Classifications

• • 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
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
• • 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
  • C08F216/14—Monomers containing only one unsaturated aliphatic 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
  • 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
  • C08F220/12—Esters of monohydric alcohols or phenols
• • 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
  • C08F220/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

• This disclosure relates to a composition.
• Detergents used for clothing have conventionally been blended with detergent builders (detergent assistants) such as zeolite, carboxymethylcellulose, and polyethylene glycol in order to improve the cleaning effect of the detergent.
• detergent builders detergent assistants
• polymers have been blended as detergent builders in detergent compositions.
• polymers in which polyalkyleneimine is the main chain and ethylene oxide or the like is added to the nitrogen atoms in the polyalkyleneimine are also called polyethyleneimine ethoxylate modified products, and can act as polymer builders.
• Patent Document 1 discloses the use of a polymer that improves the cleaning power of proteolytic enzymes in detergents, characterized in that the polymer is ethoxylated polyethyleneimine.
• This disclosure has been made in light of the current situation described above, and aims to provide a composition with excellent cleaning power.
• compositions containing an enzyme and an amino-containing copolymer having a structure derived from an amino-containing monomer and a polyalkylene glycol chain has excellent cleaning power. They came to the realization that the above-mentioned problems could be solved in an excellent manner, and arrived at the present disclosure.
• compositions comprising an amino group-containing copolymer having a structural unit (a) derived from an amino group-containing monomer represented by the following general formula (1) and a structural unit (b) derived from a monomer having a polyalkylene glycol chain, and an enzyme:
• R 1 , R 2 , and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• R 4 and R 5 each independently represent a hydrogen atom or an organic group having 1 to 12 carbon atoms
• X represents a divalent linking group.
• an asterisk represents an atom contained in another structural unit of the same type or different type to which the structural unit represented by general formula (1) is bonded.
• [2] The composition according to [1], further comprising a surfactant.
• [3] The composition according to the above [1] or [2], wherein the amino group-containing copolymer further has a structural unit (c) derived from a hydrophobic group-containing monomer.
• the content of the structural unit (a) in the amino group-containing copolymer is 2% by mass or more and 50% by mass or less, based on 100% by mass of all structural units.
• the content of the structural unit (b) in the amino group-containing copolymer is 5% by mass or more and 98% by mass or less, based on 100% by mass of all structural units.
• the amino group-containing copolymer has a content of the structural unit (c) of 0 mass% or more and 50 mass% or less, based on 100 mass% of all structural units.
• the amino group-containing copolymer has a weight average molecular weight of 4,000 or more and 500,000 or less.
• surfactant comprises an anionic surfactant and/or a nonionic surfactant.
• composition disclosed herein has the above-mentioned composition and has excellent cleaning power, making it suitable for use in detergents, etc.
• composition of the present disclosure contains an amino group-containing copolymer (hereinafter also referred to as the copolymer of the present disclosure) and an enzyme.
• the composition of the present disclosure contains the copolymer and therefore has excellent detergency against proteinaceous stains.
• the content of the copolymer in the composition of the present disclosure is not particularly limited, but is preferably 0.1 to 10% by mass relative to 100% by mass of the composition. More preferably, it is 0.5 to 5% by mass, and even more preferably, it is 0.5 to 3.5% by mass.
• the content of the enzyme in the composition of the present disclosure is not particularly limited, but is preferably 0.01 to 10% by mass relative to 100% by mass of the composition. More preferably, it is 0.02 to 1.0% by mass, even more preferably, it is 0.05 to 0.75% by mass, and particularly preferably, it is 0.1 to 0.55% by mass.
• the content ratio of the copolymer relative to 100% by mass of the enzyme is preferably 100 to 10,000% by mass. More preferably, it is 100 to 5,000% by mass, and even more preferably, it is 500 to 3,500% by mass.
• the composition may contain a surfactant in addition to the amino group-containing copolymer and the enzyme.
• the content of the surfactant is not particularly limited, but is preferably 5 to 80% by mass, more preferably 25 to 55% by mass, and even more preferably 25 to 40% by mass, based on 100% by mass of the composition.
• the composition may contain other components in addition to the amino group-containing copolymer, enzyme, and surfactant.
• the other components are not particularly limited, but include, for example, water, detergent builders, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, color transfer inhibitors, fabric softeners, alkaline substances for adjusting pH, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishing agents, disinfectants, bleaching agents, bleaching aids, dyes, solvents, and the like.
• the content of the other components is not particularly limited, but is preferably 25 to 75% relative to 100% by mass of the composition. More preferably, it is 30 to 65% by mass.
• the essential and optional components contained in the compositions of the present disclosure are further described below.
• the amino group-containing copolymer contained in the composition of the present disclosure (hereinafter also referred to as the copolymer of the present disclosure) is a copolymer having a structural unit (a) derived from an amino group-containing monomer described below and a structural unit (b) derived from a monomer having a polyalkylene glycol chain.
• the composition of the present disclosure can be obtained by including the copolymer of the present disclosure and an enzyme. Furthermore, the composition can be obtained by including a surfactant in a detergent composition, which can exhibit better detergency.
• the structural unit (a) derived from an amino group-containing monomer of the present disclosure is a structural unit represented by the following general formula (1).
• R 1 , R 2 , and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms
• R 4 and R 5 each independently represent a hydrogen atom or an organic group having 1 to 12 carbon atoms
• X represents a divalent linking group, with the exception that the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by general formula (1) is bonded.
• an atom contained in another structural unit of the same type refers to, for example, a structural unit represented by general formula (1), an atom contained in a structural unit represented by another general formula (1)
• an atom contained in another structural unit of a different type refers to, for example, a structural unit represented by general formula (1), an atom contained in a structural unit other than the structural unit represented by general formula (1).
• R 1 , R 2 and R 3 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
• the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group (amyl group), an i-propyl group, a sec-butyl group, an i-butyl group, a t-butyl group, a 1-methylbutyl group, a 1-ethylpropyl group, a 2-methylbutyl group, an i-amyl group, a neopentyl group, etc.
• alkyl groups having 1 to 3 carbon atoms such as a methyl group, an ethyl group, a propyl group, etc., more preferred are a methyl group, an ethyl group, and even more preferred is a methyl group.
