JPS5827839B2 - Alkali Senzai Seibutsu - Google Patents

Description

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

Specifically, it is based on an alkaline substance such as alkali metal hydroxide, silicate, phosphate, etc., and is blended with a copolymer obtained according to a specific procedure to achieve excellent metal surface cleaning. The present invention relates to an alkaline detergent composition that exhibits the following effects.

Alkaline detergent compositions are used to remove grease and liquid oil applied to metal surfaces to prevent rust, lubricating oil applied during rolling, and decomposition products, or to remove cutting oil, quenching oil, etc. that adhered during machining. It is used in many ways, including for removing oily substances such as machine oil and abrasive oil.

Such a detergent composition cleans the metal surface by degreasing oil applied to the metal surface or oily stains attached thereto by saponifying, emulsifying, dispersing, wetting, or the like.

Known alkaline detergent compositions are based on alkaline substances and contain small amounts of anionic and/or nonionic surfactants and also builder components to increase the detergency, such as orthophosphates, pyrophosphates. It is advisable to incorporate condensed phosphates such as , tetraphosphate, polyphosphate, hexametaphosphate, etc.

However, known alkaline detergent compositions have the following serious drawbacks.

In other words, when condensed phosphates blended as builder ingredients are used as wastewater, they flow into lakes and rivers through sewage, promoting the growth of algae, causing aging of lakes and rivers, and even causing eutrophication or red tide. It has serious drawbacks such as having a large impact on the occurrence of cancer.

Moreover, these condensed phosphates are easily decomposed at high temperatures and high alkalinity, and cannot be said to be excellent builders.

Conventionally, substitute products have not been proposed to overcome these drawbacks.

However, they were not sufficient because they were expensive and had to be used in extremely large amounts to achieve the desired effect, which caused other problems that were difficult to solve.

For example, the various organic carboxylates, organic oxycarboxylate salts, polymer electrolytes, etc. that have been proposed require a large amount of amines to exhibit the same performance as poly-IJ-IJ-phosphates. Ethylenediamine tetraacetate, which is well known as a carboxylate salt, is expensive and unsuitable for use as a detergent.Furthermore, there are reports that there is NidoIJmouth triacetate, which is harmful to the human body. It is difficult to use.

The inventors of the present invention have conducted intensive research to overcome the drawbacks of known alkaline detergent compositions and to obtain a new composition with excellent detergency, and have found that if a specific procedure is followed, a copolymer containing a terminal sulfate group can be used. The present invention was completed based on the discovery that the object can be achieved by obtaining a copolymer containing the above-mentioned components and using the copolymer as a builder component.

Therefore, the object of the present invention is to not accelerate the aging of lakes and rivers or the occurrence of red tide, to exhibit superior cleaning power compared to known alkaline detergents even in highly hard water, and to be effective against oil-based stains. The object of the present invention is to provide an alkaline detergent composition with excellent dispersion, emulsification, and wetting performance.

Other purposes will become apparent from the description below.

The alkaline detergent composition of the present invention contains 100% of the alkaline substance.
Copolymers containing terminal sulfate group-containing copolymers obtained according to the following procedure, namely alkali metal salts of maleic acid, ammonium salts of maleic acid, alkali metal salts of fumaric acid and Add 0.3 to 9 unsaturated carboxylic acids selected from the group consisting of acrylic acid and methacrylic acid to an aqueous solution of a polymerizable dibasic acid salt selected from the group consisting of ammonium salts per mole of the acid salt. .0
The copolymerization is carried out using persulfate or a combination of persulfate and hydrogen peroxide as a polymerization initiator at a temperature in the range of 50 to 150 °C, and if necessary, the reaction product is made alkaline. A copolymer '1i, o with a molecular weight in the range of 300 to 15,000 obtained by neutralization with a substance
It is characterized by being blended in an amount of ~50 parts by weight.

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

Polymerizable dibasic acid salts used in preparing the copolymer include dinatomium maleate, monosodium maleate, dilithium maleate, monolithium maleate, dipotassium maleate, monopotassium maleate, etc. Alkali metal salts of maleic acid such as; ammonium salts of maleic acid such as diammonium maleate, monoammonium maleate; disodium fumarate;
Alkali metal salts of fumaric acid such as monosodium fumarate, dilithium fumarate, monolithium fumarate, dipotassium fumarate, monopotassium fumarate, etc.; ammonium of fumaric acid such as diammonium fumarate, mono/7 ammonium fumarate, etc. It is selected from the group consisting of salts, and one or more of these monomers can be effectively used.

