JP2008138014A - Polyalkylene glycol-type polymerizable unsaturated monomer, method for producing the same, copolymer produced by using the polymerizable unsaturated monomer and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable unsaturated monomer having a vinyl monomer graft-polymerized to an alkylene glycol chain of an alkylene glycol compound having a polymerizable unsaturated double bond and expected to be a useful constituent unit of a water-soluble polymer suitable as a detergent builder, a water-treating agent and a pigment dispersing agent. <P>SOLUTION: The polyalkylene glycol-type polymerizable unsaturated monomer has a vinyl monomer graft-polymerized to the polyalkylene glycol chain of a polyalkylene glycol compound having an organic group containing a polymerizable unsaturated double bond. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyalkylene glycol-based polymerizable unsaturated monomer and a method for producing the same, a water-soluble copolymer using the polymerizable unsaturated monomer, a method for producing the same, and a suitable copolymer. Regarding usage.

  A water-soluble polymer has a function and solubility as a polymer, and is, for example, a detergent builder, a scale inhibitor, various inorganic and organic dispersants, a thickener, a pressure-sensitive adhesive, an adhesive, and a surface. Widely used in various applications such as coating agents, cross-linking agents, moisturizers and the like. Examples of such water-soluble polymers include polymers obtained by polymerizing unsaturated carboxylic acid monomers such as acrylic acid, and copolymerization of unsaturated carboxylic acid monomers with other monomers. Coalescence is known.

  However, a builder for a detergent comprising a copolymer obtained by polymerizing such an unsaturated carboxylic acid monomer has extremely poor compatibility with a surfactant which is one of the main components of the detergent composition. Therefore, for example, there is a drawback that it is not suitable for liquid detergent applications. Then, the water-soluble copolymer obtained by copolymerizing the monomer component which essentially contains an unsaturated carboxylic acid-type monomer and an unsaturated alcohol-type monomer is disclosed (for example, patent document 1). reference). It is known that such water-soluble copolymers are extremely excellent in compatibility with surfactants, have high transparency when made into liquid detergent compositions, and have excellent detergent performance, and are suitable as detergent builders. It has been.

  On the other hand, as water-soluble polymers, graft polymers obtained by graft polymerization of unsaturated carboxylic acid monomers such as acrylic acid, vinyl acetate or (meth) acrylic acid esters to polyether compounds are also widely used. Yes. In recent years, attempts have been made to graft-polymerize N-vinylpyrrolidone or the like as an improvement of the graft polymer (see, for example, Patent Document 2).

  A graft polymer obtained by graft polymerization of a monomer component containing N-vinylpyrrolidone or the like onto a polyether compound (polyalkylene glycol) obtained by polymerizing alkylene oxide is adsorbed or dispersed due to the pyrrolidone group or the like. Excellent. Further, by controlling the amount of N-vinylpyrrolidone used to a certain amount, the obtained graft polymer is excellent in safety and the color of the polymer itself is reduced. For this reason, it is known that a graft polymer obtained by graft polymerization of a monomer component on polyalkylene glycol obtained by polymerizing alkylene oxide can be suitably used as a builder for detergent.

Based on the above knowledge, a polymerizable unsaturated monomer obtained by graft polymerization of N-vinylpyrrolidone or the like onto a polyalkylene glycol chain of a polyalkylene glycol (unsaturated alcohol monomer) having a polymerizable unsaturated double bond. The meter was expected to be very useful as a building block for detergent builders.
JP 2002-60785 A Japanese Patent Application No. 2005-165997

  The present invention is a polyalkylene glycol-based compound having a polymerizable unsaturated double bond, which is considered to be a useful structural unit of a water-soluble polymer suitable as a detergent builder, a water treatment agent, or a pigment dispersant. An object is to obtain a polymerizable unsaturated monomer in which a vinyl monomer is graft-polymerized to a glycol chain portion.

  The polyalkylene glycol polymerizable unsaturated monomer of the present invention is obtained by graft polymerization of a vinyl monomer on a polyalkylene glycol chain portion of a polyalkylene glycol compound having an organic group containing a polymerizable unsaturated double bond. It is characterized by.

That is, the polyalkylene glycol-based polymerizable unsaturated monomer of the present invention is obtained by graft polymerization of a vinyl-based monomer on a polyalkylene glycol chain portion while maintaining a polymerizable unsaturated double bond.
The organic group containing a polymerizable unsaturated double bond has the following general formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group. N is an integer of 0 to 3).

  The vinyl monomer is preferably at least one selected from the group consisting of N-vinyl pyrrolidone, vinyl acetate, and styrene.

With such a configuration, it is easy to graft polymerize the vinyl monomer to the polyalkylene glycol chain portion while maintaining the polymerizable unsaturated double bond added to the polyalkylene glycol.
The polyalkylene glycol polymerizable unsaturated monomer of the present invention has the following general formula (1):

(Wherein R ¹ represents a hydrogen atom or a methyl group, n is an integer of 0 to 3), and the following general formula (2)

（式中、Ｘは

(Where X is

で表される有機基を表す。ｍは１〜５０の整数である。）で表される構成単位とを少なくとも有することを特徴とする。

An organic group represented by m is an integer of 1-50. And at least a structural unit represented by

  In addition, the polyalkylene glycol copolymer of the present invention has a structural unit derived from the polyalkylene glycol polymerizable unsaturated monomer.

  In addition, the polyalkylene glycol copolymer of the present invention can be a builder composition for detergent, a water treatment agent composition, or a pigment dispersant composition.

  In addition, the method for producing a polyalkylene glycol-based polymerizable unsaturated monomer of the present invention comprises adding an alkylene oxide to a compound having a polymerizable unsaturated double bond to form an organic group containing a polymerizable unsaturated double bond. And a step of graft-polymerizing a vinyl monomer on the polyalkylene glycol chain portion.

  The step of graft polymerization of the vinyl monomer on the polyalkylene glycol chain portion is preferably performed at 80 to 180 ° C. using an organic peroxide having a bulky organic group as a polymerization initiator.

  The compound having a polymerizable unsaturated double bond is preferably at least one selected from the group consisting of isoprenol, allyl alcohol, and methallyl alcohol.

  With this configuration, in the polyalkylene glycol compound having an organic group containing a polymerizable unsaturated double bond obtained by adding an alkylene oxide to a compound having a polymerizable unsaturated double bond, The organic group containing a heavy bond can be an organic group represented by the general formula (1).

  Since the polyalkylene glycol-based polymerizable unsaturated monomer of the present invention is a nonionic compound having a polymerizable unsaturated double bond, it is surface-active by copolymerizing with the unsaturated carboxylic acid-based monomer. It was possible to prepare a copolymer that was extremely excellent in compatibility with the agent, highly transparent when used as a liquid detergent composition, and excellent in detergent performance.

  In addition, since a vinyl monomer is graft-polymerized on the polyalkylene glycol chain portion, it is possible to prepare a copolymer having excellent adsorption ability and dispersibility in addition to the above characteristics. became.

(Polyalkylene glycol-based polymerizable unsaturated monomer)
The polyalkylene glycol polymerizable unsaturated monomer of the present invention is obtained by graft polymerization of a vinyl monomer on a polyalkylene glycol chain portion of a polyalkylene glycol compound having an organic group containing a polymerizable unsaturated double bond. It is characterized by. As used herein, “graft polymerization” refers to radical polymerization of a vinyl monomer in the presence of a polyalkylene glycol compound having an organic group containing a polymerizable unsaturated double bond. Means. The polyalkylene glycol-based polymerizable unsaturated monomer of the present invention (hereinafter sometimes simply referred to as “polymerizable unsaturated monomer”) will be described below.

<Organic group containing polymerizable unsaturated double bond>
The polymerizable unsaturated monomer of the present invention contains other monomer components such as an unsaturated carboxylic acid monomer via an organic group containing a polymerizable unsaturated double bond added to the polyalkylene glycol. It is sufficient if it can be copolymerized with. Therefore, the organic group containing a polymerizable unsaturated double bond constituting the polymerizable unsaturated monomer of the present invention is limited in any manner as long as it can play the above role. However, the following general formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group. N is an integer of 0 to 3).

  With this configuration, the vinyl monomer and the polyalkylene are prevented while preventing the later-described vinyl monomer from copolymerizing with the polymerizable unsaturated double bond contained in the organic group represented by the general formula (1). The graft polymerization with the glycol chain moiety can be preferentially advanced.

Whether or not the polymerizable unsaturated monomer of the present invention has a polymerizable unsaturated double bond can be confirmed by ¹ H-NMR. For example, when the organic group containing a polymerizable unsaturated double bond is derived from isoprenol, if the polymerizable unsaturated monomer of the present invention holds a polymerizable unsaturated double bond, ^{In the 1} H-NMR spectrum (in DMSO), a signal derived from a double bond portion is observed around 4.5 ppm. On the contrary, when the polymerizable unsaturated double bond is lost, a signal derived from the double bond portion is not observed in the vicinity of 4.5 ppm in the ¹ H-NMR spectrum (in DMSO).

  Moreover, by making n into the integer of 0-3 in the said General formula (1), the hydrolysis resistance of the polymerizable unsaturated monomer of this invention will improve. As a result, when the copolymer prepared using the polymerizable unsaturated monomer of the present invention is stored as an aqueous solution, the copolymer is added to an aqueous solution product such as a liquid detergent or a water treatment chemical solution. Or when added to washing water, cooling water, boiler water, or fiber-treated water, the copolymer of the present invention is extremely difficult to hydrolyze and can exhibit the original performance of the copolymer. .

