WO2020203694A1 - Adjuvant pour détergent ou additif pour détergent, et composition de détergent - Google Patents

Adjuvant pour détergent ou additif pour détergent, et composition de détergent Download PDF

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Publication number
WO2020203694A1
WO2020203694A1 PCT/JP2020/013829 JP2020013829W WO2020203694A1 WO 2020203694 A1 WO2020203694 A1 WO 2020203694A1 JP 2020013829 W JP2020013829 W JP 2020013829W WO 2020203694 A1 WO2020203694 A1 WO 2020203694A1
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group
detergent
mass
general formula
copolymer
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PCT/JP2020/013829
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English (en)
Japanese (ja)
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尊子 張替
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株式会社日本触媒
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Publication of WO2020203694A1 publication Critical patent/WO2020203694A1/fr

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    • 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
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/38—Esters containing sulfur
    • 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

Definitions

  • the present invention relates to a detergent builder or a detergent additive and a detergent composition.
  • the water-soluble polymer is preferably used as a detergent builder or a detergent additive.
  • a water-soluble polymer an unsaturated carboxylic acid-based monomer such as acrylic acid, methacrylic acid, ⁇ -hydroxyacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, and citraconic acid
  • a polymer or copolymer using the above as a monomer component is used. Further, in order to improve the performance of detergent builders or detergent additives, improvement studies on the above polymers and copolymers have been actively conducted in recent years (for example, Patent Document 1).
  • the applicant has excellent clay dispersibility, excellent compatibility with surfactants, and dissolution of fats in the copolymer having a specific structure. We have found that it is also excellent in solubilizing power, which is an ability, and have completed the present invention.
  • an object of the present invention is to provide a detergent builder or a detergent additive having excellent clay dispersibility, excellent compatibility with a surfactant, and excellent solubilizing power, which is the ability to dissolve fats. It is in.
  • Another object of the present invention is to provide a detergent composition containing a copolymer which can be suitably used for such a detergent builder or a detergent additive.
  • the average number of moles n of oxyalkylene groups represented by AO in the general formula (II) is 11 or more.
  • R 1 ⁇ R 3 are each independently a hydrogen atom, a methyl group, or - represents a (CH 2) z COOM groups, - (CH 2) z COOM group -COOX group Alternatively, it may form an anhydride with another ⁇ (CH 2 ) z COOM group, z is an integer of 0 to 2, and M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic substance.
  • R 4 and R 5 independently represent a hydrogen atom or a methyl group
  • R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms
  • AO represents a hydrocarbon group.
  • the detergent composition according to the embodiment of the present invention A detergent composition containing 0.01% by weight to 10% by weight of a copolymer, 1% by weight to 70% by weight of a surfactant, and alcohol.
  • the copolymer is a copolymer containing a structural unit (I) represented by the general formula (I) and a structural unit (II) represented by the general formula (II). Has a sulfide bond and The average number of moles n of oxyalkylene groups represented by AO in the general formula (II) is 11 or more.
  • Detergent composition is a copolymer containing a structural unit (I) represented by the general formula (I) and a structural unit (II) represented by the general formula (II).
  • R 1 ⁇ R 3 are each independently a hydrogen atom, a methyl group, or - represents a (CH 2) z COOM groups, - (CH 2) z COOM group -COOX group Alternatively, it may form an anhydride with another ⁇ (CH 2 ) z COOM group, z is an integer of 0 to 2, and M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic substance.
  • R 4 and R 5 independently represent a hydrogen atom or a methyl group
  • R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms
  • AO represents a hydrocarbon group.
  • a detergent builder or a detergent additive having excellent clay dispersibility, excellent compatibility with a surfactant, and excellent solubilizing power, which is the ability to dissolve fats. be able to.
  • a detergent composition containing a copolymer that can be suitably used for such a detergent builder or a detergent additive.
  • the expression “(meth) acrylic” means “acrylic and / or methacrolein”
  • the expression “(meth) acrylate” means “acrylate and / or methacrylate”.
  • the expression “(meth) allyl” is used, it means “allyl and / or methacrolein”
  • the expression “(meth) acrolein” is used, “acrolein and / or methacrolein” is used. It means “rain”.
  • the expression “acid (salt)” is used in the present specification, it means “acid and / or a salt thereof”.
  • weight which is generally used as a unit of weight
  • weight is used in the present specification.
  • mass which is commonly used as an SI system unit indicating weight.
  • the content ratio of the structural unit (I) represented by the general formula (I) is-even when it is in the form of an acid type (that is, a carboxylate such as -COONa-". Calculated as the carboxylic acid form of COOH).
  • the content ratio of the structural unit (I) represented by the general formula (I) is the salt type (-). Calculated as a form of carboxylate such as COONa).
  • the content ratio of the structural unit derived from various monomers is the ratio of the amount used (charged amount) of each of the various monomers, as it is, of the structural unit derived from the various monomers. The content ratio.
  • the detergent builder or detergent additive according to the embodiment of the present invention has a copolymer weight including a structural unit (I) represented by the general formula (I) and a structural unit (II) represented by the general formula (II). It is a coalescence, has a sulfide bond, and has an average number of moles n of oxyalkylene groups represented by AO in the general formula (II) of 11 or more.
  • the detergent builder or detergent additive is a copolymer containing a structural unit (I) and a structural unit (II).
  • a copolymer obtained by any suitable method can be adopted as long as the effect of the present invention is not impaired.
  • the structural unit (I) may be only one type or two or more types.
  • the unsaturated carboxylic acid-based monomer represented by the general formula (1) may be only one kind or two or more kinds.
  • the structural unit (II) may be of only one type or of two or more types.
  • the unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2) may be of only one type or of two or more types.
  • the detergent builder or detergent additive is a copolymer containing the structural unit (I) and the structural unit (II), and any suitable method is used as long as the effects of the present invention are not impaired.
  • the copolymer obtained by can be adopted.
  • a monomer component containing an unsaturated carboxylic acid-based monomer represented by the general formula (1) and an unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2) is copolymerized.
  • the obtained copolymer can be adopted.
  • the structural unit (I) is a structural unit derived from an unsaturated carboxylic acid-based monomer represented by the general formula (1)
  • the structural unit (II) is represented by the general formula (2). It is a structural unit derived from an unsaturated polyalkylene glycol ether-based monomer.
  • the detergent builder or detergent additive may be a copolymer obtained by such a non-copolymerization method.
  • R 1 to R 3 represent the same or different hydrogen atom, methyl group, or-(CH 2 ) z COM group.
  • - (CH 2) z COOM group -COOX groups or other - may form a (CH 2) z COOM groups and anhydride.
