Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/267—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having amino or quaternary ammonium groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
  • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
  • C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/04—Polymerisation in solution
  • C08F2/06—Organic solvent
• • 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
  • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
  • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
  • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
  • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/062—Polyethers
• • C—CHEMISTRY; METALLURGY
  • 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
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
• • 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
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
  • D06M15/27—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of alkylpolyalkylene glycol esters of unsaturated carboxylic acids
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
  • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
  • D06M2200/01—Stain or soil resistance

Definitions

• the present invention relates to an amino group-containing copolymer. More specifically, it relates to an amino group-containing copolymer useful for detergent applications such as liquid detergents and powder detergents.
• Patent Document 1 discloses that a polymer composed of a (meth)acrylic acid ester having a primary to tertiary amino group and an unsaturated bond-containing monomer having a hydrophobic group has an excellent stain release effect on cotton cloth.
• Patent Document 2 discloses that a composition containing a polymer having a quaternary ammonium group and a hydrophilic group has the effect of removing stains from cotton cloth.
• Patent No. 5014739 Special Publication No. 11-505568
• Soil release properties with polymers containing amino groups have been disclosed above. However, there is still room for further improvement in soil release properties, especially for polyester fibers that easily absorb sebum dirt.
• the present invention has been made in view of the above-mentioned current situation, and an object of the present invention is to provide an amino group-containing copolymer having excellent soil release properties and a method for producing a soil release agent using the same.
• the present inventor conducted various studies and came up with the present invention. That is, the present disclosure provides a structural unit (a) derived from an amino group-containing monomer represented by the following general formula (1), a structural unit (b) derived from a monomer having a polyalkylene glycol chain, It is an amino group-containing copolymer containing a structural unit (c) derived from a hydrophobic monomer and a structural unit (d) derived from an unsaturated carboxylic acid monomer.
• a structural unit (a) derived from an amino group-containing monomer represented by the following general formula (1) a structural unit (b) derived from a monomer having a polyalkylene glycol chain
• It is an amino group-containing copolymer containing a structural unit (c) derived from a hydrophobic monomer and a structural unit (d) derived from an unsaturated carboxylic acid monomer.
• 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 a carbon atom. It represents an organic group of numbers 1 to 12, and X represents a divalent linking group.
• 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.
• the hydrophobic monomer preferably has a homopolymer solubility parameter of 13 or less.
• the proportion of the structural unit (a) derived from the amino group-containing monomer is preferably 5 to 50% by weight based on 100% by weight of the total structural units.
• the proportion of the structural unit (b) derived from the monomer having a polyalkylene glycol chain is preferably 5 to 75% by weight based on 100% by weight of all structural units.
• the proportion of the structural unit (c) derived from the hydrophobic monomer is preferably 5 to 70% by weight based on 100% by weight of the total structural units.
• the proportion of the structural unit (d) derived from the unsaturated carboxylic acid monomer is preferably 1 to 20% by weight based on 100% by weight of the total structural units.
• the amino group-containing copolymer preferably has a weight average molecular weight of 4,000 or more and 500,000 or less.
• the present invention also provides a soil release agent containing the above amino group-containing copolymer.
• the present invention further provides a method of using the above amino group-containing copolymer as a soil release agent.
• the present invention further provides a method for producing a soil release agent, wherein the production method includes a step of mixing the amino group-containing copolymer and a surfactant.
• amino group-containing copolymer of the present disclosure has excellent soil release properties, it can be particularly suitably used in detergents for use in textile products such as polyester.
• the amino group-containing copolymer of the present disclosure (hereinafter also referred to as the copolymer of the present disclosure) is a monomer having a structural unit (a) derived from the amino group-containing monomer described below, and a polyalkylene glycol chain. It is a copolymer containing a structural unit (b) derived from a hydrophobic monomer, a structural unit (c) derived from a hydrophobic monomer, and a structural unit (d) derived from an unsaturated carboxylic acid monomer. Since the copolymer of the present disclosure has such a structure, it has excellent soil release properties, as well as antibacterial properties and anti-recontamination properties.
• the structural unit (a) derived from the 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 a carbon atom.
• It represents an organic group of numbers 1 to 12
• X represents a divalent linking group.
• 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.
• "atom contained in another structural unit of the same type” means, for example, if it is a structural unit represented by general formula (1), it is a structural unit represented by another general formula (1).
• the structure derived from the above amino group-containing monomer is, for example, an ethylenically unsaturated group and a primary to tertiary amino group represented by the following general formula (2), or an intermediate structure derived from an acid of a primary to tertiary amino group. It can be formed by radical polymerization of a monomer having a sulfate and a sulfate, but the present invention 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 amino group-containing monomer is formed, for example, by radical polymerization of the amino group-containing monomer.
