JP2002012627A - Water-soluble polymer and its use - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a specific water-soluble polymer exhibiting a high action for scavenging a calcium ion and showing a high action for dispersing clay even in high-hardness water, a detergent composition containing the polymer and to provide uses except the detergent composition by making the best of the characteristics of the water-soluble polymer. SOLUTION: This specific water-soluble polymer is characterized in that the polymer has >=0.40 calcium ion scavenging ability and >=0.50 clay dispersion ability in high-hardness water and is preferably obtained by compounding a polymer A having >=0.45 calcium ion scavenging ability with a polymer B having >=0.65 clay dispersion ability as essential components. This detergent composition obtained by using the water-soluble polymer has improved detergency even in high-hardness water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a water-soluble polymer having a specific function, a detergent composition containing the polymer, and other uses of the water-soluble polymer.

[0002]

2. Description of the Related Art Surfactants, especially anionic surfactants, are mainly used as detergents. When calcium ions, magnesium ions, and the like, which are hardness components, are present in water, the anionic surfactant forms a salt with these and insolubilizes them, so that the detergency tends to decrease significantly. Therefore, in order to capture these hardness components and improve the detergency of the detergent composition, a polymer having a high calcium ion capturing ability is added as a builder. In addition, a dispersing action on mud stains, that is, inorganic particles (clay), which is remarkably exhibited as a re-staining preventing action on a white cloth in washing, is characterized by a water-soluble polycarboxylic acid polymer. There is something.

Acrylic polymers and maleic / acrylic copolymers having a large number of carboxyl groups, which are one kind of the above water-soluble polycarboxylic acid polymers, have been known to have a calcium ion trapping action and It is known to have a clay dispersing action. Japanese Patent Application Laid-Open Nos. Sho 62-270605 and Hei 5-
239114, etc., and a method for producing a maleic acid / acrylic acid copolymer are described in JP-A-5-247143, JP-B-3-2167, JP-B-3-14046, and Patent 257.
No. 4144 and the like have been disclosed, and various measures have been taken to improve these functions. These polycarboxylic acid polymers make use of the above-mentioned properties, and in addition to the above-mentioned examples, various documents such as JP-A-11-35989 disclose that they are suitable as a detergent composition.

Although maleic acid / acrylic acid copolymers have a very high calcium ion trapping action, the clay dispersing action is satisfactory under low hardness conditions, but particularly under high water hardness conditions. Shows almost no effect. On the other hand, the acrylic acid-based polymer has a clay dispersing action even under high hardness water, but has a very poor calcium ion trapping action. This is because, generally, the higher the molecular weight, the higher the calcium ion trapping action, but the lower the clay dispersing action, especially under high hardness water. This is because the dispersing action tends to be high, but the calcium ion trapping action tends to be low. Therefore, there is a problem in that a dilemma arises in that if one performance is required, the other performance deteriorates.

[0005] Therefore, it is necessary to simultaneously determine the performance of both the action of trapping hardness components such as calcium ions and the like and the action of dispersing inorganic particles in order to improve the detergency of the detergent composition, especially in high-hardness water. It is very important to enhance the power, and various devices have been conventionally devised. For example, as exemplified in the above-mentioned literature, attempts have been made to improve the molecular weight of the polymer having a certain carboxyl group, the production method, and the like. However, as a result, a polymer is designed so that one characteristic is suppressed to a certain level and the other characteristic is very utilized, or the performance of both is balanced, that is, both are at a certain level. The design of the polymer was limited, and both features could not always be utilized at a high level. As a result, it cannot always be said that a sufficient effect is exhibited as a detergent composition.

[0006] Apart from these, Japanese Patent Application Laid-Open No. 11-100 / 1999
No. 592 discloses a detergent composition comprising a combination of two or more specific polymers. However, the effects of the individual polymers to be combined on the above-mentioned properties are not specified, and therefore, it can be said that the effects on the above-mentioned properties are improved even in a mixture of the polymers obtained by combining them. No attempt was made to raise both performances to a high level at the same time. Therefore, the detergent composition did not have sufficient detergency particularly under high hardness water.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a specific water-soluble polymer which exhibits a high calcium ion-trapping action and a high clay dispersing action even under high hardness water, and contains the polymer. Another object of the present invention is to provide a detergent composition comprising the above-mentioned water-soluble polymer and other uses other than the detergent composition utilizing the characteristics of the water-soluble polymer.

[0008]

In order to solve the above-mentioned problems, the present inventors have proposed a detergent composition having a very high detergency, particularly under high hardness water, in order to have a high calcium ion trapping action. It was particularly important to find a polymer having a high level of clay dispersing action under high hardness water, and intensive studies were conducted. As a result, as the physical properties of the polymer, it is very useful as a polymer for a detergent composition, for example, that the calcium ion capturing ability is 0.40 or more and the clay dispersing ability under high hardness water is 0.50 or more. Was found.

Such physical properties can be obtained by using only one kind of polycarboxylic acid polymer, that is, by itself,
For example, it can be obtained by combining two types of polymers having different specific functions. Then, it was confirmed that the polymer mixture obtained in the latter manner exhibited a high calcium ion trapping action and a high clay dispersing action even under high hardness water. And
It was confirmed that a detergent composition comprising the polymer alone and / or a mixture having the specific physical properties described above has a very high detergency even under high hardness water. In order to solve the above problems, the present invention provides the following configurations.

[0010] A water-soluble polycarboxylic acid-based polymer having a calcium ion trapping ability of 0.40 or more and a clay dispersing ability under high hardness water of 0.50 or more. A water-soluble polymer having a structural unit derived from a monoethylenically unsaturated monocarboxylic acid (salt) monomer and / or a monoethylenically unsaturated dicarboxylic acid (salt) monomer. As an essential component, calcium ion capturing ability is 0.4
A polymer mixture comprising a polymer A having a viscosity of 0.65 or more and a polymer B having a clay dispersibility of 0.65 or more in high-hardness water, wherein the physical properties of the polymer mixture are calcium ion trapping ability. A water-soluble polymer having a clay dispersibility of 0.40 or more and a clay dispersibility of 0.60 or more in high hardness water.

In the above-mentioned polymer mixture, the mixing ratio by weight is such that polymer A / polymer B = 20/80 to 9
A water-soluble polymer in a ratio of 5/5. A detergent composition comprising the water-soluble polymer according to any one of the above.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a specific water-soluble polymer which exhibits a high calcium ion-trapping action and a high clay dispersing action even under high hardness water, which is the present invention, and comprises the polymer The detergent composition, and further uses other than the detergent composition utilizing the characteristics of the water-soluble polymer will be described in detail. [Specific Polymer] The specific water-soluble polymer in the present invention is a single substance or a mixture, and has a calcium ion trapping ability of 0.40 or more and a clay dispersing ability under high hardness water of 0.50. It is characterized by the above.
Preferred examples of the specific polymer having such physical properties include a monoethylenically unsaturated monocarboxylic acid (salt) monomer and / or a monoethylenically unsaturated dicarboxylic acid (salt).
Examples thereof include a water-soluble polycarboxylic acid-based polymer or a polymer mixture having a structural unit derived from a monomer.

