JP2003292617A - Water-soluble polymer, process for producing it and its use - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new water-soluble polymer excellent in re-contamination preventing property, a process for producing the water-soluble polymer and a detergent composition using the polymer. <P>SOLUTION: The water-soluble polymer has a structural unit represented by formula (1) and has an amine number of not less than 3.0 mmol/g (in formula (1), R<SP>1</SP>is -H or -CH<SB>3</SB>; R<SP>2</SP>is -H, -CH<SB>3</SB>, -CH<SB>2</SB>COOM or -CH<SB>2</SB>OH; X is -NH-, NR<SP>3</SP>- or -S-; R<SP>3</SP>is -CH<SB>3</SB>, -CH<SB>2</SB>CH<SB>3</SB>-, -CH<SB>2</SB>COOM or -CH<SB>2</SB>OH; M is R<SP>2</SP>and R<SP>3</SP>are each independently H, an alkali metal or an alkaline earth metal; and n is an integer of not less than 1). The process for producing the water-soluble polymer comprises carrying out Michael addition and polymerization by using an amide compound having a specific structure. The detergent composition comprises the water-soluble polymer. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a water-soluble polymer useful for detergent applications, a method for producing the same, and the application thereof.

[0002]

2. Description of the Related Art It has been conventionally known that maleic acid-based copolymers having a carboxyl group exhibit excellent chelating action and dispersing action, and are used for detergent compositions, fiber treatment agents,
It is widely used for applications such as dispersants, flocculants, scale inhibitors, chelating agents, bleaching aids, and pH adjusters. Among them, when the detergent composition is used, it is required to have excellent calcium ion-capturing ability and clay-dispersing ability as basic performance, and at the same time, there is an extremely high need for chelating ability of heavy metal ions such as iron. . In other words, when viewed globally, there are areas where the content of iron ions in wash water is high, and since wash water is usually weakly basic, iron ions become iron particles (iron hydroxide) and adhere to clothing, causing yellowing. However, in such areas, chelating ability for iron ions is especially required. In Japan's tap water, there are no areas with a particularly high iron ion concentration, but iron ions derived from dirt or the like may cause yellowing or cause stains on black tea or blood to be difficult to remove. The need for Noh is strong.

Also, when the fiber treatment agent is used,
Especially in the bleaching process, when heavy metal ions are present in the processing solution, the peroxide, which is the main component of the bleaching agent, is catalytically decomposed, and the peroxide is wasted. It is necessary to capture and inactivate heavy metal ions, specifically, copper ions, which have a particularly high activity.

[0004]

DISCLOSURE OF INVENTION Problems to be Solved by the Invention The inventors of the present invention have proposed, as a novel water-soluble polymer for solving the above-mentioned problems, JP-A-2000
JP-A-319385, in addition to a large number of carboxyl groups directly linked to the polymer main chain, at least one functional group selected from an amide group, an amino group and a thioether group, which is effective for capturing heavy metal ions, is added to the polymer main chain. Polymers with a large number and easily incorporated in the chain have been proposed. This polymer is excellent in any of iron ion deposition preventing ability, clay dispersing ability, and copper ion hydrogen peroxide stabilizing ability, and is very useful for detergent compositions, fiber treating agents, etc.,
In particular, when it is used in a detergent composition, it has been desired that the anti-soil redeposition ability is excellent.

Therefore, it is an object of the present invention to provide a novel water-soluble polymer having an excellent anti-soil redeposition ability, a method for producing the same, and a detergent composition using the polymer.

[0006]

The water-soluble polymer according to the present invention has a structural unit represented by the following general formula (1),
It has an amine value of 3.0 mmol / g or more.

[0007]

[Chemical 4]

(In the formula (1), R ¹ is -H or -C.
H ₃ and R ² is —H, —CH ₃ , —CH ₂ COOM,
Or —CH ₂ OH, X is —NH—, —NR
³ -, or a -S-, R ³ is, -CH _3, -CH ₂ C
H ₃ , —CH ₂ COOM, or —CH ₂ OH, and M
Are independently of each other H, an alkali metal, or an alkaline earth metal, and n is an integer of 1 or more. ) In the method for producing a water-soluble polymer according to the present invention, an amide compound represented by the following general formula (2) is subjected to Michael addition polymerization.

