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WO2023210565A1 - Composition détergente comprenant un copolymère à base d'alcool vinylique - Google Patents

Composition détergente comprenant un copolymère à base d'alcool vinylique Download PDF

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Publication number
WO2023210565A1
WO2023210565A1 PCT/JP2023/016064 JP2023016064W WO2023210565A1 WO 2023210565 A1 WO2023210565 A1 WO 2023210565A1 JP 2023016064 W JP2023016064 W JP 2023016064W WO 2023210565 A1 WO2023210565 A1 WO 2023210565A1
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WIPO (PCT)
Prior art keywords
structural unit
general formula
detergent composition
group
vinyl alcohol
Prior art date
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PCT/JP2023/016064
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English (en)
Japanese (ja)
Inventor
久晶 竹嶋
務 細谷
泰弘 大野
和俊 長尾
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Nippon Shokubai Co Ltd
Original Assignee
Nippon Shokubai Co Ltd
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Priority to JP2024517301A priority Critical patent/JPWO2023210565A1/ja
Publication of WO2023210565A1 publication Critical patent/WO2023210565A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an alcohol radical
    • C08F216/04—Acyclic compounds
    • C08F216/06—Polyvinyl alcohol ; Vinyl alcohol
    • 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
    • C08F216/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical
    • C08F216/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical by an ether radical
    • 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
    • C08F226/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen
    • C08F226/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen by a single or double bond to 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/10—Acylation
    • 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
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/12—Hydrolysis
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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 disclosure relates to a detergent composition containing a vinyl alcohol-based copolymer that is biodegradable and has excellent re-stain prevention ability.
  • polyvinyl alcohol is biodegradable and has excellent processability, so it has been used in various applications such as films.
  • Patent Document 1 discloses copolymers of vinyl alcohol and N-vinyl-2-caprolactam, N-vinylacetamide, ethyl vinyl ether, and the like.
  • the present disclosure has been made in view of the deception, and aims to provide a detergent composition containing a vinyl alcohol copolymer that is biodegradable and has good anti-resoiling ability.
  • the detergent composition containing the vinyl alcohol copolymer of the present disclosure is a vinyl alcohol copolymer having a structural unit (A) of the following general formula (1) and a structural unit (B) of the following general formula (2).
  • R x represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.
  • R x is a hydrogen atom or a carbon number of 1 to 10. Represents one or more types selected from organic groups.
  • the detergent composition of the present disclosure includes: A vinyl alcohol copolymer having a structural unit (A) of the following general formula (1) and a structural unit (B) of the following general formula (2) is added in an amount of 0.1 to 15% based on the total amount of the detergent composition. Including mass%,
  • R x represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.
  • R x represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.
  • it is also a detergent composition containing 10 to 60% by mass of a surfactant based on the total amount of the detergent composition.
  • the vinyl alcohol copolymer preferably has a weight average molecular weight of 1,000 to 1,000,000.
  • the mass ratio of the structural unit (A) and the structural unit (B) is preferably 1 to 99/1 to 99.
  • the content of structural units (E) other than the structural unit (A) and the structural unit (B) is such that the total amount of the structural units (A), (B), and (E) is 100 mass. % to 50% by mass.
  • the proportion of -C ⁇ OR x in the structural unit (A) is preferably 20 mol% or less based on 100 mol% of the total amount of R 1 groups.
  • the present invention also provides a vinyl alcohol copolymer having the structural unit (A), the structural unit (B), and the structural unit (C) represented by the following general formula (4).
  • X represents a hydrocarbon group having 1 to 6 carbon atoms.
  • R 3 represents a hydrocarbon group having 2 to 6 carbon atoms.
  • m represents an integer of 1 to 2.
  • n represents an integer from 1 to 200.
  • the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit (C) represented by general formula (4) is bonded.
  • the vinyl alcohol copolymer has a content of structural units (E1) other than the structural unit (A), the structural unit (B), and the structural unit (C) such that the content of the structural unit (E1) is the structural unit (A), the structural unit (B),
  • the amount is preferably 0 to 10% by mass based on 100% by mass of the total amount of (C) and (E1).
  • the vinyl alcohol copolymer of the present disclosure is a copolymer having a structural unit (A) represented by the following general formula (1) and a structural unit (B) represented by the following general formula (2). be.
  • R x represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.
  • R x represents a hydrogen atom or an organic group having 1 to 10 carbon atoms.
  • R x represents a hydrogen atom or an organic group having 1 to 10 carbon atoms, but if a plurality of R x exist in the copolymer, all R x may be the same or different. good.
  • the monomer (A), which is a precursor of the structural unit (A) represented by the general formula (1), is a vinyl carboxylate compound such as vinyl acetate.
  • the carboxylic acid vinyl compound can be represented by the general formula (5) described below.
  • R x in the general formula (1) of the present disclosure is not particularly limited as long as it is a hydrogen atom or an organic group having 1 to 10 carbon atoms.
  • R x is an organic group having 1 to 10 carbon atoms, it may be a saturated or unsaturated chain hydrocarbon, and may be linear or branched. Further, aromatic groups and heteroatoms may be included. Specific examples of organic groups having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, n-butyl group such as isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group.
