JP2009185294A - Builder for liquid detergent and liquid detergent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new builder for a liquid detergent and a new liquid detergent composition including the same, extremely excellent in compatibility with a surfactant, high in transparency of a liquid detergent composition, and moreover remarkably excellent in performance of the detergent. <P>SOLUTION: This builder for the liquid detergent includes a water-soluble copolymer obtained by copolymerizing an unsaturated carboxylic acid-based monomer having a specific structure and a monomer component including an unsaturated alcohol-based monomer having a specific structure as indispensable components. Also the liquid detergent composition includes the builder for the liquid detergent. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a novel liquid detergent builder and liquid detergent composition.

Water-soluble polymers are preferably used for detergent builder applications, for example, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, α-hydroxyacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and citraconic acid. System (co) polymers are well known.
Furthermore, in order to improve the performance for builder use for detergents, research on improving the (co) polymer has been actively conducted in recent years.

The above conventional unsaturated carboxylic acid (co) polymer and its improved product-based detergent builder have been able to exhibit a relatively high level of performance when used as a powder detergent.
However, the above-mentioned conventional detergent builder comprising an unsaturated carboxylic acid (co) polymer has extremely poor compatibility with a surfactant, and therefore has a drawback that it is not suitable for liquid detergent applications.
Therefore, the problem to be solved by the present invention is a novel liquid detergent that is extremely excellent in compatibility with a surfactant, has high transparency when made into a liquid detergent composition, and has excellent detergent performance. And a novel liquid detergent composition comprising the liquid detergent builder.

The present inventor has intensively studied to solve the above problems. As a result, attention was focused on a water-soluble copolymer obtained by copolymerizing a monomer component containing a specific unsaturated carboxylic acid monomer and a specific unsaturated alcohol monomer. And it has been found that the above-mentioned problems that cannot be solved by a builder composed of a conventional unsaturated carboxylic acid (co) polymer can be solved brilliantly by using the specific water-soluble copolymer in a builder for a liquid detergent. It was. The present invention was thus completed.
That is, the builder for liquid detergents according to the present invention is
The unsaturated carboxylic acid monomer (1) represented by any of the following general formulas (1a) to (1c), and the unsaturated alcohol monomer represented by the following general formula (2)

It comprises a water-soluble copolymer obtained by copolymerizing a monomer component essentially containing.
Moreover, the liquid detergent composition which concerns on this invention comprises the builder for liquid detergents of this invention.

  According to the present invention, a novel liquid detergent builder having excellent compatibility with a surfactant, high transparency when used as a liquid detergent composition, and extremely excellent detergent performance, and its liquid Novel liquid detergent compositions comprising detergent builders can be provided.

[Water-soluble copolymer]
The unsaturated carboxylic acid monomer (1) in the present invention is not particularly limited as long as it is a monomer that can be represented by any one of the general formulas (1a) to (1c).
Examples of the monomer that can be represented by the general formula (1a) include acrylic acid, methacrylic acid, crotonic acid, monovalent metals of these acids, partially neutralized products of ammonia and organic amines, Although unsaturated monocarboxylic-acid type monomers, such as a hydrate, are mentioned, It is not limited to these in particular.
Examples of the monomer that can be represented by the general formula (1b) include, for example, maleic acid, fumaric acid, itaconic acid, citraconic acid, monovalent metals of these acids, and partially neutralized products of ammonia and organic amines. Alternatively, unsaturated dicarboxylic acid monomers such as completely neutralized products can be mentioned, but the invention is not particularly limited thereto.

Examples of the monomer that can be represented by the general formula (1c) include, but are not limited to, unsaturated carboxylic acid anhydride monomers such as maleic anhydride and citraconic anhydride.
The unsaturated alcohol monomer (2) that can be used in the present invention is not particularly limited as long as it is a monomer that can be represented by the general formula (2). For example, 3-methyl-3 -C2-C18 alkylene oxide with respect to 1 mol of unsaturated alcohols, such as -buten-1-ol, 3-methyl-2-buten-1-ol, and 2-methyl-3-buten-2-ol. The compound which added 1-300 mol, Preferably 1-100 mol, More preferably, 5-50 mol can be mentioned. Examples of the alkylene oxide having 2 to 18 carbon atoms include styrene oxide, ethylene oxide, propylene oxide and the like, but it is preferable to use ethylene oxide and / or propylene oxide. When ethylene oxide and propylene oxide are used in combination, the bonding order is not limited.

