JPS5827320B2 - Senzai Sosabutsu - Google Patents

Description

[Detailed description of the invention] The present invention relates to detergent compositions.

Specifically, the present invention relates to a detergent composition containing an anionic or nonionic surfactant that exhibits excellent detergency even in highly hard water.

Detergents generally consist of surfactants and builders.

Particularly required performance as a builder is the ability to chelate hard components such as calcium and magnesium and soften hard water.

Such builders include sodium tripolyphosphate,
Condensed phosphoric acid compounds such as sodium pyrophosphate are widely known.

However, if you use a builder like this,
A serious drawback arises in that builders flow as wastewater into lakes and rivers through sewage, promoting the growth of algae and accelerating the aging of lakes and rivers.

Until now, alternatives have not been proposed to overcome such drawbacks.

However, they have not been sufficient because they are expensive and must be used in extremely large quantities to achieve the desired effect, which creates other difficult problems.

For example, various proposed organic carboxylates, organic oxycarboxylate salts, and polymer electrolytes can exhibit performance comparable to that of tripolyphosphate.

The amount used must be increased.

Furthermore, ethylenediaminetetraacetate, which is well known as a chelating agent, is expensive and therefore unsuitable for use as a detergent bilge.

Furthermore, nitrotriacetic acid salts have been proposed, but there are reports that they can be harmful to the human body, making it difficult to use them in general detergents.

As a result of research into a detergent composition that overcomes the shortcomings of known detergents and exhibits excellent detergency even in hard water, the present inventors found that if a specific procedure is followed, a copolymer containing a terminal sulfate group-containing copolymer can be created. The present invention was completed by discovering that the object could be achieved by using the copolymer.Q Therefore, the object of the present invention is to obtain a copolymer that does not accelerate the aging of lakes and rivers. The object of the present invention is to provide a detergent composition that exhibits cleaning power equivalent to or superior to known detergents in highly hard water.

Other objectives will become apparent from the description below.

The detergent composition of the present invention comprises a copolymer containing a terminal sulfate group-containing copolymer obtained according to the following procedure based on 100 parts by weight of an anionic surfactant or a nonionic surfactant;
That is, acrylic acid and methacrylic acid are added to an aqueous solution of a polymerizable dibasic acid salt selected from the group consisting of alkaline earth metal salts of maleic acid, ammonium salts of maleic acid, alkali metal salts of fumaric acid, and ammonium salts of fumaric acid. An unsaturated carboxylic acid selected from the group consisting of acids is added dropwise in an amount of 0.3 to 9.0 mol per mol of the acid salt, and persulfate and hydrogen peroxide are added as a polymerization initiator. A copolymer having a molecular weight in the range of 300 to 10,000 obtained by copolymerizing at a temperature in the range of 50 to 120°C and, if necessary, neutralizing the reaction product with an alkaline substance, is used in combination. It is characterized in that it is blended in an amount of 1 to 200 parts by weight.

The molecular weight of the copolymer was measured based on gel permeation chromatography.

Various types of anionic surfactants and nonionic surfactants can be used in the present invention.

For example, alkylbenzene sulfonates having an alkyl group having an average of 10 to 16 carbon atoms, alkanesulfonic acids having an average of 10 to 18 carbon atoms, salts of these acids, and alkyl polyoxyethylene ether monosulfates having an average of 8 to 21 carbon atoms.

An alkali metal, ammonia or alkanolamine salt of dialkylphenyl polyoxyethylene ether monosulfate having an alkyl group having 8 to 12 carbon atoms, an alkyl polyoxyethylene ether having an alkyl group having an average of 8 to 21 carbon atoms.

Examples include alkylphenylethylene ether having an alkyl group having 8 to 12 carbon atoms.

The polymerizable dibasic acid salts used in preparing the copolymer are disodium maleate, monosodium maleate, and dilithium maleate.

Monolithium maleate, dipotassium maleate.

Alkali metal salts of maleic acid such as monopotassium maleate; ammonium salts of maleic acid such as diammonium maleate, monoammonium maleate, etc.
Alkali metal salts of fumaric acid such as disodium fumarate, monosodium fumarate, dilithium fumarate, monolithium fumarate, dipotassium fumarate, monopotassium fumarate, etc.; such as diammonium fumarate, monoammonium fumarate, etc. It is selected from the group consisting of ammonium salts of fumaric acid, and one or more of these monomers can be used effectively.