  • Alkyl groups such as n-hexyl, heptyl, octyl, nonyl, decyl; vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl , nonenyl group, decenyl group, and other alkenyl groups; phenyl group, naphthyl group, benzyl group, and other aryl groups.
  • the organic group is preferably an alkyl group.
  • R x is a hydrogen atom or a methyl group
  • the polymerization reactivity with the vinylamine derivative represented by the general formula (3) described below will be improved, and the hydrolysis performed after the copolymerization reaction will be improved. This is preferable because hydrolysis of the protecting group is likely to occur during (saponification) treatment.
  • the monomer (B), which is a precursor of the structural unit (B) represented by the general formula (2), is a vinylamine derivative.
  • the vinylamine derivative can be represented by the following general formula (3).
  • R x in general formula (3) is the same as R x in general formula (2).
  • vinylamine derivatives include amide compounds of vinylamine and carboxylic acid having 1 to 10 carbon atoms, such as N-vinylformamide and N-vinylacetamide. Preferred are N-vinylformamide and N-vinylacetamide.
  • the content is more preferably 90 mol% or less, even more preferably 80 mol% or less, particularly preferably 75 mol% or less.
  • R x in the general formula (2) or (3) of the present disclosure is the same as R x in the general formula (1).
  • the mass ratio of the structural unit (A) and the structural unit (B) in the vinyl alcohol copolymer of the present invention is preferably 1 to 99/1 to 99. More preferably 1-98/2-99, still more preferably 1-97/3-99, even more preferably 50-97/3-50, particularly preferably 70-97/3-30. be. It is preferable that the mass ratio of the structural unit (A) and the structural unit (B) in the vinyl alcohol-based copolymer of the present disclosure is within the above-mentioned range, since the ability to prevent re-staining is improved.
  • the mole% of the structural unit (A) is 50 mole% or more, preferably 70 mole% or more, more preferably 80 mole% or more, more preferably 90 mole% or more, based on the mole number of all the structural units constituting the polymer. It is preferable that the amount is mol% because biodegradability is improved.
  • the vinyl alcohol copolymer of the present disclosure may have a structural unit (E) other than the structural units (A) and (B).
  • the structural unit (E) is a structural unit derived from a monomer (E) other than monomer (A) and monomer (B).
  • the structural unit (A) constituting the vinyl alcohol copolymer of the present disclosure When the total amount of (B) and (E) is 100% by mass, the content of the structural unit (E) is preferably 0 to 50% by mass. More preferably 0 to 30% by mass, still more preferably 0 to 20% by mass, even more preferably 0 to 10% by mass, particularly preferably 0 to 5% by mass, and most preferably 0% by mass. It is.
  • Examples of the monomer (E) include a monomer (C) represented by the general formula (6) described below and other polymerizable monomers (E1) described below.
  • the vinyl alcohol copolymer of the present disclosure may have a structural unit (C) of the following general formula (4) in addition to the structural unit (A) and the structural unit (B).
  • X represents a hydrocarbon group having 1 to 6 carbon atoms.
  • R 3 represents a hydrocarbon group having 2 to 6 carbon atoms.
  • m represents an integer of 1 to 2.
  • n represents an integer from 1 to 200.
  • the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit (C) represented by general formula (4) is bonded.
  • a vinyl alcohol copolymer having the structural unit (A) of the above general formula (1), the structural unit (B) of the above general formula (2), and the structural unit (C) of the above general formula (4) may also be used. , is one of the inventions.
  • X in the structural unit (C) represented by the general formula (4) of the present disclosure is one or more types selected from hydrocarbon groups having 1 to 6 carbon atoms, and R 3 is one or more hydrocarbon groups having 2 to 6 carbon atoms. represents a hydrocarbon group, m is an integer of 1 to 2, and n is not particularly limited as long as it is an integer of 1 to 200.
  • the hydrocarbon group may be a chain and/or branched hydrocarbon group.
  • Specific examples of the hydrocarbon group having 1 to 6 carbon atoms include methylene group, ethylene group, n-propylene group, isopropylene group, n-butylene group, isobutylene group, n-pentyl group, neopentyl group, isopentyl group, Examples include n-hexyl group.
  • a preferred form of the X is a hydrocarbon group having 2 to 4 carbon atoms, and more preferred forms are an ethylene group, an n-propylene group, and an n-butylene group.
  • ethylene group and n-butylene group More preferred are ethylene group and n-butylene group. Moreover, when m is 2, an ethylene group is preferable. When the X is an ethylene group or an n-butylene group, it is preferable from the viewpoint of availability of raw material vinyl ether before addition of alkylene oxide and polymerizability.
  • R 3 in the structural unit (C) represented by the general formula (4) of the present disclosure represents a hydrocarbon group having 2 to 6 carbon atoms, and n is an integer of 1 to 200, and is not particularly limited. There isn't. R 3 may be a chain and/or branched hydrocarbon group. More preferably a hydrocarbon group having 2 to 4 carbon atoms, still more preferably a hydrocarbon group having 2 to 3 carbon atoms, most preferably a hydrocarbon group having 2 carbon atoms. Specific examples include ethylene group, propylene group, and butylene group.
