JPS585398A - Detergent builder and detergent composition using same - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION 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. However, the builder effect has been only vaguely understood so far, and no general rule has yet been found that can predict the effect of detergent builders.

As a result of repeated basic research on the effects of builders from various viewpoints, the present inventors found that (a) metal ion sequestering action;
It has been found that (b) Solution 1, the effect of improving emulsification, dispersion, etc., and (c) the alkaline buffering effect are particularly important as builder effects.

Additionally, builders are required to be economical, non-polluting, etc.

Conventionally known builders include sodium tripo-IJ, various phosphates, sodium silicate, sulfate, sodium carbonate, nitrilotriacetate,
Known examples include ethynediaminetetraacetate 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 purposes has been developed. Among these, phosphates, such as sodium tripolyphosphate, which is 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 birophosphate and orthophosphate, of which pyrophosphate is a compound that forms undesirable insoluble precipitates with hard water substances such as Cal/Rum and magnesium. This precipitate tends to form on the fabric. Additionally, there are seven reports that nitrilotriacetate may be harmful to the human body, making it unsuitable for use as a household detergent. (On the other hand, ethylenediamine tetraI8: acid salts and cycloalkane polycarboxylic acid salts are expensive and cannot be used as additives in general detergents. Therefore, in the field of detergents, 4 elements and phosphorus There is a great demand for a builder that does not contain any of the above, does not decompose even when used in liquids, and is both durable and economical. As a result of intensive research to develop a new builder that overcomes the drawbacks of conventional builders, it was discovered that a block copolymer with a specific composition has a remarkable effect as a detergent builder, and the present invention was developed based on this research. It has been completed.

Therefore, the purpose of the hemp 1 of the present invention is to provide a builder that has at least the same effect as phosphorus modified salt and 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 1. General formula (where m and n are 0 or positive integers and m + n=
=1-100, +C2H40+ unit and +C3H6
0+C3H60+ may be combined in a simple order. )
The repeating structural unit (A) represented by repeating structural unit (B), and the total amount of (A) and the total amount of (B) are 0.
The block copolymer #1 is in the range of 99.9 to 60:40 (hereinafter referred to as block copolymer (1)).

Still, the second invention relates to a detergent composition comprising a detergent surfactant and a block copolymer (I) as a detergent builder.

The block copolymer (I) used as a detergent builder of the present invention has the general formula 0% (wherein m and n are O or a positive integer, and m + n=
1 to 100, ÷C2H40+ unit and +C3H60
) Units may be combined in any order. ), and polyalkyle/glycol monoallyl ethers (, ), and monovalent formula % formula % (wherein R represents hydrogen or Id methyl group, and X represents hydrogen, -valent metal, divalent metal, ammonium group or It can be obtained by copolymerizing the (meth)acrylic acid monomer (b) represented by (representing an organic amine group) using a polymerization initiator and, if necessary, neutralizing (with an alkaline substance).

Polyalkylene glycol monoallyl ether (,) is represented by the above general formula, and is the total number of added moles of ethylene oxide and/or propylene oxide (m
+n) is 1 to 1 OoO. m + n is Zoo
If it exceeds 20%, the copolymerization reactivity of such polyalkylene/glycol monoallyl ether is low, and a block copolymer effective as a builder for detergents cannot be obtained.

Polyalkylene/glycol monoallyl ether (,) 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+NaOH as a catalyst.

The (meth)acrylic acid monomer (b) is represented by the above general formula, and specifically acrylic acid.

Methacrylic acid and their -valent metal salts, divalent metal salts,
Mention may be made of ammonium salts and organic amine salts. One or more of these can be used.