[0009]

[Chemical 5]

(In the formula (2), R ¹ is --H or --C
H ₃ and R ² is —H, —CH ₃ , —CH ₂ COOM,
Or —CH ₂ OH, X is —NH—, —NR
³ -, or a -S-, R ³ is, -CH _3, -CH ₂ C
H ₃ , —CH ₂ COOM, or —CH ₂ OH, and M
Are independently of each other H, an alkali metal, or an alkaline earth metal, and n is an integer of 1 or more. Further, in a preferred mode of the method for producing a water-soluble polymer according to the present invention, the amide compound is obtained by using an amine compound represented by the following general formula (3) and a maleic acid.

[0011]

[Chemical 6]

(In the formula (3), X is --NH--, --NR ³
-, or a -S-, R ³ is, -CH _3, -CH ₂ C
H ₃ , —CH ₂ COOM, or —CH ₂ OH, and M
Are independently of each other H, an alkali metal, or an alkaline earth metal, and n is an integer of 1 or more. ) A detergent composition according to the present invention contains the water-soluble polymer of the present invention.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION (Water-Soluble Polymer) The water-soluble polymer of the present invention is a homopolymer or a copolymer having the structural unit represented by the general formula (1). When the water-soluble polymer of the present invention is a copolymer, the other structural unit is not particularly limited as long as it has at least the structural unit represented by the general formula (1), and other structural units such as those described later may be used. It may include a structural unit derived from a polymer. The proportion of the structural unit represented by the general formula (1) in the water-soluble polymer structure of the present invention is 80 to 100% by mole ratio, preferably 90 to 100% by mole ratio, More preferably, the molar ratio is 100%.

The water-soluble polymer of the present invention preferably has a weight average molecular weight of 500 to 100,000, more preferably 500 to 50,000, and still more preferably 5.
00 to 20000, particularly preferably 1000 to 20
000, most preferably 1400 to 15000.
The water-soluble polymer of the present invention has an amine value of 3.0 mmol / g
The above is characterized. Since the water-soluble polymer of the present invention has a large number of amino groups in the polymer main chain, it is possible to improve the adsorptivity to cloth, and thereby to exhibit an excellent anti-soil redeposition ability. The amine value is preferably 4.0 mmol / g or more, more preferably 5.0 mmol / g or more.

The water-soluble polymer of the present invention preferably has a calcium ion-capturing ability of 20 mgCaCO ₃ / g or more. Thereby, a more excellent recontamination preventing ability can be exhibited. The calcium ion-capturing ability is preferably 25 mgCaCO ₃ / g or more, more preferably 30
It is preferable that the content is mgCaCO ₃ / g or more. The water-soluble polymer of the present invention has, in addition to a large number of carboxyl groups directly linked to the polymer main chain, at least one functional group selected from an amide group, an amino group and a thioether group, which is effective for capturing heavy metal ions. Since it is introduced in large numbers in the polymer main chain, it has excellent anti-soil redeposition ability as described above, and at the same time, it has iron ion deposition prevention ability, clay dispersion ability, and copper ion hydrogen peroxide stabilization ability. Has excellent ability. Specifically, the iron ion deposition preventing ability is preferably 30% or more, the clay dispersing ability is 20% or more, and the copper ion hydrogen peroxide stabilizing ability is 20% or more, more preferably the iron ion depositing inhibiting ability. Is 40% or more, the clay dispersing ability is 30% or more, and the copper ion hydrogen peroxide stabilizing ability is 30% or more.
Further, when focusing only on the iron ion deposition preventing ability, it is preferably 30% or more, further preferably 40% or more, even more preferably 50% or more, and when focusing only on the clay dispersing ability, preferably 20% or more. , More preferably 30% or more, and when focusing solely on the copper ion hydrogen peroxide stabilizing ability, preferably 20% or more, more preferably 30% or more, even more preferably 45% or more, and most preferably 60%. That is all.

Since the water-soluble polymer of the present invention has the above-mentioned excellent performance, it is suitable for use in detergent compositions, fiber treatment agents, and peroxide stabilizers. It may be used as an inorganic pigment dispersant, a water treatment agent, a pulp bleaching aid, a corrosion inhibitor, a cement additive and the like. (Production Method of Water-Soluble Polymer) The production method of the water-soluble polymer of the present invention requires the amide compound represented by the general formula (2) as an essential component and, if necessary, also contains other monomers. Is subjected to Michael addition polymerization.