  • R 3 is more preferably an ethylene group which is a hydrocarbon group having 2 carbon atoms.
  • n in the structural unit (C) represented by the general formula (4) of the present disclosure is more preferably 1 to 150, still more preferably 1 to 100, and even more preferably 1 to 50.
  • the number is even more preferably 1 to 30, particularly preferably 1 to 20. It is preferable that n in the structural unit (C) represented by the general formula (4) is within the above-mentioned range because the polyalkylene oxide chain improves the dispersion effect of particulate dirt such as mud.
  • the vinyl alcohol copolymer of the present disclosure may have a structural unit (E1) other than the structural units (A) to (C).
  • the structural unit (E1) is a monomer (A), a monomer (B), and other polymerizable monomers (E1) other than the monomer (C) represented by the general formula (6) described below. It is a structural unit derived from.
  • Other polymerizable monomers (E1) include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and citraconic acid; ethylene glycol monovinyl ether, hydroxybutyl vinyl ether, etc.
  • Vinyl ethers unsaturated alcohols with 3 to 10 carbon atoms such as (meth)allyl alcohol and isoprenyl alcohol; unsaturated alcohols with 3 to 10 carbon atoms such as (meth)allyl alcohol and isoprenyl alcohol with 2 carbon atoms
  • Saturated amines such as divinylbenzene; cyanurates such as triallyl cyanurate; polydimethylsiloxane propylaminomaleamide acid, polydimethylsiloxane aminopropylene aminomaleamide acid, polydimethylsiloxane bis- maleamic acid), polydimethylsiloxane-bis-(dipropyleneaminomaleamidic acid), polydimethylsiloxane-(1-propyl-3-acrylate), polydimethylsiloxane-(1-propyl-3-methacrylate), polydimethyl Siloxane derivatives such as siloxane-bis-(1-propyl-3-acrylate) and polydimethylsiloxane-bis-(1-propyl-3-methacrylate) are preferred, and one or more of these may be used. can.
  • the vinyl alcohol copolymer of the present disclosure has a mass ratio of the structural unit (A), the structural unit (B), and the structural unit (C) of 1 to 98/1 to 98/1. It is preferable that it is between 98 and 98. More preferably 19-89/1-71/10-80, still more preferably 25-83/2-60/15-73, even more preferably 30-75/2-30/20-60. , particularly preferably from 40 to 60/2 to 20/30 to 55.
  • the mass ratio of the structural unit (A), the structural unit (B), and the structural unit (C) contained in the vinyl alcohol copolymer of the present disclosure is within the above range, the recontamination prevention ability and the This is preferable because it improves degradability.
  • the structural unit (E1) is preferably contained in an amount of 0 to 10% by mass. It is more preferably 0 to 5% by weight, still more preferably 0 to 1% by weight, and most preferably 0% by weight.
  • the weight average molecular weight of the vinyl alcohol copolymer of the present disclosure is not particularly limited as long as it is from 1,000 to 1,000,000. Preferably 3,000 to 500,000, more preferably 5,000 to 200,000, still more preferably 7,000 to 100,000, even more preferably 8,000 to 50,000. , particularly preferably from 9,000 to 30,000, most preferably from 10,000 to 20,000. It is preferable that the weight average molecular weight of the vinyl alcohol-based copolymer of the present disclosure is within the above-mentioned range because it has biodegradability and exhibits excellent recontamination prevention ability.
  • the weight average molecular weight of the vinyl alcohol copolymer can be measured by the method described in Examples.
  • the method for producing the vinyl alcohol copolymer of the present disclosure is not particularly limited, and the monomer (A) represented by the following general formula (5) and the monomer (A) represented by the above general formula (3) ( It can be produced by copolymerizing monomer components containing B).
  • R x is a hydrogen atom or an organic group having 1 to 10 carbon atoms.
  • a monomer (C) represented by the following general formula (6) may be used as the monomer component. is preferred.
  • X represents a hydrocarbon group having 1 to 6 carbon atoms.
  • R 3 represents a hydrocarbon group having 2 to 6 carbon atoms.
  • m represents an integer of 1 to 2.
  • n represents an integer from 1 to 200.
  • R x is a hydrogen atom or an organic group having 1 to 10 carbon atoms. If so, there are no particular limitations. Preferred forms and the like are the same as R 1 in the above general formula (1), and R x in R 1 is also the same as R x in the above general formula (1).
  • R x in the general formula (5) is a hydrogen atom or a methyl group
  • a vinyl carboxylate corresponding to a monomer that is a precursor of the structural unit (A) represented by the general formula (1) This is preferred because the polymerization reactivity of the compound is improved and the protecting group is more likely to be hydrolyzed by the hydrolysis (saponification) treatment performed after the copolymerization reaction.
  • R x of the monomer (B) represented by the general formula (3) is not particularly limited as long as it is a hydrogen atom or an organic group having 1 to 10 carbon atoms. Preferred forms and the like are the same as R x in the general formula (2).
  • R x in the general formula (3) is a hydrogen atom or a methyl group
  • a vinylamide compound corresponding to a monomer that is a precursor of the structural unit (B) represented by the general formula (2) This is preferred because the polymerization reactivity is improved and the protecting group is more likely to be hydrolyzed by the hydrolysis (saponification) treatment performed after the copolymerization reaction.