<Polyalkylene glycol compounds>
The polyalkylene glycol compound used in the present invention has a structure in which polyalkylene glycol is added to the organic group containing the above-described polymerizable unsaturated double bond.

  Here, the polymerizable unsaturated monomer of the present invention has good hydrophilicity in the copolymer obtained by copolymerizing with other monomers such as unsaturated carboxylic acid monomers, and calcium. What is necessary is just to be able to provide the tolerance with respect to hardness components, such as ion. Therefore, the polyalkylene glycol chain portion of the polyalkylene glycol compound constituting the polymerizable unsaturated monomer of the present invention may be any embodiment as long as it can play the above role. It is preferable that the main component is an ethylene group. With this configuration, the copolymer obtained using the polymerizable unsaturated monomer of the present invention has improved hydrophilicity and hard water resistance, and can exhibit sufficient dispersibility. In this specification, “mainly composed of oxyethylene groups” means that when two or more oxyalkylene groups are present in the polyalkylene glycol chain portion, the majority of oxyethylene groups are present in the total number of oxyalkylene groups. Means to occupy.

  More specifically, when the content of oxyethylene groups is expressed as mol% of oxyethylene groups in 100 mol% of all oxyalkylene groups, 50 mol% or more is preferable, 60 mol% or more is more preferable, and 70 mol. % Or more is more preferable, 80 mol% or more is further more preferable, 90 mol% or more is especially preferable, and 100 mol% is the most preferable. If the content of the oxyethylene group is less than 50 mol%, the copolymer obtained using the polymerizable unsaturated monomer of the present invention may have reduced hydrophilicity or hard water resistance.

  The organic group other than the oxyethylene group that can be contained in the polyalkylene glycol chain portion constituting the polyalkylene glycol-based compound used in the present invention is particularly limited as long as it is copolymerizable with the oxyethylene group. For example, oxyalkylene groups such as oxypropylene group, oxy n-butylene group, oxyisobutylene group, and oxystyrene group, or glycidyl ethers such as phenyl glycidyl ether, n-butyl glycidyl ether, and 2-ethylhexyl glycidyl ether Etc. These other organic groups may be contained alone or in combination of two or more.

  The number average molecular weight of the polyalkylene glycol compound used in the present invention is preferably 100 or more, more preferably 400 or more, still more preferably 600 or more, still more preferably 800 or more, preferably 5000 or less, more preferably 4000 or less, and 3000. More preferred are: With this configuration, the polymerizable unsaturated monomer of the present invention obtained using a polyalkylene glycol compound can be efficiently and simply polymerized with other monomer components, and thus obtained. The resulting copolymer can exhibit sufficient dispersibility. If the number average molecular weight of the polyalkylene glycol compound is less than 100, the amount of polyalkylene glycol compound not graft-polymerized increases, so that the resulting copolymer may not exhibit excellent dispersibility. When the number average molecular weight of the polyalkylene glycol compound exceeds 5,000, the polymerizable unsaturated monomer of the present invention is copolymerized with another monomer such as an unsaturated carboxylic acid monomer without a solvent. When the polymerization is carried out, the viscosity of the monomer component increases vigorously, and the monomer component may not be sufficiently stirred during polymerization.

The number average molecular weight of the polyalkylene glycol compound can be determined, for example, in terms of polyethylene glycol using gel permeation chromatography (GPC) under the following conditions.
Measuring device: “Shodex SYSTEM-21” manufactured by Showa Denko KK
Column: "Asahipak GF-710 HQ" and "Asahipak GF-310 HQ" manufactured by Showa Denko KK in this order. Eluent: 0.1 N sodium acetate / acetonitrile = 7/3 (volume ratio)
Flow rate: 0.5 mL / min Temperature: 40 ° C
Calibration curve: prepared using polyethylene oxide manufactured by GL Sciences Inc. Detector: RI, UV (detection wavelength: 210 nm)

  As a polyalkylene glycol compound used in the present invention, for example, polyalkylene glycol is added to at least one selected from the group consisting of isoprenol, allyl alcohol, methallyl alcohol, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether. Compounds.

<Vinyl monomer>
As the vinyl monomer used in the present invention, excellent dispersibility and adsorption to the polymerizable unsaturated monomer of the present invention (and the copolymer formed using this polymerizable unsaturated monomer). In addition, the graft polymerization to the polyalkylene glycol chain part preferentially proceeds, and it is difficult to copolymerize with the polymerizable unsaturated double bond of the polymerizable unsaturated monomer. If there is no particular limitation, for example, N-vinylpyrrolidone, vinyl acetate, styrene, N-vinylcarbazole, 2-vinylpyridine, 4-vinylpyridine, 1-vinylimidazole, vinyl propionate, vinyl butyrate, lauric acid Although vinyl etc. are mentioned, It is preferable that it is at least 1 type selected from the group which consists of N-vinyl pyrrolidone, vinyl acetate, and styrene.

  On the other hand, acrylic acid, acrylamide, or vinyl sulfonic acid is not preferable because copolymerization to a polymerizable unsaturated double bond proceeds with priority over graft polymerization to a polyalkylene glycol chain moiety.

<Number average molecular weight of polyalkylene glycol polymerizable unsaturated monomer>
The number average molecular weight of the polymerizable unsaturated monomer of the present invention is preferably 150 or more, more preferably 400 or more, further preferably 600 or more, most preferably 800 or more, preferably 5000 or less, more preferably 4000 or less, 3000 or less is more preferable. With this configuration, the polymerizable unsaturated monomer of the present invention can be efficiently and easily polymerized with other monomer components, and the copolymer obtained thereby has sufficient dispersibility. It can be demonstrated. If the number average molecular weight is less than 150, the amount of polyalkylene glycol-based compound that is not graft-polymerized increases, and the resulting copolymer may not exhibit excellent dispersibility. On the other hand, if the number average molecular weight exceeds 5,000, it may not be possible to stir sufficiently uniformly during the polymerization when the polymerization is carried out without a solvent.

  The number average molecular weight of the polymerizable unsaturated monomer is, for example, using gel permeation chromatography (GPC) under the same conditions as those for determining the number average molecular weight of the polyalkylene glycol compound. It can be determined by glycol conversion.

<Polyalkylene glycol-based polymerizable unsaturated monomer>
As described above, the polymerizable unsaturated monomer of the present invention is obtained by graft polymerization of a vinyl monomer on a polyalkylene glycol chain portion of a polyalkylene glycol compound having an organic group containing a polymerizable unsaturated double bond. It is characterized by. For example, the polymerizable unsaturated monomer of the present invention has the following general formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, n is an integer of 0 to 3), and the following general formula (2)

（式中、Ｘは

(Where X is

An organic group represented by m is an integer of 1-50. And at least a structural unit represented by In addition, it is preferable that m in General formula (2) is an integer of 1-20.

(Polyalkylene glycol copolymer)
The polyalkylene glycol copolymer of the present invention has a constitutional unit derived from the polymerizable unsaturated monomer of the present invention. Specifically, it is constituted by copolymerizing the polymerizable unsaturated monomer component of the present invention and another monomer component.

  The other monomer used in the present invention is not particularly limited as long as it can be copolymerized with the polymerizable unsaturated monomer component of the present invention, but the unsaturated carboxylic acid monomer Is mentioned. With such a configuration, the copolymer of the present invention has sufficient hydrophilicity and can prevent re-deposition of the soil on the cloth by the action of the polyalkylene glycol, that is, the interaction with the hydrophobic soil.

  The unsaturated carboxylic acid monomer used in the present invention may be any monomer having a polymerizable unsaturated group and a carboxylic acid group, but may be an unsaturated monocarboxylic acid monomer or an unsaturated dicarboxylic acid. A system monomer or the like is preferable.

  The unsaturated monocarboxylic acid monomer may be any monomer having one unsaturated group and one carboxylic acid (or salt thereof) group in the molecule. For example, in the following general formula (3) And the compounds represented.

(In the formula, R ² represents a hydrogen atom or a methyl group. M represents a hydrogen atom, a metal atom, an ammonium group, or an organic amine group (protonated organic amine).)

  Examples of the metal atom in M of the general formula (3) 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; aluminum and iron Trivalent metal atoms and the like are preferred. As the organic amine group (protonated organic amine), alkanolamines such as ethanolamine, diethanolamine, and triethanolamine, and triethylamine are preferable. Further, it may be ammonium.

  Specific examples of the unsaturated monocarboxylic acid monomer used in the present invention include acrylic acid, methacrylic acid, crotonic acid and the like; these monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts. Etc. These unsaturated monocarboxylic acid monomers may be used alone or in combination of two or more. Among these, when the copolymer of the present invention is used as a builder for detergents, (meth) acrylic acid, its monovalent metal (especially Na) salt, divalent metal salt, ammonium are used from the viewpoint of improving dispersion performance. It is preferable to use a salt, an organic amine salt or the like.

  The unsaturated dicarboxylic acid monomer may be any monomer having one unsaturated group and two carboxylic acid (or salt thereof) groups in the molecule. Specifically, maleic acid, itacone Examples thereof include acids, citraconic acid, fumaric acid, monovalent metal (especially Na) salts, divalent metal salts, ammonium salts, organic ammonium salts (organic amine salts), and the like thereof, or anhydrides thereof. These unsaturated dicarboxylic acid monomers may be used alone or in combination of two or more.