• R 1 , R 2 and R 3 are preferably a hydrogen atom or a methyl group. In one preferred embodiment of the present invention, R 1 and R 2 are hydrogen atoms and R 3 is a methyl group.
• R 4 and R 5 each independently represent a hydrogen atom or an organic group having 1 to 12 carbon atoms.
• the organic group is not particularly limited, but examples thereof include hydrocarbon groups which may have a substituent.
• the organic group preferably has 1 to 10 carbon atoms, more preferably 1 to 8 carbon atoms, further preferably 1 to 6 carbon atoms, even more preferably 1 to 4 carbon atoms, and particularly preferably 1 to 2 carbon atoms.
• hydrocarbon group in the organic group examples include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, and an aralkyl group. Among these, an alkyl group is preferred.
• alkyl group examples include methyl, ethyl, n-propyl, n-butyl, n-pentyl (amyl), n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, i-propyl, sec-butyl, i-butyl, t-butyl, 1-methylbutyl, 1-ethylpropyl, 2-methylbutyl, i-amyl, neopentyl, 1,2-dimethylpropyl, 1,1-dimethylpropyl, t-amyl, 1,3-dimethylbutyl, 3,3-dimethylbutyl, 2-ethylbutyl, 2 -Aliphatic alkyl groups such as ethyl-2-methylpropyl group, 1-methylheptyl group,
• alkenyl group examples include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, and a dodecenyl group.
• alkynyl group examples include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, and a dodecynyl group.
• Examples of the aryl group include a phenyl group, an o-, m- or p-tolyl group, a 2,3- or 2,4-xylyl group, a mesityl group, and a naphthyl group.
• Examples of the aralkyl group include a benzyl group, a phenethyl group, and a phenylpropyl group.
• the structure derived from the amino group-containing monomer can be formed, for example, by radical polymerization of a monomer having an ethylenically unsaturated group and a primary to tertiary amino group represented by the following general formula (2), or a product of neutralization of a primary to tertiary amino group with an acid, but is not limited thereto.
• R 4 and R 5 in the above general formula (2) are the same as R 4 and R 5 in the above general formula (1).
• the structural unit (a) derived from the above amino group-containing monomer is formed, for example, by radical polymerization of an amino group-containing monomer.
• the amino group-containing monomer include N,N-dialkylamino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate, and their neutralization with acids such as hydrochloric acid and acetic acid; N,N-dialkylamino group-containing (meth)acrylamides such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N
• esters of allylamines and their neutralization with acids such as hydrochloric acid and acetic acid
• N,N-diallylmethylamine and its neutralization with acids such as hydrochloric acid and acetic acid allylamine and its neutralization with acids such as hydrochloric acid and acetic acid
• addition reaction products of unsaturated monomers having a cyclic ether-containing group with 2 to 8 carbon atoms such as 1-allyloxy-3-dibutylamino-2-ol and 1-allyloxy-3-diethanolamino-2-ol, with amine compounds having 1 to 24 carbon atoms, and their neutralization with acids such as hydrochloric acid and acetic acid.
• the structural unit (a) derived from the amino group-containing monomer is preferably a structural unit derived from N,N-dimethylaminoethyl (meth)acrylate, represented by the following general formula (3), or a product thereof neutralized with an acid.
• R6 in the above general formula (3) represents a hydrogen atom or a methyl group.
• the asterisk represents an atom contained in another structural unit of the same type or different type to which the structural unit represented by general formula (3) is bonded.
• Most preferred is a structural unit derived from N,N-dimethylaminoethyl methacrylate or a product thereof neutralized with an acid.
• the content of the structural unit (a) derived from an amino group-containing monomer is 2% by mass or more and 50% by mass or less, preferably 3% by mass or more and 45% by mass or less, more preferably 4% by mass or more and 40% by mass or less, and particularly preferably 5% by mass or more and 30% by mass or less, relative to 100% by mass of the structural units derived from all monomers constituting the copolymer of the present disclosure (hereinafter also referred to as all structural units).
• the content of the structural unit (a) may be 5% by mass or more and 50% by mass or less, 7% by mass or more and 45% by mass or less, 8% by mass or more and 40% by mass or less, and particularly preferably 10% by mass or more and 30% by mass or less. In one aspect, the content of the structural unit (a) is 15% by mass or more and 25% by mass or less, which is also one of the preferred embodiments of the present invention.
• the structural unit (b) derived from a monomer having a polyalkylene glycol chain of the present disclosure is characterized in that it contains a polyalkylene glycol chain in its structure.
• the structural unit (b) is represented, for example, by the following general formula (4).
• R 7 , R 8 and R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent
• Z represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group or a salt thereof.
• A represents an alkylene group having 1 to 10 carbon atoms which may have a substituent.
• q represents the average number of moles of (AO) added and is a number from 1 to 200.
• n represents a number from 0 to 4.
• m represents 0 or 1.
• R 7 , R 8 , and R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and the substituent is preferably at least one hydrophilic group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, and salt groups thereof.
• the alkyl group is preferably a methyl group, an ethyl group, or a propyl group, more preferably a methyl group or an ethyl group, and further preferably a methyl group. It is preferable that R 7 , R 8 , and R 9 are each independently a hydrogen atom or a methyl group. More preferably, R 7 and R 9 are hydrogen atoms, and R 8 is a hydrogen atom or a methyl group. Even more preferably, R 7 and R 9 are hydrogen atoms, and R 8 is a methyl group.
• Z represents a hydrogen atom, a hydrocarbon group having 1 to 30 carbon atoms, or a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, or a salt thereof.
• the above-mentioned hydrocarbon group is not particularly limited, and examples thereof include linear hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and cyclic hydrocarbon groups such as aryl groups, aralkyl groups, cycloalkyl groups, and cycloalkenyl groups.
• the above-mentioned hydrocarbon group may have a branch, and when the hydrocarbon group has a branch, the number of carbon atoms means the total number of carbon atoms in the main chain and the branched chains.
• alkyl group examples include ethyl, propyl, isopropyl, butyl, isobutyl, hexyl, heptyl, 2-ethylhexyl, octyl, nonyl, decyl, dodecyl, stearyl, and icosyl groups.
• alkenyl group examples include vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, octadecenyl, and icosenyl groups.
• alkynyl group examples include ethynyl, 1-propynyl, 2-propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, dodecynyl, octadecenyl, and icosenyl groups.