  • z is an integer of 0 to 2.
  • R 1 to R 3 are preferably hydrogen atoms or methyl groups independently of each other.
  • M represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.
  • X represents a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, an organic ammonium group, or an organic amine group.
  • Examples of the unsaturated carboxylic acid-based monomer represented by the general formula (1) include monocarboxylic acid-based monomers such as (meth) acrylic acid and crotonic acid or salts thereof; maleic acid, itaconic acid, and the like. Dicarboxylic acid-based monomers such as fumaric acid or salts thereof; anhydrides of dicarboxylic acid-based monomers such as maleic acid, itaconic acid, and fumaric acid or salts thereof; and the like.
  • Examples of the salt referred to here include alkali metal salts, alkaline earth metal salts, ammonium salts, organic ammonium salts, and organic amine salts.
  • the content ratio of the monocarboxylic acid-based monomer or a salt thereof in the unsaturated carboxylic acid-based monomer represented by the general formula (1) is preferably 30 in that the effect of the present invention can be more exhibited. It is from mass% to 100% by mass, more preferably 50% by mass to 100% by mass, further preferably 70% by mass to 100% by mass, particularly preferably 90% by mass to 100% by mass, and most preferably. Is substantially 100% by mass.
  • alkali metal salt examples include lithium salt, sodium salt, potassium salt and the like.
  • alkaline earth metal salt examples include calcium salt and magnesium salt.
  • organic ammonium salt examples include methylammonium salt, ethylammonium salt, dimethylammonium salt, diethylammonium salt, trimethylammonium salt, triethylammonium salt and the like.
  • organic amine salt examples include ethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt, triisopropanolamine salt, hydroxyethyldiisopropanolamine salt, dihydroxyethylisopropanolamine salt, and tetrakis (dihydroxyethylisopropanolamine salt).
  • alkanolamine salts such as 2-hydroxypropyl) ethylenediamine and pentax (2-hydroxypropyl) diethylenetriamine.
  • diisopropanolamine salt preferably diisopropanolamine salt, triisopropanolamine salt, hydroxyethyldiisopropanolamine salt, tetrakis (2-hydroxypropyl) ethylenediamine salt, pentakis (2-hydroxypropyl) diethylenetriamine salt are preferable.
  • Triisopropanolamine salt and hydroxyethyldiisopropanolamine salt are preferable.
  • the unsaturated carboxylic acid-based monomer represented by the general formula (1) is preferably (meth) acrylic acid, maleic acid, or maleic anhydride in that the effects of the present invention can be further exhibited. More preferably, it is acrylic acid or methacrylic acid.
  • R 4 and R 5 represent the same or different hydrogen atoms or methyl groups.
  • R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms.
  • the hydrocarbon group having 1 to 30 carbon atoms include an alkyl group having 1 to 30 carbon atoms (aliphatic alkyl group and alicyclic alkyl group), an alkenyl group having 1 to 30 carbon atoms, and a carbon atom number. Examples thereof include an alkynyl group having 1 to 30 and an aromatic group having 6 to 30 carbon atoms.
  • R 3 is preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, more preferably, carbon hydrogen atom or 1 to 12 carbon atoms It is a hydrogen group, more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, and particularly preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • AO is an oxyalkylene group having 2 to 18 carbon atoms, preferably an oxyalkylene group having 2 to 8 carbon atoms, and more preferably an oxyalkylene group having 2 to 8 carbon atoms. It is 2 to 4 oxyalkylene groups.
  • the AO is any two or more types selected from an oxyethylene group, an oxypropylene group, an oxybutylene group, an oxystyrene group, etc.
  • the addition form of AO is random addition, block addition, alternate addition, etc. It may be in any form of.
  • the oxyethylene group contains an oxyethylene group as an essential component, and 50 mol% or more of the total oxyalkylene group is an oxyethylene group. It is more preferable that 90 mol% or more of the total oxyalkylene group is an oxyethylene group, and 100 mol% or more of the total oxyalkylene group is particularly preferably an oxyethylene group.
  • n represents the average number of moles of oxyalkylene group represented by AO (sometimes referred to as "chain length").
  • AO sometimes referred to as "chain length"
  • n is 11 or more, preferably 11 to 500, preferably 13 to 200, more preferably 15 to 200, and further. The number is preferably 18 to 100, particularly preferably 20 to 74, and most preferably 40 to 60.
  • n is within the above range, the clay dispersibility can be improved, the compatibility with the surfactant can be improved, and the solubilizing power, which is the ability to dissolve fats, can be improved.
  • Detergent builder or detergent additive Can be obtained.
  • x is an integer of 0 to 2.
  • Examples of the unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2) include vinyl alcohol, (meth) allyl alcohol, 3-methyl-3-butene-1-ol, and 3-methyl-2.
  • Average alkylene oxide to any of -butene-1-ol, 2-methyl-3-butene-2-ol, 2-methyl-2-butene-1-ol, and 2-methyl-3-butene-1-ol It is a compound in which 1 mol to 500 mol is added, preferably a compound in which an average of 1 mol to 500 mol of alkylene oxide is added to 3-methyl-3-butene-1-ol, and an average of 1 mol to 1 mol to alkylene oxide is added to metallic alcohol. It is a compound to which 500 mol is added.
  • the content ratio of the structural unit (I) in the copolymer which is the detergent builder or detergent additive is preferably 1% by mass to 50% by mass, more preferably. Is 1% by mass to 40% by mass, more preferably 1% by mass to 35% by mass, and particularly preferably 2% by mass to 30% by mass.
  • the content ratio of the structural unit (I) in the detergent builder or the copolymer which is an additive for detergent is within the above range, the clay dispersibility can be improved, the compatibility with the surfactant can be improved, and the fat.
  • Detergent builders or detergent additives may be obtained that may be superior to the solubilizing power, which is the ability of the minutes to dissolve.
  • the content ratio of the structural unit (II) in the copolymer which is the detergent builder or detergent additive is preferably 50% by mass to 99% by mass, more preferably. Is 60% by mass to 99% by mass, more preferably 65% by mass to 99% by mass, and particularly preferably 70% by mass to 98% by mass.
  • the content ratio of the structural unit (II) derived from the unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2) in the detergent builder or the detergent additive is within the above range.
  • a detergent builder or a detergent additive can be obtained which can be excellent in clay dispersibility, can be excellent in compatibility with a surfactant, and can be excellent in solubilizing power which is the ability to dissolve fats.
