WO2007116946A1 - Copolymere de polyalkylene glycol, monomere de polyalkylene glycol et procede pour les produire - Google Patents

Copolymere de polyalkylene glycol, monomere de polyalkylene glycol et procede pour les produire Download PDF

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WO2007116946A1
WO2007116946A1 PCT/JP2007/057691 JP2007057691W WO2007116946A1 WO 2007116946 A1 WO2007116946 A1 WO 2007116946A1 JP 2007057691 W JP2007057691 W JP 2007057691W WO 2007116946 A1 WO2007116946 A1 WO 2007116946A1
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polyalkylene glycol
monomer
copolymer
mentioned
group
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PCT/JP2007/057691
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English (en)
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Atsuro Yoneda
Masato Nakano
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Nippon Shokubai Co., Ltd.
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Publication of WO2007116946A1 publication Critical patent/WO2007116946A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/062—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2603—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen
    • C08G65/2606—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups
    • C08G65/2609—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing oxygen containing hydroxyl groups containing aliphatic hydroxyl groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/26—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds
    • C08G65/2618—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen
    • C08G65/2621—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups
    • C08G65/2624—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring from cyclic ethers and other compounds the other compounds containing nitrogen containing amine groups containing aliphatic amine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/023—Water in cooling circuits
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2303/00—Specific treatment goals
    • C02F2303/08—Corrosion inhibition
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/04—Surfactants, used as part of a formulation or alone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/05—Polymer mixtures characterised by other features containing polymer components which can react with one another

Definitions

  • the present invention relates to polyalkylene glycol copolymers. More specifically, the present invention relates to: a polyalkylene glycol copolymer which is preferably used in liquid or powder detergent builders, water treatment agents, fiber treatment agents, and the like, and exhibits high detergency when used as a detergent builder, for example; a monomer which can be used as a raw material of such a copolymer; a production method thereof; and an application thereof.
  • Polyalkylene glycol copolymers exhibit various characteristics attributed to apart exhibitingwater solubility, such as an oxyalkylene group, and are useful as a high molecular detergent builder, for example.
  • the polyalkylene glycol copolymers need to respond to various soils such as hydrophilic or hydrophobic soils if the copolymers act as a detergent builder .
  • a function of dispersing such soil components in water and keeping the dispersion state, or a function of being excellent in compatibility with a liquid detergent to which the copolymers are applied, is needed for such polyalkylene glycol copolymers.
  • the polyalkylene glycol copolymers play an important role as a component in detergents, together with a bleaching agent .
  • a bleaching agent In order to improve the functions and performances and provide new functions for the copolymers, research and development have been actively carried out.
  • the polyalkylene glycol copolymers have been brought to attention as a component which can be used as treatment agents such as a water treatment agent and a fiber treatment agent in various industrial fields in addition to the detergent builder application.
  • Japanese Kokai Publication No. Sho-59-25839 discloses a copolymer obtained using an allyl ether monomer having two polyalkylene glycol chains, an unsaturated carboxylic acid monomer, and a dibasic acidmonomer, for example.
  • This copolymer is useful as an inorganic pigment dispersant.
  • Such a copolymer can be obtainedby copolymerizing suchmonomers, thereby forming a polyalkylene glycol chain in an active hydrogen-containing monomer such as a hydroxyl group.
  • such a copolymer has a structure in which one monomer unit has two polyalkylene glycol chains because the monomer in which the polyalkylene glycol chain is to be formed generally has only two active hydrogens.
  • Such a copolymer is thought to exhibit useful characteristics attributed to such a structure, as an inorganic pigment dispersant.
  • Japanese Kokai Publication No. 2005-139430 discloses a copolymer obtained by copolymerizing a polyalkyleneimine unsaturated monomer and other monomers, for example.
  • Such a copolymer has a structure in which many polyalkylene glycol chains are bonded to the polyalkyleneimine, and the polyalkylene glycol chain has a double bond derived from the allyl glycidyl ether at the end of the chain.
  • one monomer unit of the copolymer has many polyalkylene glycol chains, and due to such a structure, the copolymer can also respond to hydrophobic soils.
  • such a structure makes it difficult to control a ratio of the unsaturated carboxylic acid monomer unit.
  • the ratio of the unsaturated carboxylic acid monomer unit is increased, a cross-linking structure is formed and thereby the molecular weight is increased, generally. It is also important for performance balance of the polyalkylene glycol copolymers to adjust a ratio between the polyalkylene glycol chain and the unsaturated carboxylic acid monomer unit. This disclosed technology is useful in that the polyalkylene glycol chain is increased, but needs to be improved in order to improve preparation or stability of the copolymer, in the cases where the ratio of the unsaturated carboxylic acidmonomer unit is adjusted for improvement in performances and characteristics of the copolymer. Japanese Kohyo Publication No .
  • Hei-11-505867 discloses an aqueous detergent slurry composition containing a hydrophilic copolymer produced by copolymerizing an unsaturated hydrophilic monomer such as acrylic acid with an oxyalkylated monomer having one polyalkylene glycol chain, for example.
  • a copolymer of an allyl alcohol-ethylene oxide adduct with acrylic acid is disclosed as such a hydrophilic copolymer.
  • one monomer unit has only one polyalkylene glycol chain, and therefore the polyalkylene glycol chain exhibits the function inefficiently.
  • the present invention has been made in view of the above-mentioned state of the art.
  • the present invention has an object to provide a polyalkylene glycol copolymer which is: useful in applications such as a detergent builder application for which high detergency is required; capable of responding to various soils such as hydrophilic or hydrophobic soils in such applications; excellent in characteristics such as anti-soil redeposition capability; and can be preferably used in various applications in which polyalkylene glycol copolymers are used.
  • the present invention also has an object to provide amonomeruseful as arawmaterialof sucha copolymer, aproduction method thereof, and an application thereof.
  • apolyalkylene glycol copolymer containing a constitutional unit (a) derived from a polyalkylene glycol chain-containing unsaturated monomer (A) and a constitutional unit (b) derived ' from an unsaturated carboxylic acid monomer (B) has a polyalkylene glycol chain and a (meth) acrylic part, and the polyalkylene glycol chain has hydrophobic characteristics in comparison to the (meth) acrylic part because ion dissociation hardly occurs in the chain, although both of the polyalkylene glycol chain and the (meth) acrylic part have hydrophilic characteristics, and therefore such a copolymer can interact with hydrophobic components (soils and the like) , and also exhibit characteristics attributed to the (meth) acrylic part.
  • a copolymer has a structure in which one monomer unit has at least three polyalkylene glycol chains, and has at least one polyalkylene glycol chain-branching structure between an unsaturated bond and a nitrogen atom.
  • the copolymer has a steric structure due to the branch structure even in the same polyalkylene glycol chain amount, and the structure has a positive effect on the performances and characteristics of the polyalkylene glycol copolymer. If the copolymer has at least one polyalkylene glycol chain-branching 7691
  • the copolymer has not a conventional copolymer structure in which one part having a double bond is bonded to an end of the polyalkylene glycol chain but a structure in which a plurality of polyalkylene glycol chains are bonded to one part having a double bond.
  • the preparation or stability of the copolymer can be improved if the ratio of the unsaturated carboxylic acid monomer unit, particularly the (meth) acrylic ratio, is adjusted for improvement in performances and characteristics of the copolymer.
  • the inventors further found that, in preparation of such a polyalkylene glycol copolymer, a monomer having a structure in which at least three polyalkylene glycol chains are contained and at least one polyalkylene glycol chain-branching structure is contained between an unsaturated bond and a nitrogen atom is a novel and such a monomer is useful as a monomer having a plurality of polyalkylene glycol chains.
  • a monomer having a structure in which at least three polyalkylene glycol chains are contained and at least one polyalkylene glycol chain-branching structure is contained between an unsaturated bond and a nitrogen atom is a novel and such a monomer is useful as a monomer having a plurality of polyalkylene glycol chains.
  • the present invention is a polyalkylene glycol copolymer comprising a constitutional unit (a) derived from a polyalkylene glycol chain-containing unsaturated monomer (A) and a constitutional unit (b) derived from an unsaturated carboxylic acid monomer (B) , wherein the polyalkylene glycol chain-containingunsaturatedmonomer (A) contains at least three polyalkylene glycol chains and, between an unsaturated bond and anitrogen atom, at leastonepolyalkylene glycol chain-branching structure .
  • the present invention is also a production method of the polyalkylene glycol copolymer, comprising a step of copolymerizing a polyalkylene glycol chain-containing unsaturated monomer (A) with an unsaturated carboxylic acid monomer (B) .
