JPH07228889A - Builder for polymer electrolyte detergent having biodegradability and detergent composition - Google Patents

Abstract

PURPOSE:To obtain the subject builder having biodegradability free from environmental disruption due to possession of sequestering action, comprising a biodegradable polymer electrolyte prepared by hydrolyzing a conjugated diene-maleic anhydride copolymer and oxidizing the resultant substance as an active ingredient. CONSTITUTION:A copolymer (preferably a copolymer of 10-40mol% conjugated diene unit and 50-70mol% of maleic anhydride, having 5,000-100,000 weight- average molecular weight) of a conjugated diene (preferably 1,3-butadiene) and maleic anhydride is hydrolyzed and oxidized to give the objective builder comprising a biodegradable polymer electrolyte as an active ingredient. The polymer electrolyte, for example, is obtained by continuously adding a radical generator and the conjugated diene to give a conjugated diene-maleic anhydride copolymer, adding water to the copolymer, heating the copolymer in the presence of a basic compound to hydrolyze the copolymer and adding a Pd compound to an aqueous solution of the formed hydrolyzate and heating to oxidize the hydrolyzate.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a biodegradable substance obtained by hydrolyzing a copolymer of a conjugated diene and maleic anhydride (hereinafter referred to as a conjugated diene-maleic anhydride copolymer) and then oxidizing it. The present invention relates to a builder for detergents, which contains a polyelectrolyte having the following formula as an active ingredient.

[0002]

2. Description of the Related Art Detergent builders are incorporated into detergents,
It is a detergency enhancer having the action of improving the action of the surfactant, which is the main component of detergents. Generally, polyvalent metal ions such as calcium ions and magnesium ions are present in water, and when these are combined with a surfactant, they form a metal salt insoluble in water and the detergency is lowered. The detergent builder prevents the surfactant from forming an insoluble salt by binding with such a polyvalent metal ion and maintains the detergency. Further, the detergent builder is required to have a dispersing action such as an anti-redeposition action and an alkaline buffering action in addition to the sequestering action as described above.

Conventionally, sodium tripolyphosphate (hereinafter referred to as STPP) has been widely used as a builder for detergents, but it is almost used nowadays due to the problem of eutrophication of lakes, rivers and sea areas due to phosphate. Instead, zeolite is predominant as an alternative. However, since this zeolite is insoluble in water and has low dispersibility,
Problems such as adhesion to laundry and clogging of piping tend to occur, and liquid detergent cannot be incorporated.
Further, there is a problem that it does not have a dispersing effect on dirt or an alkaline buffering effect.

In view of the above-mentioned problems, in recent years, the excellent function of polyelectrolytes, particularly polyacrylic acid salts and acrylic acid-maleic acid copolymers, has attracted attention as detergent builders replacing STPP and zeolite ( Surface, 19,
10, 542 (1981)). These polymer electrolytes have not only the sequestering action of metal ions but also the dispersing action and the alkaline buffering action.

[0005]

However, such a polyelectrolyte has almost no biodegradability, and it cannot be used in lakes, rivers,
When released to the sea, they are accumulated in nature without being decomposed by microorganisms. Therefore, when used as a detergent builder in large quantities for a long period of time, there is a risk of environmental pollution. Therefore, the use of the polyelectrolyte as a builder for detergents is extremely limited, and the amount used is extremely small.

In order to solve such problems, it has been proposed to use a biodegradable polymer electrolyte as a builder for detergents. That is, a biodegradable monomer is copolymerized with an acrylic acid, an ethylenically unsaturated carboxylic acid such as maleic acid to obtain a biodegradable polymer electrolyte, and it is proposed to use this. ing. For example, JP-A-46-6038 discloses a carbon monoxide-maleic acid copolymer, and JP-A-63-218.
Japanese Patent No. 732 discloses a carbon monoxide-ethylene-maleic acid terpolymer. However, in the former binary copolymer, the yield based on the maleic anhydride as a raw material is 58
The content of the carbon monoxide unit that imparts biodegradability is as low as less than 4 mol%, and the latter terpolymer has a sufficient biodegradability. Is hard to say.

