JPH0329279B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a novel builder for detergents. More specifically, it relates to detergent builders used for household detergents such as residential and kitchen detergents, industrial (alkaline) detergents, and clothing detergents. Conventionally, condensed phosphates, zeolites, and the like have been used as builders in the above fields for inorganic systems.
However, condensed phosphates, for example, dissolve in laundry wastewater and flow into lakes, rivers, etc., promoting the growth of algae, causing aging of lakes and rivers, and even eutrophication.
It has serious drawbacks such as having a large impact on the occurrence of red tide. Moreover, these condensed phosphates are easily decomposed at high temperatures and high alkalis, and cannot be said to be excellent builders. In addition, zeolite is seen as a promising substitute for condensed phosphates due to its high chelating power, and has been put into practical use, but since it has low water solubility and is usually handled in a slurry state, it cannot be used in various pipes when it is discharged as wastewater. There were many problems such as clogging of the water and accumulation of sludge in lakes and rivers. Furthermore, in organic systems, ethylenediaminetetraacetate (EDTA), nitrilotriacetate (NTA), polycarboxylate, etc. have been used. However, for example, EDTA has the disadvantages of not only having a small builder effect but also being expensive. N.T.A.
Although it is a relatively good builder, there are reports that it may cause harm to the human body, so its use has decreased significantly in recent years. Polycarboxylic acid salts, such as (meth)acrylic acid (co)polymers, maleic acid (co)polymers, and fumaric acid (co)polymers, have the best overall evaluation among the above inorganic and organic builders. However, these have low ability to disperse, solubilize, and prevent redeposition of hydrophobic substances such as dirt, cholesterol, and oil, which are important properties required for builders, and they also have poor performance as surfactants for detergents. The compatibility of is extremely poor,
Therefore, there was a problem that, for example, it was not suitable for liquid detergents. In order to solve these problems, alkenes such as ethylene, propylene, isobutylene, long-chain α-olefins, (meth)acrylic esters,
It has been proposed to copolymerize hydrophobic monomers such as styrene and vinyl acetate with unsaturated carboxylic acid salts, but in order to copolymerize such hydrophobic monomers, alcohols such as methanol and isopropyl alcohol, This method requires organic solvents such as aromatic compounds such as benzene, toluene, and xylene, and ketones such as methyl isobutyl ketone, and has the disadvantage that it is difficult to obtain the copolymer easily and inexpensively. Also, Special Publication No. 59-15359, Japanese Patent Publication No. 58-47099
No. 1 proposes copolymerizing an unsaturated monocarboxylic acid and/or an unsaturated dicarboxylic acid with an unsaturated alcoholic monomer obtained by adding ethylene oxide or propylene oxide to allyl alcohol. Since the basic skeleton of the monomer obtained by adding ethylene oxide or propylene oxide to is an allyl group, it has poor copolymerizability with unsaturated monocarboxylic acids and/or unsaturated dicarboxylic acids, and therefore the resulting copolymer When used as a builder, residual monomers may cause skin irritation in some cases, and the builder performance has not always been satisfactory. As a result of intensive research in view of the current situation, the present inventors have developed an unsaturated alcohol system obtained by adding a specific alcohol or an alkylene oxide to an unsaturated monocarboxylic acid and/or an unsaturated dicarboxylic acid. We have completed the present invention by discovering that a polymer obtained by copolymerizing monomers has superior performance to the above-mentioned known builders and has no skin irritation due to extremely low residual monomer content. That is, the present invention has the general formula (However, in the formula, A ¹ and A ² are each independently hydrogen,
Represents a methyl group or -COOX ² , and A ¹ and A ² cannot be -COOX ² at the same time, A ³ is hydrogen,
represents a methyl group or -CH ₂ COOX ³ and A ³ is -
In the case of CH ₂ COOX ³ , A ¹ and A ² each independently represent hydrogen or a methyl group, and X ¹ , X ² and X ³ each independently or together represent hydrogen, a monovalent metal, a divalent metal, or an ammonium group. group or organic amine group. ) One or more unsaturated carboxylic acid monomers () represented by the general formula (However, in the formula, R ¹ and R ² each independently represent hydrogen or a methyl group, R ¹ and R ² cannot be a methyl group at the same time, and R ³ is -CH ₂ -, -
(CH ₂ ) ₂ - or -C(CH ₃ ) ₂ - and R ¹ , R ²
and the total number of carbon atoms in R ³ is 3, Y represents an alkylene group having 2 to 3 carbon atoms, and n is 0 or 1 to 3.