When the added mole number of ethylene oxide and / or propylene oxide is 0 mole, the effect of the present invention cannot be sufficiently exerted, and when it exceeds 300 moles, the improvement of the effect of the present invention is not seen, and a large amount is simply added. This is not preferable because the amount of addition of is necessary.
The water-soluble copolymer in the present invention is obtained by copolymerizing a monomer component essentially containing an unsaturated carboxylic acid monomer (1) and an unsaturated alcohol monomer (2). In the monomer component, in addition to the monomers (1) and (2), if necessary, other monomers copolymerizable with the monomers (1) and (2) May be included.
Although it does not specifically limit as said other monomer, For example, styrene; styrenesulfonic acid; vinyl acetate; (meth) acrylonitrile; (meth) acrylamide; methyl (meth) acrylate; ethyl (meth) acrylate; 2-methylhexyl (meth) acrylate; dimethylaminoethyl (meth) acrylate; diethylaminoethyl (meth) acrylate; allyl alcohol; 3-methyl-3-buten-1-ol; 3-methyl-2-butene-1 2-ol-3-methyl-3-buten-2-ol; 3- (meth) acryloxy-1,2-dihydroxypropane; 3- (meth) acryloxy-1,2-di (poly) oxyethylene ether propane; 3 -(Meth) acryloxy-1,2-di (poly) oxypropi Ether propane; 3- (meth) acryloxy-1,2-dihydroxypropane phosphate and its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt, mono- or Diester; 3- (meth) acryloxy-1,2-dihydroxypropane sulfate and its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt, or ester of an alkyl group having 1 to 4 carbon atoms; (Meth) acryloxy-2-hydroxypropanesulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt, organic amine salt, or ester of an alkyl group having 1 to 4 carbon atoms; 3- (meth) acryloxy- 2- (poly) oxyethylene ether propanesulfonic acid and its monovalent metal salt, divalent metal salt, anne A nium salt, an organic amine salt, or an ester of an alkyl group having 1 to 4 carbon atoms; 3- (meth) acryloxy-2- (poly) oxypropylene ether propanesulfonic acid and its monovalent metal salt, divalent metal salt, Ammonium salt, organic amine salt, or ester of an alkyl group having 1 to 4 carbon atoms; 3-allyloxypropane-1,2-diol; 3-allyloxypropane-1,2-diol phosphate; 3-allyloxypropane -1,2-diol sulfonate; 3-allyloxypropane-1,2-diol sulfate; 3-allyloxy-1,2-di (poly) oxyethylene ether propane; 3-allyloxy-1,2-di (poly) Oxyethylene ether propane phosphate; 3-allyloxy-1,2-di (poly) oxyethylene ether propylene 3-allyloxy-1,2-di (poly) oxypropylene ether propane; 3-allyloxy-1,2-di (poly) oxypropylene ether propane phosphate; 3-allyloxy-1,2-di (poly) 6-allyloxyhexane-1,2,3,4,5-pentaol; 6-allyloxyhexane-1,2,3,4,5-pentaol phosphate; 6-allyloxyhexane -1,2,3,4,5-pentaolsulfonate; 6-allyloxyhexane-1,2,3,4,5-penta (poly) oxyethylene ether hexane; 6-allyloxyhexane-1,2, 3,4,5-penta (poly) oxypropylene ether hexane; 3-allyloxy-2-hydroxypropanesulfur Acid and its monovalent metal salt, divalent metal salt, ammonium salt, or organic amine salt, or phosphoric acid ester or sulfuric acid ester of these compounds and their monovalent metal salt, divalent metal salt, ammonium salt Or an organic amine salt; 3-allyloxy-2- (poly) oxyethylenepropanesulfonic acid and its monovalent metal salt, divalent metal salt, ammonium salt, or organic amine salt, or phosphoric acid of these compounds Esters or sulfates and their monovalent metal salts, divalent metal salts, ammonium salts, or organic amine salts; 3-allyloxy-2- (poly) oxypropylenepropanesulfonic acid and its monovalent metal salts, divalent metals Salt, ammonium salt, organic amine salt, or phosphate ester or sulfur of these compounds Esters and monovalent metal salts thereof, divalent metal salts, ammonium salts, or organic amine salt; and the like.

  The water-soluble copolymer in the present invention is obtained by copolymerizing a monomer component essentially containing an unsaturated carboxylic acid monomer (1) and an unsaturated alcohol monomer (2). The copolymerization method is not particularly limited, and for example, a conventionally known method can be used. Specific examples include polymerization in a solvent such as water, an organic solvent, or a mixed solvent of a water-soluble organic solvent and water. The catalyst system that can be used for these polymerizations is not particularly limited, and examples thereof include persulfates and hydrogen peroxide, and accelerators (such as bisulfite and ascorbic acid) can be used in combination. In addition, azo initiators, organic peroxides, and the like can be used, and accelerators such as amine compounds can be used in combination. From the viewpoint of proceeding the reaction advantageously, a persulfate or a catalyst system using hydrogen peroxide and ascorbic acid in combination is preferable. Further, chain transfer agents such as mercaptoethanol, mercaptopropionic acid and sodium hypophosphite may be used in combination as a molecular weight adjusting agent.