• aryl group examples include a phenyl group, a methylphenyl group, a 1-methoxy-4-methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a butylmethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a dibutylphenyl group, a biphenyl group, and a naphthyl group.
• aralkyl group examples include a benzyl group, a phenethyl group, a phenylpropyl group, a benzhydryl group, a biphenylmethyl group, a biphenylethyl group, a naphthylmethyl group, and a naphthylethyl group.
• Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
• the hydrocarbon group is preferably an alkyl group or an alkenyl group, more preferably an alkyl group.
• the number of carbon atoms in the hydrocarbon group is preferably 2 to 20, more preferably 2 to 15, even more preferably 2 to 10, and particularly preferably 2 to 5.
• the above Z is preferably a hydrogen atom or a methyl group.
• the above A represents an alkylene group having 1 to 10 carbon atoms which may have a substituent.
• the substituent is preferably at least one hydrophilic group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a secondary or tertiary amino group, and salts thereof.
• the q oxyalkylene groups of AO present may all be the same or different.
• the alkylene group represented by A preferably has 2 to 10 carbon atoms, and more preferably has 2 to 4 carbon atoms.
• Examples of the oxyalkylene group represented by AO include oxyethylene, oxypropylene, oxybutylene, oxyisobutylene, oxy-2,3-butylene, oxystyrene, and oxyalkylene having 2 to 10 carbon atoms. More preferably, it is an oxyalkylene group having 2 to 4 carbon atoms such as oxyethylene, oxypropylene, and oxybutylene, and even more preferably, it is oxyethylene and oxypropylene.
• the oxyalkylene group represented by AO is not limited to a group formed by an addition reaction of an oxyalkylene group.
• the above polyalkylene glycol is an adduct of two or more types of oxyalkylene groups, it may be in any form such as random addition, block addition, or alternating addition. It is preferable that the oxyalkylene group in the polyalkylene glycol has an oxyethylene group as an essential component, more preferably 50 mol % or more of oxyethylene groups, and even more preferably 90 mol % or more of oxyethylene groups.
• q represents the average number of moles of AO added, and is a number from 1 to 200. It is preferably from 1 to 180, more preferably from 2 to 150, more preferably from 2 to 100, even more preferably from 2 to 80, particularly preferably from 2 to 50, and most preferably from 20 to 30. In one embodiment, q is preferably 2 to 180, more preferably 3 to 150, more preferably 4 to 100, even more preferably 5 to 80, and particularly preferably 9 to 50.
• n represents a number from 0 to 4, and m represents 0 or 1.
• n is preferably 0 to 3, more preferably 0 to 2, and further preferably 0.
• m is more preferably 1.
• the structural unit (b) having a polyalkylene glycol chain is formed, for example, by radical polymerization of a monomer having a polyalkylene glycol chain.
• the monomer having the polyalkylene glycol chain include polyalkylene glycol mono(meth)acrylates such as (poly)ethylene glycol mono(meth)acrylate and (poly)propylene glycol mono(meth)acrylate; alkoxy polyalkylene glycol mono(meth)acrylates such as methoxy(poly)ethylene glycol mono(meth)acrylate and methoxy(poly)propylene glycol mono(meth)acrylate; and (poly)alkylene glycol monomers such as compounds in which 10 to 100 moles of oxyalkylene groups are added to any of vinyl alcohol, (meth)allyl alcohol, 3-methyl-3-buten-1-ol (isoprenol), 3-methyl-2-buten-1-ol, 2-methyl-3-buten-2-ol, 2-methyl-2-buten-1-
• the content of the structural unit (b) having a polyalkylene glycol chain in the copolymer of the present disclosure is preferably 5% by mass or more and 98% by mass or less, more preferably 20% by mass or more and 95% by mass or less, even more preferably 30% by mass or more and 90% by mass or less, particularly preferably 40% by mass or more and 85% by mass or less, and most preferably 45% by mass or more and 80% by mass or less, relative to 100% by mass of the structural units derived from all the monomers constituting the copolymer of the present disclosure.
• the content of the structural unit (b) may be 5% by mass or more and 95% by mass or less, 20% by mass or more and 80% by mass or less, 30% by mass or more and 70% by mass or less, 40% by mass or more and 65% by mass or less, or 45% by mass or more and 60% by mass or less. In one embodiment, the content of the structural unit (b) may be 50% by mass or more.
• the copolymer of the present disclosure may have a structural unit (c) derived from a hydrophobic monomer as a structural unit other than the structural unit (a) derived from the amino group-containing monomer and the structural unit (b) derived from the monomer having a polyalkylene glycol chain.
• the hydrophobic monomer of the present disclosure constituting the structural unit (c) derived from the hydrophobic monomer of the present disclosure is not particularly limited as long as it has a solubility parameter of 13 or less in a homopolymer obtained by homopolymerization.
• the solubility parameter is a value calculated by the method described in pp.
• solubility parameter of the homopolymer obtained by polymerizing the hydrophobic monomer of the present disclosure alone is 13 or less, the hydrophobicity of the copolymer of the present disclosure is sufficient and the copolymer has excellent adsorption to hydrophobic fibers.
• the solubility parameter is preferably 12 or less, and more preferably 11 or less.
• the solubility parameter is usually 5 or more.
• the hydrophobic monomer of the present disclosure is not particularly limited as long as the solubility parameter of the homopolymer is 13 or less, but is preferably a monomer having an ethylenically unsaturated group and an alkyl group having 1 to 30 carbon atoms.
• hydrophobic monomer examples include esters of unsaturated carboxylic acids such as (meth)acrylic acid and alcohols having 1 to 30 carbon atoms which may have a substituent; aromatic vinyl monomers such as styrene; olefin monomers such as ethylene and propylene; esters of unsaturated alcohols such as vinyl acetate and carboxylic acids having 3 to 8 carbon atoms; vinyl halides such as vinyl chloride; alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether; cyclic vinyl monomers such as N-vinylpyrrolidone, and acrylonitrile.
• esters of unsaturated carboxylic acids such as (meth)acrylic acid and alcohols having 1 to 30 carbon atoms which may have a substituent
• aromatic vinyl monomers such as styrene
• olefin monomers such as ethylene and propylene
• esters of unsaturated alcohols such as vinyl acetate and carboxylic acids having
• the substituent that the alcohol may have may be any substituent other than a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, or a salt group thereof, and examples thereof include halogen atoms.