  • R 3 of the monomer (C) represented by the general formula (6) is a hydrocarbon group having 2 to 6 carbon atoms, m is an integer of 1 to 2, and n is 1 to 200. There is no particular limitation as long as it is an integer. Preferred forms and the like are the same as R 3 , m, and n in the structural unit (C) represented by the general formula (4).
  • the monomer (C) represented by the general formula (6) is obtained by adding an alkylene oxide having 2 to 6 carbon atoms to a hydroxy vinyl ether such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, or diethylene glycol monovinyl ether.
  • the method for producing a vinyl alcohol copolymer of the present disclosure includes a monomer (A) represented by the above general formula (5) and a monomer (B) represented by the above general formula (3).
  • the method includes a step of hydrolyzing them.
  • the order of the copolymerization step and the hydrolysis step is not particularly limited, but considering the stability of the monomer (A) and the monomer (B), it is preferable to It is preferable to perform the hydrolysis step after the copolymerization step in a still state.
  • the vinyl alcohol copolymer of the present disclosure is produced by copolymerizing a monomer component containing a vinyl carboxylate compound such as vinyl acetate and a vinylamine derivative represented by the general formula (3), and then adding water to the copolymer.
  • Hydrolysis is preferably carried out using a basic substance such as sodium oxide or potassium hydroxide.
  • polymerizable monomers than the carboxylic acid vinyl compound such as vinyl acetate and the vinylamine derivative represented by the general formula (3) may be used.
  • Other polymerizable monomers are as described above, and specifically include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, citraconic acid, allyl alcohol, isoprenol, allyl alcohol EO adduct, isoprenol EO Adducts, acrylamide, sodium acrylamide propane sulfonate, sodium 2-hydroxy-3-allyloxypropane sulfonate, hydroxyethyl acrylate, hydroxyethyl methacrylate, vinyl ethers such as ethylene glycol monovinyl ether, diethylene glycol monovinyl ether, hydroxybutyl vinyl ether, and ethylene oxide , alkylene oxide adducts such as propylene oxide are preferably used.
  • the ratio of a vinyl carboxylate compound such as vinyl acetate, a vinylamine derivative represented by the general formula (3), and other polymerizable monomers is as follows: There is no particular limitation, and polymerization can be carried out at any ratio. If the ratio of other polymerizable monomers is increased, biodegradability tends to decrease.
  • ⁇ Polymerization initiator> As the polymerization initiator used in the above production method, those commonly used can be used. Specifically, hydrogen peroxide; persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate; 2,2'-azobis(2-amidinopropane) hydrochloride, 4,4'-azobis-4-cyanovalerin; acids, azo compounds such as azobisisobutyronitrile, 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, peracetic acid, di-t-butyl Suitable examples include organic peroxides such as peroxide and cumene hydroperoxide.
  • polymerization initiators hydrogen peroxide, persulfate, and 2,2'-azobis(2-amidinopropane) hydrochloride are preferred; Salt is more preferred.
  • polymerization initiators may be used alone or in combination of two or more.
  • the polymerization temperature in the production method is appropriately determined depending on the polymerization method, solvent, polymerization initiator, etc. used, but is preferably 25° C. or higher.
  • the temperature is more preferably 50°C or higher, still more preferably 60°C or higher, particularly preferably 80°C or higher. Moreover, it is preferable that it is 200 degrees C or less.
  • the temperature is more preferably 150°C or lower, still more preferably 120°C or lower, particularly preferably 110°C or lower.
  • the polymerization temperature does not need to be kept almost constant during the polymerization reaction; for example, the polymerization may be started from room temperature, raised to a set temperature at an appropriate heating time or rate, and then the set temperature may be increased.
  • the temperature may be maintained, or the temperature may be varied (increased or decreased) over time during the polymerization reaction depending on the method of dropping the monomer components, initiator, etc.
  • the polymerization temperature refers to the temperature of a reaction solution in a polymerization reaction.
  • any appropriate method or means can be employed as a method for measuring or controlling the polymerization temperature. For example, it may be measured using a commonly used device.
  • the pressure during the polymerization reaction in the production method is not particularly limited, and any appropriate pressure can be employed.
  • it may be under normal pressure (atmospheric pressure), reduced pressure, or increased pressure.
  • the atmosphere in the reaction system may be air as is or may be an inert gas atmosphere.
  • the atmosphere within the reaction system is an inert gas atmosphere, this can be done, for example, by replacing the inside of the reaction system with an inert gas such as nitrogen before starting the polymerization.
  • the atmospheric gas (for example, oxygen gas, etc.) in the reaction system is dissolved in the liquid phase and acts as a polymerization inhibitor.
  • an aging step may be provided for the purpose of increasing the polymerization rate.
  • the polymerization time is not particularly limited, but is preferably 20 to 420 minutes.
  • the hydrolysis carried out in the above production method may be either acidic hydrolysis or basic hydrolysis.
  • Basic hydrolysis is preferred.