In the case of obtaining the water-soluble copolymer in the present invention, the monomer component containing the unsaturated carboxylic acid monomer (1) and the unsaturated alcohol monomer (2) as an essential component is copolymerized. The ratio of the monomers (1) and (2) in the monomer component is (1) :( 2) = 5: 95 to 95: 5 (weight ratio), preferably 10:90 to 70:30, More preferably, it is 20: 80-60: 40. When the ratio (1) is 5 or less, the chelating power is insufficient. On the other hand, when the ratio of (2) is 5 or less, the scale resistance, which is the effect of introducing a polyethylene glycol chain, decreases.
The water-soluble copolymer in the present invention can be used as it is for various uses as described below, but can be further neutralized with an alkaline substance if necessary. Examples of such an alkaline substance include monovalent and divalent metal hydroxides, chlorides, carbonates and bicarbonates; ammonia; organic amines and the like.

[Builder for liquid detergents]
The builder for liquid detergents according to the present invention is characterized by using the above-mentioned water-soluble copolymer as an essential component.
Specifically, the builder for liquid detergent according to the present invention may be composed of only the above-mentioned water-soluble copolymer, or may be used by mixing with other known detergent builder. Moreover, the water-soluble copolymer used for the builder for liquid detergents based on this invention may be what was further neutralized with the alkaline substance as needed as mentioned above.
Examples of other detergent builders include, but are not limited to, for example, sodium tripolyphosphate, sodium pyrophosphate, sodium silicate, pour glass, sodium carbonate, sodium nitrilotriacetate, sodium ethylenediaminetetraacetate and potassium, zeolite, and polysaccharides. Examples thereof include water-soluble polymers such as carboxyl derivatives, (meth) acrylic acid (co) polymer salts, and fumaric acid (co) polymer salts.

The builder for liquid detergents according to the present invention is very excellent as a liquid detergent because it is highly compatible with a surfactant and used as a highly concentrated liquid detergent composition when used in a liquid detergent composition described later. It is a thing. By being excellent in compatibility with the surfactant, the transparency of the liquid detergent composition is improved, and the problem of separation of the liquid detergent caused by turbidity can be prevented. And by being compatible, it can be set as a highly concentrated liquid detergent composition, and it leads also to the improvement of the detergent capability of liquid detergent.
The builder for liquid detergent according to the present invention is a copolymer excellent in clay dispersibility by comprising the above-mentioned specific water-soluble copolymer. Preferably, the clay dispersibility (calcium carbonate 50 ppm) is 0.3 or more, more preferably 0.5 or more, still more preferably 0.7 or more, and particularly preferably 0.9 or more. When the clay dispersibility (calcium carbonate 50 ppm) is less than 0.3, when used as a builder for a liquid detergent, the effect of increasing the detergency against mud stains is reduced, which is not preferable.

[Liquid detergent composition]
The liquid detergent composition according to the present invention comprises the builder for liquid detergent according to the present invention.
Since the liquid detergent builder according to the present invention contains the liquid detergent builder according to the present invention having excellent compatibility with the surfactant, the liquid detergent composition has excellent transparency and is caused by turbidity. The problem of separation of liquid detergent can be prevented. And by being compatible, it can be set as a highly concentrated liquid detergent composition, and it leads also to the improvement of the detergent capability of liquid detergent.

As one of the measures showing excellent compatibility, turbidity (turbidity, kaolin turbidity) measured using a turbidimeter is useful, and the turbidity of the liquid detergent composition according to the present invention at 25 ° C. The degree value is preferably 200 mg / l or less, more preferably 100 mg / l or less, and still more preferably 50 mg / l or less.
Since the liquid detergent composition according to the present invention includes the builder for liquid detergent according to the present invention that can impart excellent detergent ability, it can also exhibit superior cleaning ability as compared with conventional liquid detergent compositions. it can.
The liquid detergent composition according to the present invention usually contains a detergent surfactant in addition to the liquid detergent builder according to the present invention.

The surfactant is at least one selected from an anionic surfactant, a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant, and these surfactants are used alone or in combination of two or more. Can be used.
Specific examples of anionic surfactants include alkylbenzene sulfonate, alkyl or alkenyl ether sulfate, alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, alkane sulfonate, saturated Examples thereof include unsaturated fatty acid salts, alkyl or alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof.

