JP2000319385A - New water-soluble polymer having ability for chelating with heavy metal ion and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject polymer having functional groups which are easily introduced into the main chain of the polymer in a large amount and effective for catching heavy metal ions, in addition to carboxylic groups directly bonding to the main chain of the polymer, capable of exhibiting an iron ion deposition-inhibiting ability, a clay-dispersing ability, etc., and useful for a fiber- treating agent, etc. SOLUTION: This water-soluble polymer has structural units expressed by formulae I or/and II R1 is H or methyl; R2 is H, methyl or the like; R3 and R6 are each a group of formula III [(l) is 2-6] or the like; R4 is a group of formula IV [M is H or alkali (alkaline earth) metal] or the like; H is NH or NR5 (R5 is CH3, CH2CH3 or the like)} and a weight-average molecular weight of 500-100,000. The polymer preferably has a iron ion deposition-inhibiting ability of >=70%, a clay-dispersing ability of >=60%, and an ability for stabilizing hydrogen peroxide against copper ion of >=50%. The polymer can be obtained by utilizing a corresponding amide compound (preferably, a compound of formula V or the like) for Michael addition polymerization.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water-soluble polymer, a method for producing the same, a composition containing the polymer, and the like.

[0002]

2. Description of the Related Art Maleic acid-based copolymers having a carboxyl group have been known to exhibit excellent chelating and dispersing effects, and are known for detergent compositions, fiber treatment agents, dispersants, flocculants, scale inhibitors. It is widely used for applications such as agents, chelating agents, bleaching aids, and pH adjusters. Among these, when a detergent composition is used, it is required to have excellent calcium ion-capturing ability and clay dispersing ability as basic performance, and various improvements of polymers have been made to improve the performance.

For example, JP-A-10-45836 discloses a maleic acid-based copolymer in which an amidated product of maleic acid and a carboxylic acid-containing primary amine (eg, aspartic acid, serine, etc.) is introduced as a monomer. Structural features having a carboxyl group introduced away from the main chain and an amide group directly connected to the main chain realize excellent calcium ion trapping ability and clay dispersing ability.

[0004]

As described above, the basic performance of a detergent builder is a calcium ion trapping ability and a clay dispersing ability, but on the other hand, there is also a very high need for a chelating ability of heavy metal ions such as iron. In other words, in the world, there are some areas where the washing water contains a large amount of iron ions. Normally, the washing water is weakly basic, so the iron ions become iron particles (iron hydroxide) and adhere to clothing, causing yellowing. However, in such an area, a chelating ability for iron ions is particularly required. In Japan's tap water, there is no area where the iron ion concentration is particularly high. However, iron ions derived from dirt and the like may cause yellowing or cause black tea and blood stains to be less likely to be removed. The need for Noh is the same.

Heretofore, in maleic acid-based copolymers,
Polymers exhibiting excellent ability to prevent iron ion deposition have been disclosed,
These documents also describe that they also have excellent calcium ion capturing ability (JP-A-10-7740). However, there was no polymer excellent in copper ion hydrogen peroxide stabilizing ability and also excellent in iron ion deposition preventing ability and clay dispersing ability, that is, a polymer satisfying all of these physical properties. . In Japan's tap water, the dispersibility of clay (mud particles) does not matter much because the iron ion concentration is low and the hardness components such as calcium are also low, but in some parts of the world there is considerable hardness. Water, and clay dispersibility is very important.

Further, when used as a fiber treatment agent, particularly in the bleaching step, if heavy metal ions are present in the treatment solution, the peroxide which is the main component of the bleaching agent is catalytically decomposed, and the peroxide is decomposed. Since it is wastefully consumed, it is necessary to capture and inactivate heavy metal ions present in the processing solution, specifically, copper ions having particularly high activity.

[0007]

Means for Solving the Problems The present inventor has made intensive studies to solve the above-mentioned problems. As a result, in addition to a large number of carboxyl groups directly connected to the polymer main chain, at least one functional group selected from amide groups, amino groups, and thioether groups effective for capturing heavy metal ions is included in the polymer main chain. A novel water-soluble polymer having a large number and being easily introduced has been found, and this polymer is excellent in any of iron ion deposition preventing ability, clay dispersing ability, and copper ion hydrogen peroxide stabilizing ability. I found that. They have also found that these polymers are very useful for detergent compositions, fiber treatment agents and the like. The present invention has been completed in this manner.

That is, the water-soluble polymer according to the present invention comprises:
It has a structural unit represented by the following general formula (1) and / or (2), and has a weight average molecular weight of 500 to 100,000.

[0009]

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[0010]

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The method for producing a water-soluble polymer according to the present invention is characterized in that an amide compound represented by the following general formula (3) and / or (4) is used for Michael addition polymerization.

[0012]

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[0013]

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Further, the amide compound of the present invention, which is suitably used for producing a water-soluble polymer, is characterized by being represented by the following general formula (3) or (4).

[0015]

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[0016]

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The method for producing an amide compound according to the present invention utilizes an amidation reaction between an acid anhydride represented by the following general formula (5) and an amine compound represented by the following general formula (6). It is characterized by doing.

[0018]

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Further, the detergent composition, the fiber treating agent, or the peroxide stabilizer of the present invention is characterized by containing the water-soluble polymer of the present invention.