In particular, maleic acid sodium salt can be effectively used.

Aqueous solutions of polymerizable dibasic acid salts can be prepared by dissolving the salts in water. It can 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, but it is preferably in the range of 10 to 70 weight φ.

For example, alkali metal hydroxide is mixed with maleic acid 1
When neutralizing in an amount of 2 moles or more per mole, the excess 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 acrylic acid and methacrylic acid, and one or two types can be effectively used.

Such unsaturated carboxylic acids, such as acrylic acid, of high purity can of course be used effectively, but acrylic acid produced on an industrial scale, i.e., acrylic acid that contains polymerization inhibitors such as hydroquinone and trace amounts of impurities. Acrylic acid containing the following can also be used effectively.

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

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

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

Examples of persulfates include potassium persulfate, sodium persulfate, ammonium persulfate, and the like.
Particularly suitable is ammonium persulfate.

The amount of persulfate used is 0.5 to 10% of the raw material monomer.
The amount is a weight φ weight type or a ratio amount in the range of 2 to 8 weight φ.

When used in an amount exceeding 10% by weight, the effective amount of copolymer component in the solid content of the resulting aqueous copolymer solution decreases,
Moreover, it is not preferable because it lowers the molecular weight too much.

Conveniently, the persulfate is used as a water bath solution at a concentration of 5 to 30 gm.

In the present invention, the desired copolymer can be obtained even if persulfate is used alone as a polymerization initiator, but
By using a persulfate and hydrogen peroxide in combination, a copolymer that exhibits even more effective effects can be efficiently obtained.

The amount of hydrogen peroxide used is in a ratio of 1 to 10 weight units, preferably 5 to 8 weight units, based on the raw material monomer.

Hydrogen peroxide is conveniently used as an aqueous solution of 5 to 35 g/w.

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

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

Is it preferable to carry out the copolymerization reaction at a temperature in the range of 50-1.50°C? It is preferable to carry out the copolymerization reaction at a temperature in the range of 50°C to 1.50°C. From an economic point of view, such as simplifying the reaction equipment, it is preferable to carry out the copolymerization reaction at a temperature in the range of 50°C to 1.50°C. This is particularly preferable from the standpoint that it can be produced efficiently.

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 it under normal pressure to the boiling temperature of the aqueous solution, and adding thereto an aqueous solution of acrylic acid or methacrylic acid, and a persulfate while stirring. A copolymer can be obtained by continuously dropping an aqueous solution of hydrogen peroxide and an aqueous solution of hydrogen peroxide through separate nozzles to cause a copolymerization reaction, and then keeping the temperature at boiling after the dropwise addition to complete the copolymerization reaction. It is something.

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 copolymers obtained according to these procedures have molecular weights in the range of 300 to 15,000, contain terminal sulfate group-containing copolymers, and contain calcium, magnesium, etc., as shown in Table 1. It exhibits excellent chelating ability against hardness components of water such as.

[Calcium ion chelation ability measurement method] Sample solid matter i
Place it in a beaker with a capacity of 200ml and add 100ml of pure water to it.
Add m1.

Next, the pH was adjusted to 13.0 with a 50% by weight NaOH solution, and the mixture was titrated with M/4 calcium acetate at a temperature of 70°C to 1°C.

The end point is the point at which a permanent white precipitate of calcium hydroxide forms.

[Magnesium ion chelation ability measurement method] A
Add 900g of liquid and heat to 1°C.

While stirring this solution, 100 rIL of Solution B was added dropwise over a period of 1 hour, and after the dropwise addition was completed, the reaction was further stirred for 30 minutes to complete the reaction.

The reaction solution was left at room temperature overnight, filtered through Toyoji Shitaka 2, added with pure water to make up to 1 liter, and chelated magnesium was determined by atomic absorption.

Preparation of Solution A: Add pure water and sodium hydroxide to 2.7 g of the solid chelating agent in Chele-1 to prepare a solution with a concentration of 0.3% by weight of the chelating agent (P) (13.0), and use it as Solution A.