The block copolymer (I) used as the detergent builder of the present invention has a weight ratio of the total amount of repeating structural units (A) to the total amount of repeating structural units (B) of 0.1-299.
It is necessary that the ratio is within the range of 9 to 60:40. Therefore, when producing the block copolymer (1), polyethylene glycol monoallyl ether (, ) and (meth)
The charging ratio of the acrylic acid monomer (b) is such that the total amount of repeating structural units (A) and the total amount of repeating structural units (B) in the obtained block copolymer falls within the above ratio range. You must do so. If the ratio is outside of this range, excellent performance cannot be achieved.

In order to produce the block copolymer (I) from the polyalkylene/glycol monoallyl ether (,) and the (meth)acrylic acid monomer (b), they may be copolymerized using a polymerization initiator. 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, lower alcohols, mixed solvents of water and lower alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, Examples include ketone compounds and ethyl acetate. As the polymerization catalyst, various water-soluble polymerization initiators, peroxides, hydroperoxides, combinations thereof 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 hydrogen sulfite-oxygen may be used as a polymerization catalyst. In this case, 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, and polymerizing within a temperature range of 5 to 80°C. This can be done by advancing the reaction.

Bulk polymerization is carried out using peroxide, .
It is carried out within a temperature range of 50°C.

When producing block copolymer (I) in this way, polyalkylene glycol monoallyl ether (
1) and the (meth)acrylic acid monomer (b), the amount of polymerization initiator used, the polymerization temperature, and in the case of polymerization in a solvent, the type and amount of solvent, etc. The molecular weight of polymer (I) can be adjusted as appropriate. The molecular weight of the block copolymer (I) used as the detergent builder of the present invention is not particularly limited, and a wide range of molecular weights can be used, but among them, 500 to 50,000
The effect is excellent in the range of 0.

The block copolymer (1) thus obtained can be used as it is as a 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 arsenic carbonates of -valent metals and divalent metals, ammonia, organic amines, etc., but sodium salts and potassium salts are particularly preferred.

Detergent builders consisting of block copolymer (I) should be replaced by conventional polyelectrolyte builders such as sodium polymaleate and polyacrylic acid.
Compared to IJum, etc., it has significantly better compatibility and mixing stability with detergent surfactants, and also has a higher calcium ion trapping ability (
These known polymer electrolytes and E
It was found that this was significantly higher than that of chelating agents such as D and TA.

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, sulfate, 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, its properties as a detergent builder are enhanced.

Detergent surfactants used in the detergent composition of the present invention include alkylbenzene sulfonate/acid, alkyl sulfate ester salt, α-olefin sulfonate, alkyl sulfonate, fatty acid amide sulfonate, dialkyl sulfonate salt, and dialkyl sulfonate salt. Anionic surfactants such as phosphates: Nonionic surfactants such as polyoxyethylene alkylphenyl ether, polyoxyethylene alkyl ether, norbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester: Examples include cationic surfactants such as alkylamine salts and quaternary ammonium salts; and amphoteric ionic surfactants such as alkylbetaine.

Usage ratio of a detergent surfactant and a detergent builder consisting of block copolymer (I) in a detergent composition.

is preferably 25 parts by weight to 1000 parts by weight of the detergent builder based on 100 parts by weight of the surfactant.

If the amount 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.

Various additives commonly used in detergents can be added to the detergent composition of the present invention. For example, sodium carboxymethyl cellulose to prevent redeposition of pollutants, stain inhibitors such as benzotriazole and ethylene-thiourea, PI (alkaline substances to control, fragrances, watering agents, coloring agents, foaming agents, etc.) These include foam stabilizers, polishing agents, disinfectants, bleaching agents, chlorine, dyes, and solvents.

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, in the examples, unless otherwise specified, all "parts" mean "weight,""place" means "weight," and "lol" all mean weight.

The viscosity of the block copolymer aqueous solution in the column was measured using a Bismetron viscometer (manufactured by Seiso Kochisu Kankan) at 25'C, 6
The measurement was performed under the condition of n rpm. Furthermore, the molecular weight was measured using gel permeation chromatography (Model 244 manufactured by Waters).