  In addition to these, unsaturated carboxylic acid monomers include half esters of unsaturated dicarboxylic acid monomers and alcohols having 1 to 22 carbon atoms, unsaturated dicarboxylic acids and carbon atoms having 1 to 22 carbon atoms. Examples include a half amide with an amine, a half ester of an unsaturated dicarboxylic acid monomer and a glycol having 2 to 4 carbon atoms, and a half amide of maleamic acid and a glycol having 2 to 4 carbon atoms.

  The polyalkylene glycol copolymer of the present invention may further comprise other monomer components in addition to the unsaturated carboxylic acid monomer.

  Examples of such other monomer components include styrene monomers such as styrene, bromostyrene, chlorostyrene, methylstyrene, vinyltoluene; 3-methyl-2-buten-1-ol, 3-methyl-3 -Buten-1-ol, 2-methyl-3-buten-2-ol, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glycerol monoallyl ether , Α-hydroxyacrylic acid, N-methylol (meth) acrylamide, hydroxyl group-containing unsaturated hydrocarbons such as glycerol mono (meth) acrylate; nitrogen atom-containing unsaturated monomers such as vinylpyrrolidone, and the like.

  Other monomers include dienes such as 1,3-butadiene and isoprene; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, (meth) acrylic acid (Meth) acrylic acid esters such as methoxypropyl; α-olefins such as hexene, heptene, decene and isobutylene; alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether; vinyl esters such as vinyl acetate; allyl acetate And allyl esters.

  Further, a diester of the unsaturated dicarboxylic acid monomer and an alcohol having 1 to 22 carbon atoms, a diamide of the unsaturated dicarboxylic acid and an amine having 1 to 22 carbon atoms, the unsaturated dicarboxylic acid monomer And diesters of C2-4 glycols.

  Furthermore, bifunctional (meth) acrylates such as hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane di (meth) acrylate; vinyl sulfonate, (meth) allyl sulfonate, 2- (meth) ) Acryloxyethyl sulfonate, 3- (meth) acryloxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropyl sulfonate, 3- (meth) acryloxy-2-hydroxypropylsulfophenyl ether, 3- (meth) acryloxy 2-hydroxypropyloxysulfobenzoate, 4- (meth) acryloxybutylsulfonate, (meth) acrylamidomethylsulfonic acid, (meth) acrylamidoethylsulfonic acid, 2-methylpropanesulfuric acid Unsaturated sulfonic acids such as acid (meth) acrylamide, styrene sulfonic acid, vinyl sulfonic acid, (meth) allyl sulfonic acid, 3-allyloxy-2-hydroxypropane sulfonic acid, sulfoethylmaleimide, isoprene sulfonic acid, and the like Monovalent metal salt, divalent metal salt, ammonium salt and organic ammonium salt (organic amine salt).

  Furthermore, (meth) acrylamide, (meth) acrylalkylamide, N-methylol (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-butyl (meth) acrylamide, dimethylaminopropyl (meth) acrylamide, etc. Unsaturated amides; allyls such as allyl alcohol; unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; methoxypolyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxypolyethylene glycol mono (meth) allyl ether, polyethylene glycol Vinyl ethers or allyl ethers such as mono (meth) allyl ether; nitrile monomers such as (meth) acrylonitrile; (meth) acrylamide methanephosphonic acid, ( Data) acrylamide methane phosphonic acid methyl ester, 2- (meth) phosphorus-containing monomers such as acrylamido-2-methylpropane phosphonic acid.

  Furthermore, polyalkylene glycol monomers such as polyalkylene glycol esters of (meth) acrylic acid, isoprenol, and oxyalkylene adducts of (meth) allyl alcohol are also included.

<Weight average molecular weight of polyalkylene glycol copolymer>
The weight average molecular weight (Mw) in terms of polyacrylic acid by gel permeation chromatography (hereinafter referred to as “GPC”) of the copolymer of the present invention is preferably 1000 or more, and preferably 3000 or more. More preferably, it is more preferably 5000 or more, still more preferably 10,000 or more, preferably 100,000 or less, more preferably 80000 or less, still more preferably 50000 or less, and 30000 or less. Even more preferably. When the weight average molecular weight of the copolymer of the present invention is less than 1000, there is a risk that the dispersion performance and chelate performance of the copolymer may decrease, and the structural unit derived from the polymerizable unsaturated monomer of the present invention There is a possibility that the polymer which does not exist increases and the ability to prevent recontamination decreases. When the weight average molecular weight of the copolymer of the present invention exceeds 100,000, the dispersion performance of the copolymer may be lowered. In addition, in this specification, the weight average molecular weight (Mw) of a copolymer is a measured value by GPC (gel permeation chromatography). Examples of measurement conditions, devices, etc. are as follows.
Measuring device: “Shodex SYSTEM-21” manufactured by Showa Denko KK
Column: "Asahipak GF-710 HQ" and "Asahipak GF-310 HQ" manufactured by Showa Denko KK in this order. Eluent: 0.1 N sodium acetate / acetonitrile = 7/3 (volume ratio)
Flow rate: 0.5 mL / min Temperature: 40 ° C
Calibration curve: prepared using polyacrylic acid standard sample (manufactured by Sowa Kagaku Co., Ltd.) Detector: RI, UV (detection wavelength: 210 nm)

(Re-contamination prevention ability of polyalkylene glycol copolymer)
When the polyalkylene glycol copolymer of the present invention is used as a builder for detergents, it is preferable that the ability to prevent recontamination is 60% or more. More preferably, it is 70% or more, More preferably, it is 75% or more. The recontamination preventing ability can be obtained by the following method.

<Recontamination prevention evaluation method>
(1) A polyester cloth obtained from Test fabric is cut into 5 cm × 5 cm to create a white cloth. The whiteness of this white cloth is measured by reflectance using a colorimetric color difference meter SE2000 manufactured by Nippon Denshoku Industries Co., Ltd. in advance.
(2) Pure water is added to 4.41 g of calcium chloride dihydrate to make 15 kg, and hard water is prepared.
(3) Pure alkyl sodium sulfonate 4.0 g, sodium carbonate 6.0 g, sodium sulfate 2.0 g, and polyacrylic acid sodium (Mw5000) 0.4 g to make pure water 100.0 g to obtain an aqueous surfactant solution To prepare.
(4) Set targot meter at 25 ° C., put 1 L of hard water and 5 g of aqueous surfactant solution, 1 g of 2% by weight copolymer aqueous solution in terms of solid content, 0.15 g of zeolite, and 0.25 g of carbon black in a pot. Stir at 100 rpm for 1 minute. Then, 10 white cloths are put and stirred at 100 rpm for 10 minutes.
(5) Water of the white cloth is drained by hand, 1 L of tap water adjusted to 25 ° C. is put in the pot, and stirred at 100 rpm for 2 minutes. Do this twice.
(6) A white cloth is applied and dried while stretching the wrinkle with an iron, and then the whiteness of the white cloth is measured again with the above colorimetric colorimeter with reflectance.
(7) The recontamination prevention rate is obtained from the above measurement result by the following formula.
Recontamination prevention rate (%) = (whiteness after washing) / (whiteness of raw white cloth) × 100

(Use)
The polyalkylene glycol-based copolymer of the present invention has excellent hydrophilic properties, adsorbability, dispersibility, safety, excellent color tone, etc. It is suitable as a composition such as a builder, a water treatment agent, or a pigment dispersant. In particular, the builder for detergent and the water treatment agent constituted by using the polyalkylene glycol copolymer of the present invention can cope with various stains such as hydrophilic and hydrophobic stains, and the ability to prevent recontamination, etc. It has excellent characteristics.

  The polyalkylene glycol copolymer of the present invention is suitable as a composition for liquid detergent builders among detergent builders. This is because the polyalkylene glycol copolymer of the present invention is excellent in compatibility with a surfactant, so that the transparency when used in a liquid detergent is good, and the problem of separation of the liquid detergent caused by turbidity It is because it can prevent. Moreover, it is because a high concentration liquid detergent can be obtained and the washing | cleaning capability of a liquid detergent can be improved by being excellent in compatibility with surfactant.

  The detergent builder may contain other detergent builder components (composition) in addition to the polyalkylene glycol copolymer of the present invention, but the polyalkylene glycol copolymer of the present invention in the detergent builder. The content ratio is preferably 0.1% by mass or more, more preferably 5% by mass or more, and preferably 80% by mass or less, and 70% by mass or less, with respect to 100% by mass of the builder for detergent. More preferably, it is 65 mass% or less. When the content ratio of the polyalkylene glycol copolymer is less than 0.1% by mass, the cleaning power of the detergent may be insufficient when the detergent builder is used as a detergent composition. Moreover, when the content rate of a polyalkylene glycol-type copolymer exceeds 80 mass%, there exists a possibility that it may become uneconomical.

  The blending form of the polyalkylene glycol copolymer of the present invention may be liquid or solid, and may be determined according to the form at the time of sale of the detergent (for example, liquid or solid). it can. For example, the polyalkylene glycol copolymer of the present invention may be blended in the form of an aqueous solution after polymerization, or may be blended in a state where the water content of the aqueous solution is reduced to some extent, or dried and solidified. You may mix | blend in a state.

  When the polyalkylene glycol copolymer of the present invention is used as a detergent builder composition, the detergent composition containing the detergent builder may be a powder detergent composition or a liquid detergent composition. Good.

