JPS5927794B2 - Detergent builder and detergent composition containing the detergent builder - Google Patents

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 detergent builder effect. The present inventors conducted basic research on the effects of Builder I from various viewpoints, and found that (a) metal ion sequestering action, (b)
It has been found that the effects of improving peptization, emulsification, dispersion, etc., and (c) alkaline buffering effects are particularly important as builder effects.

In addition, as a builder, economical efficiency and non-pollution properties are also required. Conventionally known builders include sodium tripolyphosphate, various phosphates, sodium silicate, boronitrate, sodium carbonate, nitrilotriacetate, ethylenediaminetetraacetate, and cycloalkane polycarboxylate. There is.

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 present inventors have conducted extensive research to develop a new builder that overcomes the drawbacks of conventional builders, and have found that a copolymer with a specific composition has been developed as a detergent builder. The present invention was completed by discovering that the present invention has a remarkable effect.

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 comprises 25 to 70 mol% of polyalkylene glycol monoallyl ether (a), 25 to 70 mol% of a maleic acid monomer (a), and a monomer copolymerizable with these (c). O ~ 50 mol% (However, (a), (b)
The total amount of components (3) and (3) is 100 mol%.

) (hereinafter referred to as copolymer (1)). ”
``In other words, the first invention is based on the general formula (wherein m and n are O or positive integers, and m+n1 to 1
00, and the CC2H4O)- units and the FC3H6O+ units may be bonded in any order.

) 25 to 70 mol % of polyalkylene glycol monoallyl ether (a) represented by the general formula (wherein R1 and R2 each represent hydrogen or a methyl group, and X and Y each represent C2H40C3
H60÷positive R3 (R3 represents hydrogen or an alkyl group having 1 to 20 carbon atoms, p and q are O or a positive integer, p+q
-0 to 100, so C2H40) unit and C3H6
0] Units may be combined in any order.

), represents a monovalent metal, a divalent metal, an ammonium group, or an organic amine group. ) Maleic acid monomer (ex)
25 to 70 mol%, and monomers copolymerizable with these (
c) O to 50 mol% (however, (a), (mouth) and (c)
The sum of the components is 100 mol%.

) (hereinafter referred to as copolymer (1)). Moreover, the second invention relates to a detergent composition characterized by comprising a detergent surfactant and a copolymer (1) as a detergent builder.

The copolymer (1) used as the detergent builder of the present invention is the above copolymer (1). 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.

As long as it is represented by the above general formula, it can be used either as a single structure or as a mixture. Maleic acid monomers are represented by the above general formula, and specifically include maleic acid, fumaric acid, citraconic acid, mesaconic acid, and monovalent metal salts and divalent metal salts of these acids. salts, ammonium salts, organic amine salts, and their acids, p and q are O or positive integers from p+q-0 to 100, and in what order are the ←C2H40)- units and CC3H60-)- units? May be combined.

) (hereinafter referred to as alcohol (4)).
A species or two or more species can be used. In addition, monomers (c) copolymerizable with these include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts and Examples include esters obtained from these acids and alcohols, (meth)acrylamide, vinyl acetate, propenyl acetate, aromatic vinyl compounds such as styrene and p-methylstyrene, vinyl chloride, etc.
A species or two or more species can be used. Copolymer (1)
contains polyalkylene glycol monoallyl ether (a), maleic acid monomer (a), and a monomer copolymerizable with these (c), 25 to 70 mol% and 25 to 7 mol%, respectively.
0 mol % and O to 50 mol % (however, the total of components (a), (c), and (c) is 100 mol %). Copolymer (1) can be produced by copolymerizing the monomer components 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 include water; lower alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; benzene, toluene, xylene, cyclohexane, n - Aromatic or aliphatic hydrocarbons such as hexane; ethyl acetate; ketone compounds such as acetone and methyl ethyl ketone.