• the alcohol preferably has 2 to 22 carbon atoms, more preferably 2 to 16 carbon atoms, and further preferably 4 to 8 carbon atoms.
• Preferable examples of the alcohol having 1 to 30 carbon atoms include alkyl alcohols having 1 to 30 carbon atoms and aromatic alcohols having 6 to 30 carbon atoms.
• alkyl alcohols having 1 to 30 carbon atoms include methanol, ethanol, propanol, butanol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, and icosyl alcohol.
• Preferred examples of the aromatic alcohol having 6 to 30 carbon atoms include phenol, benzyl alcohol, methylphenyl alcohol (o-cresol, m-cresol, p-cresol), creosol, ethylphenyl alcohol, propylphenyl alcohol, butylphenyl alcohol, butylmethylphenyl alcohol, dimethylphenyl alcohol, diethylphenyl alcohol, dibutylphenyl alcohol, hydroxybiphenyl, 4-hydroxymethylbiphenyl, 3-hydroxymethylbiphenyl, 4-hydroxyethylbiphenyl, 3-hydroxyethylbiphenyl, naphthol, 1-hydroxymethyl-naphthalene, 1-hydroxyethyl-naphthalene, 2-hydroxymethyl-naphthalene, 2-hydroxyethyl-naphthalene, etc.
• the hydrophobic monomer is preferably represented by the following general formula (5);
• R 10 , R 11 and R 12 may be the same or different and each represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; R 13 represents a hydrocarbon group having 1 to 30 carbon atoms). That is, the structural unit (c) derived from the hydrophobic monomer of the present disclosure is represented by the following general formula (6):
• R 10 to R 13 are the same as in general formula (5), with the exception that the asterisk represents an atom contained in another structural unit of the same or different type to which the structural unit represented by general formula (6) is bonded).
• the amino group-containing copolymer of the present disclosure has a structural unit represented by the above general formula (6)
• the structural unit may be obtained by polymerization using a compound represented by the above general formula (5) or may be obtained by other methods.
• the alkyl group in the above R 10 , R 11 and R 12 is preferably a methyl group, an ethyl group or a propyl group, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
• R 10 , R 11 and R 12 are the same or different and each is preferably a hydrogen atom or a methyl group, more preferably R 10 and R 11 are a hydrogen atom and R 12 is a hydrogen atom or a methyl group.
• the number of carbon atoms in the hydrocarbon group in R 13 is preferably 1 to 22. More preferably, it is 2 to 16, even more preferably 2 to 12, particularly preferably 4 to 12, and most preferably 4 to 8.
• the hydrocarbon group in R 13 is not particularly limited, and examples thereof include chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and cyclic hydrocarbon groups such as aromatic groups, cycloalkyl groups, and cycloalkenyl groups.
• the hydrocarbon group may have a branch, and the number of carbon atoms in the hydrocarbon group when it has a branch means the total number of carbon atoms in the main chain and the branched chain.
• the hydrocarbon group for R 13 may or may not have an aromatic group, but an embodiment in which R 13 is a hydrocarbon group that does not have an aromatic group is also one of the preferred embodiments of the present disclosure.
• the number of carbon atoms in the alkyl group in R 13 is preferably 2 to 22, more preferably 2 to 16, and particularly preferably 2 to 12. Most preferably 4 to 8.
• the aromatic group for R 13 preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and particularly preferably 6 to 8 carbon atoms.
• Examples of the alkyl group in R 13 include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group, a stearyl group, and an icosyl group.
• Examples of the alkenyl group in R 13 include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group, and an icosenyl group.
• Examples of the alkynyl group in R 13 include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecynyl group, an octadecynyl group, and an icosynyl group.
• Examples of the aromatic group in R 13 include aryl groups such as a phenyl group, a benzyl group, a methylphenyl group, a 1-methoxy-4-methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a butylmethylphenyl group, a dimethylphenyl group, a diethylphenyl group, a dibutylphenyl group, a biphenyl group, and a naphthyl group; and aralkyl groups such as a benzyl group, a 4-methylbenzyl group, a phenylethyl group, a phenylpropyl group, a phenylbutyl group, a 2-(2-methylphenyl)ethyl group, a 2-(3-methylphenyl)ethyl group, a 2-(4-methylphenyl)ethyl group,
• Examples of the cycloalkyl group in R 13 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
• Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, and a cyclohexenyl group.
• the hydrocarbon group for R 13 is preferably an alkyl group, an aryl group, or an aralkyl group, more preferably an alkyl group.
• the hydrophobic monomer is preferably an alkyl (meth)acrylate, an aryl (meth)acrylate, or an aralkyl (meth)acrylate, and more preferably an alkyl (meth)acrylate.
• alkyl (meth)acrylates examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, dodecyl (meth)acrylate, stearyl (meth)acrylate, and icosyl (meth)acrylate.
• methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, and dodecyl (meth)acrylate are preferred, and ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, sec-butyl (meth)acrylate, 2-ethyl
• aryl (meth)acrylate examples include phenyl (meth)acrylate, 2-ethylphenyl (meth)acrylate, propylphenyl (meth)acrylate, butylphenyl (meth)acrylate, pentylphenyl (meth)acrylate, hexylphenyl (meth)acrylate, butylmethylphenyl (meth)acrylate, dimethylphenyl (meth)acrylate, diethylphenyl (meth)acrylate, dibutylphenyl (meth)acrylate, 4-methylphenyl (meth)acrylate, 1-methoxy-4-methylphenyl (meth)acrylate, naphthyl (meth)acrylate, and the like. Of these, phenyl (meth)acrylate is preferred.
• aralkyl (meth)acrylate examples include benzyl (meth)acrylate, 2-phenylethyl (meth)acrylate, 3-phenylpropyl (meth)acrylate, 4-phenylbutyl (meth)acrylate, 4-methylbenzyl (meth)acrylate, 2-(2-methylphenyl)ethyl (meth)acrylate, 2-(3-methylphenyl)ethyl (meth)acrylate, 2-(4-methylphenyl)ethyl (meth)acrylate, 2-(4-propylphenyl)ethyl (meth)acrylate, biphenylmethyl (meth)acrylate, biphenylethyl (meth)acrylate, naphthylmethyl (meth)acrylate, and naphthylethyl (meth)acrylate. Of these, benzyl (meth)acrylate is preferred.