  Detergents constructed using the polyalkylene glycol copolymer of the present invention include synthetic detergents for household use, textile industry and other industrial detergents, hard surface detergents, and bleaching with enhanced function of one of its components. Also included are detergents used only for specific applications such as detergents. Since the polyalkylene glycol copolymer of the present invention is excellent in chelating ability, it can stabilize hydrogen peroxide by capturing trace metals, and is excellent in stabilizing ability of bleach.

  In addition to the detergent builder, the detergent composition may contain surfactants and additives usually used in detergents.

  The surfactant which is one of the main components of the detergent composition is at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants. An activator may be used independently or may be used in combination of 2 or more type.

  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 ester salt, alkane sulfonate. , 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 The salt etc. are mentioned. The alkyl group or alkenyl group in the anionic surfactant may have a branched alkyl group such as a methyl group.

  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 mono Examples thereof include esters and alkylamine oxides. The alkyl group or alkenyl group in the nonionic surfactant may have a branched alkyl group such as a methyl group.

  Examples of the cationic surfactant include quaternary ammonium salts.

  Examples of the amphoteric surfactant include a carboxyl type amphoteric surfactant and a sulfobetaine type amphoteric surfactant.

The alkyl group and alkenyl group in the cationic surfactant and amphoteric surfactant may be branched from an alkyl group such as a methyl group.

  The blending ratio of the surfactant is usually preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 25% by mass or more, based on 100% by mass of the detergent composition. 60 mass% or less is preferable, 50 mass% or less is more preferable, 45 mass% or less is further more preferable, and 40 mass% or less is especially preferable. If the blending ratio of the surfactant is less than 10% by mass, the resulting detergent may not be able to exhibit sufficient detergency, and if it exceeds 60% by mass, the economy may be lowered.

  Additives include alkali builder, chelate builder, anti-redeposition agent to prevent redeposition of contaminants such as sodium carboxymethylcellulose, anti-fouling agent 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 , Solvent and the like. In the case of a powder detergent composition, it is preferable that zeolite is contained as an additive.

  Examples of the alkali builder include silicate, carbonate, sulfate and the like. Examples of the chelate builder include diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid), DTPA (diethylenetriaminepentaacetic acid), STPP (sodium tripolyphosphate), and citric acid.

  Examples of the enzyme include protease, lipase, cellulase and the like. Of these, protease, alkaline lipase, alkaline cellulase, and the like that are highly active in the alkaline cleaning solution are preferable. The addition amount of the enzyme is preferably 5% by mass or less with respect to 100% by mass of the cleaning composition. If the amount of the enzyme added exceeds 5% by mass, the detergency cannot be improved and the economy may be lowered.

  When the cleaning composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1% by mass or more with respect to 100% by mass of the liquid detergent composition, and 0.2% by mass. Or more, more preferably 0.5% by mass or more, particularly preferably 0.7% by mass or more, more particularly preferably 1% by mass or more, most preferably 1.5% by mass or more, and preferably 75% by mass or less. 70% by mass or less, more preferably 65% by mass or less, particularly preferably 60% by mass or less, more particularly preferably 55% by mass or less, and most preferably 50% by mass or less.

  The liquid detergent composition preferably has a kaolin turbidity of 200 mg / L or less. More preferably, it is 150 mg / L or less, More preferably, it is 120 mg / L or less, Especially preferably, it is 100 mg / L or less, Most preferably, it is 50 mg / L or less. Further, the change (difference) in kaolin turbidity when the polyalkylene glycol copolymer of the present invention is added to the liquid detergent composition as a detergent builder is preferably 500 mg / L or less. More preferably, it is 400 mg / L or less, More preferably, it is 300 mg / L or less, Especially preferably, it is 200 mg / L or less, Most preferably, it is 100 mg / L or less. Kaolin turbidity can be measured, for example, by the following method for measuring kaolin turbidity.

<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, the NDU2000 (trade name, turbidimeter) manufactured by Nippon Denshoku Co., Ltd. was used at 25 ° C. Kaolin turbidity: mg / L) is measured.

  The water treatment agent constituted by using the polyalkylene glycol copolymer of the present invention is added to an aqueous system such as a cooling water system or a boiler aqueous system, so that, for example, scale prevention property such as calcium carbonate and silica or metal This may be advantageous for corrosion prevention. In addition, the pigment dispersant may be advantageous, for example, for dispersing a slurry of calcium carbonate or kaolin and reducing the viscosity.

  The detergent builder, the water treatment agent, and the pigment dispersant may contain other copolymer components other than the polyalkylene glycol copolymer of the present invention.

(Method for producing polyalkylene glycol polymerizable unsaturated monomer)
Next, a method for producing the polymerizable unsaturated monomer of the present invention will be described.

  The method for producing a polymerizable unsaturated monomer according to the present invention comprises adding an alkylene oxide to a compound having a polymerizable unsaturated double bond, and a polyalkylene glycol system having an organic group containing a polymerizable unsaturated double bond. The method includes a step of obtaining a compound and a step of graft polymerization of a vinyl monomer on a polyalkylene glycol chain portion. As used herein, “graft polymerization” means radical polymerization of a vinyl monomer in the presence of a polyalkylene glycol compound having an organic group containing a polymerizable unsaturated double bond. To do.

<Specific embodiments of compound having polymerizable unsaturated double bond, alkylene oxide, and vinyl monomer>
The compound having a polymerizable unsaturated double bond used in the method for producing a polymerizable unsaturated monomer of the present invention includes an organic compound having a polymerizable unsaturated double bond after addition of alkylene oxide to this compound. It is preferable that the group is in an embodiment represented by the general formula (1). For this reason, the compound having a polymerizable unsaturated double bond to which alkylene oxide is added is at least one selected from the group consisting of isoprenol, allyl alcohol, methallyl alcohol, 2-hydroxyethyl vinyl ether, and 4-hydroxybutyl vinyl ether. Is preferred.

  Further, as the alkylene oxide and vinyl monomer used in the method for producing a polymerizable unsaturated monomer of the present invention, the alkylene oxide and vinyl monomer exemplified above can be used. .

  As a method for adding an alkylene oxide to a compound having a polymerizable unsaturated double bond, the compound having a polymerizable unsaturated double bond is used as a polymerization initiation point of the alkylene oxide, but the polymerizable unsaturated divalent compound has such a compound. The method is not particularly limited as long as it can be added and polymerized with an alkylene oxide while maintaining a heavy bond to form a polyalkylene glycol compound. For example, (1) an anionic polymerization method using a strong alkali such as an alkali metal hydroxide or alcoholate, an alkylamine or the like as a base catalyst, and (2) a metal or metalloid halide, mineral acid, acetic acid or the like as a catalyst. Examples include cationic polymerization methods used, and (3) coordination polymerization methods using a combination of alkoxides of metals such as aluminum, iron, and zinc, alkaline earth compounds, Lewis acids, and the like.

  The amount of the compound having a polymerizable unsaturated double bond used is preferably 1 mol or more, preferably 50 mol or less, per 100 mol of alkylene oxide. When the amount of the compound having a polymerizable unsaturated double bond is less than 1 mol, the polyalkylene glycol as an impurity may increase or the compound having a polymerizable unsaturated double bond may be decomposed. Moreover, when the usage-amount of the compound which has a polymerizable unsaturated double bond exceeds 50 mol, the compound which has the polymerizable unsaturated double bond which the alkylene oxide has not added as an impurity may increase.

  As a method of graft-polymerizing a vinyl monomer to a polyalkylene glycol chain portion of a polyalkylene glycol compound having an organic group containing a polymerizable unsaturated double bond obtained by the above method, it is added to polyalkylene glycol. It is not particularly limited as long as the vinyl monomer can be graft-polymerized to the polyalkylene glycol chain portion while retaining the polymerizable unsaturated double bond, but preferably 80 ° C. or more, more preferably 110 degreeC or more, More preferably, it is 120 degreeC or more, Preferably it is 180 degreeC or less, More preferably, it is 170 degreeC or less, More preferably, it is 160 degreeC or less, and uses the organic peroxide which has a bulky organic group as a polymerization initiator. Preferably it is done.

  By performing graft polymerization of the vinyl monomer to the polyalkylene glycol chain portion at 80 to 180 ° C., the remaining vinyl monomer in the polymerizable unsaturated monomer obtained is sufficient in a short time. Can be reduced. For this reason, by using the polymerizable unsaturated monomer of the present invention, it is possible to obtain a copolymer having excellent safety, and a copolymer that can be suitably used for various applications. Obtainable.

  If the reaction temperature at the time of graft polymerization is less than 80 ° C., the amount of the vinyl monomer remaining in the resulting polymerizable unsaturated monomer cannot be sufficiently reduced. Moreover, when it exceeds 180 degreeC, coloring of the copolymer obtained using a polymerizable unsaturated monomer cannot be prevented, for example, there exists a possibility that it may not be made suitable for a detergent additive use. In addition, the resulting polymerizable unsaturated monomer may be thermally decomposed.