  • the total content ratio of the structural unit (I) and the structural unit (II) in the copolymer which is the detergent builder or the detergent additive is preferably 50% by mass. It is ⁇ 100% by mass, more preferably 70% by mass to 100% by mass, further preferably 90% by mass to 100% by mass, particularly preferably 95% by mass to 100% by mass, and most preferably substantial. It is 100% by mass. If the total content ratio of the structural unit (I) and the structural unit (II) in the detergent builder or the copolymer which is the detergent additive is within the above range, the clay dispersibility can be improved and the surfactant can be obtained. It is possible to obtain a detergent builder or a detergent additive which can be excellent in compatibility with and can be excellent in solubilizing power which is the ability to dissolve fats.
  • a copolymer that is a detergent builder or a detergent additive may have a structural unit (III) derived from another monomer (3) in addition to the structural unit (I) and the structural unit (II). Good.
  • Examples of the other monomer (3) include the unsaturated carboxylic acid-based monomer represented by the general formula (1) and the unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2). It is a polymerizable monomer.
  • the other monomer (3) may be only one kind or two or more kinds.
  • any suitable monomer can be adopted as long as the effect of the present invention is not impaired.
  • examples of such other monomer (3) include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate; methyl (meth) acrylate and glycidyl (meth) acrylate.
  • Esters of unsaturated monocarboxylic acids such as, and alcohols having 1 to 30 carbon atoms; various (alkoxy) (poly) alkylenes such as polyethylene glycol mono (meth) acrylate and methoxy (poly) ethylene glycol mono (meth) acrylate.
  • Glycol mono (meth) acrylates Half esters of unsaturated dicarboxylic acids such as (anhydrous) maleic acid, fumaric acid, and itaconic acid with alcohols having 1 to 30 carbon atoms; (anhydrous) maleic acid, fumaric acid, itacone. Diesters of unsaturated dicarboxylic acids such as acids and alcohols having 1 to 30 carbon atoms; halfamides of the unsaturated dicarboxylic acids and amines having 1 to 30 carbon atoms; the unsaturated dicarboxylic acids and carbon atoms.
  • Diamides with 1 to 30 amines Diamides with 1 to 30 amines; half esters of alkyl (poly) alkylene glycols with an average of 1 to 500 mol of alkylene oxides with 2 to 18 carbon atoms added to the alcohols and amines and unsaturated dicarboxylic acids.
  • Diesters of alkyl (poly) alkylene glycols obtained by adding an average of 1 to 500 mol of an alkylene oxide having 2 to 18 carbon atoms to the alcohol or amine; the unsaturated dicarboxylic acids and the number of carbon atoms; Half esters of 2 to 18 glycols or polyalkylene glycols having an average addition molar number of 2 to 500 of these glycols; the unsaturated dicarboxylic acids and glycols having 2 to 18 carbon atoms or the average addition moles of these glycols.
  • (Meta) acrylates (Poly) alkylene glycol dimalay such as polyethylene glycol dimalate G: Vinyl sulfonate, (meth) allyl sulfonate, 2-methylpropanesulfonic acid (meth) acrylamide, unsaturated sulfonic acid (salt) such as styrenesulfonic acid; and unsaturated monocarboxylic acid such as methyl (meth) acrylamide.
  • Amides with amines having 1 to 30 carbon atoms Vinyl aromatics such as styrene, ⁇ -methylstyrene and vinyltoluene; Alcandiol mono (meth) acrylates such as 1,4-butanediol mono (meth) acrylate Dienes such as butadiene and isoprene; unsaturated amides such as (meth) acrylic (alkyl) amides, N-methylol (meth) acrylamides, N, N-dimethyl (meth) acrylamides; unsaturated amides such as (meth) acrylonitrile Cyanides; unsaturated esters such as vinyl acetate; unsaturated amines such as aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, vinyl pyridine; divinyl aromatics such as divinylbenzene; (meth) Allyls such as allyl alcohol and glycidy
  • the content ratio of the structural unit (III) derived from the other monomer (3) in the copolymer which is the detergent builder or the detergent additive is preferably 0% by mass. % To 50% by mass, more preferably 0% by mass to 40% by mass, further preferably 0% by mass to 30% by mass, particularly preferably 0% by mass to 20% by mass, and most preferably. It is 0% by mass to 10% by mass. If the content ratio of the structural unit (III) derived from the other monomer (3) in the detergent builder or the copolymer which is the detergent additive is within the above range, the clay dispersibility can be improved and the surface activity can be improved. Detergent builders or detergent additives may be obtained that may be superior in compatibility with the agent and in solubilizing power, which is the ability to dissolve fats.
  • Detergent builders or detergent additives have sulfide bonds in their structure.
  • the sulfide bond is a bond represented by —S—.
  • Detergent builder or detergent additive has a sulfide bond in its structure, so that it can be more excellent in clay dispersibility, more excellent in compatibility with surfactants, and solubilizing power which is the ability to dissolve fats. A better detergent builder or detergent additive may be obtained.
  • the number of sulfide bonds in the structure of the detergent builder or the detergent additive may be only one or two or more.
  • the sulfide bond in the structure of the detergent builder or detergent additive is preferably obtained through a polymerization step in the presence of a mercapto group-containing compound.
  • the mercapto group-containing compound may have a carboxylic acid group, a hydroxyl group, a sulfonic acid group, an amino group, a cationic group, or the like as a functional group.
  • the functional group is preferably a carboxylic acid group.
  • the functional group may be only one kind or two or more kinds.
  • Examples of the mercapto group-containing compound include thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosuccinic acid, thioalinic acid, mercaptoacetic acid, 2-mercaptoethanol, and sodium 3-mercapto-1-propanesulfonate. Examples include cysteine and salts thereof.
  • the mercapto group-containing compound may be only one kind or two or more kinds.
  • the content ratio of various structural units in the copolymer can be known, for example, by various structural analyzes of the copolymer (for example, NMR). Further, it may be calculated based on the content ratio of various monomers used in producing the copolymer without performing various structural analyzes as described above. In this case, the reaction rate may be considered if necessary.
  • the polyethylene glycol-equivalent weight average molecular weight (Mw) obtained by gel permeation chromatography of a detergent builder or a copolymer as a detergent additive is preferably 5000 or more, more preferably 7000 to 200,000. , More preferably 8000 to 180,000, particularly preferably 8000 to 100,000, further preferably 8000 to 80,000, and most preferably 8000 to 60000. If the weight average molecular weight (Mw) in terms of polyethylene glycol obtained by gel permeation chromatography of a detergent builder or a copolymer as a detergent additive is within the above range, the clay dispersibility can be improved and the surface activity can be improved. Detergent builders or detergent additives may be obtained that may be superior in compatibility with the agent and in solubilizing power, which is the ability to dissolve fats.