• the content of the structural unit (c) derived from a hydrophobic monomer is preferably 0% by mass or more and 50% by mass or less, more preferably 0% by mass or more and 40% by mass or less, even more preferably 0% by mass or more and 35% by mass or less, even more preferably 0% by mass or more and 30% by mass or less, particularly preferably 0% by mass or more and 25% by mass or less, and most preferably 0% by mass or more and 20% by mass or less, based on 100% by mass of the structural units derived from all the monomers constituting the copolymer of the present disclosure.
• the content of the structural unit (c) may be 5% by mass or more and 70% by mass or less, 10% by mass or more and 60% by mass or less, 15% by mass or more and 50% by mass or less, or 20% by mass or more and 45% by mass or less.
• the copolymer of the present disclosure may have a structural unit (d) derived from an unsaturated carboxylic acid monomer as a structural unit other than the structural unit (a) derived from the amino group-containing monomer and the structural unit (b) derived from the monomer having a polyalkylene glycol chain.
• the copolymer of the present disclosure having the structural units (a), (b) and (d) is one of the preferred embodiments of the present invention.
• the structural unit (d) derived from an unsaturated carboxylic acid monomer according to the present disclosure is not particularly limited as long as it is a structural unit derived from a monomer having a carboxyl group or a salt thereof and an ethylenically unsaturated hydrocarbon group (unsaturated group), but is preferably a structural unit represented by the following general formula (7) or a salt thereof:
• R 14 is one or more selected from a hydrogen atom, a methyl group, and a —CH 2 COOH group
• R 15 and R 16 are the same or different and are one or more selected from a hydrogen atom, a methyl group, an ethyl group, a carboxyl group, and a —CH 2 COOH group.
• R 14 is one or more selected from a hydrogen atom and a methyl group, and R 15 and R 16 are the same or different and are one or more selected from a hydrogen atom and a carboxyl group. In a more preferred embodiment, R 14 is at least one selected from a hydrogen atom and a methyl group, and R 15 and R 16 are each a hydrogen atom.
• Examples of unsaturated carboxylic acid monomers as precursors of structural units (d) derived from unsaturated carboxylic acid monomers prior to polymerization reaction include unsaturated carboxylic acid monomers such as (meth)acrylic acid, crotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, etc., and their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts; and unsaturated dicarboxylic acid monomers such as maleic acid, itaconic acid, mesaconic acid, citraconic acid, fumaric acid, etc., and their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts, anhydrides, and half esters.
• unsaturated carboxylic acid monomers such as (meth)acrylic acid, crotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, etc., and their monovalent metal salt
• the content of the structural unit (d) derived from an unsaturated carboxylic acid monomer, relative to 100 mass% of the structural units derived from all monomers constituting the copolymer of the present disclosure is preferably 0 mass% or more and 20 mass% or less, more preferably 0 mass% or more and 15 mass% or less, even more preferably 0 mass% or more and 10 mass% or less, and particularly preferably 0 mass% or more and 5 mass% or less.
• the content of the structural unit (d) may be 1 mass % or more and 20 mass % or less, 1 mass % or more and 10 mass % or less, or 1 mass % or more and 5 mass % or less.
• the amino group-containing copolymer of the present disclosure may have a structural unit (a) derived from an amino group-containing monomer, a structural unit (b) derived from a monomer having a polyalkylene glycol chain, a structural unit (c) derived from a hydrophobic monomer, and a structural unit (e) derived from a monomer other than the structural unit (d) derived from an unsaturated carboxylic acid monomer.
• monomers are not particularly limited, but examples include sulfonic acid group-containing monomers such as styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and salts thereof, and phosphate group-containing monomers such as 2-methacryloyloxyethyl acid phosphate, etc.
• sulfonic acid group-containing monomers such as styrene sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, and 3-allyloxy-2-hydroxy-1-propanesulfonic acid, and salts thereof
• phosphate group-containing monomers such as 2-methacryloyloxyethyl acid phosphate, etc.
• the content of structural units derived from other monomers is preferably 10% by mass or less, more preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less, relative to 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure.
• a form in which the content of structural units derived from other monomers is 0% by mass is also one of the preferred embodiments of the present invention.
• the amino group-containing copolymer of the present disclosure preferably has a weight average molecular weight (Mw) of 4000 or more and 500000 or less, more preferably 6000 or more and 400000 or less, and even more preferably 10000 or more and 300000 or less. Furthermore, it is preferably 10000 or more and 200000 or less, more preferably 10000 or more and 100000 or less, even more preferably 12000 or more and 50000 or less, particularly preferably 15000 or more and 40000 or less, and most preferably 16000 or more and 30000 or less.
• Mw weight average molecular weight
• the method for producing the amino group-containing copolymer of the present disclosure is not particularly limited, but it can be produced by polymerizing monomer components, and specific and preferred examples of the monomer components and the preferred ratio of each monomer are as described above.
• the method for producing the amino group-containing copolymer includes, for example, a step of polymerizing an amino group-containing monomer or a precursor thereof, a monomer having a polyalkylene glycol chain or a precursor thereof, a hydrophobic group monomer or a precursor thereof, and an unsaturated carboxylic acid monomer (hereinafter referred to as the polymerization step).
• Methods for initiating the polymerization of the monomer components in the polymerization step include, for example, a method of adding a polymerization initiator, a method of irradiating with UV light, a method of applying heat, a method of irradiating with light in the presence of a photopolymerization initiator, and the like. In particular, it is preferable to use a polymerization initiator.
• the polymerization initiator may be, for example, a persulfate such as sodium persulfate, potassium persulfate, or ammonium persulfate; an azo compound such as 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2-methylpropionate), 2,2'-azobis(isobutyronitrile), or 2,2'-azobis(2-methylpropionamidine) dihydrochloride; an organic peroxide such as benzoyl peroxide, lauroyl peroxide, di-t-butyl peroxide, or cumene hydroperoxide; or an oxidation-reduction initiator that generates radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, or a persulfate and a metal salt.