Specifically, for example, a polymer A having a calcium ion trapping ability of 0.45 or more and a polymer B having a clay dispersing ability of 0.65 or more under high hardness water are blended as essential components. Water-soluble polycarboxylic acid polymer mixture, and in this mixture, more preferably,
The compounding ratio is a weight ratio, polymer A / polymer B = 20 /
It is a ratio of 80 to 95/5. The definition and measurement method of the calcium ion trapping ability and the clay dispersing ability under high hardness water will be described in Examples.
Thus, for example, by mixing the polymer A and the polymer B, each having different physical properties, a water-soluble polymer having the specific physical properties of the present invention can be obtained. The method of obtaining is not limited to the method of mixing.

In a preferred example of the water-soluble polymer of the present invention which satisfies the above specific parameters, as described above, the structural unit derived from the monoethylenically unsaturated monocarboxylic acid (salt) monomer and / or the monoethylene A water-soluble polycarboxylic acid-based polymer or polymer mixture having a structural unit derived from a water-soluble unsaturated dicarboxylic acid (salt) monomer is essential, and these water-soluble polycarboxylic acid-based polymers or polymer mixtures are required. However, the content (blending amount) in the water-soluble polymer according to the present invention is not particularly limited as long as the physical properties of the water-soluble polymer as a whole satisfy the above specific parameters. When the total amount of the water-soluble polymer of the present invention is 100% by weight, the content of the water-soluble polycarboxylic acid-based polymer or the polymer mixture is preferably 50% by weight or more (specifically, 50% by weight or more). -10
Content in the range of 0% by weight). More preferably 70
% By weight (specifically, a content in the range of 70 to 100% by weight), more preferably 80% by weight or more (specifically, 8% by weight).
The content is in the range of 0 to 100% by weight), most preferably 90% by weight or more (specifically, the content in the range of 90 to 100% by weight).

When the content (blending amount) of the water-soluble polycarboxylic acid-based polymer or polymer mixture in the water-soluble polymer of the present invention is less than 50% by weight, the feature of the present invention is obtained. It is not preferable because one or both of the parameters of calcium ion trapping ability and clay dispersing ability under high hardness water may not be satisfied. In particular, it becomes difficult to provide a detergency under high hardness water. In addition, in the water-soluble polymer of the present invention, the other components other than the water-soluble polycarboxylic acid-based polymer or the polymer mixture are not particularly limited,
If necessary, it may be blended within the above range according to the purpose.

Here, in the embodiment of the water-soluble polymer of the present invention, as an essential component, a polymer A having a calcium ion trapping ability of 0.45 or more, and a clay dispersing ability under high hardness water of 0.65 are used. It is preferable to contain a polymer mixture obtained by blending the above polymer B. More preferably, the compounding ratio is a weight ratio, and polymer A / polymer B = 2
0/80 to 95/5. In this embodiment, when the object to be blended is a polymer mixture that essentially includes the polymer A and the polymer B, the total amount of the polymer A and the polymer B is determined according to the present invention. Is considered to be a blending amount (content) in the water-soluble polymer. In the water-soluble polymer of the present invention, if the content of the water-soluble polymer of the present invention, which satisfies the specific parameter properties defined in the present invention and the entire water-soluble polymer of the present invention is 100% by weight, is known, It is possible to calculate the actual blending amount (content) of the polymer A and the polymer B.

For example, one embodiment of the present invention is as follows.
A polymer mixture comprising, as essential components, a polymer A having a calcium ion trapping ability of 0.45 or more and a polymer B having a clay dispersing ability of 0.65 or more under high hardness water. Even in the water-soluble polymer of the present invention obtained by the above, the content (content based on the whole water-soluble polymer according to the present invention) which can be calculated by the total amount of the polymer A and the polymer B is as a result No particular limitation is imposed as long as the whole water-soluble polymer of the present invention satisfies the above-mentioned specific parameters. However, when the total amount of the water-soluble polymer of the present invention is 100% by weight, preferably, the polymer A and the polymer B Is 50% by weight or more (specifically, 50 to 1% by weight).
Content in the range of 00% by weight). More preferably 7
0% by weight or more (specifically, a content in the range of 70 to 100% by weight), more preferably 80% by weight or more (specifically, a content in the range of 80 to 100% by weight), and most preferably 90% by weight % Or more (specifically, the content in the range of 90 to 100% by weight).

The content of the polymer or the polymer mixture satisfying the parameter properties specified in the present invention in the water-soluble polymer of the present invention may be determined according to the desired properties of the obtained water-soluble polymer. As the content, the above content can be preferably adopted. The above-mentioned structural unit derived from a monoethylenically unsaturated monocarboxylic acid (salt) monomer and / or a monoethylenically unsaturated dicarboxylic acid (contained in the water-soluble polymer of the present invention satisfying the above specific parameters) Salt) A water-soluble polycarboxylic acid-based polymer or a polymer mixture having a structural unit derived from a monomer is more specifically a raw material for producing a predetermined polymer described in the present specification. It can be obtained by polymerization using a monomer component containing various monomers.

More specifically, in order to obtain these water-soluble polymers of the present invention, the water-soluble polycarboxylic acid-based polymer or polymer mixture used is described in the present specification. An ethylenically unsaturated monocarboxylic acid (salt) obtained by polymerization using a monomer component containing various monomers, which is a raw material for producing a predetermined water-soluble polycarboxylic acid-based polymer. It is a preferred embodiment to use a water-soluble polycarboxylic acid-based polymer or a polymer mixture having a structural unit derived from a monomer and / or a structural unit derived from a monoethylenically unsaturated dicarboxylic acid (salt) monomer. Hereinafter, each component in the specific water-soluble polymer of the present invention will be described in more detail.

(Physical Properties of Water-Soluble Polymer) The specific water-soluble polymer of the present invention has a calcium ion trapping ability of 0.40 or more and a clay dispersing ability under high hardness water of 0.50 or more, preferably 0.50 or more. The calcium ion trapping ability is 0.40 or more, and the clay dispersing ability under high hardness water is 0.60 or more. By satisfying both parameters of these calcium ion trapping ability and clay dispersing ability under high hardness water, for example, a detergent composition containing the water-soluble polymer is not only low hardness water but also high hardness water. It also demonstrates very good cleaning power. If the calcium ion trapping ability is less than 0.40, the trapping of hardness components such as calcium is not sufficient, and as described above, particularly under high-hardness water, the surfactant may be insolubilized and the detergency may decrease, which is not preferable. On the other hand, if the clay dispersing ability under high hardness water is less than 0.50, the dispersing action on mud soil (inorganic particles) is not sufficient, so that the ability to prevent re-staining of white cloth may be deteriorated, which is not preferable.

(Water-soluble polycarboxylic acid-based polymer) The water-soluble polycarboxylic acid-based polymer in the present invention may be a monoethylenically unsaturated monocarboxylic acid (salt) monomer and / or a monoethylenically unsaturated dicarboxylic acid. (Salt) A water-soluble polymer having a structure derived from a monomer. As the monoethylenically unsaturated monocarboxylic acid (salt) monomer, specifically, for example, acrylic acid (salt), methacrylic acid (salt), crotonic acid (salt), α-hydroxyacrylic acid (salt) These may be used alone or as a mixture of two or more. Among these, acrylic acid (salt), methacrylic acid (salt) and mixtures thereof are particularly preferred.

Here, the term (salt) in the present invention means that it may be an acid type, a partial salt type, a complete salt type, or a mixture thereof.
Notation only. Examples of the salt include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, ammonium salts, and organic amine salts such as monoethanolamine and triethanolamine. These salts may be used alone or 2
It may be used as a mixture of more than one species. When the salt is used, a preferred form is an alkali metal salt such as sodium or potassium, and particularly preferably a sodium salt.