  • any compound that acts on strong acidity can be used. Examples include hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, nitric acid, phosphoric acid, sulfamic acid, methanesulfonic acid, etc., but monovalent acids are preferred from the viewpoint of solubility of the hydrolyzate in water.
  • any compound that acts on strong basicity can be used. Examples include sodium hydroxide, potassium hydroxide, lithium hydroxide, and quaternary ammonium hydroxide.
  • the amount of the modifier used is usually 0.05 to 5 times the mole of the total of the formyl group in the polymer of N-vinylformamide or N-vinylacetamide moiety and the ester group of the carboxylic acid vinyl ester moiety. It is used as appropriate depending on the desired modification rate within the range.
  • the reaction temperature is usually in the range of 50 to 110°C, and the reaction time is usually in the range of 1 to 8 hours.
  • the hydrolysis is carried out in two steps by separating the acetyl group (protecting group) of a vinyl carboxylate compound such as vinyl acetate, which is a monomer corresponding to the structural unit (A), and the protecting group in the general formula (3).
  • a hydrolysis (saponification) reaction may be carried out.
  • the detergent composition of the present disclosure includes the vinyl alcohol copolymer of the present disclosure as an essential component.
  • the content of the vinyl alcohol copolymer of the present disclosure in the detergent composition of the present disclosure is not particularly limited, the vinyl alcohol copolymer of the present disclosure may be The content of is preferably 0.1 to 15% by mass based on the total amount of the detergent composition of the present disclosure. The amount is more preferably 0.3 to 10% by weight, and even more preferably 0.5 to 5% by weight.
  • Detergent compositions used in detergent applications usually contain surfactants and additives used in detergents.
  • the specific forms of these surfactants and additives are not particularly limited, and conventionally known knowledge in the field of detergents can be appropriately referred to.
  • the detergent composition may be a powder detergent composition or a liquid detergent composition.
  • the surfactant is one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
  • the total amount of anionic surfactant and nonionic surfactant is preferably 50% by mass or more, more preferably 60% by mass based on the total amount of surfactant.
  • the content is more preferably 70% by mass or more, particularly preferably 80% by mass or more.
  • anionic surfactants include alkylbenzene sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, ⁇ -olefin sulfonates, ⁇ -sulfo fatty acids or ester salts, and alkanesulfonates. , saturated fatty acid salts, unsaturated fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, amino acid type surfactants, N-acylamino acid type surfactants, alkyl phosphate esters or salts thereof, alkenyl phosphate esters, Salts thereof are suitable.
  • the alkyl group or alkenyl group in these anionic surfactants may have a branched alkyl group such as a methyl group.
  • nonionic surfactants include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkylphenyl ether, higher fatty acid alkanolamide or its alkylene oxide adduct, sucrose fatty acid ester, alkyl glycoxide, fatty acid glycerin monomer. Ester, alkylamine oxide, etc. are suitable.
  • the alkyl group and alkenyl group in these nonionic surfactants may have a branched alkyl group such as a methyl group.
  • cationic surfactant quaternary ammonium salts and the like are suitable.
  • amphoteric surfactant carboxyl-type amphoteric surfactants, sulfobetaine-type amphoteric surfactants, etc. are suitable.
  • the alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may have a branched alkyl group such as a methyl group.
  • the blending ratio of the surfactant is generally not particularly limited as long as it is 10 to 60% by mass based on the total amount of the detergent composition of the present disclosure, preferably 15 to 50% by mass, and more preferably 20 to 60% by mass.
  • the amount is 45% by weight, particularly preferably 25-40% by weight. If the blending ratio of the surfactant is too low, there is a risk that sufficient cleaning power cannot be exhibited, and if the blending ratio of the surfactant is too high, there is a risk that the economical efficiency will decrease.
  • Additives include alkali builders, chelate builders, anti-redeposition agents to prevent redeposition of pollutants such as sodium carboxymethyl cellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, and color transfer agents.
  • Inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishing agents, disinfectants, bleaching agents, bleaching aids, enzymes, dyes , a solvent, etc. are suitable.
  • zeolite it is preferable to incorporate zeolite.
  • the detergent composition may contain other detergent builders in addition to the polymer composition of the present invention.
  • other detergent builders include, but are not limited to, alkali builders such as carbonates, hydrogen carbonates, and silicates; Examples include acid salts, (meth)acrylic acid copolymer salts, acrylic acid-maleic acid copolymers, fumarates, chelate builders such as zeolites, and carboxyl derivatives of polysaccharides such as carboxymethyl cellulose.
  • the counter salt used in the builder include alkali metals such as sodium and potassium, ammonium, and amines.
  • the total blending ratio of the additives and other detergent builders is usually preferably 0.1 to 50% by mass based on 100% by mass of the detergent composition. More preferably 0.2 to 40% by mass, still more preferably 0.3 to 35% by mass, particularly preferably 0.4 to 30% by mass, and most preferably 0.5 to 20% by mass. be. If the blending ratio of additives/other detergent builders is less than 0.1% by mass, there is a risk that sufficient detergent performance will not be exhibited, and if it exceeds 50% by mass, there is a risk that economic efficiency will decrease.