• the amino group-containing monomers include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-dialkylamino group-containing (meth)acrylates such as N,N-diethylaminopropyl (meth)acrylate and their neutralized products with acids such as hydrochloric acid and acetic acid; N,N-dimethylaminoethyl (meth) N,N-dialkylamino group-containing (meth)acrylamides such as acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,
• Neutralized products with acids allylamine and its neutralized products with acids such as hydrochloric acid and acetic acid; carbon number of 1-allyloxy-3-dibutylamino-2-ol, 1-allyloxy-3-diethanolamino-2-ol, etc.
• Examples include addition reaction products of unsaturated monomers having 2 to 8 cyclic ether-containing groups and amine compounds having 1 to 24 carbon atoms, and neutralized products thereof with acids such as hydrochloric acid and acetic acid.
• the structural unit (a) derived from the above amino group-containing monomer is preferably the following general formula (3), which is a structural unit derived from N,N-dimethylaminoethyl (meth)acrylate.
• R 6 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 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.
• the content of the structural unit (a) derived from the amino group-containing monomer in the copolymer of the present disclosure is the content of the structural unit (a) derived from all the monomers constituting the copolymer of the present disclosure (hereinafter, the total structure (Also referred to as units.) Based on 100% by mass, 5% by mass or more and 50% by mass or less, preferably 7% by mass or more and 45% by mass or less, more preferably 8% by mass or more and 40% by mass or less, particularly preferably The content is 10% by mass or more and 30% by mass or less, most preferably 15% by mass or more and 25% by mass or less.
• the content of the structural unit (a) is preferably 8% by mass or more and 45% by mass or less, more preferably 10% by mass or more and 40% by mass or less, based on 100% by mass of all structural units. Particularly preferably, it is 15% by mass or more and 38% by mass or less, and most preferably 20% by mass or more and 35% by mass or less.
• the proportion of cationic moieties that can act on the base material such as fibers to which soil release properties are desired becomes appropriate, and the soil release properties and antibacterial performance of the detergent additive of the present disclosure are improved. There is a tendency to
• the structural unit (b) derived from a monomer having a polyalkylene glycol chain is characterized by containing a polyalkylene glycol chain in its structure.
• the structural unit (b) is represented by the following general formula (4), for example.
• R 7 , R 8 , and R 9 each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms that may have a substituent
• Z represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms and 30 hydrocarbon groups, or hydroxyl groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups, and salts thereof.
• A represents an alkylene group having 1 to 10 carbon atoms which may have a substituent.
• q represents the average number of added moles of (AO) 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 are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms which may have a substituent, and the substituent is a hydroxyl group, a carboxyl group, a sulfonic acid group, At least one hydrophilic group selected from the group consisting of a phosphate group, an amino group, and a salt group thereof is preferred.
• 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 still more 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. 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, a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, and salts thereof.
• the hydrocarbon group is not particularly limited, and examples include chain hydrocarbon groups such as an alkyl group, alkenyl group, and alkynyl group, and cyclic hydrocarbon groups such as an aryl group, a cycloalkyl group, and a cycloalkenyl group.
• the above hydrocarbon group may have a branch, and in the case where the hydrocarbon group has a branch, the number of carbon atoms in the hydrocarbon group means the total number of carbon atoms in the main chain and the branched chain.
• alkyl group examples include ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, decyl group, dodecyl group, stearyl group. , icosyl group, etc.
• alkenyl group examples include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, octadecenyl group, and icosenyl group. etc.
• alkynyl group examples include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, dodecynyl group, octadecynyl group, and icosynyl group. etc.
• aryl group examples include phenyl group, benzyl group, methylphenyl group, 1-methoxy-4-methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, butylmethylphenyl group, dimethylphenyl group, diethyl
• aryl group examples include phenyl group, dibutylphenyl group, biphenyl group, biphenylmethyl group, biphenylethyl group, naphthyl group, naphthylmethyl group, naphthylethyl group, and the like.
• 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, still more preferably 2 to 10, particularly preferably 2 to 5.
• Z is a hydrogen atom or a methyl group.
• 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 a salt group thereof. All of the q oxyalkylene groups of AO present in the polyalkylene glycol represented by (AO)q may be the same or different.
• the alkylene group represented by A above preferably has 2 to 10 carbon atoms, more preferably 2 to 4 carbon atoms.
• Examples of the oxyalkylene group represented by AO include oxyethylene, oxypropylene, oxybutylene, oxyisobutylene, oxy2,3-butylene, oxystyrene, and oxyalkylene having 2 to 10 carbon atoms. More preferred are oxyalkylene groups having 2 to 4 carbon atoms such as oxyethylene, oxypropylene, and oxybutylene, and even more preferred are oxyethylene and oxypropylene. Note that the oxyalkylene group represented by AO is not limited to a group formed by an addition reaction of oxyalkylene groups.
• the polyalkylene glycol when it 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.
