JP2000355615A - Water-soluble sulfo-containing maleic acid copolymer having specified function, its production, and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a water-soluble copolymer useful for detergent composition or as a water-treating agent or the like, which copolymer comprises structural units derived from a monoethylenically unsaturated dicarboxylic acid monomer, structural units derived from a monoethylenically unsaturated monocarboxylic acid monomer, and structural units derived from a sulfo-containing monoethylenically unsaturated monomer and has specified functions such as a Ca ion scavenging capacity. SOLUTION: This copolymer essentially consists of structural units derived from (A) a 4-6C monoethylenically unsaturated dicarboxylic acid (salt or anhydride) monomer, structural units derived from (B) a 3-8C monoethylenically unsaturated monocarboxylic acid (salt) monomer, and (C) structural units derived from a sulfo(sulfonate)-containing monoethylenically unsaturated monomer and has a Ca ion scavenging capacity of at feast 0.40, a capacity of dispersing clay in high-hardness water of at least 0.35, and a gelation resistance of at least 0.35. The copolymer is one prepared by polymerizing 30-70 mol% component A with 30-70 mol% component B, 2-16 mol% component C, and 0-5 mol% copolymerizable monoethylenically unsaturated monomer and having a weight-average molecular weight of 2,000-20,000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a sulfonic acid (salt)
The present invention relates to a maleic acid-based water-soluble copolymer having a group, a detergent composition comprising the polymer, an inorganic pigment dispersant, a water treatment agent, and a fiber treatment agent.

[0002]

2. Description of the Related Art Conventionally, acrylic acid polymers and maleic acid / acrylic acid copolymers having many carboxyl groups are known to have a calcium ion trapping action and a clay dispersing action. It is used in a wide range of applications such as detergent compositions, inorganic pigment dispersants, flocculants, scale inhibitors, chelating agents, and fiber treatment agents.

A method for producing an acrylic acid polymer includes the following:
JP-A-62-270605, JP-A-5-239114
And a method for producing a maleic acid / acrylic acid copolymer are described in JP-A-5-247143 and JP-B-3-216.
7, various publications, such as Japanese Patent Publication No. 3-14046 and Japanese Patent No. 2574144, have been devised to improve the above operation.

Although the maleic acid / acrylic acid copolymer has a very high calcium ion trapping action, it has almost no effect on the clay dispersing action, particularly under conditions of high water hardness. This is because, especially in a maleic acid-based polymer, as the maleic acid content increases, the gelation resistance (hardness resistance, that is, the water solubility of the polymer in the presence of a hardness component) is significantly deteriorated. Although soft water with low hardness like Japan does not cause a serious problem, there are some regions such as the United States and China where the hardness is very high, and there is a great problem when using in these regions.

[0005] In addition, the acrylic acid-based polymer exhibits a somewhat good gelation resistance because it does not contain maleic acid, and thus has a higher hardness in water than maleic acid / acrylic acid-based copolymer. Although it has some clay dispersing action, it is still not enough, and is very poor in calcium ion trapping action.

[0006]

SUMMARY OF THE INVENTION Therefore, the present inventors, while maintaining a high calcium ion capturing action,
In order to greatly improve the clay dispersing action under high-hardness water, it was particularly important to greatly improve the gelation resistance of the polymer, and intensively studied. As a result, a maleic acid / acrylic acid copolymer having a specific composition ratio and a specific molecular weight into which a specific amount of a sulfonic acid (salt) group has been introduced exhibits a high calcium ion trapping action and high gelation resistance. From this, it has been found that the polymer has a high clay dispersing action even under high hardness water.

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a maleic acid having a specific amount of a sulfonic acid group, which exhibits a high calcium ion trapping action and a very excellent gelation resistance, and thus exhibits a high clay dispersing action even under high hardness water. / Acrylic acid-based polymer, a method for producing the polymer, and a detergent composition containing the polymer, an inorganic pigment dispersant, a water treatment agent, and a fiber treatment agent.

[0008]

Means for Solving the Problems In order to solve the above problems, the present invention provides the following configurations.

(A) A water-soluble copolymer, which is derived from a monomer of a monoethylenically unsaturated dicarboxylic acid (salt) having at least 4 to 6 carbon atoms or a salt thereof. A structural unit, (b) a structural unit derived from a monoethylenically unsaturated monocarboxylic acid (salt) monomer having 3 to 8 carbon atoms, and (c) a monoethylenic unsaturated group having a sulfonic acid (salt) group. A water-soluble copolymer having a structural unit derived from a saturated monomer. As a physical property of the water-soluble copolymer, a calcium ion trapping ability is 0.40 or more, and a clay dispersing ability in high hardness water is 0.35 or more. A water-soluble copolymer having a gelation resistance of 0.35 or more. Preferably, a water-soluble copolymer having a calcium ion capturing ability of 0.40 or more, a clay dispersing ability in high hardness water of 0.40 or more, and a gelation resistance of 0.40 or more.

(B) (a) 30 to 70 mol% of a monoethylenically unsaturated dicarboxylic acid (salt) or an anhydride thereof having 4 to 6 carbon atoms, and (b) 3 to 8 carbon atoms. Monoethylenically unsaturated monocarboxylic acid (salt) monomer having 30 to 70 mol%, (c) monoethylenically unsaturated monomer having a sulfonic acid (salt) group 2 to 16 mol%, and (d) monomer 0 to 5 mol% of a monoethylenically unsaturated monomer copolymerizable with the units (a) to (c);
(D) is a water-soluble copolymer having a weight average molecular weight of 2,000 to 20,000 and a sulfonic acid group content of 100 mol%, and the above-mentioned polymer has a calcium ion-capturing ability of 0.40 or more and high hardness water. Clay dispersing ability is 0.
A water-soluble copolymer having a gelation resistance of at least 35 and a gelation resistance of at least 0.35. Preferably, a water-soluble copolymer having a calcium ion capturing ability of 0.40 or more, a clay dispersing ability in high hardness water of 0.40 or more, and a gelation resistance of 0.40 or more.

(C) A detergent composition, an inorganic pigment dispersant, a water treatment agent, and a fiber treatment agent comprising the water-soluble copolymer.

(D) A method for producing a water-soluble polymer, which comprises the following conditions: (1) an aqueous solvent containing 80% by weight or more of water; The monomer (a) of the ethylenically unsaturated dicarboxylic acid (salt) or its anhydride is initially charged in an amount of 80% by weight or more based on the total amount of the monomer (a), and the remainder is added dropwise. 3)
Monoethylenically unsaturated monocarboxylic acid (salt) monomer (b) having 8 carbons is added dropwise in an amount of 90% by weight or more based on the total amount of the monomer (b), and the rest is used as an initial charge. (4)
As a polymerization initiator, hydrogen peroxide and a persulfate salt are each used for dropping at 80% by weight or more of the respective predetermined amounts, and the remainder is used for initial charging. (5) The polymerization reaction unit at the initial charging stage is used. The polymerization starts when the pH of the monomer composition liquid is 8 to 12 and the degree of neutralization is 50 to 95 mol%, and the solid content during the polymerization reaction is adjusted to a range of 40 to 70% by weight.
(6) When the dropping of all the monomer compositions is completed, p
H is adjusted to 4-8, solid content concentration is adjusted to 40-60% by weight, and polymerization temperature is performed at 80 ° C. or more. A method for producing a water-soluble copolymer, wherein the dispersibility of clay is 0.35 or more and the gelation resistance is 0.35 or more.

Preferably, the calcium ion scavenging ability is 0.1.
40 or more, clay dispersibility in high hardness water 0.40 or more,
A method for producing a water-soluble copolymer, which has a gelation resistance of 0.40 or more.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION A maleic acid / acrylic acid copolymer containing a sulfonic acid group, a method for producing the polymer, a detergent composition containing the polymer,
The inorganic pigment dispersant, water treatment agent, and fiber treatment agent will be described in detail.

[Sulfonic acid group-containing maleic acid / acrylic acid copolymer] The copolymer of the present invention comprises (a) 4 to
30 to 70 mol% of a monoethylenically unsaturated dicarboxylic acid (salt) having 6 carbons or an anhydride thereof,
(B) 30 to 70 mol% of a monoethylenically unsaturated monocarboxylic acid (salt) monomer having 3 to 8 carbons, (c)
2 to 16 mol% of a monoethylenically unsaturated monomer having a sulfonic acid (salt) group, and (d) monomers (a) to (c)
Water-soluble monoethylenic monomer copolymerizable with 0 to 5 mo
It is a water-soluble copolymer containing a sulfonic acid group having a weight average molecular weight of 2,000 to 20,000 and a total of (a) to (d) of 100 mol%.