Therefore, an object of the present invention is to provide a novel detergent builder which is free from these problems and which comprises a biodegradable polymer electrolyte.

[0008]

Means for Solving the Problems As a result of various studies to solve the above-mentioned problems of the polymer electrolyte, the present inventors have hydrolyzed and oxidized the conjugated diene-maleic anhydride copolymer. It was found that a polyelectrolyte having biodegradability can be obtained by the treatment, and the present invention has been completed. That is, the present invention is a builder for a detergent containing a biodegradable polymer electrolyte as an active ingredient, which is obtained by hydrolyzing and oxidizing a copolymer of a conjugated diene and maleic anhydride. Further, the present invention is a detergent composition comprising such a builder for detergent.

The present invention will be described in detail below.

The copolymer used as the raw material of the present invention is a conjugated diene-maleic anhydride copolymer. The conjugated diene constituting the conjugated diene-maleic anhydride copolymer has a carbon number of 4 to 12, preferably 4 to 7,
More preferably, 4 to 5 aliphatic conjugated dienes are used. Examples of these include 1,3-butadiene and 1,3-
Pentadiene, isoprene, 1,3-hexadiene,
2,3-dimethyl-1,3-butadiene, 2-ethyl-
1,3-Butadiene, 1,3-heptadiene, and a mixture of two or more thereof may be used. Of these, 1,3-butadiene and isoprene are preferably used because of their high reactivity with maleic anhydride, inexpensiveness, and industrial availability, and 1,3-butadiene is particularly preferable. These conjugated dienes are copolymerized to form a unit having a 1,4-structure (2-butenylene structure) having a double bond as a basic skeleton.

The conjugated diene-maleic anhydride copolymer which is a raw material of the present invention has a conjugated diene unit having a double bond in an amount of preferably 5 to 50 mol%, more preferably 10 to 40 mol%. . The maleic anhydride unit content is preferably 40 to 80 mol%, more preferably 50 to 70 mol%. If the conjugated diene unit having a double bond is less than 5 mol%, the biodegradability of the polymer electrolyte may be lost, and thus 50 mol%
If it exceeds, the sequestering effect of metal ions such as calcium ions and magnesium ions is reduced, the performance as a builder for detergents is deteriorated, and water may be insoluble.
On the other hand, when the maleic anhydride unit is less than 40 mol%, the solubility in water may decrease even when the copolymer is hydrolyzed, and the performance of the detergent builder may decrease. If it exceeds%, the synthesis becomes difficult, and the biodegradability becomes difficult to be imparted even by the oxidation treatment.

The weight average molecular weight of the conjugated diene-maleic anhydride copolymer which is a raw material of the present invention is 2,000 to 20.
10,000, more preferably 5,000 to 100,0
00. When the molecular weight is lower than 2,000, the polyelectrolyte may lower the sequestering action and dispersibility required as a detergent builder, while when the molecular weight is higher than 200,000, the biodegradability is lowered. Not only that, the cohesive property appears and the performance of the detergent builder deteriorates.

The conjugated diene-maleic anhydride copolymer used as a raw material in the present invention is a structural unit other than the above if the composition of the conjugated diene unit having a double bond and the maleic anhydride unit satisfies the above range. May be contained. Examples of monomers that form other structural units include ethylene, propylene, and 1
-Butene, isobutene, 1-pentene, 1-hexene,
C2-C8 α-olefins such as 4-methyl-1-pentene, 1-heptene, 1-octene; styrene, α-
Aromatic unsaturated hydrocarbons such as methylstyrene, vinyltoluene and p-methylstyrene; unsaturated fatty acids such as acrylic acid, methacrylic acid, acrylic acid esters, methacrylic acid esters and acrylamide, unsaturated fatty acid esters,
Unsaturated fatty acid amide; vinyl ester such as vinyl acetate;
Examples thereof include vinyl ether such as ethyl vinyl ether.