Monoethylenically unsaturated dicarboxylic acid (salt)
Specific examples of the monomer include, for example, maleic acid (salt), fumaric acid (salt), itaconic acid (salt), citraconic acid (salt), Anhydrides and the like may be mentioned, and these may be used alone or as a mixture of two or more. Of these, maleic acid (salt) and anhydride thereof are particularly preferred,
Fumaric acid (salt) or a mixture thereof. In the water-soluble polymer of the present invention, if necessary, a monoethylenic monomer (salt) containing a sulfonic acid (salt) group
It may have a structure derived from a monoethylenically unsaturated monomer which can be copolymerized, for example, contains a hydroxyl group, in some cases. By introducing a sulfonic acid group, the dispersibility of clay under high hardness water, which is one of the objects of the present invention, may be greatly improved in some cases.

Examples of the monoethylenic monomer (salt) containing a sulfonic acid (salt) group include vinyl sulfonic acid (salt), allyl sulfonic acid (salt), methallyl sulfonic acid (salt), sulfoethyl Acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 3-allyloxy-2-hydroxypropanesulfonic acid (salt), styrenesulfonic acid (salt), 2-acrylamide-2-methylpropanesulfonic acid (salt), 2 -Hydroxy-3-butenesulfonic acid (salt) and the like. These may be used alone or as a mixture of two or more. Preferably, 3
-Allyloxy-2-hydroxypropanesulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, 2-hydroxy-3-butenesulfonic acid (salt).

The weight-average molecular weight of the water-soluble polymer in the present invention is not particularly limited, but is preferably from 500 to 500.
200,000, more preferably 1000-100,000
It is. More preferably, it is 2000 to 80000. If the weight-average molecular weight is less than 500, the calcium ion-capturing ability may be significantly reduced, which is not preferable. If the weight-average molecular weight is more than 200,000, the clay dispersibility under high hardness water may be significantly deteriorated. The method for measuring the weight average molecular weight will be described in Examples. The embodiment of the water-soluble polymer in the present invention may be, of course, a so-called one-part polymer obtained in one production step, or two or more kinds of polymers produced in separate production steps. It may be a mixture containing a polymer.

Specific examples of the mixture of the two polymers include, as an essential component, a polymer A having a calcium ion trapping ability of 0.45 or more and a clay dispersing ability under high hardness water of 0.65. It is a polymer mixture obtained by blending the above-mentioned polymer B, preferably in a blending ratio of polymer A / polymer B = 20/80 to 95/5 by weight. No. The polymer mixture exemplified here is hereinafter referred to as a specific polymer mixture in the present invention, and will be described in detail below. (Specific Polymer Mixture in the Present Invention) The specific polymer mixture in the present invention has a calcium ion capturing ability of 0.4 as an essential component.
A polymer A having a hardness of 5 or more and a polymer B having a clay dispersing ability of 0.65 or more under high hardness water are blended.

Thus, a water-soluble polymer, which is an essential object of the present invention and has a calcium ion trapping ability of 0.40 or more and a clay dispersing ability of 0.50 or more under high hardness water, preferably A water-soluble polymer having a calcium ion capturing ability of 0.40 or more and a clay dispersing ability under high hardness water of 0.60 or more can be obtained. The mixing ratio of the polymer A and the polymer B is not particularly limited as long as the specific parameters are satisfied,
Preferably, polymer A / polymer B = 20/8 by weight ratio.
0 to 95/5, more preferably 30/70 to 90/10
It is. If the mixing ratio is out of these ranges, any of the parameters of the ability to trap calcium ions and the ability to disperse clay under high hardness water may not be satisfied, which is not preferable.

Next, the polymer A and the polymer B which are essential components in the polymer mixture of the present invention will be described. <Polymer A> Polymer A, which is an essential component in the polymer mixture of the present invention, has a calcium ion-capturing ability of 0.45 or more, preferably 0.47 or more, more preferably 0.47 or more.
It is a polymer having physical properties of 9 or more, and has a very high calcium ion capturing ability. The polymer A is not particularly limited as long as it satisfies the above parameters, but is preferably a water-soluble polycarboxylic acid polymer shown below.

Examples of the water-soluble polycarboxylic acid-based polymer satisfying the calcium ion-capturing ability include a maleic acid (based) polymer (salt), a fumaric acid (based) polymer (salt),
Acrylic acid / maleic acid (system) copolymer (salt), methacrylic acid / maleic acid (system) copolymer (salt), acrylic acid / fumaric acid (system) copolymer (salt), methacrylic acid / fumaric acid (System) copolymers (salts) and the like may be used, and these may be used alone or as a mixture of two or more. Among these polymers, acrylic acid / maleic acid (system) copolymer (salt) and acrylic acid / fumaric acid (system) copolymer (salt) are particularly preferable. Although the composition ratio of the copolymer is arbitrary, preferably, the molar ratio is 10/90 to
90/10, more preferably 20/80 to 80/20.

The weight average molecular weight of these polymers is not particularly limited, but is preferably from 1,000 to 200,000,
More preferably, it is 3000 to 100,000. If the weight average molecular weight is less than 1000, the calcium ion trapping ability may be significantly reduced, which is not preferable. When the weight average molecular weight exceeds 200,000, for example, when used as a detergent composition, water solubility becomes a problem. There is a possibility that the speed may be significantly reduced, and as a result, a sufficient effect may not be obtained, which is not preferable. In the present invention, (system) is, for example,
In the maleic acid (based) polymer, a content of the structural unit derived from maleic acid is 90 mol% or more, and a polymer containing the structural unit derived from another copolymerizable monomer at 10 mol% or less, In the maleic acid / acrylic acid (system) polymer, the total amount of the structural units derived from each monomer of maleic acid and acrylic acid is 90 mol% or more, and the structural units derived from other copolymerizable monomers are used. Is a polymer containing 10 mol% or less, and these are simply described as (system) hereinafter. The other copolymerizable monomer is not particularly limited as long as it does not impair the physical properties of the polymer A, but is preferably a water-soluble monoethylenic monomer, and particularly preferably a carboxylic acid. Monomer, sulfonic acid-containing monomer and hydroxyl group-containing monomer.

The content of structural units derived from other copolymerizable monomers in the above polymer is preferably 10 mol.
% Or less, more preferably less than 5 mol%, further preferably less than 3 mol%, and most preferably it is not contained. That is, the content range of the structural units derived from these other copolymerizable monomers in the polymer of the present invention is 10 mol% or less. It is more preferably in the range of 0 to 5 mol%, and still more preferably in the range of 0 to 3 mol%.
A particularly preferred form of the polymer A is an acrylic acid / maleic acid (system) copolymer (salt) having a weight average molecular weight of 3,000 to 100,000 and a composition ratio of 20/80 to 80/20 by mol ratio, Acrylic acid / fumaric acid (system) copolymers (salts), and mixtures thereof, and when salts are sodium salts and potassium salts. The most preferred form is the above-mentioned acrylic acid / maleic acid copolymer (salt) containing no other components, acrylic acid /
It is a fumaric acid copolymer (salt), and when it is a salt, it is a sodium salt or a potassium salt.