Specific examples of nonionic surfactants include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin monoester And alkylamine oxide.
Specific examples of the cationic surfactant include quaternary ammonium salts.
Specific examples of the amphoteric surfactant include a carboxyl type or sulfobetaine type amphoteric surfactant.

The compounding ratio of the surfactant contained in the liquid detergent composition according to the present invention is usually 10 to 60% by weight, preferably 15 to 50% by weight in the liquid detergent composition. When the blending ratio of the surfactant is less than 10% by weight, sufficient detergent performance cannot be exhibited. On the other hand, if it exceeds 60% by weight, the economic efficiency is lowered.
The blending ratio of the builder for liquid detergent of the present invention contained in the liquid detergent composition is usually 0.1 to 60% by weight, preferably 3 to 30% by weight in the detergent composition. When the blending ratio of the builder for liquid detergent is less than 0.1% by weight, sufficient detergent performance cannot be exhibited. On the other hand, if it exceeds 60% by weight, the economic efficiency is lowered.

  Various additives conventionally used in detergents can be added to the liquid detergent composition according to the present invention. For example, sodium carboxymethylcellulose to prevent redeposition of contaminants, contamination inhibitors such as benzotriazole and ethylene-thiourea, alkaline substances for pH adjustment, fragrances, fluorescent agents, colorants, foaming agents, foams Stabilizers, polishes, bactericides, bleaches, enzymes, dyes, solvents, etc.

