JP2012057096A - Polyalkylene glycol-based polymer and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyalkylene glycol-based polymer that exhibits excellent anti-gelling properties and calcium ion capture capability during cleaning and also has excellent compatibility with a surfactant, and a method for producing the same.SOLUTION: The polyalkylene glycol-based polymer essentially includes (i) a structural unit derived from a polyalkylene glycol-based monomer and having specific structure and (ii) a structural unit derived from a carboxy group-containing monomer.

Description

The present invention relates to a polyalkylene glycol polymer and a method for producing the same. More specifically, the present invention relates to a polyalkylene glycol polymer useful as a raw material for detergent additives and the like, and a method for producing the same.

The polyalkylene glycol polymer is a useful polymer used in various industrial fields, for example, inorganic pigment dispersant, dispersant for coal, dispersant for polymerization process, detergent composition, etc. Are known to be useful (for example, Patent Documents 1 to 4).
Conventionally, as a polyalkylene glycol polymer, a polyalkylene glycol polymer having a structure represented by the following general formula (R-1) exhibits high performance in aqueous applications such as dispersants and detergent builders. (Patent Document 5).

(In General Formula (R-1), R ₁ represents a hydrogen atom or a methyl group, R ₂ represents a CH ₂ group, a CH ₂ CH ₂ group, or a single bond, and R ₃ has 2 to 4 carbon atoms. X and Y are a hydroxyl group, a group represented by the structural formula of the following general formula (R-1 (1)), and a structural formula of the following general formula (R-1 (2)). A group selected from a group (wherein one of X and Y is a hydroxyl group, and the other is a group represented by the structural formula of the following general formula (R-1 (1)), the following general formula (R-1 (It is one of the groups represented by the structural formula (2)), and n represents the average number of added moles of the oxyalkylene group, and 1 ≦ n ≦ 300.

(In the general formula (R-1 (1)) and general formula (R-1 (2)), M represents a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group, and R ₄ represents 1 to 1 carbon atoms. 8 represents an alkylene group, and R ₄ and R ₅ each represent an alkylene group having 1 to 8 carbon atoms, wherein the general formula (R-1 (1)) is introduced via an oxygen atom at the left end in the formula. In the same manner, the above general formula (R-1 (2)) is bonded to the above general formula (R-1) through the leftmost nitrogen atom in the formula. Combined with the rest of.)
Furthermore, as a conventional polyalkylene glycol polymer, a polyalkylene glycol polymer having a structure represented by the following general formula (R-2) has high performance in aqueous applications such as dispersants and detergent builders. It has been disclosed to exhibit (Patent Document 6).

（式（Ｒ−２）中、Ｒ_１は水素原子またはメチル基であり、Ｍ_１は水素原子、金属原子、アンモニウム基、または有機アンモニウム基であり、Ｘは−ＣＨ_２−または単結合であり、ｎはオキシアルキレン基の平均付加モル数を表し、１≦ｎ≦３００である。）。

(In Formula (R-2), R ₁ is a hydrogen atom or a methyl group, M ₁ is a hydrogen atom, a metal atom, an ammonium group, or an organic ammonium group, and X is —CH ₂ — or a single bond. , N represents the average number of added moles of the oxyalkylene group, and 1 ≦ n ≦ 300.

JP 2003-147254 A JP-A-1-275696 JP-A-3-28202 JP 2002-60785 A JP 2010-132814 A JP 2008-303347 A

As described above, polyalkylene glycol polymers having various structures have been studied.
By the way, in recent years, consumers' awareness of the environment has increased, and for the purpose of saving water, washing such as using the remaining hot water of a bath for washing has become established. As a result, the stain components contained in the remaining hot water of the bath adhere to the fibers during washing, and the hard water component concentrates due to reheating of the bath. The ability to capture metal ions such as Ca ions and Mg ions in water and cause gelation resistance and gelation resistance have been further demanded for polymers. In addition, liquid detergents whose demand is currently increasing are concentrated liquid detergents having a surfactant content of 50% or more, so that detergent additives are suitable for blending into such concentrated liquid detergents. Therefore, there is a need for a detergent additive that is more compatible with a surfactant than before.
However, it cannot be said that the conventional polyalkylene glycol-based polymer can sufficiently satisfy recent severe demands regarding the performance of such water-based applications, and responds to such new needs. There has been room for further improvement in the polymer that can be suitably used as a detergent additive exhibiting higher performance.
The present invention has been made in view of the above-described situation. For example, in a detergent application, excellent Ca
It is an object of the present invention to provide a polyalkylene glycol polymer that exhibits ion trapping ability and gelation resistance and a method for producing the same.

This inventor examined the polymer which can be used suitably for a detergent additive etc., and derived from the structural unit derived from the polyalkylene glycol-type monomer which has a specific structure, and a carboxyl group-containing monomer. A polyalkylene glycol-based polymer having a structural unit can exhibit extremely good gelation resistance even under extremely good Ca ion capturing ability and high hardness, and has high compatibility with a surfactant. I found out. Furthermore, by adjusting the content of each structural unit in the polymer to a specific range, the above-described performance is further improved, and such a polymer is suitable as a detergent additive that meets new needs. As a result, the inventors have found that the above problem can be solved brilliantly, and have reached the present invention.
That is, the present invention comprises (i) a structural unit (a) derived from a polyalkylene glycol monomer (A), (ii) a structural unit (b) derived from a carboxyl group-containing monomer (B), Wherein the polyalkylene glycol monomer (A) is represented by the following general formula (1);

(In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a methylene group, an ethylene group or a direct bond. Z is the same or different and represents an oxyalkylene group having 2 to 20 carbon atoms. N is the average number of moles added of the oxyalkylene group and represents a number of 1 to 300. X and Y are a hydroxyl group, a structure represented by the following general formula (2), and a general formula (3) below. A structure represented by the following formula: (wherein either one of X and Y represents a hydroxyl group, and the other is a structure represented by the following general formula (2) or a general formula (3) below) Represents the structure).

(In the general formula (2), R ₃ represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms. The general formula (2), In (3), M represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine salt (organic ammonium group).), And the polyalkylene glycol polymer is the polymer. The structural unit (a) is included in an amount of 1 to 99% by mass and the structural unit (b) is included in an amount of 1 to 99% by mass with respect to 100% by mass of the total amount of structural units derived from all monomers forming A polyalkylene glycol polymer.
The present invention is also a method for producing a polyalkylene glycol polymer comprising a step of polymerizing (i) a polyalkylene glycol monomer (A) and (ii) a carboxyl group-containing monomer (B). In the above production method, the following general formula (1):

(In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a methylene group, an ethylene group or a direct bond. Z is the same or different and represents an oxyalkylene group having 2 to 20 carbon atoms. N is the average number of moles added of the oxyalkylene group and represents a number of 1 to 300. X and Y are a hydroxyl group, a structure represented by the following general formula (2), and a general formula (3) below. A structure represented by the following formula: (wherein either one of X and Y represents a hydroxyl group, and the other is a structure represented by the following general formula (2) or a general formula (3) below) Represents the structure).

(In the general formula (2), R ₃ represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms. The general formula (2), In (3), M represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine salt (organic ammonium group). It is also a method for producing a polyalkylene glycol polymer characterized by using 1 to 99% by mass of the carboxyl group-containing monomer (B).

The polyalkylene glycol-based polymer of the present invention exhibits extremely good gelation ability, for example, even when it has a very good Ca ion scavenging ability and high hardness during washing.

2 is a ¹ H-NMR chart of the monomer (1) obtained in Synthesis Example 1. FIG.

The present invention is described in detail below.

[Polyalkylene glycol polymer of the present invention]
<Polyalkylene glycol monomer (A)>
The polyalkylene glycol polymer of the present invention (also referred to as the polymer of the present invention) is a polymer essentially comprising the structural unit (a) derived from the polyalkylene glycol monomer (A). The polyalkylene glycol monomer (A) has the following general formula (1);

(In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a methylene group, an ethylene group or a direct bond. Z is the same or different and represents an oxyalkylene group having 2 to 20 carbon atoms. N is the average number of moles added of the oxyalkylene group and represents a number of 1 to 300. X and Y are a hydroxyl group, a structure represented by the following general formula (2), and a general formula (3) below. A structure represented by the following formula: (wherein either one of X and Y represents a hydroxyl group, and the other is a structure represented by the following general formula (2) or a general formula (3) below) Represents the structure).

(In the general formula (2), R ₃ represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms. The general formula (2), In (3), M has a structure represented by a hydrogen atom, a metal atom, an ammonium group, or an organic amine salt (organic ammonium group). Since the polyalkylene glycol monomer (A) has such a structure, the polyalkylene glycol polymer of the present invention has a carboxyl group (salt) and / or near the end of the side chain having a polyalkylene glycol structure. Or, since it has a sulfonic acid group (salt), it contributes to the dispersion stabilization of inorganic particles and dirt components. Therefore, when used in detergent applications, good gel resistance is exhibited even under high hardness.
The carboxyl group (salt) represents a carboxyl group or a salt of a carboxyl group, and the sulfonic acid group (salt) represents a salt of a sulfonic acid group or a sulfonic acid group. Here, the salt represents a metal salt, an ammonium salt, or an organic amine salt (organic ammonium salt).
In addition, when the polyalkylene glycol polymer of the present invention is blended in a liquid detergent or the like, the compatibility with the surfactant is increased due to the polyalkylene glycol structure and the like. Property (separation stability) can be made excellent.
In the present invention, the polyalkylene glycol polymer means a polymer having a polyalkylene glycol chain, and the polyalkylene glycol monomer means a monomer having a polyalkylene glycol chain.
In the general formula (1), R ₁ represents a hydrogen atom or a methyl group, and among these, a methyl group is preferable.
In the general formula (1), R ₂ represents a methylene group, an ethylene group or a direct bond. Among these, a methylene group and an ethylene group are preferable, and an ethylene group is particularly preferable.
When R ₂ in the above general formula (1) is a methylene group, an ethylene group or a direct bond, when a detergent composition is prepared using the polymer of the present invention, it is neutral to weakly alkaline used suitably as a detergent. Under the conditions, it is possible to obtain a detergent composition that can stably exhibit high detergency, dispersibility of dirt components, gelation resistance, and the like.
Further, for example, as a polyalkylene glycol monomer in which R ₂ in the general formula (1) has a structure other than a methylene group, an ethylene group or a direct bond, an unsaturated double bond and a polyalkylene glycol chain have an ester bond. When a polyalkylene glycol-based monomer having a structure bonded thereto is used, the ester bond is subject to hydrolysis during monomer synthesis, polymerization, or under each application. In general, polyalkylene glycol monomers have a high molecular weight, and even if a small amount of ester bond undergoes hydrolysis, the effect on the physical properties of the polymer increases. End up. On the other hand, the polyalkylene glycol monomer (A) in which R ₂ in the general formula (1) is a methylene group, an ethylene group or a direct bond has high stability against changes in pH and temperature. It has a feature that it is extremely difficult to decompose during body synthesis, during polymerization, or under each application, for example, even under severe conditions during the manufacture of detergents. Furthermore, in the polyalkylene glycol monomer (A) in which R ₂ in the general formula (1) is an ethylene group, the unsaturated double bond site has a structure such as an allyl ether bond or a vinyl ether bond. Compared to a certain case, since it has good copolymerizability, it is possible to suppress variations in the amount of residual monomers during polymerization, and as a result, it is possible to suppress variations in the performance of the resulting polymer.
For these reasons, when R ₂ in the general formula (1) is an ethylene group, for example, when the polymer of the present invention is blended with a detergent or the like, particularly high performance is exhibited, and as described above. Therefore, it is possible to substantially avoid the occurrence of such problems and to suppress variations in product quality.
The above X is the represents a direct bond, for _example, in CH ₂ = CH ₂ -X-O- structure represented _by, indicates that a structure represented by CH _{2 =} CH ₂ -O- Yes.
In the general formula (1), Z is the same or different and represents an oxyalkylene group having 2 to 20 carbon atoms. From the viewpoint of improving the polymerizability of the polyalkylene glycol monomer (A), Z Is preferably an oxyalkylene group having 2 to 4 carbon atoms, and more preferably an oxyalkylene group having 2 to 3 carbon atoms. Particularly preferred is an oxyalkylene group having 2 carbon atoms. Specifically, it is preferably an oxyalkylene group having 2 to 4 carbon atoms such as an oxyethylene group, an oxypropylene group, or an oxybutylene group, and an oxyalkylene having 2 to 3 carbon atoms such as an oxyethylene group or an oxypropylene group. More preferably, it is a group. Among these, an oxyethylene group which is an alkylene group having 2 carbon atoms is particularly preferable.
As said Z, although 1 type (s) or 2 or more types can be used, it is preferable that 80-100 mol% is an oxyethylene group with respect to 100 mol% of all the Z which the said General formula (1) has. More preferably, 90 to 100 mol% is an oxyethylene group, and particularly preferably 100 mol% is an oxyethylene group.
In addition, when using 2 or more types as said Z, oxyalkylene groups may be any addition forms, such as random addition, block addition, and alternate addition.
In the above general formula (1), n is the average number of added moles of the oxyalkylene group and represents a number of 1 to 300. In order to express the function of the polyalkylene glycol polymer of the present invention in an aqueous system more remarkably, it is preferably an integer of 2 to 100, more preferably an integer of 3 to 55.
X and Y in the general formula (1) represent a hydroxyl group, a structure represented by the following general formula (2), and a structure represented by the following general formula (3). However, one of X and Y represents a hydroxyl group, and one of X and Y represents a structure represented by the following general formula (2) or a structure represented by the following general formula (3). By having the said structure, the dispersibility of the inorganic particle of the polyalkylene glycol polymer of this invention, a stain | pollution | contamination component, etc. improves notably.

In the general formula (2), R ₃ represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms. The alkylene group and arylene group may be an unsubstituted group, or may be a group in which one or two or more hydrogen atoms are substituted with other organic groups in the above-described range. . Examples of the other organic groups include alkyl groups, aryl groups, alkenyl groups, alkoxy groups, hydroxyl groups, acyl groups, ether groups, amide groups, ester groups, and ketone groups. As said R < ₃ >, in the case of an alkylene group, a C1-C8 thing is more preferable and a 1-4 thing is especially preferable. Moreover, as said R < ₃ >, in the case of an arylene group, a C6-C8 thing is more preferable and a C6-C7 thing is especially preferable. When R ₃ is such, it becomes possible to produce the polyalkylene glycol monomer (A) with a high yield, so that the polymerizability of the monomer and the purity of the resulting polymer are improved. To do. In addition, the gelation resistance of the resulting polymer is improved. Specific examples of the preferable R ₃ described above include a methylene group, an ethylene group, a propylene group, a butylene group, an octylene group, a phenylene group, or a part of these hydrogen atoms being an alkoxy group, a carboxyester group, Examples include a group substituted with an amino group, an amide group, a hydroxyl group, and the like, such as a hydroxyethyl group and a hydroxypropyl group. Among these, R ₃ is a methylene group or an ethylene group from the viewpoint that the production process of the polyalkylene glycol monomer (A) can be simplified to allow designing with less impurities. It is particularly preferred.

In the general formulas (2) and (3), M represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine salt (organic ammonium group). As metal atoms in M, monovalent metal atoms such as alkali metal atoms such as lithium, sodium and potassium; divalent metal atoms such as alkaline earth metal atoms such as calcium and magnesium; trivalent such as aluminum and iron The metal atoms are preferred. Moreover, as an organic amine group, alkanolamine groups, such as an ethanolamine group, a diethanolamine group, and a triethanolamine group, and a triethylamine group are suitable. Further, it may be an ammonium group. Among these, from the viewpoint of improving the gelation resistance of the polyalkylene glycol polymer of the present invention, it is preferable to use a monovalent metal atom such as sodium or potassium, an ammonium salt, or an organic amine salt, particularly a sodium atom. preferable.
The polyalkylene glycol polymer of the present invention has a structural unit (a) derived from the polyalkylene glycol monomer (A). The structural unit (a) is a structure in which the carbon-carbon double bond of the polyalkylene glycol monomer (A) is a single bond, and the following general formula (4);

_{(Wherein, R 1, R 2, X} , Y, Z, and n are in the general formula _{(1), R 1, R} 2, X, Y, are the same as Z, and n.) Be represented by Can do.
Note that the polyalkylene glycol polymer of the present invention has “structural unit (a) derived from polyalkylene glycol monomer (A)” means that the finally obtained polymer has the general formula ( It means having a structural unit represented by 4). That is, in the “structural unit (a) derived from the polyalkylene glycol monomer (A)” in the present invention, after synthesizing the polyalkylene glycol monomer (A), the other unit amount is added. In addition to those introduced into the polymer by copolymerizing with the body component, for example, first, the main chain portion of the polyalkylene glycol polymer is formed by copolymerization, and then side chains having a specific structure are introduced. In other words, the formation process includes those before and after the polymerization reaction.
Moreover, the structural unit (a) possessed by the polyalkylene glycol polymer of the present invention may be only one type or two or more types.
The polyalkylene glycol polymer of the present invention comprises a total amount of structural units derived from all monomers forming the polyalkylene glycol polymer (structural unit (a), structural units (b) and (e) described later). 1 to 99% by mass of the structural unit (a) is included with respect to 100% by mass. When the content of the structural unit (a) is within the above range, when the polymer of the present invention is used as a detergent builder, it is possible to exhibit good gelation resistance even under high hardness. Moreover, the remarkable improvement effect of compatibility with surfactant can be acquired. The content of the structural unit (a) is preferably 5 to 90% by mass, more preferably 10 to 80% by mass, and still more preferably 15 to 70% by mass.

<Production method of polyalkylene glycol monomer (A)>
The polyalkylene glycol monomer (A) may be produced by a known production method that can be applied, but is preferably produced by the following production methods (1) to (4). According to this method, the polyalkylene glycol monomer (A) of the present invention can be produced with high yield.
That is, the preferable production method (1) of the polyalkylene glycol monomer (A) of the present invention is (i) a polyalkylene glycol chain-containing monomer represented by the following general formula (5), an epihalohydrin, and an alkali compound. And (ii) a step of reacting the reaction product obtained in step A with a compound containing a sulfonic acid group (salt) described later (step B). It is a manufacturing method of a monomer (A).

In General Formula (5), R ₁ represents a hydrogen atom or a CH ₃ group. R ₂ represents a CH ₂ group, a CH ₂ CH ₂ group or a direct bond. Z is the same or different and represents an alkylene group having 2 to 20 carbon atoms. n is the average number of added moles of the oxyalkylene group and represents a number of 1 to 300.
A preferred production method (2) of the polyalkylene glycol monomer (A) of the present invention comprises (i) a polyalkylene glycol chain-containing monomer represented by the above general formula (5) and an epihalohydrin in the presence of a catalyst. A step of reacting (step C), (ii) a step of reacting the reaction product obtained in step C with an alkali compound (step D), and (iii) a reaction product obtained in step D and a sulfonic acid group described below. It is a manufacturing method of the polyalkylene glycol monomer (A) including the process (process B) with which the compound containing (salt) is made to react.
A preferred production method (3) of the polyalkylene glycol monomer (A) of the present invention comprises (i) a polyalkylene glycol chain-containing monomer represented by the above general formula (2) and an epihalohydrin in the presence of a catalyst. A polyalkylene glycol-based monomer comprising: a step of reacting (step C); and (ii) a step of reacting the reaction product obtained in step C with a compound containing a sulfonic acid group (salt) described later (step E). It is a manufacturing method of a body (A).
A preferred production method (4) of the polyalkylene glycol monomer (A) of the present invention includes (i) a polyalkylene glycol chain-containing monomer represented by the general formula (2) and an epoxy ring-containing sulfone described later. It is a manufacturing method of the polyalkylene glycol type monomer (A) including the process (process F) which makes an acid (salt) compound react.

In the polyalkylene glycol chain-containing monomer represented by the above general formula (5) in the production methods (1) to (4), preferred embodiments of R ₁ , R ₂ and Z are the above general formula (1). The same as the preferred embodiments of R ₁ , R ₂ and Z.
The polyalkylene glycol chain-containing monomer represented by the general formula (5) is a known method for converting an alkylene oxide into an alkylene glycol monovinyl ether, (meth) allyl alcohol, isoprenol or an alcohol having an alkylene oxide addition structure thereof. What was manufactured by adding by this can be used, and since the purity of a monomer can be made high, it is preferable.
The epihalohydrin in the production methods (1) to (3) has a structure represented by the following general formula (6).

In the general formula (6), X ′ represents a halogen atom. Specific examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and the like. Among these, epichlorohydrin is preferable because it is industrially inexpensive.

  The compound containing the sulfonic acid group (salt) used in the production methods (1) to (3) is (i) a compound that reacts with bisulfite or water to generate sulfite, or (ii) A compound containing one or more sulfonic acid groups (salts) and one or more hydroxyl groups, the former being sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium disulfite, potassium disulfite, etc. Examples thereof include hydroxymethanesulfonic acid and hydroxyethanesulfonic acid. Of these, bisulfite is preferable.

  The epoxy ring-containing sulfonic acid (salt) compound in the production method (4) is a compound obtained by reacting the epihalohydrin with a compound containing the sulfonic acid group (salt). For example, the following general formula (7-1) , (7-2).

(In the above general formulas (7-1) and (7-2), R ₃ represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms. , M represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine salt (organic ammonium group).

The reaction in Step A is performed in the presence of an alkali compound and, if necessary, a phase transfer catalyst and / or a solvent. Although it does not specifically limit as an alkali compound, Alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, are preferable. The amount of the alkali compound used is the molar ratio of the polyalkylene glycol chain-containing monomer represented by the general formula (5) to the hydroxyl group (in terms of hydroxyl value), usually (hydroxyl group) / (alkali compound) = 15/1. ~ 1/15. You may use an alkaline compound in the state of aqueous solution. In this case, the reaction may be performed while removing water (including water produced as a by-product with the progress of the reaction). The type of phase transfer catalyst is not particularly limited, but quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium chloride; phosphonium salts such as tetrabutylphosphonium chloride and tetrabutylphosphonium bromide; 15-crown-5 and 18 -Crown ethers, such as crown-6, are mentioned. When a phase transfer catalyst is used, the amount used is usually a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (5). ) / (Phase transfer catalyst) = 1 / 0.0001 to 1 / 0.3. If the amount of the catalyst is too small, a sufficient catalytic effect cannot be obtained. If the amount is too large, there is no further effect, which is economically disadvantageous.
The amount of epihalohydrin used in the reaction of Step A is a molar ratio of the polyalkylene glycol chain-containing monomer represented by the general formula (5) to the hydroxyl group (in terms of hydroxyl value), usually (hydroxyl group) / ( Epihalohydrin) = 1/1 to 1/15. If it is out of the range, a crosslinking component may be generated, which may cause gelation during polymerization.
The reaction in Step A is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but it can also be carried out in the presence of a solvent.

Reaction of the said process B is performed in presence of a solvent as needed. The solvent that can be used is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include water; alcohols such as methanol, ethanol, and isopropanol. These may be used alone or in combination of two or more.
The amount of the compound containing a sulfonic acid group (salt) is usually (glycidyl group) / (sulfonic acid group) in a molar ratio with respect to the number of moles of glycidyl groups in the reaction product obtained in Step A. (Compound containing (salt)) = 2/1 to 1/2, preferably 1.7 / 1 to 1 / 1.7, more preferably 1.4 / 1 to 1 / 1.4 is there. You may use the compound containing a sulfonic acid group (salt) in the state of aqueous solution.
The reaction in Step B is performed by adjusting the pH as necessary. The pH may be adjusted before or during the reaction, and it is preferable to add an alkaline compound. Examples of the alkaline compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, ammonia, and amines.

  In the production method (1), the reaction product of step A may be used as it is as the raw material of step B, or may be used after purification.

The catalyst in the reaction of the above step C may be an acid or a base, but an acid is preferable. The acid may be Lewis acid or Bronsted acid, but Lewis acid is preferred. As a Lewis acid, what is generally called a Lewis acid can be used. For example, boron trifluoride, tin tetrachloride, tin dichloride, zinc chloride, ferric chloride, aluminum chloride, titanium tetrachloride, magnesium chloride. And antimony pentachloride. The amount used is a molar ratio with respect to the hydroxyl group (hydroxyl value conversion) of the polyalkylene glycol chain-containing monomer represented by the general formula (5), and usually (hydroxyl group) / (catalyst) = 1/0. 0.0001 to 1 / 0.1.
The amount of epihalohydrin used in the reaction of Step C is usually a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the polyalkylene glycol chain-containing monomer represented by the general formula (5). ) / (Epihalohydrin) = 1/1 to 1/30. If it is out of the range, a crosslinking component may be generated, which may cause gelation during polymerization.
The reaction in Step C is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency. However, it can also be carried out in the presence of a solvent.

  The reaction in the above step D is performed in the presence of an alkali compound and, if necessary, a solvent. Although it does not specifically limit as an alkali compound, Alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, are preferable. The use amount of the alkali compound is usually (halogen group) / (alkali compound) = 1/1 to 1/100 in terms of a molar ratio with respect to the number of moles of halogen groups in the reaction product obtained in Step C. You may use an alkaline compound in the state of aqueous solution. The reaction in Step D can be performed in the presence of a solvent. The solvent that can be used is not particularly limited as long as it does not adversely affect the reaction, and examples thereof include water; alcohols such as methanol, ethanol, and isopropanol. These may be used alone or in combination of two or more.

Reaction of the said process E is performed in presence of a solvent as needed. The solvent that can be used is not particularly limited as long as it does not adversely influence the reaction, and examples thereof include water; alcohols such as methanol, ethanol, and isopropanol. These may be used alone or in combination of two or more.
The amount of the compound containing the sulfonic acid group (salt) is usually (halogen group) / (sulfonic acid group) in a molar ratio with respect to the number of moles of halogen groups in the reaction product obtained in Step C. (Compound containing (salt)) = 2/1 to 1/2, preferably 1.7 / 1 to 1 / 1.7, more preferably 1.4 / 1 to 1 / 1.4 is there. You may use the compound containing a sulfonic acid group (salt) in the state of aqueous solution.
Reaction of the process E is performed by adjusting pH as needed. The pH may be adjusted before or during the reaction, and it is preferable to add an alkaline compound. Examples of the alkaline compound include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide, ammonia, and amines.
In the production method (1), the reaction product of Step C may be used as it is as a raw material of Step E, or may be used after purification.

Reaction of the said process F is performed in presence of a catalyst as needed. Examples of the catalyst used for the reaction include alkali metal salts such as sodium hydroxide and sodium carbonate; quaternary ammonium salts such as tetramethylammonium chloride and tetraethylammonium chloride. The amount used is a molar ratio with respect to the hydroxyl group (hydroxyl value conversion) of the polyalkylene glycol chain-containing monomer represented by the general formula (5), and usually (hydroxyl group) / (catalyst) = 1/0. 0.0001 to 1 / 0.3. If the amount of the catalyst is too small, a sufficient catalytic effect cannot be obtained. If the amount is too large, there is no further effect, which is economically disadvantageous.
The reaction in step F is preferably carried out in the absence of a solvent because the reaction proceeds efficiently and is more preferable from the viewpoint of volumetric efficiency, but it can also be carried out in the presence of a solvent.
As the usage-amount of the said epoxy ring containing sulfonic acid (salt) compound used for reaction of the process F, with respect to the hydroxyl group (hydroxyl value conversion) of the polyalkylene glycol chain containing monomer represented by the said General formula (5). The molar ratio is usually (hydroxyl group) / (epoxy ring-containing sulfonic acid (salt) compound) = 5/1 to 1/5, preferably 3/1 to 1/3, more preferably 1. 5/1 to 1 / 1.5.

  The reactions of steps A, B, C, D, E, and F may be performed in an air atmosphere or in an inert gas atmosphere. Further, it can be carried out under reduced pressure, atmospheric pressure, or increased pressure. As reaction temperature, it is 0-200 degreeC normally, Preferably it is 15-150 degreeC, More preferably, it is 30-100 degreeC. From the viewpoint of fluidity of the polyalkylene glycol chain-containing monomer represented by the above general formula (5), which is a raw material, it is preferable to carry out at a temperature at which no problem occurs in stirring. Moreover, as reaction time, it is 0.1 to 50 hours normally, Preferably it is 0.5 to 30 hours, More preferably, it is 1 to 15 hours.

<Monomer (B)>
The polyalkylene glycol polymer of the present invention is a polymer essentially comprising the structural unit (b) derived from the carboxyl group-containing monomer (B).
The main role of the monomer (B) in the polyalkylene glycol polymer of the present invention is (i) improving the dispersibility of the stain component and inorganic pigment of the polyalkylene glycol polymer and improving the calcium ion scavenging ability. (Ii) Monomer for arranging the structure derived from the monomer (A) at a preferred position of the polymer or controlling the polyalkylene glycol polymer of the present invention to an appropriate molecular weight or molecular weight distribution. It plays the role of the connection between the bodies (A).

Examples of the carboxyl group-containing monomer (B) include unsaturated monocarboxylic acid monomers such as acrylic acid, methacrylic acid, crotonic acid, α-hydroxyacrylic acid, α-hydroxymethylacrylic acid, and salts thereof. ; Unsaturated dicarboxylic acids such as itaconic acid, fumaric acid, maleic acid, 2-methyleneglutaric acid and salts thereof; unsaturated dicarboxylic acid monomers such as salts thereof; an unsaturated dicarboxylic acid and an alcohol having 1 to 22 carbon atoms; Examples include half esters, half amides of unsaturated dicarboxylic acids and amines having 1 to 22 carbon atoms, and half esters of unsaturated dicarboxylic acids and glycols having 2 to 4 carbon atoms.
The salt is a metal salt, an ammonium salt, or an organic amine salt, and an alkali metal salt such as a sodium salt or a potassium salt is particularly preferable.
The polyalkylene glycol polymer of the present invention comprises a total amount of structural units derived from all monomers forming the polyalkylene glycol polymer (structural units (a) and (b) and structural units (e) described later). The structural unit (b) is contained in an amount of 1 to 99% by mass with respect to 100% by mass. When the content of the structural unit (b) is within the above range, it is possible to preferably exhibit the dispersibility of the dirt component particles and the pigment and the calcium ion capturing ability. Moreover, the remarkable improvement effect of compatibility with surfactant can be acquired. The content of the structural unit (b) is preferably 10 to 95% by mass, more preferably 20 to 90% by mass, and still more preferably 30 to 85% by mass.
In addition, when the said structural unit (b) is a structural unit (b) derived from a carboxyl group-containing monomer (B), the mass ratio (mass%) with respect to the total amount of the structural units derived from all monomers corresponds. It shall be calculated in terms of acid. For example, in the case of a structural unit derived from sodium acrylate, -CH2CH (COONa)-, the mass is calculated as a structural unit derived from acrylic acid which is the corresponding acid, -CH2CH (COOH)-. Moreover, also when calculating the mass ratio (mass%) with respect to the total amount of all the monomers of a carboxyl group-containing monomer (B), it shall calculate in corresponding acid conversion. The same applies to the calculation of the mass ratio (% by mass) of the structural units derived from the initiator and the chain transfer agent with respect to the total amount of structural units derived from all monomers.

The polyalkylene glycol polymer of the present invention has the structural unit (b) in the above range, and may have only one type of structural unit (b), or may have two or more types. .
Among the structural units (b), it is preferable to have a structure derived from (meth) acrylic acid (salt) because the effect of improving the gelation resistance of the polyalkylene glycol polymer is particularly high.

<Other monomers>
The polyalkylene glycol polymer of the present invention has a structural unit (e) derived from another monomer (E) (a monomer other than the monomer (A) and the monomer (B)). You may do it. The polyalkylene glycol-based polymer may have only one type of structural unit (e), or may have two or more types of structural units (e).

  The structural unit (e) derived from the other monomer (E) is a structural unit in which the unsaturated double bond of the other monomer (E) is replaced with a single bond. The polyalkylene glycol polymer of the present invention has “structural unit (e) derived from other monomer (E)” means that the finally obtained polymer is the monomer (E). It means having a structural unit in which an unsaturated double bond is replaced with a single bond.

Examples of the other monomer (E) include vinyl cyclic amine monomers having a cyclic amine structure such as vinyl pyridine, vinyl imidazole, morpholine, vinyl pyrrole, dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and the like. Aminoalkyl (meth) acrylates such as dimethylaminopropyl acrylate and aminoethyl methacrylate, allylamines such as diallylamine and diallyldimethylamine, (meth) allyl glycidyl ether, isoprenyl glycidyl ether, and vinyl glycidyl ether epoxy ring 1 ~ Monomers obtained by reacting tertiary amines (salts), monomers having a structure in which these amino groups are quaternized, and monomers having a structure in which these amino groups are quaternized Amino such as Containing monomer (Examples of the amines include alkylamines such as methylamine, ethylamine, dimethylamine, diethylamine, diisopropylamine and di-n-butylamine; alkanolamines such as diethanolamine and diisopropanolamine; morpholine and pyrrole, etc. In the case where the cationic group-containing monomer has a quaternized amino group, a cationic group-containing monomer having a primary to tertiary amino group may be used as a known quaternary. Examples include monomers quaternized with an agent, and examples of known quaternizing agents include alkyl halides and dialkyl sulfuric acid.
Specific examples of the tertiary amine salt include trimethylamine hydrochloride and triethylamine hydrochloride. Examples of the salt include hydrochloride and organic acid salt. ); Cyclic N-vinyl lactam monomers such as N-vinyl pyrrolidone, N-vinyl caprolactam, N-vinyl-4-butyl pyrrolidone; vinyl sulfonic acid, (meth) allyl sulfonic acid, isoprene sulfonic acid, 3-allyloxy Sulfonic acid group-containing monomers such as -2-hydroxypropane sulfonic acid, acrylamido-2-methylpropane sulfonic acid and salts thereof; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, Hydroxyalkyl (meth) acrylate monomers such as 2-hydroxybutyl (meth) acrylate and (meth) acrylic acid-hydroxymethyl; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2 -Ethylhexyl (meth) acrylate, dodecyl ( ) (Meth) acrylic esters such as acrylates; vinyl carboxylates such as vinyl acetate, vinyl propionate and vinyl butyrate; vinyl aryl monomers such as styrene and indene; alkenes such as isobutylene; N-vinylformamide, N N-vinyl cyclic amide monomers such as vinylacetamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, and N-vinyloxazolidone; acrylamides such as (meth) acrylamide and (meth) isopropylacrylamide A monomer obtained by adding 1 to 200 mol of alkylene oxide to a hydroxyl group-containing monomer such as (meth) allyl alcohol or isoprenol, or a polyalkylene glycol chain-containing unit such as a (meth) acrylic acid ester of alkoxypolyalkylene glycol Mer; etc. It is below.
Examples of the salt include metal salts, ammonium salts, organic amine salts (organic ammonium salts) and the like.
When the polyalkylene glycol polymer of the present invention has a structural unit (e) derived from the other monomer (E) as an optional component, all monomers forming the polyalkylene glycol polymer The structural unit (e) is preferably contained in an amount of 0 to 60% by mass with respect to 100% by mass of the total amount of structural units derived from (ie, the total amount of the structural units (a), (b) and (e)). More preferably, it is 0-50 mass%.
When the structural unit (e) is a structural unit derived from an acid group-containing monomer, the mass ratio (% by mass) to the total amount of structural units derived from all monomers is calculated in terms of the corresponding acid. And Moreover, when calculating the mass ratio (mass%) with respect to the total amount of all the monomers of an acid group containing monomer, it shall calculate by corresponding acid conversion. The same applies to the calculation of the mass ratio (% by mass) of the structural units derived from the initiator and the chain transfer agent with respect to the total amount of structural units derived from all monomers.
When the structural unit (e) is a structural unit derived from an amino group-containing monomer, the mass ratio relative to the total amount of structural units derived from all monomers, or the total amount of amino group-containing monomers When calculating the mass ratio with respect to the total amount of the body, it is calculated as the mass ratio of the corresponding unneutralized amine. For example, when the other monomer is vinylamine hydrochloride, the mass ratio (% by mass) of vinylamine which is the corresponding unneutralized amine is calculated. In addition, when calculating the mass ratio (mass%) of a monomer containing a quaternized amino group or a structural unit derived therefrom, the mass of the counter anion is not taken into account (not including) Shall. The same applies to the calculation of the mass ratio (% by mass) of the structural units derived from the initiator and the chain transfer agent with respect to the total amount of structural units derived from all monomers.

<Other structural units>
The polymer of the present invention has a structure derived from a compound (C) selected from bisulfite (salt) (C-1), hydrogen peroxide (C-2), and hypophosphorous acid (salt) (C-3). The unit (c) may be included. That is, it may contain a sulfonic acid (salt) group derived from bisulfite (salt) (C-1), a hydroxyl group derived from hydrogen peroxide, a phosphinate group derived from hypophosphorous acid (salt), and the like. . When the polymer of the present invention contains the structural unit (c), the gel resistance of the polymer of the present invention tends to be further improved. Since the compound (C) usually acts as an initiator or a chain transfer agent, the structural unit (c) is usually introduced at the molecular end (however, hypophosphorous acid (salt) has two reaction sites). , Introduced at the end of the molecule or into the molecule).
The structural unit (c) (in terms of acid type in the case of an acid group salt) is more preferably 0.05 to 10% by mass with respect to 100% by mass of the structure derived from all monomers. More preferably, it is -5 mass%.
<Other physical properties of polyalkylene glycol polymer>
In the polyalkylene glycol polymer of the present invention, the structural unit (a), (b) and, if necessary, the structural unit (e) may be introduced at a specific ratio as described above. Each structural unit may exist in a block shape or a random shape.
Moreover, the weight average molecular weight of the said polyalkylene glycol type-polymer can be set suitably, and is not specifically limited. Specifically, the weight average molecular weight of the polyalkylene glycol polymer is preferably 2,000 to 200,000, more preferably 3,000 to 100,000, and most preferably 4,000 to 60,000. 000. If the weight average molecular weight is within the above range, gelation resistance and calcium ion scavenging ability under high hardness tend to be improved.
The number average molecular weight of the polyalkylene glycol polymer is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, and most preferably 2,000 to 25,000. is there. If the number average molecular weight is within the above range, gelation resistance and calcium ion scavenging ability under high hardness tend to be improved.
In the present specification, the weight average molecular weight and the number average molecular weight are measured values by GPC (gel permeation chromatography), and can be measured by an apparatus and measurement conditions described in Examples described later. .
The polyalkylene glycol polymer of the present invention has high gelation resistance and calcium ion scavenging ability under high hardness, but preferably has a gelation resistance of 0.08 or less. More preferably, it is 0.07 or less. Calcium ion capturing ability is preferably 190mg · CaCO ₃ / 1g or more.
The gelation resistance and calcium ion scavenging ability can be measured in the same manner as in the examples described later.
[Polyalkylene glycol polymer composition]
The polyalkylene glycol polymer of the present invention may constitute a polyalkylene glycol polymer composition together with other components. As said other component, a polymerization initiator residue, a residual monomer, the by-product at the time of superposition | polymerization, a water | moisture content, etc. are mentioned, These 1 type (s) or 2 or more types can be contained. The polyalkylene glycol polymer composition preferably contains 1 to 100% by mass of the polyalkylene glycol polymer of the present invention with respect to 100% by mass of the total amount of the polyalkylene glycol polymer composition. One of the preferable forms of the polyalkylene glycol polymer composition is a form containing 40 to 60% by mass of the polyalkylene glycol polymer of the present invention and 40 to 60% by mass of water.
[Method for Producing Polyalkylene Glycol Polymer of the Present Invention]
The polyalkylene glycol polymer of the present invention comprises (i) a polyalkylene glycol monomer (A) (monomer (A)) represented by the general formula (1) and (ii) a carboxyl group-containing Manufacture by making monomer (B) essential and copolymerizing monomer components containing other monomer (E) (monomer (E)) at a predetermined ratio as necessary. it can.
In the method for producing a polyalkylene glycol polymer of the present invention, the composition ratio of each monomer used for polymerization is 100 in total of all monomers (monomer (A), (B), (E)). A monomer (A) is 1-99 mass% and a monomer (B) is 1-99 mass% with respect to mass%. When the content of the monomer (A) is less than 1% by mass, the detergency may decrease due to a decrease in gelation resistance. Further, if the content of the monomer (B) is less than 1% by mass, the molecular weight of the polymer and the polymerizability of the monomer (A) may not be controlled. The composition ratio of each monomer used for polymerization is preferably 5 to 90% by mass of monomer (A) and 10 to 95% by mass of monomer (B), more preferably monomer. (A) is 10 to 80% by mass, monomer (B) is 20 to 90% by mass, and particularly preferably, monomer (A) is 15 to 70% by mass and monomer (B) is 30%. It is -85 mass%.
Moreover, even if it contains the monomer (E) in the ratio of 0-50 mass% with respect to 100 mass% of total amounts of all the monomers (monomer (A), (B), (E)). Good. More preferably, it is 0-10 mass%, More preferably, it is 0-5 mass%, Most preferably, it is 0 mass%.
The polymerization method for obtaining the polyalkylene glycol polymer of the present invention is not particularly limited, and a commonly used polymerization method or a modified method thereof can be employed. Examples of the polymerization method include a radical polymerization method, specifically, an oil-in-water emulsion polymerization method, a water-in-oil emulsion polymerization method, a suspension polymerization method, a dispersion polymerization method, a precipitation polymerization method, and a solution polymerization method. An aqueous solution polymerization method, a bulk polymerization method, or the like can be employed. Among the polymerization methods exemplified above, it is preferable to employ a solution polymerization method because it is highly safe and can reduce production costs (polymerization costs).
In the solution polymerization method, the monomer component is polymerized in a solvent, but the solvent is not particularly limited, and a solvent usually used in the solution polymerization method can be used. As said solvent, water-based solvents, such as water, alcohol, glycol, glycerol, polyethyleneglycol, are suitable, for example. Among these, water is more preferable.
The said solvent may use only 1 type and may use 2 or more types together. Moreover, in order to improve the solubility of the monomer component in the solvent, an organic solvent may be appropriately added within a range that does not adversely affect the polymerization reaction.
The organic solvent is not particularly limited, and any appropriate organic solvent can be used. Examples of such an organic solvent include lower alcohols such as methanol and ethanol; amides such as dimethylformaldehyde; ethers such as diethyl ether and dioxane;
As for the said organic solvent, only 1 type may be used and 2 or more types may be used together.
The amount of the solvent used is preferably 40 to 300 parts by mass, more preferably 45 to 200, with respect to 100 parts by mass of the total amount of all monomers (monomers (A), (B), (E)). It is the range of 50 mass parts, More preferably, it is 50-150 mass parts. When the amount of the solvent used is less than 40 parts by mass relative to 100 parts by mass of the total amount of all monomers, the molecular weight of the resulting polymer may be too high. On the other hand, when the amount of the solvent used exceeds 300 parts by mass with respect to 100 parts by mass of the total amount of all monomers, the concentration of the resulting polymer is lowered, and in some cases, the solvent may need to be removed. .
The solvent may be partly or wholly charged in the reaction vessel in the initial stage of polymerization, but a part of the solvent may be added (dropped) into the reaction system during the polymerization reaction, or the monomer. Components, initiators, and the like may be added (dropped) into the reaction system during the polymerization reaction together with these components in a form in which the components and initiator are dissolved in advance.
The reaction form of the solution polymerization method is not particularly limited, and the reaction can be carried out according to a commonly used form. Typically, for example, in the solvent charged in advance in the reaction system, the single monomer is used. A mode in which a reaction is performed by dropping a solution containing a body component and a solution containing a polymerization initiator (hereinafter also referred to as “initiator”). In such a reaction form, the concentration of each solution to be dropped is not particularly limited, and any appropriate concentration can be adopted.
As a form which reacts by dripping the solution containing the said monomer component and the solution containing an initiator in the solvent previously prepared in the said reaction system, a monomer (A), a single quantity, for example During the polymerization, the body (B), the monomer (E), if necessary, the initiator component, and other additives as necessary, are dissolved in the solvent, or without being dissolved in the solvent. The form which superposes | polymerizes by adding (dropping) suitably in a reaction system is mentioned. In the reaction form, a part or all of the total amount of the monomer (A) used can be added to the reaction system in advance (initial charge) before the start of polymerization.
In the polymerization reaction by the solution polymerization method, it is preferable that the addition of the monomer (A) to the reaction system is completed earlier than the addition of the monomer (B). And it is more preferable that 5-100 mass% is unadded among the total usage-amount of a monomer (B) at the time of completion | finish of addition of a monomer (A). More preferably, 10 to 50% by mass of the total amount of the monomer (B) used is not added at the end of the addition of the monomer (A), and 15% of the total amount of the monomer (B) used. It is particularly preferable that ˜35% by mass is not added. Polymerization of the polyalkylene glycol monomer (A) can be improved by performing addition and polymerization using such an addition method. Therefore, the gelation resistance and calcium ion trapping of the obtained polymer can be improved. Performance can be improved.
<Polymerization initiator>
As the polymerization initiator used in the above production method, those usually used can be used. Specifically, hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, ammonium persulfate; 2,2′-azobis (2-amidinopropane) hydrochloride, 4,4′-azobis-4-cyanoparellin Azo compounds such as acid, azobisisobutyronitrile, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl Organic peroxides such as peroxide and cumene hydroperoxide are preferred. Of these polymerization initiators, hydrogen peroxide, persulfate, and 2,2′-azobis (2-amidinopropane) hydrochloride are preferred, and persulfate and 2,2′-azobis (2-amidinopropane) hydrochloric acid. Most preferred are salts. These polymerization initiators may be used alone or in combination of two or more.
<Chain transfer agent>
In the above production method, if necessary, a chain transfer agent may be used as a molecular weight regulator of the polymer within a range that does not adversely affect the polymerization. Specific examples of the chain transfer agent include mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropion, 3-mercaptopropion, thiomalic acid, octyl thioglycolate, octyl 3-mercaptopropionate, 2- Thiol chain transfer agents such as mercaptoethanesulfonic acid, n-dodecyl mercaptan, octyl mercaptan, butylthioglycolate; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane; Secondary alcohol; phosphorous acid, hypophosphorous acid and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionic acid, metabisulfite and salts thereof (hydrogen sulfite) Sodium, potassium bisulfite, Sodium dithionite, potassium dithionite, sodium metabisulfite, metabisulfite potassium, etc.) and the like, lower oxides and salts thereof. The said chain transfer agent may be used independently, and 2 or more types may be mixed and used for it.
When a chain transfer agent is used, there is an advantage that the polymer to be produced can be prevented from having a higher molecular weight than necessary, and a low molecular weight polyalkylene glycol-based polymer can be produced efficiently.
In the above production method, it is a preferred form to use sulfurous acid and / or sulfite (hereinafter also referred to as “sulfurous acid (salt)”) as a chain transfer agent. In that case, a polymerization initiator is used in addition to sulfurous acid (salt). Furthermore, you may use a heavy metal ion together as a reaction accelerator mentioned later.
The above sulfurous acid (salt) means sulfurous acid, hydrogen sulfite, or a salt thereof. Among these, a form in which sulfite and / or hydrogen sulfite is a salt is preferable. When sulfite and / or hydrogen sulfite is a salt, a salt of a metal atom, ammonium or organic ammonium is preferred in addition to the above examples.
Examples of the metal atom include monovalent metal atoms of alkali metals such as lithium, sodium and potassium; divalent metal atoms of alkaline earth metals such as calcium and magnesium; trivalent metal atoms such as aluminum and iron Etc. are preferred.
As the organic ammonium (organic amine), alkanolamines such as ethanolamine, diethanolamine, and triethanolamine, and triethylamine are preferable. Further, the sulfite may be an ammonium salt.
Therefore, examples of the sulfite preferably used in the present invention include sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium sulfite, potassium sulfite, ammonium sulfite and the like, and sodium bisulfite is particularly suitable. The said sulfurous acid (salt) may be used independently, and 2 or more types may be mixed and used for it.
<Reaction accelerator>
In the above production method, a reaction accelerator may be added for the purpose of reducing the amount of initiator used. Examples of the reaction accelerator include heavy metal ions. In the present invention, the heavy metal ion means a metal having a specific gravity of 4 g / cm ³ or more. As said metal ion, iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium etc. are preferable, for example. These heavy metals can be used alone or in combination of two or more. Among these, iron is more preferable. The valence of the heavy metal ion is not particularly limited. For example, when iron is used as the heavy metal, the iron ion in the initiator may be Fe ²⁺ or Fe ³⁺ , and both of them may be used. It may be included.
Although the said heavy metal ion will not be specifically limited if it is contained as a form of ion, Since it is excellent in handleability, it is suitable to use the solution formed by melt | dissolving a heavy metal compound. The heavy metal compound used in that case should just contain the heavy metal ion desired to contain in an initiator, and can be determined according to the initiator to be used. When iron is used as the heavy metal ion, the mole salt (Fe (NH ₄ ) ₂ (SO ₄ ) ₂ · 6H ₂ O), ferrous sulfate · 7 hydrate, ferrous chloride, ferric chloride, etc. It is preferable to use a heavy metal compound or the like. Moreover, when using manganese as a heavy metal ion, manganese chloride etc. can be used suitably. Since these are all water-soluble compounds, they can be used in the form of an aqueous solution and have excellent handleability. The solvent of the solution obtained by dissolving the heavy metal compound is not limited to water, and does not hinder the polymerization reaction in the production of the polyalkylene glycol polymer of the present invention, and is a heavy metal compound. As long as it dissolves.
The method for adding the heavy metal ions is not particularly limited, but it is preferably added before the monomer addition is completed, and it is particularly preferable to initially charge the entire amount. Further, the amount used is preferably 100 ppm or less, more preferably 70 ppm or less, still more preferably 50 ppm or less, and particularly preferably 30 ppm or less, based on the total amount of the reaction solution. If it exceeds 100 ppm, the effect of addition is not observed, and the resulting polymer is highly colored, which may be unusable when used as a detergent composition.
The content of the heavy metal ions is preferably 0.1 to 10 ppm with respect to the total mass of the polymerization reaction solution at the completion of the polymerization reaction. If the content of heavy metal ions is less than 0.1 ppm, the effect of heavy metal ions may not be sufficiently exhibited. On the other hand, if the content of heavy metal ions exceeds 10 ppm, the color tone of the resulting polymer may be deteriorated. Moreover, when there is much content of heavy metal ion, when using the polymer which is a product as a detergent builder, there exists a possibility of becoming a cause of coloring stain | pollution | contamination.
The time when the polymerization reaction is completed means the time when the polymerization reaction is substantially completed in the polymerization reaction solution and a desired polymer is obtained. For example, when the polymer polymerized in the polymerization reaction solution is neutralized with an acid component, the content of heavy metal ions is calculated based on the total mass of the polymerization reaction solution after neutralization. When two or more kinds of heavy metal ions are included, the total amount of heavy metal ions may be in the above range.
In the above production method, in the polymerization, a decomposition catalyst for the polymerization initiator or a reducing compound may be added to the reaction system in addition to the above-described compounds.
Examples of the decomposition catalyst for the polymerization initiator include metal halides such as lithium chloride and lithium bromide; metal oxides such as titanium oxide and silicon dioxide; hydrochloric acid, hydrobromic acid, perchloric acid, sulfuric acid, nitric acid and the like. Metal salts of inorganic acids; Carboxylic acids such as formic acid, acetic acid, propionic acid, lactic acid, isolacic acid, benzoic acid, their esters and their metal salts; heterocyclic amines such as pyridine, indole, imidazole, carbazole and their derivatives Can be mentioned. These decomposition catalysts may be used alone or in combination of two or more.
Examples of the reducing compound include organic metal compounds such as ferrocene; iron naphthenate, copper naphthenate, nickel naphthenate, cobalt naphthenate, manganese naphthenate, and the like, such as iron, copper, nickel, cobalt, and manganese. Inorganic compounds capable of generating metal ions; boron trifluoride ether adducts, potassium permanganate, perchloric acid and other inorganic compounds; sulfur dioxide, sulfite, sulfate, bisulfite, thiosulfate, sulfoxide, Sulfur-containing compounds such as benzenesulfinic acid and its substitutes, and homologues of cyclic sulfinic acid such as para-toluenesulfinic acid; octyl mercaptan, dodecyl mercaptan, mercaptoethanol, α-mercaptopropionic acid, thioglycolic acid, thiopropionic acid, α -Sodium thiopropionate sulfopropyl ester Mercapto compounds such as stealth and α-thiopropionic acid sodium sulfoethyl ester; nitrogen-containing compounds such as hydrazine, β-hydroxyethylhydrazine and hydroxylamine; formaldehyde, acetaldehyde, propionaldehyde, n-butyraldehyde, isobutyraldehyde, isovaleraldehyde Aldehydes such as ascorbic acid and the like. These reducing compounds may also be used alone or in combination of two or more. Further, a reducing compound such as a mercapto compound may be added as a chain transfer agent.
The combination of the chain transfer agent, the initiator, and the reaction accelerator is not particularly limited, and can be appropriately selected from the above examples. For example, combinations of chain transfer agent, initiator and reaction accelerator include sodium bisulfite / sodium persulfate, sodium bisulfite / Fe (ion), sodium bisulfite / hydrogen peroxide / Fe (ion), sodium bisulfite Forms such as / sodium persulfate / Fe (ion), sodium bisulfite / sodium persulfate / hydrogen peroxide, sodium bisulfite / oxygen / Fe (ion) are preferable. More preferred are sodium persulfate / hydrogen peroxide, sodium persulfate / hydrogen peroxide / Fe (ion), sodium bisulfite / sodium persulfate, sodium bisulfite / sodium persulfate / Fe (ion), and most preferred. Are sodium bisulfite / sodium persulfate / Fe (ion) and sodium persulfate / hydrogen peroxide / Fe (ion).
<Amount of polymerization initiator used>
The amount of the polymerization initiator used is not particularly limited as long as it is an amount capable of initiating copolymerization of monomers, but the total amount of all monomer components (monomer (A), (B) and (E)) is 1 It is preferable that it is 15 g or less with respect to mol. More preferably, it is 1-12g.
When hydrogen peroxide is used as an initiator, the amount of hydrogen peroxide added is preferably 1.0 to 10.0 g with respect to 1 mol of the total amount of all monomer components, and 2.0 to 8 More preferably, it is 0.0 g. If the amount of hydrogen peroxide added is less than 1.0 g, the polymerization average molecular weight of the resulting polymer tends to increase. On the other hand, when the addition amount exceeds 10.0 g, an effect sufficient to meet the increase in the addition amount cannot be obtained, and further, the remaining hydrogen peroxide amount is adversely affected.
When using a persulfate as an initiator, the amount of the persulfate added is preferably 1.0 to 5.0 g with respect to 1 mol of the total amount of all monomer components, and 2.0 to 4 More preferably, it is 0.0 g. If the amount of persulfate added is less than the above range, the molecular weight of the resulting polymer tends to increase. On the other hand, if the addition amount is more than the above range, an effect corresponding to the increase in the addition amount cannot be obtained, and further, the purity of the obtained polymer is adversely affected.
When hydrogen peroxide and persulfate are used together as an initiator, the addition ratio of hydrogen peroxide and persulfate is such that the weight ratio of persulfate to hydrogen peroxide is 0.1 to 5.0. Preferably, it is 0.2-2.0. If the weight ratio of persulfate is less than 0.1, the weight average molecular weight of the resulting copolymer tends to be high. On the other hand, if the weight ratio of persulfate exceeds 5.0, the effect of lowering the molecular weight due to the addition of persulfate cannot be obtained enough to meet the increase in the amount added, and the persulfate is wasted in the polymerization reaction system. Will be consumed.
As a method for adding hydrogen peroxide, the amount to be added by dripping substantially continuously is preferably 85% by weight or more of the necessary predetermined amount, more preferably 90% by weight or more, and 100 Most preferably, the weight percent, ie the whole amount, is added dropwise. When hydrogen peroxide is continuously dropped, the dropping speed may be changed.
When hydrogen peroxide is dropped under the appropriate reaction conditions (temperature, pressure, pH, etc.) described later, it is delayed after the start of dropping of the monomer (excluding the initially charged monomer). It is preferable to start. Specifically, preferably after 1 minute or more has elapsed since the start of dropping of the monomer (A), more preferably after 3 minutes or more, still more preferably after 5 minutes or more, and most preferably after 10 minutes or more have elapsed. It is to start dropping of hydrogen oxide. By delaying the start of the dropwise addition of hydrogen peroxide, it is possible to smooth the initial polymerization start and narrow the molecular weight distribution.
The time for delaying the start of dropwise addition of hydrogen peroxide is preferably within 60 minutes, more preferably within 30 minutes after the start of dropping of the monomer.
It is possible to start the dropping of hydrogen peroxide simultaneously with the dropping of the monomer, or to charge hydrogen peroxide in advance before dropping of the monomer. Is preferably 10% or less. More preferably, it is 7% or less, More preferably, it is 5% or less, Most preferably, it is 3% or less.
If more than 10% of the required amount of hydrogen peroxide is added before the start of the dropwise addition of the monomer, for example, when a persulfate is used in combination, the ratio of the concentration of hydrogen peroxide to the persulfate increases, and polymerization is May stop. On the other hand, if it starts later than 60 minutes from the start of the dropping of the monomer, the chain transfer reaction due to hydrogen peroxide does not occur, so the molecular weight at the initial stage of polymerization increases.
Further, the dropping of hydrogen peroxide is preferably terminated simultaneously with the end of dropping of the monomer when the reaction is performed under suitable reaction conditions (temperature, pressure, pH, etc.) described later. Moreover, it is more preferable to complete | finish 10 minutes or more earlier than monomer dropping completion time, and it is especially preferable to complete | finish 30 minutes or more early. In addition, even if it complete | finishes later than the dripping completion time of a monomer, it does not have a bad influence in a polymerization system especially. However, since the added hydrogen peroxide is not completely decomposed by the end of the polymerization, unreacted hydrogen peroxide cannot be obtained and is wasted. Further, it is not preferable that a large amount of hydrogen peroxide remains because it may adversely affect the thermal stability of the obtained polymer.
The method for adding the persulfate is not particularly limited, but considering the decomposability and the like, it is preferable that the amount added by dripping continuously is 50% by weight or more of the required predetermined amount. . More preferably, it is 80 weight% or more, and it is most preferable that 100 weight%, ie, the whole quantity is dripped. When the persulfate is continuously dropped, the dropping speed may be changed.
Although the dropping time is not particularly limited, in the case of performing the reaction under the preferable reaction conditions (temperature, pressure, pH, etc.) described later, since persulfate is a relatively quick initiator, It is preferable to continue dropping until the dropping end time. Moreover, it is more preferable to complete | finish dripping within 30 minutes after completion | finish of monomer dripping, and it is especially preferable to complete dripping within 5 to 20 minutes after monomer dripping. Thereby, the residual amount of the monomer in the produced polymer can be remarkably reduced.
It should be noted that, even if the dropping of these initiators is completed before the dropping of the monomer is completed, it does not particularly adversely affect the polymerization, and the initiator depends on the residual amount of the monomer in the obtained polymer. What is necessary is just to set the dripping end time.
For initiators that are relatively quick to decompose, such as the persulfate, the preferred range for the dropping end time has been described, but the dropping start time is not limited in any way and may be set as appropriate. For example, the start of dropping of the initiator may be started before the start of dropping of the monomer. When two or more kinds of initiators are used in combination, the start of dropping of one initiator is started and a certain time has elapsed. You may start dripping another initiator after or after dripping is complete | finished. In either case, the initiator dropping start time may be appropriately set according to the decomposition rate of the initiator and the reactivity of the monomer.
The concentration of the initiator solution when the polymerization initiator is added dropwise is not particularly limited, but is preferably 5 to 60% by weight, particularly preferably 10 to 50% by weight. If the concentration of the initiator is less than 5% by weight, the monomer concentration during the polymerization will be very low as a result. The residual amount of becomes very large. Further, the efficiency and productivity of transportation and the like are lowered, which is not preferable from the economical aspect. On the other hand, if it exceeds 60% by weight, there is a problem in terms of safety and ease of dripping.
The addition amount of the chain transfer agent is not limited as long as the monomers (A), (B) and (E) are polymerized satisfactorily, but preferably the monomers (A), (B) and (E ) To 1 to 20 g, more preferably 2 to 15 g, based on 1 mol of all monomer components. If it is less than 1 g, the molecular weight may not be controlled. On the other hand, if it exceeds 20 g, a large amount of impurities may be produced, and the pure polymer content may be reduced. In particular, when sulfite is used, surplus sulfite is decomposed in the reaction system, and sulfurous acid gas may be generated. Furthermore, there is a risk that it may be economically disadvantageous.
As a combination of the initiator and the chain transfer agent, it is most preferable to use one or more persulfates and sulfites. In this case, the mixing ratio of persulfate and sulfite is not particularly limited, but it is preferable to use 0.5 to 5 parts by mass of sulfite with respect to 1 part by mass of persulfate. The lower limit of the amount of sulfite is more preferably 1 part by mass with respect to 1 part by mass of persulfate, and most preferably 2 parts by mass. Moreover, as for the upper limit of the amount of sulfites, it is more preferable that it is 4 mass parts with respect to 1 mass part of persulfate, Most preferably, it is 3 mass parts. If the sulfite is less than 0.5 parts by mass with respect to 1 part by mass of the persulfate, the total amount of initiator required may be increased when the molecular weight is lowered. There is a risk that the reaction will increase and impurities will increase.
The total amount of the chain transfer agent, the initiator, and the reaction accelerator used is 2 to 20 g with respect to 1 mol of the total amount of all monomer components composed of the monomers (A), (B), and (E). It is preferable that By setting it as such a range, the polymer of this invention can be produced efficiently and the molecular weight distribution of a polyalkylene glycol type polymer can be made into a desired thing. More preferably, it is 4-18g, More preferably, it is 6-15g.
In the above production method, as a method for adding the monomer component, the polymerization initiator and the chain transfer agent to the reaction vessel, a continuous charging method such as dropping or divided charging can be applied. In addition, each may be introduced alone into the reaction vessel, or may be mixed in advance with other components, a solvent, or the like.
As a specific addition method, a method in which all of the monomer components are charged into a reaction vessel and copolymerization is performed by adding a polymerization initiator into the reaction vessel; a portion of the monomer components are charged into the reaction vessel. A method of carrying out copolymerization by adding a polymerization initiator and the remaining monomer component continuously or stepwise (preferably continuously) into a reaction vessel; charging a polymerization solvent into the reaction vessel; A method of adding the total amount of the monomer component and the polymerization initiator; and the like. Among these methods, since the molecular weight distribution of the polymer obtained can be narrowed (sharpened) and the dispersibility of dirt and gelation resistance can be improved, a polymerization initiator and a monomer component It is preferable to carry out the copolymerization by successively dropping them into a reaction vessel. Such polymerization can be carried out either batchwise or continuously.
<Polymerization conditions>
In the said manufacturing method, superposition | polymerization conditions, such as superposition | polymerization temperature, are suitably determined by the superposition | polymerization method used, a solvent, a polymerization initiator, etc., However, It is preferable that it is 25-200 degreeC as superposition | polymerization temperature. More preferably, it is 50-150 degreeC, More preferably, it is 60-120 degreeC, Most preferably, it is 80-110 degreeC. If the polymerization temperature is too low, the weight average molecular weight of the resulting polymer may be too high, or the amount of impurities generated may increase.
The polymerization temperature does not necessarily need to be kept almost constant in the polymerization reaction. For example, the polymerization is started from room temperature, the temperature is raised to a set temperature with an appropriate temperature increase time or rate, and then the set temperature is increased. You may make it hold | maintain and you may carry out temperature fluctuation (temperature rise or temperature fall) with time during a polymerization reaction according to dripping methods, such as a monomer component and an initiator. The polymerization temperature refers to the temperature of the reaction solution for the polymerization reaction. Moreover, about the measuring method and control means of superposition | polymerization temperature, arbitrary appropriate methods and means can be employ | adopted. For example, the measurement may be performed using a generally used apparatus.
The pressure during the polymerization in the above production method is not particularly limited, and any appropriate pressure can be adopted. For example, it may be under normal pressure (atmospheric pressure), reduced pressure, or increased pressure. Further, the atmosphere in the reaction system may be an air atmosphere or may be an inert gas atmosphere. When the atmosphere in the reaction system is an inert gas atmosphere, for example, the reaction system can be replaced with an inert gas such as nitrogen before the start of polymerization. As a result, atmospheric gas (for example, oxygen gas) in the reaction system is dissolved in the liquid phase and acts as a polymerization inhibitor.
In the said manufacturing method, it is preferable that solid content concentration in the reaction solution (polymer solution) at the time of completion | finish of addition of the said addition component complete | finished and the polymerization reaction in a reaction system is 35 mass% or more. If it is less than 35% by mass, the productivity of the resulting polymer may not be significantly improved. More preferably, it is 40-70 mass%, More preferably, it is 45-65 mass%. Thus, if the solid content concentration at the end of the polymerization reaction is 35% by mass or more, the polymerization can be carried out at a high concentration and in one stage. Therefore, a polymer can be obtained efficiently. For example, the concentration step can be omitted, the productivity of the polymer is greatly improved, and an increase in manufacturing cost can be suppressed. The time point at which the polymerization reaction is completed represents the time point at which the addition of all the added components is completed. However, even when a predetermined aging time thereafter (when the polymerization is completed), The solid content concentration is preferably in the above-described range.
The solid content concentration can be calculated by obtaining the non-volatile content after processing for 1 hour with a 130 ° C. hot air dryer.
The aging time is preferably 1 to 120 minutes, more preferably 5 to 60 minutes, and still more preferably 10 to 30 minutes. When the aging time is less than 1 minute, the monomer component may remain because of insufficient aging, and there is a possibility that performance may be deteriorated due to impurities derived from the remaining monomer. If the aging time exceeds 120 minutes, the polymer solution may be colored.
In the above production method, the polymerization time is not particularly limited, but is preferably 30 to 420 minutes, more preferably 45 to 390 minutes, still more preferably 60 to 360 minutes, and most preferably 90 to 300 minutes. It is. In the present invention, “polymerization time” represents the time during which a monomer is added, that is, the time from the start of addition of the monomer to the end unless otherwise specified.
The polyalkylene glycol polymer of the present invention that can be produced by the above production method can exhibit high performance in aqueous applications, and is resistant to gelation and calcium ion scavenging, detergency, recontamination prevention, clay (Cray) ) Since the dispersibility, interaction with the surfactant, etc. are high, particularly excellent performance can be exhibited when used in a dispersant, a detergent builder, a detergent composition, a cleaning agent, or a water treatment agent.
[Use of polyalkylene glycol polymer and polyalkylene glycol polymer composition of the present invention]
The polyalkylene glycol polymer (or polyalkylene glycol polymer composition) of the present invention comprises a coagulant, a flocculant, a printing ink, an adhesive, a soil conditioner (modifier), a flame retardant, a skin care agent, and a hair care agent. , Shampoos, hair sprays, soaps, cosmetic additives, anion exchange resins, dye mordants and auxiliaries for fibers and photographic films, pigment spreaders in papermaking, paper strength enhancers, emulsifiers, preservatives, textiles and paper As softener, lubricant additive, water treatment agent, fiber treatment agent, dispersant, detergent additive, scale inhibitor (scale inhibitor), metal ion sealant, thickener, various binders, emulsifier, etc. Can be used. As a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, dwelling, hair, body, toothpaste, and automobile.
<Water treatment agent>
The polyalkylene glycol polymer (or polyalkylene glycol polymer composition) of the present invention can be used as a water treatment agent. For the water treatment agent, polymerized phosphates, phosphonates, anticorrosives, slime control agents, and chelating agents may be used as other compounding agents as necessary.
The water treatment agent 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 concentration tank, and the like. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effects.
<Fiber treatment agent>
The polyalkylene glycol polymer (or polyalkylene glycol polymer composition) of the present invention can also be used as a fiber treatment agent. The fiber treatment agent contains at least one selected from the group consisting of a dye, a peroxide and a surfactant, and the polyalkylene glycol polymer (or polyalkylene glycol polymer composition) of the present invention.
The content of the polyalkylene glycol polymer of the present invention in the fiber treatment agent is preferably 1 to 100% by weight, more preferably 5 to 100% by weight, based on the entire fiber treatment agent. Further, any appropriate water-soluble polymer may be included as long as the performance and effects are not affected.
Below, the compounding example of a fiber processing agent is shown. This fiber treatment agent can be used in the steps of refining, dyeing, bleaching and soaping in fiber treatment. Examples of dyeing agents, peroxides, and surfactants include those usually used for fiber treatment agents.
The blending ratio of the polyalkylene glycol polymer of the present invention to at least one selected from the group consisting of a dye, a peroxide, and a surfactant is, for example, the whiteness of the fiber, uneven color, and dyeing tempering degree. For the improvement, at least one selected from the group consisting of a dye, a peroxide and a surfactant is 0.1 to 0.1 part by weight of the polymer of the present invention in terms of a pure amount of the fiber treatment agent. It is preferable to use a composition blended at a ratio of 100 parts by weight as a fiber treatment agent.
Arbitrary appropriate fibers can be adopted as a fiber which can use the above-mentioned textile treating agent. Examples thereof include cellulosic fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven fabrics and blended products thereof.
When the fiber treatment agent is applied to the refining process, it is preferable to blend the polymer of the present invention with an alkali agent and a surfactant. When applied to the bleaching step, it is preferable to blend the polymer of the present invention, a peroxide, and a silicic acid-based agent such as sodium silicate as a decomposition inhibitor for the alkaline bleaching agent.
<Inorganic pigment dispersant>
The polyalkylene glycol polymer (or polyalkylene glycol polymer composition) of the present invention can also be used as an inorganic pigment dispersant. In the inorganic pigment dispersant, condensed phosphoric acid and a salt thereof, phosphonic acid and a salt thereof, and polyvinyl alcohol may be used as other compounding agents as necessary.
The content of the polyalkylene glycol polymer of the present invention in the inorganic pigment dispersant is preferably 5 to 100% by weight with respect to the whole inorganic pigment dispersant. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance and effect.
The inorganic pigment dispersant can exhibit good performance as a dispersant for heavy or light calcium carbonate or clay inorganic pigment used in paper coating. For example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, high concentration calcium carbonate having low viscosity and high fluidity and good aging stability of their performance. High concentration inorganic pigment slurries such as slurries can be produced.
When the inorganic pigment dispersant is used as a dispersant for an inorganic pigment, the amount of the inorganic pigment dispersant used is preferably 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the inorganic pigment. When the amount of the inorganic pigment dispersant used is within the above range, a sufficient dispersion effect can be obtained, and an effect commensurate with the addition amount can be obtained, which can be economically advantageous.
<Detergent Builder>
The polyalkylene glycol-based polymer (or polyalkylene glycol-based polymer composition) of the present invention can also be used as a detergent builder. As a detergent builder, it can be used by adding to detergents for various uses such as clothing, tableware, residential, hair, body, toothpaste, and automobile.
<Detergent composition>
The polyalkylene glycol polymer (or polyalkylene glycol polymer composition) of the present invention can also be added to a detergent composition.
The content of the polyalkylene glycol polymer in the detergent composition is not particularly limited. However, from the viewpoint of exhibiting excellent builder performance, the content of the polyalkylene glycol polymer is preferably 0.1 to 15% by mass with respect to 100% by mass of the total amount of the detergent composition, More preferably, it is 0.3-10 mass%, More preferably, it is 0.5-5 mass%.
Detergent compositions used in detergent applications usually include surfactants and additives used in detergents. Specific forms of these surfactants and additives are not particularly limited, and knowledge generally known in the detergent field can be appropriately referred to. The detergent composition may be a powder detergent composition or a liquid detergent composition.
The surfactant is one or more selected from the group consisting of an anionic surfactant, a nonionic surfactant, a cationic surfactant and an amphoteric surfactant. When two or more kinds are used in combination, the total amount of the anionic surfactant and the nonionic surfactant is preferably 50% by mass or more, more preferably 100% by mass based on the total amount of the surfactant. It is 60 mass% or more, More preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more.
Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or its ester salt, alkane sulfonate Salt, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or salt thereof, alkenyl phosphate ester Or its salt etc. are suitable. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these anionic surfactants.
Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanolamides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters. Esters, alkylamine oxides and the like are preferred. An alkyl group such as a methyl group may be branched from the alkyl group or alkenyl group in these nonionic surfactants.
As the cationic surfactant, a quaternary ammonium salt or the like is suitable. As the amphoteric surfactant, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, and the like are suitable. The alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may be branched from an alkyl group such as a methyl group.
The blending ratio of the surfactant is usually 10 to 60% by mass, preferably 15 to 50% by mass, and more preferably 20 to 45% by mass with respect to 100% by mass of the total amount of the detergent composition. Especially preferably, it is 25-40 mass%. If the blending ratio of the surfactant is too small, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too large, the economy may be lowered.
Additives include anti-redeposition agent to prevent redeposition of contaminants such as alkali builder, chelate builder, sodium carboxymethyl cellulose, stain inhibitor such as benzotriazole and ethylene-thiourea, soil release agent, color transfer Inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, dyes A solvent or the like is preferable. In the case of a powder detergent composition, it is preferable to blend zeolite.
In addition to the polyalkylene glycol polymer (or polyalkylene glycol polymer composition) of the present invention, the detergent composition may contain other detergent builders. Other detergent builders are not particularly limited, but include, for example, alkali builders such as carbonates, bicarbonates, silicates, tripolyphosphates, pyrophosphates, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, citric acid. Examples thereof include acid salts, (meth) acrylic acid copolymer salts, acrylic acid-maleic acid copolymers, chelate builders such as fumarate and zeolite, and carboxyl derivatives of polysaccharides such as carboxymethylcellulose. Examples of the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium and amine.
The total blending ratio of the additive and other detergent builder is preferably 0.1 to 50% by mass with respect to 100% by mass of the cleaning composition. More preferably, it is 0.2-40 mass%, More preferably, it is 0.3-35 mass%, Most preferably, it is 0.4-30 mass%, Most preferably, it is 0.5-20 mass% or less. It is. If the total blending ratio of additives and other detergent builders is less than 0.1% by mass, sufficient detergent performance may not be exhibited, and if it exceeds 50% by mass, the economy may be reduced.
In addition, the concept of the above-mentioned detergent composition includes specific detergents such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of the components. Detergents that are only used are also included.
When the said detergent composition is a liquid detergent composition, it is preferable that the moisture content contained in a liquid detergent composition is 0.1-75 mass% with respect to the whole quantity of a liquid detergent composition, More preferably, it is 0. .2 to 70% by mass, more preferably 0.5 to 65% by mass, even more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, and most preferably It is 1.5-50 mass%.
When the detergent composition is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg / L or less, more preferably 150 mg / L or less, and even more preferably 120 mg / L or less. Especially preferably, it is 100 mg / L or less, Most preferably, it is 50 mg / L or less.
<Measurement method of kaolin turbidity>
A sample (liquid detergent) uniformly stirred in a 50 mm square cell having a thickness of 10 mm was removed and air bubbles were removed. Then, a NDU2000 manufactured by Nippon Denshoku Co., Ltd. Kaolin turbidity: mg / L) is measured.
Proteases, lipases, cellulases, and the like are suitable as enzymes that can be incorporated into the cleaning composition. Of these, proteases, alkaline lipases, and alkaline cellulases that are highly active in an alkaline cleaning solution are preferred.
The amount of the enzyme added is preferably 5% by mass or less with respect to 100% by mass of the cleaning composition. If it exceeds 5% by mass, improvement in detergency cannot be seen, and the economy may be reduced.
As the alkali builder, silicate, carbonate, sulfate and the like are preferable. As the chelate builder, diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), STPP (sodium tripolyphosphate), citric acid and the like are preferable. Other water-soluble polycarboxylic acid-based polymers other than the polymer of the present invention may be used.
The above detergent composition should be a detergent with excellent dispersibility, extremely high quality agent performance and excellent stability that is less likely to cause performance degradation when stored for a long time and precipitation of impurities when held at low temperatures. Can do.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by weight” and “%” means “mass%”.
The quantification of monomers and reaction intermediates and the measurement of various physical properties were performed by the following methods.
<Measurement conditions of weight average molecular weight and number average molecular weight (GPC)>
Device: HLC-8320GPC manufactured by Tosoh Corporation
Detector: RI
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko
Column temperature: 40 ° C
Flow rate: 0.5 ml / min
Calibration curve: Sowa Kagaku Co., Ltd. Polyacrylic acid standard eluent: 0.1N sodium acetate aqueous solution.
<Measurement of solid content>
In an oven heated to 130 ° C. in a nitrogen atmosphere, 1.0 g of water added to 1.0 g of the polyalkylene glycol polymer composition containing the polyalkylene glycol polymer of the present invention was left to stand for 1 hour to dry. Processed. From the mass change before and after drying, the solid content (%) and the volatile component (%) were calculated.
<Synthesis example of polyalkylene glycol monomer (A)>
In the following monomer synthesis examples, the following compound was used as the polyalkylene glycol chain-containing monomer represented by the general formula (5).
Isoprenol ethylene oxide average 10 mol adduct (hereinafter also referred to as “IPN10”): hydroxyl value 106.5 (mgKOH / g)
[Synthesis Example 1]
In a 1 liter four-necked flask equipped with a stirring blade, a thermometer, and a condenser tube, 400 g of IPN10, 351.7 g of epichlorohydrin, and 94.9 g of 48% aqueous sodium hydroxide (hereinafter also referred to as “48% NaOH”). The mixture was stirred and allowed to react for 6 hours while maintaining at 50 ° C. After the reaction, the generated salt is removed, and then the epichlorohydrin and water are removed from the remaining organic layer to contain an intermediate (A) (a compound having a structure where n is an average of 10 in the following general formula (6)). 451.2g of reaction liquid was obtained. As a result of analysis by liquid chromatography, 324.9 g of intermediate (A) and 64.1 g of IPN10 were contained.
Next, while introducing nitrogen into a 1 L SUS separable flask equipped with a stirrer, thermometer, nitrogen inlet tube and cooling trap at the nitrogen outlet, pure water 129.5 g, 48% NaOH 6.0 g, 40 50.0 g of% sodium bisulfite (hereinafter also referred to as “40% SBS”) was charged, and the temperature was raised to 63 ° C. while stirring to prepare a reaction system. Next, 140.0 g of the reaction solution containing the intermediate (A) was continuously added dropwise at a constant rate over 120 minutes to the reaction system maintained at 63 ° C. with stirring. Thus, 325.5 g of a solution of the monomer (1) (a compound having a structure where n is an average of 10 in the following general formula (7)) was obtained. As a result of analysis by ¹ H-NMR as shown in FIG. 1, formation of the monomer (1) was confirmed.

[Example 1]
In a 1 L SUS separable flask equipped with a reflux condenser and a stirrer (paddle blade), 25.0 g of pure water, 45.1 g of maleic anhydride (hereinafter also referred to as “MA”), 48% NaOH 60. 5 g was charged and the temperature was raised to the boiling point while stirring to obtain a polymerization reaction system. Next, 222.3 g of the monomer (1) solution, 80% aqueous acrylic acid solution (hereinafter also referred to as “80% AA”) in a polymerization reaction system maintained at the boiling point reflux state with stirring. 4 g, 15% sodium persulfate (hereinafter also referred to as “15% NaPS”) 16.3 g, 35% hydrogen peroxide solution (hereinafter also referred to as “35% H ₂ O ₂ ”) 2.9 g, respectively. It was dripped from the nozzle. Each solution started dripping simultaneously. The dropping time of each solution was 120 minutes for the monomer (1) solution, 80% AA and 15% NaPS, and 75 minutes for 35% H ₂ O ₂ . Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of the 80% AA solution, the polymerization reaction solution was maintained (ripened) at the boiling point reflux for 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool, and 8.1 g of 48% NaOH was gradually added dropwise to the polymerization reaction solution while stirring to neutralize. In this way, an aqueous solution of the polymer (1) was obtained.
The weight average molecular weight of the polymer (1) was 48,000.

[Example 2]
In a 1 L SUS separable flask equipped with a reflux condenser and a stirrer (paddle blade), 25.0 g of pure water, 45.1 g of MA, 222.3 g of monomer (1) solution, 48% NaOH 60. 5 g was charged and the temperature was raised to the boiling point while stirring to obtain a polymerization reaction system. Next, 41.4 g of 80% AA, 16.3 g of 15% NaPS, and 2.9 g of 35% H ₂ O ₂ were dropped from separate nozzles into the polymerization reaction system maintained at the boiling point reflux state with stirring. . Each solution started dripping simultaneously. The dropping time of each solution was 120 minutes for 80% AA and 15% NaPS and 75 minutes for 35% H ₂ O ₂ . Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of the 80% AA solution, the polymerization reaction solution was maintained (ripened) at the boiling point reflux for 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool, and 8.1 g of 48% NaOH was gradually added dropwise to the polymerization reaction solution while stirring to neutralize. In this way, an aqueous polymer (2) solution was obtained.

[Example 3]
102.5 g of pure water was charged into a 2.5 L SUS separable flask equipped with a reflux condenser and a stirrer (paddle blade), and the temperature was raised to 90 ° C. while stirring to obtain a polymerization reaction system. Next, 653.7 g of the monomer (1) solution, 513.0 g of 80% AA, 23.8 g of 48% NaOH, and 160.0 g of 15% NaPS were placed in the polymerization reaction system maintained at 90 ° C. with stirring. 40% SBS 60.0 g was dropped from separate nozzles. The dropping time of each solution was 180 minutes for the monomer (1) solution, 80% AA and 48% NaOH, 210 minutes for 15% NaPS, and 170 minutes for 40% SBS. Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of 15% NaPS, the polymerization reaction solution was kept (ripened) at 90 ° C. for 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool, and 427.5 g of 48% NaOH was gradually added dropwise to the polymerization reaction solution while stirring to neutralize. In this way, an aqueous polymer (3) solution was obtained.

[Comparative Example 1]
A 1 L SUS separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 25.0 g of pure water, 45.1 g of MA, and 60.5 g of 48% NaOH, and heated to the boiling point while stirring. Thus, a polymerization reaction system was obtained. Next, an unsaturated polyalkylene glycol (hereinafter referred to as “30”) obtained by adding 10 mol of ethylene oxide to 30% 3-methyl-2-buten-1-ol in a polymerization reaction system maintained at a boiling point reflux state with stirring. % IPN10 ") 222.3 g, 80% AA 41.4 g, 15% NaPS" 16.3 g and 35% H2O2 2.9 g were added dropwise from separate nozzles. Each solution started dripping simultaneously. The dropping time of each solution was 120 minutes for 30% IPN10, 80% AA and 15% NaPS, and 75 minutes for 35% H ₂ O ₂ . Moreover, the dropping rate of each solution was made constant, and each solution was dropped continuously. After completion of the dropwise addition of the 80% AA solution, the polymerization reaction solution was maintained (ripened) at the boiling point reflux for 30 minutes to complete the polymerization. After completion of the polymerization, the polymerization reaction solution was stirred and allowed to cool, and 8.1 g of 48% NaOH was gradually added dropwise to the polymerization reaction solution while stirring to neutralize. In this way, an aqueous solution of the comparative polymer (1) was obtained.

[Evaluation example]
About the polymer (1) and comparative polymer (1) obtained in Example 1 and Comparative Example 1, the calcium ion scavenging ability and the gelation resistance were evaluated as follows. The results are shown in Table 1.

<Method for evaluating calcium ion scavenging ability>
As a calcium ion standard solution for a calibration curve, 50 g of 0.01 mol / L, 0.001 mol / L, 0.0001 mol / L aqueous solutions were prepared using calcium chloride dihydrate, and 1.0% NaOH aqueous solution was used. Adjust to pH 9.9 to 10.2, add 1 ml of 4 mol / L potassium chloride aqueous solution (hereinafter abbreviated as 4M-KCl aqueous solution), and further stir well using a magnetic stirrer. A sample solution was prepared. In addition, as a test calcium ion standard solution, a necessary amount (50 g per sample) of a 0.001 mol / L aqueous solution was similarly prepared using calcium chloride dihydrate.
Next, 10 mg of the test sample (polymer) in a 100 cc beaker was weighed in terms of solid content, added with 50 g of the above-mentioned calcium ion standard solution for test, and sufficiently stirred using a magnetic stirrer. The polymer used as a test sample was neutralized with a 48% aqueous sodium hydroxide solution (hereinafter also referred to as “48% NaOH”) so that the pH was 7.5 when the solid content was 40% by weight. Was used. Next, as with the calibration curve sample, the pH was adjusted to 9.9 to 10.2 with a 1.0% aqueous sodium hydroxide solution, and 1 ml of 4M-KCl aqueous solution was added to prepare a test sample solution. .
The calibration curve sample solution and the test sample solution thus prepared were measured with the Orion 9720BNWP Sure-Flow calcium composite electrode manufactured by Thermo Fisher Scientific Co., Ltd. using a titration device COM-1700 manufactured by Hiranuma Sangyo Co., Ltd. went.

<Evaluation method of gelation resistance>
To a 500 ml tall beaker, add deionized water, boric acid-sodium borate pH buffer, 1% aqueous solution of copolymer, calcium chloride solution in this order, pH 8.5, copolymer 100 mg solids / L, calcium hardness 500 mg CaCo 3 / L 500 ml of the test solution was prepared. The tall beaker was sealed with a polyethylene film and left in a constant temperature water bath at 90 ° C. for 1 hour. Then, the turbidity of the test solution caused by the gel formed by combining the copolymer and calcium ions is detected by measuring the absorbance with a quartz cell having a UV wavelength of 380 nm and 50 mm, and the gelation resistance is obtained based on the obtained absorbance value. Noh was evaluated. It shows that gel-proof ability is excellent, so that a value is small.

From the results of Examples and Comparative Examples, it was revealed that the polymer of the present invention has good gel resistance and calcium capturing ability.

Claims (2)

(I) a structural unit (a) derived from the polyalkylene glycol monomer (A) and (ii) a structural unit (b) derived from the carboxyl group-containing monomer (B) An alkylene glycol polymer, wherein the polyalkylene glycol monomer (A) is represented by the following general formula (1);

(In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a methylene group, an ethylene group or a direct bond. Z is the same or different and represents an oxyalkylene group having 2 to 20 carbon atoms. N is the average number of moles added of the oxyalkylene group and represents a number of 1 to 300. X and Y are a hydroxyl group, a structure represented by the following general formula (2), and a general formula (3) below. A structure represented by the following formula: (wherein either one of X and Y represents a hydroxyl group, and the other is a structure represented by the following general formula (2) or a general formula (3) below) Represents the structure).

(In the general formula (2), R ₃ represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms. The general formula (2), In (3), M represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine salt (organic ammonium group)).
The polyalkylene glycol polymer has a structure represented by the formula (1) with respect to 100 mass% of the total amount of structural units derived from all monomers forming the polymer: A polyalkylene glycol polymer containing 99% by mass and containing 1 to 99% by mass of the structural unit (b). (I) A method for producing a polyalkylene glycol polymer comprising a step of polymerizing a polyalkylene glycol monomer (A) and (ii) a carboxyl group-containing monomer (B), the production method Is the following general formula (1) with respect to 100% by mass of the total amount of all monomers used:

(In the formula, R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a methylene group, an ethylene group or a direct bond. Z is the same or different and represents an oxyalkylene group having 2 to 20 carbon atoms. N is the average number of moles added of the oxyalkylene group and represents a number of 1 to 300. X and Y are a hydroxyl group, a structure represented by the following general formula (2), and a general formula (3) below. A structure represented by the following formula: (wherein either one of X and Y represents a hydroxyl group, and the other is a structure represented by the following general formula (2) or a general formula (3) below) Represents the structure).

(In the general formula (2), R ₃ represents a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms or a substituted or unsubstituted arylene group having 6 to 10 carbon atoms. The general formula (2), In (3), M represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine salt (organic ammonium group)).
1 to 99% by mass of the polyalkylene glycol monomer (A) represented by the formula (1) and 1 to 99% by mass of the carboxyl group-containing monomer (B). Production method.

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