  • the present invention is also apolyalkylene glycolmonomer represented by the following formula (1) : 057691
  • R 1 , R 2 , and R 3 being the same or different and each representing a hydrogen atom or a methyl group; R 4 , R 5 , and R 6 being the same or different and each representing an alkylene group containing 1 to 4 carbon atoms; X representing amethylene group or a carbonyl group; 1, m, and nbeing an average molar number of addition of oxyalkylene; and 1+m+n being 3 to 300) .
  • the present invention is also a detergent builder, a water treatment agent, or a fiber treatment agent, comprising the polyalkylene glycol copolymer.
  • Thepolyalkylene glycol copolymer of thepresent invention essentially contains: a polyalkylene glycol chain-containing constitutional unit (a) ; 'and a constitutional unit (b) having a carboxylic acid group or a salt thereof, and, if necessary, contains another constitutional unit.
  • the above-mentionedpolyalkylene glycol chain-containing constitutional unit (a) has a structure derived from the polyalkylene glycol chain-containing unsaturated monomer (A) .
  • Such a constitutional unit (a) is preferably formed by polymerization of the polyalkylene glycol chain-containing unsaturated monomer (A) , but may be formed after or during polymerization of an unsaturatedmonomer having no polyalkylene glycol chain.
  • the above-mentionedpolyalkylene glycol chain-containing unsaturated monomer (A) has at least three polyalkylene glycol chains, and at least one polyalkylene glycol chain-branching structure between an unsaturated bond and a nitrogen atom.
  • polyalkylene glycol chain-containing unsaturated monomer (A) has at least three polyalkylene glycol chains, and at least one polyalkylene glycol chain-branching structure between an unsaturated bond and a nitrogen atom
  • the above-mentioned polyalkylene glycol chain-containing monomer (A) has a structure in which at least one of three or more polyalkylene glycol chains is bonded to a carbon atom and the like between an unsaturated bond and a nitrogen atom in the unsaturated monomer (A) , and the other polyalkylene glycol chains arenotbondedbetweentheunsaturated bond and the nitrogen atom in the unsaturated monomer (A) but bonded to the nitrogen atom through the carbon atom and the like .
  • Preferable embodiments of the unsaturated monomer (A) include an embodiment in which if a monomer containing: an unsaturated bond; a nitrogen atom-containing group; and one or more active hydrogen-containing functional groups, such as hydroxyl group, amino group, and imino group, thereby having a total of three or more active hydrogens, and having a structure in which the active hydrogen-containing functional group is bondedto a carbon atom between an unsaturated bond and a nitrogen atom, is used as a raw material, the monomer (A) has a structure in which an oxyalkylene group is added to the hydroxyl group and the like of the monomer.
  • active hydrogen-containing functional groups such as hydroxyl group, amino group, and imino group
  • the ratio of the polyalkylene glycol chain can be increased because one monomer contains at least three polyalkylene glycol chains, which is important for 057691
  • the monomer contains the at least one polyalkylene glycol chains as a branching structure, and therefore the copolymer has not a conventional copolymer structure in which one part having a double bond is bonded to an end of the polyalkylene glycol chain, but a structure in which a plurality of polyalkylene glycol chains are bonded to one part having a double bond.
  • the preparation or stability of the copolymer can be improved if the ratio of the unsaturated carboxylic acid monomer unit, particularly the (meth) acrylic ratio, is adjusted.
  • one (as an average value) unsaturated group is contained per the above-mentioned polyalkylene glycol chain-containing unsaturated monomer (A).
  • a copolymerization reaction using such monomers can suppress formation of a cross-linking structure, and therefore form a copolymer not causing gelling or reduction in water-solubility even if the ratio by weight of the above-mentioned unsaturated carboxylic acid monomer (B) in the copolymerization is increased.
  • the above-mentioned polyalkylene glycol chain is generally formed as a chain containing two or more oxyalkylene groups, but may be formed of one oxyalkylene group.
  • the chain formed of two or more oxyalkylene groups is formed of one or two or more different oxyalkylene groups. If the chain is formed of two or more different oxyalkylene groups, the two or more different oxyalkylene groups may be added randomly, alternatively, or in block.
  • the above-mentioned at least three polyalkylene glycol chains contained in the above-mentioned unsaturated monomer (A) may be the same or different.
  • the average molar number of addition of the oxyalkylene group in the above-mentioned unsaturated monomer (A) is preferably 1 to 100. If it is smaller than 1, the copolymer may insufficiently respond to hydrophobic soils and the like.
  • the average molar number of addition of the oxyalkylene group is more preferably 5 or more and still more preferably 25 or more, and more preferably 80 or less and still more preferably 60 or less .
  • the average molar number of addition means an average value of amolar number of the oxyalkylene groups adding in one r ⁇ ol of the polyalkylene glycol chain contained in the unsaturated monomer (A) .
  • the above-mentioned polyalkylene glycol chain mainly contains an oxyethylene group.
  • the term "mainly” means that if two or more different oxyalkylene groups exist in the above-mentioned unsaturated monomer (A) , the oxyethylene group occupies the majority of the present number of all the oxyalkylene groups. As a result, the hydrophilicity of the polyalkylene glycol copolymer is enhanced and the functional effects can be sufficiently exhibited.
  • the oxyethylene group preferably accounts for 50 to 100% by mol. If it accounts for less than 50% by mol, the hydrophilicity of the copolymer of the present invention may be reduced.
  • the oxyethylene group more preferably accounts for 60% by mol or more, still more preferably 70% by mol or more, and particularly preferably 80% by mol or more, and most preferably 90% bymol or more.
  • the polyalkylene glycol copolymer, the polyalkylene glycol monomer, the polyalkylene glycol chain of the present invention are referred to as polyethylene glycol (PEG) copolymer, polyethylene glycol (PEG) monomer, and polyethylene glycol (PEG) chain, respectively.
  • polyalkylene glycol chain-containing unsaturated monomer (A) is represented by the following formula (1) :
  • R 1 , R 2 , and R 3 being the same or different and each representing a hydrogen atom or a methyl group;
  • R 4 , R 5 , and R 6 being the same or different and each representing an alkylene group containing 1 to 4 carbon atoms;
  • X representing a methylene group or a carbonyl group; 1, m, and n being an average molar number of addition of oxyalkylene; and 1+m+n being 3 to 300
  • X in the above formula (1) is a methylene group. If X is a methylene group, hydrolysis resistance is improved. Therefore, the copolymer is extremely hardly hydrolyzed and can exhibit the copolymer' s original performances in the cases where the copolymer is stored as a copolymer aqueous solution, or added in liquid detergents or products in aqueous solution form such as a water treatment solution, or added in washing water, a cooling water system, a boiler water system, a fiber treatment water, and the like. It is more preferable that the above-mentioned polyalkylene glycol chain-containing unsaturated monomer (A) is represented by the following formula (2) :
  • the polyalkylene glycol copolymer of the present invention can sufficiently exhibit the hydrophilicity and the adaptability to hydrophobic soils, and thereby can more sufficiently exhibit the functional effect of improving the adaptability to various applications.
  • polyalkylene glycol chain-containing unsaturated monomer (A) in which 1 is 5, m and n are each 6 is represented by the following formula (3) .
  • the constitutional unit (b) derived from the unsaturated carboxylic acid monomer (B) of the present invention has a structure derived from the unsaturated carboxylic acid monomer (B) .
  • Examples of the unsaturated carboxylic acid monomer (B) of thepresent invention include unsaturatedmonocarboxylic acid monomers and unsaturated dicarboxylic acid monomers. It is preferable that the unsaturated carboxylic acid monomer (B) essentially contains anunsaturatedmonocarboxylic acidmonomer . It is more preferable that the monomer (B) essentially contains (meth) acrylic acid.
  • the polyalkylene glycol copolymer of the present invention is provided with sufficient hydrophilicity and can exhibit the functional attributed to the polyalkylene glycol chain, that is, the functional effect of preventing redeposition and the like, attributed to the interaction to hydrophobic soils.
  • the above-mentioned unsaturated carboxylic acid monomer (B) is a monomer containing a polymerizable unsaturated group and a carboxylic acid group. Unsaturated monocarboxylic acid monomers, unsaturated dicarboxylic acid monomers, and the like, are preferable as the above-mentioned unsaturated carboxylic acid monomer (B) .
  • the above-mentioned unsaturated monocarboxylic acid monomer is a monomer containing one unsaturated group and one carboxylic acid group in the molecule, and a compound represented by the following formula (4) is mentioned as a preferable embodiment of such a monomer.
  • R 7 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) .
  • Preferred examples of the metal atom in M of the above-mentioned formula (4) 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; and trivalent metal atoms such as aluminum and iron.
  • Preferredexamples of the organicamine group (protonatedorganic amine) include alkanolamines such as ethanolamine, diethanolamine and triethanolamine, and triethylamine.
  • M may be ammonium.