  The amount of the vinyl monomer used in the present invention is 100% by mass of the total amount of the polyalkylene glycol compound having an organic group containing a polymerizable unsaturated double bond of the present invention and the vinyl monomer. In this case, it is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 5% by mass or more, preferably 30% by mass or less, and 20% by mass or less. More preferably, it is more preferably 15% by mass or less. If the amount of the vinyl monomer used is less than 1% by mass, the dispersibility and adsorption ability attributable to the vinyl monomer may not be sufficiently exhibited. On the other hand, if the amount of vinyl monomer used exceeds 30% by mass, a large amount of vinyl monomer remains after graft polymerization, or a copolymer obtained using the polymerizable unsaturated monomer of the present invention. The polymer is easily colored. In addition, when N-vinylpyrrolidone is selected as the vinyl monomer, the production cost is increased because N-vinylpyrrolidone is expensive. In addition, when styrene is selected as the vinyl monomer, if the amount of styrene used is too large, the resulting polymerizable unsaturated monomer (and the copolymer obtained using this) will not be water soluble. May be sufficient.

  Moreover, the graft efficiency of a vinyl-type monomer can fully be improved by using the organic peroxide which has a bulky organic group as a polymerization initiator. In addition, by specifying the temperature and the polymerization initiator in this manner, the functions and effects of each can be synergized, and it is possible to efficiently obtain a polyalkylene glycol-based polymerizable unsaturated monomer excellent in various performances. Therefore, it can be an industrially very useful production method.

  In the present specification, the bulky organic group means that the organic peroxide conforms to the conformation of the organic peroxide or the bias of the electron to the extent that the organic peroxide improves the grafting efficiency of the vinyl monomer to the polyalkylene glycol chain portion. The organic group is not particularly limited as long as it can affect the organic group, and examples thereof include organic groups having 4 or more carbon atoms such as a tert-butyl group, a phenyl group, a benzyl group, and a benzoyl group.

  The polymerization initiator used in the production method of the present invention is not particularly limited as long as it is an organic peroxide having a bulky organic group. For example, di-tert-butyl peroxide, tert-butyl-peroxy -Iso-propyl monocarbonate, tert-butyl-peroxy-benzoate, benzoyl peroxide and the like. These polymerization initiators may be used alone or in combination of two or more.

  Although the usage-amount of a polymerization initiator is not specifically limited, For example, it is preferable to set it as 0.1 mass part or more with respect to 100 mass parts of all the monomer components used for superposition | polymerization, and to be 0.5 mass part or more Is more preferably 1.0 part by mass or more, further preferably 3.0 part by mass or more, more preferably 30 parts by mass or less, and more preferably 20 parts by mass or less. Preferably, the amount is 10 parts by mass or less. If the amount of the polymerization initiator used is less than 0.1 parts by mass, the graft polymerization rate to the vinyl monomer on the polyalkylene glycol chain portion may not be sufficient. Moreover, when the usage-amount of a polymerization initiator exceeds 30 mass parts, when using an organic peroxide as a polymerization initiator, for example, it may be unable to be set as the manufacturing method excellent in economical efficiency.

  In the production method of the present invention, the method for graft polymerization of a vinyl monomer is not particularly limited. For example, it is carried out by a usual polymerization method such as solvent-free polymerization, solution polymerization, emulsion polymerization, suspension polymerization, precipitation polymerization or the like. be able to.

  The polyalkylene glycol-based compound having an organic group containing a polymerizable unsaturated double bond of the present invention may be initially charged or added sequentially, but the reaction time is shortened and productivity is improved. From the viewpoint, it is preferable to use initial batch charging. The vinyl monomer component is preferably added sequentially in view of reaction control and the like. However, the vinyl monomer component is not limited to this, and can be charged all at once in the initial stage. In addition, you may dilute and use monomer components, such as a polyalkylene glycol type compound and a vinyl monomer which have an organic group containing a polymerizable unsaturated double bond, in the solvent mentioned later beforehand.

  The method for adding the polymerization initiator is not particularly limited, and it may be initially charged all at once or by a continuous charging method such as dropping or divided charging. Note that a polymerization initiator that is liquid at normal temperature is preferable because it can be dropped without using a solvent and is not easily limited by the addition method. In addition, the polymerization initiator may be introduced alone into the reaction vessel, and is previously mixed with a polyalkylene glycol compound having an organic group containing a polymerizable unsaturated double bond, a vinyl monomer, a solvent, or the like. May be.

  The method for producing a polymerizable unsaturated monomer of the present invention can be carried out by using a bulky organic group in combination with another polymerization initiator, a chain transfer agent and a reducing agent. In this case, the amount of other polymerization initiator, chain transfer agent, and reducing agent is preferably 300 parts by mass or less with respect to 100 parts by mass of the organic peroxide having a bulky organic group. More preferably, it is 100 parts by mass or less.

  In the present invention, the step of graft polymerization of the vinyl monomer on the polyalkylene glycol chain portion may be performed using a solvent. As the solvent, for example, those having a chain transfer constant to the solvent of the monomer used as a raw material as small as possible are preferable. Examples of such solvents include alcohols such as isobutyl alcohol, n-butyl alcohol, tert-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, ethylene glycol monoalkyl ether, and propylene glycol monoalkyl ether; Diethers such as ethylene glycol dialkyl ether and propylene glycol dialkyl ether; ethyl acetate, propyl acetate, butyl acetate, ethylene glycol monoalkyl ether acetate, acetate compounds such as propylene glycol monoalkyl ether acetate, etc. These may be used alone or in combination of two or more. In addition, it does not specifically limit as an alkyl group in the said alcohols and diethers, For example, a methyl group, an ethyl group, a propyl group, a butyl group etc. are mentioned. In addition, water as such a solvent is not preferable because N-vinylpyrrolidone is decomposed to generate 2-pyrrolidone.

  Although the usage-amount of a solvent is not specifically limited, For example, when the whole reaction system shall be 100 mass%, it is preferable to set it as 20 mass% or less. If it exceeds 20% by mass, for example, the graft efficiency of the monomer component may not be sufficient. More preferably, it is 0% by mass, that is, substantially no solvent is used, whereby, for example, the grafting efficiency can be remarkably increased, and a polymer superior in various performances can be obtained. Thus, the form in which the graft polymerization step is carried out in the absence of a solvent is also a preferred form of the present invention. In addition, the solvent may be initially charged all at once or may be added sequentially.

  The reaction pressure at the time of graft polymerization is not particularly limited, and may be, for example, normal pressure (atmospheric pressure), reduced pressure, or increased pressure. In addition, it is suitable to set it as a normal pressure (atmospheric pressure) at the point which can superpose | polymerize simply and at low cost.

  In addition, the polymerization is preferably performed in an atmosphere of an inert gas such as nitrogen gas, argon gas, carbon dioxide gas, but is not limited thereto.

(Method for producing polyalkylene glycol copolymer)
The present invention also includes a method for producing a polyalkylene glycol copolymer characterized by using a polymerizable unsaturated monomer obtained by the above production method.

  The polymerizable unsaturated monomer obtained by the above-mentioned production method includes a by-product such as a homopolymer of a vinyl monomer, but is particularly purified in the production of the copolymer of the present invention. There is no need to do.

  Moreover, as the monomer component copolymerizable with the polyalkylene glycol-based polymerizable unsaturated monomer used in the method for producing the polyalkylene glycol-based copolymer of the present invention, the monomers exemplified above can be used. Each can be used.

  In the polyalkylene glycol copolymer of the present invention, the total mass of the polymerizable unsaturated monomer of the present invention and other monomers is 100 as the mass ratio of each monomer forming the copolymer. When expressed in terms of% by mass, the polymerizable unsaturated monomer of the present invention is preferably 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and more preferably 20% by mass or more. More preferably, 30% by mass or more is particularly preferable, 99% by mass or less is preferable, 95% by mass or less is more preferable, 80% by mass or less is further preferable, and 60% by mass or less is more preferable. Further, the other monomer is preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass or less, still more preferably 80% by mass or less, particularly preferably 70% by mass or less, and 1% by mass. The above is preferable, 5% by mass or more is more preferable, 20% by mass or more is further preferable, and 40% by mass or more is more preferable. If the mass ratio of these monomers is out of the above range, the function of the repeating unit formed by each monomer cannot be exhibited effectively, and the effects of the present invention can be fully expressed. It will not be possible.

  The production of the polyalkylene glycol copolymer of the present invention is preferably carried out using at least one polymerization initiator selected from the group consisting of sulfite (salt), hydrogen sulfite and hydrogen peroxide. By using such a polymerization initiator, the polyalkylene glycol copolymer of the present invention can be produced more efficiently.

  Further, it is more preferable that a heavy metal ion is included as an essential component in addition to the polymerization initiator. For example, a combination of heavy metal ions and sulfurous acid (salt), heavy metal ions and bisulfite, heavy metal ions and hydrogen peroxide is preferable as the polymerization initiator.

  As said salt, the salt of a metal atom, ammonium, or organic ammonium is suitable. Examples of metal atoms 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 Salt and the like are preferable. As the organic ammonium (organic amine), alkanolamines such as ethanolamine, diethanolamine, and triethanolamine, and triethylamine are preferable. Further, it may be ammonium. Of these, sodium salts are preferred.

The heavy metal ion contained in the polymerization initiator means a metal having a specific gravity of 4 g / cm ³ or more. As the heavy metal ions, for example, iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium and the like are preferable. These heavy metals can be used alone or in combination of two or more. Among these, iron is more preferable.

The ionic value 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 these are combined. May be.

  The heavy metal ion is not particularly limited as long as it is contained in the polymerization initiator as an ion form. However, it is preferable to use a method using a solution obtained by dissolving a heavy metal compound because it is excellent in handleability. The heavy metal compound used in that case should just contain the heavy metal ion desired to contain in a polymerization initiator, and can be determined according to the polymerization initiator to be used.