• the oxyalkylene group in the polyalkylene glycol preferably has an oxyethylene group as an essential component, more preferably 50 mol% or more is an oxyethylene group, and still more preferably 90 mol% or more is an oxyethylene group. preferable.
• q represents the average number of moles of AO added, and is a number from 1 to 200. Preferably it is 1 to 180, more preferably 2 to 150, more preferably 2 to 100, even more preferably 2 to 80, particularly preferably 2 to 50, most preferably 20 to 30. It is. In one embodiment, q is preferably 2 to 180, more preferably 3 to 150, more preferably 4 to 100, still more preferably 5 to 80, 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 still more preferably 0. More preferably, m is 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 above polyalkylene glycol chain includes polyalkylene glycol mono(meth)acrylates such as (poly)ethylene glycol mono(meth)acrylate and (poly)propylene glycol mono(meth)acrylate; methoxy Alkoxypolyalkylene glycol mono(meth)acrylates such as (poly)ethylene glycol mono(meth)acrylate, methoxy(poly)propylene glycol mono(meth)acrylate, 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-ol, 2-methyl- Preferred are (poly)alkylene glycol monomers such as compounds in which 10 to 100 moles of
• the content of the structural unit (b) having a polyalkylene glycol chain in the copolymer of the present disclosure is 5% by mass based on 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure. % by mass or more and 75% by mass or less, more preferably 20% by mass or more and 70% by mass or less, still more preferably 30% by mass or more and 70% by mass or less, particularly preferably 40% by mass or more and 65% by mass or less. , most preferably 45% by mass or more and 60% by mass or less.
• the content of the structural unit (b) is preferably 10% by mass or more and 75% by mass or less, more preferably 15% by mass or more and 70% by mass or less, and more preferably 15% by mass or more and 70% by mass or less, based on 100% by mass of all structural units. Preferably, it is 17% by mass or more and 65% by mass or less.
• the hydrophobic monomer of the present disclosure constituting the structural unit (c) derived from the hydrophobic monomer of the present disclosure has a solubility parameter of 13 or less in a homopolymer (homopolymer) obtained by homopolymerization. If so, there are no particular limitations.
• the solubility parameter is a value calculated by the method described in "POLYMER ENGINEERING AND SCIENCE” (1974, Vol. 14, No. 2), pages 147 to 154. The method is outlined below.
• the solubility parameter for the homopolymer obtained when the hydrophobic monomer of the present disclosure is polymerized alone is 13 or less, the copolymer of the present invention has sufficient hydrophobicity. , excellent adsorption to hydrophobic fibers.
• the solubility parameter is preferably 12 or less, more preferably 11 or less.
• the above-mentioned solubility parameter is usually 5 or more.
• the hydrophobic monomer of the present disclosure is not particularly limited as long as the solubility parameter in the homopolymer is 13 or less, but monomers having an ethylenically unsaturated group and an alkyl group having 1 to 30 carbon atoms are used. It is preferable that there be.
• hydrophobic monomers examples include esters of unsaturated carboxylic acids such as (meth)acrylic acid and alcohols having 1 to 30 carbon atoms which may have substituents; aromatic vinyl monomers such as styrene; olefinic 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; alkyls such as methyl vinyl ether and ethyl vinyl ether Vinyl ethers; cyclic vinyl monomers such as N-vinylpyrrolidone, acrylonitrile, and the like.
• esters of unsaturated carboxylic acids such as (meth)acrylic acid and alcohols having 1 to 30 carbon atoms which may have substituents
• aromatic vinyl monomers such as styrene
• olefinic monomers such as ethylene and propylene
• esters of unsaturated alcohols such as vinyl acetate and carboxylic
• the substituents that the alcohol may have may be any substituents other than hydroxyl groups, oxyalkylene groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups, and salt groups thereof, but for example, Examples include halogen atoms.
• the alcohol preferably has 2 to 22 carbon atoms, more preferably 2 to 16 carbon atoms, and even more preferably 4 to 8 carbon atoms.
• Preferred examples of the alcohol having 1 to 30 carbon atoms include alkyl alcohols having 1 to 30 carbon atoms and aryl alcohols having 6 to 30 carbon atoms.
• alkyl alcohol having 1 to 30 carbon atoms examples include methanol, ethanol, propanol, butanol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), These include decyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol, and icosyl alcohol.
• the above-mentioned aryl alcohol having 6 to 30 carbon atoms is preferably phenol, benzyl alcohol, methylphenyl alcohol (o-cresol, m-cresol, p-cresol), creosol, ethylphenyl alcohol, propylphenyl alcohol, butylphenyl alcohol, butyl Methylphenyl alcohol, dimethylphenyl alcohol, diethylphenyl alcohol, dibutylphenyl alcohol, hydroxybiphenyl, 4-hydroxymethylbiphenyl, 3-hydroxymethylbiphenyl, 4-hydroxyethylbiphenyl, 3-hydroxyethylbiphenyl, naphthol, 1-hydroxymethyl- Examples include naphthalene, 1-hydroxyethyl-naphthalene, 2-hydroxymethyl-naphthalene, and 2-hydroxyethyl-naphthalene.