Although not particularly limited, as a method for producing the polymer A, a conventionally known method may be used.
When producing a maleic acid copolymer (salt) or the like, it is preferable to carry out stirring uniform polymerization in an aqueous solvent. <Polymer B> The polymer B, which is another essential component in the polymer mixture of the present invention, has a clay dispersing ability under high hardness water of 0.65 or more, preferably 0.70 or more, and more preferably 0.1 or more. It is a polymer having physical properties of 75 or more, and has a very high clay dispersing ability even under high hardness water. The polymer B is not particularly limited as long as it satisfies the above parameters, but is preferably a water-soluble polycarboxylic acid polymer shown below.

Examples of the water-soluble polycarboxylic acid polymer satisfying the clay dispersing ability under the high hardness water include, for example,
Acrylic acid (based) polymer (salt), methacrylic acid (based) polymer (salt), α-hydroxyacrylic acid (based) polymer (salt), acrylic acid / sulfonic acid group-containing monomer (based) Polymer (salt), methacrylic acid / sulfonic acid group-containing monomer (system) copolymer (salt), acrylic acid / hydroxyl group-containing monomer (system) copolymer (salt), methacrylic acid / hydroxyl group-containing monomer Monomer (system) copolymer (salt), etc., and these may be used alone or as a mixture of two or more. Among these polymers, an acrylic acid (system) polymer (salt) and an acrylic acid / sulfonic acid group-containing monomer (system) copolymer (salt) are particularly preferable. The content of the structural unit derived from the sulfonic acid group-containing monomer is preferably 5 to
It is 50 mol%, more preferably 10 to 30 mol%.

Examples of the sulfonic acid group-containing monomer include vinyl sulfonic acid (salt), allyl sulfonic acid (salt), methallyl sulfonic acid (salt), sulfoethyl acrylate, sulfoethyl methacrylate, sulfopropyl acrylate, and sulfoethyl acrylate. Propyl methacrylate, 3-
Allyloxy-2-hydroxypropanesulfonic acid (salt), styrenesulfonic acid (salt), 2-acrylamido-2-methylpropanesulfonic acid (salt), 2-hydroxy-3-butenesulfonic acid (salt) and the like. These may be used alone or as a mixture of two or more. Preferred are 3-allyloxy-2-hydroxypropanesulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, and 2-hydroxy-3-butenesulfonic acid (salt).

The weight average molecular weight of these polymers is not particularly limited, but is preferably from 1,000 to 100,000.
More preferably, it is 1,000 to 10,000. If the weight-average molecular weight deviates from these ranges, the clay dispersibility under high-hardness water may significantly decrease, which is not preferable. Therefore, a particularly preferred form of the polymer B is
An acrylic acid (system) polymer (salt), an acrylic acid / sulfonic acid group-containing monomer (system) copolymer (salt) and a mixture thereof having a weight average molecular weight of 1,000 to 10,000; In the case of using the contained monomer, preferred monomers are -allyloxy-2-hydroxypropanesulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, and 2-hydroxy-3-butenesulfonic acid (salt). The content of the structural unit derived from the body is preferably 10 to 30 mol%. In addition, when it is a salt, it is a sodium salt or a potassium salt. And the most preferred form is the above-mentioned acrylic acid polymer (salt), acrylic acid / sulfonic acid group-containing monomer copolymer (salt) and a mixture thereof containing no other components,
When a sulfonic acid group-containing monomer is used, preferred monomers are 3-allyloxy-2-hydroxypropanesulfonic acid, sulfoethyl acrylate, sulfoethyl methacrylate, and 2-hydroxy-3-butenesulfonic acid (salt). The content of the structural units derived from these monomers is preferably 10 to 30 mol%. In addition, when it is a salt, it is a sodium salt or a potassium salt.

In the production of the polymer B, similarly to the production of the polymer A, there is no particular limitation, and a conventionally known method may be used. However, the acrylic acid polymer ( When producing a salt), an acrylic acid / sulfonic acid group-containing monomer copolymer (salt), etc., it is preferable to carry out stirring uniform polymerization in an aqueous solvent. <Method for Producing Specific Water-Soluble Polymer> Next, the method for producing the specific water-soluble polymer of the present invention will be described in detail. The method for producing a specific water-soluble polymer having a calcium ion-capturing ability of 0.40 or more and a clay dispersing ability under high hardness water of 0.50 or more in the present invention is not particularly limited. Preferably, for example, a polymer A having a calcium ion capturing ability of 0.45 or more and a polymer B having a clay dispersing ability of 0.65 or more under high hardness water are used.
A / Polymer B = 20 / 80-95 / 5 by weight ratio
And mixing the polymer mixture in an amount of 50% by weight or more.

Here, the polymer A and the polymer B are as described above. The mixing ratio of the polymer A and the polymer B is also the same as described above, and the weight ratio of the polymer A / polymer B = 20/8.
0 to 95/5, more preferably 30/70 to 90/10
It is. Further, the blending amount of the polymer mixture in the specific water-soluble polymer is as described above, and the total amount of the polymer A and the polymer B is 50% by weight or more, more preferably 80% by weight, It is preferably at least 90% by weight. Hereinafter, a method of mixing the polymer A and the polymer B in the production method of the present invention will be described. The method for mixing the polymer A and the polymer B is not particularly limited, and examples thereof include the following method.

After both the polymer A and the polymer B have been prepared in advance, they are mixed so as to have a desired ratio. One polymer is prepared beforehand. Next, while the other polymer is being manufactured, the pre-manufactured polymer is added in a desired ratio to produce a mixture. Produce one polymer, so that the desired ratio,
Subsequently, the other polymer is produced, and as a result, a mixture is produced. Among them, the method is preferable from the viewpoint of simplicity of designing the polymer mixture and stability of quality.

Next, the above (1) will be described in more detail. Specifically, the method of (a) is a solution-powder mixing in which both are mixed in a solution state, a powder-powder mixing in which both are mixed in a powder state, and a solution-powder mixing in which one is mixed in a solution state and the other is mixed in a powder state. And the like. In the solution-solution mixing and the solution-powder mixing in which the state after mixing is a solution state, a mixture solution that is uniform as a whole is obtained by stirring. In a powder-powder mixture in which the state after mixing is a powder state, it is preferable that both polymers are finely pulverized powder and sufficiently mixed and stirred in order to make the whole uniform. If the whole is not uniform, that is, if the mixture components are biased,
The specific part having the bias may not satisfy the specific function of the present invention in which the calcium ion trapping ability is 0.40 or more and the clay dispersing ability under high hardness water is 0.50 or more.

In the present method, the polymer A and the polymer B
May be produced in advance, and as described above, the production method thereof is not particularly limited, but is preferably a homogeneous stirring polymerization in an aqueous solvent. The powdering method when both or one of them is used as a powder state is not particularly limited, and may be powdered by a conventionally known method. Here, the term “powder state” is used in a broad sense.
It includes all of granules, pellets, and, in some cases, pastes and gels. By the method as described above, a homogeneous mixture as a whole is obtained in the form of a solution or a powder. Of course, the properties of the mixture may be in accordance with the purpose, and the mixture obtained in the form of a solution may be made into a powder in some cases, and the mixture obtained in the form of a powder may be used as a solution in some cases. It does not matter.

Next, the following method will be described. In this method, a mixture is obtained by adding one preformed polymer to another in a desired ratio during the production of one polymer. The method for producing the polymer is as described above. The method of adding the polymer that has been produced in advance is not particularly limited, and may be at any time during the initial stage of polymerization, during the polymerization, or immediately before the end of the polymerization, and may be batch charging, intermittent charging, or continuous charging. Alternatively, the charging may be uniform or non-uniform.
It may be added in the form of a solution or a powder. What is necessary is just to set suitably as needed according to the objective. However, adding the polymer produced beforehand after the polymerization is substantially completed is nothing but the above method.