From the solubility of the raw material monomer and the obtained copolymer (1) and the use of the copolymer (1), water and carbon number 1
It is preferable to use at least one selected from the group consisting of lower alcohols of 1 to 4. Among the lower alcohols having 1 to 4 carbon atoms, methyl alcohol, ethyl alcohol, and isopropyl alcohol are particularly effective. When polymerization is carried out in an aqueous medium, a water-soluble polymerization initiator such as ammonium or alkali metal persulfate or hydrogen peroxide is used as the polymerization initiator. At this time, an accelerator such as sodium hydrogen sulfite can also be used in combination. In addition, for polymerization using lower alcohols, aromatic hydrocarbons, aliphatic hydrocarbons, ethyl acetate, or ketone compounds as solvents, hydroperoxide molecules such as peroxide ricmene hydroperoxide such as benzoyl peroxide and lauroyl peroxide are used. Aliphatic azo compounds such as zobisisobutyronitrile are used as polymerization initiators. At this time, a promoter such as an amine compound can also be used in combination. Furthermore, when a water-lower alcohol mixed solvent is used, it can be appropriately selected from among the various polymerization initiators or combinations of polymerization initiators and accelerators mentioned above. The polymerization temperature is appropriately determined depending on the solvent and polymerization initiator used, but is usually 0.
It is carried out within the range of ~120°C. Bulk polymerization is carried out using an aliphatic azo compound such as hydroperoxide azobisisobutyronitrile such as peroxide cumene hydroperoxide such as benzoyl peroxide or lauroyl peroxide as a polymerization initiator, and at a temperature of 50 to 150°C. carried out within the temperature range of Further, the molecular weight of the copolymer (1) can be in a wide range, but it is preferably in the range of 500 to 50,000.

The copolymer (1) thus obtained 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 copolymer (1) is more compatible with detergent surfactants than conventional polymer electrolyte builders such as sodium polymaleate and sodium polyacrylate. It has extremely good solubility and mixing stability, and has better calcium ion trapping ability (chelating ability) than these known polymer electrolytes and EDT.
It was found that it exhibits chelating ability equivalent to that of chelating agents such as A. 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. Other such detergent builders include, for example, sodium tripolyphosphate, sodium pyrophosphate,
Examples include sodium silicate, boronic acid, sodium carbonate, sodium nitrilotriacetate, sodium ethylenetetraacetate, potassium, and carboxyl derivatives of 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 surfactant; polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether,
Nonionic surfactants such as zorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene fatty acid ester; cationic surfactants such as alkylamine salts and quaternary ammonium salts; zwitterions such as alkyl betaine Examples include surfactants.

The ratio of detergent surfactant to detergent builder consisting of copolymer (1) in the detergent composition is as follows:
00 parts by weight of the detergent builder - 25 parts by weight to 10 parts by weight
00 parts by weight is preferred.

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.

Various additives commonly used in detergents can be added to the detergent composition of the present invention.

For example, sodium carboxymethylcellulose to prevent redeposition of pollutants, stain inhibitors such as benzotriazole and ethylene-thiourea, alkaline substances to adjust pH, fragrances, fluorescent agents, colorants, foaming agents, and foam. Stabilizers, polishing agents, disinfectants, bleaches, enzymes, dyes, solvents, etc. 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 copolymer aqueous solutions in the examples were all measured using a Bismetron viscometer (manufactured by Seiki Kogyo Kenkyusho) at 25° C. and 60 rpm.

Reference Example 1 334 parts of polyalkylene glycol monoallyl ether (containing an average of 5 ethylene oxide units per molecule) and 100 parts of water was charged, and the inside of the reaction vessel was purged with nitrogen while stirring, and heated to 95° C. in a nitrogen atmosphere.

Then, 117.7 parts of maleic anhydride and 14.2 parts of ammonium persulfate were dissolved in 246.6 parts of water.
Added in 20 minutes. After the addition is complete, add 14 more parts and 2 parts of 20
% ammonium persulfate solution was added over 20 minutes. After the addition was completed, the temperature inside the reaction vessel was maintained at 95° C. for 100 minutes to complete the polymerization reaction, and then a 40% aqueous solution of caustic soda was added for neutralization to obtain an aqueous solution of copolymer (1).
The pH and viscosity of the aqueous solution of copolymer (1) were as shown in Table 1. Reference Example 2 In the same reaction vessel as Reference Example 1, 378.9 parts of polyalkylene glycol monoallyl ether (containing an average of 10 ethylene oxide units per molecule) and 188.5 parts of water were added.
The inside of the reaction vessel was purged with nitrogen while stirring, and heated to 95°C in a nitrogen atmosphere.

Then 88.2 parts of maleic acid and 1 part of ammonium persulfate
An aqueous solution of 4 parts dissolved in 132.3 parts of water was added over 120 minutes. After the addition was complete, 14 parts of a 20% aqueous ammonium persulfate solution was added over 20 minutes. After the addition was completed, the temperature inside the reaction vessel was maintained at 95° C. for 100 minutes to complete the polymerization reaction, and then a 40% aqueous solution of caustic soda was added for neutralization to obtain an aqueous solution of copolymer (2). This copolymer (2)
The pH and viscosity of the aqueous solution were as shown in Table 1.

Reference Example 3 In the same reaction vessel as in Reference Example 1, 10.3 parts of maleic anhydride and 141.0 parts of water were charged and uniformly dissolved under stirring.