It is an integer of 100. ) One or more unsaturated alcoholic monomers () shown in () and a monomer copolymerizable with these monomers ()
, unsaturated carboxylic acid monomer () 40 to 99.5 mol%, unsaturated alcohol monomer () 0.5 to 60 mol%, and monomer () 0 to 40 mol% (However, (),
The sum of () and () is 100 mol%. This invention relates to a builder for detergents comprising the copolymer (A) derived using the ratio of Examples of the unsaturated carboxylic acid monomer () represented by the above general formula used in the present invention include:
Partially or completely neutralized products of acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, or other acids with monovalent metals, divalent metals, ammour, and organic amines are listed. It will be done. Monovalent metals include sodium, potassium, etc., and divalent metals include:
Examples include calcium, magnesium, and zinc. In addition, organic amines include alkylamines such as monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, and triethylamine; monoethanolamine,
Examples include alkanolamines such as diethanolamine, triethanolamine, monoisopropanolamine, and dimethylethanolamine; pyridine; and the like. Further, as the unsaturated alcohol monomer () represented by the above general formula, for example, 3-methyl-3
- Unsaturated alcohols such as buten-1-ol, 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, or ethylene oxide per mole of these unsaturated alcohols. and/or propylene oxide from 1 to 100
Compounds with molar addition can be mentioned. Among these, unsaturated alcoholic monomers (2) with an added mole number of ethylene oxide and/or propylene oxide in the range of 2 to 40 moles have high copolymerizability with unsaturated carboxylic acid monomers (2) and builder properties. It is preferable because it has better performance. The types of ethylene oxide and propylene oxide to be added may be one or two types, and when multiple types are added, there is no restriction on the bonding order, but if the number of moles of alkylene oxide added exceeds 100 moles, However, no improvement in builder performance is observed, and on the contrary, a large amount of addition is required, which is not preferable. The monomer () is added to the resulting copolymer (A ) is used in an amount of 40 mol % or less as long as it is water-soluble. Examples of such monomers () include styrene; styrene sulfonic acid; vinyl acetate; (meth)acrylonitrile; meth)acrylamide; methyl (meth)acrylate; ethyl (meth)acrylate; butyl (meth)acrylate; 2-ethylhexyl (meth)acrylate; dimethylaminoethyl (meth)acrylate; diethylaminoethyl (meth)acrylate; 3-(meth) Acryloxy-1,2-dihydroxypropane; 3-(meth)
Acryloxy-1,2-di(poly)oxyethylene ether propane; 3-(meth)acryloxy-1,2-di(poly)oxypropylene ether propane; 3-(meth)acryloxy-1,2-
Dihydroxypropane phosphate and its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt or mono- or diester of an alkyl group having 1 to 4 carbon atoms; 3-(meth)acryloxy-1,
2-dihydroxypropane sulfate and its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt or ester of an alkyl group having 1 to 4 carbon atoms; 3-(meth)acryloxy-2-hydroxypropanesulfonic acid and Its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt or ester of an alkyl group having 1 to 4 carbon atoms; 3-(meth)
Acryloxy-2-(poly)oxyethylene ether propane sulfonic acid and its monovalent metal salt, 2
valent metal salt, ammonium salt, organic amine salt or ester of an alkyl group having 1 to 4 carbon atoms; 3-(meth)acryloxy-2-(poly)oxypropylene ether propane sulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt or ester of an alkyl group having 1 to 4 carbon atoms; 3
-allyloxypropane-1,2-diol; 3-
Allyloxypropane-1,2-diol phosphate; 3-allyloxypropane-1,2-diol sulfonate; 3-allyloxypropane-1,
2-diol sulfate; 3-allyloxy-
1,2-di(poly)oxyethylene ether propane; 3-allyloxy-1,2-di(poly)oxyethylene ether propane phosphate; 3-
Allyloxy-1,2-di(poly)oxyethylene ether propane sulfonate; 3-allyloxy-1,2-di(poly)oxypropylene ether propane; 3-allyloxy-1,2-di(poly)
Oxypropylene ether propane phosphate; 3-allyloxy-1,2-di(poly)oxypropylene ether propane sulfonate; 6-
Allyloxyhexane-1,2,3,4,5-pentaol; 6-allyloxyhexane-1,2,