[0020]

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 a structural unit represented by the above general formula (1) and / or (2). is there. When the water-soluble polymer of the present invention is a copolymer, the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2)
May be included, or may include one of the structural units of the general formula (1) or (2) and a structural unit derived from another monomer.

The proportion of the structural unit represented by the above general formula (1) and / or (2) in the water-soluble polymer structure of the present invention is from 80 to 100% by mole ratio, preferably The ratio is 90 to 100%, more preferably 100% in a molar ratio. The water-soluble polymer of the present invention is characterized in that its weight average molecular weight is from 500 to 100,000, preferably from 500 to 50,000, more preferably from 500 to 20,000, more preferably from 1,000 to 20,000.
000, most preferably from 1400 to 15000.

The water-soluble polymer of the present invention comprises, in addition to a large number of carboxyl groups directly bonded to the polymer main chain, at least one amide group, amino group, or thioether group which is effective for capturing heavy metal ions. Since a large number of functional groups are introduced into the polymer main chain, it has excellent ability to prevent iron ion deposition, disperse clay, and stabilize copper ion hydrogen peroxide, preferably Iron ion deposition preventing ability is 70% or more, clay dispersing ability is 60% or more, copper ion hydrogen peroxide stabilizing ability is 50% or more, more preferably iron ion depositing preventing ability is 80% or more, clay dispersing ability Is 70% or more, copper ion hydrogen peroxide stabilizing ability is 60%
That is all. When focusing only on the ability to prevent iron ion deposition, it is preferably 70% or more, and more preferably 80%.
Above, even more preferably 90% or more, when focusing only on clay dispersing ability, preferably 60% or more, further preferably 70% or more, focusing only on copper ion hydrogen peroxide stabilizing ability, Preferably at least 50%,
More preferably 60% or more, even more preferably 7% or more.
It is at least 5%, most preferably at least 90%. (Method for Producing Water-Soluble Polymer) The method for producing a water-soluble polymer according to the present invention comprises the above-mentioned general formula (3) and / or (4)
Wherein the amide compound represented by the formula is used for Michael addition polymerization.

As a polymerization method for carrying out Michael addition polymerization in the present invention, solution polymerization is preferable. In this case, any of stirring and standing may be employed. The solvent used in the solution polymerization is preferably an aqueous solvent, and 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 or two or more of lower alcohols such as methanol, ethanol, and isopropyl alcohol; amides such as dimethylformamide; ethers such as diethyl ether and dioxane; .

A catalyst for performing the solution polymerization is basically unnecessary. However, if necessary, any catalyst that does not adversely affect the polymerization may be appropriately used. The monomer concentration during the solution polymerization is not particularly limited, but is preferably 10%.
Or more, more preferably 20% or more. Further, the pH of the polymerization solution is arbitrary, but in Michael addition polymerization, generally, the higher the pH, the better the polymerizability, and depending on the solubility of the monomer, is preferably 7 or more, more preferably 10 or more. It is.

The polymerization temperature at the time of carrying out the solution polymerization is 20
To 100 ° C, preferably at 80 ° C or lower to prevent cleavage of the amide bond. The polymerization time is not particularly limited, and the polymerization pressure may be any of normal pressure (atmospheric pressure), pressurization, and reduced pressure. (Amide compound) The amide compound of the present invention, which is suitably used for producing a water-soluble polymer, is characterized by being represented by the general formula (3) or (4).

The amide compound represented by the general formula (3) or (4) has a double bond in which a carboxyl group (and / or a salt thereof) is conjugated in one molecule and an X group (X is N
H, NR ⁵ , and S, wherein R ⁵ is —CH ₃ , —CH
₂ CH ₃ , —CH ₂ COOM, and —CH ₂ OH, wherein M independently represents H, an alkali metal such as K or Na, or an alkaline earth metal such as Mg or Ca. ), A polymer is produced by the above-mentioned Michael addition polymerization. (Method for Producing Amide Compound) The method for producing the amide compound according to the present invention comprises amidating the acid anhydride represented by the general formula (5) with the amine compound represented by the general formula (6). It is characterized by utilizing a reaction.

Examples of the acid anhydride represented by the general formula (5) include various compounds depending on the selection of R ¹ and R ² , and among them, maleic anhydride is particularly preferably used. Examples of the amine compound represented by the general formula (6) include, for example, when X is NH or NR ⁴ , ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tris (2-aminoethyl) amine, lysine, and arginine , Cystine, etc., and when X is S, cysteine, cysteamine and the like can be mentioned, among which ethylenediamine, lysine, tris (2-aminoethyl) amine and cysteine are particularly preferred.

An acid anhydride represented by the general formula (5);
Examples of the method of the amidation reaction with the amine compound represented by the above general formula (6) include, for example, a method in which an amine compound (6) in an aqueous solvent (preferably in water) is added to an acid anhydride (5) (solid form). Is preferably in the form of a powder), and the mixture is gradually added with stirring to amidate while the temperature is kept at 35 ° C. or lower, preferably 20 ° C. or lower.