Then polyalkylene glycol monoallyl ether (
346.3 parts of ethylene oxide (containing an average of 10 ethylene oxide units per molecule) were added, the inside of the reaction vessel was purged with nitrogen while stirring, and the mixture was heated to 95°C in a nitrogen atmosphere. Thereafter, an aqueous solution of 92.7 parts of maleic anhydride and 8.5 parts of ammonium persulfate dissolved in 181.5 parts of water was added over 120 minutes. After the addition was complete, 21 parts of a 20% aqueous ammonium persulfate solution was further added over 60 minutes. After addition is complete, 60 minutes9
The temperature in the reaction vessel was maintained at 5°C to complete the polymerization reaction,
Next, a 40% aqueous solution of caustic soda was added to neutralize the mixture to obtain an aqueous solution of copolymer (3). The pH and viscosity of the aqueous solution of copolymer (3) were as shown in Table 1. Reference Example 4 In the same reaction vessel as Reference Example 1, 348.5 parts of polyalkylene glycol monoallyl ether (containing an average of 5 propylene oxide units per molecule) and 11 parts of maleic acid were added.
6.1 parts of benzoyl peroxide and 119.6 parts of isopropyl alcohol were charged, and the inside of the reaction vessel was replaced with nitrogen while stirring, and the mixed solution was heated in a nitrogen atmosphere. heated to the boiling point.

Thereafter, 418.7 parts of the remaining mixed solution was added over 120 minutes. After the addition was completed, three equal parts of a suspension of 4.6 parts of benzoyl peroxide and 18.4 parts of isopropyl alcohol were added at 60 minute intervals. After the final addition, 12
The polymerization reaction was continued by maintaining the temperature in the reaction vessel at the boiling point for 0 minutes. After that, the temperature inside the reaction vessel was returned to room temperature,
Neutralization was performed by adding a 40% aqueous solution of caustic soda and deionized water, heating was performed again, and isopropyl alcohol was distilled off to obtain an aqueous solution of copolymer (4). The pH and viscosity 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, 110.7 parts of polyalkylene glycol monoallyl ether (containing an average of 5 ethylene oxide units per molecule), maleic acid and
alcohol 3 mole ethoxylate (!1S0FTAN
171.1 parts of monoester with 0L-30 (manufactured by Nippon Shokubai Chemical Co., Ltd.) and 307 parts of isopropyl alcohol
．． Two parts were charged, and the inside of the reaction vessel was replaced with nitrogen while stirring, and heated to the boiling point in a nitrogen atmosphere.

Thereafter, a mixed solution consisting of 38.2 parts of acrylic acid, 3.2 parts of benzoyl peroxide, and 152.8 parts of isopropyl alcohol was added over 240 minutes. After the addition was completed, a suspension of 1.28 parts of benzoyl peroxide and 20 parts of isopropyl alcohol was divided into four equal parts and added at 30 minute intervals. After the final addition, the temperature in the reaction vessel was maintained at the boiling point for 120 minutes to continue the polymerization reaction. Thereafter, the temperature inside the reaction vessel was returned to room temperature, neutralized by adding a 40% aqueous solution of caustic soda and deionized water, heated again, and the isopropyl alcohol was distilled off to obtain an aqueous solution of copolymer (5). Ta. The pH and viscosity of the aqueous solution of copolymer (5) were as shown in Table 1. Suspension underwater 3CTfL
Fix the tip of the pipette in the position shown below, and use the pipette to pipette 15ml of the suspension, keeping it as undisturbed as possible.
Suction and 300ml of IP
9 ml of lT sulfuric acid, 1 ml of polyethylene glycol monoallyl ether (containing an average of 10 ethylene oxide units per molecule) 34
9 parts and 64.7 parts of water were charged, and the inside of the reaction vessel was purged with nitrogen while stirring, and heated to 65° C. in a nitrogen atmosphere. Thereafter, an aqueous solution of 116 parts of maleic acid and 24.5 parts of ammonium persulfate dissolved in 174 parts of water, an aqueous solution of 11.2 parts of sodium bisulfite dissolved in 44.8 parts of water, and 25.8 parts of vinyl acetate were each added in 120 minutes. Added. After the addition was completed, the temperature inside the reaction vessel was maintained at 65° C. for 120 minutes to complete the polymerization reaction, and then a 40% aqueous solution of caustic soda was added for neutralization to obtain an aqueous solution of copolymer (6). The pH and viscosity of the aqueous solution of copolymer (6) were as shown in Table 1. 0.6N Shin? Ko Rc memory? Add 10ml of a solution containing 40y of heptadium hexahydrate and shake until the manganese dioxide is completely dissolved. Titrate with a 0.1N potassium permanganate standard solution to dissolve the dioxide. A manganese dispersion power test was conducted.