The amide compound represented by the general formula (2) can be obtained, for example, by an amidation reaction of an acid anhydride or ester with an amine compound. Examples of acid anhydrides and esters include R in the general formulas (1) and (2).
^Although various compounds can be mentioned depending on the selection of ¹ and R ² , maleic acids such as maleic anhydride, monomethyl maleate, dimethyl maleate, monoethyl maleate and diethyl maleate are particularly preferably used. As the amine compound, the amine compound represented by the general formula (3) is preferable, and specifically, for example, X in the general formulas (1) and (2) is —NH— or —NR.
^In the case of ^3- , diethylenetriamine, triethylenetetramine, tetraethylenepentamine, tris (2-aminoethyl) amine and the like can be mentioned. When X is -S-, aminoethylmercaptoethylethylamine and the like can be mentioned. Among them, especially diethylenetriamine,
Triethylenetetramine is preferred.

A preferred form of the production method of the present invention is to obtain the amide compound by using the amine compound represented by the general formula (3) and the maleic acid, and the amide compound will be described below. It can be obtained by an amidation reaction. In the production method of the present invention, after obtaining an amide compound by an amidation reaction described below, the obtained amide compound may be once isolated and subjected to Michael addition polymerization. You may make it carry out addition polymerization. Examples of the method for the amidation reaction between the acid anhydride or ester and the amine compound include, for example, 1) conversion of an amine compound in an aqueous solvent (preferably in water) into an acid anhydride (a solid one is preferably powdered). ) Is gradually added with stirring to amidate. 2) A method of amidating an acid anhydride and an amine compound or a hydrolyzate of an acid anhydride and an amine compound in an inert organic solvent such as toluene or xylene by a conventionally known method.
3) A method of amidating a monoester of an acid anhydride and an amine compound by a conventionally known transesterification reaction in an inert organic solvent such as toluene or xylene. Etc., but the method of 1) is preferable. The method of 1) does not require an organic solvent removal step or the like because it is synthesized with an aqueous solvent, and since it is possible to synthesize at a high concentration, it is safe, environmentally friendly, and economical. Preferably
Furthermore, the polymerization in the next step is also preferable in that it is carried out with an aqueous solvent (preferably water).

The aqueous solvent used in the above method 1) is preferably water, but in order to improve the solubility of the amine, preferably an aqueous solvent having no active proton is appropriately added in an amount of 10% or less. May be. Specifically, lower alcohols such as methanol, ethanol and isopropyl alcohol; amides such as dimethylformamide;
One kind or two or more kinds can be appropriately selected and used from ethers such as diethyl ether and dioxane; and the like. The temperature of the amidation reaction is preferably 50 ° C or lower, more preferably 40 ° C or lower, and further preferably 30 ° C or lower. When the temperature exceeds 50 ° C, simple hydrolysis of the acid anhydride proceeds rather than the amidation reaction, which is not preferable. The reaction time is preferably such that the acid anhydride is added substantially continuously over 10 minutes or more, and after all the acid anhydride is added, aging is further performed for 10 minutes or more.

In the amidation reaction of the acid anhydride or ester with the amine compound, an acid is generated as the reaction proceeds, and the amine compound may be neutralized to decrease the reaction rate. In such a case, the basic compound may be added in an amount corresponding to the neutralized amine, and for example, an alkali metal hydroxide such as sodium hydroxide may be used. The molecular weight of the amide compound is 100 to
It is preferably 1,000, more preferably 150 to 800, further preferably 180 to 500.

The other monomer is not particularly limited as long as it is a monomer capable of Michael addition polymerization with the amide compound represented by the general formula (2). Examples thereof include amide compounds in which n = 0 in 2) and amide compounds having no —COOM in general formula (2). When the other monomer is also used, the content of the other monomer is preferably less than 20 mol% based on the total amount of the amide compound represented by the general formula (2), More preferably, it is less than 10 mol%. As a polymerization method for carrying out the Michael addition polymerization in the present invention, solution polymerization is preferable, and in this case, either stirring or standing may be performed.