3,4,5-pentaol phosphate; 6-allyloxyhexane-1,2,3,4,5-pentaol sulfonate; 6-allyloxy-1,2,
3,4,5-penta(poly)oxyethyleneetherhexane; 6-allyloxy-1,2,3,
4,5-penta(poly)oxypropylene ether hexane; 3-allyloxy-2-hydroxypropanesulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt or organic amine salt, or phosphoric acid of these compounds Ester or sulfuric acid ester and their monovalent metal salt, divalent metal salt, ammonium salt or organic amine salt; 3-allyloxy-2-(poly)oxyethylenepropanesulfonic acid and its monovalent metal salt, divalent metal salt , ammonium salts or organic amine acids, or phosphoric or sulfuric esters of these compounds, and monovalent metal salts, divalent metal salts, ammonium salts or organic amine salts thereof; 3-allyloxy-2-(poly)
Oxypropylenepropanesulfonic acid and 1
valent metal salts, divalent metal salts, ammonium salts, or organic amine salts, or phosphoric acid esters or sulfuric esters of these compounds, and monovalent metal salts, divalent metal salts, ammonium salts, or organic amine salts thereof; etc. can be given. The usage amounts of unsaturated carboxylic acid monomer () and unsaturated alcohol monomer () are as follows: ) can be 40 to 99.5 mol% and 0.5 to 60 mol%, respectively. Even if either the unsaturated carboxylic acid monomer () or the unsaturated alcohol monomer () is out of the above range, the excellent detergent builder of the present invention cannot be obtained. The copolymer (A) can be obtained from the unsaturated carboxylic acid monomer (2), the unsaturated alcohol monomer (2), and the monomer (2) by a conventionally known method. For example, polymerization can be carried out in a solvent such as water, an organic solvent, or a mixed solvent of a water-soluble organic solvent and water. At this time, persulfate, hydrogen peroxide, etc. are used as a polymerization initiator for polymerization in an aqueous medium, and a promoter such as sodium bisulfite or ascorbic acid may be used in combination. For polymerization in an organic solvent, an azo compound, an organic peroxide, or the like is used as a polymerization initiator, and a promoter such as an amine compound can be used in combination. For polymerization in a mixed solvent of a water-soluble organic solvent and water, an appropriate polymerization initiator or a combination of a polymerization initiator and an accelerator can be selected from among the various polymerization initiators described above. The copolymer (A) thus obtained can be used as it is as the detergent builder of the present invention, but if necessary, it can be further neutralized with an alkaline substance before use. Examples of such alkaline substances include monovalent metal salts and divalent metal hydroxides, chlorides, carbonates, and bicarbonates; ammonia; organic amines, and the like. The detergent builder of the present invention can be mixed with other known detergent builders to the extent that the effects of the present invention are not impaired. Such other detergent builders include, for example, sodium tripolyphosphate, sodium pyrophosphate, sodium silicate, sulfate, sodium carbonate, sodium nitrilotriacetate, sodium and potassium ethylenediaminetetraacetate, zeolites, carboxyl derivatives of polysaccharides, (meth) Examples include water-soluble polymers such as acrylic acid (co)polymer salts, maleic acid (co)polymer salts, and fumaric acid (co)polymer salts. The detergent builder of the present invention can be combined with a known detergent surfactant to form a detergent composition. Examples of the detergent surfactant used in this case include alkylbenzene sulfonate, alkyl sulfate salt, α- Anionic surfactants such as olefin sulfonate, alkyl sulfonate, fatty acid amide sulfonate, dialkyl sulfosuccinate; polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene Examples include nonionic surfactants such as sorbitan fatty acid ester and polyoxyethylene fatty acid ester; cationic surfactants such as alkylamine salts and quaternary ammonium salts; and zwitterionic surfactants such as alkyl betaine. . Detergent surfactants and copolymers in detergent compositions
The ratio of detergent builder (A) used is 15 parts by weight of the detergent builder per 100 parts by weight of the surfactant.