In an inert organic solvent such as toluene or xylene, (5) and (6) or the hydrolyzate of (5) and (6)
Is amidated by a conventionally known method. A method in which a monoester of (5) and (6) are amidated by a conventionally known ester amide exchange reaction in an inert organic solvent such as toluene or xylene. And the like, but the method is preferably used. Since the synthesis is performed using an aqueous solvent, a step of removing the organic solvent is not required. In addition, since synthesis at a high concentration is possible, it is preferable from the viewpoint of safety, environment, and economy. Further, the polymerization in the next step is also preferable in that it is carried out with an aqueous solvent (preferably water).

The above-mentioned aqueous solvent is preferably water, but an aqueous solvent having no active protons may be suitably added in an amount of 10% or less in order to improve the solubility of the amine. Specifically, lower alcohols such as methanol, ethanol and isopropyl alcohol; amides such as dimethylformamide; diethyl ether;
One or two or more ethers such as dioxane can be appropriately selected and used.

The temperature of the amidation reaction is preferably 35 ° C. or lower, more preferably 20 ° C. or lower. 35 ° C
If it exceeds, the simple hydrolysis of the acid anhydride (5) proceeds more than the amidation reaction, which is not preferable. The reaction time is preferably such that (5) is added substantially continuously over 10 minutes or more, and after all (5) is added, aging is further performed for 10 minutes or more. (Use of Water-Soluble Polymer) The detergent composition of the present invention contains the water-soluble polymer of the present invention and a surfactant described below. The amount of the water-soluble polymer in the detergent composition is preferably 0.1 to 20% by weight, and the amount of the surfactant is preferably 5 to 70% by weight. More preferably, the compounding amount of the water-soluble polymer is 0.5 to 15% by weight, and the compounding amount of the surfactant is 20 to 60% by weight.

A surfactant and, if necessary, an enzyme may be added to the detergent composition containing the water-soluble polymer of the present invention. As the surfactant, at least one selected from the group consisting of an anionic surfactant, a nonionic surfactant, an amphoteric surfactant and a cationic surfactant can be preferably used.

Examples of the anionic surfactant include alkyl benzene 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-acyl amino acid type surfactant, Alkyl or alkenyl phosphates or salts thereof can be mentioned.

Examples of the nonionic surfactant include polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycooxide, and fatty acid glycerin monoester. Esters and alkylamine oxides can be mentioned.

Examples of the amphoteric surfactant include carboxy type or sulfobetaine type amphoteric surfactants, and examples of the cationic surfactant include quaternary ammonium salts. As the enzyme to be added to the detergent composition containing the maleic acid-based copolymer of the present invention, protease, lipase, cellulase and the like can be used. Particularly, protease, alkaline lipase and alkaline cellulase having high activity in an alkaline washing solution are preferable. The amount of the enzyme is preferably 0.01 to 5% by weight. If the ratio is out of this range, the balance with the surfactant is lost, and the cleaning power cannot be improved.

The detergent composition containing the water-soluble polymer of the present invention may be used, if necessary, in a detergent composition such as a known alkali builder, chelate builder, anti-redeposition agent, fluorescent agent, bleaching agent, and fragrance. May be blended. Further, zeolite may be blended. Silicates, carbonates, sulfates and the like can be used as the alkali builder.
As the chelate builder, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), D
TPA (diethylenetriamine hexaacetic acid), citric acid and the like can be used as needed.

The detergent composition containing the water-soluble polymer of the present invention is suitably used as a detergent for clothing. In particular, the detergent composition of the present invention is very effective because it has an excellent ability to capture heavy metal ions such as iron ions present in the washing liquid and an excellent clay dispersing ability. The fiber treating agent of the present invention comprises at least one selected from the group consisting of the water-soluble polymer of the present invention, a dye, a peroxide and a surfactant.
And scouring in fiber processing,
It can be used in dyeing, bleaching and soaping processes. In this case, the content of the water-soluble polymer of the present invention in the fiber treatment agent is not particularly limited, and the addition amount can be adjusted as desired. Dyes, peroxides and surfactants include those commonly used in fiber treatments. The ratio of the water-soluble polymer and at least one selected from the group consisting of a dye, a peroxide and a surfactant is as follows:
For example, in order to improve the whiteness, color unevenness, and dyeing consistency of the fiber, at least one selected from the group consisting of a dye, a peroxide and a surfactant is added to 1 part by weight of the water-soluble polymer. Are mixed in a ratio of 0.1 to 100 parts by weight. The fibers for which the fiber treating agent of the present invention can be used are not particularly limited. Examples thereof include cellulosic fibers such as cotton and hemp; chemical fibers such as nylon and polyester; animal fibers such as wool and silk; Fibers and their fabrics and blends.

When the fiber treating agent of the present invention is applied to the scouring step, it is preferable to blend the water-soluble polymer of the present invention, an alkali agent and a surfactant. When applied to the bleaching step, the water-soluble polymer of the present invention, a peroxide,
It is preferable to add a silicic acid-based agent such as sodium silicate as a decomposition inhibitor of the alkaline bleaching agent. The water-soluble polymer of the present invention can effectively capture heavy metal ions, particularly highly active copper ions, in a system where a peroxide is present. ,
It can also act effectively as a peroxide stabilizer.
Therefore, the peroxide stabilizer containing the water-soluble polymer of the present invention is a preferred embodiment. The peroxide stabilizer containing the water-soluble polymer of the present invention may contain other stabilizers and additives as necessary. The peroxide stabilizer containing the water-soluble polymer of the present invention can be preferably used in various methods for stabilizing peroxide. Also,
The peroxide to be stabilized is not particularly limited. In addition, in a system in which a water-soluble peroxide is present, more specifically, in a water system, the addition of a peroxide stabilizer containing the water-soluble polymer of the present invention may exhibit a stabilizing effect. preferable. More specifically, it is suitable as a stabilizer such as an aqueous solution of hydrogen peroxide. Further, the content of the water-soluble polymer of the present invention in the above-mentioned peroxide stabilizer is not particularly limited, and the addition amount can be adjusted as desired.