The conjugated diene-maleic anhydride copolymer, which is the raw material of the present invention, can be produced by a known method by copolymerizing a conjugated diene and maleic anhydride. When it contains a structural unit other than the conjugated diene unit and the maleic anhydride unit as described above, the conjugated diene and maleic anhydride may be copolymerized with the monomer forming the structural unit. For example, Japanese Patent Publication No. 46-31
972, JP-B-46-31336, JP-B-58-35205, JP-A-4-65408, JP-A-5-1121 and the like describe methods for producing the copolymer. .

According to these known methods, for example, a conjugated diene-maleic anhydride copolymer can be produced as follows. That is, the polymerization can be carried out by dissolving maleic anhydride using cyclohexanone or the like as a solvent and continuously adding the radical generator and the conjugated diene to this mixed solution. At this time, examples of the radical generator include t-butylperoxybenzoate and t-butylperoxy-
An organic peroxide such as 2-ethylhexanoate is used, the reaction temperature is 80 to 150 ° C., the reaction time is appropriately 1 to 5 hours, and 30 minutes after the continuous supply of the conjugated diene or the radical generator is completed. The polymerization reaction is continued for about 1 hour. The pressure is generally from atmospheric pressure to 30 kg / cm ² G, and the polymerization is carried out in an inert atmosphere such as nitrogen. After completion of the reaction, the reaction solution is added to toluene or the like which is a poor solvent for the copolymer to precipitate and precipitate the copolymer, which is separated by filtration, washed and dried to obtain the copolymer. .

In the present invention, the above conjugated diene-maleic anhydride copolymer is subjected to an oxidation treatment after hydrolyzing a maleic anhydride unit into a maleic acid unit. Hydrolysis at this time, the conjugated diene-maleic anhydride copolymer is added to water and heated for a certain time, or the conjugated diene-maleic anhydride copolymer is added to water, the presence of a basic compound. It can be done by heating down. Also,
In the hydrolysis, the degree of hydrolysis of the conjugated diene-maleic anhydride copolymer may be at least a 50% or more partial hydrolyzate as a maleic anhydride unit, from the viewpoint of the performance of the final product detergent builder, The higher the hydrolysis rate, the more preferable.

In the above hydrolysis, the amount of the conjugated diene-maleic anhydride copolymer added to water is preferably 1 to 50% by weight, more preferably 10 to 40% by weight. When the amount added is more than 50% by weight, the conjugated diene-maleic anhydride copolymer may have a high viscosity in the aqueous solution after hydrolysis or may be difficult to dissolve in water, while less than 1% by weight. The amount added is uneconomical because it requires time and energy in the step of concentrating and recovering or drying treatment of the product polymer electrolyte in the final step.

When the basic compound is used for the hydrolysis, examples of this compound include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, amine compounds such as alkylamines, and ammonia. Of these, sodium hydroxide is more preferable. The amount of the basic compound is 0.5 to 3 mol ratio, preferably 1 to 2 mol ratio, based on the maleic anhydride unit of the conjugated diene-maleic anhydride copolymer.

The temperature of the above hydrolysis is 60 ° C to 150 ° C,
It is preferably 80 ° C to 110 ° C. If the hydrolysis temperature is too low, the reaction may not proceed sufficiently or the time required for the reaction may increase. On the other hand, if the temperature is too high, it is uneconomical and a water-insoluble polymer may be produced. The hydrolysis is usually carried out under normal pressure, but it can be carried out under pressure if necessary.

Further, the hydrolysis time is usually 30 minutes to 10 hours, preferably 1 to 5 hours. If the time is too short, the reaction does not proceed sufficiently and becomes insoluble in water. A polymer electrolyte with low performance may be obtained. On the other hand, if the time is too long, it is energetically uneconomical and a water-insoluble polymer may be produced.

If desired in the hydrolysis, organic solvents can be used. Examples of the organic solvent include cyclic ethers such as tetrahydrofuran, ketones such as acetone, methyl ethyl ketone and cyclohexanone, and secondary or tertiary alcohols such as isopropyl alcohol and t-butyl alcohol.

As another aspect of the hydrolysis, in the production of the above-mentioned conjugated diene-maleic anhydride copolymer, even if water or a basic compound is added to the reaction solution after the completion of the polymerization, the hydrolysis is performed. It doesn't matter.