The solvent for carrying out the solution polymerization is preferably an aqueous solvent, more preferably water. Further, in order to improve the solubility of the monomer, preferably, an aqueous solvent having no active proton may be appropriately added in an amount of 10% or less. Specifically, one kind or two or more kinds can be appropriately selected and used from lower alcohols such as methanol, ethanol and isopropyl alcohol; amides such as dimethylformamide; ethers such as diethyl ether and dioxane. . A catalyst for carrying out the solution polymerization is basically unnecessary, but may be appropriately used if necessary so long as it does not adversely affect the polymerization.

The concentration of the monomer used in the solution polymerization is not particularly limited, but is preferably 10% or more, more preferably 20% or more. The pH of the polymerization solution is arbitrary, but in Michael addition polymerization, a higher pH generally has better polymerizability and depends on the solubility of the monomer, but is preferably 7 or more, more preferably 10 or more. Is. The polymerization temperature during the solution polymerization is preferably 20 to 100 ° C., and preferably 80 ° C. or lower in order to prevent cleavage of the amide bond. The polymerization time is not particularly limited, and the polymerization pressure may be normal pressure (atmospheric pressure), increased pressure, or reduced pressure. (Detergent Composition) The detergent composition of the present invention essentially contains the water-soluble polymer of the present invention, and usually further contains a surfactant described below. The content of the water-soluble polymer in the detergent composition is 0.1 to 20% by weight, and the content of the surfactant is 5.
It is preferably about 70% by weight. More preferably,
The content of the water-soluble polymer is 0.5 to 15% by weight, and the content of the surfactant is 20 to 60% by weight.

As the surfactant, at least one selected from the group consisting of anionic surfactants, nonionic surfactants, amphoteric surfactants and cationic surfactants can be preferably used. Examples of the anionic surfactant 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 or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N
Mention may be made of acylamino acid type surfactants, alkyl or alkenyl phosphate esters or salts thereof.

Examples of nonionic surfactants include polyoxyalkylene alkyl or alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, sucrose fatty acid esters, alkylglycoxides, and fatty acid glycerin mono. Examples thereof include esters and alkylamine oxides. Examples of the amphoteric surfactant include a carboxy type or sulfobetaine type amphoteric surfactant, and examples of the cationic surfactant include a quaternary ammonium salt.

The detergent composition of the present invention may optionally contain an enzyme. As the enzyme, protease, lipase, cellulase or the like can be used.
Particularly, protease, alkaline lipase and alkaline cellulase which have high activity in the alkaline washing solution are preferable.
The blending amount of the enzyme is preferably 0.01 to 5% by weight. If the amount is out of this range, the balance with the surfactant is lost and the detergency cannot be improved. The detergent composition of the present invention contains, if necessary, known components such as alkali builder, chelate builder, anti-redeposition agent, fluorescent agent, bleaching agent and perfume, which are commonly used in detergent compositions and zeolite. Good. Alkali builders include silicates, carbonates,
Sulfate or the like can be used. As a chelate builder, diglycolic acid, oxycarboxylic acid salt, EDTA
(Ethylenediaminetetraacetic acid), DTPA (diethylenetriaminehexaacetic acid), citric acid and the like can be used as necessary.

The detergent composition of the present invention is excellent in anti-soil redeposition ability, and at the same time excellent in trapping heavy metal ions such as iron ions present in the washing liquid and in clay dispersing ability. Therefore, for example, detergent for clothes. As very effective. Further, the detergent composition of the present invention can be used as a powder detergent, a liquid detergent or a gel detergent.