• persulfates and azo compounds are preferred, and azo compounds are more preferred, since they tend to reduce the amount of residual monomer
• the amount of the polymerization initiator used is preferably 0.01% by mass or more and 10% by mass or less, more preferably 0.02% by mass or more and 8% by mass or less, even more preferably 0.03% by mass or more and 7% by mass or less, and most preferably 0.04% by mass or more and 4% by mass or less, based on the total amount of monomers constituting the structural units used.
• a chain transfer agent may be used as a molecular weight regulator for the polymer, if necessary.
• chain transfer agents include mercaptocarboxylic acids such as thioglycolic acid (mercaptoacetic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid (thiolactic acid), 4-mercaptobutanoic acid, thiomalic acid, and salts thereof, mercaptoethanol, thioglycerol, 2-mercaptoethanesulfonic acid, and the like, halides such as carbon tetrachloride, methylene chloride, bromoform, and bromotrichloroethane, secondary alcohols such as isopropanol and glycerin, phosphorous acid, hypophosphorous acid, hypophosphites, and hydrates thereof, hydrogen sulfite (salt), and compounds capable of generating hydrogen sulfite (salt) (bisulfite (salt), pyro
• the amount of chain transfer agent used in the production of the copolymer of the present disclosure is preferably 0.1 mol% or more and 20 mol% or less, more preferably 0.2 mol% or more and 15 mol% or less, even more preferably 0.3 mol% or more and 10 mol% or less, and most preferably 0.5 mol% or more and 5 mol% or less, relative to 100 mol% of the total amount of monomers constituting the structural units used.
• the solvent used during polymerization can be selected as necessary from those capable of dissolving the monomer components, polymerization initiator, chain transfer agent, and copolymer after production.
• water alcohols having 1 to 8 carbon atoms such as ethanol, 1-propanol, 2-propanol, 1-butanol, and phenoxyethanol
• glycols such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol
• glycol ethers such as diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether are preferably used.
• water, ethanol, ethylene glycol, propylene glycol, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether are preferred, and a mixture of two or more of these may be used.
• the polymerization temperature is preferably 40°C or higher, and preferably 150°C or lower. More preferably, it is 45°C or higher, and even more preferably, it is 50°C or higher. Also, it is more preferably 100°C or lower, and even more preferably, it is 90°C or lower.
• the method of feeding the monomer components, polymerization initiator, and chain transfer agent into the reaction vessel is not particularly limited, and examples of such methods include feeding the entire amount into the reaction vessel all at once at the beginning, feeding the entire amount into the reaction vessel in portions or continuously, feeding a portion into the reaction vessel at the beginning, and feeding the remainder into the reaction vessel in portions or continuously.
• a preferred method is to charge the solvent described below at the beginning, and then feed the monomer components, polymerization initiator, and chain transfer agent continuously.
• the monomer components may also be neutralized with an organic acid such as acetic acid or propionic acid, or a mineral acid such as hydrochloric acid, sulfuric acid, or nitric acid, before polymerization.
• organic acid such as acetic acid or propionic acid
• mineral acid such as hydrochloric acid, sulfuric acid, or nitric acid
• the copolymer obtained by polymerization can be used as it is as a detergent additive, such as an additive for liquid detergents, but if necessary, it may be further neutralized with an alkaline substance before use.
• an alkaline substance inorganic salts such as hydroxides and carbonates of monovalent or divalent metals, ammonia, and organic amines can be used.
• concentration of the copolymer can be adjusted as necessary after the reaction is completed.
• the enzyme contained in the composition of the present disclosure is not particularly limited as long as it exhibits cleaning performance, and examples thereof include protease, lipase, phospholipase, hemicellulase, peroxidase, cellulase, xylanase, esterase, cutinase, pectinase, keratanase, reductase, oxidase, phenoloxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, ⁇ -glucanase, arabinosidase, hyaluronidase, chondroitinase, laccase, amylase, or a combination thereof. Protease and amylase are preferred, and protease is more preferred.
• the surfactant contained in the composition of the present disclosure is not particularly limited, and may be an anionic surfactant, a nonionic surfactant, a cationic surfactant, or an amphoteric surfactant. One or more of these surfactants may be used.
• the composition contains an anionic surfactant and/or a nonionic surfactant.
• the combined amount of the anionic surfactant and the nonionic surfactant is preferably 5 to 100% by mass, more preferably 50 to 100% by mass, even more preferably 75 to 100% by mass, and particularly preferably 80 to 100% by mass, based on 100% by mass of the total surfactants.
• the composition of the present disclosure preferably contains an anionic surfactant as a surfactant.
• anionic surfactants have a large effect on enzyme activity, so that it is of great technical significance to stabilize the enzyme by the copolymer of the present invention in a composition containing an anionic surfactant.
• the content of the anionic surfactant is preferably 10 to 100% by mass, more preferably 10 to 50% by mass, still more preferably 10 to 45% by mass, and particularly preferably 10 to 40% by mass, based on 100% by mass of the total surfactants.
• anionic surfactant examples include alkylbenzenesulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, ⁇ -olefinsulfonates, ⁇ -sulfofatty acids or ester salts, alkanesulfonates, saturated fatty acid salts, unsaturated fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, amino acid surfactants, N-acylamino acid surfactants, alkyl phosphates or salts thereof, and alkenyl phosphates or salts thereof.
• the alkyl group and alkenyl group in the anionic surfactant may be a branched alkyl group such as a methyl group.
• nonionic surfactant examples include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, sucrose fatty acid esters, alkyl glycoxides, fatty acid glycerin monoesters, and alkylamine oxides.
• the alkyl and alkenyl groups in the nonionic surfactants may have branched alkyl groups such as methyl groups.
• cationic surfactant a quaternary ammonium salt or the like is preferable.
• amphoteric surfactant a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant, etc. are preferable.
• the alkyl group and alkenyl group in the above cationic surfactants and amphoteric surfactants may be branched alkyl groups such as methyl groups.
• composition of the present disclosure may contain other components in addition to the above-mentioned copolymer, enzyme, and surfactant.
• other components are not particularly limited, but include, for example, detergent builders; stain inhibitors such as benzotriazole and ethylene-thiourea; soil release agents; color transfer inhibitors; fabric softeners; alkaline substances for adjusting pH; fragrances; solubilizing agents; fluorescent agents; colorants; foaming agents; foam stabilizers; polishing agents; disinfectants; bleaching agents; bleaching aids; dyes; solvents, etc.