Another feature of the water-soluble copolymer containing a sulfonic acid group of the present invention is that the calcium ion trapping ability is 0.40 or more and the clay dispersing ability in high hardness water is 0.35. As described above, the gelation resistance is 0.35 or more, preferably the calcium ion trapping ability is 0.40 or more, the clay dispersibility in water of high hardness is 0.40 or more, and the gelation resistance is 0.10 or more.
It is characterized by being 40 or more. More preferably,
The ability to capture calcium ions is 0.43 or more. More preferably, the calcium ion scavenging ability is 0.1.
45 or more. More preferably, the clay dispersing ability in high hardness water is 0.45 or more, more preferably 0.55 or more. More preferably, the gel resistance is 0.5 or more,
More preferably, it is 0.7 or more. In addition, it is a very preferable embodiment that the maleic acid-based water-soluble copolymer of the present invention has these three properties in a well-balanced manner.

Hereinafter, each item will be described specifically.

<Monomer> Monoethylenically unsaturated dicarboxylic acids (salts) having 4 to 6 carbon atoms as the monomer (a) include, for example, maleic acid, itaconic acid, mesaconic acid, fumaric acid , Citraconic acid, etc., and those having a salt or an anhydride form include the anhydrides thereof. These may be used alone or as a mixture of two or more. In addition, as long as the characteristics of the water-soluble copolymer of the present invention are not hindered and the polymerization reaction of the present invention is not hindered, derivatives of these exemplified compounds can be used. Particularly preferred is maleic acid (salt) or maleic anhydride.

In the present invention, the term "salt" used herein means an alkali metal salt such as sodium, potassium or the like.
Examples thereof include alkaline earth metal salts such as calcium and magnesium, ammonium salts, and organic amine salts such as monoethanolamine and triethanolamine. These may be used alone or as a mixture of two or more. Preferred are alkali metal salts such as sodium and potassium, and particularly preferred are sodium salts. Hereinafter, in the present invention, these are simply described as "salts" only.

Examples of the monoethylenically unsaturated monocarboxylic acid (salt) having 3 to 8 carbon atoms as the monomer (b) include acrylic acid, methacrylic acid, crotonic acid,
Examples include isocrotonic acid, α-hydroxyacrylic acid, and the like, and salts thereof. These may be used alone or as a mixture of two or more. In addition, as long as the characteristics of the water-soluble copolymer of the present invention are not hindered and the polymerization reaction of the present invention is not hindered, derivatives of these exemplified compounds can be used. Particularly preferably,
Acrylic acid, methacrylic acid, and salts thereof.

Sulfonic acid (salt) as monomer (c)
Examples of the monoethylenically unsaturated monomer having a group include, for example, 3-allyloxy-2-hydroxypropanesulfonic acid, vinylsulfonic acid, allylsulfonic acid, methallylsulfonic acid, styrenesulfonic acid, and 2-acrylamide-
Examples include 2-methylpropanesulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy-3-butenesulfonic acid, and the like, and salts thereof. These may be used alone or as a mixture of two or more. Preferably, 3-allyloxy-
2-hydroxypropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, 2-hydroxy-3-butenesulfonic acid, and salts thereof.

As the monomer (d), unless it impairs the water solubility of the obtained copolymer, the monomers (a) to (d)
It is not particularly limited as long as it is a monoethylenically unsaturated monomer copolymerizable with (c), and may be water-soluble or water-insoluble.

<Composition Ratio of Copolymer> These monomers (a)
The composition ratio of the copolymer in the present invention of to (d) is mol
(A) / (b) / (c) / (d) = 30-70 / 3
0 to 70/2 to 16/0 to 5, preferably 40 to 60 /
40 ~ 60/5 ~ 16/0 ~ 5, total 100mo
1%.

The monomer (a) is a monomer having a dicarboxylic acid and greatly contributes to the improvement of the ability to capture calcium ions, but has an adverse effect on the gelation resistance. Therefore,
If the content is less than 30 mol%, a sufficient calcium ion-trapping ability cannot be obtained, and if it exceeds 70 mol%, the gelation resistance remarkably deteriorates and the clay dispersing ability under high hardness water is unpreferably reduced.

The monomer (b) is a monomer having a monocarboxylic acid and is effective for improving clay dispersing ability in high hardness water, but not so effective for improving calcium ion capturing ability. Absent. Therefore, when the content exceeds 70 mol%, a sufficient calcium ion trapping ability may not be obtained, and when the content is less than 30 mol%, the clay dispersing ability may be deteriorated due to the balance with the monomer (a). Absent.

The monomer (c) is a monomer having a sulfonic acid group and does not contribute to the improvement of the calcium ion-capturing ability at all. It greatly contributes to the improvement and greatly improves the clay dispersibility under high hardness water. Therefore, the content is 2 mol
%, Sufficient gelation resistance cannot be obtained, and 16 mo
If it exceeds 1%, the calcium ion-capturing ability is greatly reduced, which is not preferable.

The monomer (d) is optionally used depending on the purpose.
For example, a hydrophobic monomer, a monomer having a hydroxyl group,
It may be used at 1% or less. If it exceeds 5 mol%, the high calcium ion trapping ability, the clay dispersing ability in high hardness water, and the high gelation resistance, which are the objects of the present invention, may be undesirably reduced.

<Weight average molecular weight of copolymer> The weight average molecular weight of the copolymer in the present invention is from 2,000 to 20,000.
And preferably 5,000 to 15,000. Generally, copolymers having the same composition have a weight average molecular weight of 10
If the weight average molecular weight is higher than 00, the calcium ion trapping ability tends to increase as the weight average molecular weight increases, and conversely, the clay dispersing ability in high hardness water tends to increase as the weight average molecular weight decreases (ie, approaches 1000). Are known.

Also in the copolymer of the present invention, if the weight average molecular weight is less than 2,000, there is a possibility that calcium ion trapping ability may be reduced, and if it exceeds 20,000, clay dispersing ability in high hardness water may be significantly reduced. Is not preferred.

<Physical Properties of Copolymer> Further, the copolymer of the present invention has a calcium ion trapping ability of 0.40
As described above, the clay dispersing ability in high-hardness water is 0.35 or more, and the gelation resistance is 0.35 or more. More preferably, the calcium ion trapping ability is 0.40 or more, and the clay dispersing ability is 0.1 or more.
It is 40 or more and the gelation resistance is 0.40 or more. More preferably, the ability to capture calcium ions is 0.43 or more. More preferably, the calcium ion scavenging ability is 0.4
5 or more. More preferably, the clay dispersing ability in high hardness water is 0.45 or more, more preferably 0.55 or more. More preferably, it is 0.57 or more. Most preferably, it is 0.61 or more. On the other hand, also in the gel resistance (represented by the gelation resistance in the table), the gel resistance is more preferably 0.5 or more, more preferably 0.7 or more, more preferably, Gel resistance is 0.9 or more. In the water-soluble copolymer of the present invention, it is a very preferable form to combine these three physical properties in a well-balanced manner.

If any of these physical properties are not satisfied, these copolymers, which are another object of the present invention, were used in detergent compositions, inorganic pigment dispersants, water treatment agents, and fiber treatment agents. Sometimes, a sufficient effect cannot be obtained, which is not preferable.

[Production Method of Copolymer] The production method of the copolymer in the present invention is not particularly limited, but the polymerization is carried out in an aqueous solvent in the presence of a radical polymerization initiator, and optionally using a chain transfer agent. It is preferred to do so. It is particularly preferable to use hydrogen peroxide, persulfate, and a combination thereof as the radical polymerization initiator.

The following is a specific description of each condition.

<Solvent> The solvent used in the method for producing a copolymer of the present invention is not particularly limited, but is preferably an aqueous solvent, more preferably 80% by weight or more of water, and particularly preferably water. preferable. In order to improve the solubility of the monomer used for the polymerization in the solvent, an organic solvent may be appropriately added as needed within a range that does not adversely affect the polymerization.

Examples of the organic solvent include lower alcohols such as methanol, ethanol and isopropyl alcohol; lower ketones such as acetone, methyl ethyl ketone and diethyl ketone; ethers such as dimethyl ether, diethyl ether and dioxane; Examples thereof include amides such as formaldehyde, and these may be used alone or as a mixture of two or more.