The aqueous solution of the hydrolyzed product of the conjugated diene-maleic anhydride copolymer obtained as described above has a concentration of 1 to 50% by weight, preferably 10 to 40% by weight, and a pH of 0.1 to 0.1%. Adjust to 7. Then, the oxidation treatment is performed in the state of the aqueous solution as it is. After the hydrolysis step, the concentration and p
If H is within the above range, no particular adjustment is necessary. If the concentration exceeds the above range, adjustment is performed by adding or concentrating water. If the pH exceeds the above range,
The pH is adjusted by adding an acidic compound such as hydrochloric acid or sulfuric acid or by using an ion exchange resin or the like.

The oxidation treatment in the present invention can be carried out, for example, in an aqueous solution. Specifically, the oxidation treatment can be performed as follows. That is, for example, a palladium compound is added to an aqueous solution of the hydrolyzate of the conjugated diene-maleic anhydride copolymer, and the mixture is heated and stirred. At this time, the palladium compound is used as a main catalyst for the oxidation treatment, and for example, palladium chloride, palladium bromide, palladium sulfate, palladium nitrate, palladium cyanide, palladium acetate, lithium palladium chloride, potassium palladium chloride, sodium palladium chloride, metal Palladium and the like can be mentioned, but palladium chloride or palladium sulfate is preferably used. Further, the addition amount of the palladium compound is preferably in the range of 1 to 150 parts by weight with respect to 100 parts by weight of the hydrolyzate of the conjugated diene-maleic anhydride copolymer.

Further, if necessary, a cocatalyst can be used in addition to the palladium compound as the main catalyst. Examples of the promoter include copper salts such as cupric chloride, cupric bromide, cupric nitrate, cupric acetate, cuprous chloride; ferric sulfate, ferric chloride, and other iron salts. Can be used. The amount of these promoters added is
A molar ratio of 1 to 50 relative to the palladium compound is suitable, and a molar ratio of 2 to 20 is preferable.

The reaction temperature of the oxidation treatment is usually 30 to
The temperature is 150 ° C, preferably 40 to 100 ° C, and the reaction time is 0.5 to 10 hours. The oxidation treatment is carried out in an oxygen-containing gas atmosphere, and there is no limitation on the oxygen partial pressure, but in consideration of practicality, 0.1 to 5 absolute atmospheric pressure is suitable. The oxygen-containing gas is preferably pure oxygen gas or air, but if necessary oxygen is an inert gas such as helium,
You may dilute with argon etc.

The conjugated diene-maleic anhydride copolymer oxidized as described above using a palladium compound as a catalyst can be separated from the palladium compound by the following method, for example. That is, after the oxidation treatment, the basic compound is added to the aqueous solution of the copolymer to adjust the pH to 8-14. Examples of the basic compound added at this time include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, amine compounds such as alkylamines, and ammonia. Of these, sodium hydroxide is more preferable. Then, the palladium compound precipitated or liberated by the oxidation treatment and pH adjustment is removed by filtration or centrifugation. If necessary, the aqueous solution of the copolymer may be subjected to ultrafiltration or membrane separation such as dialysis membrane,
It is also possible to separate the copolymer and the catalyst. Also,
Even when a co-catalyst is used, separation can be performed by this method.

A biodegradable polymer electrolyte can be obtained by the method described above. The present invention is a builder for detergents containing the polymer electrolyte as an active ingredient. In the present invention, this polymer electrolyte is usually preferably obtained as an aqueous solution, and can be obtained by adjusting the desired concentration by adding water or performing a concentration operation as necessary.
This aqueous solution has a concentration of 10 to 40% by weight and a pH of 7-1.
Adjusting to 0 is appropriate. Further, this polymer electrolyte can be used in a solid state if necessary.For example, an aqueous solution of the polymer electrolyte obtained by oxidizing and separating the catalyst is added to excess alcohol such as methanol, ethanol, isopropanol and various butanols. Or by adding an acidic compound such as hydrochloric acid or sulfuric acid to the aqueous solution of the above-mentioned polymer electrolyte to precipitate the polymer electrolyte, and then filtering and separating, washing and drying the solid polymer electrolyte. Can be Further, the aqueous solution of the above-mentioned polymer electrolyte may be directly concentrated to dryness.