A further method will be described. In this method, one polymer is produced, and subsequently, the other polymer is produced in a desired ratio. This method is a modification of the above-described method in which a polymer that has been produced in advance during the production of one polymer is initially added at once. The difference from the above method is that the production of one polymer is started before the production of the other polymer is completed, which has a kind of continuous polymerization element. This kind of continuous polymerization method may be carried out in the same reaction vessel or may be continuously produced in two or more reaction vessels.

[Detergent Composition Containing Specific Water-Soluble Polymer] Subsequently, a detergent composition containing a specific water-soluble polymer, which is still another object of the present invention, will be described. The detergent composition according to the present invention has the above water-soluble polymer, that is, calcium ion trapping ability of 0.40 or more and clay dispersibility under high hardness water of 0.50 or more, preferably calcium ion trapping ability of 0.40 or more. And a water-soluble polymer having a clay dispersing ability of 0.60 or more under high hardness water, as one embodiment, a polymer A having a calcium ion capturing ability of 0.45 or more as an essential component
And a polymer B having a clay dispersibility of 0.65 or more under high hardness water.

In the detergent composition of the present invention, the content of the water-soluble polymer, that is, the content of the water-soluble polymer of the present invention when the detergent composition is 100% by weight, of the entire detergent composition The amount is preferably 1 to 20% by weight, and the amount of the surfactant is preferably 5 to 70% by weight of the whole detergent composition. In some cases, the enzyme may be added in a range of 5% by weight or less. If the amount of the water-soluble polymer is less than 1% by weight, the effect of addition does not appear, and if it exceeds 20% by weight, the effect of addition does not lead to improvement in detergency and is disadvantageous economically, which is not preferable. . 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 the detergency, but if it exceeds 5% by weight, the effect of the addition is no longer exhibited, which is economically disadvantageous and is not preferred.

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 its alkylene oxide adduct, sucrose fatty acid ester, alkyl Glycoxide, fatty acid glycerin monoester, alkylamine oxide and the like can be mentioned. The amphoteric surfactant is not particularly limited, but includes, for example, a carboxy-type or sulfobetaine-type amphoteric surfactant, and the cationic surfactant is not particularly limited. Ammonium salts and the like can be mentioned.

As the enzyme to be incorporated in 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. In the detergent composition of the present invention, if necessary, a known alkali builder, chelate builder, anti-redeposition agent, soil release agent, anti-color transfer agent,
Components commonly used in detergent compositions such as softeners, fluorescent agents, bleaching agents, bleaching aids, and fragrances may be blended. Further, zeolite may be blended. Silicates, carbonates, sulfates and the like can be used as the alkali builder. As chelate builders, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA
(Diethylenetriamine hexaacetic acid), citric acid and the like can be used as needed. Known water-soluble polycarboxylic acid-based polymers may be used as long as the effects of the present invention are not impaired.

[Other Applications in Specific Water-Soluble Polymer] Finally, another object of the present invention other than the detergent composition utilizing the characteristics of the specific water-soluble polymer of the present invention. Will be described. Specifically, the specific water-soluble polymer of the present invention can be used for applications such as an inorganic pigment dispersant, a water treatment agent, and a fiber treatment agent. Hereinafter, these preferred embodiments will be described. (Inorganic pigment dispersant) The inorganic pigment dispersant comprising the above water-soluble polymer preferably comprises the water-soluble polymer of the present invention, and if necessary, as other compounding agents, condensed phosphoric acid and Salts, phosphonic acids and salts thereof, and polyvinyl alcohol may be used.

The content of the water-soluble polymer 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. 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 inorganic pigments such as heavy or light calcium carbonate and clay 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 treatment agent) The water treatment agent containing the above water-soluble polymer preferably comprises the water-soluble polymer of the present invention, and if necessary, as other compounding agents, polymerized phosphate, phosphonic acid A composition containing a salt, an anticorrosive, a slime control agent, and a chelating agent can also be prepared. A known water-soluble polymer may be contained within a range that does not affect the performance and the effect. In any case, it is useful for scale prevention in a cooling water circulation system, a boiler water circulation system, a seawater desalination apparatus, a pulp digester, a black liquor concentrator, and the like.

(Fiber treatment agent) The fiber treatment agent containing the water-soluble polymer is at least one selected from the group consisting of a dye, a peroxide and a surfactant, and the water-soluble polymer of the present invention. including. The content of the water-soluble polymer of the present invention in the fiber treating agent of the present invention is not particularly limited, and is preferably 1 to 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.
However, in consideration of physical properties, the polymer component in the fiber treatment agent is more preferably in the form of a fiber treatment agent comprising the water-soluble polymer of the present invention.

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 mixing ratio of the copolymer and at least one selected from the group consisting of dyes, peroxides and surfactants is, for example, to improve the whiteness of the fiber, uneven color, and the degree of dyeing. And 0.1 to 100 parts by weight of at least one selected from the group consisting of a dye, a peroxide, and a surfactant based on 1 part by weight of the water-soluble polymer of the present invention, in terms of a fiber treatment agent pure content. It is preferable to use a composition blended in such a ratio as a fiber treatment agent.

For example, an aqueous solution having a predetermined concentration of the fiber treating agent compounded in terms of the pure content is a preferred embodiment of the fiber treating agent of the present invention. 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, animal fibers such as wool and silk yarn, and half fibers such as human silk. Synthetic fibers and their fabrics and blends. 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 of an alkaline bleaching agent.

[0054]

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”. (Method of Measuring Physical Properties) First, a method of measuring calcium ion trapping ability and clay dispersing ability under high hardness water, which are important parameters forming the basis of the present invention, will be described. For reference, since the weight average molecular weight of the polymer used was also measured, the method of measuring the weight average molecular weight is also 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 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).

Then, 10 mg of the test sample (polymer) was weighed in terms of solid content in a 100 cc beaker, and 50 g of a test calcium ion standard solution prepared in the above was added, followed by sufficiently stirring using a magnetic stirrer. Further, similarly to the sample solution for the calibration curve, 4.8% NaOH
The pH is adjusted to 9 to 11 with an aqueous solution, and 4M-KCl
A test sample solution was prepared by adding 1 ml of the aqueous solution. The sample solution for the calibration curve and the sample solution for the test prepared in this manner were combined with an Orion Ion Analyzer EA.
920 using Orion calcium ion electrode 9
The measurement was performed according to 3-20.

Using the calibration curve, the amount of calcium ions captured by the sample (polymer) was calculated from the measured value of the test sample solution, and the value was calculated as g of calcium carbonate.
After conversion into a number, the trapping amount per 1 g of the polymer solid content was determined, and this value was defined as a calcium ion trapping ability value. <Clay dispersing ability under high hardness water> First, 67.56 g of glycine, sodium chloride 5
Ion-exchanged water was added to 2.6 g of a 1 mol / l NaOH aqueous solution of 2.6 g to prepare a glycine buffer solution of 600 g.