Reference Example 1 30 parts of Noah 4-nor ether on polyethylene glycol (containing an average of 10 ethylene oxide units per molecule) was placed in a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, gas inlet tube, and reflux condenser. and 475 parts of water were charged, and the inside of the reaction vessel was purged with nitrogen while stirring, and heated to 95° C. in a nitrogen atmosphere. After that, 447 parts of 38 sodium acrylate aqueous solution and 40 parts of 5 preferential ammonium sulfate aqueous solution
parts were added in 120 minutes each. 8 after the addition
5 parts of an aqueous ammonium persulfate 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 pH, viscosity, and molecular weight of the aqueous solution of copolymer (1) were as shown in Table 1.

Reference Example 2 In the same reaction vessel as in Example 1, polypropylene glycol, 49 parts of coal monoallyl ether (containing an average of 10 propylene/oxide units per molecule) and 531 parts of isopropyl alcohol (hereinafter abbreviated as IPA) were added. The inside of the reaction vessel was purged with nitrogen while stirring, and heated to the boiling point in a nitrogen atmosphere. A mixture of 151 parts of acrylic acid, 2 parts of benzoyl peroxide and 227 parts of IPA was then added over 120 minutes. After the addition was completed, 0.4 parts of penzoyl peroxide was dispersed in 39.6 parts of IPA, and the mixture was 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 4011 strength sei soda aqueous solution. Next, IPA was distilled off to obtain copolymer +21.

The PH1 viscosity and molecular weight of the aqueous solution of this copolymer 12) were as shown in Table 1.

Reference Example 3 Polyalkylene glycol monoallyl ether (average 4 per molecule (D: r-f) was added to the same reaction vessel as Reference Example 1-.
70 parts (containing 7 oxide units and 4 propylene oxide units) and 492 parts of water were charged, and the inside of the reaction vessel was purged with nitrogen while stirring, and heated to 95° C. in a nitrogen atmosphere. After that, 38 ml of sodium acrylate aqueous solution 342 ml
5 parts and 80 parts of aqueous ammonium sulfate solution were added over 120 minutes each. After addition path f, 16 parts of an aqueous 5-functional ammonium persulfate solution was further added over 20 minutes. After the addition of the monomer aqueous solution was completed, the temperature was maintained at 95° C. for 100 minutes to complete the polymerization reaction, and an aqueous solution of copolymer 13) was obtained.

The pH, viscosity and molecular weight of the aqueous solution of this copolymer (3) are shown in Table 1, and it was found to have good running properties.

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% preferential ammonium sulfate aqueous solution was added.
The mixture was added in 20 minutes, and after the addition was completed, 8 parts of an aqueous solution of 5-superior ammonium sulfate was further added in 20 minutes. 120 minutes after monomer addition is complete? The temperature was maintained at 5° C. to complete the polymerization reaction, and an aqueous solution of copolymer 14) was obtained.

The pH, viscosity, and molecular weight of the aqueous solution of copolymer (4) were as shown in Table 1.

Reference Example 5 In the same reaction vessel as 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 stirred. The interior of the reaction vessel was replaced with nitrogen, and heated to the boiling point in a nitrogen atmosphere. Thereafter, a mixture of 126 parts of acrylic acid, 2 parts of benzoyl peroxide, and 294 parts of IPA was added over 120 minutes, and after the addition was complete, a mixture of 0.4 parts of penzoyl peroxide dispersed in 7.6 parts of IPA was added every 30 minutes. It was added in two parts. 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 15). This copolymer15)
The pH, viscosity, and molecular weight of the aqueous solution were as shown in Table 1.