The detergent builder of the present invention is obtained by subjecting the polymer electrolyte thus oxidized and separated from the catalyst to heat treatment (hereinafter referred to as alkali treatment) in an aqueous solution under alkaline conditions. A molecular electrolyte may be used as an active ingredient. The concentration of the polymer electrolyte during this alkaline treatment is 1 to
It is 50% by weight, preferably 10-40% by weight. If the concentration of the polymer electrolyte separated from the catalyst is within the above range, the alkali treatment can be performed as it is. If it is out of this range, it is appropriately diluted or concentrated and then alkali-treated.

In the alkali treatment, the basic compound is added to the maleic anhydride unit of the copolymer in a ratio of 1.5 to 4 molar ratio, preferably 2 to 3 molar ratio, and the pH is adjusted.
Is heat-treated in an aqueous solution of 8 to 14. Examples of the basic compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, amine compounds such as alkylamines, and ammonia. Of these, sodium hydroxide is more preferable. The temperature of alkali treatment is 30
-150 degreeC, Preferably it is the range of 70-110 degreeC.
If necessary, it can be carried out under pressure. The treatment time is 30 minutes to 10 hours, preferably 1 hour to 5 hours. If the heating temperature is low and the treatment time is short, the alkali treatment cannot be sufficiently performed. On the other hand, the heating temperature is high,
If the processing time is too long, it is uneconomical in terms of energy,
In some cases water-insoluble polymers are formed.

The finally alkali-treated polymer electrolyte is preferably obtained as an aqueous solution. This aqueous solution
It is suitable to adjust the concentration to 10 to 40% by weight and the pH to 7 to 10. Further, if necessary, this polymer electrolyte can be recovered in the form of solid such as powder. This recovery is performed by concentrating the aqueous solution of the polymer electrolyte to dryness, and by recovering the aqueous solution of the polymer electrolyte in excess of methanol or the like. It can be carried out by adding it to alcohol or adding an acidic compound such as hydrochloric acid or sulfuric acid to an aqueous solution of a polymer electrolyte to precipitate a solid, separating by filtration, washing and drying.

The polymer electrolyte obtained as described above is used as a component of a builder for a detergent by being mixed in a detergent composition. This detergent composition contains, in addition to the polyelectrolyte of the present invention, an anionic or nonionic surfactant, an alkaline buffer, an anti-redeposition agent, a bulking agent, an enzyme, a solubilizing agent, an optical brightening agent. , And fragrances and flavors.
The blending ratio of the detergent composition is, for example, in the case of a synthetic detergent for clothes, the polymer electrolyte of the present invention is 0.1% by weight to 50% by weight, preferably 1% by weight to 30% by weight, and the surfactant is It is 1% by weight to 60% by weight, and other components are blended in necessary amounts.

Further, the polyelectrolyte of the present invention is a conventional detergent builder such as STPP, zeolite, sodium silicate, sodium carbonate, sodium citrate, and polyacrylate or acrylic acid-maleic acid copolymer. It can also be used in combination with a polymer electrolyte such as.

[0034]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto.

Reference Example 1 (Synthesis of butadiene-maleic anhydride copolymer) 100 g of maleic anhydride and 290 g of cyclohexanone were charged in an autoclave and heated to 135 ° C. in a nitrogen atmosphere. 5 g of t-butyl peroxybenzoate
And a mixed solution of 110 g of cyclohexanone and 55 g of butadiene were continuously added separately over 2 hours. After that, the reaction was terminated by heating at 135 ° C. for 1 hour. After concentrating the reaction solution with a rotary evaporator, T
180 g of HF was added to bring the total amount to 400 g. This solution was gradually added dropwise to 6 liters of toluene heated to about 60 ° C. The precipitate was collected by hot filtration, washed with toluene heated to about 60 ° C, and hot filtered again. After drying under reduced pressure at 40 ° C. overnight, the weight of the obtained white powder was 63.
It was g.