  • Preferred examples of such an unsaturated monocarboxylic acid monomer include acrylic acid, methacrylic acid, crotonic acid; monovalentmetal salts thereof, divalentmetal salts thereof, ammoniumsalts thereof; andorganic amine salts thereof.
  • the copolymer is used as a detergent builder, (meth) acrylic acid, monovalent metal salts thereof, divalent metal salts thereof, ammonium salts thereof, organic amine salts thereof, and the like are preferably used as the unsaturated carboxylic acid monomer (B) in view of improvement in dispersion performances.
  • the above-mentioned unsaturated dicarboxylic acid monomer is a monomer containing one unsaturated group and two carboxylic acid groups in the molecule.
  • Preferred examples of such a monomer include maleic acid, itaconic acid, citraconic acid, fumaric acid, monovalent metal salts thereof, divalent metal salts thereof, ammonium salts thereof, organic ammonium salts thereof (organic amine salts thereof) , and anhydrides thereof.
  • unsaturated carboxylic acid monomer (B) in addition to the above compounds, preferably used may be half esters of unsaturated dicarboxylic acid monomers with alcohols containing 1 to 22 carbon atoms, half amides of unsaturated dicarboxylic acids with amines containing 1 to 22 carbon atoms, half esters of unsaturated dicarboxylic acid monomers with glycols containing 2 to 4 carbon atoms, and half amides of maleamide acid with glycols containing 2 to 4 carbon atoms .
  • the above-mentioned polyalkylene glycol copolymer may contain another constitutional unit.
  • the another constitutional unit has a structure derived fromanothermonomer .
  • the another constitutional unit is preferably formed by polymerization of the another monomer, but may be formed by a reaction other than the polymerization reaction, after or during the polymerization of the unsaturated monomer. If the polyalkylene glycol copolymer contains another constitutional unit, the another constitutional unit may be one or two or more species.
  • styrene monomers such as styrene and chlorostyrene
  • hydroxyl group-containing unsaturated hydrocarbons such as
  • Diene compounds such as 1, 3-butadiene and isoprene; (meth) acrylic esters such as methyl (meth) acrylate, butyl (meth) acrylate, lauryl (meth) acrylate, methoxyethyl (meth) acrylate; ⁇ -olefins such as decene and isobutylene; alkyl vinyl ethers such as ethyl vinyl ether; vinyl esters such as vinyl acetate; and allyl esters such as allyl acetate.
  • Difunctional (meth) acrylates such as hexanediol di (meth) acrylate; unsaturated sulfonic acids such as
  • Unsaturated amide compounds such as (meth) acrylamide, (meth) acryl alkylamide, and dimethylaminopropyl
  • (meth) acrylamide (meth) acrylamide; allyl compounds such as allyl alcohol; unsaturated amino compounds such as dimethylaminoethyl (meth) acrylate; vinyl ethers or allyl ethers such as methoxy polyethylene glycol monovinyl ether, polyethylene glycol monovinyl ether, methoxy polyethylene glycol mono (meth) allyl ether, and polyethylene glycol mono (meth) allyl ether; nitrile monomers such as (meth) acrylonitrile; phosphorus-containing monomers such as (meth) acrylamide methane phosphonic acid and 2- (meth) acrylamide-2-methylpropane phosphonic acid.
  • the present invention is also a production method of the 91
  • polyalkylene glycol copolymer comprising a step of copolymerizing the above-mentioned polyalkylene glycol chain-containing unsaturated monomer (A) with the above-mentioned unsaturated carboxylic acid monomer (B) .
  • the utility of the production method of the present invention is that the polyalkylene glycol copolymer of the present invention, which is excellent in basic performances such as anti-soil redeposition capability, can be produced with efficiency.
  • the ratio by weight of each monomer forming the polyalkylene glycol copolymer of the present invention it is preferable that the polyalkylene glycol chain-containing unsaturated monomer (A) accounts for 1 to 99% by weight and the unsaturated carboxylic acid monomer (B) accounts for 99 to 1% by weight. If the ratio by weight of these monomers is out of the above-mentioned range, the copolymer can not exhibit a function attributed to a repeating unit formed by each monomer effectively, which fails to exhibit the functional effects of the present invention sufficiently.
  • the polyalkylene glycol chain-containing unsaturated monomer (A) accounts for 5 to 95% by weight and the unsaturated carboxylic acid monomer (B) accounts for 95 to 5% by weight. It is particularly preferable that the polyalkylene glycol chain-containing unsaturated monomer (A) accounts for 20 to 50% by weight and the unsaturated carboxylic acid monomer (B) accounts for 80 to 50% by weight.
  • the ratio by weight of the polyalkylene glycol chain-containing unsaturated monomer (A) and the unsaturated carboxylic acid monomer (B) is represented by ⁇ % by weight" when the total weight amount of the polyalkylene glycol chain-containing unsaturated monomer (A) and the unsaturated carboxylic acid monomer (B) is defined as 100% by weight.
  • the above-mentioned polymerization may be performed by amethodsuchas solutionpolymerization, andbulkpolymerization, and the polymerization method is not especially limited.
  • the structure, the species, and the like of the above-mentioned polyalkylene glycol chain-containing unsaturatedmonomer (A) , the unsaturated carboxylic acidmonomer (B) , andanothermonomerwhich canbe used in the copolymerization are as mentioned above.
  • the above-mentionedpolyalkylene glycol chain-containing unsaturatedmonomer (A) is formed by adding an oxyalkylene group to an unsaturated compound, for example, by reacting an alkylene oxide with an active hydrogen atom-containing functional group such as a hydroxyl group, contained in an unsaturated compound.
  • the above-mentioned unsaturated compound is a monomer containing: an unsaturated bond; a nitrogen-containing group; and one or more active hydrogen-containing functional groups, such as hydroxyl group, amino group, and imino group, thereby having a total of three or more active hydrogens, and having a structure in which at least one active hydrogen-containing functional group is bonded to a carbon atom and the like between the unsaturated bond and the nitrogen atom.
  • active hydrogen-containing functional groups such as hydroxyl group, amino group, and imino group
  • R 8 , R 9 , and R 10 being the same or different and each representing a hydrogen atom or a methyl group; R 11 and R 12 being the same or different and each representing a hydroxyl 91
  • the compound of the above formula (5) is produced by adding an alkanolamine to an epoxy compound.
  • the epoxy compound include (meth) allyl glycidyl ether and glycidyl (meth) acrylate.
  • Preferred examples of the alkanolamine include diethanolamine, and di-2-propanolamine.
  • the above-mentioned unsaturated compound obtained by adding diethanolamine to allyl glycidyl ether is represented by the following formula (6) :
  • the step is performed using at least one initiator selected from the group consisting of sulfurous acid (sulfite), hydrogen sulfite, and hydrogen peroxide.
  • an initiator selected from the group consisting of sulfurous acid (sulfite), hydrogen sulfite, and hydrogen peroxide.
  • Salts of metal atoms, ammonium, or organic ammoniums are preferable as the above-mentioned sulfite.
  • Preferred examples of the above-mentioned 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.
  • Preferred examples of the organic ammoniums (organic amines) include alkanolamines such as ethanolamine, diethanolamine and triethanolamine, and triethylamine.
  • the sulfite may be an ammonium salt. Among them, sodium salt is preferable.
  • the use amount of the initiator in the present invention is preferably 1 to 20 g relative to 1 mol of the monomer, and more preferably 2 to 15 g, and still more preferably 3 to 10 g.
  • compounds used in copolymerization methods as in the present invention may be used singly or in combination as the above-mentioned initiator.
  • persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate
  • pyrosulfites pyrosulfites
  • azo compounds such as 2, 2' -azobis (2-aminodipropane) hydrochloride
  • initiators which can be used in copolymerizationmethods as in the present invention maybe used, other than the above-mentioned sulfurous acid (sulfite) , hydrogen sulfite, and hydrogen peroxide. However, if an initiator other than the above-mentioned sulfurous acid (sulfite) , hydrogen sulfite, and hydrogen peroxide. However, if an initiator other than the above-mentioned sulfurous acid (sulfite) , hydrogen sulfite, and hydrogen peroxide. However, if an initiator other than the above-mentioned sulfurous acid
  • the use amount of such an initiator is preferably 0.1 to 20 g relative to 1 mol of the monomer. If the initiator is used within such a range, the polyalkylene glycol copolymer can be produced with efficiency.
  • the use amount of the initiator is more preferably 0.5 to 10 g, and still more preferably 1 to 5 g.
  • the above-mentioned initiator in the production method essentially contains a heavy metal ion and at least one selected from the group consisting of sulfurous acid (sulfite), hydrogen sulfite, and hydrogen peroxide.
  • the above-mentioned initiator contains a heavy metal ion as an essential component, and, in combination with this heavy metal ion, further contains sulfurous acid (sulfite) , hydrogen sulfite, or hydrogen peroxide as another essential component.