Calcium chloride dihydrate was added to 0.326
8 g of the adjustment liquid (60 g), add pure water and add 1000 g
g, and a dispersion was prepared. In addition, 0.1
% Polymer aqueous solution was prepared. A common test tube used for an experiment of about 30 cc is JI
Dispersion 27 of S test powder I, 8 kinds (Kanto loam, fine powder: Japan Powder Industry Association) with 0.3 g of clay
g and 3 g of an aqueous polymer solution. At this time, the calcium concentration of the test solution was 200 ppm in terms of calcium carbonate. Test tubes in Parafilm (American National
After sealing with a polypropylene film (manufactured by Can Co., Ltd.), the clay was gently shaken so as to be dispersed throughout, and shaken up and down 20 times. 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 liquid was subjected to wavelength 3 using a UV spectrometer.
Absorbance (ABS) was measured in a 1 cm cell under the condition of 80 nm, and this value was defined as a clay dispersing ability value under high hardness water. <Method of measuring weight average molecular weight (Mw)> The weight average molecular weight (Mw) was measured by GPC (gel permeation chromatography). The column used for the measurement was G-300
0PWXL (manufactured by Tosoh Corporation), and the mobile phases were 34.5 g of disodium hydrogen phosphate dodecahydrate and 46.2 g of sodium dihydrogen phosphate dihydrate (each of which was a special grade, all reagents used in the following measurement are special grades) To the total amount of 5
000 g, and then an aqueous solution filtered through a 0.45 micron membrane filter was used.

The pump used was L-7110 (manufactured by Hitachi), and the flow rate of the mobile phase was set to 0.5 ml / min.
The detector was UV at a wavelength of 214 nm (Model 481 manufactured by Waters). At that time, the column temperature was 35 ° C.
It was fixed. Further, as a calibration curve, a sodium polyacrylate standard sample (manufactured by Souwa Kagaku) was used, and the weight average molecular weight of the polymer was measured using these samples. (Reference Example) In Reference Example, polymers A1 and A2, which are components of the water-soluble polymer of the present invention and which have a calcium ion trapping ability of 0.45 or more, as polymers A, and under high hardness water The following production was performed with respect to the polymer B1 as the polymer B having a clay dispersing ability of 0.65 or more.

Reference Example 1 As polymer A, a molar ratio of 5 was used.
Polymer A1, a 0/50 maleic / acrylic acid copolymer, was prepared. That is, in a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser, ion-exchanged water (hereinafter referred to as pure water) was added.
8g, 48% aqueous sodium hydroxide solution (hereinafter 48% Na
400 g of OH) and 235.2 g of maleic anhydride (hereinafter referred to as MA) were initially charged, and the aqueous solution was heated to a boiling point reflux under stirring. Next, an 80% aqueous solution of acrylic acid (80
216 g of a 35% aqueous hydrogen peroxide solution over a period of 180 minutes from the start of polymerization and 96 g of a 15% aqueous sodium persulfate solution (hereinafter abbreviated as 15% NaPS) over a period of 90 minutes from the start of polymerization. And pure water 160
g was continuously dropped at a uniform rate from separate dropping nozzles over a period of 100 minutes from 90 minutes to 190 minutes after 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 the completion of the polymerization, the pH and the concentration were adjusted, and p
Polymer A1 having an H of 7.5 and a solid concentration of 45% was obtained. When the weight average molecular weight was measured as described above, it was 10,000. In addition, the calcium ion trapping ability of the polymer A1 was measured as described above, and was 0.49, which confirmed that the polymer A1 satisfied the parameters of the polymer A in the present invention. Reference Example 2 As a polymer A, a polymer A2 which was a maleic acid / acrylic acid copolymer in a molar ratio of 30/70 was produced.

That is, in a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser, 83.0 g of pure water, 250 g of 48% NaOH, and 147.0 g of anhydrous MA were initially charged. Then, the temperature of the aqueous solution was raised to the boiling point reflux state under stirring. Then, while stirring and maintaining the reflux state, 315.0 g of 80% AA was added to 156.7 g of 15% NaPS over 120 minutes from the start of polymerization.
g, and 393.3 g of pure water were continuously dropped from each of the dropping nozzles at a uniform rate over a period of 130 minutes from the start of the 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 the completion of the polymerization, the pH and concentration are adjusted, and p
A polymer A2 having H7.5 and a solid concentration of 40% was obtained. The weight-average molecular weight measured as described above was 50,000. The calcium ion-scavenging ability of the polymer A2 was measured as described above, and was 0.50, which confirmed that the polymer A2 satisfied the parameters of the polymer A in the present invention. (Reference Example 3) As a polymer B, a polymer B1 which is a low molecular weight acrylic acid homopolymer was produced.

That is, 560 g of pure water was initially charged into a 2.5-liter SUS separable flask equipped with a thermometer, a stirrer, and a reflux condenser, and the temperature was raised to a boiling point reflux state with stirring. Then, while maintaining the reflux state under stirring, 360 g of 80% AA and 283 g of 48% Na
Over a period of 240 minutes from the start of polymerization, OH was added to 56 g of 15
% NaPS and 600 g of pure water were continuously dropped from respective dropping nozzles at a uniform rate over 250 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 the completion of the polymerization, the pH and the concentration were adjusted to obtain a polymer B1 having a pH of 7.5 and a solid content of 45%. It was 3500 when the weight average molecular weight was measured similarly.

The clay dispersing ability of the polymer B1 in high-hardness water was measured to be 0.90, and it was confirmed that the polymer B1 satisfied the parameters of the polymer B in the present invention. (Example 1) In Example 1, the polymers A1 and A2 as the polymer A having a calcium ion trapping ability of 0.45 or more obtained in the reference example, and the clay dispersing ability under high-hardness water were as follows. The water-soluble polymer of the present invention was produced using the polymer B1 as the polymer B of 0.65 or more. Then, the calcium ion scavenging ability and the clay dispersing ability under high hardness water of the obtained water-soluble polymer were measured.

Example 1-1 Reference Example 1 as Polymer A
3 g of a powder obtained by drying the polymer A1 obtained in
As a polymer B, 7 g of the powder obtained by drying the polymer B1 obtained in Reference Example 3 was placed in a mortar and mixed with a pestle until completely uniform. Thus, a water-soluble polymer 1-1 having a weight ratio of polymer A / polymer B of 30/70 was produced. Table 1 shows the measurement results of the calcium ion trapping ability of the water-soluble polymer 1-1 and the clay dispersing ability under high hardness water. (Example 1-2) In Example 1-1, 5 g of powder of polymer A1 was used as polymer A, and polymer B1 was used as polymer B.
The same operation was carried out except that the powder was 5 g of polymer A.
/ Water-soluble polymer 1 having a weight ratio of polymer B of 50/50
-2 was produced.

Table 1 shows the measurement results of the calcium ion trapping ability of the water-soluble polymer 1-2 and the clay dispersing ability under high hardness water. (Example 1-3) In Example 1-1, 7 g of polymer A1 powder was used as polymer A, and polymer B1 was used as polymer B.
The same operation was carried out except that the powder was 3 g of the polymer A.
/ Water-soluble polymer 1 having a weight ratio of polymer B of 70/30
-3 was produced. Table 1 shows the measurement results of the calcium ion trapping ability of the water-soluble polymer 1-3 and the clay dispersing ability under high hardness water.