• the hydrophobic monomer preferably has the following general formula (5);
• R 10 , R 11 , and R 12 are the same or different and represent 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.
• c the structural unit (c) derived from the hydrophobic monomer of the present disclosure has the following general formula (6);
• R 10 to R 13 are the same as in general formula (5).
• the asterisk indicates another structural unit of the same or different type to which the structural unit represented by general formula (6) is bonded.
• it is a structural unit represented by (representing an atom contained in).
• the amino group-containing copolymer of the present disclosure has a structural unit represented by the above general formula (6), the structural unit can be polymerized using a compound represented by the above general formula (5). It may be obtained by other methods.
• the alkyl group in 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 still more preferably a methyl group. It is preferable that R 10 , R 11 and R 12 are the same or different and are a hydrogen atom or a methyl group. More preferably, R 10 and R 11 are hydrogen atoms, 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 from 2 to 16, even more preferably from 2 to 12, particularly preferably from 4 to 12, and most preferably from 4 to 8.
• the hydrocarbon group for R 13 above is not particularly limited, and examples include chain hydrocarbon groups such as alkyl groups, alkenyl groups, and alkynyl groups, and cyclic hydrocarbon groups such as aryl groups, cycloalkyl groups, and cycloalkenyl groups. .
• the above hydrocarbon group may have a branch, and in the case where the hydrocarbon group has a branch, the number of carbon atoms in the hydrocarbon group means the total number of carbon atoms in the main chain and the branched chain.
• the hydrocarbon group in R 13 may or may not have an aryl group, but a form in which R 13 is a hydrocarbon group without an aryl group is also preferred in the present invention. This is one of the embodiments.
• the number of carbon atoms in the alkyl group in R 13 is preferably 2 to 22, more preferably 2 to 16, particularly preferably 2 to 12. Most preferably it is 4-8.
• the number of carbon atoms in the aryl group in R 13 is preferably 6 to 12, more preferably 6 to 10, particularly preferably 6 to 8.
• alkyl group for R 13 above examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, hexyl group, heptyl group, 2-ethylhexyl group, octyl group, nonyl group, and decyl group. , dodecyl group, stearyl group, icosyl group, etc.
• alkenyl group for R 13 above examples include vinyl group, allyl group, 1-butenyl group, 2-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, and octadecenyl group. , icosenyl group, etc.
• alkynyl group for R 7 above examples include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, dodecynyl group, octadecynyl group. , icosinyl group, etc.
• Examples of the aryl group for R 13 above include phenyl group, benzyl group, methylphenyl group, 1-methoxy-4-methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, butylmethylphenyl group, dimethylphenyl group.
• Examples of the cycloalkyl group for R 13 above 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 or an aryl group, more preferably an alkyl group.
• the hydrophobic monomer is preferably an alkyl (meth)acrylate or an aryl (meth)acrylate, more preferably an alkyl (meth)acrylate.
• alkyl (meth)acrylate 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, Examples include dodecyl (meth)acrylate, stearyl (meth)acrylate, and icosyl (meth)acrylate.
• methyl (meth)acrylate preferred are methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl (meth)acrylate.
• aryl (meth)acrylates examples include phenyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylphenyl (meth)acrylate, propylphenyl (meth)acrylate, butylphenyl (meth)acrylate, and pentylphenyl (meth)acrylate.
• acrylate hexylphenyl (meth)acrylate, butylmethylphenyl (meth)acrylate, dimethylphenyl (meth)acrylate, diethylphenyl (meth)acrylate, dibutylphenyl (meth)acrylate, 2-phenylethyl (meth)acrylate, 4- Methylphenyl (meth)acrylate, 4-methylbenzyl (meth)acrylate, 1-methoxy-4-methylphenyl (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, naphthyl (meth)acrylate, nap
• the content of the structural unit (c) derived from a hydrophobic monomer in the copolymer of the present disclosure is based on 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure. Preferably 5% by mass or more and 70% by mass or less, more preferably 10% by mass or more and 60% by mass or less, even more preferably 15% by mass or more and 50% by mass or less, most preferably 20% by mass or more and 45% by mass or less. It is. By being within the above range, the proportion of hydrophobic sites becomes appropriate, and the soil release properties, anti-recontamination properties, and antibacterial performance of the detergent additive of the present disclosure tend to improve. In one embodiment, the content of the structural unit (c) may be 5 to 40% by weight, and preferably 5 to 35% by weight, based on 100% by weight of the total structural units.
• the structural unit (d) derived from the unsaturated carboxylic acid monomer of the present disclosure is not particularly limited as long as it is a structural unit derived from a monomer having a carboxyl group and an ethylenically unsaturated hydrocarbon group (unsaturated group). is preferably a structural unit represented by the following general formula (7).
• 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 a hydrogen atom, a methyl group, One or more types selected from ethyl group, carboxyl group, and -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 selected from a hydrogen atom and a carboxyl group.
• R 14 is one or more selected from a hydrogen atom and a methyl group, and R 15 and R 16 are hydrogen atoms.
• Examples of the unsaturated carboxylic acid monomer as a precursor before the polymerization reaction of the structural unit (d) derived from the unsaturated carboxylic acid monomer include (meth)acrylic acid, crotonic acid, tiglic acid, - Unsaturated carboxylic acid monomers such as methyl crotonic acid, 2-methyl-2-pentenoic acid, and their monovalent metal salts, divalent metal salts, ammonium salts, and organic amine salts; maleic acid, itaconic acid, Unsaturated dicarboxylic acid monomers such as mesaconic acid, citraconic acid, fumaric acid, their monovalent metal salts, divalent metal salts, ammonium salts, organic amine salts, etc., their anhydrides, or half esters can be mentioned.
• preferred are (meth)acrylic acid, maleic acid, and salts thereof, and more preferred is (meth)acrylic acid.
• the content of the structural unit (d) derived from the unsaturated carboxylic acid monomer in the copolymer of the present disclosure is 100% by mass of the structural unit derived from all the monomers constituting the copolymer of the present disclosure. It is preferably 1% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 10% by mass or less, still more preferably 1% by mass or more and 5% by mass or less. By being within the above range, the ratio of hydrophobic sites to hydrophilic sites becomes appropriate, and the soil release properties and re-staining prevention performance of the detergent additive of the present disclosure tend to improve.
• the amino group-containing copolymer of the present disclosure includes a structural unit (a) derived from an amino group-containing monomer, a structural unit (b) derived from a monomer having a polyalkylene glycol chain, and a hydrophobic monomer.
• the structural unit (c) may have 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, phosphate group-containing monomers such as 2-methacryloyloxyethyl acid phosphate, and the like.
• 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, and the like.
• the content of structural units derived from other monomers in the copolymer of the present disclosure is 10% by mass based on 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure. It is preferably at most 5% by mass, more preferably at most 3% by mass, particularly preferably at most 1% by mass.
• the weight average molecular weight (Mw) of the amino group-containing copolymer of the present disclosure is preferably 4,000 or more and 500,000 or less, more preferably 6,000 or more and 400,000 or less, and preferably 10,000 or more and 300,000 or less. More preferred. Furthermore, it is preferably 10,000 or more and 200,000 or less, more preferably 10,000 or more and 100,000 or less, even more preferably 12,000 or more and 50,000 or less, particularly preferably 15,000 or more and 40,000 or less, and most preferably 18,000 or more and 30,000 or less. Within the above range, the soil release performance of the copolymer of the present disclosure tends to be further improved.
• 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. The preferred ratio is as described above.
• the method for producing an amino group-containing copolymer of the present disclosure is also one of the present invention.
• the method for producing the amino group-containing copolymer includes, for example, an amino group-containing monomer or its precursor, a monomer having a polyalkylene glycol chain or its precursor, and a hydrophobic group monomer or its precursor. and an unsaturated carboxylic acid monomer (hereinafter referred to as polymerization step).
• methods for initiating the polymerization of the monomer components include, for example, adding a polymerization initiator, irradiating UV, applying heat, and irradiating light in the presence of a photopolymerization initiator. Examples include methods. In particular, it is preferable to use a polymerization initiator.
• polymerization initiator examples include persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate, 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl 2,2'-azobis(2 - methylpropionate), 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2-methylpropionamidine) dihydrochloride; benzoyl peroxide, lauroyl peroxide, Redox that generates radicals by combining an oxidizing agent and a reducing agent, such as organic peroxides such as di-t-butyl peroxide and cumene hydroperoxide, ascorbic acid and hydrogen peroxide, and persulfates and metal salts.
• mold initiators etc. Among these, persulfates and azo compounds are preferred, and azo compounds are more preferred since they tend to reduce residual monomers.
• These polymerization initiators may be used alone or in the form of
• the amount of the polymerization initiator used is preferably 0.01% by mass or more and 10% by mass or less, 0.02% by mass or more, based on the total amount of monomers constituting the structural unit. It is more preferably 8% by mass or less, even more preferably 0.03% by mass or more and 7% by mass or less, most preferably 0.04% by mass or more and 4% by mass or less.
• a chain transfer agent may be used as a molecular weight regulator of 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, and mercaptoethanol.
• thioglycerol 2-mercaptoethanesulfonic acid, etc.
• halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, isopropanol, secondary alcohols such as glycerin, phosphorous acid, hypophosphorous acid, hypophosphorous Acid acids and their hydrates, etc.
• compounds that can generate hydrogen sulfite (salt) and hydrogen sulfite (salt) bisulfite (salt), pyrosulfite (salt), dithionite (salt), sulfite (salt) etc.
• compounds having a mercapto group are preferred, and mercapto group-containing compounds having a carboxyl group are more preferred.
• the amount of the 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 based on 100 mol% of the total amount of monomers constituting the structural unit. , more preferably 0.2 mol% or more and 15 mol% or less, still 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. be.
• 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.
• alcohols with 1 to 8 carbon atoms such as water, ethanol, 1-propanol, 2-propanol, 1-butanol, and phenoxyethanol
• glycols such as ethylene glycol, propylene glycol, butylene glycol, and hexylene glycol , diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, and other glycol ethers are preferably used.
• water, ethanol, ethylene glycol, propylene glycol, diethylene glycol monobutyl ether, and propylene glycol monomethyl ether are preferred, and mixtures of two or more of these may also be used.
• the polymerization temperature is preferably 40°C or higher, and preferably 150°C or lower.
• the temperature is more preferably 45°C or higher, and still more preferably 50°C or higher. Further, the temperature is more preferably 100°C or lower, and still more preferably 90°C or lower.
• the method of charging the monomer components, polymerization initiator, and chain transfer agent into the reaction container is not particularly limited, and the method is to initially charge the entire amount into the reaction container at once, or to divide the entire amount into the reaction container or continuously.
• Examples include a method in which a portion is initially charged into a reaction vessel and a method in which the remainder is dividedly or continuously introduced into the reaction vessel.
• a method is used in which a solvent, which will be described later, is initially charged, and a monomer component, a polymerization initiator, and a chain transfer agent are continuously added.
• the monomer components may be polymerized after being 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.
• 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 detergent, but if necessary, it may be further neutralized with an alkaline substance before use.
• an alkaline substance monovalent or divalent metal hydroxides, inorganic salts such as carbonates, ammonia, and organic amines can be used. Further, the concentration of the copolymer can be adjusted as necessary after the reaction is completed.
• the amino group-containing copolymers of the present disclosure are used in soil release agents, antibacterial agents, and anti-resoiling agent applications.
• Soil release agents, antibacterial agents and anti-resoiling agents can be used as additives in detergents.
• soil release agents, antimicrobial agents, and anti-resoiling agents are used in detergents intended for textiles and hard surfaces.
• the detergent mentioned here includes detergents for household clothing, kitchen, housing, textile industry, and other industrial uses.
• the present invention further provides a method of using the amino group-containing copolymer as a soil release agent, antibacterial agent, or anti-recontamination agent.
• the present invention also provides a method for producing a soil release agent, which includes a step of mixing the amino group-containing copolymer and a surfactant.
• the soil release agent of the present disclosure is a soil release agent containing the amino group-containing copolymer of the present disclosure. Soil release property is detergency performance that can be measured by the method described in the Examples below.
• the soil release agent of the present disclosure can be effective under both immersion conditions and cleaning conditions.
• the soil release agent of the present disclosure may be the amino group-containing copolymer of the present disclosure alone, and is not particularly limited as long as it is an additive commonly used in detergents in addition to the amino group-containing copolymer of the present disclosure. It can also include The soil release agent of the present disclosure preferably contains 0.1 to 100% by mass of the amino group-containing copolymer.
• the additive include surfactants, including anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
• Additives other than the above-mentioned surfactants include anti-redeposition agents such as sodium carboxymethylcellulose, color transfer prevention agents, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, and Examples include foaming agents, foam stabilizers, polishing agents, disinfectants, bleaching agents, bleaching aids, enzymes, dyes, and solvents. In the case of powder detergent compositions, it is also preferred to incorporate zeolite.
• the antibacterial agent of the present disclosure contains the above amino group-containing copolymer and exhibits excellent antibacterial performance.
• the antibacterial performance is the antibacterial performance of a base material such as a fiber treated with an antibacterial agent, which can be evaluated by the method described in the Examples below.
• the antibacterial agent of the present disclosure preferably contains 0.1 to 100% by mass of the amino group-containing copolymer.
• Antibacterial performance refers to properties such as bactericidal (kills microorganisms), bacteriostatic (suppresses the proliferation of microorganisms), sterilization, disinfection, antibacterial, sterilization, antiseptic, and antifungal properties, and the target microorganisms are , bacteria, and fungi.
• bacteria examples include Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella enterica, Moraxella bacteria, and Legionella bacteria; Gram-positive bacteria such as Staphylococcus aureus and Clostridium bacteria.
• fungi examples include yeasts such as Candida, Rhodotorula, and baker's yeast; and molds such as red mold and black mold.
• the antibacterial agent of the present disclosure exhibits antibacterial properties by containing such an amino group-containing copolymer is presumed as follows.
• the cationic group derived from the structural unit represented by the general formula (1) of the amino group-containing copolymer is adsorbed onto the negatively charged surface of the microorganism. do.
• the hydrophobic group of the amino group-containing copolymer shows affinity with cell membrane parts, and by interacting with the cell membrane, destroys the interaction between lipids, etc. that constitute the cell membrane, and/or binds to the membrane. It is presumed that by inhibiting the functions of proteins and the like, cells are destroyed and/or physiological activity of cells is inhibited, resulting in the death of microorganisms.
• the antibacterial agent of the present disclosure may be the amino group-containing copolymer of the present disclosure alone, and especially if it is an additive used in ordinary detergent compositions in addition to the amino group-containing copolymer of the present disclosure. It can be included without restriction.
• the antibacterial agent of the present disclosure preferably contains 0.1 to 100% by mass of the amino group-containing copolymer.
• the additive include surfactants, including anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants.
• Additives other than the above surfactants include other antibacterial agents, anti-redeposition agents such as sodium carboxymethyl cellulose, color transfer prevention agents, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, and fluorescent agents. , colorants, foaming agents, foam stabilizers, polishing agents, disinfectants, bleaching agents, bleaching aids, enzymes, dyes, solvents, and the like. In the case of powder detergent compositions, it is also preferred to incorporate zeolite.
• the re-staining prevention agent of the present disclosure contains the above-mentioned amino group-containing copolymer and exhibits excellent re-staining prevention ability.
• the anti-restaining agent of the present disclosure preferably contains 0.1 to 100% by mass of the amino group-containing copolymer.
• the anti-resoiling agent of the present disclosure can be used by being added to a detergent composition.
• the form of the detergent composition is not particularly limited, and may be in the form of liquid, solid, powder, or the like.
• the detergent compositions of the present disclosure may contain various ingredients used in detergent compositions in addition to soil release agents, antimicrobial agents, and anti-resoiling agents.
• As components contained in the detergent composition surfactants and detergent additives commonly used in detergent compositions can be used.
• the above-mentioned surfactant may be any of anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants, and one type or two or more types can be used.
• anionic surfactants include alkylbenzene sulfonates, alkyl ether sulfates, alkenyl ether sulfates, alkyl sulfates, alkenyl sulfates, ⁇ -olefin sulfonates, ⁇ -sulfo fatty acids or their ester salts, and alkanesulfonic acids.
• salt saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acyl amino acid type surfactant, alkyl phosphate ester or its salt, alkenyl phosphate ester Or its salt etc.
• 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.
• examples include esters and alkylamine oxides.
• the alkyl group and alkenyl group in these nonionic surfactants may have a branched alkyl group such as a methyl group.
• Examples of the cationic surfactant include quaternary ammonium salts.
• Examples of the amphoteric surfactant include carboxyl-type amphoteric surfactants, sulfobetaine-type amphoteric surfactants, and the like.
• 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 content of the surfactant is preferably 10 to 60% by mass, more preferably 15 to 50% by mass, even more preferably 20 to 45% by mass, and even more preferably 25% by mass based on the total amount of the detergent composition. Particularly preferred is 40% by mass.
• the surfactant content is 10 to 60% by mass based on the total amount of the detergent composition, detergency and economic efficiency tend to be compatible.
• Polyester taffeta (polyester fiber manufactured by Irosensha Co., Ltd.) was cut into 5 ⁇ 5 cm pieces.
• (Creation of contaminated cloth) 61.5 g of olive oil, 37 g of oleic acid, 1 g of iron (III) oxide, and 0.5 g of oil red were mixed to prepare an oil and fat contaminated solution.
• a 1% copolymer aqueous solution was added and mixed so that the copolymer concentration was 7.3 ppm.
• a total of 16.7 g of five contaminated cloths whose Z values had been measured using a spectrophotometer (SE6000 manufactured by Nippon Denshoku Kogyo Co., Ltd.) and a bath ratio adjustment cloth were placed in a pot and washed by stirring at 120 rpm for 10 minutes. After discarding the water in the pot and rinsing once for 3 minutes, the cloth was dehydrated and air-dried for 1 day. After air drying, the Z value of the washed contaminated cloth was measured again using a color difference meter, and the cleaning rate was calculated using the following formula.
• Cleaning rate (%) ((Zs-Zw)/(Zs-Zo)) x 100
• Zs represents the Z value of the contaminated cloth before cleaning
• Zw represents the Z value of the contaminated cloth after cleaning
• Zo represents the Z value of the white cloth before staining.
• the cleaning power was evaluated using the following criteria. The results are shown in Table 5.
• ⁇ Cleaning rate 88% or more
• ⁇ Cleaning rate 86% or more, less than 88%
• Emulgen 108 manufactured by Kao Corporation, PAE was diluted with ion exchange water to create a 10% solution.
• Preparation of hardness mother liquor 5.90 g of calcium chloride dihydrate and 2.72 g of magnesium chloride hexahydrate were weighed into a beaker, and ion-exchanged water was added to make 100 g.
• Preparation of aqueous sodium hydrogen carbonate solution 1.54 g of sodium hydrogen carbonate and 10 g of 0.1N hydrogen chloride were placed in a beaker and diluted with ion exchange water to make 100 g.
• Recontamination prevention rate (%) [(whiteness after washing) / (whiteness of original white cloth)] ⁇ 100 The ability to prevent recontamination was judged based on the following criteria.
• Re-stain prevention ability for cotton Re-stain prevention rate is +1.0% or more compared to the condition where no polymer is added: ⁇ Re-staining prevention rate with respect to the condition where no polymer is added is +0.5% or more and less than +1.0%: ⁇ Re-staining prevention rate with respect to the condition where no polymer is added is less than +0.5%: ⁇ Re-stain prevention ability for polyester Re-stain prevention rate is +4.0% or more compared to the condition where no polymer is added: ⁇ Re-staining prevention rate with respect to polymer-free conditions is +2.0% or more and less than +4.0%: ⁇ Re-staining prevention rate with respect to polymer-free conditions is less than +2.0%: ⁇
• Antibacterial activity value ⁇ log (control sample, number of viable bacteria after inoculation) - log (control sample, number of viable bacteria immediately after inoculation) ⁇ - ⁇ log (test sample, number of viable bacteria after inoculation) - log (test sample, number of viable bacteria immediately after inoculation) number) ⁇ Antibacterial properties were evaluated based on the following criteria.
• Antibacterial activity value is 2.5 or more: ⁇ Antibacterial activity value is 2.0 or more and less than 2.5: ⁇ Antibacterial activity value less than 2.0: ⁇
• ⁇ Manufacture example 1> A glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 62.3 g of ethanol, and while stirring, nitrogen was flowed at 100 ml/min for 60 minutes, and the temperature was raised to 70°C. After the nitrogen flow was set to 50 ml/min, 20.3 g of dimethylaminoethyl acrylate (manufactured by Fuji Film Wako Pure Chemical Industries, hereinafter also referred to as DAM) and 11.0 g of ethanol were added to the polymerization reaction system at a constant state of 70° C. under stirring.
• DAM dimethylaminoethyl acrylate
• Monomer solution 1 consisting of 8g of acetic acid and 7.3g of acetic acid; 72.2g of methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide 23, trade name "M-230G” manufactured by Shin Nakamura Chemical, hereinafter also referred to as PGM23E), methacrylate Monomer solution 2 consisting of 6.0 g of acid (hereinafter also referred to as MAA) and 33.5 g of ethanol; Monomer solution 3 consisting of 36.5 g of benzyl methacrylate (manufactured by Fuji Film Wako Pure Chemical, hereinafter also referred to as BnMA); 2 , 2'-Azobis(2,4-dimethylvaleronitrile) (trade name "V-65” manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in 3.5% ethanol solution (50.1 g) was added to each initiator aqueous solution separately.
• MAA methoxypolyethylene glycol monomethacrylate
• Copolymer 2 was produced in the same manner as in Production Example 1, except that the amount of solvent, amount of monomer, type of monomer, and amount of initiator used were changed so that the composition and molecular weight were as shown in Table 1. I got ⁇ 20.
• the monomer species not used in Production Example 1 but used in the polymerization of Production Examples 2 to 20 are shown below.
• Lauryl methacrylate (trade name "Light Ester L” of Kyoeisha Chemical Co., Ltd., hereinafter also referred to as LMA), butyl methacrylate (hereinafter also referred to as BMA), cyclohexyl methacrylate (hereinafter also referred to as CHMA), 2-ethylhexyl acrylate (hereinafter referred to as 2EHA) ), methoxypolyethylene glycol monomethacrylate (average number of added moles of ethylene oxide is 9, NOF Corporation's trade name "Blemmer PME-400", hereinafter also referred to as PGM9E). The results are shown in Table 1.
• the copolymer of the present disclosure was found to have excellent soil release properties.
• Examples 15 to 23 show the results of anti-restaining properties on cotton using the copolymers produced in Production Examples, and Comparative Example 3 shows the evaluation results using Comparative Copolymer 1 produced in Comparative Production Examples. It is shown in Table 3.
• Table 5 shows the results of antibacterial evaluation of Examples 42 to 46, which used the copolymers produced in Production Examples, and Comparative Example 5, a system in which no polymer was used.
• the copolymers of the present disclosure were found to have excellent anti-recontamination properties and antibacterial properties.

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