Since the water-soluble polymer of the present invention has the above-mentioned excellent performance, it is suitably used for 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.

[0040]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, "%"
Represents "% by weight", and "parts" represents "parts by weight". (Weight average molecular weight) Weight average molecular weight of the polymer (hereinafter, M
w) was measured by GPC (gel permeation chromatography). The measurement conditions, equipment, etc. are as follows.

Column: G-3000PWXL (manufactured by Tosoh) Mobile phase: 34.5 g of disodium hydrogen phosphate dodecahydrate
And 46.2 g of sodium dihydrogen phosphate dihydrate (each of which is a special grade, all reagents used in the following measurement use special grades)
To a total weight of 5000 g by adding pure water to
Aqueous solution filtered with a micron membrane filter Detector: UV 214 nm (Waters model 481) Pump: L-7110 (Hitachi), flow rate: 0.5 ml /
min, temperature; 35 ° C. Calibration curve: sodium polyacrylate standard sample (manufactured by Sowa Kagaku) (Iron ion deposition prevention ability) Iron ion deposition prevention ability was measured by the following procedure.

First, an aqueous solution of a measurement sample was prepared. That is, 150 g of a 0.05% aqueous sample solution in terms of solid content was prepared (Solution A). Next, the iron ion aqueous solution was adjusted as follows. That is,
Take 2 g of iron (III) chloride hexahydrate, add pure water and add 100 g.
0 g (Solution B). Further, an aqueous sodium hydroxide solution was prepared as follows. That is, 2.08 g of sodium hydroxide was taken, and pure water was added to make 1000 g (Solution C).

100 g of Solution A, Solution B, and Solution C were mixed in this order, stirred for 5 minutes, and allowed to stand for 2 hours. After suction filtration using a 5C filter paper (55 mm) and a Buchner funnel, the mixture was dried in a vacuum desiccator for 1 hour. The value indicating the whiteness of the filter paper measured by a color difference meter as a percentage with respect to the blank was defined as the ability to prevent iron ion deposition (iron ion capturing ability). (Clay dispersing ability) Clay dispersing ability was measured by the following procedure.

First, a glycine buffer solution was prepared by adding ion-exchanged water to 67.56 g of glycine, 52.6 g of sodium chloride and 60 ml of 1N NaOH to make 600 g. Take 60 g of the prepared solution of 0.3268 g of calcium chloride dihydrate, and add ion-exchanged water to 1000 g.
To prepare a dispersion. Next, 0.1% in terms of solid content of the polymer (adjusted to pH 7)
Was prepared.

In a test tube, 0.3 g of a clay of JIS test powder I, 8 kinds (Kanto Rohm, fine particles: Japan Powder Industry Technical Association) was added, and 27 g of an adjustment solution of 3 g was added. At this time, the calcium concentration of the test solution was 200 ppm in terms of calcium carbonate. After the test tube was sealed with parafilm, the clay was gently shaken so as to be dispersed throughout, and further shaken up and down 20 times.

This test tube was allowed to stand for 20 hours in a place not exposed to direct sunlight, and then 5 ml of the supernatant of the dispersion was collected with a whole pipette. Using a UV spectrometer, this liquid was used for wavelength 380 nm, 1c
The transmittance (T%) was measured in the cell of m. The value obtained by subtracting the value of T% from 100 was defined as the clay dispersing ability (turbidity). (Copper ion hydrogen peroxide stabilizing ability) The copper ion hydrogen peroxide stabilizing ability was measured by the following procedure.

A pinhole was made in a pig in a 250 ml polyvin. About 10 g of a 5% aqueous polymer solution was prepared. About 100 g of a 0.0393% copper sulfate aqueous solution was prepared. A 0.1% aqueous solution of magnesium sulfate was prepared. 48% sodium hydroxide and 35% hydrogen peroxide were prepared.