  • the builder for detergent or the copolymer as an additive for detergent can be obtained by any appropriate method as long as the effect of the present invention is not impaired.
  • Such a method preferably includes an unsaturated carboxylic acid-based monomer represented by the general formula (1) and an unsaturated polyalkylene glycol ether-based monomer represented by the general formula (2). It is obtained by copolymerizing a monomer component in the presence of a mercapto group-containing compound. According to such a method, it is a copolymer containing the structural unit (I) represented by the general formula (I) and the structural unit (II) represented by the general formula (II), and has a sulfide bond.
  • a detergent builder or a detergent additive having an average addition mole number n of an oxyalkylene group represented by AO in the general formula (II) of 11 or more can be easily obtained.
  • the mercapto group-containing compound can mainly act as a chain transfer agent in the polymerization step.
  • the mercapto group-containing compound include thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thiosuccinic acid, thioalinic acid, mercaptoacetic acid, 2-mercaptoethanol, and sodium 3-mercapto-1-propanesulfonate.
  • Examples include cysteine and salts thereof.
  • the mercapto group-containing compound may be only one kind or two or more kinds.
  • the mercapto group-containing compound is preferably a mercapto group-containing compound having a carboxyl group.
  • a mercapto group-containing compound having a carboxyl group As the mercapto group-containing compound, it is possible to obtain excellent clay dispersibility, excellent compatibility with a surfactant, and excellent solubilization ability, which is the ability to dissolve fats. Obtaining Detergent Builders or Detergent Additives can be obtained.
  • the mercapto group-containing compound can mainly act as a chain transfer agent, and therefore is preferably a builder for detergents or a copolymer which is an additive for detergents.
  • One of the ends of the main chain of can be a carboxyl group via a sulfide bond.
  • the amount of the mercapto group-containing compound used is preferably 0.3 mol to 30 mol, more preferably 0.4 mol to 25 mol, based on 100 mol of the monomer (total monomer) used. Yes, more preferably 0.5 mol to 20 mol, most preferably 0.7 mol to 10 mol.
  • the detergent dispersibility can be improved, the compatibility with the surfactant can be improved, and the solubilizing power, which is the ability to dissolve fats, can be obtained.
  • detergent additives can be obtained.
  • another chain transfer agent may be used in combination in addition to the mercapto group-containing compound.
  • chain transfer agents include thiol-based chain transfer agents other than the above-mentioned mercapto group-containing compounds such as n-dodecyl mercaptan and octyl mercaptan; and carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane and the like.
  • Halogens secondary alcohols such as isopropanol and glycerin; phosphite, hypophosphate, hypophosphate (sodium bisulfite, potassium hypophosphate, etc.), hydrates thereof, etc. , Phosphates (salts); sodium bisulfite, bisulfite, metabisulfite, these salts (sodium bisulfite, potassium bisulfite, sodium bisulfite, potassium bisulfite, sodium metabisulfite, meta Sodium bisulfite (salts) such as potassium bisulfite; etc.;
  • the other chain transfer agent may be only one kind or two or more kinds.
  • the amount of the other chain transfer agent used is preferably 0 g to 10 g with respect to 1 mol of all the monomer components.
  • the clay dispersibility can be improved, the compatibility with the surfactant can be improved, and the solubilizing power, which is the ability to dissolve fats, can be obtained.
  • Additives for builders or detergents may be obtained.
  • a polymerization initiator When obtaining a copolymer for a detergent builder or a detergent additive by copolymerization, a polymerization initiator is preferably used.
  • the polymerization initiator may be only one kind or two or more kinds.
  • polymerization initiator examples include hydrogen peroxide; persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate; 2,2'-azobis (2-amidinopropane) hydrochloride, and 4,4'-azobis-.
  • Azo compounds such as 4-cyanopalelic acid, azobisisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, peracetic acid, di- Organic peroxides such as t-butyl peroxide and cumene hydroperoxide; and the like can be mentioned.
  • the ratio is preferably 80% by mass to 100% by mass, more preferably 85% by mass to 100% by mass, further preferably 90% by mass to 100% by mass, and particularly preferably 95% by mass to 100% by mass. %, Most preferably substantially 100% by mass.
  • Hydrogen peroxide can be used in any suitable form, for example, in the form of an aqueous solution or in the form of a complex with another compound.
  • a detergent builder or a copolymer as a detergent additive, it is preferable to use hydrogen peroxide in the form of an aqueous solution.
  • By using hydrogen peroxide in the form of an aqueous solution it is possible to obtain better clay dispersibility, better compatibility with surfactants, and better solubilizing power, which is the ability to dissolve fats.
  • Additives can be obtained.
  • the hydrogen peroxide can act as a polymerization initiator, and thus is preferably a detergent builder or a copolymer which is an additive for detergent.
  • One of the ends of the main chain can be a hydroxyl group.
  • the hydrogen peroxide does not contain a dispersibility inhibitor (for example, sulfate ion).
  • the copolymer, which is an additive for use can be excellent in stability at low temperatures.
  • the amount of the polymerization initiator used to obtain the builder for detergent or the copolymer as an additive for detergent may be any appropriate amount as long as the copolymerization of the monomer component can be initiated. .. Such an amount is preferably 0.1 mol to 30 mol, more preferably 0.1 mol to 20 mol, still more preferably 0.1 mol, based on 100 mol of the total monomer component. ⁇ 10 mol.
  • the polymerization initiator may be used in combination with a reducing agent.
  • the reducing agent may be only one kind or two or more kinds.
  • Examples of the reducing agent include ascorbic acid, ascorbic acid salt, erythorbic acid, erythorbic acid salt, ascorbic acid ester, formic acid, formate, oxalic acid, oxalate, and hydroquinone.
  • the "salt" here is a carboxyl group salt represented by COOM, and M is a hydrogen atom, a metal atom, an ammonium group (consisting of an ammonium salt), or an organic amino group (consisting of an organic amine salt). is there.
  • Examples of the metal atom include alkali metals such as sodium and potassium, alkaline earth metals such as calcium, and transition metals such as iron.
  • the organic amine salt examples include primary to quaternary amine salts such as methylamine salt, n-butylamine salt, monoethanolamine salt, dimethylamine salt, diethanolamine salt, morpholine salt and trimethylamine salt.
  • the reducing agent is preferably ascorbic acid, ascorbic acid salt, erythorbic acid, or erythorbic acid salt, and more preferably L-ascorbic acid or L-ascorbic acid salt.
  • an inorganic compound reducing agent may be used as the reducing agent.
  • the reducing agent for the inorganic compound include heavy metal ions (heavy metal salts).