<Method of Adding Monomer> The method of adding a monomer in the method for producing a copolymer of the present invention will be described in order.

(Monomer (a)) The monomer (a) is used in an amount of 50% by weight or more, preferably 80% by weight or more, particularly preferably the total amount, based on the total amount of the monomer (a) used. To be prepared. If the initial charge is less than 50% by weight, the amount of unreacted substances increases in the latter half of the polymerization, the monomer (a) is not uniformly introduced into the copolymer, and the calcium ion trapping ability of the obtained copolymer is reduced. The gelation resistance is undesirably reduced. In addition,
The degree of neutralization will be described later.

(Monomer (b)) The monomer (b) is used in an amount of at least 70% by weight, preferably at least 90% by weight, particularly preferably at least 90% by weight, based on the total amount of the monomer (b). It is added to the reaction system by dropping substantially continuously. Dropping ratio is less than 70% by weight (that is, the initial charge amount is 30% by weight or more)
In this case, the monomer (b) may be polymerized blockwise in the early stage of polymerization and may have a high molecular weight. Therefore, calcium ion trapping ability, clay dispersing ability in high hardness water, and gelation resistance are all increased. This has an adverse effect and is not preferred. The dropping time of the monomer (b) is 30 to 240 minutes, preferably 60 to 180 minutes, particularly preferably 90 to 150 minutes. If the dropping time is shorter than 30 minutes, the monomer (b) polymerizes in a block manner, and if it exceeds 240 minutes, the monomer (a) polymerizes in a block manner. It is not preferable because it adversely affects the ability of clay to disperse in water and the gelation resistance. The degree of neutralization will be described later.

(Monomers (c) and (d)) Monomer (c)
The method of addition of the monomer (d) is not particularly limited. In consideration of the reactivity of the monomer, the ratio between the initial charge amount and the drop amount, and when dropping, the drop time may be appropriately set. The degree of neutralization will be described below.

(Degree of Neutralization of Monomer) The degree of neutralization of the monomer is 50 to 50% of the total amount of the monomers (a) to (d) before the polymerization initiator is charged. 100 mol%, preferably 50
~ 95%. If the degree of neutralization is less than 50 mol%, the monomer (a) having a large initial charge is polymerized in a block manner, and if it exceeds 100 mol%, the introduction efficiency of the monomer (a) becomes poor. It is also not preferable because calcium ion trapping ability and gelation resistance of the obtained copolymer are lowered. As the neutralizing agent for the monomer, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, ammonia, monoethanolamine, Organic amine salts such as triethanolamine are exemplified. These may be used alone or as a mixture of two or more. Preferred are hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, and particularly preferred is sodium hydroxide. Hereinafter, in the present invention, these are simply described as "neutralizing agents".

The degree of neutralization during polymerization (that is, during dropping of the monomer) is as follows:
The neutralization degree is not particularly limited as long as it is within the range of the polymerization pH described later. If necessary, the neutralization degree may be appropriately set with a neutralizing agent in consideration of the reactivity of the monomer.

<Polymerization Initiator> The polymerization initiator in the method for producing a copolymer of the present invention is not particularly limited, but it is preferable to carry out polymerization using a radical polymerization initiator. It is particularly preferable to use hydrogen peroxide, persulfate, and a combination thereof. In some cases, a polyvalent metal ion may be used as a chain transfer agent or a decomposition accelerator for the initiator. Less than,
This will be specifically described.

(Radical polymerization initiator) Examples of the radical polymerization initiator include persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate; 2,2'-azobis (2-amidinopropane) hydrochloride; Azo compounds such as 4,4'-azobis-4-cyanovaleric acid, azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide , Peracetic acid, organic peroxides such as di-t-butyl peroxide and cumene hydroperoxide, and hydrogen peroxide. These may be used alone or in combination of two or more as necessary. Particularly preferred are persulfates such as ammonium persulfate, potassium persulfate and sodium persulfate, hydrogen peroxide, and a combination thereof.

The total amount of the radical polymerization initiator used is 2 g to 10 g, preferably 3 g to 8 g, per 1 mol of the monomer. If the amount used is less than 2 g, the residual amount of the monomer is undesirably greatly increased. Also one
Even if it is used in excess of 0 g, the effect of adding the initiator no longer appears, which is economically disadvantageous.
The pure amount of the obtained copolymer decreases, and physical properties such as calcium ion trapping ability decrease, which is not preferable.

The method of adding the radical polymerization initiator is not particularly limited in view of its decomposability and the like. It is preferably at least 50% by weight of the required predetermined amount, particularly preferably at least 80% by weight, and most preferably the entire amount is dropped.

Although the dropping time is not particularly limited, an initiator such as hydrogen peroxide which has a relatively slow decomposition under the conditions of a polymerization temperature and a polymerization pH described below may be used.
It is preferably completed 10 minutes or more earlier than the monomer dropping time, and particularly preferably completed 20 minutes or more earlier. It should be noted that, even if the polymerization is completed 10 minutes or more earlier than the completion time of the dropping of the monomer, no particular adverse effect is caused in the polymerization system. However, since the added initiator does not completely decompose by the end of the polymerization, the effect as the initiator cannot be obtained, and the initiator is wasted. It is not preferable because it may adversely affect the thermal stability of the polymer.

In addition, in the case of initiators that are relatively fast decomposing, such as persulfates such as ammonium persulfate, potassium persulfate, and sodium persulfate, it is preferable to drop the monomer until the end of the dropping of the monomer. It is more preferably completed within 30 minutes after the completion, and 5 minutes to 20 minutes after the dropwise addition of the monomer.
It is particularly preferred to finish within minutes. As a result, it is possible to find an effect that the residual amount of the monomer in the copolymer can be significantly reduced. Note that, even before the completion of the dropping of the monomer, even if the dropping of these initiators is completed, the polymerization is not particularly adversely affected, and is set according to the remaining amount of the monomer in the obtained copolymer. It is good to do.

With respect to the initiator having a relatively slow decomposition and the initiator having a relatively fast decomposition, preferred ranges are described only with respect to the dropping end time. However, the dropping start time is not limited at all, and may be appropriately set. Good. For example, in some cases, the initiator dripping may be started before the monomer dripping is started, or, particularly in the case of a combined system, one initiator is started to be dripped and a certain time elapses. after,
Alternatively, another initiator may be started to be dripped after completion.
Any of them may be appropriately set according to the decomposition rate of the initiator and the reactivity of the monomer.

(Chain transfer agent) If necessary, a chain transfer agent may be used in combination with a radical initiator as a molecular weight regulator of the copolymer within a range that does not adversely affect the polymerization. Examples of the chain transfer agent include sulfites, bisulfites, and hypophosphites, but are not particularly limited. These may be used alone or in combination of two or more.

The amount used is preferably within twice the amount of the initiator by weight. Even if you use more than twice,
The effect of the addition no longer appears, which is unfavorable because the pure content of the copolymer is reduced. The method of adding the chain transfer agent and the time of the dropping are not particularly limited as long as the dropping is performed, and may be appropriately set according to the case.

(Polyvalent metal ion) Further, if necessary, a polyvalent metal ion may be used in combination as a decomposition accelerator of the radical polymerization initiator. Effective polyvalent metal ions that can be used include Fe ²⁺ , Fe ³⁺ , Cu ²⁺ , and Cu ²⁺ .
⁺ , V2 ⁺ , V3 ⁺ , VO ^{2+ and the} like. These may be used alone or in combination of two or more.

The method of adding these polyvalent metal ions is not particularly limited, but it is preferable to add them before the completion of the dropping of the monomer, and it is particularly preferable to initially charge the entire amount. The amount used is preferably 100 ppm or less based on the total amount of the reaction solution. If it exceeds 100 ppm, the effect of the addition will no longer be seen, and the resulting copolymer will be too colored and may not be usable as a detergent composition, which is not preferred.