Preparation of B solution: Magnesium sulfate (MgSO,i・
Weigh 5.095.9 of 7H20) accurately and dissolve it in pure water to make 11.

*1. The molar ratio of acrylic acid and maleic acid is 1i:i,
Copolymer molecular weight obtained according to the copolymer preparation procedure of the present invention - about 3,000 *2. Same as *l except that the molar ratio of acrylic acid and maleic acid is 1:2.

Molecular weight - approx. 1,000*3. When the molar ratio of methacrylic acid and maleic acid is 1:1, the molecular weight of the copolymer obtained according to the copolymer preparation procedure of the present invention is approximately 6,000. Copolymer molecular weight obtained according to the copolymer preparation procedure of the invention - about 2,000 Examples of the alkaline substances used in the present invention include sodium orthosilicate, sodium metasilicate, No. 1 sodium silicate, No. 2 storium silicate, etc. silicate;
Alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; carbonates such as sodium carbonate and sodium bicarbonate; phosphates such as monobasic sodium phosphate, dibasic sodium phosphate, and tertiary sodium phosphate; sodium cyanide, etc. These can be used alone or as a mixture of two or more.

The alkaline detergent composition of the present invention is prepared by blending the bottom type compound in a ratio of 1 to 50 parts by weight to 100 parts by weight of these alkaline substances, and making it into various forms such as liquid or powder. It is something that can be done.

If necessary, add surfactant to 100% alkaline substance.
It can be added in an amount of 0.1 to 30 parts by weight based on parts by weight.

As the surfactant, there are various surfactants such as anionic surfactants and nonionic surfactants, such as those having an average carbon number of 10 to 10.
Alkylbenzenesulfonic acid salts having 16 alkyl groups, alkanesulfonic acids having an average of 10 to 18 carbon atoms, salts of these acids, alkyl polyoxyethylene ether monosulfates having 8 to 21 carbon atoms, alkyl groups having 8 to 12 carbon atoms Alkyl metal ammonia or alkanolamine salt of dialkylphenyl polyoxyethylene ether monosulfate having the following, alkyl polyoxyethylene ether having an alkyl group having an average of 8 to 21 carbon atoms, alkylphenyl ethylene having an alkyl group having 8 to 12 carbon atoms Examples include ether.

In addition, various types of virgoos used as known metal surface detergents, such as condensed phosphates and gluconates such as orthophosphates, pyrophosphates, tetraphosphates, polyphosphates, hexametaphosphates, glyco/42 salts, Organic acid salts such as citrate, malate, tartrate, succinate, etc., aminocarboxylic acid salts such as sodium ethylenediaminetetraacetate, etc. can also be blended.

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
A solo flask was charged with 98 g of maleic anhydride and 59.9 g of water, and neutralized using sodium hydroxide aqueous solution I with a concentration of 48 parts by weight to prepare an aqueous solution of disodium maleate with a concentration of 50 parts by weight. Boiling temperature under pressure (approximately 11
The temperature was raised to 0°C.

Next, under stirring, an acrylic acid aqueous solution ci with a concentration of 80% by weight was added.
o & (1 mol), 50 g of ammonium persulfate aqueous solution with a concentration of 20% by weight, 40 g of an aqueous solution of hydrogen peroxide with a concentration of 35% by weight
g 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 and neutralized using a 48 wt % aqueous sodium oxide solution 5L9 (0.6 mol) to give a pH of 8.
, 0, a viscosity of 600 c, p (at 25° C.), and a solid content of 45% by weight, an aqueous copolymer solution of Hazen Nα70 was obtained.

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

) was obtained. The copolymer molecular weight was determined by gel permeation chromatography (Shimadzu LC830 model, column: glass beads, inner diameter: 7.9 m/mX 500 m)
/m.

2 bottles, mobile phase: water, column inlet pressure = 6 to 9/Cl7L,
Temperature: room temperature, detector: UV 254 nm) It was 3,000.

Regarding the copolymer thus obtained, the chelating ability for calcium ions was measured at P)f13.0 according to the above method, and it was found that 300 m9 CaC037g
Met.

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, oo&) to make 100.00 g, and the mixture was stirred and dissolved.

Separately, add pure water to 1.40 g of magnesium chloride and
．． 00g 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 hot bath at 80° C. 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, and the
2g of copolymer Mg salt was obtained.

After finely pulverizing the obtained copolymer Mg salt and performing normal press molding, a fluorescent X-ray analyzer (manufactured by Rigaku Denki Kogyo ■,
3064-M type, voltage: 50kV, current: 50mA, full scale: 10000 counts, target (tube)
The sulfur content was measured using: rhodium, spectroscopic crystal: germanium, detector: proportional counter, pass: vacuum).

Two types of sulfur standard samples were prepared by adding 0.030.9 (standard sample I) and 0.061 g (standard sample ■) of sodium lauryl sulfate to copolymer Mg salt 1.00.9.

These standard samples have a sulfur content of 3200 ppm (standard sample I) and 6500 ppm based on t-'Ium lauryl sulfate in addition to the sulfur content based on the sulfate group of the copolymer Mg salt.
(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 has a count of 1700, the standard sample ■ has a count of 4100, and the standard sample ■
The count was 6,700.

The 1,700 counts of the copolymer Mg salt corresponds to a sulfur content of 2,600 ppm when calculated from the counts of standard samples I and (2).

This sulfur content indicates that a sulfuric acid group is contained at one end of the molecule, which corresponds to 25% in copolymers A and M-11.

Separately, a powdered copolymer (hereinafter referred to as copolymer AM
It is written as -12.

) was obtained. The molecular weight was approximately 1,000.

Separately, a powdered copolymer (hereinafter referred to as copolymer MEAM-1
It is written as 1.

) was obtained. The molecular weight was approximately 4,000.

Separately, 58.9 (0.5 mol) of fumaric acid and 336 g of water were charged, and neutralized with an aqueous solution of hydroxide having a concentration of 48 wt. The salt was prepared and heated to 130°C under pressure.

Next, under stirring, add acrylic acid aqueous solution i45 with a concentration of 800% by weight.
．． 9 (0.5 mol) and neutralized after the copolymerization reaction with a concentration of 48 wt % sodium oxide aqueous solution M2L9 (o, 35
A powdered copolymer (hereinafter referred to as copolymer AF-1
It is written as 1.

) was obtained. The molecular weight was approximately 2,000. Using each of the copolymers thus obtained, alkaline detergent compositions having various compositions as shown in Table 2 were prepared.

In order to measure the detergency of the alkaline detergent composition, the surface of a steel plate was degreased and cleaned according to the following method.

In other words, add 1 part of Nippon Oil +640 to a 5XIQcm steel plate.
After baking at 20°C for 30 minutes, it was immersed in an alkaline cleaning composition aqueous solution with a concentration of 3% by weight (hardness of the water used: 200ppm) for 4 minutes at 70°C, then washed with water, and then washed with water at a concentration of 1%.
It was immersed in a 0 weight polysulfuric acid aqueous solution at 70° C. for 10 minutes, and then washed with water, and the cleaning rate was visually determined by area ratio.

The results were as shown in Table 2.

For comparison, a detergent composition without using the copolymer as shown in Table 2 was prepared, and then the surface of the steel plate was degreased and cleaned in the same manner.

The results were as shown in Table 2.

As is clear from Table 2, the alkaline cleaning composition of the present invention exhibits excellent cleaning power even in highly hard water, emulsifies and moistens oily substances, and cleans without leaving any oil by pickling and water washing. It is something to remove.

Example 2 Using each copolymer obtained in the same manner as in Example 1, the third
Alkaline detergent compositions having various compositions as shown in the table were prepared.

Defat cleaning was carried out in the same manner as in Example 1, except that a steel plate quenched with rapeseed oil at 160° C. for 30 minutes was used.

The results were as shown in Table 3.

Claims (1)

[Claims] 1. Acrylic acid and methacrylic acid are added to 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. An unsaturated carboxylic acid selected from the group is added dropwise in an amount of 0.3 to 9.0 mol per mol of the acid salt, and a persulfate and hydrogen peroxide are used together as a polymerization initiator. , 50-150
The copolymer has a molecular weight in the range of 300 to 15,000 and contains a terminal sulfate group. Copolymer with alkaline substance 100%
An alkaline detergent composition characterized in that the alkaline detergent composition is blended in an amount of 1 to 50 parts by weight.