• the detergent builder is not particularly limited, and examples thereof include alkali builders such as carbonates, hydrogen carbonates, and silicates; chelate builders such as tripolyphosphates, pyrophosphates, Glauber's salt, nitrilotriacetates, ethylenediaminetetraacetates, citrates, (meth)acrylic acid copolymer salts, acrylic acid-maleic acid copolymers, fumarates, and zeolites; and carboxyl derivatives of polysaccharides such as carboxymethylcellulose.
• Examples of counter salts used in the detergent builder include alkali metals such as sodium and potassium, and alkali agents such as sodium hydroxide, ammonium and amines. As the other components, one or more of these can be used.
• the above-mentioned solvent is not particularly limited, but examples thereof include water; alcohols having 1 to 8 carbon atoms, such as ethanol, 1-propanol, 2-propanol, 1-butanol, and phenoxyethanol; glycols, such as propylene glycol, butylene glycol, and hexylene glycol; polyalkylene glycols, such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and tetrapropylene glycol; diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, and diethylene glycol monobutyl
• Preferred hydrophilic solvents include alkyl ethers such as diethyl ether; sulfone, diethyl sulfone, bis(2-hydroxyethyl) sulfone, and other sulfoxides (e.g., dimethyl sulfoxide); cyclic ethers (e.g.
• the blending ratio is usually preferably 0.1 to 20% by mass relative to 100% by mass of the cleaning composition. More preferably, it is 0.2 to 15% by mass, more preferably 0.3 to 10% by mass, even more preferably 0.4 to 8% by mass, and particularly preferably 0.5 to 5% by mass.
• the amount of water contained in the liquid detergent is usually preferably 0.1 to 75% by mass relative to 100% by mass of the liquid detergent. More preferably, it is 0.5 to 65% by mass, and particularly preferably 1 to 55% by mass.
• the composition of the present disclosure has excellent detergency and can be suitably used in detergents and the like.
• the composition of the present disclosure is used in detergents for fibers and hard surfaces.
• the detergents referred to here include household detergents for clothing, kitchens, housing, textile industry, and other industrial detergents.
• the compositions of the present disclosure are also detergent compositions.
• the present invention also includes a method for producing a detergent composition, which comprises a step of mixing the composition of the present disclosure with a surfactant.
• the present invention also includes a soil release agent containing the composition of the present disclosure.
• a soil release agent is an agent that imparts the effect of making it easier to remove sebum stains and the like that adhere to fibers by treating the fibers in advance with a compound that adsorbs to the fibers.
• the present invention also includes a method of using the composition of the present disclosure as a soil release agent.
• Detergent solutions (x) and (ix) were prepared by adding 9 g of pure water to 1 g of detergent solution (viii) or (ix), respectively. (12) 994.2 g of the cleaning solution (iii) was added to each pot in a Tergot-o-meter (manufactured by Daiei Scientific Co., Ltd., product name: TM-4) and the temperature was adjusted to 15° C., and 5.8 g of the detergent solutions (x) and (ix) were further added to each pot and stirred for 1 minute. (13) Seven pieces of EMPA-117 were placed in each pot and stirred at 120 ppm for 15 minutes. (14) The soiled cloth was removed from each pot, and the water was squeezed out by hand.
• ⁇ Detergency evaluation test 4 including soil release effect> (Fabric pretreatment) Using tap water, 55 g of an aqueous solution was prepared, in which Emulgen 108 (manufactured by Kao Corporation) was 1000 ppm, the copolymer obtained in the example was 100 ppm in terms of non-volatile content, and protease Progress Uno 101L (manufactured by Novozymes) was 8.3 ppm. 2.7 g of polyester de chine cut into 5 x 5 cm was added to this aqueous solution and stirred for 10 minutes with a roller shaker. After stirring, the mixture was dehydrated and air-dried for 1 day.
• Emulgen 108 manufactured by Kao Corporation
• the copolymer obtained in the example was 100 ppm in terms of non-volatile content
• protease Progress Uno 101L manufactured by Novozymes
• An oil-stained solution was prepared by mixing 61.5 g of olive oil, 37 g of oleic acid, 1 g of iron (III) oxide, and 0.5 g of oil red. 15 ⁇ L of this stained solution was dropped onto the polymer-treated cloth obtained by the above pretreatment, and left at 40° C. for 1 hour to prepare a stained cloth.
• (Cleaning power evaluation) (1) Preparation of an Aqueous Surfactant Solution 10 g of Emulgen 108 (Kao Corporation) was weighed out into a beaker, and ion-exchanged water was added to make up to 100 g to prepare a 10% surfactant solution.
• +++ The cleaning rate differs from the evaluation result of a product without added polymer by 40% or more.
• ++ The cleaning rate differs from the evaluation result of a product without added polymer by 20% or more and less than 40%.
• + The cleaning rate differs from the evaluation result of a product without added polymer by 5% or more and less than 20%.
• - The cleaning rate differs from the evaluation result of a product without added polymer by less than 5%.
• a monomer solution consisting of 48 g of methoxypolyethylene glycol monoacrylate (average number of moles of ethylene oxide added: 23; trade name "AM-230G” manufactured by Shin-Nakamura Chemical Co., Ltd.; hereinafter referred to as PGA23E), 12 g of dimethylaminoethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.; hereinafter referred to as DAM), 25.9 g of pure water, 4.36 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.5 g of 3-mercaptopropionic acid (manufactured by SC Organic Chemical Industries, Ltd.); and an initiator aqueous solution consisting of 24.4 g of an 8% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (trade name "V-50" manufactured by Fujifilm Wa
• the monomer solution and the aqueous initiator solution were dropped simultaneously, and the monomer solution was dropped for 180 minutes, and the aqueous initiator solution was dropped for 240 minutes. After the entire dropwise addition was completed, the reaction solution was kept at 70° C. for another 60 minutes to mature, and the polymerization was completed to obtain Copolymer 1.
• a monomer solution consisting of 68.4 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23, trade name "M-230G” manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as PGM23E), 5.36 g of methacrylic acid, 40.5 g of DAM, 37.9 g of ethanol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 14.7 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 20.3 g of benzyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as BnMA); and an aqueous initiator solution consisting of 43.2 g of a 6% ethanol solution of 2,2'-azobis(2,4-dimethylvaleronitrile) (trade name
• the monomer solution and the aqueous initiator solution were dropped simultaneously, the monomer solution was dropped for 180 minutes, and the aqueous initiator solution was dropped for 240 minutes. After the entire dropping was completed, the reaction solution was kept at 70° C. for another 60 minutes to mature, and the polymerization was completed to obtain Copolymer 2.