It is preferably 1000 parts by weight. If the amount is less than 15 parts by weight, no practical benefit can be expected from its addition, and if it is used in excess of 1000 parts by weight, it is economically undesirable. Various additives commonly used in detergents can be added to detergent compositions containing the detergent builder of the present invention. For example, sodium carboxymethylcellulose to prevent redeposition of pollutants, antifouling agents such as benzotriazole and ethylene-thiourea, alkaline substances to adjust pH, fragrances, fluorescent agents, colorants, foaming agents, foam stabilizers. agents, polishing agents, disinfectants, bleaches, enzymes, dyes,
Solvents, etc. The present invention will be described below with reference to Reference Examples and Examples, but the present invention is not limited to these Examples. Further, in the examples, unless otherwise specified, all parts are by weight, and all percentages are by weight. Reference Example 1 Put 451 g of ion-exchanged water into a 1.5-capacity 5-neck round bottom flask equipped with a reflux condenser, raise the temperature to 75°C, and then add 195 g of 40% ammonium acrylate aqueous solution and 33 g of 80% acrylic acid aqueous solution while stirring. ,3
- 191 g of a 50% aqueous solution of an unsaturated alcohol (hereinafter referred to as IEO-5) prepared by adding 5 moles of ethylene oxide to methyl-3-buten-1-ol and 3
% ammonium persulfate aqueous solution was added dropwise from separate dropping nozzles. Note that the dropping time was 150 minutes for the ammonium persulfate aqueous solution and 120 minutes for the others. After dropping the ammonium persulfate aqueous solution,
After continuing the copolymerization reaction at 100℃ for 30 minutes, it was cooled.
Neutralize by adding 20g of 28% ammonia water to form a copolymer.
An aqueous solution of (1) was obtained. GPC analysis revealed that the obtained copolymer (1) had a number average molecular weight of 22,000, and that unreacted acrylic acid monomers (including ammonium acrylate) were
The amount of unreacted IEO-5 was 0.3 mol% (based on the amount charged), and 2.8 mol% (based on the amount charged). Reference example 2 3-methyl-3 was added to the reaction vessel used in reference example 1.
-10 ethylene oxide to buten-1-ol
Molar addition of unsaturated alcohol (hereinafter referred to as IEO−10
It is called. ) and 164 g of ion-exchanged water were charged. After purging with nitrogen, the temperature was raised to 95°C, and a solution of 91.6 g of maleic anhydride and 9.34 g of ammonium persulfate dissolved in 177 g of ion-exchanged water was added dropwise over 120 minutes. After the addition of the solution was completed, 67 g of a 7% ammonium persulfate aqueous solution was added dropwise over 60 minutes at the same temperature to complete the polymerization. Next, 400g of the polymerization reaction product obtained by cooling was collected, 400g of ion-exchanged water was added,
The mixture was neutralized with 60 g of 48% aqueous sodium hydroxide solution while stirring to obtain an aqueous solution of copolymer (2). From GPC analysis, the obtained copolymer (2) has a number average molecular weight of 4300.
No unreacted monomer was detected. Reference Example 3 Add ion exchange water to the reaction vessel used in Reference Example 1.
After charging 218g and raising the temperature to 100℃, add 447g of 37% sodium methacrylate aqueous solution, 10
%α-sodium crotonate aqueous solution 155g, 3-
38.4 g of a 50% aqueous solution of an unsaturated alcohol (hereinafter referred to as PPO-5) prepared by adding 5 moles of propylene oxide to methyl-2-buten-1-ol and 142 g of a 3% ammonium persulfate aqueous solution were each added from separate dropping nozzles. It was dripped in 120 minutes. After finishing dropping,
After continuing the copolymerization reaction for another 30 minutes at the same temperature,
It was cooled to obtain an aqueous solution of copolymer (3). From GPC analysis, the obtained copolymer (3) has a number average molecular weight of 4000.
So, unreacted sodium methacrylate is 0.2% (based on the amount charged), and unreacted sodium α-crotonate is 0.4%.
% (based on the amount charged), but no unreacted PPO-5 was detected. Reference example 4 3-methyl-3 was added to the reaction vessel used in reference example 1.