When iron is used as a heavy metal ion, a heavy metal such as a mole salt (Fe (NH ₄ ) ₂ (SO ₄ ) ₂ .6H ₂ O), ferrous sulfate heptahydrate, ferrous chloride, ferric chloride, etc. It is preferable to use a compound or the like. Moreover, when using manganese as a heavy metal ion, manganese chloride etc. can be used suitably. In the case of using these heavy metal compounds, since they are 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 copolymer of the present invention, and dissolves the heavy metal compound. Anything is acceptable.

  The amount of the polymerization initiator used is preferably 1 g or more, more preferably 2 g or more, further preferably 3 g or more, preferably 20 g or less, more preferably 15 g or less, relative to 1 mol of the monomer. More preferably, it is 10 g or less.

  The heavy metal ions are preferably included in a catalytic amount in the polymerization step in the present invention. The amount of catalyst referred to in the present specification is not incorporated in the final target product but acts as a catalyst. Specifically, it is 100 ppm or less, preferably 10 ppm or less, more preferably 5 ppm or less. It is.

  In the method for producing a copolymer of the present invention, a polymerization initiator other than the above polymerization initiator can be used. Examples of such polymerization initiators include persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; pyrosulfites; 2,2′-azobis (2-amidinopropane) hydrochloride, 4,4′-azobis. Azo compounds such as -4-cyanoparellic acid, azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, peracetic acid, di Examples thereof include organic peroxides such as -t-butyl peroxide and cumene hydroperoxide. These polymerization initiators may be used alone or in combination of two or more. Moreover, you may use together 1 type (s) or 2 or more types with the at least 1 sort (s) of polymerization initiator selected from the group which consists of the above-mentioned sulfurous acid (salt), hydrogen sulfite, and hydrogen peroxide.

  In the method for producing a copolymer of the present invention, when using the above other polymerization initiator, the amount of such polymerization initiator used is 0.1 g or more per 1 mol of the monomer. Is preferably 0.5 g or more, more preferably 1 g or more, further preferably 20 g or less, more preferably 10 g or less, and even more preferably 5 g or less. Thereby, a polyalkylene glycol copolymer can be produced efficiently.

  The method for producing a copolymer of the present invention is preferably carried out by appropriately changing the neutralization rate at the time of copolymerization with a polymerization initiator. For example, when persulfate and bisulfite are used in combination, the above-mentioned other monomers used to obtain a copolymer that can form a salt, the neutralization rate is 0 mol% or more It is preferable to carry out copolymerization of monomer components as 60 mol% or less, more preferably 50 mol% or less, still more preferably 40 mol% or less, still more preferably 30 mol% or less, particularly preferably 20 mol% or less. It is preferable to carry out the copolymerization of the monomer components at preferably 10 mol% or less. In the present specification, the neutralization rate refers to the moles of the other monomers forming the salt when the total number of moles of the other monomers that can form a salt is 100 mol%. It is expressed in%. When the neutralization rate exceeds 60 mol%, the polymerization rate in the copolymerization step does not increase, and the molecular weight of the resulting copolymer may decrease, production efficiency may decrease, or impurities may increase.

  As a method for carrying out the copolymerization by setting the neutralization rate of other monomers capable of forming a salt to 0 to 60 mol%, the other monomers are converted into a salt form such as sodium salt or ammonium salt using an alkaline substance. What is necessary is just to attach | subject what made the neutralization rate 0-60 mol% at the time of neutralizing to copolymerization.

  In the method for producing a copolymer of the present invention, as a method for adding a monomer component or a polymerization initiator to a reaction vessel, all of the monomer components are charged into the reaction vessel, and then the polymerization initiator is placed in the reaction vessel. A method of carrying out copolymerization by adding to a reactor; a method of carrying out copolymerization by charging a part of the monomer component into a reaction vessel and adding a polymerization initiator and the remaining monomer component into the reaction vessel; reaction Examples thereof include a method in which a polymerization solvent is charged in a container and the whole amount of monomer components and a polymerization initiator is added. Among such methods, it is preferable to carry out copolymerization by a method in which a polymerization initiator and a monomer component are successively dropped into a reaction vessel. Thereby, distribution of the monomer unit of the copolymer obtained becomes more uniform, and the dispersibility when used as a builder for a detergent can be improved.

  In the method for producing a copolymer of the present invention, the solvent used as necessary is not particularly limited as long as it is generally used in the method for producing a copolymer of the present invention. , Water; alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; glycerin; polyethylene glycol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane and n-heptane; esters such as ethyl acetate; Examples thereof include ketones such as acetone and methyl ethyl ketone; amides such as dimethylformaldehyde; ethers such as diethyl ether and dioxane. These may be used alone or in combination of two or more. Among these, from the viewpoint of the solubility of the monomer component and the resulting copolymer, one or more solvents selected from the group consisting of water and lower alcohols having 1 to 4 carbon atoms may be used. preferable.

  As a usage-amount of a solvent, 40 mass parts or more are preferable with respect to 100 mass parts of monomer components, 45 mass parts or more are more preferable, 50 mass parts or more are more preferable, 200 mass parts or less are preferable, 180 mass parts is preferable. The following is more preferable, and 150 parts by mass or less is further preferable. If the amount of the solvent used is less than 10 parts by mass, the resulting copolymer may have a high molecular weight. If it exceeds 200 parts by mass, the concentration of the resulting copolymer will be low, and solvent removal will be required. There is a risk. 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, polymerization initiators, and the like may be added (dropped) into the reaction system during the polymerization reaction together with these components in a form that has been previously dissolved in a solvent.

  In the method for producing a copolymer of the present invention, the copolymerization conditions such as the copolymerization temperature are appropriately determined depending on the copolymerization method used, the solvent, and the polymerization initiator, and the copolymerization temperature is preferably 0 ° C. or higher. 40 ° C or higher is more preferable, 60 ° C or higher is more preferable, 80 ° C or higher is particularly preferable, 150 ° C or lower is preferable, 130 ° C or lower is more preferable, 120 ° C or lower is further preferable, and 110 ° C or lower is particularly preferable. .

  The copolymerization temperature need not always be kept substantially constant in the course of the polymerization reaction. For example, the polymerization is started from room temperature, the temperature is increased to a set temperature at an appropriate temperature increase time or rate, and then the set temperature is reached. Depending on the dropping method of the monomer component, the polymerization initiator, etc., the temperature may be changed over time (temperature increase or decrease) during the polymerization reaction.

  The copolymerization time is preferably 30 minutes or more, more preferably 60 minutes or more, further preferably 120 minutes or more, preferably 300 minutes or less, more preferably 260 minutes or less, and further preferably 210 minutes or less.

  The pH during the polymerization reaction is preferably acidic. In particular, when a persulfate and a bisulfite are used in combination as a polymerization initiator, the polymerization is preferably performed under acidic conditions. By carrying out the method for producing a copolymer of the present invention under acidic conditions, an increase in the viscosity of the aqueous solution of the polymerization reaction system can be suppressed, and the copolymer can be produced satisfactorily. In addition, since the polymerization reaction can proceed under high concentration conditions, the production efficiency can be greatly increased, and the final solid content concentration can be high concentration polymerization of 40% by mass or more. A total residual monomer concentration of 15000 ppm or less can be obtained. Furthermore, the polymerizability of the polyalkylene glycol polymerizable unsaturated monomer can be improved.

  As acidic conditions, the pH of the reaction solution during polymerization is preferably 1 or more, preferably 6 or less, more preferably 5 or less, and even more preferably 3 or less. .

The copolymer obtained by the production method of the present invention can be used as it is as a main component of a detergent builder, but may be used after neutralization with an alkaline substance, if necessary. Examples of the alkaline substance include inorganic salts such as hydroxides, chlorides and carbonates of monovalent metals and divalent metals; ammonia; organic ammonium (organic amine) and the like.

  As described above, the polyalkylene glycol polymerizable unsaturated monomer of the present invention and a production method thereof, a polyalkylene glycol copolymer using the polyalkylene glycol polymerizable unsaturated monomer, a production method thereof, and the method The preferred use of the copolymer has been described, but the present invention can be implemented in variously modified, modified, and modified embodiments based on the knowledge of those skilled in the art without departing from the spirit of the present invention.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, this invention is not limited at all by these. In the following description, “part” indicates “part by mass”, and “%” indicates “mass%”.

(Synthesis of polyalkylene glycol polymerizable unsaturated monomer)
<Synthesis Example 1>
To a glass reactor having a capacity of 1000 ml equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, an ethylene oxide 50 mol adduct (hereinafter referred to as IPN50) of isoprenol, which is a polyalkylene glycol polymerizable unsaturated monomer, Abbreviated.) 302.2 g was charged, heated and dissolved in a nitrogen stream, and then heated to 150 ° C. with stirring. Next, while maintaining the temperature at 150 ° C., 40.0 g of N-vinylpyrrolidone (hereinafter abbreviated as NVP) which is a vinyl monomer and di-tert which is an organic peroxide having a bulky organic group. -2.0 g of butyl peroxide (trade name “Perbutyl D” manufactured by Nippon Oil & Fats Co., Ltd.) (hereinafter abbreviated as “PBD”) was dropped continuously and separately. The dropping time was 200 minutes for PBD and 180 minutes for NVP 20 minutes after the start of dropping of PBD. After completion of the dropwise addition, the temperature was maintained for 60 minutes to ripen the reaction. Then, after cooling to about 60 ° C., 344.2 g of pure water is added, and the polyalkylene glycol system of the present invention is formed by graft polymerization of a vinyl monomer (NVP) having a concentration of 50% to the polyalkylene glycol chain portion. A polymerizable unsaturated monomer (1) was obtained.