  • the initiator may contain one or two or more species of sulfurous acid (sulfite), hydrogen sulfite, or hydrogen peroxide.
  • Preferred examples of such a combination include ' : heavy metal ion and sulfurous acid (sulfite) ; heavy metal ion and hydrogen sulfite; and heavy metal ion and hydrogen peroxide.
  • the species and the addition amount of the above-mentioned initiator are not especially limited as long as the initiator contains the essential components and can adjust the molecular weight distribution of the produced polymer to a specific value or less.
  • the following compounds can be preferably used.
  • Themetal ion essentially contained in the above-mentioned initiator means a metal having a specific gravity of 4 g/cm 3 or more.
  • Preferred examples of the above-mentioned metal ion include iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, and ruthenium.
  • iron is more preferable.
  • the ionic valency of the above-mentioned heavy metal ion is not especially limited. If iron is used as the heavy metal, the iron ion in the initiator may be Fe 2+ or Fe 3+ , and Fe 2+ and Fe 3+ may be contained in combination.
  • the above-mentioned heavy metal ion is not especially limited as long as it is contained in ion form in the initiator.
  • a solution into which a heavy metal compound is dissolved is excellent in handling, and therefore a method using such a solution is preferable.
  • the heavy metal compound used in such a case contains a heavy metal ion which the initiator needs to contain, and may be determined depending on a used initiator. If iron is used as the above-mentioned heavy metal ion, heavy metal compounds such as Mohr' s salt (Fe (NH 4 ) 2 (SO 4 ) 2 " 6H 2 O) , ferrous sulfate heptahydrate, ferrous chloride, and ferric chloride are preferably used.
  • manganese chloride and the like can be preferably used. Theseheavymetal compounds canbe used in aqueous solution form because they are water-soluble compounds, and therefore such compounds are excellent in handing.
  • a solvent in the above-mentioned solution into which the heavy metal compound is dissolved is not limited to water as long as it does not interfere with the polymerization reaction and can dissolve the heavy metal compound in the production of the water-soluble copolymer of the present invention.
  • the initiator contains a catalytic amount of the above-mentioned heavy metal ion in the polymerization step of the present invention.
  • the catalytic amount used in the present description means an amount of the ion which functions as a catalyst without being adsorbed by the final object.
  • the amount of the heavy metal ion is 100 ppm or less, and preferably 10 ppm or less, and more preferably 5 ppm or less.
  • a chain transfer agent is also used in the above-mentioned copolymerization method, if necessary. Chain transfer agents used in copolymerization methods as in the present invention can be appropriately selected and used.
  • the above-mentioned polymerization initiator and chain transfer agent can be added continuously, for example, added dropwise or in portions, into a reaction container.
  • the chain transfer agent may be singly charged into a reaction container, or may be previouslymixed with the above-mentionedpolyalkylene glycol chain-containing unsaturated monomer (A) or the above-mentioned unsaturated carboxylic acid monomer (B) each constituting the monomer component, the solvent, and the like.
  • preferable examples of the method of adding the monomer component, the polymerization initiator, and the like, into a reaction container include: a method in which the copolymerization is performed by charging the whole of the monomer component into a reaction container and adding the polymerization initiator into the reaction container; a method in which the copolymerization is performed by charging part of the monomer component into a reactioncontainer andadding thepolymerization initiator and the rest of the monomer component into the reaction container; a method in which the polymerization solvent is charged into a reaction container and thereinto the whole of the monomer component and the polymerization initiator is added.
  • the copolymerization is preferably performed by a method of sequentially adding dropwise the polymerization initiator and the monomer component into a reaction container because the dispersibility of the copolymer can be improved when the copolymer is used as a detergent builder .
  • the above-mentioned copolymerization method can be performed in a batch-wise method or a continuous method.
  • Solvents used in copolymerization methods as in the present invention may be used as the solvent which is used in the copolymerization according to need.
  • Preferredexamples thereof include: water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; glycerin; polyethylene glycol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, n-heptane; esters such as ethyl acetate; ketones such as acetone, methyl ethyl ketone; amides such as dimethyl formaldehyde; and ethers such as diethyl ether and dioxane.
  • one or two or more different solvents selected from the group consisting of water and lower alcohols containing 1 to 4 carbon atoms are preferably used in terms of solubility for the monomer component and the obtained copolymer .
  • the use amount of the above-mentionedsolvent is preferably 40 to 200% by weight relative to 100% by weight of the monomer component.
  • the use amount is more preferably 45% by weight or more and still more preferably 50% by weight or more.
  • the use amount is more preferably 180% by weight or less and still more preferably 150% by weight or less. If the use amount of the solvent is less than 10% by weight, the molecular weight of the obtained copolymer may be increased.
  • the concentration of the obtained copolymer is decreased, and the solvent may need to be removed.
  • Part or the whole of the solvent is charged into a reaction container in the initial stage of the polymerization.
  • Part of the solvent may be added (dropwise) into the reaction system during the polymerization reaction.
  • the solvent may be added (dropwise) into the reaction system during the polymerization, together with the monomer component, the initiator, or other additives, each previously dissolved in the solvent .
  • the copolymerization conditions such as copolymerization temperature are appropriately determined depending on the used copolymerization method, solvent, and polymerization initiator .
  • the copolymerization temperature is preferably 0°C or more and 150 0 C or less, generally.
  • the copolymerization temperature is more preferably 4O 0 C or more, and still more preferably 60 0 C or more, and particularly preferably 80 0 C or more. It is more preferably 130 0 C or less, and still more preferably 120 0 C or less, and particularly preferably 110 0 C or less.
  • the above-mentioned copolymerization temperature during the polymerization reaction needs not to be kept at a nearly-constant temperature.
  • the polymerization is initiated at a room temperature, and the temperature is raised to a predetermined temperature for a proper rising time or at a proper rising rate, and then the predetermined temperature may be kept.
  • the temperature may be varied (raised or lowered) with time during the polymerization reaction depending on themethod of adding dropwise themonomer component, the initiator, and the like.
  • the above-mentioned copolymerization time is preferably 30 to 300 minutes, and more preferably 60 to 260 minutes, and still more preferably 120 to 210 minutes.
  • the inside of the reaction system may be under ordinary pressure (atmospheric pressure) , reduced pressure, or increased pressure. It is preferable in view of the molecular weight of the obtained copolymer that the reaction is performed under ordinary pressure, or increased pressure with the reaction system closed. It is preferable in view of equipment such as pressurization device, depressurizing device, and reaction container or piping with resistance to pressure that the reaction is performed under ordinary pressure (atmospheric pressure) .
  • the atmosphere inside the reaction system may be air atmosphere, but it is preferably inert atmosphere. It is preferable that the gas inside of the system is substituted with inert gas such as nitrogen before the initiation of the polymerization.
  • the pH during the polymerization in the above-mentioned copolymerization is preferably acid.
  • the polymerization is performed under an acid condition if persulfate and hydrogen sulfite are used in combination as the above-mentioned initiator. If the copolymerization is performedunder the acidcondition, increase in viscosity of the aqueous solution of the polymerization reaction system is suppressed and therefore the copolymer can be produced well.
  • the polymerization reaction can proceed under a high concentration condition, and therefore the production efficiency canbe significantly increased andahighly concentrated polymer with a final solid content concentration of 40% or more can be produced and in such a copolymer, a total concentration of residual monomers is 15000 ppm or less.
  • the polymerizability of. the polyalkylene glycol monomer can be enhanced .
  • the pH of the reaction solution during the polymerization at 25°C is 1 to 6.
  • the pH is more preferably 5 or less and still more preferably 3 or less.
  • the copolymer produced by the above-mentioned copolyraerization method can be used as it is as a main component of a detergent builder, and the like. However, the copolymer may be used after neutralized with an alkali substance, if necessary. Inorganic salts such as hydroxides, chlorides, and carbonates of monovalent metals and divalent metals; ammonia; and organic ammoniums (organic amines) are preferably used as the alkali substance.
  • the neutralization rate in the copolymerization may be appropriately varied depending on the initiator . Ifpersulfate and hydrogen sulfite are used in combination, for example, it is preferable that the monomer component is copolymerized in such a way that the neutralization rate of the above-mentioned unsaturated carboxylic acid monomer (B) and the above-mentioned another monomer which can form a salt is 0 to 60 mol% in the above-mentioned unsaturated carboxylic acidmonomer (B) and the above-mentioned another monomer which can form a salt.
  • the neutralization rate of the above-mentioned unsaturated carboxylic acid monomer (B) and another monomer which can form a salt is represented by % by mol of the above-mentioned unsaturated carboxylic acidmonomer (B) and another monomer each forming a salt, if the total molar number of the above-mentioned unsaturatedcarboxylic acidmonomer (B) andanothermonomerwhich can form a salt is defined as 100% by mol. If the neutralization rate of the above-mentioned unsaturated carboxylic acid monomer
  • the neutralization rate is more preferably 50% by mol or less, and still more preferably 40% by mol or less, and particularlypreferably 30%bymol or less, andmore particularly preferably 20% by mol or less, and most preferably 10% by mol or less.