The supply form of the polyvalent metal ion is not particularly limited, and any metal compound or metal may be used as long as it can be ionized in the polymerization reaction system. Examples of such metal compounds and metals include vanadium oxytrichloride, vanadium trichloride, vanadium oxalate, vanadium sulfate, vanadic anhydride, ammonium metavanadate, ammonium hypovanadas [(N
H ₄ ) ₂ SO ₄ .VSO ₄ .6H ₂ O], ammonium sulfate vanadas [(NH ₄ ) V (SO ₄ ) ₂ .12H ₂ O], copper acetate (II), copper (II) bromide, copper ( II) acetyl acetate, cupric chloride, cupric ammonium chloride, copper carbonate, copper (II) chloride, copper (II) citrate, copper (II) formate, copper (II) hydroxide, copper nitrate, copper naphthenate, Copper (II) oleate,
Copper maleate, copper phosphate, copper (II) sulfate, cuprous chloride,
Copper (I) cyanide, Copper iodide, Copper oxide (I), Copper thiocyanate, Iron acetylacetonate, Ferric ammonium citrate, Ferric ammonium oxalate, Ferrous ammonium sulfate, Ferric ammonium sulfate, Water-soluble metal salts such as iron citrate, iron fumarate, iron maleate, ferrous lactate, ferric nitrate, iron pentacarbonyl, ferric phosphate, ferric pyrophosphate, vanadium pentoxide, copper oxide (II), metal oxides such as ferrous oxide and ferric oxide, metal sulfides such as copper (II) sulfide and iron sulfide, copper powder, iron powder and the like. The monomer composition for polymerization of the present invention contains the above-mentioned monomers, a polymerization initiator, a chain transfer agent, and additives such as polyvalent metal ions. In addition, in addition to the range in which the polymerization reaction of the present invention is not impaired, the range in which the physical properties of the resulting water-soluble copolymer are not impaired, other additives other than these exemplified additives may be contained in the monomer composition. I don't care.

<Other polymerization conditions> Other polymerization conditions in the method for producing a copolymer of the present invention include p.
H, temperature, concentration, pressure. These will be specifically described in order.

(PH at the time of polymerization) The pH range at the time of polymerization is determined at the point of time after the end of the initial preparation (that is, immediately before the start of the dropwise addition of the monomer to be added dropwise, or when the polymerization initiator is added dropwise to the monomer). When the dropping is started before, it is 5 to 13, preferably 5 to 12. Immediately before the start of the dropping of the polymerization initiator, more preferably 8 to 12. Thereafter, the polymerization is started by the dropping start. PH gradually as the polymerization proceeds
Is preferably set so as to decrease, and is preferably adjusted to 4 to 8 at the end of the dropping of the monomer.

In general, the monomer (a) is much less polymerizable than the monomer (b), so that a large amount of the monomer (a) is added at the stage of initial preparation. ,In that case,
In the initial stage of polymerization, the concentration of the monomer (a) is overwhelmingly higher than that of the monomer (b), so that the monomer (a) may be polymerized in a block manner. Therefore, in the production method of the present invention, it is considered that the adjustment of pH is important to control the polymerizability of the monomer (a), and the pH is set in the above range. The monomer (a) is a monomer having a dicarboxylic acid, and there are three types of carboxyl groups, both of which are acid type, one of which is acid type, and both of which are neutralized type. Among them, one of them is an acid type, that is, a semi-neutralized type is the most polymerizable. Therefore, by controlling the abundance of the monomer (a) in the semi-neutralized type, the polymerization of the monomer (a) is controlled. Sex can be controlled. That is, in the initial stage of polymerization, the amount of the semi-neutralized type is suppressed to some extent, and as the polymerization proceeds and the concentration of the monomer (a) itself decreases, the polymerizability also decreases. It is necessary to increase the amount of the sum type. In view of these, the above-mentioned pH was set.

As the pH adjusting agent, the "neutralizing agent" described in the method of adding the monomer may be used as needed. Note that the final pH may be set to a desired pH after the polymerization is completed, by using a "neutralizing agent" as necessary.

(Polymerization temperature) The temperature at the time of polymerization is not particularly limited at the time of initial charging, and is from the start of polymerization due to the start of dropping of the monomer or the polymerization initiator to the end of polymerization (that is, the monomer and the polymerization initiator). In some cases, when the dropping of the chain transfer agent or the like is completed, and when the aging time is further set after the completion of the dropping in some cases, the aging time is preferably 80 ° C. or higher, particularly preferably around the boiling point of the polymerization solvent. When the pH and concentration are adjusted after the completion of the polymerization, it is not particularly limited and may be appropriately performed.

If the temperature during the polymerization is lower than 80 ° C., the decomposition efficiency of the polymerization initiator becomes poor, and the residual amount of the monomer in the obtained copolymer becomes extremely large, which is not preferable. In addition, it is very preferable to carry out the polymerization at the boiling point, since the temperature control becomes very easy, the reproducibility of the polymerization is good, and the quality of the resulting copolymer is very stable.

(Polymerization Concentration) The concentration of each monomer at the time of polymerization of the monomer composition for polymerization reaction is not particularly limited, but the concentration at the initial preparation is 35 to 75% by weight, preferably 40 to 75% by weight.
70% by weight, particularly preferably 45-60% by weight.
If the concentration of each monomer at the time of initial preparation is less than 35% by weight, the reactivity of the monomer (a) becomes extremely poor, and it is not preferable from the viewpoint of productivity. The monomer is no longer water-soluble and the reaction solution is in the form of a slurry or precipitate, which is not preferable because uniform polymerization is not achieved.

The polymer solid content at the end of the polymerization is 3
It is 5 to 65% by weight, preferably 40 to 60% by weight or more, particularly preferably 45 to 60% by weight or more, and the concentration of the dropped material (that is, each monomer) is adjusted to meet this.
When the polymer solid content concentration at the end of the polymerization is less than 35% by weight, the polymer solid content concentration during the polymerization becomes extremely low. Further, since the polymerizability of the monomer becomes extremely poor, the residual amount of the monomer in the obtained copolymer becomes extremely large, and the productivity becomes low, which is not preferable from the economical viewpoint. Conversely, if the polymer solids concentration exceeds 65% by weight, the resulting polymer solids concentration during polymerization becomes extremely high, so that the reaction solution has a very high viscosity and does not become homogeneously polymerized. In addition, there is a possibility that the molecular weight may become very high, and particularly, since the clay dispersing ability in high-hardness water is adversely affected, the solution viscosity of the obtained copolymer becomes extremely high, and from the handling point of view, it is also very undesirable. . Note that the final polymer solid content concentration after the completion of the polymerization may be appropriately adjusted.

(Polymerization pressure) The pressure at the time of polymerization is not particularly limited, and may be any of pressurization, normal pressure (atmospheric pressure), and reduced pressure, and may be appropriately set in some cases.

(Solid Content Concentration) During the above-mentioned polymerization reaction of the present invention, the solid content concentration of the polymer in the reaction vessel, that is, the solid content concentration during the polymerization reaction is between 40 and 70% by weight. Adjustment is a preferred mode for obtaining the water-soluble copolymer of the present invention. At the stage when the dropping of all the monomer compositions is completed, the pH is adjusted to 8 to 12, and the concentration of the solid content in the polymerization reaction solution at that time is 40 to 60.
Adjustment in the range of weight% is also a preferred mode for obtaining the water-soluble copolymer of the present invention. If the polymerization reaction is performed outside of these solid contents, it becomes difficult to obtain a water-soluble copolymer having predetermined physical properties.

[Use of Copolymer] Next, another object of the present invention is to provide a detergent composition, an inorganic pigment dispersant, a water treatment agent, and a fiber, comprising the above copolymer. Each of the treatment agents will be specifically described.

(Detergent Composition) In the present invention, the detergent composition comprising the above-mentioned copolymer has a blending amount of the copolymer of 1 to 20% by weight of the entire detergent composition, The amount of the surfactant is preferably 5 to 70% by weight of the entire detergent composition, and in some cases, the enzyme may be added in a range of 5% by weight or less. 1% by weight of copolymer
If the amount is less than 20% by weight, the effect of addition will not be exhibited. If the amount exceeds 20% by weight, the effect of addition will not lead to improvement in detergency and will be economically disadvantageous. On the other hand, if the amount of the surfactant, which is the main component of the detergent composition, is out of the above range, the balance with other components may be lost and the detergency of the detergent composition may be adversely affected. When the enzyme is blended, it contributes to the improvement of detergency, but if it exceeds 5% by weight,
The effect of the addition is no longer exhibited, and it is economically disadvantageous, which is not preferable.

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 used. As the anionic surfactant,
Although not particularly limited, for example, alkyl benzene sulfonate, alkyl or alkenyl ether sulfate,
Alkyl or alkenyl sulfate, α-olefin sulfonate, α-sulfofatty acid or ester salt, alkane sulfonate, saturated or unsaturated fatty acid salt, alkyl or alkenyl ether carboxylate, amino acid type surfactant, N-acyl Examples thereof include an amino acid type surfactant, an alkyl or alkenyl phosphate, or a salt thereof.