  • the concept of the detergent composition mentioned above includes synthetic detergents for household detergents, detergents for the textile industry and other industries, hard surface cleaners, as well as bleaching detergents with enhanced functionality of one of their components, and other specific uses. Also includes detergents that are only used.
  • the amount of water contained in the liquid detergent composition is usually preferably 0.1 to 75% by mass, more preferably 0.1 to 75% by mass based on the total amount of the liquid detergent composition. is 0.2 to 70% by mass, more preferably 0.5 to 65% by mass, even more preferably 0.7 to 60% by mass, particularly preferably 1 to 55% by mass, and most preferably Preferably it is 1.5 to 50% by mass.
  • the detergent composition when the detergent composition is a liquid detergent composition, the detergent composition preferably has a kaolin turbidity of 200 mg/L or less, more preferably 150 mg/L or less, and even more preferably 120 mg/L or less. It is particularly preferably 100 mg/L or less, most preferably 50 mg/L or less.
  • the change (difference) in kaolin turbidity between when the polymer composition of the present invention is added to a liquid detergent composition as a detergent builder and when it is not is preferably 500 mg/L or less, more preferably It is 400 mg/L or less, more preferably 300 mg/L or less, particularly preferably 200 mg/L or less, and most preferably 100 mg/L or less.
  • the value of kaolin turbidity the value measured by the following method shall be adopted.
  • Preferred enzymes that can be incorporated into the cleaning composition include protease, lipase, cellulase, and the like.
  • proteases, alkaline lipases, and alkaline cellulases, which have high activity in alkaline cleaning solutions, are preferred.
  • the amount of the enzyme added is preferably 5% by mass or less based on 100% by mass of the cleaning composition. If it exceeds 5% by mass, no improvement in detergency will be seen and there is a risk that economic efficiency will decrease.
  • the vinyl alcohol copolymer of the present disclosure can be used in water treatment agents, fiber treatment agents, dispersants, etc. in addition to the detergent compositions described above.
  • the vinyl alcohol copolymer of the present disclosure can be used in a water treatment agent.
  • the water treatment agent may contain other additives such as polymerized phosphates, phosphonates, anticorrosive agents, slime control agents, and chelating agents, as required.
  • the water treatment agent is useful for preventing scale in cooling water circulation systems, boiler water circulation systems, seawater desalination equipment, pulp digesters, black liquor concentrators, and the like. Further, any appropriate water-soluble polymer may be included as long as it does not affect the performance or effect.
  • the vinyl alcohol copolymer of the present disclosure can be used as a fiber treatment agent.
  • the fiber treatment agent includes at least one selected from the group consisting of a dye, a peroxide, and a surfactant, and the vinyl alcohol copolymer of the present disclosure.
  • the content of the vinyl alcohol copolymer of the present disclosure in the fiber treatment agent is preferably 1 to 100% by weight, more preferably 5 to 100% by weight, based on the entire fiber treatment agent.
  • any appropriate water-soluble polymer may be contained within a range that does not affect performance or effects. Below, a blending example of a fiber treatment agent that is closer to the embodiment is shown. This fiber treatment agent can be used in the steps of scouring, dyeing, bleaching, and soaping in fiber treatment.
  • the dyes, peroxides and surfactants include those commonly used in fiber treatment agents.
  • the blending ratio of the vinyl alcohol copolymer of the present disclosure and at least one selected from the group consisting of dyeing agents, peroxides, and surfactants may be determined, for example, by controlling the whiteness, color unevenness, and dyeing strength of the fibers.
  • at least one selected from the group consisting of dyes, peroxides, and surfactants is added to 1 part by weight of the polymer composition of the present invention in terms of pure fiber treatment agent content. It is preferable to use a composition blended in a proportion of 1 to 100 parts by weight as a fiber treatment agent. Any suitable fiber can be used as the fiber that can be used with the fiber treatment agent.
  • Examples include cellulose fibers such as cotton and hemp, chemical fibers such as nylon and polyester, animal fibers such as wool and silk, semi-synthetic fibers such as human silk, and woven and blended products thereof.
  • the fiber treatment agent it is preferable to mix the vinyl alcohol copolymer of the present disclosure with an alkali agent and a surfactant.
  • a peroxide When applied to a bleaching process, it is preferable to blend the vinyl alcohol copolymer of the present disclosure, a peroxide, and a silicic acid agent such as sodium silicate as a decomposition inhibitor for alkaline bleaching agents.
  • the vinyl alcohol copolymer of the present disclosure can be used as an inorganic pigment dispersant. If necessary, condensed phosphoric acid and its salts, phosphonic acid and its salts, and polyvinyl alcohol may be used as other compounding agents in the inorganic pigment dispersant.
  • the content of the vinyl alcohol copolymer of the present disclosure in the inorganic pigment dispersant is preferably 5 to 100% by weight based on the entire inorganic pigment dispersant. Further, any suitable water-soluble polymer may be contained within a range that does not affect the performance and effects.
  • the inorganic pigment dispersant can exhibit good performance as a dispersant for inorganic pigments such as heavy or light calcium carbonate and clay used in paper coating.
  • an inorganic pigment dispersant for example, by adding a small amount of an inorganic pigment dispersant to an inorganic pigment and dispersing it in water, we can create a highly concentrated calcium carbonate that has low viscosity, high fluidity, and good stability over time.