(Example 1-4) In Example 1-1,
The same operation was performed except that 8 g of the powder of the polymer A1 was used as the polymer A and 2 g of the powder of the polymer B1 was used as the polymer B. A water-soluble polymer A / polymer B having a weight ratio of 80/20 was used. Polymer 1-4 was produced. Table 1 shows the measurement results of the calcium ion trapping ability of the water-soluble polymer 1-4 and the clay dispersing ability under high hardness water. (Example 1-5) In Example 1-1, 3 g of a powder obtained by drying polymer A2 obtained in Reference Example 2 as polymer A and a polymer B obtained in Reference Example 3 as polymer B were obtained. Polymer B
The same operation was carried out except that 7 g of the powder obtained by drying Example 1 was used, and the weight ratio of polymer A / polymer B was 30/7.
Water-soluble polymer 1-5 which was 0 was produced.

Table 1 shows the measurement results of the calcium ion trapping ability of the water-soluble polymer 1-5 and the clay dispersing ability under high hardness water. (Example 1-6) In Example 1-1, 5 g of polymer A2 powder was used as polymer A, and polymer B1 was used as polymer B.
The same operation was carried out except that the powder was 5 g of polymer A.
/ Water-soluble polymer 1 having a weight ratio of polymer B of 50/50
-6 was produced. Table 1 shows the measurement results of the calcium ion trapping ability of the water-soluble polymer 1-6 and the clay dispersing ability under high hardness water.

(Example 1-7) In Example 1-1,
The same operation was performed except that 7 g of the powder of the polymer A2 was used as the polymer A and 3 g of the powder of the polymer B1 was used as the polymer B. The water-soluble polymer A / polymer B had a weight ratio of 70/30. Polymer 1-7 was produced. Table 1 shows the measurement results of the water-soluble polymer 1-7 for calcium ion trapping ability and clay dispersing ability under high hardness water. (Comparative Examples 1-8 to 1-10) As Comparative Examples, the polymers A1, A2 and B1 obtained in Reference Example 1 were measured for calcium ion trapping ability and clay dispersing ability under high hardness water. Table 1 summarizes the results.

[0072]

[Table 1]

From the above results, it was confirmed that the water-soluble polymer of the present invention simultaneously exhibited high effects on both calcium ion trapping ability and clay dispersing ability under high hardness water. (Example 2) In Example 2, a detergent composition comprising the water-soluble polymer of the present invention obtained in Example 1 and comprising the water-soluble polymer, which is another object of the present invention, was prepared. In order to evaluate, the ability to prevent re-contamination was measured by the following method.

<Resoil Prevention Ability> A JIS-L0803 cotton cloth obtained from the Laundry Science Association was cut into 5 cm × 5 cm to prepare a white cloth. This white cloth is previously measured with a colorimetric colorimeter ND-1001D manufactured by Nippon Denshoku Industries Co., Ltd.
Using a P-type, whiteness was measured by reflectance. Pure water was added to 1.47 g of calcium chloride dihydrate to make 5000 g, and hard water was prepared. Hard water and tap water for rinsing were placed in a thermostat at 25 ° C. Set the turgot meter to 25 ° C and add 1 L of hard water
And 1 g of clay were placed in a pot and stirred at 100 rpm for 1 minute. Thereafter, 10 pieces of white cloth were put and stirred at 100 rpm for 1 minute.

4 g of 5% aqueous sodium carbonate solution, 5%
Sodium linear alkyl benzene sulfonate (LAS)
4 g of aqueous solution, 0.15 g of zeolite, 1% in terms of solid content
5 g of a polymer aqueous solution of
Stirred for 0 minutes. The white cloth was drained by hand, 1 L of tap water at 25 ° C. was put into a pot, and the mixture was stirred at 100 rpm for 2 minutes. This is 2
I went there. Was repeated three times. After applying a cloth to the white cloth and drying it while wrinkling with an iron, the whiteness of the white cloth was measured again by the reflectance using the above colorimeter.

From the above measurement results, the re-contamination prevention rate was determined by the following equation. Recontamination prevention rate (%) = (whiteness after washing) / (whiteness of original white cloth) × 100 (Examples 2-1 to 2-7) The water-soluble polymer of the present invention obtained in Example 1 Regarding 1-1 to 1-7, the measurement of the ability to prevent re-contamination was performed based on the above method. Table 2 summarizes the results. (Comparative Examples 2-8 to 2-10) Similarly, measurements were performed on the polymers A1, A2, and B1 obtained in Reference Examples, and the results are summarized in Table 2.

[0077]

[Table 2]

As is clear from Table 2, the water-soluble polymer of the present invention has an excellent ability to prevent re-contamination as compared with conventionally known polymers. (Example 3) In Example 3, the water-soluble polymer of the present invention obtained in Example 1 is further evaluated as a detergent composition containing the water-soluble polymer, which is another object of the present invention. Therefore, the cleaning ability was measured by the following method. <Washing ability> A JIS-L0803 cotton cloth obtained from the Washing Science Association was cut into 5 cm x 5 cm to prepare a white cloth. Wet artificially stained cloth was also obtained from the Washing Science Association. A white cloth and a contaminated cloth are previously measured with a colorimeter ND-1001D manufactured by Nippon Denshoku Industries Co.
Using a P-type, whiteness was measured by reflectance.

Pure water was added to 1.47 g of calcium chloride dihydrate to make 5000 g, and hard water was prepared. Hard water and tap water for rinsing were placed in a thermostat at 25 ° C. Set the turgot meter at 25 ° C,
Put 0ml, 5 contaminated cloths and 5 white cloths in a pot,
Stirred for 1 minute at rpm. 2 g of a 5% aqueous solution of sodium carbonate, 2 g of a 5% aqueous solution of LAS, 0.075 g of zeolite, and 10 g of a 1% aqueous solution of a polymer in terms of solid content are placed in a pot, and 10 g of the aqueous solution is prepared at 100 rpm.
Stirred for minutes. Drain the white cloth by hand, and tap water 500m
was placed in a pot and stirred at 100 rpm for 2 minutes. This was done twice.

A white cloth and a contaminated cloth were applied to each other, and dried while smoothing wrinkles with an iron. Then, the whiteness of the white cloth was measured again by the reflectance using the above colorimeter. From the above measurement results, the cleaning ability was determined by the following equation. Cleaning ability (%) = [(whiteness of stained cloth after washing−whiteness of stained cloth before washing) / (whiteness of original white cloth−whiteness of stained cloth before washing)] × 100 (Example 3) -1 to 3-4) The cleaning ability of each of the water-soluble polymers 1-1 to 1-4 of the present invention obtained in Example 1 was measured based on the above method. Table 3 summarizes the results.

(Comparative Examples 3-5 and 3-6) Similarly, the polymers A1 and B1 obtained in Reference Example were measured, and
The results are summarized in Table 3.

[0082]

[Table 3]

As is evident from Table 3, the water-soluble polymer of the present invention has a much better cleaning ability than conventionally known polymers. Also, by combining the results of Example 2 and Example 3, it became clear that the detergent composition of the present invention was very excellent. Example 4 In Example 4, in order to evaluate the inorganic pigment dispersant containing the water-soluble polymer of the present invention obtained in Example 1, a B-type viscometer was used according to the following method. The viscosity of the pigment dispersion was measured indefinitely.