Next, 1 m of 0.0393% copper sulfate aqueous solution
1, 5% polymer aqueous solution 4ml, pure water 80g, 0.1%
10 ml of an aqueous solution of magnesium sulfate, 2 ml of 48% sodium hydroxide, and 3 ml of 35% hydrogen peroxide were added in this order for 2 minutes.
Added to 50 ml polyvin. (The concentration of hydrogen peroxide in this test solution was 1.05%.) After standing in a thermostat at 50 ° C. for 2 hours, the concentration of hydrogen peroxide in the solution was measured by a redox titration method. The hydrogen peroxide concentration was defined as X (%), and the copper ion hydrogen peroxide stabilizing ability was determined by the following equation. Copper ion hydrogen peroxide stabilizing ability = (X / 1.05) × 10
0 (Example 1-1) Capacity provided with a reflux condenser and a stirrer
In a 5-liter SUS separable flask, 188 g of ion-exchanged water and 167 g of a 48% aqueous sodium hydroxide solution were placed.
And 183 g of L-lysine hydrochloride was added. Then, 98 g of maleic anhydride pulverized in a mortar was gradually added while stirring and keeping the temperature at 15 ° C. or lower by ice cooling. After allowing the reaction to proceed for 30 minutes or more after the completion of the addition, 84 g of a 48% aqueous sodium hydroxide solution was gradually added to neutralize the solution, thereby obtaining an aqueous solution of maleic acid-lysine monoamide monomer. The water was removed from the aqueous solution to isolate maleic acid-lysine monoamide monomer (1-1a). The aqueous solution of maleic acid-lysine monoamide monomer obtained as described above was allowed to stand at 60 ° C. for 5 hours to obtain a solid content concentration of 4%.
A water-soluble polymer (1-1) having 8% and a final degree of neutralization of 100% was obtained. The weight average molecular weight of this polymer was 5,600.

For maleic acid-lysine monoamide monomer (1-1a) and water-soluble polymer (1-1), ¹ H
-The result of the NMR measurement was as follows. ¹ H-NMR (D ₂ O): (1-1a) δ 6.28 (1
H), 5.83 (1H), 4.04 (1H), 3.12
(2H), 2.38 (2H), 1.29 to 1.64 (4
H); (1-1) δ 4.02 (1H), 3.08-3.
32 (2H), 2.41 (3H), 1.26 to 1.65
(6H).

From the above results, the maleic acid-lysine monoamide monomer (1-1a) and the water-soluble polymer (1-1)
Has a structure represented by R ^{1 in the} general formulas (3) and (1), respectively.
^{= H, R 2 = H,} R 3 = CH (COONa) -C
It became clear that this was the case when ₄ H ₈ , M = Na and X = NH. (Example 1-2) Capacity provided with a reflux condenser and a stirrer
118 g of ion-exchanged water was charged into a 5-liter SUS separable flask, and 60 g of ethylenediamine was added. Then, 98 g of maleic anhydride pulverized in a mortar was gradually added while stirring and keeping the temperature at 15 ° C. or lower by ice cooling. After reacting for 30 minutes or more after completion of the addition, 84 g of a 48% aqueous sodium hydroxide solution was gradually added to neutralize the solution,
An aqueous solution of maleic acid-ethylenediamine monoamide monomer was obtained. By removing water from the aqueous solution, maleic acid-ethylenediamine monoamide monomer (1-2a)
Was isolated. Further, the maleic acid obtained as described above
80 ° C. aqueous solution of ethylenediamine monoamide monomer
For 1 hour to obtain a water-soluble polymer (1-2) having a solid content of 50% and a final degree of neutralization of 100%. The weight average molecular weight of this polymer was 1500.

Maleic acid-ethylenediamine monoamide
About monomer (1-2a) and water-soluble polymer (1-2)
hand,¹The results of the H-NMR measurement are as follows.
Was. ¹ H-NMR (D_TwoO): (1-2a) δ 6.16 (1
H), 5.76 (1H), 3.38 (2H), 3.00
(2H); (1-2) δ 3.28 (1H), 3.16
(2H), 2.50 (2H), 2.34 (2H).

From the above results, the structures of the maleic acid-ethylenediamine monoamide monomer (1-2a) and the water-soluble polymer (1-2) are represented by R ¹ = H and R ¹ in the general formulas (3) and (1), respectively. ² = H, R ³ = CH ₂ CH ₂ , M =
It became clear that this was the case when Na, X = NH. (Example 1-3) Capacity provided with a reflux condenser and a stirrer
A 5-liter SUS separable flask was charged with 336 g of ion-exchanged water, and 60 g of ethylenediamine was added. Thereafter, 196 g of maleic anhydride pulverized in a mortar was gradually added while maintaining the temperature at 15 ° C. or lower by ice cooling with stirring. After reacting for 30 minutes or more after completion of addition, 48%
168 g of an aqueous sodium hydroxide solution was gradually added to neutralize the solution to obtain an aqueous solution of maleic acid-ethylenediaminediamide monomer. The water was removed from the aqueous solution to obtain a maleic acid-ethylenediaminediamide monomer (1-3).
a) was isolated. Further, 60 g of ethylenediamine was added to the aqueous solution of maleic acid-ethylenediaminediamide monomer obtained as described above, and the mixture was stirred at 80 ° C. for 1 hour to obtain a water-soluble polymer having a solid content of 44% and a final neutralization degree of 100%. (1-3) was obtained. The weight average molecular weight of this polymer was 1,400.

The results of ¹ H-NMR measurement of the maleic acid-ethylenediamine diamide monomer (1-3a) and the water-soluble polymer (1-3) are as follows. ¹ H-NMR (D ₂ O): (1-3a) δ 6.24 (2
H), 5.84 (2H), 3.27 (4H);
3) δ 3.26 (2H), 3.15 (4H), 2.50
(4H), 2.36 (4H).