Reference Example 6 464 parts of water was charged in the same reaction vessel as in Reference Example 1, and the inside of the reaction vessel was replaced with nitrogen while stirring, and the mixture was heated to the boiling point in a nitrogen atmosphere. Containing 20 ethylene oxide units) 120 tons of aqueous solution! I5, 368 parts of a 38% aqueous solution of partially neutralized sodium acrylate (75 molar neutralization) and 40 parts of a 5% aqueous solution of ammonium sulfate were each added over 120 minutes. After the addition was complete, 8 parts of 5-ammonium thipersulfate aqueous 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 PI, 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 interior of the reaction vessel was replaced with nitrogen while stirring, and the temperature was increased to 95% in a nitrogen atmosphere.
heated to ℃. Thereafter, 120 parts of a 38% aqueous acrylic acid aqueous solution and 120 parts of a 5% ammonium persulfate aqueous solution were each added over 120 minutes. After addition, 'NK2
Four parts of an aqueous solution of ammonium persulfate were 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 17) was obtained.

The pH, viscosity, and molecular weight of the aqueous solution of this copolymer 17) were as shown in Table 1.

Table 1 (Note 1) Viscosity of a copolymer aqueous solution with a concentration of 40 parts (measured with a B-type viscometer, 25°C, 60 rpm. However, copolymers (2) and (5) were measured with a 4541 II degree aqueous solution.

(Note 2) Measured by gel permeation chromatography.

Example 1 A 10-scale stoppered test tube (inner diameter 2a4 (: tnl height 22-5 ryn) was filled with manganese dioxide (Tokyo Kasei Kogyo KK).

First grade reagent) 2. Take Of and add reference example 1 to this.
The o, o s 4 concentration aqueous solution of the copolymer (1) obtained in
The mixture was then shaken vigorously up and down by hand 100 times, and then left in a constant temperature bath at 25° C. for 4 hours.

Then 15m7! Using a whole pipette, fix the tip of the pipette at a position 3/-rn below the surface of the suspension water, and use a pipettor to aspirate the suspension 15%, trying to disturb the suspension as much as possible. Take 300rnt Meyer,
This was added to 6N sulfuric acid 9- and iron sulfate (6
) 10 t of solution containing ammonium hexahydrate 409
After adding nl and shaking until the manganese dioxide was completely dissolved, 0. A dispersion power test for manganese dioxide was conducted by titration with IN potassium permanganate standard solution. In addition, the iron ion solution was also standardized with a potassium permanganate standard solution each time. Also, the dispersion force is 100m
It is expressed as the number of manganese dioxide suspended in j. The results are shown in Table 2.

Examples 2 to 7 Manganese dioxide was dispersed in the same manner as in Example 1 except that copolymers 12) to 171 obtained in reference rows 2 to 7 were used instead of copolymer fil. A force test was conducted. The results are shown in Table 2.

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

Comparative Example 2 In Example 1, Tolipo I was used instead of copolymer ill.
A dispersion force test for bilayered manganese was conducted in the same manner as in Example 1 except that sodium J IJ phosphate was used.

The results are shown in Table 2.

Table 2 As shown in Table 2, it is clear that the detergent builder of the present invention exhibits excellent manganese dioxide dispersion ability.

Example 8 In a beaker with a capacity of 200 d, 1 g of copolymer (1) was placed as solid content, and 100 ml of pure water was added. Next, add 21d of 3-superior oxalic acid sodium, and adjust the pH to 2N-NaOH or 2N-
10.0 to 10.5 with HCl, and this solution was i4'
Titration was performed using an aqueous solution of 4-calcium acetate. The point at which a permanent cloudy precipitate appeared was defined as the end point. Furthermore, M/
During titration with 4-calcium acetate aqueous solution, PI (PI) decreases, so 2N-NaOH is used to reduce PH10.0 to 1.
It was necessary to continue to maintain 0.5. Liquid temperature is 20-25
It was carried out at ℃. In addition, the chelate value (C, V,) was calculated by the following formula.

The results are shown in Table 3.

Examples 9 to 15 Chelate values were determined in the same manner as in Example 8 except that copolymers (21 to (7)) were used instead of copolymer (1), and the results were Shown in the table.