In particular, the sulfur-IJium salt of maleic acid can be used effectively.

An aqueous solution of a polymerizable dibasic acid salt can be prepared by dissolving the salt in water. It can also be prepared by neutralizing with a compound or ammonia in a ratio of 1 mole or more.

The concentration of the aqueous solution is not particularly limited and can be in a wide range of concentrations, but it is preferably in the range of 10 to 70% by weight.

For example, when an alkali metal hydroxide is neutralized in an amount of 2 moles or more per mole of maleic acid, an excess of the hydroxide remains and the acrylic acid and/or
Or it neutralizes methacrylic acid and the copolymer produced.

The unsaturated carboxylic acids are selected from the group consisting of alkaline acids and methacrylic acids, and one or two types can be effectively used.

Such unsaturated carboxylic acids 1, such as acrylic acid, can be effectively used if they are of high purity, but acrylic acid produced on an industrial scale.

That is, acrylic acid containing a polymerization inhibitor such as hydroquinone or a trace amount of impurities can also be effectively used.

Unsaturated carboxylic acids can be used directly or as an aqueous solution of the acid.

When used as an aqueous solution, the concentration can be in the range of 10% by weight or more.

In the copolymerization reaction, persulfate and hydrogen peroxide are used together as a polymerization initiator.

Examples of persulfates include potassium persulfate, sodium persulfate, ammonium persulfate, etc.
Particularly suitable is ammonium persulfate.

The amount of persulfate used is 0.5 to 10% of the raw material monomer.
The amount is in a proportion by weight, preferably in the range 2-8% by weight.

If it is used in an amount exceeding 10% by weight, the effective amount of the copolymer component in the solid content of the resulting copolymer decreases, and the molecular weight also decreases too much, which is not preferable.

Persulfates are conveniently used as aqueous solutions with a concentration of 5 to 30% by weight.

The amount of hydrogen peroxide used is in the range of 1 to 10% by weight, preferably 5 to 8% by weight, based on the raw material monomer.

Hydrogen peroxide is conveniently used as an aqueous solution with a concentration of 5 to 35% by weight.

The ratio of hydrogen peroxide to persulfate is 100% of the former.
The ratio is 10 to 2,000 parts by weight of the latter.

If it falls outside this range, it will be substantially the same as using either one alone, and a detergent composition containing the resulting polymer will not be able to achieve the object of the present invention, which is not preferred.

The polymerization initiator can be used by dissolving it in advance in an aqueous solution of monopolymerizable dibasic acid salt, but the persulfate aqueous solution and the hydrogen peroxide aqueous solution are prepared separately and added separately to the reaction system during the copolymerization reaction. A method of continuously or intermittently dropping the copolymer is preferred from the viewpoint of improving the copolymerization conversion rate.

It is preferable to carry out the copolymerization reaction at a temperature in the range of 50 to 120°C, but it is preferable to carry out the copolymerization reaction at a temperature in the range of 50 to 120°C, but it is preferable to carry out the reaction at a boiling temperature under normal pressure from an economic point of view, such as simplifying the reaction equipment, and at the same time, it is preferable to carry out the copolymerization reaction at a temperature in the range of 50 to 120°C. This is particularly preferred from the viewpoint of efficient production.

To give a specific example of the procedure for preparing the copolymer used in the present invention, maleic anhydride and/or fumaric acid, water and alkali metal hydroxide are added to a reactor equipped with a thermometer, a stirrer and a reflux condenser. An aqueous solution of the polymerizable dibasic acid salt is prepared by charging and neutralizing the aqueous solution, and then heating the aqueous solution under normal pressure to the boiling temperature of the aqueous solution, and adding thereto an aqueous solution of acrylic acid or mekacrylic acid and an aqueous solution of persulfate under stirring. A copolymer can be obtained by continuously dropping an aqueous solution of hydrogen peroxide from separate nozzles to cause a copolymerization reaction, and after each drop is finished, the solution is kept at boiling temperature to complete the copolymerization reaction. be.

If necessary, the carboxyl groups of the copolymer can be neutralized with an alkali substance such as an alkali metal hydroxide at boiling temperature after the completion of the copolymerization reaction.

The copolymer obtained according to such a procedure is.

Surprisingly, it contains a copolymer containing a terminal sulfate group and has a molecular weight in the range of 300 to 10,000, and the first
As shown in the table, it exhibits excellent chelating ability for polyvalent metals such as calcium and magnesium.