From the above results, the structures of the maleic acid-ethylenediaminediamide monomer (1-3a) and the water-soluble polymer (1-3) are represented by R ¹ = H and R ¹ in the general formulas (4) and (2), respectively. ² = H, R ³ = CH ₂ CH ₂ , R ⁴
= H, R ⁵ = H, R ⁶ = CH ₂ CH ₂ , M = Na, X =
It became clear that this was the case for NH. (Example 1-4) Capacity equipped with a reflux condenser and a stirrer.
133 g of ion-exchanged water was charged into a 5 liter glass separable flask, and 73 g of tris (2-aminoethyl) amine (abbreviation: Tren) was added. Then, with stirring,
While maintaining the temperature at 15 ° C. or lower by ice cooling, 49 g of maleic anhydride pulverized in a mortar was gradually added. After addition 3
After stirring for 0 minute or more, 42 g of a 48% aqueous sodium hydroxide solution was gradually added to neutralize the solution, and an aqueous solution of maleic acid-trenmonoamide monomer was obtained. By removing water from the aqueous solution, the maleic acid-tren monoamide monomer (1
-4a) was isolated.

A 0.5-liter glass separable flask equipped with a reflux condenser and a stirrer was charged with ion-exchanged water 5.
5 g and 84 g of a 48% aqueous sodium hydroxide solution were charged, and 67 g of L-aspartic acid was added. Thereafter, 49 g of maleic anhydride pulverized in a mortar was gradually added while stirring and maintaining the temperature at 15 ° C. or lower by ice cooling. After stirring for 30 minutes or more after the completion of the addition, 42 g of a 48% aqueous sodium hydroxide solution was gradually added and neutralized to obtain an aqueous solution of maleic acid-L-aspartic acid monoamide monomer. Water was removed from this aqueous solution to isolate maleic acid-L-aspartic acid monoamide monomer (1-4b).

The aqueous solution of maleic acid-tren monoamide monomer (1-4a) obtained above was mixed with maleic acid-L-
Mixing an aqueous solution of aspartic acid monoamide monomer,
By stirring at 80 ° C. for 1 hour, the solid content concentration was 47%,
A water-soluble polymer (1-4) having a final degree of neutralization of 100% was obtained.
The weight average molecular weight of this polymer was 14,000. Maleic acid-tren monoamide monomer (1-4a), maleic acid-L-aspartic acid monoamide monomer (1
-4b), ¹ H-N for the water-soluble polymer (1-4)
The results of the MR measurement were as follows. ¹ H-NMR (D ₂ O): (1-4a) δ 6.22 (1
H), 5.79 (1H), 3.21 (2H), 2.55
(6H), 2.43 (4H); (1-4b) δ 6.28
(1H), 5.82 (1H), 4.34 (1H), 2.
48 (2H); (1-4) δ 4.26 (1H), 3.2
7 (2H), 3.21 (2H), 2.34 to 2.58
(16H).

From the above results, maleic acid-tren mono
The structure of the amide monomer (1-4a) is represented by the general formula (3)
Then R¹= H, R^Two= H, R^Three= CH_TwoCH_TwoN (C
H_TwoCH_TwoNH_Two) CH_TwoCH_Two, M = Na, X = NH
And the structure of the water-soluble polymer (1-4) is
In general formula (1), R¹= H, R^Two= H, R^Three= CH _Two
CH_TwoN (CH_TwoCH_TwoNHCH (COONa) CH_Two
CONHCH (COONa) CH_TwoCOONa) CH_Two
CH_Two, M = Na and X = NH.
It was clear. (Example 1-5) A capacity of 0,0 equipped with a reflux condenser and a stirrer.
Ion exchange in 5 liter glass separable flask
133 g of water was charged, and tris (2-aminoethyl) amido was added.
73 g (abbreviation: Tren) was added. Then, with stirring,
Crushed in a mortar while keeping the temperature below 15 ° C by ice cooling
49 g of maleic anhydride were slowly added. After addition 3
After stirring for 0 minutes or more, 48% aqueous sodium hydroxide solution
42 g was gradually added to neutralize the mixture, and
An aqueous solution of the amide monomer was obtained. Water from this aqueous solution
After removal, the maleic acid-tren monoamide monomer (1
-4a) was isolated.

A 0.5-liter glass separable flask equipped with a reflux condenser and a stirrer was charged with ion-exchanged water 1.
7 g and 84 g of a 48% aqueous sodium hydroxide solution were charged, and 105 g of L-histidine hydrochloride monohydrate was added. Thereafter, 49 g of maleic anhydride pulverized in a mortar was gradually added while stirring and maintaining the temperature at 15 ° C. or lower by ice cooling. After stirring for 30 minutes or more after completion of the addition, 42 g of a 48% aqueous sodium hydroxide solution was gradually added and neutralized to obtain an aqueous solution of maleic acid-L-histidine monoamide monomer. By removing water from this aqueous solution, maleic acid-
The L-histidine monoamide monomer (1-5b) was isolated.

The aqueous solution of maleic acid-tolene monoamide monomer (1-4a) obtained above was mixed with maleic acid-L-
An aqueous solution of a histidine monoamide monomer (1-5b) is mixed and stirred at 80 ° C. for 1 hour to give a water-soluble polymer (1-5) having a solid content of 52% and a final neutralization degree of 100%.
I got The weight average molecular weight of this polymer was 1,400.