As a result of measuring the ¹ H-NMR spectrum (in DMSO) of the monomer (1), a signal derived from the double bond portion of IPN50 was observed.

<Synthesis Example 2>
360.0 g of IPN50 was charged into a 1000 ml glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, dissolved under heating in a nitrogen stream, and then stirred up to 150 ° C. The temperature rose. Next, while maintaining the temperature at 150 ° C., 40.0 g of NVP and 2.0 g of PBD were continuously dropped separately. The dropping time was 200 minutes for PBD and 180 minutes for NVP 20 minutes after the start of dropping of PBD. After completion of the dropwise addition, the temperature was maintained for 60 minutes to ripen the reaction. Then, after cooling to about 60 ° C., 402.0 g of pure water is added, and the polyalkylene glycol system of the present invention is formed by graft polymerization of a vinyl monomer (NVP) having a concentration of 50% to the polyalkylene glycol chain portion. A polymerizable unsaturated monomer (2) was obtained.

The ¹ H-NMR spectrum (in DMSO) of the monomer (2) is shown in FIG. In FIG. 1, a signal derived from the double bond portion of IPN50 was observed.

<Synthesis Example 3>
180.0 g of IPN50 was charged in a glass reactor having a capacity of 500 ml equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a reflux condenser, and heated and dissolved in a nitrogen stream to have a bulky organic group. 1.0 g of organic peroxide benzoyl peroxide (hereinafter abbreviated as BzPO) was added, and the temperature was raised to 90 ° C. with stirring. Next, 20.0 g of vinyl acetate (hereinafter abbreviated as VA) as a vinyl monomer was continuously dropped over 30 minutes while maintaining the temperature at 90 ° C. After completion of the dropwise addition, the temperature was maintained for 210 minutes to ripen the reaction. Then, after cooling to about 60 ° C., 201.0 g of pure water is added, and the polyalkylene glycol system of the present invention is formed by graft polymerization of a vinyl monomer (VA) having a concentration of 50% onto the polyalkylene glycol chain portion. A polymerizable unsaturated monomer (3) was obtained.

FIG. 2 shows the ¹ H-NMR spectrum (in DMSO) of the monomer (3). In FIG. 2, a signal derived from the double bond portion of IPN50 was observed.

<Synthesis Example 4>
190.0 g of IPN50 was charged into a 500 ml glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, dissolved under heating in a nitrogen stream, and then 0.5 g of BzPO was added. The temperature was raised to 90 ° C. with stirring. Next, 10.0 g of styrene (hereinafter abbreviated as St), which is a vinyl monomer, was continuously dropped over 30 minutes while maintaining the temperature at 90 ° C. After completion of the dropwise addition, the temperature was maintained for 210 minutes to ripen the reaction. Then, after cooling to about 60 ° C., 200.5 g of pure water is added, and the polyalkylene glycol system of the present invention is formed by graft polymerization of a vinyl monomer (St) having a concentration of 50% to the polyalkylene glycol chain portion. A polymerizable unsaturated monomer (4) was obtained.

FIG. 3 shows the ¹ H-NMR spectrum (in DMSO) of the monomer (4). In FIG. 3, a signal derived from the double bond portion of IPN50 was observed.

<Comparative Synthesis Example 1>
A glass reactor having a capacity of 1000 ml equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser was charged with 360.0 g of a methacrylic acid ester of methanol 25-methylene oxide adduct (hereinafter abbreviated as PGM25), After heating and dissolving in a nitrogen stream, the temperature was raised to 150 ° C. with stirring. Next, while maintaining the temperature at 150 ° C., 40.0 g of NVP and 2.0 g of PBD were continuously dropped separately. The dropping time was 200 minutes for PBD and 180 minutes for NVP 20 minutes after the start of dropping of PBD. After completion of the dropwise addition, the temperature was maintained for 60 minutes to ripen the reaction. Then, after cooling to about 60 ° C., 402.0 g of pure water is added, and a graft polymer (5) having a concentration of 50% and a vinyl monomer (NVP) graft-polymerized to the polyalkylene glycol chain portion is obtained. Obtained.

As a result of measuring the ¹ H-NMR spectrum (in DMSO) of the polymer (5), the signal derived from the double bond portion of PGM25 was completely lost.

<Comparative Synthesis Example 2>
360.0 g of IPN50 was charged into a 1000 ml glass reactor equipped with a thermometer, a stirrer, a nitrogen inlet tube, and a reflux condenser, dissolved under heating in a nitrogen stream, and then stirred up to 150 ° C. The temperature rose. Next, 40.0 g of acrylic acid (hereinafter abbreviated as AA) and 2.0 g of PBD were continuously dropped dropwise while maintaining the temperature at 150 ° C. The dropping time was 200 minutes for PBD and 180 minutes for NVP 20 minutes after the start of dropping of PBD. After completion of the dropwise addition, the temperature was maintained for 60 minutes to ripen the reaction. Then, after cooling to about 60 ° C., 402.0 g of pure water was added, and a graft polymer (6) having a concentration of 50% and AA graft-polymerized to the polyalkylene glycol chain portion was obtained.

As a result of measuring the ¹ H-NMR spectrum (in DMSO) of the polymer (6), the signal derived from the double bond portion of IPN50 was completely lost.

(Example 1)
A 2.5 L SUS316 separable flask equipped with a reflux condenser and a stirrer was charged with 188.0 g of pure water and 0.0233 g of molle salt, heated to 90 ° C. with stirring, and then subjected to polyalkylene glycol polymerization. 288.0 g of a 50% aqueous solution of the unsaturated unsaturated monomer (1), 270.0 g of an 80% aqueous acrylic acid solution (hereinafter abbreviated as 80% AA) as another monomer, an aqueous 48% sodium hydroxide solution (hereinafter referred to as 80% AA) 48) NaOH 12.5 g, 15% sodium persulfate aqueous solution (hereinafter abbreviated as 15% NaPS) 81.5 g, 35% sodium hydrogen sulfite aqueous solution (hereinafter abbreviated as 35% SBS) 78. 6 g was dripped from another dripping port. Each dropping time is 120 minutes for the polyalkylene glycol polymerizable unsaturated monomer (1), 180 minutes for 80% AA, 180 minutes for 48% NaOH, 210 minutes for 15% NaPS, and 35% SBS. 180 minutes. The start of dropping was all simultaneous. The temperature was maintained at 90 ° C. until the end of dropping 80% AA. Further, the same temperature was maintained for 30 minutes after completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 187.5 g of 48% NaOH. In this way, the polyalkylene glycol copolymer of the present invention obtained by copolymerizing the polymerizable unsaturated monomer (1) having a solid content concentration of 45% by mass and a final neutralization degree of 80 mol% and AA ( 1) was obtained.

  The resulting polyalkylene glycol copolymer (1) was measured for weight average molecular weight (Mw) and anti-recontamination ability. The results are shown in Table 1.

(Example 2)
A 2.5 L SUS316 separable flask equipped with a reflux condenser and a stirrer was charged with 188.0 g of pure water and 0.0235 g of Mole salt, heated to 90 ° C. with stirring, and then subjected to polyalkylene glycol polymerization. 288.0 g of a 50% aqueous solution of the unsaturated unsaturated monomer (2), 270.0 g of 80% AA, 12.5 g of 48% NaOH, 81.5 g of 15% NaPS, and 87.3 g of 35% SBS were added dropwise from separate dropping ports. Each dropping time is 120 minutes for polyalkylene glycol polymerizable unsaturated monomer (2), 180 minutes for 80% AA, 180 minutes for 48% NaOH, 210 minutes for 15% NaPS, and 35% SBS. 180 minutes. The start of dropping was all simultaneous. The temperature was maintained at 90 ° C. until the end of dropping 80% AA. Further, the same temperature was maintained for 30 minutes after completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 187.5 g of 48% NaOH. Thus, the polyalkylene glycol copolymer of the present invention obtained by copolymerizing the polymerizable unsaturated monomer (2) and AA having a solid content concentration of 45 mass% and a final neutralization degree of 80 mol% ( 2) was obtained.

  The resulting polyalkylene glycol copolymer (2) was measured for weight average molecular weight (Mw) and anti-recontamination ability. The results are shown in Table 1.

(Example 3)
A 2.5 L SUS316 separable flask equipped with a reflux condenser and a stirrer was charged with 188.0 g of pure water and 0.0233 g of molle salt, heated to 90 ° C. with stirring, and then subjected to polyalkylene glycol polymerization. 288.0 g of a 50% aqueous solution of the unsaturated unsaturated monomer (3), 270.0 g of 80% AA, 12.5 g of 48% NaOH, 81.5 g of 15% NaPS, and 78.6 g of 35% SBS were added dropwise from separate dropping ports. Each dropping time is 120 minutes for polyalkylene glycol polymerizable unsaturated monomer (3), 180 minutes for 80% AA, 180 minutes for 48% NaOH, 210 minutes for 15% NaPS, and 35% SBS. 180 minutes. The start of dropping was all simultaneous. The temperature was maintained at 90 ° C. until the end of dropping 80% AA. Further, the same temperature was maintained for 30 minutes after completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 187.5 g of 48% NaOH. Thus, the polyalkylene glycol copolymer of the present invention obtained by copolymerizing the polymerizable unsaturated monomer (3) and AA having a solid content concentration of 45 mass% and a final neutralization degree of 80 mol% ( 3) was obtained.