[0028]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. The weight average molecular weight, amine value and calcium ion trapping ability of the polymers obtained in the examples were measured as follows. <Weight average molecular weight> The weight average molecular weight was measured by gel permeation chromatography (GPC) analysis under the following conditions. Device: Hitachi L-7000 series Detector: RI Column: SHODEX SB-G ＋ SB-804HQ ＋ SB-803HQ ＋ SB-8
02.5HQ Column temperature: 40 ℃ Calibration curve: GL Sciences "POLYET HYLENE OXIDE"
"STANDARD" GPC software: "BORWIN" manufactured by JASCO Corporation Eluent: 0.5M acetic acid + 0.5M sodium acetate Flow rate: 0.8 ml / min <Amine number> Test sample (polymer) solid concentration of 0.
It was prepared to be a 5% by weight aqueous solution. The obtained 0.
Weigh 0.8 g of 5 wt% aqueous solution, and add 70 g of deionized water.
After diluting to g, the pH was adjusted to 2.0 with 0.1N hydrochloric acid. Further, 4 drops of toluidine blue indicator were added, and with good stirring, colloid titration was performed with a N / 400 polyvinyl potassium sulfate (hereinafter abbreviated as PVSK) solution, and the amine value was calculated from the following formula. The end point was the point at which the color changed from blue to purple. Amine value (mmol / g) = (f × N × a) / (sample amount (0.8 g) × solid content concentration (0.5 wt%) / 10
0) f: Factor of PVSK N: Normality of PVSK (N / 400) a: PVSK titration amount of measurement sample (ml) <Calcium ion scavenging ability> First, using calcium chloride dihydrate, 0.01 mol / L, 0.001 mol
/ L, 0.0001 mol / L aqueous solution of 50 g each was prepared and used as a calcium ion standard solution for a calibration curve. Calcium ion standard solution for this calibration curve is 4.8% N
Adjust to pH 9-11 with aq.
mol / L potassium chloride aqueous solution (hereinafter 4M-KCl
1 ml of an aqueous solution) was added and sufficiently stirred with a magnetic stirrer to prepare a sample solution for a calibration curve.
In addition, 0.001mo using calcium chloride dihydrate
A necessary amount (50 g per sample) of an aqueous solution of 1 / L was prepared and used as a test calcium ion standard solution.

Next, a test sample (polymer) was weighed in an amount of 10 mg in terms of solid content in a 100 cc beaker, 50 g of a test calcium ion standard solution was added, and the mixture was sufficiently stirred with a magnetic stirrer and further 4.8%. The pH was adjusted to a range of 9 to 11 with an aqueous NaOH solution, and 1 ml of a 4M-KCl aqueous solution was added to prepare a test sample solution. Regarding the prepared calibration curve sample solution and test sample solution, a titrator (“COMMITITE-5” manufactured by Hiranuma Sangyo Co., Ltd.) was used.
50 "), a calcium ion electrode (" 93-20 "manufactured by Orion) and a reference electrode (" 90-0 manufactured by Orion ").
1 ”), and from the measured value of each sample liquid,
The amount of calcium ions captured by the sample (polymer) was calculated. Then, the obtained value was expressed as mg of calcium carbonate equivalent per 1 g of the polymer solid content, and this value was taken as the calcium ion trapping ability (mgCaCO ₃ / g).

Example 1 In a glass reactor equipped with a reflux condenser, a thermometer and a stirrer, diethylenetriamine 2 was added.
Charge 0.6 g and ion-exchanged water 32.3 g, and stir,
19.6 g of maleic anhydride crushed in a mortar was gradually added while keeping the temperature below 15 ° C by cooling with ice. After the reaction was completed for 30 minutes or more after the completion of the addition, 16.7 g of a 48% sodium hydroxide aqueous solution was gradually added to neutralize the maleic acid-
An aqueous solution of diethylenetriamine monoamide monomer was obtained. Next, this maleic acid-diethylenetriaminemonoamide monomer aqueous solution was heated to 80 ° C. and reacted for 1 hour to give a solid content concentration of 50% by weight and a final neutralization degree of 10
0% of water-soluble polymer was obtained.

A part of the obtained water-soluble polymer was put into a petri dish and dried under reduced pressure at room temperature to obtain a white solid, which was dissolved in heavy water and ¹ H-NMR was measured. ¹ H-NMR (δinD ₂ O): 2.25 to 2.75 ppm
(8H), 3.22 to 3.38 ppm (3H) From this result, the obtained water-soluble polymer was R ¹ = H, R ² = H, X = N, M = in the general formula (1). Na,
It became clear to have structural units with n = 1.