[Method for measuring chelating ability]

Take 1 g of the sample in a beaker with a capacity of 200 ml, and add 100 ml of pure water to it.

Next, add 2 ml of sodium oxalate with a concentration of 3%, 2N=N
Adjust pH to 10 with aOH.

Titrate with 0.25N calcium acetate, and the end point is the point at which a permanent white precipitate forms.

*1 A copolymer obtained according to the copolymer preparation procedure of the present invention with a molar ratio of acrylic acid and maleic acid of 1:1.

Molecular weight - approx. 3,000 *2 Same as *1 except that the molar ratio of acrylic acid and maleic acid is 1:2.

Molecular weight = approximately 600 *3 A copolymer obtained according to the copolymer preparation procedure of the present invention with a molar ratio of methacrylic acid and maleic acid of 1:1 - neutralized with sodium hydroxide.

Molecular weight 2: about 6,000 *4 Sodium ethylenediaminetetraacetate The detergent composition of the present invention contains 0.1 parts by weight of the copolymer obtained according to the above procedure per 100 parts by weight of the anionic surfactant.
It can be blended in a proportion of up to 200 parts by weight and can be made into various forms such as liquid or powder.

A detergent composition can be easily prepared by blending an anionic surfactant with a copolymer according to a conventionally known procedure, and exhibits excellent detergency even in hard water. If necessary, a condensed phosphate or nitrilotriacetate may be included.

Also, various builders used in general clothing and industrial detergents, such as silicates and carbonates.

Inorganic acid salts such as bicarbonates, hydroxides, mirabilite, etc.; polyvinyl alcohol, polymaleates, polyacrylates, maleic acid-vinyl alcohol copolymer salts, maleic anhydride-vinyl acetate copolymers.

Polymeric substances such as maleic anhydride-ethylene copolymer; organic acid salts such as glycolate, gluconate, citrate, malate, tartrate, succinate, etc.; such as ethylenediaminetetraacetic acid, etc. Aminocarboxylic acids and the like can also be blended.

Furthermore, if necessary, corrosion inhibitors, dyes, fragrances, fluorescent dyes, enzymes, antifoaming agents, inhibitors, bactericidal agents, etc. can also be added.

Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.

Example 1 4 of 11 volumes equipped with thermometer, stirrer and reflux condenser
In a second flask, add 98 g (1 mol) of maleic anhydride and 5 ml of water.
Prepare 9 g of disodium maleate and neutralize it with an aqueous solution of IJ (hydroxide) with a concentration of 48% by weight to prepare an aqueous solution of disodium maleate with a concentration of 50% by weight, and heat it to boiling temperature (approximately 110°C) under normal pressure while stirring. The temperature was raised.

Next, under stirring, 90 g of an acrylic acid aqueous solution with a concentration of 80% by weight was added.
, @ (1 mol), 50 g of ammonium persulfate aqueous solution with a concentration of 20 wt □, hydrogen peroxide aqueous solution with a concentration of 35 wt % 41
were continuously added dropwise from separate nozzles over a period of 4 hours to cause a copolymerization reaction.

After the reaction, it was aged for 1 hour, neutralized using 50 g (0.6 mol) of an aqueous sodium hydroxide solution with a concentration of 48% by weight, and the PI
-I8. O1 viscosity 600C, I) (25℃), solid content 4
An aqueous copolymer solution of 5% by weight and 6.70% of Hazen I was obtained.

The copolymer aqueous solution was concentrated under reduced pressure and then dried to obtain a powdery copolymer (hereinafter referred to as copolymer AM-11).

) was obtained. The copolymer molecular weight was determined by gel permation chromatography (Shimadzu Corporation, LC830 type, column: glass beads, inner diameter 7.9 mm x 500 mm,
2 bottles, mobile phase: water, column inlet pressure: 6%, temperature: room temperature,
Detector: UV, as measured by 254) 3.0
It was 00.

The ability of the copolymer thus obtained to chelate calcium ions was measured at pH 10 according to the method described above, and it was found to be 310 mfI-CaC037 g.

Next, the following test was conducted regarding the amount of the terminal sulfate group-containing copolymer contained in the copolymer AM-11.

Pure water was added to the solid content of copolymer AM-11 (i, oog) to make 100.00 g, and the mixture was stirred and dissolved.