<Evaluation Method of Inorganic Pigment Dispersant> First, a 10% aqueous solution of a copolymer in terms of solid content was prepared. Next, 150 g of ultrapure water is placed in a 600 ml plastic container, and the TK homomixer manufactured by Tokushu Kika Kogyo Co., Ltd. is used.
While stirring with, 70 g of light calcium carbonate, 105 g of heavy calcium carbonate and 175 g of Alpha Coat were gradually added in this order. During the addition, if it became difficult to disperse the pigment, a 10% aqueous solution of a copolymer in terms of solid content was appropriately added. After all the pigments were added, a 10% aqueous solution of the copolymer in terms of solid content was added to a total amount of 10.5 g.
The mixture was further stirred at 0 rpm for 15 minutes.

After the stirring, the mixture was placed in a thermostat at 25 ° C. for 30 minutes, and then the viscosity was measured by rotating the rotor for 3 minutes using a B-type viscometer. (Examples 4-1 and 4-2) Each of the water-soluble polymers 1-2 and 1-3 of the present invention obtained in Example 1 was evaluated as an inorganic pigment dispersant based on the above method.
As a result, the viscosity of the inorganic pigment dispersion using the water-soluble polymer 1-2 was 464 mPa · s. The viscosity using the water-soluble polymer 1-3 was 492 mPa · s.

(Comparative Example 4-3) Similarly, measurement was performed on the polymer B1 obtained in Reference Example 3. The viscosity using the polymer B1 was 6,640 mPa · s. From the above results, the inorganic pigment dispersant using the water-soluble polymer of the present invention,
It was found that it had excellent dispersion performance. Example 5 In Example 5, in order to evaluate the water treatment agent containing the water-soluble polymer of the present invention obtained in Example 1, the ability to prevent calcium carbonate scale was measured by the following method. Was performed.

<Calcium Carbonate Scale Inhibiting Ability> First, a 1.56% aqueous solution of calcium chloride dihydrate and a 3% aqueous solution of sodium hydrogen carbonate, and an aqueous solution of a polymer composition having a solid content of 0.2% were prepared. did. Next, 170 g of pure water was placed in a 225 ml glass bottle.
And add 1.56% calcium chloride dihydrate aqueous solution to 10
g, 3 g of an aqueous solution of a polymer composition at a solid content of 0.2%, and 10 g of an aqueous sodium hydrogen carbonate solution and 7 g of sodium chloride were further added to make a total amount of 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 K010.
The analysis was performed according to 1. From the above measurement results, the calcium carbonate scale inhibition rate (%) was determined by the following equation. Scale suppression rate (%) = [(CB) / (AB)] × 1
A: The concentration of calcium dissolved in the liquid before the test (ppm) B: The calcium concentration in the filtrate of the solution without the water-soluble polymer after the test (ppm) C: The solution with the water-soluble polymer after the test (Examples 5-1 and 5-2) Scale prevention of the water-soluble polymers 1-2 and 1-3 of the present invention obtained in Example 1 based on the above method. Noh was measured.

As a result, the scale preventing ability of the scale inhibitor using the water-soluble polymer 1-2 was 49%, and the scale preventing ability of the scale inhibitor using the aqueous polymer 1-3 was 58%.
%Met. (Comparative Example 5-3) Similarly, polymer A1 obtained in Reference Example
Was measured. The scale preventing ability of the scale preventing agent using the polymer A1 was 21%. From the above results, it was found that the water-soluble polymer of the present invention can be effectively used as a water treatment agent.

Example 6 In Example 6, a bleaching test was carried out by the following method in order to evaluate the fiber treating agent containing the water-soluble polymer of the present invention obtained in Example 1 as follows. Was. <Bleaching Test> First, a fiber treating agent solution was prepared. That is, calcium chloride dihydrate was dissolved in pure water, and 10 g of hydrogen peroxide, 2 g of sodium hydroxide, 2 g of sodium hydroxide, and 5 g of sodium silicate No. 3 were added to 1 L of water prepared to have a concentration of 50 ppm in terms of calcium carbonate.
g and 2 g of the water-soluble polymer 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. 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 and 6-2) The texture and whiteness of each of the water-soluble polymers 1-5 and 1-7 of the present invention obtained in Example 1 were evaluated based on the above methods.

As a result, the texture of the fiber treating agent using the water-soluble polymer 1-5 was soft and the whiteness was 85.
The texture of the fiber treatment agent using the water-soluble polymer 1-7 was soft and the whiteness was 80. (Comparative Example 6-3) Similarly, polymer B1 obtained in Reference Example
Was measured. The hand of the fiber treating agent comprising the polymer B1 was slightly hard, and the whiteness was 66. Therefore, it was found that the fiber treating agent using the water-soluble polymer of the present invention exhibited good bleaching performance.

The high-hardness water in the present invention refers to water adjusted under predetermined conditions as described in Examples, and powders of JIS test type I, 8 types (Kanto Rohm, fine granules) Calcium concentration was 200 pp in terms of calcium carbonate, obtained by using 0.3 g of clay from Japan Powder Industry Technology Association) and adjusting it under predetermined conditions using a test tube or the like.
It is water that is m.

[0094]

According to the present invention, a polymer A having a calcium ion-capturing ability of 0.45 or more and a polymer B having a clay dispersing ability under high hardness water of 0.65 or more are expressed by A in weight ratio. / B = 50% by weight of a water-soluble polycarboxylic acid polymer mixture obtained by mixing at a ratio of 20/80 to 95/5
By containing the above, etc., a water-soluble polymer having high characteristics that could not be obtained conventionally, that is, calcium ion trapping ability is 0.40 or more, clay dispersibility under high hardness water is 0.50 or more. In addition, it is possible to provide a water-soluble polymer which is extremely excellent in both calcium ion trapping ability and clay dispersing ability under high hardness water.

The detergent composition according to the present invention contains a water-soluble polymer having a calcium ion trapping ability of 0.40 or more and a clay dispersing ability of 0.50 or more under high hardness water. It exhibits very excellent detergency not only in low hardness water but also in high hardness water. According to the present invention, excellent inorganic pigment dispersants, water treatment agents, and fiber treatment agents can be provided in the same manner as the detergent composition.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C11D 3/37 C11D 3/37 (72) Inventor Shigeru Yamaguchi 5-8, Nishiminaburi-cho, Suita-shi, Osaka Stock Company N-catalyst F-term (Reference) 4H003 AB19 DA01 EA16 EA28 EB32 FA06 FA07 FA37 4J100 AB07R AJ01P AJ02P AJ03P AJ08Q AJ09Q AK03P AK08P AK13P AK31Q AK32Q AL08R AM21R AP01R BA03P BA0357

Claims (5)

[Claims] (1) a calcium ion capturing ability of 0.40 or more;
A water-soluble polymer having a clay dispersibility of 0.50 or more under high hardness water. 2. A water-soluble polycarboxylic acid polymer having a structural unit derived from a monoethylenically unsaturated monocarboxylic acid (salt) monomer and / or a monoethylenically unsaturated dicarboxylic acid (salt) monomer. The water-soluble polymer according to claim 1, which is essential. 3. A polymer comprising, as essential components, a polymer A having a calcium ion-capturing ability of 0.45 or more and a polymer B having a clay dispersing ability of 0.65 or more under high hardness water. A mixture, wherein the physical properties of the polymer mixture are
The calcium ion trapping ability is 0.40 or more, and the clay dispersing ability under high hardness water is 0.60 or more.
Or the water-soluble polymer according to 2. 4. A polymer A / polymer B compounding ratio by weight.
The water-soluble polymer according to claim 3, wherein the ratio is 20/80 to 95/5. 5. A detergent composition comprising the water-soluble polymer according to any one of claims 1 to 4.