-propylene oxide to buten-1-ol
665 g of unsaturated alcohol with 20 moles of ethylene oxide added to it (hereinafter referred to as IPOEO-2040), 12.8 g of fumaric acid, and ion-exchanged water
I prepared 214g. After purging with nitrogen, the temperature was raised to 100°C, and 63.8 g of a 34% maleic anhydride aqueous solution and 27.6 g of a 10% ammonium persulfate aqueous solution were added dropwise thereto over 120 minutes. After the dropwise addition was completed, 16.5 g of a 10% ammonium persulfate aqueous solution was added dropwise over 60 minutes at the same temperature to complete the polymerization. Next, the resulting polymerization reaction product was cooled.
400 g was taken out, 400 g of ion-exchanged water was added, and the mixture was neutralized with 20 g of a 48% aqueous sodium hydroxide solution while stirring to obtain an aqueous solution of copolymer (4). From GPC analysis,
The obtained copolymer (4) had a number average molecular weight of 6800, and 3 mol % (based on the amount charged) of unreacted fumaric acid was detected, but no unreacted maleic acid or unreacted IPOEO-2040 was detected. Reference example 5 2-methyl-3 was added to the reaction vessel used in reference example 1.
-30 ethylene oxide to buten-2-ol
593 g of unsaturated alcohol with 5 moles of propylene oxide added (hereinafter referred to as BEOPO-305), 22.8 g of itaconic acid, and ion-exchanged water
I prepared 214g. After purging with nitrogen, the temperature was raised to 100℃, and 100.7 g of 34% maleic anhydride aqueous solution and 10%
43.6 g of ammonium persulfate aqueous solution was added dropwise over 120 minutes. After the dropwise addition was completed, 26.2 g of a 10% ammonium persulfate aqueous solution was added dropwise over 60 minutes at the same temperature to complete the polymerization. Next, the reaction product obtained by cooling is
400 g was taken out, 400 g of ion-exchanged water was added, and the mixture was neutralized with 33 g of a 48% aqueous sodium hydroxide solution while stirring to obtain an aqueous solution of copolymer (5). According to GPC analysis, the obtained copolymer (5) had a number average molecular weight of 6400,
Unreacted maleic acid was detected at 1.5 mol % (based on the amount charged) and unreacted itaconic acid was detected at 2 mol % (based on the amount charged), but unreacted BEOPO-305 was not detected at all. Reference Example 6 Add ion-exchanged water to the reaction vessel used in Reference Example 1.
After preparing 451g and raising the temperature to 75℃, while stirring
40% ammonium acrylate aqueous solution 195g, 80%
33 g of an acrylic acid aqueous solution, 191 g of a 14% 3-methyl-3-buten-1-ol aqueous solution, and 130 g of a 3% ammonium persulfate aqueous solution were each dropped from separate dropping nozzles. Note that the dropping time was 150 minutes for the ammonium persulfate aqueous solution and 120 minutes for the others. After dropping the ammonium persulfate aqueous solution, the copolymerization reaction was continued at 100° C. for 30 minutes, and then cooled and neutralized by adding 20 g of 28% aqueous ammonia to obtain an aqueous solution of copolymer (6). According to GPC analysis, the obtained copolymer (6) had a number average molecular weight of 3900, and the unreacted acrylic acid monomer (including ammonium acrylate) was 0.7 mol% (based on the amount charged), and the unreacted 3-methyl- The amount of 3-buten-1-ol was 3.5 mol% (based on the amount charged). Comparative Reference Example 1 Instead of 191 g of 50% IEO-5 aqueous solution used in Reference Example 1, unsaturated alcohol (hereinafter referred to as AEO) was prepared by adding 5 moles of ethylene oxide to allyl alcohol.