  • Preferred examples of the method of performing the copolymerization in such a way that the neutralization of the above-mentioned unsaturated carboxylic acid monomer (B) and another monomer which can form a salt is 0 to 60% by mol include: if the above-mentioned another monomer which can form a salt is not used, a method in which unsaturated carboxylic acid monomers (B) all of which are acid, that is, those corresponding to the above-mentioned (4) in which M is a hydrogen atom, are subjected to the copolymerization without being neutralized; and a method in which the unsaturated carboxylic acid monomer (B) after neutralized to be a salt such as a sodium salt and an ammonium salt using the alkali substance in such a way that the neutralization rate is 0 to 60% by mol, is subjected to the copolymerization .
  • a salt such as a sodium salt and an ammonium salt
  • the copolymer of the present invention is produced by copolymerizing the monomer component, as mentioned above, for example.
  • the weight average molecular weight (Mw) on polyacrylic acid equivalent basis by gel permeation chromatography (hereinafter, referred to as "GPC") is preferably 1000 or more and 100000 or less. If the weight average molecular weight is less than 1000, the dispersion performance or the chelating performance of the copolymer may be reduced.
  • the copolymer not containing the constitutional unit (a) derived from the polyalkylene glycol chain-containing unsaturated monomer (A) is increased and the anti-soil redeposition capability may be reduced.
  • the weight average molecular weight is more than 100000, the dispersion performance of the copolymer may be reduced.
  • the weight average molecular weight is more preferably 3000 ormore andmost preferably 5000 ormore.
  • the weight average molecular weight is more preferably 80000 or less and most preferably 30000 or less.
  • the weight averagemolecularweight (Mw) of the copolymer is avaluemeasured by GPC (gel permeation chromatography) .
  • GPC gel permeation chromatography
  • Calibration curve drawnusing apolyacrylic acid standard sample (product of Sowa Science Corp.) Detector: RI, UV (detection wavelength: 210 nm)
  • the present invention is further a polyalkylene glycol monomer represented by the following formula (1) :
  • R 1 , R 2 , and R 3 being the same or different and each representing a hydrogen atom or a methyl group/ R 4 , R 5 , and R 6 being the same or different and each presenting an alkylene group containing 1 to 4 carbon atoms;
  • X representing a methylene group or a carbonyl group; 1, m, and n being an average molar number of addition of oxyalkylene; and 1+m+n being 3 to 300
  • the utility of the polyalkylene glycol monomer in the present invention is that the amount of the polyalkylene glycol chain can be controlled in the polymer formed from this monomer .
  • such a copolymer can exhibit adaptability to hydrophobic soils.
  • the preparation or stability of the copolymer can be improved in the case where the ratio of the unsaturated carboxylic acid monomer unit, particularly the (meth) acrylic ratio is adjusted. Therefore, the polyalkylene glycol copolymer of the present invention, which is excellent in basic performances such as anti-soil redeposition capability, canbe efficientlyproduced.
  • X in the above formula (1) is a methylene group.
  • the above-mentioned polyalkylene glycol monomer is preferably represented by the following formula (2) :
  • the present invention is also a detergent builder, a water treatment agent, or a fiber treatment agent, comprising the polyalkylene glycol copolymer.
  • the utility of the detergent builder, the water-treatment agent, or the fiber-treatment agent of the present invention is that each can respond to various soils such as hydrophilic or hydrophobic soils and is excellent in characteristics such as anti-soil redeposition capability because each contains the above-mentioned polyalkylene glycol copolymer.
  • the above-mentioned detergent builder includes a builder for liquid detergents and exhibits a function ofpreventing soils from re-depositing on cloths and the like under cleaning. If thepolyalkylene glycol copolymer prevents redepositionof soils, the copolymer exhibits not only the repulsion attributed to the steric structure formed by the polyalkylene oxide group, the above-mentioned unsaturated carboxylic acid monomer, and the like, but also a function of dispersing soils when the copolymer has a hydrophilic group derived from the above-mentioned unsaturated carboxylic acid monomer or another monomer.
  • the above-mentioned detergent builder is excellent in compatibility with a surfactant and can form a highly-concentrated liquid detergent. Therefore, the above-mentioned detergent builder can be preferably used as a builder for liquid detergents.
  • the detergent builder is excellent in compatibilitywith a surfactant and therefore shows excellent transparency when used as a liquid detergent and a problem of separation of the liquid detergent, caused by turbidity, canbe prevented.
  • the detergent builder can form a highly-concentrated liquid detergent because of the excellent compatibility. Therefore, detergency of the liquid detergent can be improved.
  • the above-mentioned detergent builder can be a detergent builder excellent in anti-soil redeposition capability and further in stabilitybecause of agentperformanceswithextremely high quality in which reduction in the performances after a long period of storage or impurity precipitation during storage at low temperatures is hardly generated.
  • the detergent builder shows an anti-soil redeposition capability of 60% or more, and more preferably 70% or more, and still more preferably 75% or more.
  • the anti-soil redeposition capability can be measured by the following method. "Anti-soil redeposition capability"
  • a polyester cloth obtained from testfabrics, Inc. is cut into 5 cm x 5cmpieces to prepare white cloths .
  • This white cloth is previously measured for reflectance as whiteness using a colorimetric difference meter SE 2000 type produced by Nippon Denshoku Industries Co., Ltd.
  • Atargotometer is set at 25°C, andhardwater IL, the surfactant aqueous solution 5 g, a 2% by weight aqueous solution of the polymer (on solid content equivalent basis) 1 g, zeolite 0.15 g, carbon black 0.25 g are charged into a pot, and the mixture is stirred at 100 rpm for 1 minute. Thereto, ten white cloths are put into the pot and stirring is performed at 100 rpm for 10 minutes.
  • the white cloths are pressed with a filler cloth to dry them while smoothing wrinkles.
  • the dried cloths are measured for reflectance as whiteness again with the above-mentioned colorimetric difference meter.
  • Anti-soil redeposition ratio (%) (Whiteness after cleaning) / (whiteness of original white cloth) x 100
  • the proportion of the polyalkylene glycol copolymer in the above-mentioned detergent builder is preferably 0.1 to 80% by weight relative to 100% by weight of the detergent builder, for example. If the proportion is less than 0.1% by weight, the detergency may be insufficient when the detergent builder is used as a detergent composition. If the proportion is more than 80% by weight, the economic efficiency may be reduced.
  • the proportion of the polyalkylene glycol copolymer is more preferably 1% by weight or more and still more preferably 5% byweigh ormore .
  • the proportion thereof is also more preferably 70% by weight or less, and still more preferably 65% by weight or less.
  • the detergent composition containing the detergent builder may be a powder or liquid detergent composition.
  • the detergent composition may contain an additive generally used in detergents, in addition to the detergent builder.
  • Examples of the above-mentioned additive include alkali builders, chelate builders, anti-redeposition agents for preventing redeposition of contamination, such as sodium carboxymethyl cellulose, soil inhibitors such as benzotriazol and ethylene-thiourea, soil release agents, color transfer inhibitors, softening agents, alkaline substances for pH control, perfumes, solubilizing agents, fluorescence agents, coloring agents, foaming agents, foam stabilizers, lustering agents, fungicides, bleaching agents, bleaching assistants, enzymes, dyes, and solvents. It is preferable that the detergent composition contains zeolite when the detergent composition is apowder detergent composition .
  • the mixing proportion of the above-mentioned detergent builder is preferably 0.1 to 20% by weight, relative to 100% by weight of the detergent composition.
  • the mixing proportion of the detergent builder is more preferably 0.2% by weight or more and 15% by weight or less, and still more preferably 0.3% by weight or more and 10% by weight or less, and particularly preferably 0.4% by weight or more and 8% by weight or less, and most preferably 0.5% by weight or more and 5% by weight or less . If the mixing proportion of the detergent builder is less than 0.1% by weight, sufficient detergent performances may not be exhibited. If it is more than 20% by weight, the economic efficiency may be reduced.
  • Themixing formof the above-mentionedpolyalkylene glycol copolymer in the above-mentioned detergent composition may be a liquid form or solid form, and can be determined depending on the formof the detergent at the time of delivery (for example, liquid substance or solid substance) .
  • the above-mentioned detergent composition includes detergents used for only a specific application such as a bleach agent in which one function in the component is improved, in addition to synthetic detergents such as household detergents, detergents for industrial use such as fiber industry, and hard surface detergents.