The results of ¹ H-NMR measurement of the maleic acid-L-histidine monoamide monomer (1-5b) and the water-soluble polymer (1-5) are as follows. ¹ H-NMR (D ₂ O): (1-5b) δ 7.53 (1
H), 6.78 (1H), 6.20 (1H), 5.72
(1H), 4.29 (1H), 2.92 (2H); (1
-5) δ 7.54 (1H), 6.78 (1H), 4.2
9 (1H), 3.22 (4H), 2.90 (2H),
2.37-2.50 (14H).

From the above results, the water-soluble polymer (1-5)
Is represented by the general formula (1) ¹= H, R^Two= H,
R^Three= CH_TwoCH_TwoN (CH_TwoCH_TwoNHCH (COO
Na) CH_TwoCONHCH (COONa) CH_Two(C_Three
N_TwoH_Three) CH_TwoCH_Two, M = Na and X = NH
It turned out to be the case. (Example 1-6) Capacity provided with a reflux condenser and a stirrer
Ion exchange into 5 liter SUS separable flask
188 g of water, 167 g of a 48% aqueous sodium hydroxide solution
And 183 g of L-lysine hydrochloride was added. That
After stirring, keep the temperature below 15 ° C with ice cooling, and put in a mortar.
98 g of maleic anhydride, which had been ground in this manner, was gradually added. Attachment
After reacting for 30 minutes or more after the addition, 48%
84 g of aqueous lithium solution was gradually added to neutralize
-An aqueous solution of lysine monoamide monomer was obtained. This water soluble
The water is removed from the solution, and maleic acid-lysine monoamide is removed.
Monomer (1-1a) was isolated. Also, as mentioned above
Of maleic acid-lysine monoamide monomer obtained by
The solution was stirred at 80 ° C. for 1 hour to obtain a solid concentration of 48.
%, A water-soluble polymer (1-6) having a final degree of neutralization of 100%.
Was. The weight average molecular weight of this polymer was 2,000. (Example 1-7) Capacity provided with a reflux condenser and a stirrer
Ion exchange into 5 liter SUS separable flask
114 g of water and 84 g of a 48% aqueous sodium hydroxide solution
First, 88 g of L-cysteine hydrochloride monohydrate was added.
Was. Then, keep the temperature below 15 ° C with ice cooling under stirring.
And gradually add 49 g of maleic anhydride ground in a mortar.
Added. After reacting for 30 minutes or more after completion of the addition, 48%
42 g of sodium hydroxide aqueous solution is gradually added for neutralization,
Aqueous solution of maleic acid-cysteine monoamide monomer
Obtained. The water was removed from the aqueous solution to give maleic acid
The stain monoamide monomer (1-7a) was isolated.
Further, the maleic acid-cysteine monomer obtained as described above is used.
Stir the aqueous solution of noamide monomer at 80 ° C for 1 hour.
With 43% solids concentration and 100% final neutralization degree
The polymer (1-7) was obtained. Weight average molecule of this polymer
The amount was 2100.

For the water-soluble polymer (1-7), ¹ H-
The result of the NMR measurement was as follows. In addition,
Maleic acid-cysteine monoamide monomer (1-7
a) was unstable and could not be measured. ¹ H-NMR (D ₂ O): (1-7) δ 4.26 (1
H), 3.49 (1H), 2.94 (2H), 2.41
-2.74 (2H).

From the above results, the water-soluble polymer (1-7)
Is represented by the general formula (1) ¹= H, R^Two= H,
R^Three= CH (COONa) CH_Two, M = Na, X = S
It became clear that this was the case. (Example 1-8) Capacity provided with a reflux condenser and a stirrer
Ion exchange into 5 liter SUS separable flask
114 g of water and 84 g of a 48% aqueous sodium hydroxide solution
First, 88 g of L-cysteine hydrochloride monohydrate was added.
Was. Then, keep the temperature below 15 ° C with ice cooling under stirring.
And gradually add 49 g of maleic anhydride ground in a mortar.
Added. After reacting for 30 minutes or more after completion of the addition, 48%
42 g of sodium hydroxide aqueous solution is gradually added for neutralization,
Aqueous solution of maleic acid-cysteine monoamide monomer
Obtained. The water was removed from the aqueous solution to give maleic acid
The stain monoamide monomer (1-7a) was isolated.

A 2.5 liter SUS separable flask equipped with a reflux condenser and a stirrer was charged with ion-exchanged water 9.
4 g and 84 g of a 48% aqueous sodium hydroxide solution were charged, and 92 g of L-lysine hydrochloride was added. Thereafter, 49 g of maleic anhydride pulverized in a mortar was gradually added while stirring and maintaining the temperature at 15 ° C. or lower by ice cooling. After the completion of the addition, the mixture was allowed to react for 30 minutes or more. After that, 42 g of a 48% aqueous sodium hydroxide solution was gradually added and neutralized to obtain an aqueous solution of maleic acid-lysine monoamide monomer. The water was removed from the aqueous solution to isolate maleic acid-lysine monoamide monomer (1-1a).

The aqueous solution of maleic acid-cysteine monoamide monomer (1-7a) thus obtained and the aqueous solution of maleic acid-lysine monoamide monomer (1-1a) are mixed, and the mixture is stirred at 80 ° C. for 1 hour to obtain a solid. Water-soluble polymer (1-8) having a partial concentration of 45% and a final degree of neutralization of 100%
I got The weight average molecular weight of this polymer was 1500.