The nonionic surfactant is not particularly restricted but includes, for example, polyoxyalkylene alkyl or alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl Glycoxide, fatty acid glycerin monoester, alkylamine oxide and the like can be mentioned.

The amphoteric surfactant is not particularly restricted but includes, for example, carboxy-type or sulfobetaine-type amphoteric surfactants. The cationic surfactant is not particularly limited. And quaternary ammonium salts.

As the enzyme to be added to the detergent composition 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 detergent composition of the present invention may further contain a known alkali builder, chelate builder,
Components commonly used in detergent compositions such as anti-redeposition agents, soil release agents, color transfer inhibitors, softeners, fluorescent agents, bleaching agents, bleaching aids, and fragrances may be added. Further, zeolite may be blended.

As the alkali builder, silicates, carbonates, sulfates and the like can be used. Chelate builders include diglycolic acid, oxycarboxylate, ED
TA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminehexaacetic acid), citric acid and the like can be used as needed.

(Inorganic pigment dispersant) In the present invention, the inorganic pigment dispersant characterized by comprising the above-mentioned copolymer is preferably composed of the copolymer of the present invention. As a compounding agent, condensed phosphoric acid and its salt, phosphonic acid and its salt, and polyvinyl alcohol may be used.

The content of the copolymer of the present invention in the inorganic pigment dispersant of the present invention is not particularly limited, but is preferably 5 to 100% by weight. Also performance,
A known water-soluble polymer may be contained as long as the effect is not affected.

In any case, the dispersant exhibits good performance as a dispersant for heavy or light calcium carbonate or clay inorganic pigments used in paper coating. For example, by adding a small amount of the inorganic pigment dispersant of the present invention to an inorganic pigment and dispersing the same in water, it has a low viscosity and high fluidity, and the aging stability of the performance thereof is high. Highly concentrated inorganic pigment slurries such as concentrated calcium carbonate slurries can be produced.

The use amount of the inorganic pigment dispersant of the present invention is preferably 0.05 to 2.0 parts by weight based on 100 parts by weight of the inorganic pigment. If the amount is less than 0.05 part, a sufficient dispersing effect cannot be obtained, and if it exceeds 2.0 parts by weight, the effect corresponding to the added amount can no longer be obtained, which may be economically disadvantageous. It is not preferable because there is.

(Water-treating agent) The water-treating agent according to the present invention, which comprises the above-mentioned copolymer, preferably comprises the copolymer of the present invention. As the agent, a composition containing a polymerized phosphate, a phosphonate, an anticorrosive, a slime control agent, and a chelating agent can be used. In any case, the cooling water circulation system,
It is useful for scale prevention in boiler water circulation systems, seawater desalination equipment, pulp digesters, black liquor concentrators, and the like. Further, a known water-soluble polymer may be contained within a range not affecting the performance and the effect.

(Fiber treatment agent) In the present invention, the fiber treatment agent characterized by containing the above-mentioned copolymer is at least one selected from the group consisting of a dye, a peroxide and a surfactant; It includes the above copolymer of the present invention. The content of the copolymer of the present invention in the fiber treatment agent of the present invention,
It is not particularly limited. Preferably, 1-100
% By weight. More preferably, it is 5 to 100% by weight. A known water-soluble polymer may be contained within a range that does not affect the performance and the effect.

Hereinafter, examples of blending of the fiber treating agent of the present invention in a form closer to the embodiment will be described. This fiber treatment agent can be used in the steps of refining, dyeing, bleaching, and soaping in fiber treatment. Dyes, peroxides and surfactants include those commonly used in fiber treatments.

The compounding ratio of the above-mentioned copolymer and at least one selected from the group consisting of a dye, a peroxide and a surfactant is, for example, to improve the whiteness, unevenness of color and the degree of dyeing of the fiber. In order to achieve this, at least one selected from the group consisting of a dye, a peroxide and a surfactant is used in an amount of 0.1 to 100 based on 1 part by weight of the copolymer of the present invention in terms of a fiber treatment agent pure component. It is preferable to use a composition blended in a ratio of parts by weight as a fiber treatment agent.

For example, a preferred embodiment of the fiber treatment agent of the present invention is an aqueous solution having a predetermined concentration of the fiber treatment agent mixed in terms of the pure content. The predetermined concentration can be determined depending on the use form and purpose of use. There is no particular limitation.

The fibers for which the fiber treating agent of the present invention can be used are not particularly limited. For example, cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, wool,
Examples include animal fibers such as silk yarn, semi-synthetic fibers such as human silk, and woven or blended products thereof.

When the fiber treating agent of the present invention is applied to the refining step, it is preferable to blend the copolymer of the present invention, an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the copolymer of the present invention, a peroxide, and a silicate-based agent such as sodium silicate as a decomposition inhibitor for an alkaline bleaching agent.

[0083]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to examples, but the present invention is not limited to these examples. “%” Indicates “% by weight”.

Example 1 Example 1 is an example of a method for producing a copolymer in the present invention. The weight average molecular weight (hereinafter, referred to as Mw) of the copolymer was measured by the following method.

<Measurement method of weight average molecular weight (Mw)> Measured by GPC (gel permeation chromatography) Column: G-3000PWXL (manufactured by Tosoh) Mobile phase: disodium hydrogen phosphate dodecahydrate 34.5
g and sodium dihydrogen phosphate dihydrate 4
Pure water was added to 6.2 g (special grade reagent, all reagents used in the following measurement were used for the special grade) to make the total amount 5000 g,
Aqueous solution filtered with a 0.45 micron membrane filter. Detector: UV 214 nm (Waters model 481 type) Pump: L-7110 (Hitachi) Flow rate: 0.5 ml
/ Min ・ Temperature; 35 ° C ・ Calibration curve: Sodium polyacrylate standard sample (manufactured by Souwa Kagaku) (Example 1-1) Maleic acid (hereinafter abbreviated as MA) as monomer (a), monomer ( b) acrylic acid (hereinafter A)
A), 2-hydroxy-3- as monomer (c)
Sodium allyloxypropanesulfonate (hereinafter HA)
PS (abbreviated as PS) in molar ratio of (a) / (b) / (c)
= 47/48/5 was synthesized.

That is, 38.27 g of ion-exchanged water (hereinafter referred to as pure water) was placed in a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser.
275 g of a 48% aqueous sodium hydroxide solution (hereinafter abbreviated as 48% NaOH), 192.08 g of anhydrous MA, and 25%
Initially, 183.12 g of the HAPS aqueous solution was charged, and under stirring.
The temperature of the aqueous solution was raised to the boiling point reflux state. Then, while maintaining the reflux state under stirring, an 80% aqueous solution of AA 180
g of 50% aqueous solution of 35% hydrogen peroxide (abbreviated as 35% H ₂ O ₂ ) over a period of 120 minutes from the start of polymerization, and 50% aqueous solution of sodium persulfate (hereinafter referred to as 15% 55.6 g of pure water and 192.9 g of pure water were added for 8 minutes from 50 minutes to 130 minutes after the start of polymerization.
Over a period of 0 minutes, the liquid was continuously dropped at a uniform rate from separate dropping nozzles. Further, the boiling point reflux state was maintained for 30 minutes after the completion of all the dropwise additions to complete the polymerization.

After completion of the polymerization, the pH and concentration were adjusted, and p
The copolymer 1-1 having H7.5 and a solid concentration of 45% was obtained.
Mw was 8000.

(Examples 1-2 and 1-3) As in Example 1-1, MA was used as the monomer (a), AA was used as the monomer (b), and HAPS was used as the monomer (c). A copolymer having a composition as summarized in Table 1 was synthesized.

That is, in the same manner as in Example 1-1, the polymerization was carried out at the initial charge amount, the drop amount, the drop time, and the aging time as summarized in Table 1. In Example 1-3, 25% HAPS, which is the monomer (c), was prepared by initially charging half of the amount used, and half of the amount was added dropwise.

After completion of the polymerization, the pH was adjusted in the same manner as in Example 1-1.
Copolymers 1-2 and 1-3 prepared at 7.5 and a solid concentration of 45% were obtained. Mw was 7,500 and 5000, respectively.

(Examples 1-4 to 1-6) MA was used as the monomer (a), AA and methacrylic acid (hereinafter abbreviated as MAA) as the monomer (b), and sulfo as the monomer (c). Using sodium salt of ethyl methacrylate (hereinafter abbreviated as SEMS), copolymers having compositions as summarized in Table 2 were synthesized.