Comparative Example 3 The chelate value was determined in the same manner as in Example 8, except that commercially available sodium polyacrylate (molecule-i 5,000) was used instead of copolymer H1O, and the results are shown in Table 3. Ta.

Comparative Example 4 In Example 8, the chelate value was determined in the same manner as in Example 8 except that sodium tripolyphosphate was used instead of the copolymer. The results are shown in Table 3.

Table 3 As shown in Table 3, it is clear that the detergent builder of the present invention exhibits excellent chelating ability.

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

1. Composition of standard detergent (JIS K 3371-1
976゜Indicator detergent for determining detergent power) Linear alkylbenzene sulfone 30 parts Sodium tripolyphosphate 17 parts Sodium silicate 10 parts Sodium carbonate
3-part carboxymethyl cellulose
1 part Sodium sulfate 58 parts 2 Artificially contaminated fabric T/C broad artificially contaminated fabric 10. -mX 10cm
Composition of 3 stains (regret) Myristic acid 8.3 Oleic acid
8.3 Tristearin
8.3 Triolein 8.3 Cholesterol 4.4 Cholesterol stearate
1.1 Paraffin wax 5.5 Squalene 5.5 Carbon black 0.5 Kanto loam layer soil 4
9.83. Cleaning Test Cleaning was carried out using Terg-0-Tometer under the following conditions.

Measurement conditions Rotation speed 10 Orpm Washing time, 14 minutes each 5 minutes Washing temperature 250 Contaminated cloth T/C broad artificially contaminated cloth (10x10I!'7113 sheets) Water used Calculated as CaCO3 in pure water lt is 50 ppm Addition of CaCl2 detergent concentration 0.12 weight factor 4, Calculation of cleaning index Detergent power (DEN) is calculated according to the following formula by measuring the reflectance in a conventional manner, and the cleaning index is calculated using the standard detergent. It is expressed as an index with the detergency when washed under the same conditions set as 100.

Ro: Reflectance of original fabric R8: Reflectance of contaminated fabric RW'' Reflectance of cleaning fabric Linear sodium alkylbenzene sulfonate (hereinafter referred to as LAS) and/or 1 as a detergent surfactant
Using 30 parts of Softanol 901 (Nippon Shokubai Kagaku Kogyo Co., Ltd., Gokusei, nonionic surfactant), copolymer fl) with sodium tripolyphosphate as a detergent builder.
A cleaning test was conducted according to the composition of the reference detergent, except that 17 parts of 171 were used.

The results are shown in Table 4.

Table 4 (Note 1) The weight ratio of LAS and 1 Softanol 90'' is 1:1.As shown in Table 4, the detergent composition of the present invention has a higher cleaning power than that using sodium tripolyphosphate. It is clear that they exhibit almost the same excellent performance.

805-

Claims (1)

[Claims] l) General formula (where m and n are 0 or a positive integer, and m+n=1 to
100 T foot, +C2H40÷unit and +c31-16
The 0+ units may be combined in any order. )
The repeating structural unit (4) represented by the general formula (wherein R represents hydrogen or a methyl group, and X represents hydrogen, a -valent metal, a divalent metal, an ammonium group, or an organic amine group). The total amount of the repeating structural unit shown by ゛ and the total amount of 0) is 0.1 in weight ratio:
A detergent building block comprising a block copolymer having a ratio of 99.9 to 60:40. 2) Detergent surfactant and general formula (wherein m and n are O or positive integers and m+ n =
1 to 100 with L +CgH4o+ units and 4c3H6
The o+ units may be combined in any order. )
A repeating structure represented by a single repeating structure (wherein R represents hydrogen or a methyl group, and X represents hydrogen, a -valent metal, a divalent metal, an ammonium group, or an organic amine group). A detergent builder consisting of a block co-electrolytic composite consisting of units (B) and in which the total amount of particles and the total amount of (B) is within the range of 0.1:99.9 to 60:40 by weight. A detergent composition characterized by: