JP2012057089A - Polymer having ether bond and its manufacturing method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer having an ether bond, which can exhibit excellent ability to prevent resoiling during washing while having excellent compatibility with a surfactant, and also to provide its manufacturing method.SOLUTION: The polymer having an ether bond contains, as necessary components, followings having specific structures: (i) a structural unit having a specific structure, originated from a monomer having an ether bond; and (ii) a structural unit originated from a nonionic monomer and/or a monomer containing a cationic group.

Description

The present invention relates to an ether bond-containing polymer and a method for producing the same. More specifically, the present invention relates to an ether bond-containing polymer useful as a raw material for detergent additives and the like, and a method for producing the same.

Conventionally, polymers have been used in various industrial fields such as inorganic pigment dispersants, dispersants for coal, detergent compositions, water treatment agents, etc., for example, detergent effects for clothing, cleaning effects In order to improve the above, it has been practiced to blend detergent aids such as carboxymethyl cellulose, polyethylene glycol, polyvinyl pyrrolidone, sodium polyallylate and the like.
For example, Patent Document 1 discloses a detergent composition containing a low polymer having a repeating unit and a terminal group represented by the following general formulas [1] to [3]. It is disclosed that by using the low polymer, high cleaning performance can be maintained even when hard water is used as the cleaning water.

(R ¹ in the formulas [1] and [2] represents a hydrogen atom or a methyl group, R ² in the formula [1] represents an alkyl group having 6 to 20 carbon atoms, and R 1 in the formula [3] ³ represents a hydrogen atom or a residue of a compound having one or more groups selected from the group of amino group, hydroxyl group, thiol group and carboxyl group, and M in the formula [2] is an alkali metal Is shown.)

JP 2002-275500 A

As described above, for example, polymers having various structures have been studied as a polymer to be added to a detergent composition or the like.
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, it becomes a problem that the dirt component contained in the remaining hot water of the bath adheres to the fibers during washing, or the hard water component is concentrated due to the chasing of the bath, so even under higher hardness, The ability to suppress the reattachment of dirt components to the fiber during washing (referred to as “recontamination prevention ability”) has been demanded more severely than before. 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 polymer can sufficiently satisfy the recent severe requirements regarding the performance of the above-mentioned applications, and exhibits higher performance corresponding to such new needs. There was room for further improvement of the polymer that can be suitably used as a detergent additive.
The present invention has been made in view of the above-described present situation, can exhibit an excellent anti-recontamination ability at the time of washing, and has an ether bond-containing polymer excellent in compatibility with a surfactant, and a method for producing the same The purpose is to provide.

The present inventor has studied a polymer that can be suitably used for detergent additives and the like, and has a structural unit derived from an ether bond-containing monomer having a specific structure, a nonionic monomer and / or a cationic property. An ether bond-containing polymer having a structural unit derived from a group-containing monomer can exhibit a very good ability to prevent recontamination even under high hardness and has high compatibility with a surfactant. I found. 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 relates to (i) a structural unit (a) derived from an ether bond-containing monomer (A), (ii) a nonionic monomer (B-1) and / or a cationic group-containing monomer. An ether bond-containing polymer essentially comprising the structural unit (b) derived from (B-2), wherein the ether bond-containing 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. X and Y are a hydroxyl group, a structure represented by the following general formula (2), The structure represented by the following general formula (3) and the structure represented by the following general formula (3 ′) are represented (however, one of X and Y represents a hydroxyl group, and the other represents the following general formula (2) And a structure represented by the following general formula (3) or a structure represented by the following general formula (3).

(In the above general formulas (2) and (3 ′), 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 12 carbon atoms. In the formulas (2), (3), and (3 ′), M represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine salt (organic ammonium group). The bond-containing polymer contains 1 to 99% by mass of the structural unit (a) and 1% of the structural unit (b) with respect to 100% by mass of the total amount of structural units derived from all monomers forming the polymer. It is an ether bond containing polymer characterized by containing -99 mass%.
The present invention also polymerizes (i) an ether bond-containing monomer (A) and (ii) a nonionic monomer (B-1) and / or a cationic group-containing monomer (B-2). A method for producing an ether bond-containing polymer comprising the step of: wherein the production method comprises the following general formula (1) with respect to 100% by mass of the total amount of all monomers used:

（式中、Ｒ_１は、水素原子又はメチル基を表す。Ｒ_２は、メチレン基、エチレン基又は直接結合を表す。Ｘ、Ｙは、水酸基、下記一般式（２）で表される構造、下記一般式（３）で表される構造、下記一般式（３’）で表される構造を表す（但しＸ、Ｙのいずれか一方は水酸基を表し、残りの一方は下記一般式（２）で表される構造、下記一般式（３）で表される構造、または下記一般式（３’）で表される構造を表す）。

(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. X and Y are a hydroxyl group, a structure represented by the following general formula (2), The structure represented by the following general formula (3) and the structure represented by the following general formula (3 ′) are represented (however, one of X and Y represents a hydroxyl group, and the other represents the following general formula (2) A structure represented by the following general formula (3), or a structure represented by the following general formula (3 ′)).

(In the above general formulas (2) and (3 ′), 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 12 carbon atoms. In formulas (2), (3), and (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 A) and 1 to 99% by mass of nonionic monomer (B-1) and / or cationic group-containing monomer (B-2) It is also a method for producing a polymer.

The ether bond-containing polymer of the present invention can exhibit, for example, an excellent ability to prevent recontamination at the time of washing, and is excellent in compatibility with a surfactant, so that it can be blended into a highly concentrated liquid detergent. It can be suitably used as a raw material for detergent additives and the like.

Below obtained in Synthesis Example 1 monomer (1) (monomer hydroxyl group of sodium glycolate to glycidyl groups of the allyl glycidyl ether was added structure) after the drying is a chart obtained by measuring ¹ HNMR.

The present invention is described in detail below.
[Ether bond-containing polymer of the present invention]
<Ether bond-containing monomer (A)>
The ether bond-containing 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 ether bond-containing monomer (A). The containing 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. X and Y are a hydroxyl group, a structure represented by the following general formula (2), The structure represented by the following general formula (3) and the structure represented by the following general formula (3 ′) are represented (however, one of X and Y represents a hydroxyl group, and the other represents the following general formula (2) A structure represented by the following general formula (3), or a structure represented by the following general formula (3 ′)).

(In the above general formulas (2) and (3 ′), 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 12 carbon atoms. In the formulas (2), (3), and (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 ether bond-containing monomer (A) has such a structure, the ether bond-containing polymer of the present invention has a carboxyl group (salt) and / or a sulfonic acid group near the end of the side chain having an ether bond. (Salt) contributes to the stabilization of dispersion of inorganic particles and dirt components. Therefore, when used for detergent applications, a good ability to prevent recontamination is exhibited.
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 ether bond-containing polymer of the present invention is blended in a liquid detergent or the like, the compatibility with the surfactant is increased due to the ether structure and the like. (Stability) can be made excellent.
In the present invention, the ether bond-containing polymer means a polymer having an ether bond in the side chain, and the ether bond-containing monomer means a monomer having an ether bond in the molecule.
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 soil components, recontamination prevention ability, and the like.
Further, for example, the general formula (1) in R ₂ is a methylene group, a monomer having an ethylene group or a structure other than a direct bond, a single of R ₂ in the general formula (1) has a structure which is a carbonyl group When a monomer (that is, a monomer having an ester group) is used, an ester bond is subject to hydrolysis during monomer synthesis, polymerization, or under each application. Generally, ether bond-containing 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 is increased, resulting in large variations in the performance of the resulting polymer. . In contrast, the ether bond-containing 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 at the time of synthesis, polymerization, or under each application, for example, even under severe conditions during manufacture of a detergent. Further, in the ether bond-containing 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 the case, since it has good copolymerizability, it is possible to suppress variation in the amount of residual monomer during polymerization, and as a result, it is possible to suppress variation in 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.
Note that X represents a direct bond, for example, in a structure represented by CH ₂ ═CH—X—O—, a structure represented by CH ₂ ═CH—O—.
X and Y in the general formula (1) are a hydroxyl group, a structure represented by the following general formula (2), a structure represented by the following general formula (3), and a structure represented by the following general formula (3 ′). Represents. However, one of X and Y represents a hydroxyl group, and one of X and Y has the structure represented by the following general formula (2), the following general formula (3) structure, or the following general formula (3 ′). Represents the structure represented. By having the said structure, the dispersibility of the inorganic particle of the ether bond containing polymer of this invention, a stain | pollution | contamination component, etc. improves notably.

In the above general formulas (2) and (3 ′), 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 12 carbon atoms. The alkylene group may be an unsubstituted group, or a group in which one or two or more hydrogen atoms are substituted with another organic group with a carbon number in the above 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 the _{R 3,} and more preferably has 1 to 8 carbon atoms, particularly preferably from 1 to 4. When R ₃ is such, it becomes possible to produce the ether bond-containing monomer (A) with a high yield, so that the polymerizability of the monomer and the purity of the resulting polymer are improved. . In addition, the dispersibility of the polymer obtained and the ability to prevent recontamination are also 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, or a part of these hydrogen atoms being an alkoxy group, a carboxyester group, an amino group, Examples thereof include a group substituted with 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 point that it is possible to simplify the production process of the ether bond-containing monomer (A) and to design with less impurities. Is particularly preferred.

In the general formulas (2), (3), 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, it is preferable to use monovalent metal atoms such as sodium and potassium, ammonium salts, and organic amine salts from the viewpoint of improving the dispersibility and the ability to prevent recontamination of the ether bond-containing polymer of the present invention. Is particularly preferred.
The ether bond-containing polymer of the present invention has a structural unit (a) derived from the ether bond-containing monomer (A). The structural unit (a) is a structure in which the carbon-carbon double bond of the ether bond-containing monomer (A) is a single bond, and the following general formula (4);

_(Wherein, R _{1, R} 2, X, and Y, in Formula _{(1), R 1, R} 2, X, and is the same as Y.) Can be represented by.
The ether bond-containing polymer of the present invention has “the structural unit (a) derived from the ether bond-containing monomer (A)” means that the finally obtained polymer has the general formula (4). It means having a structural unit represented by. That is, in the “structural unit (a) derived from the ether bond-containing monomer (A)” in the present invention, after synthesizing the ether bond-containing monomer (A), it is used as another monomer component. For example, the main chain portion of the ether bond-containing polymer is first formed by copolymerization, and then a side chain having a specific structure is introduced. In some cases, the forming process extends before and after the polymerization reaction.
Moreover, the structural unit (a) possessed by the ether bond-containing polymer of the present invention may be only one type or two or more types.
The ether bond-containing polymer of the present invention is a total amount of structural units derived from all monomers forming the ether bond-containing polymer (structural unit (a), total amount of structural units (b) and (e) described later). The structural unit (a) is contained in an amount of 1 to 99% by mass with respect to 100% by mass. If 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, the dirt component particles can be dispersed and the ability to prevent recontamination can be exhibited. It becomes. 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.

<Method for producing ether bond-containing monomer (A)>
It does not restrict | limit especially as a preparation method of the said ether bond containing monomer (A), It can prepare by arbitrary appropriate methods. As such a preparation method, since the said ether bond containing monomer (A) can be manufactured with a high yield, it is preferable to manufacture with the following manufacturing method (1)-(3).
Production method (1) comprises (i) a glycidyl ether group-containing monomer represented by the following general formula (5), (ii) one or more carboxylic acid groups (salts), and one or more hydroxyl groups. A compound containing hydrogensulfite or water to generate a bisulfite, a compound containing one or more sulfonic acid groups (salts) and one or more hydroxyl groups (hereinafter referred to as compounds ( (also referred to as α)), and a production method including a step (step 1).
In the present invention, the compound containing 1 or 2 or more carboxylic acid groups (salts) and 1 or 2 or more hydroxyl groups is one or more groups that hydrolyze to generate carboxyl groups (salts). A compound containing one or two or more hydroxyl groups may be used. The group that undergoes hydrolysis to generate a carboxyl group (salt) is a carboxylic acid ester group or a carboxylic acid amide group. In this case, the hydrolysis reaction can be performed during the synthesis of the ether bond-containing monomer (A), after the synthesis, during the polymerization, or after the polymerization.

In general formula (5), R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a methylene group, an ethylene group or a direct bond.
_R 1, _{R 2} in the general formula (5), of the preferred embodiment, _R 1, _{R 2} in the general formula (1) are the same as.

  Examples of the compound containing 1 or 2 or more carboxylic acid groups (salts) and 1 or 2 or more hydroxyl groups include compounds represented by the following general formula (6).

In the general formula (6), 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 12 carbon atoms, and M represents a hydrogen atom or a metal atom. Represents an ammonium salt or a quaternary amine salt.

  Examples of the compound containing 1 or 2 or more carboxylic acid groups (salts) and 1 or 2 or more hydroxyl groups include glycolic acid, lactic acid, tartronic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, γ-Hydroxybutyric acid, malic acid, tartaric acid, citramalic acid, citric acid, isocitric acid, leucine acid, mevalonic acid, pantoic acid, ricinoleic acid, ricinaleic acid, sebronic acid, quinic acid, shikimic acid, salicylic acid, creosote acid, vanillic acid , Syringic acid, mandelic acid, benzylic acid, atrolactic acid, and salts thereof, and compounds in which these carboxyl groups are ester groups or amide groups, preferably glycolic acid, hydroxybutyric acid, and salts thereof It is. In addition, as a salt, although it is a metal salt, ammonium salt, and organic amine salt (organic ammonium salt), alkali metal salts, such as sodium, are preferable.

  Examples of the compound capable of generating bisulfite by reacting with bisulfite or water include sodium bisulfite, potassium bisulfite, ammonium bisulfite, sodium disulfite, potassium disulfite and the like. Of these, bisulfite is preferable.

  Examples of the compound containing 1 or 2 or more sulfonic acid groups (salts) and 1 or 2 or more hydroxyl groups include compounds represented by the following general formula (6 ').

上記一般式（６）において、Ｒ_３は、炭素数１〜１０の置換または無置換のアルキレン基、または炭素数６〜１２の置換または無置換のアリーレン基を表し、Mは水素原子、金属原子、アンモニウム塩、４級アミン塩を表す。

In the general formula (6), 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 12 carbon atoms, and M represents a hydrogen atom or a metal atom. Represents an ammonium salt or a quaternary amine salt.

  Examples of the compound containing 1 or 2 or more sulfonic acid groups (salts) and 1 or 2 or more hydroxyl groups include hydroxymethanesulfonic acid and hydroxyethanesulfonic acid.

  Examples of the glycidyl ether group-containing monomer represented by the general formula (5) include vinyl glycidyl ether, (meth) allyl glycidyl ether, isoprenyl glycidyl ether and the like, which are commercially available or used after purification. can do.

The amount of the compound (α) used in the production method (1) is a molar ratio with respect to the number of moles of the glycidyl group of the glycidyl ether group-containing monomer represented by the general formula (5). ) / (Compound (α)) = 2/1 to 1/2. More preferably, it is 1.5 / 1-1 / 1.5, More preferably, it is 1.3 / 1-1 / 1.3.
The reaction in step 1 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 may also be carried out in the presence of a solvent.

  The glycidyl ether group-containing monomer represented by the general formula (5) includes, for example, a step of reacting a hydroxyl group-containing monomer represented by the following general formula (7), an epihalohydrin, and an alkali compound (step A). You may manufacture by the manufacturing method containing.

（一般式（７）中、Ｒ_１は、水素原子又はＣＨ_３基を表す。Ｒ_２は、ＣＨ_２基、ＣＨ_２ＣＨ_２基を表す。）
上記一般式（７）で表される水酸基含有単量体としては、（メタ）アリルアルコール、イソプレノールを好ましく使用することができる。これにより、得られるエーテル結合含有単量体（Ａ）の純度を高くすることができる。
上記工程（Ａ）において用いられるエピハロヒドリンとしては、下記一般式（８）で表されるものが好ましい。

(In General Formula (7), R ₁ represents a hydrogen atom or a CH ₃ group. R ₂ represents a CH ₂ group or a CH ₂ CH ₂ group.)
As the hydroxyl group-containing monomer represented by the general formula (7), (meth) allyl alcohol and isoprenol can be preferably used. Thereby, the purity of the ether bond containing monomer (A) obtained can be made high.
As an epihalohydrin used in the said process (A), what is represented by following General formula (8) is preferable.

In the formula, 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 reaction of the above 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 said 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 hydroxyl group (hydroxyl value converted) of the hydroxyl group-containing monomer represented by the general formula (7) to the alkali compound (hydroxyl group) / (alkali compound) = 15/1. It is preferable to set it to ~ 1/15. More preferably, it is 5/1-1/5, More preferably, it is 3/1-1/3.
The alkali compound may be added to the reaction system as it is or may be used in the form of an aqueous solution. When used as an aqueous solution, the reaction may be carried out while removing water (including water produced as a by-product as the reaction proceeds).
The type of the phase transfer catalyst is not particularly limited, but quaternary ammonium salts such as tetramethylammonium chloride, tetrabutylammonium chloride, tetraoctylammonium chloride, benzyltrimethylammonium chloride, triethylammonium chloride, triethylammonium bromide; tetrabutylphosphonium chloride And phosphonium salts such as tetrabutylphosphonium bromide; crown ethers such as 15-crown-5 and 18-crown-6.
The amount of epihalohydrin used in the reaction of the above step A is the molar ratio of the hydroxyl group (hydroxyl value converted) of the hydroxyl group-containing monomer represented by the general formula (7) to the epihalohydrin (hydroxyl group) / (epihalohydrin) = 1/1 to 1/30 is preferable. More preferably, it is 1/1 to 1/10, and more preferably 1/1 to 1/5. Outside the above range, a cross-linking component may occur, and there is a risk of 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 can also be carried out in the presence of a solvent.
After step A, purification steps such as distillation, evaporation, and desalting may be provided.

  The production method (2) is a production method including a step (step 4) of reacting the halide represented by the following general formula (9) with the compound (α).

In General Formula (9), R ₁ represents a hydrogen atom or a methyl group. R ₂ represents a methylene group, an ethylene group or a direct bond. X ₂ represents a halogen atom.
_R 1, _{R 2} in the general formula (9), of the preferred embodiment, _R 1, _{R 2} in the general formula (1) are the same as.

  The amount of the compound (α) used in the production method (2) is (halogen atom) / (compound (molar ratio)) with respect to the number of moles of halogen atoms of the halide represented by the general formula (9). α)) = 2/1 to 1/2 is preferable. More preferably, it is 1.5 / 1-1 / 1.5, More preferably, it is 1.3 / 1-1 / 1.3.

  Reaction of the process 4 is performed 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.

  The halide represented by the general formula (9) may be produced, for example, by a production method including a step (step B) of reacting the hydroxyl group-containing monomer represented by the general formula (7) with an epihalohydrin. good.

The reaction in Step B may be an acid or a base as a catalyst, but an acid is preferred. 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 (in terms of hydroxyl value) of the hydroxyl group-containing monomer represented by the general formula (7), and usually (hydroxyl group) / (catalyst) = 1 / 0.0001- 1 / 0.1, preferably 1 / 0.0005 to 1 / 0.05, more preferably 1 / 0.001 to 1 / 0.03. 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 B is usually (hydroxyl group) / (molar ratio) with respect to the hydroxyl group (hydroxyl value converted) of the hydroxyl group-containing monomer represented by the general formula (7). Epihalohydrin) = 1/1 to 1/30, preferably 1/1 to 1/10, more preferably 1/1 to 1/5. If it is out of the range, a crosslinking component may be generated, which may cause gelation during polymerization.

  The production method (3) is a step of reacting the hydroxyl group-containing monomer represented by the general formula (7) and the epoxy compound represented by the following general formulas (10-1) to (10-3) (step) 5) is an essential method.

In the general formulas (10-1) and (10-3), 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 12 carbon atoms. . In the general formulas (10-1) to (10-3), M represents a hydrogen atom, a metal atom, an ammonium salt, or a quaternary amine salt.

The reaction of step 5 is performed in the presence of a catalyst as necessary. Examples of the catalyst used in the reaction include alkali metal salts such as sodium hydroxide, potassium hydroxide, potassium carbonate, sodium carbonate; tetramethylammonium chloride, tetrabutylammonium chloride, tetraoctylammonium chloride, benzyltrimethylammonium chloride, triethylammonium. Examples thereof include quaternary ammonium salts such as chloride and triethylammonium bromide. The amount used is a molar ratio with respect to the hydroxyl group (in terms of hydroxyl value) of the hydroxyl group-containing monomer represented by the general formula (7), and usually (hydroxyl group) / (catalyst) = 1 / 0.0001- 1 / 0.3, preferably 1 / 0.001 to 1 / 0.2, more preferably 1 / 0.005 to 1 / 0.1. 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 5 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 can also be carried out in the presence of a solvent.
As the usage-amount of the epoxy compound represented by said general formula (10-1)-(10-3) used for reaction of the process 5, the hydroxyl group of the hydroxyl-containing monomer represented by the said general formula (7) ( The molar ratio is usually (hydroxyl group) / (epoxy compound represented by the above general formulas (10-1) to (10-3)) = 5/1 to 1/5. , Preferably 3/1 to 1/3, more preferably 1.5 / 1 to 1 / 1.5.
It is preferable to implement reaction in the said process 1-process 5 and process A, B at the temperature which does not produce a problem in stirring. Specifically, the reaction temperature is preferably 0 to 200 ° C. More preferably, it is 15-150 degreeC, More preferably, it is 30-100 degreeC.
The reaction time of the above steps 1 to 5 and steps A and B is preferably 0.1 to 50 hours. More preferably, it is 0.5-30 hours, More preferably, it is 1-15 hours.
The reaction of the above steps 1 to 5, and steps A and B 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.
In each step, the raw material may be used after purification, but when a catalyst is used in the previous step, the reaction may be performed as it is under the remaining catalyst.
Reaction of each process may be performed by a batch type or a continuous type, for example, can be implemented by any apparatus of a tank type and a tube type reactor.
Although the said ether bond containing monomer (A) can be manufactured by said method, you may provide a refinement | purification process as needed. By performing a purification step by extraction or washing, the amount of the crosslinking component that causes gelation during polymerization can be reduced. <Monomer (B)>
The ether bond-containing polymer of the present invention comprises a nonionic monomer (B-1) and / or a cationic group-containing monomer (B-2) (hereinafter referred to as a monomer (B). It is a polymer having the structural unit (b) derived from
The main role of the monomer (B) in the ether bond-containing polymer of the present invention is to arrange the structure derived from the ether bond-containing monomer (A) at a preferred position of the polymer, Since (A) is poor in homopolymerizability, it is a connecting role between the monomers (A) for controlling to an appropriate molecular weight and molecular weight distribution. Therefore, the copolymerizability with the monomer (A) is good, the monomer (B) itself is homopolymerizable, and the structure derived from the monomer (B) ) Is not required to inhibit the effects of the derived structure.

The nonionic monomer (B-1) is a nonionic monomer. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2- (Meth) acrylic acid alkyl ester monomers such as ethylhexyl (meth) acrylate and dodecyl (meth) acrylate; hydroxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2- Such as hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, α-hydroxymethylethyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyneopentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, etc. Meta) Acry Acid hydroxyalkyl monomers; vinyl aryl monomers such as styrene, indene and vinylaniline; alkenes such as isobutylene; vinyl carboxylates such as vinyl acetate; N-vinylpyrrolidone, N-vinylformamide, N-vinyl N-vinyl cyclic amide monomers such as acetamide, N-vinyl-N-methylformamide, N-vinyl-N-methylacetamide, N-vinyloxazolidone; acrylamides such as (meth) acrylamide and (meth) isopropylacrylamide; Monomers obtained by adding 1 to 200 moles of alkylene oxide to hydroxyl group-containing monomers such as (meth) allyl alcohol and isoprenol, and polyalkylene glycol chain-containing monomers such as (meth) acrylic acid esters of alkoxypolyalkylene glycol And the like are exemplified.
Of these, hydroxyethyl (meth) acrylate and methyl acrylate are preferred.

The above cationic group-containing monomer (B-2)
As the cationic group-containing monomer (B-2), a monomer having a polymerizable carbon-carbon unsaturated double bond and a primary to quaternary amino group and / or a salt thereof (monomer (A) For example, vinyl cyclic amine monomers having a cyclic amine structure such as vinyl pyridine, vinyl imidazole, morpholine, vinyl pyrrole; dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate, 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 to Tertiary amines (salts) Monomer obtained by reacting; and monomers having a structure quaternization these amino group.
Examples of the amines include alkylamines such as methylamine, ethylamine, dimethylamine, diethylamine, diisopropylamine, and di-n-butylamine; alkanolamines such as diethanolamine and diisopropanolamine; and cyclic amines such as morpholine and pyrrole. Can be mentioned. 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 is quaternized with a known quaternizing agent. Examples of the quaternizing agent include alkyl halides and dialkyl sulfuric acid.
Specific examples of the tertiary amine salt include trimethylamine hydrochloride and triethylamine hydrochloride. As the salt, the ether bond-containing polymer of the present invention including hydrochloride, organic acid salt and the like is the total amount of structural units derived from all monomers forming the ether bond-containing polymer (structural unit (a), 1 to 99% by mass of the structural unit (b) with respect to 100% by mass of (b) and the total amount of the structural unit (e) described later). If the content of the structural unit (b) is within the above range, the molecular weight of the polymer to be produced and the polymerizability of the monomer (A) can be suitably controlled. It is possible to preferably exhibit the dispersibility of the soil component particles and the pigment and the ability to prevent recontamination. 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 the case where the structural unit (b) is a structural unit derived from a cationic group-containing monomer, the mass ratio relative to the total amount of structural units derived from all monomers, or the cationic group-containing monomer When calculating the mass ratio with respect to the total amount of all monomers, it shall be calculated as the mass ratio of the corresponding unneutralized amine. For example, when the cationic group-containing monomer (B-2) is vinylamine hydrochloride, the mass ratio (% by mass) of vinylamine that 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.

<Other monomers>
The ether bond-containing 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)). It may be. The ether bond-containing 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 ether bond-containing polymer of the present invention has the “structural unit (e) derived from other monomer (E)” means that the finally obtained polymer is a monomer having no monomer (E). It means having a structural unit in which a saturated double bond is replaced with a single bond.

Examples of the other monomer (E) 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; Half ester, half amide of unsaturated dicarboxylic acid and amine having 1 to 22 carbon atoms, half ester of unsaturated dicarboxylic acid and glycol having 2 to 4 carbon atoms; vinyl sulfonic acid, (meth) allyl sulfonic acid, isoprene sulfone Acid, 3-allyloxy-2-hydroxypropanesulfonic acid, acrylamido-2-methylpropanesulfonic acid and these Sulfonic acid group-containing monomers such as salts thereof; and the like.
Examples of the salt include metal salts, ammonium salts, organic amine salts (organic ammonium salts) and the like.
When the ether bond-containing polymer of the present invention has a structural unit (e) derived from an optional other monomer (E), it is derived from all monomers forming the ether bond-containing polymer. It is preferable that the structural unit (e) is included in an amount of 0 to 60% by mass with respect to 100% by mass of the total amount of structural units (that is, 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.
<Other physical properties of ether bond-containing polymer>
In the ether bond-containing polymer of the present invention, the structural units (a) and (b) and, if necessary, the structural unit (e) may be introduced at a specific ratio as described above.
Moreover, the weight average molecular weight of the said ether bond containing polymer can be set suitably, and is not specifically limited. Specifically, the weight average molecular weight of the ether bond-containing polymer is preferably 2,000 to 200,000, more preferably 3,000 to 100,000, and most preferably 4,000 to 60,000. It is. If the weight average molecular weight is within the above range, the ability to prevent recontamination tends to be improved.
The number average molecular weight of the ether bond-containing polymer is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, and most preferably 2,000 to 25,000. . If the number average molecular weight is within the above range, the recontamination preventing ability tends 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 ether bond-containing polymer of the present invention has a high recontamination prevention ability, but the recontamination prevention ratio is preferably 73% or more. More preferably, it is 74% or more.
The recontamination prevention rate can be measured in the same manner as in the examples described later.
(Ether bond-containing polymer composition)
The ether bond-containing polymer of the present invention may constitute an ether bond-containing 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 ether bond-containing polymer composition preferably contains 1 to 100% by mass of the ether bond-containing polymer of the present invention with respect to 100% by mass of the total amount of the ether bond-containing polymer composition. One of the preferable forms of the said ether bond containing polymer composition is a form which contains 40-60 mass% of ether bond containing polymers of this invention, and contains 40-60 mass% of water.
[Method of producing ether bond-containing polymer of the present invention]
The ether bond-containing polymer of the present invention comprises (i) an ether bond-containing monomer (A) (monomer (A)) represented by the general formula (1) and (ii) a nonionic monomer. Monomer component containing (B-1) and / or a cationic group-containing monomer (B-2) as essential, and containing other monomer (E) (monomer (E)) as necessary Can be copolymerized at a predetermined ratio.
In the method for producing an ether bond-containing polymer of the present invention, the composition ratio of each monomer used for polymerization is 100 mass of the total amount of all monomers (monomer (A), (B), (E)) % Of the monomer (A) is 1 to 99% by mass, and the monomer (B) is 1 to 99% by mass. If the content of the monomer (A) is less than 1% by mass, the detergency of the stain component and the ability to prevent recontamination may be reduced, which may reduce the cleaning power. 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 0-60 mass% with respect to the total amount 100 mass% of all the monomers (monomer (A), (B), (E)). Good. More preferably, it is 0-50 mass%, More preferably, it is 0-10 mass%, Most preferably, it is 0 mass%.
The polymerization method for obtaining the ether bond-containing 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. By performing polymerization by adding by such an addition method, the polymerizability of the ether bond-containing monomer (A) can be improved, so that the dispersibility of the obtained polymer, the ability to prevent recontamination, etc. are improved. 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 ether bond-containing 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 interfere with the polymerization reaction in the production of the ether bond-containing polymer of the present invention. Any material that dissolves may be used.
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 / hydrogen peroxide, sodium bisulfite / sodium persulfate, sodium bisulfite / Fe (ion), sodium bisulfite / hydrogen peroxide / Forms such as Fe (ion), sodium bisulfite / 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 an ether bond containing 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 the ability to prevent recontamination 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 production method of the present invention may include a neutralization step and a purification step in addition to the polymerization step, and any neutralization method or purification method can be applied.
The ether bond-containing polymer of the present invention that can be produced by the above production method can exhibit high performance in aqueous applications, hard water resistance, detergency, recontamination prevention ability, clay dispersibility, and surfactant. Therefore, when used as a dispersant, a detergent builder, a detergent composition, a cleaning agent, or a water treatment agent, particularly excellent performance can be exhibited.
[Use of ether bond-containing polymer and ether bond-containing polymer composition of the present invention]
The ether bond-containing polymer (or ether bond-containing 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, a hair care agent, and a shampoo.・ Hair spray, soap, cosmetic additives, anion exchange resins, dye mordants and auxiliaries for fibers and photographic films, pigment spreaders in papermaking, paper strength enhancers, emulsifiers, preservatives, textile and paper softeners , Lubricating oil additives, water treatment agents, fiber treatment agents, dispersants, detergent additives, scale inhibitors (scale inhibitors), metal ion sealants, thickeners, various binders, emulsifiers, etc. Can do. 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 ether bond-containing polymer (or ether bond-containing 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 ether bond-containing polymer (or ether bond-containing polymer composition) of the present invention can also be used as a fiber treatment agent. The fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide and a surfactant, and the ether bond-containing polymer (or ether bond-containing polymer composition) of the present invention.
The content of the ether bond-containing 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 ether bond-containing polymer of the present invention and at least one selected from the group consisting of a dye, a peroxide, and a surfactant is, for example, an improvement in the whiteness of the fiber, uneven color, and dyeing tempering For this purpose, at least one selected from the group consisting of a dye, a peroxide and a surfactant is added in an amount of 0.1 to 100 per 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 the composition mix | blended in the ratio of the weight part as a fiber processing 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 ether bond-containing polymer (or ether bond-containing 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 ether bond-containing 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 ether bond-containing polymer (or ether bond-containing 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 ether bond-containing polymer (or ether bond-containing polymer composition) of the present invention can also be added to a detergent composition.
The content of the ether bond-containing polymer in the detergent composition is not particularly limited. However, from the viewpoint that excellent builder performance can be exhibited, the content of the ether bond-containing polymer is preferably 0.1 to 15% by mass with respect to 100% by mass of the total amount of the detergent composition, and 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.
The detergent composition may contain another detergent builder in addition to the ether bond-containing polymer (or ether bond-containing polymer composition) of the present invention. 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)>
Apparatus: L-7000 series manufactured by Hitachi, Ltd. Detector: HITACHI RI Detector L-7490
Column: SHODEX Asahipak GF-310-HQ, GF-710-HQ, GF-1G 7B manufactured by Showa Denko Co., Ltd.
Column temperature: 40 ° C
Flow rate: 0.5 ml / min
Calibration curve: POLYETHYLENE GLYCOL STANDARD made by GL Sciences Inc.
Eluent: 0.1N sodium acetate / acetonitrile = 3/1 (mass ratio).
<Method for quantifying ether bond-containing monomer>
The quantification of the ether bond-containing monomer was performed using liquid chromatography under the following conditions.
Measuring device: L-7000 series detector manufactured by Hitachi, Ltd .: UV detector L-7400 manufactured by Hitachi, Ltd.
Column: SHODEX RSpak DE-413 manufactured by Showa Denko Co., Ltd.
Temperature: 40.0 ° C
Eluent: 0.1% phosphoric acid aqueous solution Flow rate: 1.0 ml / min.
<Quantification method for nonionic monomer, cationic group-containing monomer, etc.>
Quantification of the nonionic monomer and the cationic group-containing monomer was performed using high-speed chromatography under the following conditions.
Measuring device: 8020 series manufactured by Tosoh Corporation Column: CAPCELL PAK C1 UG120 manufactured by Shiseido Co., Ltd.
Temperature: 40.0 ° C
Eluent: 10 mmol / L Disodium hydrogen phosphate.12 hydrate aqueous solution (adjusted to pH 7 with phosphoric acid) / acetonitrile = 45/55 (volume ratio)
Flow rate: 1.0 ml / min
Detector: RI, UV (detection wavelength: 215 nm).
<Measurement of solid content>
In an oven heated to 130 ° C. in a nitrogen atmosphere, 1.0 g of an ether bond-containing polymer composition containing the ether bond-containing polymer of the present invention and 1.0 g of water were allowed to stand for 1 hour for drying treatment. . From the mass change before and after drying, the solid content (%) and the volatile component (%) were calculated.
<Synthesis of ether bond-containing monomer (A)>
[Synthesis Example 1]
In a 1000 ml glass separable flask equipped with a thermometer, a stirrer, a nitrogen inlet pipe and a cooling trap at the nitrogen outlet, 1,4-dioxane 500.0 g, AGE 114.0 g, and methyl glycolate 90 0.0 g was charged. After heating to 60 ° C., 1.1 g of boron trifluoride diethyl ether complex was added while flowing in nitrogen, and the mixture was stirred for 300 minutes. To this, 83.3 g of 48% sodium hydroxide was added and stirred at 90 ° C. for 120 minutes. After confirming that the pH was 9 or less, the solvent was removed with a rotary evaporator to obtain a 50% aqueous solution. As a result, the AGEE monomer (1) was obtained. The progress of the reaction was confirmed by liquid chromatography and ¹ HNMR.

[Synthesis Example 2]
500.0 g of 1,4-dioxane and allyl glycidyl ether (hereinafter referred to as AGE) are placed in a 1000 ml glass separable flask equipped with a thermometer, a stirrer, a nitrogen inlet pipe and a cooling trap at the nitrogen outlet. 114.0 g, 62.0 g of KOH, and 76.0 g of glycolic acid were added and stirred at 90 ° C. for 300 minutes. The solvent was removed by a rotary evaporator to obtain an AGEE monomer (2) as a 50% aqueous solution. The progress of the reaction was confirmed by liquid chromatography and ¹ HNMR.

[Example 1]
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0043 g of Mole salt, and heated to 90 ° C. while stirring to polymerize. The reaction system was used. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 200.0 g of hydroxyethyl acrylate (hereinafter referred to as HEA), 40% aqueous solution of sodium 3-allyloxy-2-hydroxypropanesulfonate ( Made by Aldrich Chemical Company, Inc., hereinafter referred to as 40% HAPS) 125.0 g, 15% sodium persulfate aqueous solution (hereinafter referred to as 15% NaPS) 52.1 g, 35% sodium bisulfite (hereinafter 35% SBS) 44.7 g and 41.4 g of pure water were dropped from separate nozzles.
The start of dropping of each solution is simultaneous, and the dropping time of each solution is 120 minutes for HEA, 60 minutes for monomer (1), 130 minutes for 15% NaPS, 120 minutes for 35% SBS, and The pure water was 120 minutes. 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 reaction solution was maintained at 90 ° C. for 30 minutes (ripening) to complete the polymerization. In this way, an aqueous solution (polymer composition (1)) containing the copolymer (1) having a solid content concentration of 45% was obtained.

[Example 2]
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0052 g of Mohr's salt and polymerized by heating to 90 ° C. while stirring. The reaction system was used. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 200.0 g of HEA, 235.3 g of 40% HAPS, 57.5 g of 15% NaPS, 49.3 g of 35% SBS, and 52.1 g of pure water was dropped from separate nozzles.
The dripping start of each solution is simultaneous, and the dropping time of each solution is 120 minutes for HEA, 60 minutes for 40% HAPS, 130 minutes for 15% NaPS, 120 minutes for 35% SBS, and pure water. About 120 minutes. 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 reaction solution was maintained at 90 ° C. for 30 minutes (ripening) to complete the polymerization. In this way, an aqueous solution (polymer composition (2)) containing the copolymer (2) having a solid content concentration of 45% was obtained.

[Example 3]
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0046 g of Mole salt, and the temperature was raised to 90 ° C. while stirring to polymerize. The reaction system was used. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 200.0 g of HEA, 100.0 g of monomer (1), 53.6 g of 15% NaPS, 46.0 g of 35% SBS, And 104.7 g of pure water was dripped from each separate nozzle.
The start of dropping of each solution is simultaneous, and the dropping time of each solution is 120 minutes for HEA, 60 minutes for monomer (1), 130 minutes for 15% NaPS, 120 minutes for 35% SBS, and The pure water was 120 minutes. 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 reaction solution was maintained at 90 ° C. for 30 minutes (ripening) to complete the polymerization. In this way, an aqueous solution (polymer composition (3)) containing the copolymer (3) having a solid content concentration of 44% was obtained.

[Example 4]
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0053 g of Mole salt, and heated to 90 ° C. while stirring to polymerize. The reaction system was used. Next, in a polymerization reaction system maintained at 90 ° C. with stirring, 200.0 g of HEA, 188.2 g of monomer (1), 60.4 g of 15% NaPS, 51.8 g of 35% SBS, And 96.8 g of pure water was dropped from separate nozzles.
The start of dropping of each solution is simultaneous, and the dropping time of each solution is 120 minutes for HEA, 60 minutes for monomer (1), 130 minutes for 15% NaPS, 120 minutes for 35% SBS, and The pure water was 120 minutes. 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 reaction solution was maintained at 90 ° C. for 30 minutes (ripening) to complete the polymerization. In this way, an aqueous solution (polymer composition (4)) containing the copolymer (4) having a solid concentration of 45% was obtained.

[Example 5]
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0042 g of Mole salt, and the temperature was raised to 90 ° C. while stirring to polymerize. The reaction system was used. Next, 200.0 g of dimethylaminoethyl acrylate (hereinafter referred to as DAA), 125.0 g of 40% HAPS, and 43.4 g of 15% NaPS in a polymerization reaction system maintained at 90 ° C. with stirring. , And 48.4 g of pure water were dropped from separate nozzles.
The dropping start of each solution was simultaneous, and the dropping time of each solution was 120 minutes for DAA, 60 minutes for 40% HAPS, 130 minutes for 15% NaPS, and 120 minutes for pure water. 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 reaction solution was maintained at 90 ° C. for 30 minutes (ripening) to complete the polymerization. Thus, the aqueous solution (polymer composition (5)) containing the copolymer (5) with a solid content concentration of 45% was obtained.

[Example 6]
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0052 g of Mohr's salt and polymerized by heating to 90 ° C. while stirring. The reaction system was used. Next, 200.0 g of DAA, 235.3 g of 40% HAPS, 48.8 g of 15% NaPS, and 59.1 g of pure water were respectively added to the polymerization reaction system maintained at 90 ° C. with stirring. Dropped from separate nozzles.
The dropping start of each solution was simultaneous, and the dropping time of each solution was 120 minutes for DAA, 60 minutes for 40% HAPS, 130 minutes for 15% NaPS, and 120 minutes for pure water. 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 reaction solution was maintained at 90 ° C. for 30 minutes (ripening) to complete the polymerization. In this way, an aqueous solution (polymer composition (6)) containing the copolymer (6) having a solid content concentration of 45% was obtained.

[Example 7]
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0045 g of Mole salt and heated to 90 ° C. while stirring to polymerize. The reaction system was used. Next, 200.0 g of DAA, 100.0 g of monomer (1), 45.0 g of 15% NaPS, and 111.7 g of pure water were added to the polymerization reaction system maintained at 90 ° C. with stirring. Each was dropped from a separate nozzle.
The dropping start of each solution is simultaneous, and the dropping time of each solution is 120 minutes for DAA, 60 minutes for monomer (1), 130 minutes for 15% NaPS, and 120 minutes for pure water. did. 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 reaction solution was maintained at 90 ° C. for 30 minutes (ripening) to complete the polymerization. In this way, an aqueous solution (polymer composition (7)) containing the copolymer (7) having a solid concentration of 44% was obtained.

[Example 8]
A 1000 mL glass separable flask equipped with a reflux condenser and a stirrer (paddle blade) was charged with 150.0 g of pure water and 0.0052 g of Mohr's salt and polymerized by heating to 90 ° C. while stirring. The reaction system was used. Next, 200.0 g of DAA, 188.2 g of monomer (1), 51.7 g of 15% NaPS, and 103.8 g of pure water were added to the polymerization reaction system maintained at 90 ° C. with stirring. Each was dropped from a separate nozzle.
The dropping start of each solution is simultaneous, and the dropping time of each solution is 120 minutes for DAA, 60 minutes for monomer (1), 130 minutes for 15% NaPS, and 120 minutes for pure water. did. 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 reaction solution was maintained at 90 ° C. for 30 minutes (ripening) to complete the polymerization. Thus, the aqueous solution (polymer composition (8)) containing the copolymer (8) with a solid content concentration of 45% was obtained.

[Comparative Example 1]
In a separable flask having a capacity of 300 mL equipped with a reflux condenser and a stirrer (paddle blade), 31.2 g of n-hexyl acrylate (hereinafter referred to as HA) and 14.4 g of acrylic acid (hereinafter referred to as AA), Then, 6.2 g of 2-aminoethanethiol as a chain transfer agent and 500 mg of azobisisobutyronitrile as a polymerization initiator were added together with 60 mL of a solvent acetone, and then reacted at 60 ° C. with stirring for 5 hours. After completion of the reaction, the resulting low polymer was neutralized by adding an aqueous sodium hydroxide solution to the reaction solution to adjust the pH to 8.5. Subsequently, acetone was added to the reaction solution, and a low polymer was precipitated and collected to obtain a comparative polymer (1).

  As a result of the liquid chromatography measurement of the copolymer compositions (1) to (8), the residual monomer was 1000 ppm or less, and a polymer having a composition (see Table 1) according to the charged amount was obtained. It could be confirmed.

[Example 9]
For the copolymers (1) to (8) and the comparative copolymer (1) obtained in Examples 1 to 8 and Comparative Example 1, the compatibility with the surfactant was evaluated as follows. The results are shown in Table 1.
<Compatibility with surfactant>
A detergent composition containing a test sample (ether bond-containing polymer or ether bond-containing polymer composition) was prepared with the following formulation.
SFT-70H (Nippon Shokubai Co., Ltd., polyoxyethylene alkyl ether); 40 g
Neoperex F-65 (manufactured by Kao Corporation, sodium dodecylbenzenesulfonate); 7.7 g (active ingredient 5 g)
Coatamine 86W (manufactured by Kao Corporation, stearyltrimethylammonium chloride); 17.9 g (active ingredient 5 g)
Diethanolamine; 5g
Ethanol; 5 g
Propylene glycol; 5g
Test sample (solid content conversion): 1.5 g
Ion-exchanged water; balance (the amount of ion-exchanged water is appropriately adjusted so that the total amount is 100 g, with the amount of test sample used as the actual amount used).
Thoroughly stir the components so that they are uniform, and the turbidity value at 25 ° C. is measured using a turbidimeter (“NDH2000” manufactured by Nippon Denshoku Co., Ltd.) and Turbidity (kaolin turbidity: mg / l) Measured with
Evaluation was made according to the following criteria.
○: Kaolin turbidity (0 or more, less than 50 (mg / l)), visually separated, not precipitated or clouded.
(Triangle | delta): Kaolin turbidity (50 or more, less than 200 (mg / l)), and it is slightly cloudy visually.
X: Kaolin turbidity (200 or more (mg / l)), visually turbid.

[Example 10]
Further, the copolymer (2) obtained in Example 2, the copolymer (4) obtained in Example 4, the copolymer (6) obtained in Example 6, and the copolymer obtained in Example 8. (8) About the comparative copolymer (1) obtained by the comparative example 1, the recontamination prevention ability was evaluated as follows.
The recontamination prevention rate of the copolymer (2) was 78%, the recontamination prevention rate of the copolymer (4) was 79%, the recontamination prevention rate of the copolymer (6) was 75%, and the copolymer (8 ) Recontamination prevention rate was 74%. On the other hand, the recontamination prevention rate of the comparative copolymer (1) was 72%.
<Recontamination prevention test>
The recontamination prevention test was performed according to the following procedure.
(1) A polyester cloth obtained from Test fabric was cut into 5 cm × 5 cm to prepare a white cloth. The whiteness of the white cloth was measured by reflectance using a colorimetric color difference meter SE2000 type manufactured by Nippon Denshoku Industries Co., Ltd. in advance.
(2) Pure water was added to 1.1 g of calcium chloride dihydrate to 15 kg to prepare hard water.
(3) Polyethylene glycol (20) Pure water was added to 4.0 g of lauryl ether to make 100.0 g to prepare an aqueous surfactant solution. The pH was adjusted to 8.5 with sodium hydroxide.
(4) A targot meter was set at 25 ° C., 1 L of hard water, 5 g of an aqueous surfactant solution, 1 g of a 5% polymer aqueous solution in terms of solid content, and 1.0 g of carbon black were placed in a pot and stirred at 150 rpm for 1 minute. . Then, 5 white cloths were put and stirred at 100 rpm for 10 minutes.
(5) The white cloth was drained by hand, 1 L of hard water brought to 25 ° C. was put in the pot, and stirred at 100 rpm for 2 minutes.
(6) A white cloth was applied and dried while stretching the wrinkles with an iron, and then the whiteness of the white cloth was measured again with the above colorimetric colorimeter with reflectance.
(7) The recontamination prevention rate was calculated from the above measurement results using the following equation.
Recontamination prevention rate (%) = (whiteness after washing) / (whiteness of raw white cloth) × 100.

From the results of Examples and Comparative Examples, it can be seen that the polyalkylene glycol polymer of the present invention is excellent in compatibility with a surfactant and has excellent anti-recontamination ability under high hardness. It was.

Claims (2)

(I) Structural unit (a) derived from ether bond-containing monomer (A), (ii) Nonionic monomer (B-1) and / or cationic group-containing monomer (B-2) An ether bond-containing polymer essentially comprising the structural unit (b) derived from the above, wherein the ether bond-containing 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. X and Y are a hydroxyl group, a structure represented by the following general formula (2), The structure represented by the following general formula (3) and the structure represented by the following general formula (3 ′) are represented (however, one of X and Y represents a hydroxyl group, and the other represents the following general formula (2) A structure represented by the following general formula (3), or a structure represented by the following general formula (3 ′)):

(In the above general formulas (2) and (3 ′), 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 12 carbon atoms. In formulas (2), (3), and (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). An ether comprising a step of polymerizing (i) an ether bond-containing monomer (A) and (ii) a nonionic monomer (B-1) and / or a cationic group-containing monomer (B-2) It is a manufacturing method of a coupling | bonding containing polymer, Comprising: The said manufacturing method is the following general formula (1); with respect to 100 mass% of total amounts of all the monomers to be 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. X and Y are a hydroxyl group, a structure represented by the following general formula (2), The structure represented by the following general formula (3) and the structure represented by the following general formula (3 ′) are represented (however, one of X and Y represents a hydroxyl group, and the other represents the following general formula (2) A structure represented by the following general formula (3), or a structure represented by the following general formula (3 ′)):

(In the above general formulas (2) and (3 ′), 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 12 carbon atoms. In formulas (2), (3), and (3 ′), M represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine salt (organic ammonium group).
1 to 99 mass% of the ether bond-containing monomer (A) represented by the formula, 1 to 99 mass% of the nonionic monomer (B-1) and / or the cationic group-containing monomer (B-2). %. A method for producing an ether bond-containing polymer, wherein:

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