  • heavy metal ions include ions such as iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, and ruthenium; sodium sulfite.
  • Sulfites such as sodium; Heavy sulfites such as sodium hydrogen sulfite; Dithionate such as sodium dithionite; Hypophosphorous acid such as sodium hypophosphate; Hypophosphates such as sodium bisulfite; Boron Compounds; and the like.
  • the clay dispersibility can be improved, the compatibility with the surfactant can be improved, and the solubilizing power, which is the ability to dissolve fats, can be improved.
  • the solubilizing power which is the ability to dissolve fats, can be improved.
  • detergent builders or detergents. Additives can be obtained.
  • the amount of the reducing agent used is preferably 0 mol to 20 mol, more preferably 0.1 mol to 15 mol, and further 0, based on 100 mol of the total monomer component. . 1 mol to 10 mol.
  • the clay dispersibility can be improved, the compatibility with the surfactant can be improved, and the solubilizing power, which is the ability to dissolve fats, can be improved.
  • Detergents can be obtained.
  • the amount of the glycol ether-based monomer and, if necessary, the other monomer (3) used is each unit in the total structural unit constituting the copolymer for the detergent builder or the detergent additive. It may be appropriately adjusted so that the ratio of the structural unit derived from the polymer is as described above.
  • the polymerization reaction proceeds quantitatively, at the same ratio as the ratio of the structural units derived from each monomer in the total structural units constituting the above-mentioned detergent builder or the copolymer which is an additive for detergent.
  • Each monomer may be used.
  • Copolymerization of monomer components can be performed by any suitable method.
  • solution polymerization and bulk polymerization can be mentioned, and solution polymerization is preferable.
  • solution polymerization method include batch type and continuous type.
  • Solvents that can be used in solution polymerization include water; alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol; aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane; and esters such as ethyl acetate.
  • Alcohols such as methyl alcohol, ethyl alcohol, and isopropyl alcohol
  • aromatic or aliphatic hydrocarbons such as benzene, toluene, xylene, cyclohexane, and n-hexane
  • esters such as ethyl acetate.
  • Compounds; ketone compounds such as acetone and methyl ethyl ketone
  • cyclic ether compounds such as tetrahydrofuran and dioxane; and the like.
  • the solvent used is water, and the content ratio of water in the solvent used is more preferably 70% by mass to 100% by mass. It is more preferably 90% by mass to 100% by mass, particularly preferably 95% by mass to 100% by mass, and most preferably substantially 100% by mass.
  • the amount of the solvent used is preferably 20% by mass to 500% by mass, and more preferably 50% by mass to 300% by mass with respect to 100% by mass of the monomer component.
  • heavy metal ions may be used as a reaction accelerator.
  • the heavy metal ion may be only one kind or two or more kinds.
  • the heavy metal ion used as a reaction accelerator means a metal having a specific gravity of 4 g / cm 3 or more.
  • Examples of such heavy metal ions include iron, cobalt, manganese, chromium, molybdenum, tungsten, copper, silver, gold, lead, platinum, iridium, osmium, palladium, rhodium, ruthenium and the like.
  • the heavy metal ion is preferably iron.
  • the amount of heavy metal ions that can be used to obtain a detergent builder or a copolymer as a detergent additive is preferably 0.1 ppm to 10 ppm with respect to the total mass of the polymerization reaction solution at the completion of the polymerization reaction. ..
  • the reaction temperature at the time of copolymerization of the monomer components is appropriately determined depending on the polymerization method, solvent, polymerization initiator, chain transfer agent, etc. used.
  • Such a reaction temperature is preferably 0 ° C. or higher, more preferably 30 ° C. or higher, further preferably 50 ° C. or higher, and preferably 150 ° C. or lower, more preferably 120 ° C. or lower. It is more preferably 100 ° C. or lower.
  • the copolymerization time at the time of copolymerization of the monomer components is preferably 30 minutes to 800 minutes, more preferably 60 minutes to 700 minutes, and further preferably 120 to 500 minutes.
  • the pressure in the reaction system during copolymerization of the monomer components may be under normal pressure (atmospheric pressure), under reduced pressure, or under pressure, and may be a combination of two or more of these. Good.
  • the atmosphere in the reaction system during the copolymerization of the monomer components may be an air atmosphere or an inert atmosphere.
  • the atmosphere in the reaction system during the copolymerization of the monomer components is preferably an inert atmosphere in which the inside of the system is replaced with an inert gas such as nitrogen before the start of polymerization.
  • any appropriate method can be adopted as the method for charging the monomer component into the reaction vessel.
  • a charging method include a method in which the entire amount is initially charged into the reaction vessel, a method in which the entire amount is divided or continuously charged into the reaction vessel, a part is initially charged into the reaction vessel, and the rest is charged into the reaction vessel.
  • Examples thereof include a method of dividing or continuously feeding. Specifically, a method in which the entire amount of the monomer (a) and the total amount of the monomer (b) are continuously charged into the reaction vessel, and a part of the monomer (a) is initially charged into the reaction vessel.
  • Examples thereof include a method in which the residue of the monomer (a) and the residue of the monomer (b) are alternately charged into the reaction vessel in several batches.
  • the charging mass ratio of each monomer per unit time is continuously or stepwise changed.
  • Two or more kinds of copolymers having different ratios of the structural unit (I) and the structural unit (II) may be synthesized at the same time during the polymerization reaction.
  • the polymerization initiator may be charged into the reaction vessel from the beginning, may be added dropwise to the reaction vessel, or these may be combined depending on the intended purpose.
  • the copolymer which is a detergent builder or a detergent additive, may be used as it is after being obtained by the above-mentioned production method, or the pH of the reaction solution after production may be 5 or more from the viewpoint of handleability. It may be adjusted to. In the latter case, in order to improve the polymerization rate, it is preferable to carry out the copolymerization at a pH of less than 5, and adjust the pH to 5 or more after the copolymerization.
  • the pH can be adjusted, for example, by using an inorganic salt such as a hydroxide or carbonate of a monovalent metal or a divalent metal; an alkaline substance such as ammonia; an organic amine;
  • the concentration of the obtained detergent builder or the copolymer as a detergent additive may be adjusted as necessary.
  • the detergent builder or detergent additive may be a powder detergent builder or a powder detergent additive, or a liquid detergent builder or a liquid detergent additive.
  • the detergent builder or detergent additive is preferably a liquid detergent builder or liquid detergent additive in that the effects of the present invention can be more exhibited.
  • the above-mentioned copolymer disclosed in the present specification can be used as an additive for various detergents.
  • Detergent builders or detergent additives can be used as additives for various detergents.