Separately, add pure water to 1.41 parts of magnesium chloride and make 100.
01 and stirred to dissolve.

This magnesium chloride aqueous solution was added to the above copolymer AM-11.
It was gradually added to the aqueous solution and stirred in a SO'C hot bath for 24 hours.

Magnesium salt of the produced copolymer AM-11 (hereinafter referred to as
It is written as copolymer Mg salt.

) was filtered using a membrane filter and washed with pure water.

Next, it was dried in a constant temperature air bath at 105°C for 5 hours to obtain a 0.62
g copolymer Mg salt was obtained.

The obtained copolymer Mg salt was finely pulverized and subjected to normal press molding.
3064-M type, voltage: 50kV.

The sulfur content was measured using a current: 50 mA, full scale: 10,000 counts, target (tube): rhodium 1, spectroscopic crystal: germanium, detector: proportional counter, path: vacuum).

As a standard sample of sulfur, sodium lauryl sulfate was used at 0.031 (standard sample ■) and 0.061. ? Two types were prepared in which (standard sample ■) was added.

These standard samples are. In addition to the sulfur content based on the sulfate group of the copolymer Mg salt, the sulfur content is 3 based on sodium lauryl sulfate.
200ppm I11 (standard sample I) and 65ooppm (
Standard sample (■) was added.

The sulfur content of these standard samples was also measured using a fluorescent X-ray analyzer.

As a result of fluorescent X-ray analysis, the copolymer Mg salt had a count of 1700, the standard sample I had a count of 4100, and the standard sample ■
The count was 6,700.

The 1700 counts of the copolymer Mg salt are calculated from the counts of standard samples 1 and 2, and the sulfur content is 2600 pI)
This corresponds to II.

This sulfur content indicates that a sulfuric acid group is contained at one end of the molecule corresponding to 25% of the copolymer AM-11.

Separately, in the above method, a powdery copolymer (
Hereinafter, it will be referred to as copolymer AM-12.

) was obtained.

The molecular weight was 600. Separately, the above copolymer AM
A powdery copolymer (hereinafter referred to as copolymer MEAM-11) was prepared in the same manner as in the method for preparing MEAM-11, except that mecacrylic acid was used instead of acrylic acid.

) was obtained. The molecular weight was 4.000.

Using each of the copolymers thus obtained, detergent compositions having various compositions as shown in Table 2 were prepared.

In order to measure the detergency of a detergent composition, a sample of the Japan Oil Chemists' Association standard contaminated cloth was used, and the cleaning power of the detergent composition was measured using a tabometer under the following conditions.
Washed for minutes.

Cleaning conditions Hardness of water used: 100pp [Il, 300ppm Cleaning agent concentration: 0.1%, 0.2% Temperature: 25°C Bath ratio contaminated cloth: 6 sheets 1500CC Rotation speed: 100rI"' 5 minutes after cleaning The reflectance of the sample before contamination (Ro) and the reflectance of the contaminated cloth before cleaning (Rs)
The reflectance (Rw) of the contaminated cloth after cleaning was measured, and the cleaning rate (D%) was calculated according to the first-order calculation formula.

The results were as shown in Table 2.

For comparison, detergent compositions without the copolymer as shown in Table 2 were prepared, and the cleaning rates were then calculated.

The results were as shown in Table 2.

As is clear from Table 2 of the calculation formula, the detergent composition using the copolymer of the present invention exhibits excellent detergency in highly hard water.

Claims (1)

[Scope of Claims] 1. 0.1 to 200 parts by weight of a copolymer containing a terminal sulfate group, obtained according to the following procedure, per 100 parts by weight of an anionic surfactant or nonionic surfactant. A detergent composition characterized in that the detergent composition is comprised of the following: An aqueous solution of a polymerizable dibasic acid salt selected from the group consisting of an alkali metal salt of maleic acid, an ammonium salt of maleic acid, an alkali metal salt of fumaric acid, and an ammonium salt of fumaric acid is mixed with acrylic acid and methacrylic acid. An unsaturated carboxylic acid selected from the group consisting of 0.3 to 9.0 moles per mole of the acid salt is added dropwise, and persulfate and hydrogen peroxide are used together as a polymerization initiator. , 50-12
A copolymer having a molecular weight in the range of 300 to 10,000 obtained by copolymerization at a temperature in the range of 0°C and, if necessary, neutralizing the reaction product with an alkaline substance.