EXAMPLES Hereinafter, although an Example etc. demonstrate this invention further in detail, this invention is not limited to these Examples at all.
In addition, the weight average molecular weight of the water-soluble copolymer obtained in the following synthesis examples was measured as follows.
<Weight average molecular weight measurement (GPC analysis)>
Device: Hitachi L-7000 Series Detector: RI
Column: SB-G, SB-804, SB-803, SB-8 manufactured by SHODEX
02.5
Column temperature: 40 ° C
Calibration curve: POLYACRYLIC ACID STANDARD made by Soka Science Co., Ltd.
GPC software: JASCO BORWIN
Eluent: 0.1 M phosphate buffer (pH 8.0) / acetonitrile = 9/1 (weight ratio)
[Synthesis Example 1]
A 300 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, and an unsaturated alcohol (hereinafter referred to as IPN) obtained by adding 10 mol of ethylene oxide to 3-methyl-2-buten-1-ol. 150 g) and 100 g of pure water were charged, and after replacing with nitrogen, the temperature was raised to 95 ° C. with stirring. When the temperature reached 95 ° C., a solution prepared by dissolving 33.1 g of maleic acid and 6.5 g of ammonium persulfate in 70 g of pure water was added dropwise over 120 minutes. After dropwise addition of the solution, the mixture was aged at the same temperature (95 ± 5 ° C.) for 1 hour to complete the polymerization to obtain a water-soluble copolymer (1). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 2]
An unsaturated alcohol (hereinafter referred to as IPN) obtained by adding 25 moles of ethylene oxide to 3-methyl-2-buten-1-ol to a 200 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube and a dropping funnel. (Referred to as -25) 50 g and 60 g of pure water were charged, and after replacing with nitrogen, the temperature was raised to 95 ° C. with stirring. When the temperature reached 95 ° C., a solution prepared by dissolving 4.13 g of maleic anhydride and 0.96 g of ammonium persulfate in 10 g of pure water was added dropwise over 65 minutes. After the dropwise addition of the solution, the mixture was aged at the same temperature (95 ± 5 ° C.) for 1 hour to complete the polymerization to obtain a water-soluble copolymer (2). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 3]
An unsaturated alcohol (hereinafter referred to as IPN) obtained by adding 50 mol of ethylene oxide to 3-methyl-2-buten-1-ol to a 200 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel. 80 g) and 100 g of pure water were charged. After purging with nitrogen, the temperature was raised to 95 ° C. with stirring. When the temperature reached 95 ° C., 3.4 g of maleic anhydride and 0.8 g of ammonium persulfate dissolved in 10 g of pure water were added dropwise over 60 minutes. After the dropwise addition of the solution, the mixture was aged at the same temperature (95 ± 5 ° C.) for 1 hour to complete the polymerization to obtain a water-soluble copolymer (3). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 4]
A 300 ml separable flask equipped with a stirrer, a condenser, a thermometer, a nitrogen inlet tube, and a dropping funnel is charged with 40.0 g of pure water and 0.0042 g of a Mole salt. After purging with nitrogen, the mixture is refluxed with stirring. The temperature was raised (about 103 ° C.). When the temperature reaches a predetermined temperature, 20 g of pure water is added to a solution obtained by adding 28 g of pure water to 70 g of IPN-10, 27.6 g of 80% methacrylic acid (MAA) aqueous solution, and 8.55 g of 35% hydrogen peroxide water. .4 g of the added solution was added dropwise over 120 minutes. After dropwise addition of the solution, the mixture was aged at reflux temperature for 1 hour to complete the polymerization and obtain a water-soluble copolymer (4). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 5]
A 1000 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel was charged with 451.0 g of pure water, and the temperature was raised to 75 ° C. while stirring, after stirring. When the temperature reached a predetermined temperature, 130.0 g of 3% by weight aqueous ammonium persulfate solution, 191.0 g of 50% by weight IPN-10 aqueous solution, 33.0 g of 80% aqueous acrylic acid solution and 195.0 g of 40% ammonium acrylate were mixed. Each aqueous solution was added dropwise. However, IPN-10 and the acrylic acid monomer were dropped over 120 minutes, and the aqueous ammonium persulfate solution was dropped over 150 minutes. After completion of dropping of IPN-10 and acrylic acid monomer, the temperature was raised to 100 ° C. After completion of the dropwise addition of the ammonium persulfate aqueous solution, the mixture was aged at the same temperature for 30 minutes to complete the polymerization. After the polymerization, 22.4 g of 28% ammonium water was added to obtain a water-soluble copolymer (5). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 6]
In a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, 113.0 g of pure water was charged, and the temperature was raised to the reflux temperature while stirring, after stirring. When the temperature reaches a predetermined temperature, 32.5 g of 3% by weight ammonium persulfate aqueous solution, 47.6 g of 50% by weight IPN-10 aqueous solution, 8.25 g of 80% aqueous acrylic acid solution and 48.75 g of 40% ammonium acrylate are mixed. Each aqueous solution was added dropwise. However, IPN-10 and the acrylic acid monomer were dropped over 120 minutes, and the aqueous ammonium persulfate solution was dropped over 150 minutes. After completion of the dropwise addition of the ammonium persulfate aqueous solution, the mixture was aged at the same temperature for 30 minutes to complete the polymerization. After the polymerization, 5.46 g of 28% ammonium water was added to obtain a water-soluble copolymer (6). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 7]
A 1000 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel was charged with 500.0 g of pure water, and the temperature was raised to 75 ° C. while stirring, after stirring. When the temperature reaches a predetermined temperature, 130.0 g of 3% by weight aqueous ammonium persulfate solution, 26.7 g of 100% by weight IPN-10 aqueous solution, 164.3 g of water, 33.0 g of 80% aqueous acrylic acid solution and 40% ammonium acrylate An aqueous solution in which 195.0 g was mixed was dropped. However, IPN-10 and the acrylic acid monomer were dropped over 120 minutes, and the aqueous ammonium persulfate solution was dropped over 150 minutes. After completion of dropping of IPN-10, water and acrylic acid monomer, the temperature was raised to 100 ° C. After completion of the dropwise addition of the ammonium persulfate aqueous solution, the mixture was aged at the same temperature for 30 minutes to complete the polymerization. After the polymerization, 22.4 g of 28% ammonium water was added to obtain a water-soluble copolymer (7). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 8]
A 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel was charged with 100 g of a 60 wt% IPN-10 aqueous solution, and the temperature was raised to 65 ° C. while stirring, after stirring. When the temperature reached a predetermined temperature, 51.7 g of 0.6% by weight hydrogen peroxide solution was added all at once. Thereafter, 24.5 g of 100 wt% acrylic acid, 80.0 g of 0.5 wt% aqueous L-ascorbic acid solution, and 63.0 g of 1 wt% mercaptopropionic acid aqueous solution were added dropwise. However, acrylic acid monomer and mercaptopropionic acid were added dropwise over 60 minutes, and L-ascorbic acid was added dropwise over 90 minutes. After completion of the dropwise addition of the L-ascorbic acid aqueous solution, the mixture was aged at the same temperature for 120 minutes to complete the polymerization, thereby obtaining a water-soluble copolymer (8). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 9]
A 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel was charged with 100 g of a 60 wt% IPN-10 aqueous solution, and the temperature was raised to 65 ° C. while stirring, after stirring. When the temperature reached a predetermined temperature, 25.8 g of 0.6 wt% hydrogen peroxide solution was added all at once. Thereafter, 8.2 g of 100 wt% acrylic acid, 40.0 g of 0.5 wt% aqueous L-ascorbic acid solution, and 18.0 g of 1 wt% mercaptopropionic acid aqueous solution were added dropwise. However, acrylic acid monomer and mercaptopropionic acid were added dropwise over 60 minutes, and L-ascorbic acid was added dropwise over 90 minutes. After completion of the dropwise addition of the L-ascorbic acid aqueous solution, the mixture was aged at the same temperature for 120 minutes to complete the polymerization, thereby obtaining a water-soluble copolymer (9). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 10]
A 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel was charged with 167.0 g of pure water, and the temperature was raised to the reflux temperature while stirring, after stirring. When the temperature reaches a predetermined temperature, 32.5 g of 3% by weight ammonium persulfate aqueous solution, 82.67 g of 50% by weight IPN-10 aqueous solution, 8.25 g of 80% aqueous acrylic acid solution and 48.75 g of 40% ammonium acrylate are mixed. Each aqueous solution was added dropwise. However, IPN-10 and the acrylic acid monomer were dropped over 120 minutes, and the aqueous ammonium persulfate solution was dropped over 150 minutes. After completion of the dropwise addition of the ammonium persulfate aqueous solution, the mixture was aged at the same temperature for 30 minutes to complete the polymerization. After the polymerization, 5.5 g of 28% ammonium water was added to obtain a water-soluble copolymer (10). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 11]
A 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel was charged with 167.24 g of pure water, and the temperature was raised to the reflux temperature while stirring, after stirring. When the temperature reaches a predetermined temperature, 28.9 g of 3 wt% ammonium persulfate aqueous solution, 82.67 g of 50 wt% IPN-25 aqueous solution, 8.25 g of 80% acrylic acid aqueous solution and 48.75 g of 40% ammonium acrylate are mixed. Each aqueous solution was added dropwise. However, IPN-25 and acrylic acid monomer were added dropwise over 120 minutes, and the aqueous ammonium persulfate solution was added dropwise over 150 minutes. After completion of the dropwise addition of the ammonium persulfate aqueous solution, the mixture was aged at the same temperature for 30 minutes to complete the polymerization. After the polymerization, 5.5 g of 28% ammonium water was added to obtain a water-soluble copolymer (11). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 12]
A 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel was charged with 167.24 g of pure water, and the temperature was raised to the reflux temperature while stirring, after stirring. When the temperature reaches a predetermined temperature, 27.4 g of 3% by weight ammonium persulfate aqueous solution, 82.67 g of 50% by weight IPN-50 aqueous solution, 8.25 g of 80% aqueous acrylic acid solution and 48.75 g of 40% ammonium acrylate are mixed. Each aqueous solution was added dropwise. However, IPN-50 and acrylic acid monomer were dropped over 120 minutes, and the aqueous ammonium persulfate solution was dropped over 150 minutes. After completion of the dropwise addition of the ammonium persulfate aqueous solution, the mixture was aged at the same temperature for 30 minutes to complete the polymerization. After the polymerization, 5.5 g of 28% ammonium water was added to obtain a water-soluble copolymer (12). The physical properties of the obtained polymer are shown in Table 1.

