight of sodium carbonate, 5 parts by weight of sodium sulfate and 13 parts by weight of water Was blended to prepare a detergent composition. (2) Evaluation of Detergency of Detergent Composition Next, the detergent composition obtained in the above (1) was subjected to an evaluation test of its detergency in the same manner as in (2) of Example 4. Table 2 shows the evaluation results.

[0067]

[Table 2]

Example 7 (1) Preparation of Dispersion The polymer obtained in (1) of Example 1 was prepared so that the concentration thereof was 10 ppm, and the concentration of activated clay was 1%.
A dispersion was prepared by dissolving both in water so as to obtain a weight%. (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 this dispersion was sampled, the absorbance was measured using a light source having a wavelength of 400 nm, and the value was evaluated as an index of the dispersion performance of the polymer. The absorbance when this polymer was used as a dispersant was 0.100. In the blank test, the absorbance was 0.000. Table 3 shows the evaluation results of the dispersion performance.

Example 8 (1) Preparation of Dispersion A dispersion was prepared in the same manner as (1) of Example 7, except that the polymer obtained in (1) of Example 2 was used as a dispersant. Was prepared. (2) Evaluation of dispersion performance For the dispersion prepared in the above (1), (2) of Example 7
In the same manner as in the above, the dispersion performance of the dispersant was evaluated. Table 3 shows the evaluation results.

Example 9 (1) Preparation of Dispersion A dispersion was prepared in the same manner as (1) of Example 7, except that the polymer obtained in (1) of Example 3 was used as a dispersant. Was prepared. (2) Evaluation of dispersion performance For the dispersion prepared in the above (1), (2) of Example 7
In the same manner as in the above, the dispersion performance of the dispersant was evaluated. Table 3 shows the evaluation results.

[0071]

[Table 3]

[0072]

Industrial Applicability The unsaturated carboxylic acid polymer of the present invention is excellent in calcium ion trapping ability and biodegradability, so that it is highly useful as a detergent builder.
In addition, a detergent composition having high detergency and biodegradability can be obtained by being blended with the surfactant component, and a biodegradable dispersant can be obtained.

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Claims (6)

[Claims] (A) The following general formula [1]: [In the formula [1], X represents a hydrogen atom, an alkali metal atom or an ammonium group, Y represents a hydrogen atom or a COOX group, and R ¹ represents a hydrogen atom or a methyl group.] 99.5 mol%, and (b) the following general formula [2]: [In the formula [2], Y represents a hydrogen atom or a COOX group (where X has the same meaning as X in the formula [1]), R ¹ represents a hydrogen atom or a methyl group, and R ² represents A hydrocarbon group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom, an alkali metal atom or a hydrocarbon group having 1 to 8 carbon atoms;
m is an integer of 0 to 4, n is 1 or 2, and m + n
≦ 5. And a number average molecular weight of from 500 to 1,000,000.
00 is an unsaturated carboxylic acid polymer. 2. The following general formula [3]: [In the formula [3], X represents a hydrogen atom, an alkali metal atom or an ammonium group, Y represents a hydrogen atom or a COOX group, and R ¹ represents a hydrogen atom or a methyl group.] And the following general formula [4]: [In Formula [4], Y represents a hydrogen atom or a COOX group (where X has the same meaning as X in Formula [1]), R ¹ represents a hydrogen atom or a methyl group, and R ² represents A hydrocarbon group having 1 to 10 carbon atoms, R ³ represents a hydrogen atom, an alkali metal atom or a hydrocarbon group having 1 to 8 carbon atoms;
m is an integer of 0 to 4, n is 1 or 2, and m + n
≦ 5. And an aromatic hydrocarbon compound represented by
The method for producing an unsaturated carboxylic acid polymer according to claim 1, wherein the copolymerization is carried out in the presence of a polymerization initiator. 3. A compound represented by the following general formula [5]: [Wherein, in the formula [5], Z represents a hydroxyl group or an amino group, and p represents an integer of 1 to 6], a compound represented by the formula: The method for producing an unsaturated carboxylic acid polymer according to claim 2, wherein the copolymerization is carried out by heating. 4. A biodegradable builder comprising the unsaturated carboxylic acid polymer according to claim 1 as a constituent. 5. A detergent composition comprising the unsaturated carboxylic acid polymer according to claim 1 and a surfactant as constituents. 6. A dispersant comprising a polymer obtained by neutralizing the unsaturated carboxylic acid polymer according to claim 1 with an alkali.