• a monomer solution consisting of 33.3 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 25, hereinafter also referred to as PGM25E), 2.7 g of methacrylic acid, 9.0 g of DAM, 21.0 g of ion-exchanged water, 3.3 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.74 g of mercaptopropionic acid; and an aqueous initiator solution consisting of 42.2 g of a 1.5 wt % aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (trade name "V-50" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were dropped from separate dropping nozzles into the polymerization reaction system under stirring at a constant temperature of 70°C.
• the monomer solution and the aqueous initiator solution were dropped simultaneously, and the monomer solution was dropped for 180 minutes, and the aqueous initiator solution was dropped for 240 minutes. After the entire dropwise addition was completed, the reaction solution was kept at 70° C. for an additional 60 minutes for maturation, and the polymerization was completed to obtain Copolymer 3.
• a monomer solution consisting of 48 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23, trade name "M-230G” manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as PGM23E), 12 g of dimethylaminoethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as DAM), 25.9 g of pure water, 4.35 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.5 g of 3-mercaptopropionic acid (manufactured by SC Organic Chemical Industries, Ltd.); and an initiator aqueous solution consisting of 46.6 g of a 4% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (trade name "V-50" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• the monomer solution and the aqueous initiator solution were dropped simultaneously, and the monomer solution was dropped for 180 minutes, and the aqueous initiator solution was dropped for 240 minutes. After the entire dropwise addition was completed, the reaction solution was kept at 70° C. for another 60 minutes to mature, and the polymerization was completed to obtain Copolymer 4.
• a monomer solution consisting of 54 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23, trade name "M-230G” manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as PGM23E), 6 g of dimethylaminoethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as DAM), 25.9 g of pure water, 2.18 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.4 g of 3-mercaptopropionic acid (manufactured by SC Organic Chemical Industries, Ltd.); and an initiator aqueous solution consisting of 35.3 g of a 4% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (trade name "V-50" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
• the monomer solution and the aqueous initiator solution were dropped simultaneously, and the monomer solution was dropped for 180 minutes, and the aqueous initiator solution was dropped for 240 minutes. After the entire dropwise addition was completed, the reaction solution was kept at 70° C. for another 60 minutes to mature, and the polymerization was completed to obtain Copolymer 5.
• a monomer solution consisting of 57 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added: 23, trade name "M-230G” manufactured by Shin-Nakamura Chemical Co., Ltd., hereinafter referred to as PGM23E), 3.0 g of dimethylaminoethyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., hereinafter referred to as DAM), 25.8 g of pure water, 1.09 g of acetic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 0.3 g of 3-mercaptopropionic acid (manufactured by SC Organic Chemical Industries, Ltd.); and an initiator aqueous solution consisting of 28.6 g of a 4% aqueous solution of 2,2'-azobis(2-methylpropionamidine) dihydrochloride (trade name "V-50" manufactured by Fujifilm Wako Pure Chemical Industries,
• the monomer solution and the aqueous initiator solution were dropped simultaneously, and the monomer solution was dropped for 180 minutes, and the aqueous initiator solution was dropped for 240 minutes. After the entire dropwise addition was completed, the reaction solution was kept at 70° C. for another 60 minutes to mature, and the polymerization was completed to obtain Copolymer 6.
• aqueous initiator solution consisting of 50.4 g of a 4% ethanol solution of V-65 was dropped from each of the dropping nozzles.
• the monomer solution and the aqueous initiator solution were dropped at the same time, and the monomer solution was dropped for 180 minutes and the aqueous initiator solution was dropped for 240 minutes.
• the reaction solution was kept at 70 ° C. for another 60 minutes to mature, and the polymerization was completed to obtain a copolymer 7.
• a monomer solution consisting of 93.0 g of PGM23E, 7.8 g of methacrylic acid, 28.8 g of DAM, 66.2 g of ethanol, 10.5 g of acetic acid, and 14.4 g of BnMA was dropped into the polymerization reaction system at a constant state under stirring; an aqueous initiator solution consisting of 40.9 g of a 4% ethanol solution of V-65 was dropped from each of the dropping nozzles.
• the monomer solution and the aqueous initiator solution were dropped at the same time, and the monomer solution was dropped for 180 minutes and the aqueous initiator solution was dropped for 240 minutes. After the completion of all the dropping, the reaction solution was kept at 70 ° C. for another 60 minutes to mature, and the polymerization was completed to obtain a copolymer 8.
• a monomer solution consisting of 47.3 g of PGM25E, 4.0 g of methacrylic acid, 50.0 g of DAM, 38.6 g of ethanol, 18.1 g of acetic acid, and 33.8 g of BnMA; an aqueous initiator solution consisting of 34.5 g of a 6-ethanol solution of V-65 were dropped from separate dropping nozzles into the polymerization reaction system at a constant state of 70 ° C. with stirring.
• the monomer solution and the aqueous initiator solution were dropped at the same time, and the monomer solution was dropped for 180 minutes and the aqueous initiator solution was dropped for 240 minutes. After the completion of all the dropping, the reaction solution was kept at 70 ° C. for another 60 minutes to mature, and the polymerization was completed to obtain a copolymer 9.
• Table 2 shows the results of protein stain cleaning power test 1 for Examples 1 and 2, which used copolymers 1 and 2, and Comparative Example 1, which did not use any copolymers.
• Table 3 shows the results of protein stain cleaning power test 2 for Example 3, which used copolymer 3, and Comparative Example 2, which did not use the copolymer.
• Table 4 shows the results of protein stain cleaning power test 3 for Examples 4, 5, and 6, which used copolymers 4, 5, and 6, and Comparative Example 3, which did not use any copolymer.
• Table 5 shows the results of protein stain cleaning power test 3 for Examples 7 and 8, which used copolymers 7 and 8 instead of copolymers 4, 5 and 6, and Comparative Example 4, which did not use any copolymers.
• Table 6 shows the results of detergency evaluation test 4, including the soil release effect, for Examples 9, 10, and 11, which used copolymers 3, 4, and 9, and Comparative Example 5, which did not use any copolymer.

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