  The resulting polyalkylene glycol copolymer (3) was measured for weight average molecular weight (Mw) and anti-recontamination ability. The results are shown in Table 1.

Example 4
A 2.5 L SUS316 separable flask equipped with a reflux condenser and a stirrer was charged with 188.0 g of pure water and 0.0233 g of molle salt, heated to 90 ° C. with stirring, and then subjected to polyalkylene glycol polymerization. 288.0 g of a 50% aqueous solution of the polyunsaturated monomer (4), 270.0 g of 80% AA, 12.5 g of 48% NaOH, 81.6 g of 15% NaPS, and 78.7 g of 35% SBS were added dropwise from separate dripping ports. Each dropping time was 120 minutes for polyalkylene glycol polymerizable unsaturated monomer (4), 180 minutes for 80% AA, 180 minutes for 48% NaOH, 210 minutes for 15% NaPS, and 35% SBS. 180 minutes. The start of dropping was all simultaneous. The temperature was maintained at 90 ° C. until the end of dropping 80% AA. Further, the same temperature was maintained for 30 minutes after completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 187.5 g of 48% NaOH. Thus, the polyalkylene glycol copolymer of the present invention obtained by copolymerizing the polymerizable unsaturated monomer (4) having a solid content concentration of 45% by mass and a final neutralization degree of 80 mol% and AA ( 4) was obtained.

  The resulting polyalkylene glycol copolymer (4) was measured for weight average molecular weight (Mw) and anti-recontamination ability. The results are shown in Table 1.

(Comparative Example 1)
A 2.5 L SUS316 separable flask equipped with a reflux condenser and a stirrer was charged with 235.0 g of pure water and 0.0240 g of Mole salt, heated to 90 ° C. with stirring, and then a 60% aqueous solution of IPN50. 240.0 g, 80% AA 270.0 g, 15% NaPS 81.7 g, and 35% SBS 78.8 g were added dropwise from separate dropping ports. The dropping time was 60 minutes for IPN50, 180 minutes for 80% AA, 210 minutes for 15% NaPS, and 180 minutes for 35% SBS. The start of dropping was all simultaneous. The temperature was maintained at 90 ° C. until the end of dropping 80% AA. Further, the same temperature was maintained for 30 minutes after completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 200.0 g of 48% NaOH. In this way, a comparative copolymer (1) having a solid content concentration of 45 mass% and a final neutralization degree of 80 mol% and having no vinyl monomer introduced therein was obtained.

  The comparative copolymer (1) obtained was measured for weight average molecular weight (Mw) and ability to prevent recontamination. The results are shown in Table 1.

(Comparative Example 2)
A 2.5 L SUS316 separable flask equipped with a reflux condenser and a stirrer was charged with 188.0 g of pure water and 0.0240 g of Mole salt, heated to 90 ° C. with stirring, and then a 50% aqueous solution of IPN50. 259.2 g, NVP 14.4 g, 80% AA 270.0 g, 48% NaOH 12.5 g, 15% NaPS 85.0 g, and 35% SBS 91.0 g were added dropwise from separate dropping ports. The dropping times were 120 minutes for IPN 50, 120 minutes for NVP, 180 minutes for 80% AA, 180 minutes for 48% NaOH, 210 minutes for 15% NaPS, and 180 minutes for 35% SBS. The start of dropping was all simultaneous. The temperature was maintained at 90 ° C. until the end of dropping 80% AA. Further, the same temperature was maintained for 30 minutes after completion of dropping of 80% AA, and aging was performed to complete the polymerization. After completion of the polymerization, the reaction solution was allowed to cool and then neutralized by adding 187.5 g of 48% NaOH. In this way, vinyl monomer (NVP) having a solid content concentration of 45 mass% and a final neutralization degree of 80 mol% is not introduced into the alkylene glycol chain and copolymerized with the polymerizable unsaturated double bond of IPN50. A comparative copolymer (2) was obtained.

  The comparative copolymer (2) obtained was measured for weight average molecular weight (Mw) and recontamination prevention ability. The results are shown in Table 1.

(Comparative Example 3)
By mixing the comparative copolymer (1) obtained in Comparative Example 1 and polyvinylpyrrolidone K25 (hereinafter abbreviated as PVP) (manufactured by Wako Pure Chemical Industries, Ltd.) at a mass ratio of 95: 5, A comparative copolymer composed of a vinyl monomer polymer (PVP) that is not introduced into the alkylene glycol chain and does not copolymerize with the polymerizable unsaturated double bond of IPN50. Combined (3) was obtained.

  The ability to prevent recontamination of the obtained comparative copolymer (3) was measured. The results are shown in Table 1.

  From the results of Synthesis Examples 1 to 4 and Comparative Synthesis Example 1, when the organic group containing a polymerizable unsaturated double bond added to the polyalkylene glycol is an organic group represented by the general formula (1), It was found that the graft polymerization of the vinyl monomer and the polyalkylene glycol chain proceeds preferentially while maintaining the polymerizable unsaturated double bond contained in the organic group represented by the general formula (1).

  Further, from the results of Synthesis Examples 1 to 4 and Comparative Synthesis Example 2, the organic group containing a polymerizable unsaturated double bond added to the polyalkylene glycol is an organic group represented by the general formula (1). However, it was found that unless a vinyl monomer was appropriately selected, the vinyl monomer would also polymerize with a polymerizable unsaturated double bond contained in the organic group represented by the general formula (1).

  From the results of Examples 1 to 4 and Comparative Examples 1 to 3, the copolymer according to the present invention (Examples 1 to 4) in which a vinyl monomer was introduced into the polyalkylene glycol chain portion by graft polymerization was as follows. , A copolymer in which no vinyl monomer is introduced (Comparative Example 1), or a copolymer in which a vinyl monomer is introduced into the copolymer but is not introduced into the polyalkylene glycol chain portion by graft polymerization (Comparative Example 2) or compared to a copolymer (Comparative Example 3) comprising a polymer composed solely of a vinyl monomer without the vinyl monomer being introduced into the copolymer It was found that the ability to prevent recontamination was excellent.

  The polyalkylene glycol copolymer obtained in the present invention is suitably used for at least one selected from the group consisting of detergent builders, water treatment agents, and pigment dispersants.

¹ shows a ¹ H-NMR spectrum of a polyalkylene glycol-based polymerizable unsaturated monomer (2). ¹ shows a ¹ H-NMR spectrum of a polyalkylene glycol polymerizable unsaturated monomer (3). ¹ shows a ¹ H-NMR spectrum of a polyalkylene glycol polymerizable unsaturated monomer (4).

Claims (13)

  A polyalkylene glycol-based polymerizable unsaturated monomer obtained by graft polymerization of a vinyl monomer on a polyalkylene glycol chain portion of a polyalkylene glycol-based compound having an organic group containing a polymerizable unsaturated double bond Mass. The organic group containing the polymerizable unsaturated double bond is represented by the following general formula (1):

The polyalkylene glycol-based polymerizable unsaturated monomer according to claim 1, wherein R ¹ represents a hydrogen atom or a methyl group. N is an integer of 0 to 3.   The polyalkylene glycol polymerizable unsaturated monomer according to claim 1, wherein the vinyl monomer is at least one selected from the group consisting of N-vinyl pyrrolidone, vinyl acetate, and styrene. The following general formula (1)

(Wherein R ¹ represents a hydrogen atom or a methyl group, n is an integer of 0 to 3), and the following general formula (2)

(Where X is

An organic group represented by m is an integer of 1-50. A polyalkylene glycol-based polymerizable unsaturated monomer characterized by having at least a structural unit represented by:   A polyalkylene glycol-based copolymer comprising a structural unit derived from the polyalkylene glycol-based polymerizable unsaturated monomer according to claim 1.   A builder composition for detergent, comprising the polyalkylene glycol copolymer according to claim 5.   A water treatment agent composition comprising the polyalkylene glycol copolymer according to claim 5.   A pigment dispersant composition comprising the polyalkylene glycol copolymer according to claim 5. Adding an alkylene oxide to a compound having a polymerizable unsaturated double bond to obtain a polyalkylene glycol compound having an organic group containing a polymerizable unsaturated double bond;
And a step of graft-polymerizing a vinyl monomer on the polyalkylene glycol chain portion. A method for producing a polyalkylene glycol-based polymerizable unsaturated monomer.   The process of graft-polymerizing a vinyl monomer on the polyalkylene glycol chain part is performed at 80 to 180 ° C using an organic peroxide having a bulky organic group as a polymerization initiator. A method for producing a polyalkylene glycol-based polymerizable unsaturated monomer. The organic group containing the polymerizable unsaturated double bond is represented by the following general formula (1):

(In the formula, R ¹ represents a hydrogen atom or a methyl group. N is an integer of 0 to 3) The polyalkylene glycol-based polymerizable unsaturated monomer according to claim 9 or 10 represented by Production method.   The polyalkylene glycol-based polymerizable compound according to any one of claims 9 to 11, wherein the compound having a polymerizable unsaturated double bond is at least one selected from the group consisting of isoprenol, allyl alcohol, and methallyl alcohol. A method for producing a saturated monomer.   A method for producing a polyalkylene glycol copolymer, comprising using the polyalkylene glycol polymerizable unsaturated monomer obtained by the production method according to claim 9.

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