From the CHN elemental analysis, the maleic anhydride unit in the copolymer was 60 mol%. Also, ¹ H-
In the NMR spectrum, a peak derived from a double bond was observed at 5.5 ppm. By GPC analysis, the molecular weight (Mw) of the copolymer after hydrolysis was 17,000, and the molecular weight distribution (Mw / Mn) was 1.7. GPC
The measurement conditions of are as follows. Column: TSO gel manufactured by Tosoh Corporation; G4000PWXL + G300
0PWXL + G2000PWXL, column temperature: 40
C, eluent: phosphate buffer (pH 7), flow rate: 0.7 m
1 / min, detector: RI, standard sample: polyethylene oxide.

Reference Example 2 (Biodegradability Test) The biodegradability test was carried out in accordance with the collection of polymer articles, 45, 4, 317 (1).
988) and was carried out as follows.

(1) Composition of culture solution Evaluation sample 150 mg (solid content) Activated sludge (collected from sewage treatment plant of Kasumi Joint Venture) 8 mg (SS content) Ammonium chloride 2 g Potassium dihydrogen phosphate 200 mg Magnesium sulfate Heptahydrate 200 mg Calcium chloride 2 mg Ferric sulfate heptahydrate 1 mg Manganese sulfate tetrahydrate 2 mg Zinc sulfate heptahydrate 7 mg Copper sulphate pentahydrate 50 μg Vitamin B1 hydrochloride (thiamine hydrochloride) Salt) 50 μg water (amount that makes the total volume of the culture solution 1000 ml) (2) Culture 500 ml of the above culture solution was weighed into a 500 ml Erlenmeyer flask and placed in a constant temperature water bath at 25 ° C. The mouth of the Erlenmeyer flask was covered with gauze and stirred with a stirrer tip for 3 weeks.

(3) Measurement of Biodegradation Rate After adding an evaporation amount of pure water to the above-mentioned culture solution cultured for 3 weeks, a fixed amount was sampled. Centrifugation was carried out, a fixed amount of the supernatant was separated, an appropriate amount of ethanol-acetone mixed solution was added, and then the mixture was concentrated to dryness by a rotary evaporator. The dried solid was dissolved in an eluent of GPC, filtered through a membrane filter, and then analyzed by GPC. Also, for the culture solution immediately after preparation, the same operation as above is performed to
C analysis was performed. From the peak area (A) of the evaluation sample in the culture solution immediately after preparation and the peak area (B) of the evaluation sample after 3 weeks of culture, the biodegradation rate (%) = ((A−B) / A) ×
I asked for 100. The GPC measurement conditions are the same as those described in Reference Example 1.

As a comparative sample, polyvinyl alcohol known to have biodegradability as a vinyl polymer (polymerization degree = 500, manufactured by Wako Pure Chemical Industries, Ltd.) was similarly tested.

Reference Example 3 (Evaluation of Detergent Builder) The detergent builder was evaluated by measuring the calcium ion-capturing ability according to the method described in JP-A-4-149203.

That is, 0.1 g of the evaluation sample (as solid content) was added to 10 parts of ammonium chloride-ammonia buffer solution (pH 10).
It was dissolved in 0 ml. To this solution, add a solution of the above buffer solution containing calcium chloride of a predetermined concentration from a buret to 0.2 m.
Then, the potential of the calcium ion electrode at that time was read. A blank measurement was also made in the same manner.

The calculation was performed as follows. That is, the free calcium ion concentration was determined from the potential based on the blank measurement results. After correcting the change in the liquid amount by titration, a graph of drop amount-calcium ion concentration was prepared. The plot of the evaluation sample was extrapolated to the calcium ion concentration of 0, and the calcium ion concentration corresponding to the appropriate amount at that time was taken as the calcium ion trapping ability of the evaluation sample. In addition,
The unit is CaCO ₃ mg / g.