  • a highly concentrated inorganic pigment slurry such as a slurry can be produced.
  • the amount of the inorganic pigment dispersant used is preferably 0.05 to 2.0 parts by weight per 100 parts by weight of the inorganic pigment.
  • the amount of the inorganic pigment dispersant used is within the above range, it becomes possible to obtain a sufficient dispersion effect, and it becomes possible to obtain an effect commensurate with the amount added, which may be economically advantageous.
  • ⁇ Manufacture example 1> In a glass reaction vessel equipped with a thermometer, nitrogen inlet tube, reflux condenser, and stirrer chip, 14.57 g of ethanol, 13.52 g of vinyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and N-vinylacetamide (hereinafter also referred to as NVA) were added. .) 1.48g (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.43g of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-65) were charged, and the inside of the reaction vessel was heated with nitrogen.
  • NVA N-vinylacetamide
  • the temperature was raised to 60°C while stirring. Further, the reaction solution was stirred for 18 hours while being kept at 60°C, and after confirming the consumption of each monomer, the solvent was distilled off under reduced pressure using an evaporator.
  • the weight average molecular weight of the obtained intermediate 1 was 16,500.
  • ⁇ Manufacture example 2> In a glass reaction vessel equipped with a thermometer, nitrogen inlet tube, reflux condenser, and stirrer chip, 14.56 g of ethanol, 13.74 g of vinyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and N-vinylformamide (hereinafter also referred to as NVF) were added. ) 1.26g (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.44g of 2,2'-azobis(2,4-dimethylvaleronitrile) (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., V-65), and the inside of the reaction vessel was heated with nitrogen.
  • NVF N-vinylformamide
  • the temperature was raised to 60°C while stirring. Further, the reaction solution was stirred for 18 hours while being kept at 60°C, and after confirming the consumption of each monomer, the solvent was distilled off under reduced pressure using an evaporator.
  • the weight average molecular weight of the obtained intermediate 2 was 15,500.
  • Examples 1 to 3> 5.12 g of Intermediate 1 was placed in a glass reaction vessel equipped with a thermometer and a stirrer tip, and dissolved in 20.19 g of methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). After confirming that Intermediate 1 was completely dissolved, 1.19 g of a 4% NaOH-methanol suspension was added so that the concentration was 2 mol % based on the acyl group, and the temperature was raised to 50° C. with stirring. After 3 hours, it was confirmed that the reaction product had precipitated, and the temperature was returned to room temperature. The solvent was distilled off under reduced pressure using an evaporator from the suspension in which the reactant was precipitated, to obtain a polymer (1). Intermediates 2 and 3 were also saponified by the same procedure to obtain polymers (2) and (3).
  • Example 3-2 A glass reaction vessel equipped with a thermometer and a stirrer tip was charged with 0.51 g of the polymer (3) obtained in Example 3, and 9.54 g of sulfuric acid (1%) was added thereto. The temperature was raised to 80°C while stirring to dissolve all the polymer, and the mixture was stirred for 3 hours. Thereafter, the temperature was returned to room temperature, and 1.94 g of NaOH aqueous solution (1M) was added to neutralize it, thereby obtaining an aqueous solution of polymer (3') obtained by deamidating polymer (3). The hydrolysis rate of the polymer (3') after deamidation was 99% for vinyl ester groups and 86% for vinylamide groups.
  • VE-10 an ethylene oxide
  • Example 4 8.04 g of Intermediate 1 was placed in a glass reaction vessel equipped with a thermometer and a stirrer tip, and dissolved in 32.4 g of methanol (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.). After confirming that Intermediate 1 was completely dissolved, 0.75 g of 5% NaOH-methanol suspension was added, and the temperature was raised to 50° C. with stirring. After 3 hours, it was confirmed that the reaction product had precipitated, and the temperature was returned to room temperature. The solvent was distilled off under reduced pressure using an evaporator from the suspension in which the reactant was precipitated, to obtain a polymer (4).
  • Cotton cloth (1) Five pieces of cotton knitted fabric (manufactured by Tanigashira Shoten) 5 cm x 5 cm were prepared as recontamination determination cloth.
  • Cotton fabric (2) Cotton fabric obtained from Testfabrics was prepared in a total weight of 30 g together with cotton fabric (1). As surfactants, a 3% LAS aqueous solution and 0.1% by mass aqueous solutions of polymers (1) to (4) obtained in Examples were prepared.
  • Recontamination prevention rate (Z value of cotton fabric (1) after washing process) ⁇ (Z value of cotton fabric (1) before washing process) x 100
  • Table 2 shows the re-staining prevention rate (2) of the cotton fabric (1) after the above washing treatment.
  • ⁇ Biodegradability test> A biodegradability test of the obtained polymer was conducted in accordance with OECD301F.
  • Preparation of medium Culture medium stock solutions A to D were prepared by the following method.
  • Solution A 0.850 g of potassium dihydrogen phosphate (KH 2 PO 4 ), 2.175 g of dipotassium hydrogen phosphate (K 2 HPO 4 ), disodium hydrogen phosphate dodecahydrate (Na 2 HPO 4 12H 6.7217 g of ammonium chloride (NH 4 Cl) and 0.050 g of ammonium chloride (NH 4 Cl) were weighed into a 50 ml sample bottle, dissolved in an appropriate amount of water, transferred to a 100 ml volumetric flask, and water was added up to the marked line.