  • the term "detergent” as used herein is a concept including a cleaning agent, and the field of use is not limited to household, industrial, medical, agricultural, and the like.
  • Detergent additives include, for example, anti-adhesion agents, stain inhibitors, soil release agents, color transfer inhibitors, fabric softeners, solubilizers, fluorescent agents, and foaming agents to prevent re-deposition of contaminants. , Foam stabilizers, polishes, bactericides and the like.
  • the detergent composition according to the embodiment of the present invention is a detergent composition containing 0.01% by weight to 10% by weight of a copolymer, 1% by weight to 70% by weight of a surfactant, and alcohol.
  • the copolymer is a copolymer containing a structural unit (I) represented by the general formula (I) and a structural unit (II) represented by the general formula (II), and has a sulfide bond.
  • the average number of moles n of the oxyalkylene group represented by AO in the general formula (II) is 11 or more.
  • R 1 ⁇ R 3 are each independently a hydrogen atom, a methyl group, or - represents a (CH 2) z COOM groups, - (CH 2) z COOM group -COOX group Alternatively, it may form an anhydride with another ⁇ (CH 2 ) z COOM group, z is an integer of 0 to 2, and M is a hydrogen atom, an alkali metal, an alkaline earth metal, an ammonium group, or an organic substance.
  • R 4 and R 5 independently represent a hydrogen atom or a methyl group
  • R 6 represents a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms
  • AO represents a hydrocarbon group.
  • detergent composition is used only for specific applications such as synthetic detergents for household detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance one of its components.
  • Detergent is also included.
  • the detergent composition may be a powder detergent composition or a liquid detergent composition.
  • the detergent composition is preferably a liquid detergent composition in that the effects of the present invention can be more exhibited.
  • the content of the copolymer in the detergent composition is 0.01% by mass to 10% by mass, preferably 0.01, based on the total amount of the detergent composition, from the viewpoint of exhibiting excellent builder performance. It is from mass% to 8% by mass, particularly preferably 0.05% by mass to 6% by mass, and most preferably 0.1% by mass to 5% by mass.
  • a detergent builder or a detergent additive As the copolymer contained in the detergent composition, a detergent builder or a detergent additive according to the embodiment of the present invention may be used.
  • the detergent composition may contain a surfactant that is usually used in detergents.
  • a surfactant any suitable surfactant can be adopted as long as the effects of the present invention are not impaired.
  • the surfactant may be only one kind or two or more kinds.
  • the surfactant is typically at least one selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
  • anionic surfactant examples include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, ⁇ -olefin sulfonate, ⁇ -sulfo fatty acid or ester salt, and alkane sulfone.
  • Acid salt saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acylamino acid type surfactant, alkyl phosphate ester or its salt, alkenyl phosphate Examples include esters or salts thereof.
  • the alkyl group and alkenyl group that the anionic surfactant may have may have an alkyl group such as a methyl group branched.
  • 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 glycolides, and fatty acids. Examples thereof include glycerin monoester and alkylamine oxide.
  • the alkyl group and alkenyl group that the nonionic surfactant may have may have an alkyl group such as a methyl group branched.
  • Examples of the cationic surfactant include a quaternary ammonium salt and the like.
  • the alkyl group and alkenyl group that the cationic surfactant may have may have an alkyl group such as a methyl group branched.
  • amphoteric surfactant examples include a carboxyl type amphoteric surfactant and a sulfobetaine type amphoteric surfactant.
  • alkyl group and alkenyl group that the amphoteric surfactant can have an alkyl group such as a methyl group may be branched.
  • the blending ratio of the surfactant is usually preferably 10% by mass to 70% by mass, more preferably 15% by mass to 65% by mass, still more preferably 18% by mass, based on the total amount of the detergent composition. It is about 60% by mass, and particularly preferably 20% by mass to 55% by mass. If the blending ratio of the surfactant is too small, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too large, the economic efficiency may be lowered.
  • Detergent compositions include ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, glycerin, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, diethylene glycol.
  • Contains alcohols such as monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, diethylene glycol monobutyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol. May be good.
  • the blending ratio of the alcohol as described above is usually preferably 5% by mass to 40% by mass, more preferably 5% by mass to 35% by mass, and further preferably 5 with respect to the total amount of the detergent composition. It is by mass% to 30% by mass, and particularly preferably 10% by mass to 30% by mass.
  • the detergent composition may contain additives usually used in detergents.
  • any suitable additive can be adopted as long as the effect of the present invention is not impaired.
  • the additive may be only one type or two or more types.
  • Additives include, for example, anti-redeposition agents for preventing re-deposition of contaminants such as sodium carboxymethyl cellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, anti-color transfer agents, and fabric softeners.
  • Agents alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, dyes, solvents, etc. Can be mentioned.
  • zeolite it is preferable to add zeolite.
  • the detergent composition may include any suitable detergent builder (other than that if the copolymer is used as a detergent builder).
  • suitable detergent builder include alkali builders such as carbonates, bicarbonates and silicates; tripoliphosphate, pyrophosphate, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, citrate, (meth).
  • Chelate builder such as copolymer salt of acrylic acid, acrylic acid-maleic acid copolymer, fumarate, zeolite; carboxyl derivative of polysaccharide such as carboxymethyl cellulose; and the like.
  • the anti-salt used in the above-mentioned other detergent builders include alkali metals such as sodium and potassium, ammonium and amines.
  • the total blending ratio of the additive and the detergent builder is usually 0.1% by mass to 50% by mass, and more preferably 0.2% by mass or more, based on 100% by mass of the cleaning agent composition. It is 40% by mass, more preferably 0.3% by mass to 35% by mass, particularly preferably 0.4% by mass to 30% by mass, and most preferably 0.5% by mass to 20% by mass. .. If the total blending ratio of the additive and the detergent builder is less than 0.1% by mass, sufficient detergent performance may not be exhibited. If the total blending ratio of the additive and the detergent builder exceeds 50% by mass, the economic efficiency may decrease.
  • the amount of water contained in the liquid detergent composition is usually 0.1% by mass to 60% by mass, more preferably 0.1% by mass, based on the total amount of the liquid detergent composition. It is preferably 0.2% by mass to 55% by mass, more preferably 0.5% by mass to 50% by mass, still more preferably 0.7% by mass to 40% by mass, and particularly preferably 1% by mass. It is about 35% by mass, and most preferably 1.5% by mass to 30% by mass.
  • the detergent composition may contain an enzyme.
  • an enzyme examples include protease, lipase, cellulase, amylase and the like.
  • the blending ratio of the enzyme is usually 5% by mass or less with respect to the total amount of the detergent composition.