[Synthesis Example 13]
A 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel was charged with 100 g of a 60 wt% IPN-10 aqueous solution, and the temperature was raised to 65 ° C. while stirring, after stirring. When the temperature reached a predetermined temperature, 28.3 g of 0.6 wt% hydrogen peroxide water was added all at once. Thereafter, 9.8 g of 100 wt% acrylic acid, 44.0 g of 0.5 wt% aqueous L-ascorbic acid solution, and 34.5 g of 1 wt% mercaptopropionic acid aqueous solution were dropped. However, acrylic acid monomer and mercaptopropionic acid were added dropwise over 60 minutes, and L-ascorbic acid was added dropwise over 90 minutes. After completion of the dropwise addition of the L-ascorbic acid aqueous solution, the mixture was aged at the same temperature for 120 minutes to complete the polymerization. After the polymerization, 45 g of a 20% NaOH aqueous solution was added to obtain a water-soluble copolymer (13). The physical properties of the obtained polymer are shown in Table 1.

[Example 1]
The water-soluble copolymer obtained in the above synthesis example was used as a builder for liquid detergent, and the calcium ion scavenging ability and clay dispersibility were evaluated as follows. The results are shown in Table 2.
<Calcium ion scavenging ability>
As a calcium ion standard solution for a calibration curve, 50 g of 0.01 mol / l, 0.001 mol / l, 0.0001 mol / l aqueous solutions were prepared using calcium chloride dihydrate, and 4.8% NaOH aqueous solution was used. Adjust to pH 9 to 11, add 1 ml of 4 mol / l potassium chloride aqueous solution (hereinafter abbreviated as 4M-KCl aqueous solution), and further stir well using a magnetic stirrer to prepare a sample solution for calibration curve did. In addition, as a test calcium ion standard solution, a necessary amount (50 g per sample) of a 0.001 mol / l aqueous solution was similarly prepared using calcium chloride dihydrate.