The water-soluble polymer obtained had a weight average molecular weight of 3900 and an amine value of 5.2 mmol / g.
And the calcium ion-capturing ability was 72. Example 2 A glass reactor equipped with a reflux condenser, a thermometer, and a stirrer was charged with 24.8 g of triethylenetetramine.
34.7 g of ion-exchanged water was charged, and 16.7 g of maleic anhydride crushed in a mortar was gradually added while maintaining the temperature at 15 ° C. or lower by stirring while cooling with ice. After reacting for 30 minutes or more after completion of addition, 48% aqueous sodium hydroxide solution 14.
2 g was gradually added for neutralization to obtain an aqueous solution of maleic acid-triethylenetetramine monoamide monomer. Next, this maleic acid-triethylenetetramine monoamide monomer aqueous solution is heated to 80 ° C. and reacted for 1 hour to obtain a solid content concentration of 50% by weight and a final neutralization degree of 100%.
A water-soluble polymer of was obtained.

A part of the obtained water-soluble polymer was put into a petri dish and dried under reduced pressure at room temperature to obtain a white solid, which was dissolved in heavy water and ¹ H-NMR was measured. ¹ H-NMR (δinD ₂ O): 2.25 to 2.75 ppm
(12H), 3.22 to 3.38 ppm (3H) From these results, the obtained water-soluble polymer was R ¹ = H, R ² = H, X = N, M = in the general formula (1). Na,
It was revealed to have structural units with n = 2.

The water-soluble polymer thus obtained had a weight average molecular weight of 6,500 and an amine value of 6.2 mmol / g.
And the calcium ion-capturing ability was 38. [Comparative Example 1] A water-soluble solution having a solid content concentration of 47% by weight and a final neutralization degree of 100% in the same manner as in Example 2 except that 19.7 g of hexamethylenediamine was used instead of 24.8 g of triethylenetetramine. A polymer was obtained. The weight average molecular weight of the obtained water-soluble polymer was 1200, the amine value was 2.3 mmol / g, and the calcium ion-trapping ability was 10.

[Reference Example 1 (Recontamination Prevention Ability)] The water-soluble polymers obtained in the above Examples and Comparative Examples were used as builders for detergents, and the anti-redeposition performance was evaluated as follows.
For comparison, the same evaluation was performed when the water-soluble polymer was not added. The results are shown in Table 1. A detergent aqueous solution containing a water-soluble polymer in an amount of 17.5 ppm in terms of solid content (active ingredient) was formulated with the following detergent to prepare a surfactant (SFT-7).
OH, Neoperex F-25) concentration was adjusted to 350 ppm. (Detergent formulation) Nonionic surfactant (SFT-70H) * 1): 10 g Anionic surfactant (NeoPerex F-25) * 2): 40 g
(Active ingredient 10g) Diethanolamine: 2.5g Ethanol: 2.5g Propylene glycol: 2.5g Water: 42.5g Note 1) SFT-70H: polyoxyethylene alkyl ether "Softanol 70H" manufactured by Nippon Shokubai Note 2) Neohelex F-25: Sodium dodecyl benzene sulfonate "NeoPerex F-25" manufactured by Kao Next, 8 pieces of white cloth were prepared by cutting a cotton cloth (JIS-L0803 cotton cloth (gold width 3)) into 5 cm x 5 cm. Clay (test dust 11
Seed (Kanto Loam, Japan)
After adding 5 g and 8 sheets of white cloth, washing and rinsing were repeated 3 times by using a targo meter with a washing time of 10 minutes (tergotometer 100 rpm) and a rinsing time of 2 minutes (tergotometer 100 rpm), and then the cloth was ironed and dried. . The hardness of the water used was 50 ppm (calcium carbonate conversion) and the water temperature was 25 ° C.

The reflectance (Hunter whiteness) of the white cloth (base cloth) before the test and the white cloth (contaminated cloth) after the test were measured with a color difference meter (“SE2000” manufactured by Nippon Denshoku Industries Co., Ltd.), The average value of 8 sheets of each of the original cloth and the contaminated cloth was calculated, and the redeposition prevention rate was calculated by the following formula using the average value, and the anti-redeposition property was evaluated. Redeposition prevention rate (%) = (reflectance of contaminated cloth / reflectance of original cloth) × 100

[0037]

[Table 1]