  • the polyalkylene glycol copolymer of the present invention is excellent in chelating ability, and therefore can stabilize hydrogen peroxide by capturing a trace metal. Therefore, such a copolymer is excellent in stabilization ability forbleaching agents, andcanbe preferably used.
  • the above-mentioned surfactant is at least one selected from anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants. One or two or more species of these surfactants may be used. If two or more different surfactants are used, the use amount of the anionic surfactant and the nonionic surfactant is totally 50% by weight or more relative to 100% by weight of the whole of the surfactant. The use amount is more preferably 60% by weight or more, and still more preferably 70% by weight or more, and particularly preferably 80% by weight or more.
  • anionic surfactants include alkylbenzene sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, cx-olefin sulfonates, ⁇ -sulfofatty acid or ester salts thereof, alkane sulfonates, saturated fatty acid salts, unsaturated fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, amino acid surfactants, N-acylamino acid surfactants, alkyl phosphates or salts thereof, and alkenyl phosphates or salts thereof.
  • the alkyl group or the alkenyl group of the above-mentioned anionic surfactant may have a branch structure of the alkyl group such as a methyl group .
  • nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkyl phenyl ethers, higher fatty acid alkanol amides or alkylene oxide adducts thereof, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters, and alkylamine oxides.
  • the alkyl group or the alkenyl group of the above-mentioned nonionic surfactants may have a branch structure of the alkyl group such as a methyl group.
  • Quarternary ammonium salts and the like are preferred as the above-mentioned cationic surfactants.
  • Carboxyl type or sulfobetaine type amphoteric surfactants are preferably used as the above-mentioned amphoteric surfactants.
  • the alkyl group or the alkenyl group of the above-mentioned cationic surfactants or the above-mentioned amphoteric surfactants may have a branch structure of the alkyl group such as a methyl group.
  • the mixing proportion of the above-mentioned surfactant is generally preferably 10 to 60% by weight relative to 100% by weight of the detergent composition.
  • the mixing proportion is more preferably 15% by weight or more and 50% by weight or less, and still more preferably 20% by weight or more and 45% by weight or less, and particularly preferably 25% by weight or more and 40% by weight or less. If the mixing proportion of the surfactant is less than 10% by weight, sufficient detergencymaynotbe exhibited. If it is more than 60% byweight, the economic efficiency may be reduced. If the above-mentioned detergent composition is a liquid detergent composition, the moisture content in the liquid detergent composition is generally preferably 0.1 to 75% by weight, relative to 100% by weight of the liquid detergent composition.
  • the moisture content is more preferably 0.2% by weight ormore and 70% byweight or less, and still more preferably 0.5% by weight or more and 65% by weight or less, andparticularly preferably 0.7% by weight or more and 60% by weight or less, and more particularly preferably 1% by weight or more and 55% by weight or less, and most preferably 1.5 % by weight or more and 50% by weight or less.
  • the above-mentioned liquid detergent composition preferablyhas a kaolin turbidity of 200mg/Lor less.
  • the kaolin turbidity is more preferably 150 mg/L or less, and still more preferably 120 mg/L or less, and particularly preferably 100 mg/L or less, and most preferably 50 mg/L or less.
  • the kaolin turbidity can be determined by the following method for kaolin turbidity measurement, for example.' "Measurement method of kaolin turbidity"
  • a uniform stirred sample (liquid detergent) is charged into a 50 mm square cell in 10 mm thickness, and therefrom bubbles are removed. Then, the liquid is measured for turbidity (kaolin turbidity: mg/L) at 25°C withNDH2000 (trade name, turbidimeter) produced by Nippon Denshoku Industries Co., Ltd.
  • Examples of the enzymes which can be added to the above-mentioned detergent composition include protease, lipase, and cellulase. Among them, preferred are protease, alkali lipase, and alkali cellulase each showing high activity in alkaline detergent solutions.
  • the addition amount of the above-mentioned enzyme is preferably 5% by weight or less, relative to 100% by weight of the detergent composition. If the addition amount is more than 5% by weight, the detergency is not improved anymore, resulting in economic inefficiency.
  • Preferred examples of the above-mentioned alkali builders include silicates, carbonates, and sulfates.
  • Preferred examples of the above-mentioned chelate builders include diglycolic acid, oxycarboxylate, EDTA (ethylenediaminetetraacetic acid) , DTPA
  • the water treatment agent of the present invention is added to water systems such as a cooling water system and a boiler water system, thereby possibly functioning advantageously for a property of preventing scale of calcium carbonate, silica, and the like, or a property of preventing metal corrosion, for example.
  • the fiber treatment agent of the present invention treats various fibers, thereby possibly functioning advantageously for absorptivity, flexibility, wear resistance, soil-preventing property, tactile property, and the like.
  • the polyalkylene glycol copolymer may be added as it is or an agent containing another component in addition to the polyalkylene glycol copolymer maybe added to the water treatment agent or the fiber treatment agent.
  • composition or the mixing proportion of other components other than the polyalkylene glycol copolymer in the detergent builder, the water treatment agent, or the fiber treatment agent canbe appropriately determinedbased on various components which can be used in the detergent builder, the water treatment agent, or the fiber treatment agent, and the mixing proportion thereof, unless effects of the present invention are sacrificed.
  • the detergent builder, the water treatment agent or the fiber treatment agent of the present invention can respond to various soils such as hydrophilic or hydrophobic soils and is excellent in characteristics such as anti-soil redeposition capability.
  • DEA Diethanol amine
  • AGE-DEA 181.1 g and potassium hydroxide 1Og were charged into a 3750 mL autoclave equipped with a stirrer, and the container was sealed. Then, while the inner pressure was reduced to 0.015 hPa with a depressurization pump, the temperature was raised to 110 0 C and the mixture was stirred for 30 minutes. Then, the inner pressure was increased to 0.3 MPa by nitrogen addition and further reduced to 0.1 MPa by degassing . This operation was repeated three times and the inside of the device was substituted with nitrogen. After the nitrogen substitution, ethylene oxide (EO) was charged at an inner pressure of 0.32 MPa and at 110 0 C.
  • EO ethylene oxide
  • AGE-DEA-6EO 405.4 g was charged into a 3750 mL autoclave equipped with a stirrer, and the container was sealed. Then, while the inner pressure was reduced to 0.015 hPa with a depressurization pump, the temperature was raised to 110 0 C and the mixture was stirred for 30 minutes. Then, the inner pressurewas increasedto 0.3 MPabynitrogen addition and further reduced to 0.1 MPa by degassing. This operation was repeated three times and the inside of the device was substituted with nitrogen. After the nitrogen substitution, EO was charged at an inner pressure of 0.5MPa and at 110 0 C. While the nitrogen/EO partial pressure during the reaction was kept to be out of the explosion risk range, EO 1404.6 g was charged.
  • the reaction solution was matured for 1 hour after the charging, and then the temperature was lowered to 80°C and the reaction solution was degassed. While the gas was released into water, nitrogen was added into the inside of the container and thereby the inside was sufficiently substituted. Then, the content was removed to obtain an AGE-DEA-EO 45 mol adduct (hereinafter, AGE-DEA-45EO) .
  • AGE-DEA-45EO 461.7 g was charged into a 3750 mL autoclave equipped with a stirrer, and the container was sealed. Then, while the inner pressure was reduced to 0.015 hPa with a depressurization pump, the temperature was raised to 110 0 C and the mixture was stirred for 30 minutes. Then, the inner pressure was increased to 0.3MPabynitrogen addition and further reduced to 0.1 MPa by degassing. This operation was repeated three times and the inside of the device was substituted with nitrogen. After the nitrogen substitution, EO was charged at an inner pressure of 0.5MPa and at 125°C. While the nitrogen/EO partial pressure during the reaction was kept to be out of the explosion risk range, EO 972.2 g was charged.
  • the reaction solution was matured for 1 hour after the charging, and then the temperature was lowered to 80°C and the reaction solution was degassed. While the gas was released into water, nitrogen was added into the inside of the container and thereby the inside was sufficiently substituted. Then, the content was removed to obtain an AGE-DEA-EO 150 mol adduct (hereinafter, AGE-DEA-15OEO) .
  • the obtained AGE-DEA, AGE-DEA-6EO, AGE-DEA-45EO, and AGE-DEA-150EO were measured for 1 H-NMR (solvent: heavy water) .
  • AGE-DEA a peak of the methine group derived from the secondary hydroxyl group was observed at near 3.8 ppm, but in AGE-DEA-6EO, AGE-DEA-45EO, and AGE-DEA-15OEO, such a peak was not observed.