That is, in the same manner as in Example 1-1, polymerization was carried out with the initial charge, the amount of drop, the time of drop and the aging time as summarized in Table 2. After completion of the polymerization, the pH was adjusted in the same manner as in Example 1-1.
7.5, a copolymer 1-4 prepared to a solid concentration of 45%,
1-5 and 1-6 were obtained. Mw is 8500 and 7 respectively
500, 8500.

(Examples 1-7 to 1-9) MA as monomer (a), AA as monomer (b), and 2-acrylamido-2-methylpropanesulfonic acid as monomer (c) (Hereinafter abbreviated as AMPS), a copolymer having a composition as summarized in Table 3 was synthesized.

That is, in the same manner as in Example 1-1, polymerization was carried out at the initial charge amount, drop amount, drop time and aging time as summarized in Table 3. After completion of the polymerization, the pH was adjusted in the same manner as in Example 1-1.
7.5, a copolymer 1-7 prepared to a solid concentration of 45%,
1-8 and 1-9 were obtained. Mw is 9000 and 8 respectively
500, 8000.

(Examples 1-10 to 1-11) MA was used as the monomer (a), AA was used as the monomer (b), and sodium methallylsulfonate (hereinafter referred to as S) was used as the monomer (c).
(Abbreviated as MAS), a copolymer having a composition as summarized in Table 4 was synthesized.

That is, in the same manner as in Example 1-1, polymerization was carried out with the initial charge, the amount of drop, the time of drop and the aging time as summarized in Table 4. After completion of the polymerization, the pH was adjusted in the same manner as in Example 1-1.
7.5, Copolymer 1-10 adjusted to a solid concentration of 45%
And 1-11 were obtained. Mw is 5100,490 respectively
It was 0.

Examples 1-11-2-13 MA was used as the monomer (a), AA was used as the monomer (b), and sodium allyl sulfonate (hereinafter referred to as SA) was used as the monomer (c).
(Abbreviated as S) to synthesize copolymers having compositions as summarized in Table 5.

That is, in the same manner as in Example 1-1, polymerization was carried out with the initial charge, the drop amount, the drop time, and the aging time as summarized in Table 5. After completion of the polymerization, the pH was adjusted in the same manner as in Example 1-1.
7.5, Copolymer 1-12 prepared to a solid concentration of 45%
And 1-13. Mw is 6700 and 610, respectively.
It was 0.

As is clear from the above, the copolymer of the present invention can be produced by the production method of the present invention. Also,
The abbreviations in the table are described below.

Pure water: ion-exchanged water 48% NaOHaq 48% sodium hydroxide aqueous solution MA anhydrous maleic anhydride 80% Aaq 80% acrylic acid aqueous solution 100% MAA methacrylic acid・ 44% SEMSaq …… 44% sulfoethyl methacrylate sodium salt aqueous solution ・ 35% H ₂ O ₂ aq …… 35% hydrogen peroxide aqueous solution ・ 15% NaPSaq …… 15% sodium persulfate aqueous solution ・ 25% HAPSaq …… 25% (Sodium 2-hydroxy-3-allyloxypropanesulfonate) Aqueous solution ・ Mw ...... weight average molecular weight

[0101]

[Table 1]

[0102]

[Table 2]

[0103]

[Table 3]

[0104]

[Table 4]

[0105]

[Table 5]

(Comparative Reference Example 1) Here, comparative polymers used in Examples 2 and thereafter were synthesized.

(Comparative Reference Example 1-14) AA homopolymer sodium salt having a pH of 7.5 and a solid content of 45%, that is, a monomer (b) was prepared by a conventionally known method, as compared with the present invention.
Was synthesized.

That is, basically, the same operation as in Example 1-1 was carried out, and 557.34 g of pure water was added as an initial charge, and the temperature was raised to a boiling point under reflux with stirring. Next, while maintaining the reflux state under stirring, the 80% AA aqueous solution 360
g, and 283.33 g of a 48% aqueous NaOH solution over a period of 180 minutes from the start of polymerization, and 5% aqueous NaPS solution
3.33 g and 600 g of pure water were continuously and uniformly dripped from respective dripping nozzles over 190 minutes from the start of polymerization. Further, the boiling point reflux state was maintained for 30 minutes after the completion of all the dropwise additions to complete the polymerization.

After completion of the polymerization, pH and concentration were adjusted, and p
Thus, a comparative polymer 1-14 having H7.5 and a solid content of 45% was obtained. Mw was 5000.

COMPARATIVE REFERENCE EXAMPLES 1-15, 1-16 MA / AA copolymer sodium having a pH of 7.5 and a solid content of 45% for 1-15 and 40% for 1-16 by a conventionally known method. A salt, that is, a copolymer composed of the monomer (a) and the monomer (b) (a polymer not containing the monomer (c)) as compared with the present invention was synthesized.

That is, in the same manner as in Example 1-1, polymerization was carried out with the initial charge, the amount of drop, the time of drop and the aging time as summarized in Table 4. After completion of the polymerization, the pH was adjusted in the same manner as in Example 1-1.
And the solid content was prepared, and the comparative polymers 1-15 and 1-
16 was obtained. Mw was 10,000 and 50,000, respectively.

(Comparative Reference Example 1-17) AA / AMPS having a pH of 7.5 and a solid content of 45% by a conventionally known method.
A copolymer sodium salt, that is, a copolymer composed of monomer (b) and monomer (c) (a polymer not containing monomer (a)) was synthesized as compared with the present invention.

That is, in the same manner as in Example 1-1, polymerization was carried out with the initial charge, the amount of drop, the time of drop and the aging time as summarized in Table 6. After completion of the polymerization, the pH was adjusted in the same manner as in Example 1-1.
And the solid content was prepared to obtain Comparative Polymer 1-17.
Mw 5000.

[0114]

[Table 6]

Example 2 In Example 2, the physical properties of the copolymers 1-1 to 1-17 obtained in Example 1 and Comparative Reference Example 1 were evaluated. First, the measurement methods of the respective physical property evaluations will be described.

<Calcium ion scavenging ability> First, as a calcium ion standard solution for a calibration curve, using calcium chloride dihydrate, 0.01 mol / l
50 g of each of 0.001 mol / l and 0.0001 mol / l aqueous solutions were prepared, the pH was adjusted to a range of 9 to 11 with a 4.8% NaOH aqueous solution, and further a 4 mol / l aqueous potassium chloride solution (hereinafter 4M-KCl (Abbreviated as aqueous solution)
Was added thereto, and the mixture was sufficiently stirred using a magnetic stirrer to prepare a sample solution for a calibration curve. As a test calcium ion standard solution, calcium chloride dihydrate was also used to obtain 0.0012 mol / l.
Was prepared in a required amount (using 50 g per sample).

Next, 10 mg of the test sample (polymer) was weighed in a 100 cc beaker in terms of solid content, and 50 g of a test calcium ion standard solution prepared in the above was added, and the mixture was sufficiently stirred using a magnetic stirrer. Further, similarly to the sample solution for the calibration curve, the pH was adjusted to a range of 9 to 11 with a 4.8% NaOH aqueous solution, and 1 ml of a 4M-KCl aqueous solution was added to prepare a test sample solution.

The sample solution for the calibration curve and the sample solution for the test thus prepared were measured using an ion analyzer EA920 manufactured by Orion with a calcium ion electrode 93-20 manufactured by Orion.

From the calibration curve and the measured value of the test sample solution, the amount of calcium ions captured by the sample (polymer) was determined by calculation, and the value was used to calculate the captured amount per g of polymer solids in terms of g of calcium carbonate. This value was designated as a calcium ion trapping ability value.

<Clay dispersing ability in high hardness water> First, 67.56 g of glycine and 52.g of sodium chloride were used.
A glycine buffer solution was prepared by adding ion-exchanged water to 6 g and 60 ml of a 1 mol / l NaOH aqueous solution to make 600 g.

Calcium chloride dihydrate 0.3268
g, 60 g of the adjusted liquid, and add pure water to make 1000 g.
g and the dispersion was adjusted. In addition, 0.1
% Polymer aqueous solution was prepared.

In a general test tube used for an experiment of about 30 cc, JIS test powder I, 8 kinds (Kanto Rohm, fine particles:
0.3 g of clay of Japan Powder Industry Technology Association) was added, and 27 g of the dispersion liquid prepared above and 3 g of an aqueous polymer solution having a solid content of 0.1% were added. At this time, the calcium concentration of the test solution was 200 ppm in terms of calcium carbonate.

After sealing the test tube with parafilm, gently shake it so that the clay is dispersed all over, and gently shake it up and down.
Shake around. After the test tube was allowed to stand for 20 hours in a place not exposed to direct sunlight, 5 ml of the supernatant of the dispersion was collected with a whole pipette.

This solution was subjected to UV spectroscopy at a wavelength of 38.
Absorbance (ABS) was measured in a 1 cm cell under the condition of 0 nm, and this value was defined as a clay dispersing ability value in high hardness water.

<Geling resistance> First, 0.1 mol of calcium chloride dihydrate was used.
A 1 / l calcium ion standard solution was prepared and added to a tank attached to a burette head H-900, which is an auxiliary unit of an automatic titrator manufactured by Hiranuma Sangyo Co., Ltd.
Set with 900. Separately, a 1% aqueous polymer solution was prepared.

80 g of pure water in a 100 cc beaker, glycine buffer solution 1c used for measurement of clay dispersing ability
c and 2.5 g of a 1% aqueous polymer solution were added, followed by sufficient stirring.

The sample solution was measured using an automatic titrator COM-550 manufactured by Hiranuma Sangyo Co., Ltd., using an attached photometric titration unit M-500 under the condition of a wavelength of 530 nm. The solution was added dropwise in 0.05 ml increments to a maximum of 10 ml, and the turbidity was measured each time. Then, the end point, that is, the drop amount of the cloudy point was determined based on the F intersection detection method described in the instruction manual for the device.

The value obtained by multiplying the obtained end drop amount by 1/10 was defined as the gelation resistance value.

(Examples 2-1 to 2-13) The copolymers 1-1 to 1-13 of the present invention obtained in Example 1 were evaluated for calcium ion trapping ability, clay dispersing ability in high hardness water, The gelation resistance was measured based on each of the above methods.
Table 7 summarizes the results.

(Comparative Examples 2-14 to 2-17) Similarly, conventionally known polymers 1-14 to 1-1 obtained in Comparative Reference Examples
7 was measured, and the results are summarized in Table 7.

[0131]

[Table 7]

As is evident from Table 7, the copolymer of the present invention exhibits high performance in all of calcium ion trapping ability, clay dispersing ability in high hardness water, and gelation resistance, and only a specific function is improved. It is much better than conventionally known polymers that did not show performance. Next, practical examples of detergent compositions and fiber treatment agents will be described by effectively utilizing this high performance.

(Example 3) In Example 3, the copolymer obtained by the present invention is evaluated as a detergent composition characterized by including the copolymer, which is another object of the present invention. Therefore, the cleaning ability was measured by the following method.

<Cleaning Ability> First, an artificially stained cloth and a non-stained cloth for performing a washing power test were prepared. That is, 8.3 parts of myristic acid, 8.3 parts of oleic acid, 8.3 parts of tristearin, 8.3 parts of triolein, 1.1 parts of cholesterol stearate, and 5.5 of paraffin wax (melting point: 48 to 50 ° C.). Part, 5.5 parts of squalene, 4.4 parts of cholesterol, 0.6 part of carbo black, and 49.7 clay of JIS test powder I, 8 kinds (Kanto Rohm, fine particles: Japan Powder Industry Technical Association)
Part of artificial soil is prepared, and the artificial soil is dispersed in carbon tetrachloride, and a white cloth of JIS-L0803 cotton cloth (Kankin No. 3) obtained from the Washing Science Association is used as the artificial soil. After allowing the liquid to dry, cut and cut
A 10 cm soiled cloth was prepared. In addition, the obtained white cloth was cut into 10 cm × 10 cm without being contaminated to prepare a non-contaminated cloth. Then, these contaminated cloths and uncontaminated cloths are previously measured with a colorimetric colorimeter N
The whiteness was measured by reflectance using a D-1001DP type.

Next, a detergent composition was prepared. That is, sodium linear alkyl benzene sulfonate (C = 1)
1.5) 20 parts, sodium lauryl sulfate 5 parts, polyoxyethylene alkyl ether (C = 12, EO = 8)
15 parts, zeolite A4 powder 20 parts, sodium carbonate 2
0 parts, 1 part sodium silicate 5 parts, enzyme (protease)
A powdery detergent composition comprising 1.5 parts, 1.5 parts of a fragrance, and 12 parts of a polymer was obtained.

Further, calcium ion water was prepared as washing water. That is, calcium chloride dihydrate 1
4.7 g was dissolved in pure water to make a total amount of 5000 g, and a washing water having 50 ppm in terms of calcium carbonate was prepared.
It was kept at 25 ° C.

Under a constant condition of 25 ° C., in a pot of a targot meter, 1 liter of the washing water prepared in 1.3 g of the detergent composition prepared in 1 liter, 5 stained cloths prepared in 5 liters, and 5 unpolluted cloths After loading, the turgot meter was operated at 100 rpm for 10 minutes to wash. Thereafter, rinsing for 3 minutes was performed twice using the washing water prepared in the above, and similarly at 100 rpm using a tergot meter.

After washing, the cloth was dried, ironed, and the wrinkles were stretched. Then, the whiteness of the contaminated cloth after washing was measured again by the reflectance using the above colorimeter and colorimeter.

From the above measurement results, the cleaning rate was determined by the following equation, which was taken as the cleaning ability value.

Cleaning rate = (reflectance after cleaning−reflectance before cleaning) / (reflectance of white cloth−reflectance before cleaning) × 100 (Examples 3-1 to 3-13) Obtained in Example 1. The cleaning performance of each of the obtained copolymers 1-1 to 1-13 of the present invention was measured based on the above method. Table 8 summarizes the results.

(Comparative Examples 3-14 to 3-17) Similarly, conventionally known polymers 1-14 to 1-1 obtained in Comparative Reference Examples
7 were measured, and the results are summarized in Table 8.

[0142]

[Table 8]

As is evident from Table 8, the copolymer of the present invention has a very excellent cleaning ability as compared with conventionally known polymers.

(Example 4) In Example 4, the copolymer obtained by the present invention was evaluated as an inorganic pigment dispersant characterized by including the copolymer, which is another object of the present invention. For this purpose, the viscosity of the inorganic pigment dispersion was measured using a B-type viscometer by the following method.

<Preparation of Dispersion> First, a 10% aqueous solution of a copolymer in terms of solid content was prepared.

Next, ultrapure water 1 was placed in a 600 ml plastic container.
Add 50 g, and use TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd.
While stirring at 00 rpm, light calcium carbonate 70
g, 105 g of heavy calcium carbonate and Alpha Coat 1
75 g were gradually added in this order. During the addition, if it became difficult to disperse the pigment, a 10% aqueous copolymer solution was appropriately added.

After all the pigments were added, a 10% aqueous solution of the copolymer was added so that the total amount was 10.5 g, and 3000 g was added.
Stirred for another 15 minutes at rpm.

After stirring, put in a thermostat at 25 ° C. for 30 minutes,
Thereafter, the viscosity was measured by rotating the rotor for 3 minutes using a B-type viscometer.

(Examples 4-1 to 4-13) Each of the copolymers 1-1 to 1-13 of the present invention obtained in Example 1 was evaluated as an inorganic pigment dispersant based on the above method. Was. Table 9 summarizes the results.

(Comparative Examples 4-14, 4-17) Similarly, conventionally known polymers 1-14, 1-1 obtained in Comparative Reference Examples.
7 were measured, and the results are summarized in Table 9.

[0151]

[Table 9]

As is clear from Table 9, the copolymer of the present invention has an excellent inorganic pigment dispersing ability as compared with conventionally known polymers.

(Example 5) In Example 5, the copolymer obtained by the present invention is evaluated as a water treatment agent characterized by including the copolymer, which is another object of the present invention. Therefore, the ability to prevent calcium carbonate scale was measured by the following method.

<Calcium Carbonate Scale Inhibiting Ability> First, a 1.56% aqueous solution of calcium chloride dihydrate, a 3% aqueous sodium hydrogen carbonate solution, and a 0.02% aqueous copolymer solution were prepared.

Next, 170 g of pure water was put into a glass bottle having a capacity of 225 ml, 10 g of a 1.56% aqueous solution of calcium chloride dihydrate, 3 g of a 0.02% aqueous solution of a copolymer were mixed, and 10 g of an aqueous sodium hydrogen carbonate solution was further added. And 7 g of sodium chloride were added to make the total amount 200 g.

The obtained 530 ppm supersaturated aqueous solution of calcium carbonate was sealed and heated at 70 ° C.

After cooling, the precipitate was filtered through a 0.1 μm membrane filter, and the filtrate was subjected to JIS K0101.
The analysis was performed according to the above.

From the above measurement results, the calcium carbonate scale inhibition rate (%) was determined by the following equation.

Scale inhibition rate (%) = [(CB) /
(AB)] × 100 where A: concentration of calcium dissolved in the liquid before the test (%) B: calcium concentration in the solution without the copolymer (%) C: in the filtrate after the test Calcium concentration (%) (Examples 5-1 to 5-13) For the copolymers 1-1 to 1-13 of the present invention obtained in Example 1, the scale prevention ability was measured based on each of the above methods. Was. Table 10 summarizes the results.

(Comparative Examples 5-14, 5-15) Similarly, conventionally known polymers 1-14, 1-1 obtained in Comparative Reference Examples
5 were measured, and the results are summarized in Table 10.

[0161]

[Table 10]

As is evident from Table 10, the copolymer of the present invention has an excellent inorganic pigment dispersing ability as compared with conventionally known polymers.

Example 6 In Example 6, the copolymer obtained by the present invention is evaluated as a fiber treating agent characterized by containing the copolymer, which is another object of the present invention. Therefore, a bleaching test was performed by the following method.

<Bleaching Test> First, a fiber treating agent solution was prepared. That is, calcium chloride dihydrate is dissolved in pure water and converted to calcium carbonate by 5%.
In 1 liter of water prepared to be 0 ppm, 10 g of hydrogen peroxide, 2 g of sodium hydroxide, 5 g of No. 3 sodium silicate and 2 g of the copolymer were dissolved.

Next, the refined cotton sheet knit was bleached at a bath ratio of 1/25 at a temperature of 85 ° C. for 30 minutes. Table 7 shows the results.

After bleaching, the fabric was evaluated for texture and whiteness. The texture of the cloth was evaluated by a sensory test in three stages: soft, slightly hard, and fairly hard.
The whiteness was evaluated by the colorimeter used in the evaluation of the cleaning ability.

(Examples 6-1 to 6-13) The cleaning ability of each of the copolymers 1-1 to 1-13 of the present invention obtained in Example 1 was measured based on the above method. Table 11 summarizes the results.

(Comparative Examples 6-14 to 6-17) Similarly, conventionally known polymers 1-14 to 1-1 obtained in Comparative Reference Examples
7 was measured, and the results are summarized in Table 11.

[0169]

[Table 11]

As apparent from Table 11, the copolymer of the present invention is very useful as a fiber treating agent, as compared with conventionally known polymers.

[0171]

The sulfonic acid group-containing maleic acid / acrylic acid copolymer according to the present invention exhibits high performance in all of calcium ion trapping ability, clay dispersing ability in high hardness water and gelation resistance. . Further, in the present invention, for example, the above-mentioned high-performance polymer can be provided by a production method characterized by causing a monomer composition having a specific composition to undergo a polymerization reaction under specific conditions. Since the water-soluble copolymer of the present invention has unprecedented specific physical properties, detergent compositions, inorganic pigment dispersants, water treatment agents, and fiber treatment agents using the water-soluble copolymer are extremely difficult. Demonstrates excellent performance.

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[Procedure amendment]

[Submission date] August 22, 2000 (2008.2.
2)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

7. A process for producing a water-soluble polymer, which comprises the following conditions: (1) in an aqueous solvent containing 80% by weight or more of water, (2) a monoethylenic compound having 4 to 6 carbon atoms. Unsaturated dicarboxylic acid (salt) or its anhydride monomer (a)
Is initially charged in an amount of 80% by weight or more based on the total amount of the monomer (a), and the remainder is added dropwise. (3) Monoethylenically unsaturated monocarboxylic acid (salt) having 3 to 8 carbon atoms 90% by weight of monomer (b) based on the total amount of monomer (b) used
(4) As a polymerization initiator, hydrogen peroxide and persulfate were used as dripping at 80% by weight or more of their respective predetermined amounts, and the remainder was used as an initial charge. 5) The pH of the monomer composition liquid for polymerization reaction at the stage of initial preparation is 8 to 12, and the degree of neutralization is 50 to 95 m.
The polymerization was initiated with ol%, solids concentration in the polymerization reaction is adjusted to a range of 40 to 70 wt%, (6) at the stage the addition was finished the monomer composition of the whole hand, pH 4 The solid content concentration is adjusted in the range of 40 to 60% by weight, and the polymerization temperature is carried out at 80C or higher.
A method for producing the water-soluble copolymer according to the above.

[Procedure amendment]

[Submission date] August 24, 2000 (2008.2.
4)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claims

[Correction method] Change

[Correction contents]

[Claims]

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09C 3/10 C09C 3/10 C11D 3/37 C11D 3/37 D06M 15/263 D06M 15/263 // ( C08F 220/04 228: 02) F-term (reference) 4H003 EB32 FA04 FA21 4J011 BA06 BB01 BB02 HA02 HB02 HB05 HB06 HB22 4J037 AA10 AA27 CC17 CC29 EE08 EE28 EE43 FF15 4J100 AB07R AJ01P18 AK08AJAQP AP01R BA03Q BA03R BA56R CA05 CA06 DA00 DA01 FA03 FA19 FA28 FA30 JA11 JA18 JA57 4L033 AB01 AC15 CA18

Claims (7)

[Claims] 1. A water-soluble copolymer having a structure derived from a monomer derived from a monoethylenically unsaturated dicarboxylic acid (salt) having at least 4 to 6 carbon atoms or an anhydride thereof. A unit, (b) a structural unit derived from a monoethylenically unsaturated monocarboxylic acid (salt) monomer having 3 to 8 carbon atoms, and (c) a monoethylenically unsaturated group having a sulfonic acid (salt) group In a water-soluble copolymer having a structural unit derived from a monomer, as a physical property of the water-soluble copolymer, calcium ion trapping ability is 0.40 or more, clay dispersing ability in high hardness water is 0.35 or more, A water-soluble copolymer having a gelation resistance of 0.35 or more. 2. (a) 30 to 70 mol% of a monoethylenically unsaturated dicarboxylic acid (salt) having 4 to 6 carbons or an anhydride thereof, (b) having 3 to 8 carbons Monoethylenically unsaturated monocarboxylic acid (salt) monomer 30 to
70 mol%, (c) 2 to 16 mol% of a monoethylenically unsaturated monomer having a sulfonic acid (salt) group, and (d)
Monomeric unsaturated monomers copolymerizable with the monomers (a) to (c) are 0 to 5 mol%, and the total of (a) to (d) is 100 mol%. A water-soluble copolymer obtained by polymerization, having a weight average molecular weight of 200
A water-soluble copolymer having a sulfonic acid group of 0 to 20,000, and the physical properties of the water-soluble copolymer are calcium ion trapping ability of 0.40 or more and clay dispersing ability in high hardness water of 0.35 or more. A water-soluble copolymer having a gelation resistance of 0.35 or more. 3. A detergent composition comprising the water-soluble copolymer according to claim 1. 4. An inorganic pigment dispersant comprising the water-soluble copolymer according to claim 1 or 2. 5. A water treatment agent comprising the water-soluble copolymer according to claim 1. 6. A fiber treating agent comprising the water-soluble copolymer according to claim 1. 7. A process for producing a water-soluble polymer, which comprises the following conditions: (1) in an aqueous solvent containing 80% by weight or more of water, (2) a monoethylenic compound having 4 to 6 carbon atoms. Unsaturated dicarboxylic acid (salt) or its anhydride monomer (a)
Is initially charged in an amount of 80% by weight or more based on the total amount of the monomer (a), and the remainder is added dropwise. (3) Monoethylenically unsaturated monocarboxylic acid (salt) having 3 to 8 carbon atoms 90% by weight of monomer (b) based on the total amount of monomer (b) used
(4) As a polymerization initiator, hydrogen peroxide and persulfate were used as dripping at 80% by weight or more of their respective predetermined amounts, and the remainder was used as an initial charge. 5) The pH of the monomer composition liquid for polymerization reaction at the stage of initial preparation is 8 to 12, and the degree of neutralization is 50 to 95 m.
ol%, the solid content concentration during the polymerization reaction is adjusted to the range of 40 to 70% by weight, and when the dropping of the monomer composition i ≠ Uj ¢ S is completed, the pH is increased. The method for producing a water-soluble polymer according to claim 1, wherein the solid content concentration is adjusted to a range of 4 to 8 and the polymerization temperature is 80 ° C or higher.