For the water-soluble polymer (1-8), ¹ H-
The result of the NMR measurement was as follows. ¹ H-NMR (D ₂ O): (1-8) δ 4.28 (1
H), 4.05 (1H), 3.55 (1H), 3.12
~ 3.35 (2H), 2.97 (2H), 2.68 (2
H), 2.47 (3H), 1.32-1.68 (6
H).

From the above results, the water-soluble polymer (1-8)
Is represented by the general formula (1) ¹= H, R^Two= H,
R^Three= CH_TwoCH_Two, M = Na, X = NH, and
In general formula (1), R¹= H, R^Two= H, R^Three= CH
(COONa) CH_Two, M = Na and X = S
It is clear that this is a copolymer having structural units.
Was. (Examples 2-1 to 2-6) The polymer obtained in Example 1
Regarding (1-1) to (1-6), prevention of iron ion deposition
Capacity, clay dispersing ability, hydrogen peroxide stabilizing ability
Was. The results are summarized in Table 1.

[0068]

[Table 1]

(Comparative Example 2-9) A polymer (1-9) was obtained by the method disclosed in Example 1 of JP-A-10-7740, which is a conventionally known production method. Table 1 summarizes various measurement results of the obtained polymer. (Comparative Example 2-10) Table 1 summarizes various measurement results when citric acid, a conventionally known compound, was used. (Example 3) In order to evaluate the performance of the polymers (1-1) to (1-6) as a detergent composition, the following detergency test was performed.

The artificial soil shown in Table 2 was dispersed in carbon tetrachloride, a cotton white cloth was passed through an artificial soil liquid, dried and cut to prepare a 10 cm × 10 cm soiled cloth.

[0071]

[Table 2]

The detergent compositions shown in Table 3 were blended and washed under the conditions shown in Table 4. After washing and drying the cloth, the reflectance was measured.

[0073]

[Table 3]

[0074]

[Table 4]

The cleaning rate was determined from the reflectance according to the following equation, and the cleaning performance was evaluated. The results are shown in Table 5. Washing rate = (Reflectance after washing−Reflectance before washing) / (Reflectance of white cloth−Reflectance before washing) × 100

[0076]

[Table 5]

Example 4 Polymers (1-1) to (1-)
In order to evaluate the performance as a fiber treatment agent of 6), a fiber bleaching test shown below was performed. That is, a smelted cotton sheet knit was bleached under the conditions shown in Table 6 using 2 g / l of each polymer as a fiber treatment agent, and the texture and whiteness were evaluated.

The texture was determined by a sensory test. The whiteness is measured by using a 3M color computer SM-3 manufactured by Suga Test Instruments Co., Ltd., and the whiteness formula of Lab system W = 100 − [(100−L) ² + a ² + b ² ] ^1/2 However, L = measured lightness a = measured chromaticness index b = measured chromaticness index Whiteness (W) was determined and evaluated.

Table 7 shows the evaluation results.

[0080]

[Table 6]

[0081]

[Table 7]

[0082]

Industrial Applicability The novel water-soluble polymer of the present invention is excellent in any of iron ion deposition preventing ability, clay dispersing ability and copper ion hydrogen peroxide stabilizing ability, and has a detergent composition, a fiber treating agent, It is also very useful for peroxide stabilizers and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07C 407/00 C07C 407/00 C08G 75/04 C08G 75/04 C11D 3/37 C11D 3/37 D06M 15 / 59 D06M 15/59 (72) Inventor Shigeru Yamaguchi 5-8 Nishiburi-cho, Suita-shi, Osaka F-term in Nippon Shokubai Co., Ltd. (Reference) 4H003 AB19 AC08 BA09 DA01 EA15 EA16 EA28 EB28 EB38 EC02 EE05 FA07 FA44 4H006 AA01 AA02 AB46 AC28 AC53 BS10 BV22 4J030 BA04 BA05 BA45 BB07 BB62 BC02 BC05 BC08 BC09 BF01 BF03 BG17 BG22 BG31 4J043 QC01 QC02 QC03 RA05 RA08 SB01 UA761 ZB31 ZB32 ZB34 ZB45 4L033 AC15 CA18 CA55 DA06

Claims (8)

[Claims] 1. A resin having a structural unit represented by the following general formula (1) and / or (2), and having a weight average molecular weight of 500 to 1
00000, a water-soluble polymer. Embedded image Embedded image 2. An iron ion deposition preventing ability of 70% or more, a clay dispersing ability of 60% or more, and a copper ion hydrogen peroxide stabilizing ability of 5% or more.
The water-soluble polymer according to claim 1, which is 0% or more. 3. The water-soluble polymer according to claim 1, wherein an amide compound represented by the following general formula (3) and / or (4) is used for Michael addition polymerization. Manufacturing method of coalescence. Embedded image Embedded image 4. It is preferably used for producing a water-soluble polymer.
An amide compound represented by the following general formula (3) or (4): Embedded image 5. An acid anhydride represented by the following general formula (5):
The method for producing an amide compound according to claim 4, wherein an amidation reaction with an amine compound represented by the following general formula (6) is used. Embedded image 6. A detergent composition comprising the water-soluble polymer according to claim 1. 7. A fiber treating agent comprising the water-soluble polymer according to claim 1. 8. A peroxide stabilizer comprising the water-soluble polymer according to claim 1 or 2.