  • KH 2 PO 4 potassium dihydrogen phosphate
  • K 2 HPO 4 dipotassium hydrogen phosphate
  • disodium hydrogen phosphate dodecahydrate Na 2 HPO 4 12H 6.7217 g of ammoni
  • Solution B 3.640 g of calcium chloride dihydrate (CaCl 2 .2H 2 O) was dissolved in an appropriate amount of water and transferred to a 100 ml volumetric flask, and then water was added up to the marked line.
  • Solution C 2.250 g of magnesium sulfate heptahydrate (MgSO 4 .7H 2 O) was dissolved in an appropriate amount of water, transferred to a 100 ml volumetric flask, and water was added up to the marked line.
  • MgSO 4 .7H 2 O magnesium sulfate heptahydrate
  • Solution D 0.025 g of iron (III) chloride hexahydrate (FeCl 3 .6H 2 O) was dissolved in an appropriate amount of water and transferred to a 100 ml volumetric flask, and then water was added up to the marked line.
  • the temperature of the above culture medium stock solutions A to D was adjusted to 25°C, and 10 ml of A was put into a 1 L volumetric flask using a whole pipette, and diluted with approximately 800 ml of water. Thereafter, 1 ml each of B, C, and D was added using a whole pipette, and the mixture was diluted to the marked line with water adjusted to 25°C. Multiple volumes of the above medium were prepared according to the amount required for the test.
  • the prepared medium was transferred to a 5L beaker, mixed, and bubbled for over 1 hour while stirring.
  • Preparation of sludge solution The sludge used for the biodegradability test was obtained from Minami Suita Sewage Treatment Plant. First, the concentration of the sludge obtained was measured using the method described below. Bubbling was performed while stirring the obtained sludge, 5 ml was taken using a whole pipette, and suction filtration was performed using filter paper. Five sheets of filter paper from which sludge was collected in this manner were prepared, and after drying in a drier at 105° C. for 1 hour, the concentration of the sludge was calculated from the average weight loss of the five sheets.
  • This sludge was diluted with the medium prepared above to prepare a 1000 ppm sludge solution.
  • Preparation of polymer aqueous solution Polymers (1) to (4) obtained in Examples (1) to (4) were diluted with pure water to obtain a 2% by mass aqueous polymer solution. Further, as a standard substance, sodium benzoate was diluted with pure water to obtain a 2% by mass aqueous sodium benzoate solution.
  • BOD test A pressure sensor type BOD meter was used to measure BOD. After weighing 144.75 g of the medium prepared above into a flan bottle, 0.75 g of a 2% aqueous polymer solution was added.

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Abstract

Le but de la présente invention est de fournir une composition détergente qui comprend un copolymère à base d'alcool vinylique qui a d'excellentes performances d'inhibition de resalissure et est biodégradable. La présente invention concerne une composition détergente comprenant un copolymère à base d'alcool vinylique qui a une unité structurale (A) représentée par la formule générale (1) et une unité structurale (B) représentée par la formule générale (2).
PCT/JP2023/016064 2022-04-26 2023-04-24 Composition détergente comprenant un copolymère à base d'alcool vinylique Ceased WO2023210565A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04308274A (ja) * 1991-03-30 1992-10-30 Kuraray Co Ltd 繊維用糊剤
JPH0987667A (ja) * 1995-09-21 1997-03-31 Kanebo Ltd 洗浄剤組成物
JP2000219706A (ja) * 1999-02-01 2000-08-08 Mitsubishi Chemicals Corp Ｎ−ビニルアミド−酢酸ビニル系共重合体加水分解物の製造方法及びその用途
WO2012033183A1 (fr) * 2010-09-10 2012-03-15 株式会社日本触媒 Polymère à teneur en groupe amino, son procédé de fabrication et composition de détergent
WO2015146196A1 (fr) * 2014-03-28 2015-10-01 株式会社日本触媒 Nouveau polymère, composition de résine, article moulé en résine et procédé de production du nouveau polymère

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07316590A (ja) * 1994-05-26 1995-12-05 Lion Corp 色移り・再汚染防止剤および洗剤組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04308274A (ja) * 1991-03-30 1992-10-30 Kuraray Co Ltd 繊維用糊剤
JPH0987667A (ja) * 1995-09-21 1997-03-31 Kanebo Ltd 洗浄剤組成物
JP2000219706A (ja) * 1999-02-01 2000-08-08 Mitsubishi Chemicals Corp Ｎ−ビニルアミド−酢酸ビニル系共重合体加水分解物の製造方法及びその用途
WO2012033183A1 (fr) * 2010-09-10 2012-03-15 株式会社日本触媒 Polymère à teneur en groupe amino, son procédé de fabrication et composition de détergent
WO2015146196A1 (fr) * 2014-03-28 2015-10-01 株式会社日本触媒 Nouveau polymère, composition de résine, article moulé en résine et procédé de production du nouveau polymère

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