  • a 80% aqueous solution of acrylic acid (hereinafter, abbreviated as 80% AA) 270.0 g; a 50% aqueous solution of AGE-DEA-45EO (hereinafter, abbreviated as 50%AGE-DEA-45EO) 168.Og; a 48% aqueous solution of sodium hydroxide (hereinafter, abbreviated as 48% NaOH) 12.5g; a 35% aqueous solution of sodium hydrogen sulfite (hereinafter, abbreviated as 35% SBS) 69.4 g (corresponding to sodium hydrogen sulfite 8.0 g relative to the monomer 1 mol in the monomer composition) ; and a 15% aqueous solution of sodium persulfate
  • 15% NaPS 81.0 g (corresponding to sodium persulfate 4.Og relative to the monomer 1 mol in the monomer composition) .
  • the components began to be added dropwise at one time.
  • the 80%AA, 48%NaOH, and 35%SBS were added dropwise for 180 minutes, and the 50%AGE-DEA-45EO for 120 minutes, and the 15%NaPS for 210 minutes.
  • Each aqueous solution was continuously added dropwise at a constant rate.
  • the above-mentioned reaction solution was kept (matured) for a further 30 minutes at 9O 0 C to complete the polymerization.
  • the polymerization reaction solution that is a polymer mixture-containing aqueous solution was left to cool, and neutralized by gradually adding 48% NaOH 221.6 g thereinto under stirring.
  • the polymerization reaction solution after neutralized had a solid content concentrationof 41%byweight .
  • the obtainedpolymer had aweight average molecular weight of 6000.
  • Deionized water 145.0 g and Mohr's salt 0.0068 g were charged into a 2.5 L-SUS separable flask equipped with a reflux condenser and a stirrer, and the mixture was heated to 90°C under stirring to prepare a polymerization reaction system. Then, under stirring, the following aqueous solutions were added dropwise from separate nozzles into the above-mentioned polymerization reaction system kept at about 90°C to prepare a reaction solution. 80%AA 270.0 g; 50%AGE-DEA-45EO 168.
  • the polymerization reaction solution that is a polymer mixture-containing aqueous solution was left to cool, and neutralized by gradually adding 48%NaOH 221.6 g thereinto under stirring.
  • the polymerization reaction solution after neutralized had a solid content concentration of 41% byweight .
  • the obtainedpolymer had aweight average molecular weight of 9000.
  • Deionized water 120.0 g and Mohr's salt 0.0152 g were charged into a 2.5 L-SUS separable flask equipped with a reflux condenser and a stirrer, and the mixture was heated to 90°C under stirring to prepare a polymerization reaction system. Then, under stirring, the following aqueous solutions were added dropwise from separate nozzles into the above-mentioned polymerization reaction system kept at about 90°C to prepare a reaction solution.
  • the above-mentioned reaction solution was kept (matured) at90°C for a further 30 minutes to complete the polymerization.
  • the polymerization reaction solution that is a polymer mixture-containing aqueous solution was left to cool, and neutralized by gradually adding 48%NaOH 146.7 g thereinto under stirring.
  • the polymerization reaction solution after neutralized had a solid content concentration of 40% by weight.
  • the obtained polymer had a weight average molecular weight of 5000.
  • Example 4 Deionized water 120.0 g and Mohr's salt 0.0149 g were charged into a 2.5 L-SUS separable flask equipped with a reflux condenser and a stirrer, and the mixture was heated to 90°C under stirring to prepare a polymerization reaction system. Then, under stirring, the following aqueous solutions were added dropwise from separate nozzles into the above-mentioned polymerization reaction system kept at about 90°C to prepare a reaction solution.
  • the above-mentioned reaction solution was kept (matured) at90°C for a further 30 minutes to complete the polymerization.
  • the polymerization reaction solution that is a polymer mixture-containing aqueous solution was left to cool, and neutralized by gradually adding 48%NaOH 146.7 g thereinto under stirring.
  • the polymerization reaction solution after neutralized had a solid content concentration of 41% by weight.
  • the obtained polymer had a weight average molecular weight of 10000.
  • Deionized water 143.0 g and Mohr' s salt 0.0146 g were charged into a 2.5 L-SUS separable flask equipped with a reflux condenser and a stirrer, and the mixture was heated to 90°C under stirring to prepare a polymerization reaction system. Then, under stirring, the following aqueous solutions were added dropwise from separate nozzles into the above-mentioned polymerization reaction system kept at about 90 0 C to prepare a reaction solution.
  • the above-mentioned reaction solution was kept (matured) at90°C for a further 30 minutes to complete the polymerization.
  • the polymerization reaction solution that is a polymer mixture-containing aqueous solution was left to cool, and neutralized by gradually adding 48%NaOH 146.7 g thereinto under stirring.
  • the polymerization reaction solution after neutralized had a solid content concentration of 40% by weight.
  • the obtained polymer had a weight average molecular weight of 18000.
  • Deionized water 120.0 g and Mohr' s salt 0.0139 g were charged into a 2.5 L- SUS separable flask equipped with a reflux condenser and a stirrer, and the mixture was heated to 90°C under stirring to prepare a polymerization reaction system. Then, under stirring, the following aqueous solutions were added dropwise from separate nozzles into the above-mentioned polymerization reaction system kept at about 90°C to prepare a reaction solution.
  • the above-mentioned reaction solution was kept (matured) at90°C for a further 30 minutes to complete the polymerization.
  • the polymerization reaction solution that is a polymer mixture-containing aqueous solution was left to cool, and neutralized by gradually adding 48%NaOH 95.2 g thereinto under stirring.
  • the polymerization reaction solution after neutralized had a solid content concentration of 40% by weight.
  • the obtained polymer had a weight average molecular weight of 12000.
  • Deionized water 120.0 g and Mohr' s salt 0.0144 g were charged into a 2.5 L- SUS separable flask equipped with a reflux condenser and a stirrer, and the mixture was heated to 90°C under stirring to prepare a polymerization reaction system. Then, under stirring, the following aqueous solutions were added dropwise from separate nozzles into the above-mentioned polymerization reaction system kept at about 90°C to prepare a reaction solution.
  • the components began to be added dropwise at one time.
  • the 80%AA and 35%SBS were added dropwise for 180 minutes, and the 50%AGE-DEA-6EO for 60 minutes, and the 15%NaPS for 210 minutes.
  • Each aqueous solution was continuously added dropwise at a constant rate.
  • the above-mentioned reaction solution was kept (matured) at 90 0 C for a further 30 minutes to complete the polymerization.
  • the polymerization reaction solution that is a polymer mixture-containing aqueous solution was left to cool, and neutralized by gradually adding 48%NaOH
  • the polymerization reaction solution after neutralized had a solid content concentration of 40% by weight.
  • the obtained polymer had a weight average molecular weight of 21000.
  • Deionized water 120.0 g and Mohr' s salt 0.0148 g were charged into a 2.5 L- SUS separable flask equipped with a reflux condenser and a stirrer, and the mixture was heated to 90°C under stirring to prepare a polymerization reaction system. Then, under stirring, the following aqueous solutions were added dropwise from separate nozzles into the above-mentioned polymerization reaction system kept at about 90°C to prepare a reaction solution.
  • the above-mentioned reaction solution was kept (matured) at90°C for a further 30 minutes to complete the polymerization.
  • the polymerization reaction solution that is a polymer mixture-containing aqueous solution was left to cool, and neutralized by gradually adding 48%NaOH 132.7 g thereinto under stirring.
  • the polymerization reaction solution after neutralized had a solid content concentration of 40% by weight.
  • the obtained polymer had a weight average molecular weight of 12000.
  • Deionized water 149.0 g and Mohr' s salt 0.0152 g were charged into a 2.5 L- SUS separable flask equipped with a reflux condenser and a stirrer, and the mixture was heated to 90°C under stirring to prepare a polymerization reaction system. Then, under stirring, the following aqueous solutions were added dropwise from separate nozzles into the above-mentioned polymerization reaction system kept at about 90°C to prepare a reaction solution.
  • the components began to be added dropwise at one time.
  • the 80%AA and 35%SBS were added dropwise for 180 minutes, and the 50%AGE-DEA-150EO for 60 minutes, and the 15%NaPS for 210 minutes .
  • Each aqueous solution was continuously added dropwise at a constant rate.
  • the above-mentioned reaction solution was kept (matured) at90°C for a further 30 minutes to complete the polymerization.
  • the polymerization reaction solution that is a polymer mixture-containing aqueous solution was left to cool, and neutralized by gradually adding 48%NaOH 153.0 g thereinto under stirring.
  • the polymerization reaction solution after neutralized had a solid content concentration of 40% by weight.
  • the obtained polymer had a weight average molecular weight of 25000.
  • Deionized water 145.0 g and Mohr's salt 0.0068 g were charged into a 2.5 L-SUS separable flask equipped with a reflux condenser and a stirrer, and the mixture was heated to 90°C under stirring to prepare a polymerization reaction system. Then, under stirring, the following aqueous solutions were added dropwise from separate nozzles into the above-mentioned polymerization reaction system kept at about 90°C to prepare a reaction solution.
  • 50%PEA-15EO 50% aqueous solution of allyl alcohol-EO 15 mol adduct
  • 35%SBS 71.2 g corresponding to sodium hydrogen sulfite 8.0 g relative to the monomer 1 mol in the monomer composition
  • 15%NaPS 83.1 g corresponding to sodium persulfate 4.O g relative to the monomer 1 mol in the monomer composition
  • the 80%AA, 48%NaOH, and 35%SBS were added dropwise for 180 minutes, and the 50%AGE-DEA-45EO for 60 minutes, and 15%NaPS for 210 minutes. Each aqueous solution was continuously added dropwise at a constant rate.
  • the above-mentioned reaction solution was kept (matured) at 90 0 C for a further 30 minutes to complete the polymerization.
  • the polymerization reaction solution that is a polymer mixture-containing aqueous solution was left to cool, and neutralized by gradually adding 48%NaOH 221.6 g thereinto under stirring.
  • the polymerization reaction solution after neutralized had a solid content concentration of 41% by weight.
  • the obtained comparison polymer had a weight average molecular weight of 5000.
  • Comparative Example 2 A compound prepared by adding EO 20 mol to each active hydrogen of polyethyleneimine with a molecular weight of 600
  • the polymer was measured for weight average molecular weightbyGPC (gel permeation chromatography) under the following measurement conditions and with the following device.
  • Calibration curve drawnusing apolyacrylic acid standard sample (product of Sowa Science Corp.) Detector: RI, UV (detection wavelength: 220 nm) "Anti-soil redeposition capability"
  • a polyester cloth obtained from testfabrics, Inc. was cut into 5 cm x 5cm pieces to prepare white cloths .
  • This white cloth was previously measured for reflectance as whiteness using a colorimetric difference meter SE 2000 type produced by Nippon Denshoku Industries Co., Ltd.
  • a targotometer was set at 25°C, and hard water IL, the surfactant aqueous solution 5 g, a 2% aqueous polymer solution on solid content equivalent basis of the polymer 1 g, zeolite 0.15 g, carbon black 0.25 g were charged into a pot, and the mixture was stirred at 100 rpm for 1 minute. Thereto, ten white cloths were put into the pot and stirring was performed at 100 rpm for 10 minutes. (5) The white cloths were wringed by hand, and tap water 1 L kept at 25°C was put in a pot and stirring was performed at 100 rpm for 2 minutes. This operation was performed twice.
  • Anti-soil redeposition ratio (%) (Whiteness after cleaning) / (whiteness of original white cloth) x 100
  • the copolymer having a structure in which many polyalkylene glycol chains are bonded to polyalkyleneimine and a double bond derived from the allyl glycidyl ether exists at an end of the polyalkylene glycol chain causes a cross-linking reaction during the copolymerization and therefore produces gelling by increase in acrylic ratio of the raw material.
  • the copolymer has at least one PEG chain-branching structure between the unsaturated bond and the nitrogen atom, even if the ratio of the unsaturated carboxylic acid monomer unit, particularly the (meth) acrylic ratio, is increased, there is no problems on preparation or stabilization of the copolymer, and for example, the detergency is improved.
  • the above-mentioned improvement in performances and characteristics is also observed if the copolymer is used in other applications, and the copolymer can be preferably used in water treatment agents and fiber treatment agents, for example.
  • polyalkylene glycol copolymers which can be produced by copolymerizing the polyalkylene glycol monomer having three polyalkylene glycol chains and at least one polyalkylene glycol chain-branching structure between the unsaturated bond and the nitrogen atom with the unsaturated carboxylic acid monomer have the same mechanism in which the anti-soil redeposition ratio is improved due to the three or more polyalkylene glycol chains existing in one monomer unit, that is, a mechanism capable of responding to hydrophobic soils.
  • the copolymer has not a conventional copolymer structure in which one part having a double bond is bonded to an end of the polyalkylene glycol chain but a structure in which plural polyalkylene glycol chains are bonded to one part having a double bond. Therefore, the preparation or stabilization of the copolymer is improved even if the ratio of the unsaturated carboxylic acid monomer unit, particularly the (meth) acrylic ratio, is increased.
  • the polyalkylene glycol copolymer of the present invention has the above-mentioned configuration.
  • Such a copolymer is excellent in compatibility with liquid detergents, detergent ratio and the like, and can respond to various soils such as hydrophilic or hydrophobic soils and exhibit high basic performances such as anti-soil redeposition capability.
  • the copolymer can be preferably used in applications of a detergent builder (including liquid detergent builder) , a water treatment agent, a fiber treatment agent, and the like.

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  • Detergent Compositions (AREA)
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Abstract

La présente invention concerne un copolymère de polyalkylène glycol qui soit utile en tant par exemple qu'adjuvant de détergent requérant une détergence élevée, et capable de traiter dans ce cadre diverses salissures telles que des salissures hydrophiles ou hydrophobes, doté d'excellentes caractéristiques telles qu'un pouvoir anti-redéposition des salissures, et qui puisse être utilisé dans le cadre de diverses applications faisant appel aux copolymères de polyalkylène glycol. L'invention concerne également un monomère utile en tant que matière première pour former un tel copolymère, un procédé pour produire ledit copolymère et une application dudit copolymère. Le copolymère de polyalkylène glycol proposé par l'invention comprend un motif constitutionnel (a) dérivé d'un monomère (A) insaturé contenant une chaîne polyalkylène glycol et un motif constitutionnel (b) dérivé d'un monomère (B) acide carboxylique insaturé, ledit monomère (A) insaturé contenant une chaîne polyalkylène glycol contenant au moins trois chaînes polyalkylène glycol et, entre une liaison insaturée et un atome d'azote, au moins une structure de ramification de chaîne polyalkylène glycol.
PCT/JP2007/057691 2006-03-31 2007-03-30 Copolymere de polyalkylene glycol, monomere de polyalkylene glycol et procede pour les produire WO2007116946A1 (fr)

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Publication number Priority date Publication date Assignee Title
CN102504238A (zh) * 2011-10-10 2012-06-20 江苏博特新材料有限公司 一种不饱和聚醚单体、采用该单体制备的梳形支化共聚物水泥分散剂及其制备方法
CN107474236A (zh) * 2017-07-07 2017-12-15 联泓(江苏)新材料研究院有限公司 一种反应性乳化剂、其制备方法和应用
CN112409734A (zh) * 2020-11-20 2021-02-26 长春工业大学 一种使聚乙烯醇具备优异形状记忆与可修复功能的聚合物

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JP2002301353A (ja) * 2000-12-28 2002-10-15 Asahi Denka Kogyo Kk 界面活性剤
JP2004075812A (ja) * 2002-08-14 2004-03-11 Nippon Shokubai Co Ltd （ポリ）アルキレングリコール鎖及び／又はエステル結合を有する不飽和単量体の水溶液、その製造方法並びにセメント添加剤用重合体の製造方法
JP2005139430A (ja) * 2003-10-14 2005-06-02 Nippon Shokubai Co Ltd 洗浄剤用ポリカルボン酸系共重合体
JP2006241372A (ja) * 2005-03-04 2006-09-14 Nippon Shokubai Co Ltd 末端変性ポリアルキレンイミンアルキレンオキシド共重合体

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JP2002301353A (ja) * 2000-12-28 2002-10-15 Asahi Denka Kogyo Kk 界面活性剤
JP2004075812A (ja) * 2002-08-14 2004-03-11 Nippon Shokubai Co Ltd （ポリ）アルキレングリコール鎖及び／又はエステル結合を有する不飽和単量体の水溶液、その製造方法並びにセメント添加剤用重合体の製造方法
JP2005139430A (ja) * 2003-10-14 2005-06-02 Nippon Shokubai Co Ltd 洗浄剤用ポリカルボン酸系共重合体
JP2006241372A (ja) * 2005-03-04 2006-09-14 Nippon Shokubai Co Ltd 末端変性ポリアルキレンイミンアルキレンオキシド共重合体

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102504238A (zh) * 2011-10-10 2012-06-20 江苏博特新材料有限公司 一种不饱和聚醚单体、采用该单体制备的梳形支化共聚物水泥分散剂及其制备方法
CN107474236A (zh) * 2017-07-07 2017-12-15 联泓(江苏)新材料研究院有限公司 一种反应性乳化剂、其制备方法和应用
CN107474236B (zh) * 2017-07-07 2021-03-16 联泓(江苏)新材料研究院有限公司 一种反应性乳化剂、其制备方法和应用
CN112409734A (zh) * 2020-11-20 2021-02-26 长春工业大学 一种使聚乙烯醇具备优异形状记忆与可修复功能的聚合物
CN112409734B (zh) * 2020-11-20 2022-07-01 长春工业大学 一种具备形状记忆与可修复功能的pva/ptmg-paa共混薄膜

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