In addition, the iron ion solution was also standardized with a potassium permanganate standard solution each time. Further, the dispersion force was expressed as the η number of manganese dioxide suspended in 100 ml of the suspension. The results are shown in Table 2. Examples 2 to 6 The same procedure as in Example 1 was carried out except that copolymers (2) to (6) obtained in Reference Examples 2 to 6 were used instead of copolymer (1). A dispersion power test of manganese dioxide was conducted.

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 for manganese dioxide was conducted in the same manner as in Example 1 except that sodium tripolyphosphate was used instead of copolymer (1).

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 ability.

Example 7 In a beaker with a capacity of 200 ml, 17 ml of copolymer (1) was taken as solid content, and 100 ml of pure water was added.

Next, add 2ml of 3% sodium oxalate and adjust the pH to 2N-N.
10.0 to 10.5 with aOH or 2N-HCl,
This solution was titrated with an M/4 aqueous calcium acetate solution. The point at which a permanent cloudy precipitate appeared was defined as the end point. In addition, since the pH decreases when titrating with M/4 calcium acetate aqueous solution, PHlO
．． It was necessary to continue to maintain the temperature between O and 10.5. The liquid temperature is 2
It was carried out at 0-25°C. Note that the chelate value (C.V.) was calculated using the following formula. The results are shown in Table 3. Example
8-12 In Example 7, the chelate value was determined in the same manner as in Example 7 except that copolymers (2) to (6) were used instead of copolymer (1), and the results are shown in Table 3. It was shown to.

Comparative Example 3 The chelate value was determined in the same manner as in Example 7, except that commercially available sodium polyacrylate (molecular weight 5000) was used instead of copolymer (1), and the results were reported in the third example.
Shown in the table.

Comparative Example 4 The chelate value was determined in the same manner as in Example 7, except that sodium tripolyphosphate was used instead of copolymer (1), and the results are shown in Table 3.

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

Examples 13 to 18 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) 2 Artificially contaminated fabric T/C Prode artificially contaminated fabric 10? XlO? 3 sheets 4 Calculation of cleaning index The cleaning power (DE%) is calculated according to the following formula by measuring the reflectance using a conventional method.The cleaning index is the cleaning power when cleaning under the same conditions using a standard detergent. It is expressed as an index with 100.

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

) and/or Softanol 90" (manufactured by Nippon Shokubai Kagaku Kogyo Co., Ltd., nonionic surfactant), using 30 parts of copolymers (1) to (7) instead 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_4O■ unit and ■C_3H_
It may be combined with the 6O■ unit in any order. ) Polyalkylene glycol monoallyl ether (A) 25 to 70 mol%, general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R_1 and R_2 each represent hydrogen or a methyl group, and Each Y is ■C_2H_4O■
_p■C_3H_6O■_qR_3 (R_3 represents hydrogen or an alkyl group having 1 to 20 carbon atoms, p and q are 0
Or a positive integer, p+q=0 to 100, and ■C_2H
The _4O■ unit and the ■C_3H_6O■ unit may be combined in any order. ), represents a monovalent metal, a divalent metal, an ammonium group, or an organic amine group. ) Maleic acid monomer (b)
25 to 70 mol%, and monomers copolymerizable with these (
c) 0 to 50 mol% (however, (a), (b) and (c)
The sum of the components is 100 mol%. ) is a detergent builder made of a copolymer derived from 2
Detergent surfactants and general formulas▲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. ) Polyalkylene glycol monoallyl ether (A) 25 to 70 mol%, general formula ▲ Numerical formula, chemical formula, table, etc. ▼ (However, in the formula, R_1 and R_2 each represent hydrogen or a methyl group, and Each Y is ■C_2H_4O■
_p■C_3H_6O■_qR_3 (R_3 represents hydrogen or an alkyl group having 1 to 20 carbon atoms, p and q are 0
Or a positive integer, p+q=0 to 100, and ■C_2H
The _4O■ unit and the ■C_3H_6O■ unit may be combined in any order. ), represents a monovalent metal, a divalent metal, an ammonium group, or an organic amine group. ) Maleic acid monomer (b)
25 to 70 mol%, and monomers copolymerizable with these (
c) 0 to 50 mol% (however, (a), (b) and (c)
The sum of the components is 100 mol%. ) A detergent composition comprising a detergent builder comprising a copolymer derived from