JPS5915359B2 - Detergent builder and detergent composition using the detergent builder - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION 5 The present invention relates to a novel detergent builder and a detergent composition containing the same.

It is well known that the performance of soaps or synthetic surfactants can be increased by the presence of certain substances, commonly referred to in the detergent field as builders.

:o However, the builder effect has so far only been vaguely understood, and no general rule has yet been found to predict the effect of detergent builders. The present inventors have various views regarding the effect of builders.
As a result of repeated basic research from the viewpoint of
and (c) it has been found that alkaline buffering is particularly important as a builder effect.

In addition, other builders are required to be economical and non-polluting; conventionally known builders include sodium tripolyphosphate, various phosphates, sodium silicate, boronic acid, and carbonate. Known examples include sodium, nitrilotriacetate, ethylenediaminetetraacetate, and cycloalkane polycarboxylate.

However, there is no builder that satisfies all of the above characteristics, and it cannot be said that a builder that is fully satisfactory for practical use has been developed. Among these, phosphates, such as sodium tripolyphosphate, which is the most commonly used, exhibits an excellent builder effect, but its waste liquid is becoming a problem in terms of environmental pollution, so its use is gradually becoming obsolete. Furthermore,
When sodium tripolyphosphate is used as a builder for liquid detergents, it undergoes hydrolysis to form pyrophosphate and orthophosphate, of which pyrophosphate removes hard water substances such as calcium and magnesium and undesirable insoluble precipitates. This precipitate tends to form on the fabric. Furthermore, it has been reported that nitrilotriacetate may be harmful to the human body, making it unsuitable for use as a household detergent. Furthermore, ethylenediaminetetraacetate and cycloalkane polycarboxylate salts have a problem in price and cannot be used as additives in general detergents. Therefore, in the field of detergents, there is a great need for a builder that does not contain either nitrogen or phosphorus, does not decompose even when used in liquids, and is also economical. In view of the current situation, the inventors of the present invention have conducted intensive research to develop a new builder that overcomes the drawbacks of conventional builders. As a builder, I discovered that this has a remarkable effect and completed the present invention.

Therefore, a first object of the present invention is to provide a builder which has at least the same effect as phosphates and which does not contain either nitrogen or phosphorus.

A second object of the present invention is to provide an excellent detergent composition comprising the above builder and a detergent surfactant. That is, the first invention is based on the general formula (where m and n are O or positive integers, and m+n=1 to
100, and +C2H4O+ units and +C3H6O+ units may be combined in any order.

) and the general formula (however,
In the formula, R represents hydrogen or a methyl group, and X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group.

) and the repeating structural unit (8) shown in (4).
The weight ratio of the total amount of ) and the total amount of 03) is 0.1:99.9
~60:40 block copolymer (hereinafter referred to as
It is called block copolymer (1). ) is concerned with a detergent builder consisting of: Further, the second invention relates to a detergent composition characterized by comprising a detergent surfactant and a block copolymer (1) as a detergent builder.

The block copolymer (1) used as the detergent builder of the present invention has, for example, the general formula CH,=CH CHρ-(-C2H4O〒C3H6OH (where m and n are O or a positive integer and =1~
100, +C2H4O)- unit and +C3H6O+
Units may be combined in any order.

), and the general formula (wherein R represents hydrogen or a methyl group, and X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group); represent.

It can be obtained by copolymerizing the (meth)acrylic acid monomer (b) shown in ) using a polymerization initiator, and further neutralizing with an alkaline substance if necessary. The polyalkylene glycol monoallyl ether (a) is represented by the above general formula, and the total number of added moles of ethylene oxide and/or propylene oxide (m+n) is 1 to 100.
belongs to.

When m+n exceeds 100, the copolymerization reactivity of such polyalkylene glycol monoallyl ether is low, and a block copolymer that is effective as a detergent builder cannot be obtained. Polyalkylene glycol monoallyl ether (a) can be synthesized by a known method of directly adding ethylene oxide and/or propylene oxide to allyl alcohol using an alkali such as KOH or NaOH as a catalyst.

(Meth)acrylic acid monomers (collectively represented by the general formula above, specifically acrylic acid, methacrylic acid, their monovalent metal salts, divalent metal salts, ammonium salts, and organic Mention may be made of amine salts.

One or more of these can be used. In the block copolymer (1) used as the detergent builder of the present invention, the total amount of repeating structural units (4) and the total amount of repeating structural units (B) are in a weight ratio of 0.1:99.
It is necessary that the ratio is within the range of 9 to 60:40.

Therefore, when producing a block copolymer (2), the charging ratio of polyethylene glycol monoallyl ether (a) and (meth)acrylic acid monomer (b) is determined by the amount of repeating structural units in the obtained block copolymer. The total amount of (4) and the total amount of repeating structural unit 03) must be within the above ratio range. No. If the ratio is outside this range, excellent performance cannot be achieved. In order to produce block copolymer (1) from polyalkylene glycol monoallyl ether (a) and (meth)acrylic acid monomer (b), a polymerization initiator is used. Copolymerization may be carried out by

Copolymerization can be carried out by methods such as polymerization in a solvent or bulk polymerization. Polymerization in a solvent can be carried out either batchwise or continuously, and the solvents used in this case include water,
Examples include lower alcohols, mixed solvents of water and lower alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ketone compounds, and ethyl acetate. As the polymerization catalyst, various water-soluble polymerization initiators, peroxides, hydroperoxides, combinations of these with polymerization promoters, azo compounds, etc. are used depending on the solvent used. The polymerization temperature is appropriately determined depending on the solvent and polymerization initiator used, but it is usually carried out within the range of 0 to 120°C. When water is used as a solvent, sodium bisulfite monooxygen may be used as a polymerization catalyst.

In this case, the polymerization is carried out by blowing oxygen gas or a mixed gas of oxygen and an inert gas into the solvent while adding sodium bisulfite to the solvent containing the raw material monomer at 5 to 80°C.
Bulk polymerization can be carried out by proceeding the polymerization reaction within the temperature range of
Using hydroperoxide or azo compound, etc., 5
It is carried out within a temperature range of 0 to 150°C.

When producing the block copolymer (1) in this way, polyalkylene glycol monoallyl ether (
The resulting product will vary depending on the charging ratio of a) and (meth)acrylic acid monomer (b), the amount of polymerization initiator used, the polymerization temperature, the type and amount of solvent in the case of polymerization in a solvent, etc. The molecular weight of the polymer (1) can be adjusted as appropriate. There is no particular restriction on the molecular weight of the block copolymer (1) used as the detergent builder of the present invention, and a wide range of molecular weights can be used;
The effect is excellent in the range of 0. The thus obtained block copolymer (1) can be used as it is as the detergent builder of the present invention, but it may be further neutralized with an alkaline substance if necessary.

Examples of such alkaline substances include hydroxides, chlorides and carbonates of monovalent metals and divalent metals, ammonia, organic amines, etc., and sodium salts and potassium salts are particularly preferred. Surprisingly, the detergent builder made of PROTSUCH copolymer (1) is more compatible with detergent surfactants than conventional polymer electrolyte builders such as sodium polymaleate and sodium polyacrylate. It has been found that the compatibility and mixing stability are extremely good, and the calcium ion trapping ability (chelating ability) is also significantly higher than those of these known chelating agents such as polymer electrolytes and EDTA. It is also stable against hydrolysis and maintains its effectiveness even when used in liquids. Although the detergent builder of the present invention is sufficiently effective when used alone, it can be used in combination with other known detergent builders.

Such other detergent builders include, for example, sodium tripolyphosphate, sodium pyrophosphate, sodium silicate, boronic acid, sodium carbonate, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate, and carboxyl derivatives of potassium and polysaccharides. It has been found that when the detergent builder of the present invention is used in combination with some of the other builders mentioned above, the properties of the detergent builder can be enhanced. Detergent surfactants used in the detergent composition of the present invention include alkylbenzene sulfonates, alkyl sulfate ester salts, α-olefin sulfonates, alkyl sulfonates, fatty acid amide sulfonates, dialkyl sulfosuccinates, etc. Anionic surfactants; nonionic surfactants such as polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester; alkyl amines; Cationic surfactants such as salts and quaternary ammonium salts; amphoteric ionic surfactants such as alkyl betaines, and the like.

The ratio of the detergent surfactant and the detergent builder consisting of PROC copolymer (1) in the detergent composition is from 25 parts by weight to 100 parts by weight of the surfactant. Preferably, it is 1000 parts by weight.

If it is less than 25 parts by weight, no practical benefit can be expected from its addition, and if it exceeds 1000 parts by weight, it is economically undesirable.

The detergent composition of the present invention may contain various additives commonly used in detergents, such as sodium carboxymethyl cellulose to prevent redeposition of pollutants, benzotriazole and ethylene-thiourea. These include inhibitors, alkaline substances for pH adjustment, fragrances, fluorescent coloring agents, foaming agents, foam stabilizing agents, polishing agents, disinfectants, bleaching agents, enzymes, dyes, solvents, and the like. The present invention will be described below with reference to Reference Examples and Examples, but the present invention is not limited to these Examples.

In addition, unless otherwise specified in the examples, all parts are parts by weight.
All percentages are by weight. The viscosities of aqueous PROTSU copolymers in the examples were all measured using a Bismetron viscometer (manufactured by Seiki Kogyo Kenkyusho) at 25° C. and 60 rpm.

In addition, the molecular weight was measured using gel permation chromatography (Model 244 manufactured by Waters).
Reference Example 1 30 parts of polyethylene glycol monoallyl ether (containing an average of 10 ethylene oxide units per molecule) and 47 parts of water were placed in a glass reaction vessel equipped with a thermometer, stirrer, dropping load, gas inlet tube, and reflux condenser.
After charging 5 parts, the inside of the reaction vessel was purged with nitrogen while stirring, and heated to 95° C. in a nitrogen atmosphere.

Then 447 parts of 38% sodium acrylate aqueous solution and 5
% ammonium persulfate aqueous solution and 120 parts of each
Added in minutes. After the addition was complete, 8 parts of 570 ammonium persulfate aqueous solution was added over 20 minutes. After the addition of the monomer aqueous solution was completed, the temperature was maintained at 95° C. for 120 minutes to complete the polymerization reaction, and an aqueous solution of copolymer (1) was obtained. The PHL viscosity and molecular weight of the aqueous solution of this copolymer (1) were as shown in Table 1.

Reference Example 2 In the same reaction vessel as in Example 1, 49 parts of polypropylene glycol monoallyl ether (containing an average of 10 propylene oxide units per molecule) and isopropyl alcohol (hereinafter abbreviated as PA).

), and the inside of the reaction vessel was purged with nitrogen while stirring, and heated to the boiling point in a nitrogen atmosphere. Then, 151 parts of acrylic acid, 2 parts of benzoyl peroxide and IPA
227 parts of the mixture were added in 120 minutes. After addition,
Additionally, 0.4 parts of benzoyl peroxide was added to IPA39.
The mixture was dispersed in 6 parts and added in two portions every 30 minutes. After the addition of the monomer mixture was completed, the temperature was maintained at the boiling point for 120 minutes to complete the polymerization reaction. Thereafter, it was neutralized with 210 parts of a 40% caustic soda aqueous solution. Next, IPA was distilled off to obtain a copolymer (2). The PHs viscosity and molecular weight of the aqueous solution of this copolymer (2) were as shown in Table 1.

Reference Example 3 Into the same reaction vessel as in Reference Example 1, 70 parts of polyalkylene glycol monoallyl ether (containing on average 4 ethylene oxide units and 4 propylene oxide units per molecule) and 492 parts of water were charged, and the mixture was stirred. The interior of the reaction vessel was purged with nitrogen and heated to 95° C. in a nitrogen atmosphere.

Thereafter, 12 parts each of 342 parts of a 38% sodium acrylate aqueous solution and 80 parts of a 5% ammonium persulfate aqueous solution were added.
Added at 0 minutes. After the addition was complete, an additional 16 parts of 570 ammonium persulfate aqueous solution was added over 20 minutes. After the addition of the monomer aqueous solution was completed, the temperature was maintained at 95° C. for 120 minutes to complete the polymerization reaction, and a copolymer (3) 0 aqueous solution was obtained. The PHL viscosity and molecular weight of the aqueous solution of this copolymer (3) were as shown in Table 1.

Reference Example 4 Into the same reaction vessel as in Reference Example 1, 60 parts of polyethylene glycol monoallyl ether (containing an average of 30 ethylene oxide units per molecule) and 524 parts of water were charged.
While stirring, the inside of the reaction vessel was purged with nitrogen and heated to 95°C.

Then, 1 part each of 368 parts of 38% sodium methacrylate aqueous solution and 40 parts of 5% ammonium persulfate aqueous solution was added.
After the addition was completed, 8 parts of a 5% aqueous ammonium persulfate solution was added over a period of 20 minutes. After the addition of the monomers was completed, the temperature was maintained at 95° C. for 120 minutes to complete the polymerization reaction, and an aqueous solution of copolymer (4) was obtained. The PHL viscosity and molecular weight of the aqueous solution of this copolymer (4) were as shown in Table 1. Reference Example 5 Into the same reaction vessel as in Reference Example 1, 54 parts of polyethylene glycol monoallyl ether (containing an average of 20 ethylene oxide units per molecule) and 126 parts of isopropyl alcohol (hereinafter abbreviated as PA) were charged, and the mixture was reacted with stirring. The inside of the container was purged with nitrogen and heated to the boiling point in a nitrogen atmosphere.

Then 126 parts of acrylic acid, 2 parts of benzoyl peroxide
A mixture of 294 parts of IPA and 294 parts of IPA was added over 120 minutes, and after the addition was complete, an additional 0.4 part of benzoyl peroxide was added to the IPA.
7.6 parts of the solution was added in two portions every 30 minutes. After the monomer addition was completed, the temperature was maintained at the boiling point for 120 minutes to complete the polymerization reaction. Thereafter, complete neutralization was performed with a caustic soda aqueous solution, and IPA was distilled off to obtain an aqueous solution of copolymer (5). The PHL viscosity and molecular weight of the aqueous solution of this copolymer (5) were as shown in Table 1. Reference Example 6 464 parts of water was charged into the same reaction vessel as in Reference Example 1, and the inside of the reaction vessel was replaced with nitrogen while stirring, and heated to the boiling point in a nitrogen atmosphere.

Next, 120 parts of a 50% aqueous solution of polyethylene glycol monoallyl ether (containing on average 20 ethylene oxide units per molecule), 368 parts of a 3870 aqueous solution of partially neutralized sodium acrylate (75 mol% neutralization), and 5% ammonium persulfate. 12 parts each of 40 parts of aqueous solution
Added at 0 minutes. After the addition is complete, add 8 parts of 5? Aqueous ammonium persulfate solution was added over 20 minutes. After the addition of the aqueous monomer solution was completed, the temperature was maintained at the boiling point for 120 minutes to complete the polymerization reaction. Thereafter, complete neutralization was performed with a caustic soda aqueous solution to obtain an aqueous solution of copolymer (6). The PHL viscosity and molecular weight of the aqueous solution of this copolymer (6) were as shown in Table 1.

Reference Example 7 Into the same reaction vessel as in Reference Example 1, 10 parts of polyethylene glycol monoallyl ether (containing an average of 10 ethylene oxide units per molecule) and 346 parts of water were charged.
The inside of the reaction vessel was replaced with nitrogen while stirring, and the temperature was increased to 95% in a nitrogen atmosphere.
heated to ℃.

Then, 500 parts of a 38% potassium acrylate aqueous solution and 5
% ammonium persulfate aqueous solution and 120 parts of each
Added at 0 minutes. After the addition was complete, an additional 24 parts of 5% ammonium persulfate aqueous solution was added over 20 minutes. After the addition of the monomer aqueous solution was completed, the temperature was maintained at 95° C. for 120 minutes to complete the polymerization reaction, and an aqueous solution of copolymer (7) was obtained. The PH of this copolymer (7) (7) aqueous solution. The viscosity and molecular weight were as shown in Table 1.

Example 1 A stoppered test tube with a 10mj scale (inner diameter 2.4mm and height 22mm).
Weigh out 2.09 g of manganese dioxide (Tokyo Kasei Kogyo KKl reagent first grade) into 5C1rL), add 100 d of 0.05% aqueous solution of copolymer (1) obtained in Reference Example 1, and then shake it up and down by hand. After shaking vigorously 100 times,
It was left standing in a constant temperature bath at 25°C for 4 hours.

Next, using a 15Tn1 whole pipette, fix the tip of the pipette at a position 3CrL below the surface of the suspension, and use the pipette to aspirate the suspension 15d without disturbing the suspension as much as possible. To this, add 9 ml of 6N sulfuric acid and iron sulfate (4) in 0.6N sulfuric acid.
After adding 10 d of a solution containing ammonium hexahydrate 409 and shaking until the manganese dioxide was completely dissolved, titration was performed with a 0.1N potassium permanganate standard solution to test the dispersion power of manganese dioxide. I did this. In addition, the iron ion solution was also standardized with a potassium permanganate standard solution each time. Further, the dispersion power was expressed by the number of manganese dioxide suspended in 100 ml of suspension. The results are shown in Table 2. Examples 2 to 7 In Example 1, copolymers (2) to (7) obtained in Reference Examples 2 to 7 were used instead of copolymer (1). A dispersion power test of manganese dioxide was conducted in the same manner as in Example 1, except that the test results were as follows.

The results are shown in Table 2. Comparative Example 1 In Example 1,
A dispersion power test for manganese dioxide was conducted in the same manner as in Example 1, except that commercially available sodium polyacrylate (molecular weight 5,000) was used in place of copolymer (1).

The results are shown in Table 2. Comparative Example 2 A dispersion power test of manganese dioxide was conducted in the same manner as in Example 1 except that sodium tripolyphosphate was used instead of copolymer (1). Ta.

The results are shown in Table 2. As shown in Table 2, it is clear that the detergent builder of the present invention exhibits excellent manganese dioxide dispersion power. As a result, 100 ml of pure water per 19 parts was added.

Next, add 2 d of 3% sodium oxalate and adjust the pH to 2N-Na.
Titrate the solution with OH or 2N-HCI to 10.0 to 10.5 with M/4 aqueous calcium acetate solution.The end point is the point at which a permanent white cloudy precipitate appears.
In addition, when titrating with M/4 calcium acetate aqueous solution, P
In order to cause a decrease in H, PHlO. O
It was necessary to continue to maintain -10.5. Liquid temperature is 20~
It was carried out at 25°C. Note that the chelate value (C.V.) was calculated using the following formula. The results are shown in Table 3. Example 9~
15 In Example 8, the chelate value was determined in the same manner as in Example 8 except that copolymers (2) to (7) were used instead of copolymer (1), and the results are shown in Table 3. Comparative Example 3 The chelate value was determined in the same manner as in Example 8, except that commercially available sodium polyacrylate (molecular weight 5,000) was used instead of copolymer (1), and the results were It is shown in Table 3.

Comparative Example 4 Chelate value was determined in the same manner as in Example 8 except that sodium tripolyphosphate was used instead of copolymer (1), and the results are shown in Table 3. It is clear that the detergent builder of the present invention exhibits excellent chelating ability.

Examples 15-21 A detergency test of the detergent composition of the present invention was conducted based on the method shown below.

1. Composition of reference detergent (JISK337l-1976, index detergent for determining detergency) Composition (%) of artificially contaminated cloth stain of T/C Prode 10cm><10CTrL 3 pieces 3 cleaning test Using Terg-0-TOmeter under the following conditions Washed with.

Measurement conditions 4. Calculation of Cleaning Index The cleaning power (DE%) is calculated according to the formula below by measuring the reflectance using a conventional method. Expressed as an index.

Linear sodium alkylbenzene sulfonate (hereinafter referred to as LAS) is used as a surfactant for detergents.

) and/or Softanol 90'' (manufactured by Nippon Shokubai Chemical Co., Ltd., nonionic surfactant) and copolymers (1) to (7) in place of sodium tripolyphosphate as a detergent builder. A cleaning test was conducted according to the composition of the standard detergent except that 17 parts of sodium tripolyphosphate was used.The results are shown in Table 4. It is clear that it shows almost the same excellent performance in terms of cleaning power when compared to the one used.

Claims (1)

[Claims] 1 General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, m and n are 0 or a positive integer, and m + n = 1 ~
100, ■C_2H_6O■ unit and ■C_3H_
It may be combined with the 6O■ unit in any order. ) The repeating structural unit (A) shown by the general formula ▲mathematical formula,
There are chemical formulas, tables, etc. ▼ (However, in the formula, R represents hydrogen or a methyl group, and X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or an organic amine group.) Repeating structural unit ( B) and (A
) and (B) in a weight ratio of 0.1:99.9.
A detergent builder comprising a block copolymer having a ratio of 60:40 to 60:40. 2. Surfactants for detergents and general formulas ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (However, in the formula, m and n are 0 or positive integers, and m + n = 1 ~
100, ■C_2H_4O■ unit and ■C_3H_
It may be combined with the 6O■ unit in any order. ) and ▲mathematical formulas, chemical formulas, tables, etc.▼(However, in the formula, R represents hydrogen or a methyl group, and X represents hydrogen, a monovalent metal, a divalent metal, an ammonium group, or represents an organic amine group.) Consisting of a repeating structural unit (B) represented by
The weight ratio of the total amount of ) and the total amount of (B) is 0.1:99.9
A detergent composition comprising a detergent builder comprising a block copolymer having a ratio of 60:40 to 60:40.