-5. ), and the number average molecular weight was
A comparative copolymer (1) of 3300 was obtained. The amount of unreacted acrylic acid monomer was 4.6 mol % (based on the amount charged), and the amount of unreacted AEO-5 was 8.0 mol % (based on the amount charged). Comparative Reference Example 2 In place of 192 g of IEO-10 used in Reference Example 2, 466 g of unsaturated alcohol (hereinafter referred to as AEO-10), which is obtained by adding 10 moles of ethylene oxide to allyl alcohol, was used for initial ion exchange. water
A comparative copolymer (2) having a number average molecular weight of 2,700 was obtained in exactly the same manner as in Reference Example 2, except that 190 g of ion-exchanged water was used instead of 164 g. Unreacted maleic acid is 7.3 mol% (based on the amount charged), unreacted AEO-10 is 8.4 mol%
(vs. amount of preparation). Example 1 The dispersion performance for carbon black, which is necessary as a detergent builder, was evaluated as follows. A predetermined amount of the copolymer (1) obtained in Reference Example 1 was taken as a detergent builder into a glass separating funnel with a capacity of 250 ml, and water was added to make the total amount 190 g. 10 g of carbon black (HAF manufactured by Mitsubishi Kasei Co., Ltd. crushed in a mortar and passed 32 meshes) was added thereto, and the mixture was shaken for 30 minutes using a shaker. Then, the obtained carbon black dispersion was immediately poured into a volume of 200ml.
The liquid was transferred to a graduated cylinder, and the state of the liquid was observed after standing for 1 minute. The minimum amount of copolymer (1) added that made the upper liquid layer transparent was defined as the limit amount added, and the results are shown in Table 1. In addition, the limit addition amount was expressed as the solid content % of the copolymer relative to carbon black. Examples 2 to 6 Copolymers (2) to (6) obtained in Reference Examples 2 to 6 were used as detergent builders, but in the same manner as in Example 1, the limit addition amount of each was determined. I asked for it. The results are shown in Table 1. Comparative Examples 1 to 2 Comparative copolymers (1) to (2) obtained in Comparative Reference Examples 1 to 2 were used as detergent builders, but in the same manner as in Example 1, and the respective limit additions were I asked for the quantity. The results are shown in Table 1. Comparative Example 3 Commercially available sodium polyacrylate (average molecular weight
The limit addition amount was determined in exactly the same manner as in Example 1 except that 4000) was used. The results are shown in Table 1. Comparative Example 4 The limit addition amount was determined in exactly the same manner as in Example 1, except that commercially available sodium tripolyphosphate was used. The results are shown in Table 1.

【table】

[Table] Example 7 The chelating power required as a detergent builder was evaluated as follows. In a beaker with a capacity of 200ml, add 1 of the copolymer (1) obtained in Reference Example 1 as a detergent builder in terms of solid content.
g, and added ion-exchanged water to make the total amount 100 g. Next, add 2 ml of 3% sodium oxalate aqueous solution,
Adjust the pH to 10.0 with 2N-NaOH or 2N-HC.
10.5, and this solution was titrated with a 0.25 mol/aqueous calcium acetate solution. The point at which a permanent cloudy precipitate appeared was defined as the end point. In addition, when titrating with 0.25 mol/calcium acetate aqueous solution,
To lower the pH, adjust the pH with 2N-NaOH.
It continued to be maintained at 10.0-10.5. Note that the chelate value (CV) was calculated using the following formula. CV=(ml)×25(mgCaCO ₃ /g) The results are shown in Table 2. Examples 8 to 12 The chelate value of each was calculated in exactly the same manner as in Example 7, except that each of the copolymers (2) to (6) obtained in Reference Examples 2 to 6 was used as a detergent builder. did. The results are shown in Table 2. Comparative Examples 5 to 6 The same procedure as in Example 7 was carried out except that each of the comparative copolymers (1) to (2) obtained in Comparative Reference Examples 1 to 2 was used as a builder for detergent, and each chelate value was was calculated. The results are shown in Table 2. Comparative Example 7 Commercially available sodium polyacrylate (average molecular weight
The chelate value was calculated in exactly the same manner as in Example 7, except that 2500) was used. The results are shown in Table 2. Comparative Example 8 Chelate value was calculated in exactly the same manner as in Example 7 using commercially available zeolite. The results are shown in Table 2.

[Table] Examples 13 to 18 Detergent compositions (1) to (6) of the present invention were prepared according to the following detergent composition formulations. When blending, as shown in Table 3, sodium linear alkylbenzene sulfonate (hereinafter referred to as
It is called LAS. ) and/or “Softanol 90”
(Nonionic surfactant manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd.)