Next, 10 mg of the test sample (polymer) in a 100 cc beaker was weighed in terms of solid content, 50 g of the above-mentioned calcium ion standard solution for test was added, and the mixture was sufficiently stirred using a magnetic stirrer. Further, as with the calibration curve sample, a pH of 9 to 11 was adjusted with a 4.8% NaOH aqueous solution, and 1 ml of 4M-KCl aqueous solution was added to prepare a test sample solution.
The calibration curve sample solution and the test sample solution thus prepared were measured with a calcium ion electrode 93-20 and a reference electrode 90-01 manufactured by Orion Co., Ltd. using a titration device COMITE-550 manufactured by Hiranuma Sangyo Co., Ltd. I did it.

From the calibration curve and the measured value of the sample solution for the test, the amount of calcium ions captured by the sample (polymer) is obtained by calculation, and the value is expressed in mg of calcium carbonate equivalent of the amount captured per 1 g of polymer solids. This value was defined as the calcium ion scavenging ability value.
<Clay dispersibility (50 ppm calcium carbonate)>
Pure water was added to 67.56 g of glycine, 52.6 g of sodium chloride, and 2.4 g of NaOH to make 600 g (this is referred to as buffer (1)). 0.0817 g of calcium chloride dihydrate was added to 60 g of buffer (1), and pure water was further added to make 1000 g (this is referred to as buffer (2)). 36 g of buffer (2) was added to 4 g of a 0.1 wt% aqueous solution (in terms of solid content) of the copolymer to be measured, and stirred to obtain a dispersion. After putting 0.3 g of clay (made by Japan Powder Industrial Technology Association, 11 types of test dust) into a test tube (IWAKI GLASS: diameter 18 mm, height 180 mm), add 30 g of the above dispersion and seal To do.

The test tube was shaken to uniformly disperse the clay. Thereafter, the test tube was left in a place not exposed to direct sunlight for 20 hours. After 20 hours, 5 cc of the supernatant of the dispersion was taken and the absorbance was measured with a UV spectrometer (Shimadzu Corporation, UV-1200; 1 cm cell, wavelength 380 nm).
<Clay dispersibility (calcium carbonate 200ppm)>
Pure water was added to 67.56 g of glycine, 52.6 g of sodium chloride, and 2.4 g of NaOH to make 600 g (this is referred to as buffer (1)). To 60 g of buffer (1), 0.3268 g of calcium chloride dihydrate was added, and pure water was further added to make 1000 g (this is referred to as buffer (3)). 36 g of buffer (3) was added to 4 g of a 0.1 wt% aqueous solution (in terms of solid content) of the copolymer to be measured, and stirred to obtain a dispersion. After putting 0.3 g of clay (made by Japan Powder Industrial Technology Association, 11 types of test dust) into a test tube (IWAKI GLASS: diameter 18 mm, height 180 mm), add 30 g of the above dispersion and seal To do.

  The test tube was shaken to uniformly disperse the clay. Thereafter, the test tube was left in the dark for 20 hours. After 20 hours, 5 cc of the supernatant of the dispersion was taken and the absorbance was measured with a UV spectrometer (Shimadzu Corporation, UV-1200; 1 cm cell, wavelength 380 nm).

[Examples 2 to 6, Comparative Example 1]
The water-soluble copolymer obtained in the above synthesis example was used as a builder for liquid detergents, and the recontamination prevention performance was evaluated. That is, a cotton cloth (JIS-L0803 cotton cloth (gold width 3)) is cut into 5 cm × 5 cm to form a set of 8 sheets, and clay and 8 white cloths are added to 1 L of the detergent aqueous solution for evaluation containing the copolymer to be measured, The test was conducted with a targotometer under the following conditions. As a comparative example, the case where no builder was added was also evaluated. The results are shown in Table 3.
<Test conditions>
Detergent concentration: The following detergent formulation was used, and the surfactant (SFT-70H) concentration was added to 350 ppm.

Detergent formulation: SFT-70H (Softanol 70H, Nippon Shokubai Co., Ltd.,
Polyoxyethylene alkyl ether); 50 g
Diethanolamine; 10g
Ethanol; 5 g
Propylene glycol; 5g
Water; 30g
Builder addition amount: 44ppm (solid content conversion)
Water hardness: 3 ° DH (53.6 ppm, converted to calcium carbonate)
Water temperature: 25 ° C
Amount of water used: 1 L including detergent and polymer.

Use cloth: Cotton cloth (JIS-L0803 cotton cloth (gold width 3)), 5 cm × 5 cm,
8 pieces of clay: 11 kinds of test dust (Kanto loam, ultra fine particles) (Japan Powder Industrial Technology Cooperation)
Meeting)
Washing time: 10 minutes (tergotometer 100 rpm)
Rinse time: 2 minutes (tartometer 100 rpm)
Test method: Washing and rinsing were repeated three times, and the reflectance (hunter whiteness) of the untreated cloth (white cloth) and the contaminated cloth after the test was measured with a color difference meter (manufactured by Nippon Denshoku Industries Co., Ltd .: SE2000). Then, the recontamination prevention rate was obtained by the following equation.

    Recontamination prevention rate (%) = (reflectance after test / reflectance of base fabric) × 100

[Examples 7 to 11, Comparative Example 2]
The water-soluble copolymer obtained in the above synthesis example was used as a builder for liquid detergent, and a detergency test was performed to evaluate the performance of the liquid detergent composition containing the builder. In other words, wet artificially contaminated cloth (made by the Laundry Science Association) is used in a set of 5 sheets, 5 sheets of contaminated cloth are added to 500 mL of an evaluation detergent aqueous solution containing a polymer, and a targotometer is used under the following conditions. A test was conducted. The results are shown in Table 4. In addition, the numerical value of the addition amount in a table | surface represents solid content or active ingredient conversion, and the numerical value of a detergent mixing | blending and a builder amount represents weight%.
<Test conditions>
Detergent concentration: The following detergent formulation was used, and the surfactant (SFT-70H, Neoperex F-65) concentration was added to 350 ppm.

Detergent formulation: SFT-70H (Softanol 70H, Nippon Shokubai Co., Ltd.,
Polyoxyethylene alkyl ether); 10 g
Neoperex F-65 (made by Kao Corporation, dodecylbenzenesulfur
Sodium fonate); 46.2 g (active ingredient 30 g)
Diethanolamine; 10g
Ethanol; 5 g
Propylene glycol; 15g
Water; 13.8 g
Polymer addition amount: 44 ppm (solid content conversion)
Water hardness: 3 ° DH (53.6 ppm, converted to calcium carbonate)
Water temperature: 25 ° C
Water consumption: 500mL
Contaminated cloth: Made by Laundry Science Association, wet artificial contaminated cloth Washing time: 10 minutes (Targometer 100 rpm)
Rinse time: 2 minutes (tartometer 100 rpm)
Test method: After washing and rinsing, the reflectance (hunter whiteness) of the raw cloth (contaminated cloth) before washing and the contaminated cloth after the test is measured with a color difference meter (Nippon Denshoku Industries Co., Ltd., SE2000). The washing rate was determined by the following formula.

Washing rate (%) = ((reflectance of contaminated cloth after washing−reflectance of contaminated cloth before washing) /
(Reflectance of white cloth-reflectance of contaminated cloth before washing)) × 100

[Examples 12 to 54, Comparative Examples 3 to 8]
About the liquid detergent composition containing the water-soluble copolymer obtained by the said synthesis example, the compatibility evaluation with respect to liquid detergent was performed.
That is, various detergent compositions were prepared using the water-soluble copolymers obtained in Synthesis Examples and the components described in Tables 5 to 10 below. The mixture was sufficiently stirred so that each component was uniform, and after removing bubbles, the turbidity value at 25 ° C. was measured. Turbidity value measured Turbidity (kaolin turbidity: mg / l) using NDH2000 (turbidimeter) manufactured by Nippon Denshoku Co., Ltd.
The evaluation results were based on the following three stages.

○: Turbidity value (0 to 50), not visually separated, precipitated or clouded.
Δ: Turbidity value (50 to 200), slightly clouded visually.
X: Turbidity value (200 or more), visually turbid.
The above results are shown in Tables 5-10. In addition, the numerical value of the addition amount in a table | surface represents solid content or active ingredient conversion, and the numerical value of a detergent mixing | blending and a builder amount represents weight%. Further, Cotamine 86W in the table represents stearyltrimethylammonium chloride manufactured by Kao Corporation.
As a comparative sample, polyacrylic acid Na (weight average molecular weight Mw 7000, manufactured by Nippon Shokubai Co., Ltd.) was used.

Claims (3)

The unsaturated carboxylic acid monomer (1) represented by any of the following general formulas (1a) to (1c), and the unsaturated alcohol monomer represented by the following general formula (2)

Comprising a water-soluble copolymer obtained by copolymerizing a monomer component essentially containing
Builder for liquid detergent.   The builder for liquid detergents of Claim 1 whose clay dispersibility (50 ppm of calcium carbonate) is 0.3 or more.   A liquid detergent composition comprising the builder for liquid detergent according to claim 1 or 2.