Example 1 (Hydrolysis of butadiene-maleic anhydride copolymer) The butadiene-maleic anhydride copolymer 60 obtained in Reference Example 1
g and 240 g of pure water are put in a beaker, and the temperature is 90 ° C under normal pressure.
The mixture was heated to 1, and stirred for about 3 hours while adding pure water in an amount of evaporation at appropriate times. Finally, an aqueous solution of a copolymer hydrolyzate having a solid content concentration of 20% was obtained. The pH of this aqueous solution was 1. In the infrared absorption spectrum of the copolymer, 1857 cm ^-1 and 17 derived from the carbonyl of the maleic anhydride unit
The peak at 80 cm ^-1 disappeared, and the peak derived from the carbonyl and CO bond of the maleic acid unit was 1571c.
It was observed at m ^-1 and 1408 cm ^-1 , respectively. This indicates that the maleic anhydride unit is 100% hydrolyzed.

For comparison, the results of the biodegradability test and the calcium ion-capturing ability of the copolymer hydrolyzate obtained here are shown in Table 1. The copolymer hydrolyzate was measured as a sodium salt by adding sodium hydroxide to the aqueous solution to adjust the pH to 9.

(Treatment with Palladium Compound) 25 g of a 20 wt% aqueous solution of a hydrolyzate of butadiene-maleic anhydride copolymer (pH 1) and 2.45 g of palladium chloride.
Was placed in a glass three-necked flask equipped with a reflux tube, a stirrer, and a thermometer, and was placed in an oil bath at 70
The mixture was heated to ° C and stirred for 5 hours. After the reaction was completed, sodium hydroxide was added to adjust the pH to 9. Then, the catalyst was removed by filtration to obtain an aqueous solution of polymer electrolyte. ¹ H-NMR
From the decrease rate of the peak at 5.5 ppm in the spectrum, the reaction rate of the double bond was 80%. Table 1 shows the biodegradability test results and the calcium ion-capturing ability of the obtained polymer electrolyte.

Example 2 1.2 g of sodium hydroxide was further added to an aqueous solution of a polymer electrolyte obtained by treating with a palladium compound in the same manner as in Example 1, and the mixture was heated with stirring at 90 ° C. for 5 hours under normal pressure. Then, alkali treatment was performed. After cooling, the pH was adjusted to 9 with an ion exchange resin. The biodegradability test results and the calcium ion-capturing ability of the thus obtained polymer electrolyte are shown in Table 1.

[0048]

[Table 1]

Example 3 A detergent composition having the following composition was prepared.

Main Detergent Linear Dodecyl Benzene Sulfonate Sodium (LAS) 18% by weight Polyoxyethylene alkyl ether sulphate sodium (AES) 5% by weight Soap 2% by weight Builder 2% Polyelectrolyte obtained in Example 2 Sodium silicate (alkaline buffer) 10% by weight Sodium carbonate (alkaline buffer) 10% by weight Carboxymethyl cellulose sodium salt (recontamination inhibitor) 1% by weight Bulking agent sodium sulfate 28% by weight Other compounding agents Enzyme 0.5% % Fluorescent whitening agent 0.3% by weight Fragrance, flavoring, appropriate amount Total 100% by weight

[0051]

Industrial Applicability The detergent builder of the present invention can be easily produced from a known conjugated diene-maleic anhydride copolymer that can be produced at low cost. Further, since the detergent builder of the present invention is biodegradable and has a sequestering action for sequestration, it can be used as a detergent builder without environmental damage. Furthermore, since the detergent builder of the present invention can be incorporated in a detergent component at a high concentration, the performance of the detergent can be further improved, and since it is water-soluble, it can be incorporated in a liquid detergent. It becomes possible and the cleaning power can be improved.

Claims (4)

[Claims] 1. A builder for a detergent containing a biodegradable polymer electrolyte as an active ingredient, which is obtained by hydrolyzing a copolymer of a conjugated diene and maleic anhydride and subjecting it to an oxidation treatment. 2. The detergent builder according to claim 1, wherein the oxidation treatment is carried out using a palladium compound as a catalyst. 3. A polymer electrolyte obtained by further treating a biodegradable polymer electrolyte with an alkali is used as an active ingredient.
Or the builder for a detergent according to 2. 4. A detergent composition comprising the detergent builder according to any one of claims 1, 2 and 3.