  • Detergent compositions can usually be produced with the step of blending the copolymer as essential.
  • ⁇ Weight average molecular weight analysis conditions The weight average molecular weight was measured under the following measurement conditions.
  • Equipment Waters Alliance (2695) Analysis software: Waters, Emper Professional + GPC option Column used: Tosoh, TSKgel guard column (inner diameter 6.0 mm x 40 mm) + TSKgel G4000SWXL (inner diameter 7.8 mm x 300 mm) + G3000SWXL (inner diameter 7.8 mm x 300 mm) + G2000SWXL (inner diameter 7.8 mm x 300 mm) Inner diameter 7.8 mm x 300 mm) Detectors: Differential Refractometer (RI) Detector (Waters 2414), Photodiode Array (PDA) Detector (Waters 2996) Eluent: 115.6 g of sodium acetate trihydrate dissolved in a mixed solvent of 10999 g of water and 6001 g of acetonitrile, and the pH was adjusted to 6.0 with acetic acid.
  • GPC standard sample Polyethylene glycol manufactured by GL Science (peak top molecular weight (peak top molecular weight (peak top molecular weight)) Mp) 272500, 219300, 107000, 50000, 24000, 11840, 6450, 4250, 1470)
  • Calibration curve Prepared by a cubic formula using the Mp value of the above polyethylene glycol. Flow rate: 1.0 mL / min Column temperature: 40 ° C Measurement temperature: 40 ° C Measurement time: 45 minutes Sample solution injection volume: 100 ⁇ L (eluent solution with a sample concentration of 0.5% by mass) Standard sample injection volume: 100 ⁇ L (eluent solution with a concentration of 0.1% by mass)
  • Emargen 108 manufactured by Kao Corporation
  • Neoperex G-65 manufactured by Kao Corporation
  • Example 1 An unsaturated flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel with an average of 50 mol of ethylene oxide added to 80% by mass of 3-methyl-3-butene-1-ol.
  • An aqueous solution of polyalkylene glycol ether (MB-50): 221.24 g and ion-exchanged water: 102.9 g were charged, and after nitrogen substitution, the temperature was raised to 58 ° C. with stirring.
  • Example 2 In a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, 181.72 g of an 80 mass% MB-50 aqueous solution and 118.4 g of ion-exchanged water were charged, and after nitrogen substitution. The temperature was raised to 60 ° C. with stirring. When the temperature reached a predetermined temperature, 0.65 g of 35% by mass hydrogen peroxide solution (H 2 O 2 ) was added all at once.
  • H 2 O 2 hydrogen peroxide solution
  • Example 3 80% by mass MB-50 aqueous solution: 260.2 g and ion-exchanged water: 66.6 g were charged in a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, and after nitrogen replacement. The temperature was raised to 58 ° C. with stirring. When the temperature reached a predetermined temperature, 0.57 g of 35% by mass hydrogen peroxide solution (H 2 O 2 ) was added all at once.
  • H 2 O 2 hydrogen peroxide solution
  • Example 4 80% by mass MB-50 aqueous solution: 235.4 g and ion-exchanged water: 81.6 g were placed in a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, and after nitrogen replacement. The temperature was raised to 57 ° C. with stirring. When the temperature reached a predetermined temperature, 35% by mass of hydrogen peroxide solution (H 2 O 2 ): 0.38 g was added all at once.
  • H 2 O 2 hydrogen peroxide solution
  • Example 5 In a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel, 80% by mass of MB-50 aqueous solution: 220.1 g, ion-exchanged water: 81.9 g, molle salt: 0. After charging 0017 g and replacing with nitrogen, the temperature was raised to 60 ° C. with stirring. When the temperature reached a predetermined temperature, 35% by mass of hydrogen peroxide solution (H 2 O 2 ): 0.49 g was added all at once.
  • H 2 O 2 hydrogen peroxide solution
  • the weight average molecular weight of the obtained water-soluble copolymer (5) was 15,000, the solid content was 55.5% by mass, and the pH was 6.9.
  • Various evaluations were carried out using the obtained water-soluble copolymer (5) as a detergent builder or a detergent additive. The results are shown in Table 2.
  • Example 6 250 g of ion-exchanged water was charged into a glass reaction vessel equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube, and a reflux condenser, and the inside of the reaction vessel was replaced with nitrogen under stirring to raise the temperature to 58 ° C. .. Next, an aqueous solution obtained by diluting 80% by mass of MB-50 aqueous solution: 435.6 g and 100% by mass of AA: 51.5 g with ion-exchanged water: 155 g was added dropwise to the reaction vessel over 5 hours.
  • Various evaluations were carried out using the obtained water-soluble copolymer (6) as a detergent builder or a detergent additive. The results are shown in Table 2.
  • Example 7 In a glass reaction vessel equipped with a thermometer, stirrer, dropping funnel, nitrogen introduction tube, and reflux condenser, 300 parts of ion-exchanged water, 10 mol of ethylene oxide in 3-methyl-3-buten-1-ol on average. Add 165 parts of unsaturated polyalkylene glycol ether (MB-10) and 430 parts of MB-50: 430 parts, and after raising the temperature to 65 ° C., hydrogen peroxide: 3.3 parts and ion-exchanged water: 6 parts. A hydrogen peroxide aqueous solution containing 2 parts was added.
  • MB-10 unsaturated polyalkylene glycol ether
  • 430 parts of MB-50 430 parts
  • Example 8 85 parts of ion-exchanged water, MB-10: 26.4 parts, and MB-50: 172 parts were charged in a glass reaction vessel equipped with a thermometer, a stirrer, a dropping funnel, a nitrogen introduction tube, and a reflux condenser. After raising the temperature to 65 ° C., an aqueous hydrogen peroxide solution containing 1.3 parts of hydrogen peroxide and 2.3 parts of ion-exchanged water was added thereto. Next, 100% by mass of AA: 26.3 parts was added dropwise into the reaction vessel over 5 hours, and at the same time, ion-exchanged water: 68 parts, LAs: 1.0 part and MPA: 3.6 parts. Was added dropwise over 5.5 hours.
  • Example 9 Ion-exchanged water: 86 parts, MB-10: 5.8 parts, MB-50: 176 parts were charged in a glass reaction vessel equipped with a thermometer, agitator, a dropping funnel, a nitrogen introduction tube, and a reflux condenser. After raising the temperature to 65 ° C., an aqueous hydrogen peroxide solution containing 0.6 part of hydrogen peroxide and 1.1 parts of ion-exchanged water was added thereto. Next, 100% by mass of AA: 18.4 parts was added dropwise into the reaction vessel over 5 hours, and at the same time, ion-exchanged water: 59.4 parts, L-As: 0.8 parts and MPA: 2.