The vacuum-dried products of copolymers (1) to (6) obtained in Reference Examples 1 to 6 were used as detergent builders. Next, using the obtained detergent compositions (1) to (6) of the present invention, the following cleaning test was conducted using the following artificially contaminated cloth as a test piece to evaluate the cleaning power of the detergent compositions. Note that the detergency was determined according to the detergency calculation described below. The evaluation results are shown in Table 3. 1 Detergent composition formulation surfactant (LAS and/or softanol)
90) 30 parts detergent builder (vacuum dried product of copolymers (1) to (6)) 12 parts sodium silicate 10 parts sodium carbonate 5 parts carboxymethyl cellulose 1 part sodium sulfate 61 parts 2 Artificially contaminated fabric T/C broad Composition of stain on three 10cm x 10cm artificially contaminated cloths (%) Myristic acid 8.3 Oleic acid 8.3 Tristearin 8.3 Triolein 8.3 Cholesterol 4.4 Cholesterol stearate 1.1 Paraffin wax 5.5 Squalene 5.5 Carbon black 0.5 Kanto loam soil 49.8 3 Cleaning test Terg− Washing was performed using an O-Tometer under the following conditions. Measurement conditions Rotation speed 100 rpm Washing time, rinsing time 5 minutes each Washing temperature 25℃ Contaminated cloth T/C broad artificially contaminated cloth (10 cm
(×10cm 3 sheets) Water used: 50ppm of _CaCO3 in pure water 1
Add CaCl ₂ so that Detergent concentration 0.12% by weight 4 Calculation of detergency The detergency (DE%) was determined according to the following formula by measuring the reflectance using a conventional method. Cleaning power (DE%) = Rw-Rs/Ro-Rs×100 Ro: Reflectance of original cloth Rs: Reflectance of contaminated cloth Rw: Comparative example of reflectance of washed cloth 9-15 Table 3 as a builder for detergent As shown, comparative copolymers (1) and (2) obtained in Comparative Reference Examples 1 and 2
Comparative detergent compositions were prepared in exactly the same manner as in Examples 13 to 18, except that commercially available sodium polyacrylate (average molecular weight 5000) and sodium tripolyphosphate were used. Prepare 1) to (7) and test the detergency of each.
Calculated using the same method as 13-18. The results are shown in Table 3.

[Table] Comparative Examples 16-17 Sodium polyoxycarboxylate (with an average polymerization degree of 3 obtained by oxidizing homopolymerization of acrolein and then subjecting it to Canitzaro reaction in the presence of sodium hydroxide) as a detergent builder.
Comparative detergent Compositions (8) to (9) were prepared, and the detergency of each was calculated in the same manner as in Examples 13 to 18. 4th result
Shown in the table.

【table】

Claims (1)

[Claims] 1. General formula (However, in the formula, A ¹ and A ² are each independently hydrogen,
represents a methyl group or -COOX ² , and A ¹ and A ² cannot be -COOX ² at the same time, A ³ represents hydrogen, a methyl group, or -CH ₂ COOX ³ , and A ³ is -CH ₂ COOX ³ . In this case, A ¹ and A ² each independently represent hydrogen or a methyl group, and X ¹ ,
X ² and X ³ are each independently or together hydrogen, 1
Represents a valent metal, a divalent metal, an ammonium group, or an organic amine group. ) One or more unsaturated carboxylic acid monomers () represented by the general formula (However, in the formula, R ¹ and R ² each independently represent hydrogen or a methyl group, and R ¹ and R ² cannot be a methyl group at the same time, and R ³ is -CH ₂ -, -(CH ₂ ) ₂ -or-C( _CH3 ) _2-
and the total number of carbon atoms in R ¹ , R ² and R ³ is 3
, Y represents an alkylene group having 2 to 3 carbon atoms, and n
is 0 or an integer from 1 to 100. ) One or more unsaturated alcoholic monomers () shown in () and a monomer copolymerizable with these monomers ()
, unsaturated carboxylic acid monomer () 40 to 99.5 mol%, unsaturated alcohol monomer () 0.5 to 60
Mol% and monomer () 0 to 40 mol% (however,
The sum of (), () and () is 100 mol%. ) Detergent builder consisting of copolymer (A) derived using the ratio of