[Reference Example 2 (Detergency)] Using the water-soluble polymers obtained in the above Examples and Comparative Examples as a builder for detergent, the detergency was evaluated as follows. For comparison, the same evaluation was performed when the water-soluble polymer was not added. The results are shown in Table 2. A detergent aqueous solution containing a water-soluble polymer in an amount of 50 ppm or 100 ppm in terms of solid content (in terms of active ingredient) was used in the same detergent formulation as used in the evaluation of Reference Example 1 (recontamination preventing ability), and a surfactant (SFT- 70
H, Neoperex F-25) concentration was adjusted to 350 ppm, and in the case of containing zeolite (zeolite A4 powder), the concentration was adjusted to 175 ppm. The detailed composition is shown in Table 2. The numerical values in Table 2 are expressed in solids or parts by weight in terms of active ingredients.
In addition, the amount of water was appropriately adjusted so that the total of all components was 100 parts by weight, and was expressed as balance.

Next, five pieces of wet artificially contaminated cloth (manufactured by Japan Institute of Washing Science) were prepared. And the detergent aqueous solution 500m
Five pieces of contaminated cloth were added to L, and after washing and rinsing with a targo meter for a washing time of 10 minutes (tergotometer 100 rpm) and a rinsing time of 2 minutes (tergotometer 100 rpm), the cloth was ironed and dried. The hardness of the water used was 50 ppm (calcium carbonate conversion) and the water temperature was 25 ° C. The reflectance (hunter whiteness) of the contaminated cloth and the white cloth (obtained from the Japan Institute of Laundry Science) before and after the above test was measured by a color difference meter (SE200 manufactured by Nippon Denshoku Industries Co., Ltd.).
0 "), and an average value of 5 sheets of each of the contaminated cloths before and after the test was calculated, and the cleaning rate was calculated by the following equation using the average value to evaluate the cleaning power. Cleaning rate (%) = [(reflectance of contaminated cloth after test-reflectance of contaminated cloth before test) / (reflectance of white cloth-reflectance of contaminated cloth before test)] × 100

[0040]

[Table 2]

[0041]

The novel water-soluble polymer according to the present invention is
It has excellent anti-soil redeposition ability and is very useful as a detergent composition.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yoshikazu Fujii             5-8 Nishiomitabicho Suita City, Osaka Prefecture             Within Nippon Shokubai (72) Inventor Shigeru Yamaguchi             5-8 Nishiomitabicho Suita City, Osaka Prefecture             Within Nippon Shokubai F-term (reference) 4H003 AB27 AC08 DA01 EB04 EB14                       EB38 FA06 FA07                 4J030 BA03 BB24 BC02                 4J043 QB15 QC01 RA05 RA08 SA06                       SB01 YB19 ZB41

Claims (4)

[Claims] 1. A water-soluble polymer having a structural unit represented by the following general formula (1) and having an amine value of 3.0 mmol / g or more. [Chemical 1] (In the formula (1), R ¹ is —H or —CH ₃ , and R ¹ is
_{^2, -H, -CH 3, -CH 2} COOM or -CH _2,
OH and X is —NH—, —NR ³ —, or —S
And R ³ is —CH ₃ , —CH ₂ CH ₃ , —CH ₂ C.
OOM or —CH ₂ OH, M is, independently of each other, H, an alkali metal, or an alkaline earth metal, and n is an integer of 1 or more. ) 2. A method for producing a water-soluble polymer, which comprises subjecting an amide compound represented by the following general formula (2) to Michael addition polymerization. [Chemical 2] (In formula (2), R ¹ is —H or —CH ₃ , and R ¹ is
_{^2, -H, -CH 3, -CH 2} COOM or -CH _2,
OH and X is —NH—, —NR ³ —, or —S
And R ³ is —CH ₃ , —CH ₂ CH ₃ , —CH ₂ C.
OOM or —CH ₂ OH, M is, independently of each other, H, an alkali metal, or an alkaline earth metal, and n is an integer of 1 or more. ) 3. The amide compound is obtained by using an amine compound represented by the following general formula (3) and maleic acids.
The method for producing the water-soluble polymer according to claim 2. [Chemical 3] (In the formula (3), X is —NH—, —NR ³ —, or —
A S-, R ³ _{is, -CH 3, -CH 2 CH 3} , -CH 2
COOM or —CH ₂ OH, M independently of one another is H, an alkali metal or an alkaline earth metal, and n is an integer of 1 or more. ) 4. A detergent composition comprising the water-soluble polymer according to claim 1.