  • Ion-exchanged water 104 parts, MB-10: 28.3 parts, MB-50: 166 parts were charged in a glass reaction vessel equipped with a thermometer, agitator, a dropping funnel, a nitrogen introduction tube, and a reflux condenser. After raising the temperature to 65 ° C., an aqueous hydrogen peroxide solution containing 0.9 part of hydrogen peroxide and 1.7 parts of ion-exchanged water was added thereto. Next, 100% by mass of AA: 30.4 parts was added dropwise into the reaction vessel over 5 hours, and at the same time, ion-exchanged water: 81 parts, L-As: 1.2 parts and MPA: 3.0 parts. Was added dropwise over 5.5 hours.
  • Aqueous solution 26.9 g, 3% by mass sodium hydrogen sulfite (SBS) aqueous solution: 13.5 g were added dropwise.
  • the AA aqueous solution and the NaOH aqueous solution were added dropwise over 180 minutes, the MB-10 aqueous solution was added dropwise over 110 minutes, the NaPS aqueous solution was added dropwise over 220 minutes, and the SBS aqueous solution was added dropwise over 210 minutes.
  • the polymer was aged at the same temperature for 30 minutes to complete the polymerization, and after the polymerization, 36 g of a 49% by mass NaOH aqueous solution was added to obtain a water-soluble copolymer (C1).
  • the weight average molecular weight of the obtained water-soluble copolymer (C1) was 90500, and the solid content was 44.1% by mass.
  • Various evaluations were carried out using the obtained water-soluble copolymer (C1) as a detergent builder or a detergent additive. The results are shown in Table 2.
  • the polymer was aged at the same temperature for 30 minutes to complete the polymerization, and after the polymerization, 15.6 g of a 49% by mass NaOH aqueous solution was added to obtain a water-soluble copolymer (C2).
  • the weight average molecular weight of the obtained water-soluble copolymer (C2) was 77400, and the solid content was 25.9% by mass.
  • Various evaluations were carried out using the obtained water-soluble copolymer (C2) as a detergent builder or a detergent additive. The results are shown in Table 2.
  • the polymer was aged at the same temperature for 30 minutes to complete the polymerization, and after the polymerization, 15.5 g of a 49% by mass NaOH aqueous solution was added to obtain a water-soluble copolymer (C3).
  • the weight average molecular weight of the obtained water-soluble copolymer (C3) was 132,000, and the solid content was 25.9% by mass.
  • Various evaluations were carried out using the obtained water-soluble copolymer (C3) as a detergent builder or a detergent additive. The results are shown in Table 2.
  • the weight average molecular weight of the obtained water-soluble copolymer (C4) was 23,700, and the solid content was 30.7% by mass.
  • Various evaluations were carried out using the obtained water-soluble copolymer (C4) as a detergent builder or a detergent additive. The results are shown in Table 2.
  • the AA aqueous solution was added dropwise over 180 minutes, the MB-10 aqueous solution was added dropwise over 110 minutes, and the V-50 aqueous solution was added dropwise over 210 minutes.
  • the polymer was aged at the same temperature for 30 minutes to complete the polymerization, and after the polymerization, 18.6 g of a 49% by mass NaOH aqueous solution was added to obtain a water-soluble copolymer (C5).
  • the weight average molecular weight of the obtained water-soluble copolymer (C5) was 36,800, and the solid content was 23.9% by mass.
  • Various evaluations were carried out using the obtained water-soluble copolymer (C5) as a detergent builder or a detergent additive. The results are shown in Table 2.
  • the detergent builder or detergent additive according to the embodiment of the present invention can be used in various detergent compositions.

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Abstract

L'invention fournit un adjuvant pour détergent ou un additif pour détergent qui se révèle excellent en termes de propriétés de dispersion d'argile, de compatibilité avec un agent tensio-actif, et de puissance de solubilisation, c'est-à-dire capacité de dissolution d'une graisse. En outre, l'invention fournit une composition de détergent qui contient un copolymère pouvant être mis en œuvre de manière appropriée dans un tel adjuvant pour détergent ou additif pour détergent.　L'adjuvant pour détergent ou l'additif pour détergent de l'invention consiste en un copolymère qui contient une unité structurale (I) spécifique et une une unité structurale (II), possède une liaison sulfure, et présente un nombre molaire moyen (n) de groupes oxyalkylène représenté par AO supérieur ou égal à 11.
PCT/JP2020/013829 2019-03-29 2020-03-26 Adjuvant pour détergent ou additif pour détergent, et composition de détergent WO2020203694A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002060785A (ja) * 2000-08-22 2002-02-26 Nippon Shokubai Co Ltd 液体洗剤用ビルダーおよび液体洗剤組成物
JP2003012704A (ja) * 2001-04-02 2003-01-15 Nippon Shokubai Co Ltd 化学反応物質の製造方法及びそれにより製造されてなるポリカルボン酸並びにセメント添加剤、分散剤、粉末洗剤用ビルダー及び液体洗剤用ビルダー
JP2008266619A (ja) * 2007-03-23 2008-11-06 Nippon Shokubai Co Ltd ポリアルキレングリコール鎖含有チオール重合体及びその製造方法
JP2010285556A (ja) * 2009-06-12 2010-12-24 Kao Corp 衣料洗剤用高分子ビルダー
JP2019006914A (ja) * 2017-06-26 2019-01-17 株式会社日本触媒 洗浄剤用分散剤
JP2019006913A (ja) * 2017-06-26 2019-01-17 株式会社日本触媒 疎水性基含有共重合体

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002060785A (ja) * 2000-08-22 2002-02-26 Nippon Shokubai Co Ltd 液体洗剤用ビルダーおよび液体洗剤組成物
JP2003012704A (ja) * 2001-04-02 2003-01-15 Nippon Shokubai Co Ltd 化学反応物質の製造方法及びそれにより製造されてなるポリカルボン酸並びにセメント添加剤、分散剤、粉末洗剤用ビルダー及び液体洗剤用ビルダー
JP2008266619A (ja) * 2007-03-23 2008-11-06 Nippon Shokubai Co Ltd ポリアルキレングリコール鎖含有チオール重合体及びその製造方法
JP2010285556A (ja) * 2009-06-12 2010-12-24 Kao Corp 衣料洗剤用高分子ビルダー
JP2019006914A (ja) * 2017-06-26 2019-01-17 株式会社日本触媒 洗浄剤用分散剤
JP2019006913A (ja) * 2017-06-26 2019-01-17 株式会社日本触媒 疎水性基含有共重合体

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