Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • 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
  • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
  • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
• • 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
• • 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
  • 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
• • 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

Definitions

• the present invention relates to amino group-containing copolymers. More particularly, it relates to amino group-containing copolymers 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 an effect of removing dirt from cotton cloth.
• Soil releasability with polymers containing amino groups has been disclosed above. However, there is still room for further improvement in terms of soil release properties, especially for polyester fibers, etc., which tend to absorb sebum stains.
• 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 disclosure includes 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, and a substituent
• An amino group-containing copolymer comprising a structural unit (c) derived from a (meth) acrylic acid ester containing an aryl group optionally having an amino group-containing monomer derived from is an amino group-containing copolymer characterized in that the ratio of the structural unit (a) of is 5 to 50% by mass with respect to 100% by mass of all structural units.
• 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 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 ratio of the structural unit (b) derived from the monomer having the polyalkylene glycol chain is preferably 5 to 70% by weight with respect to 100% by weight of all structural units.
• the ratio of the structural unit (c) derived from the (meth)acrylic acid ester containing an aryl group optionally having a substituent is 10 to 70% by weight with respect to 100% by weight of the total structural units. preferable.
• 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 is also a soil release agent containing the amino group-containing copolymer.
• the present invention is also a method of using the amino group-containing copolymer as a soil release agent.
• the present invention further provides a method for producing a soil release agent, the method for producing a soil release agent comprising the step of mixing the amino group-containing copolymer and a surfactant.
• amino group-containing copolymer of the present disclosure is excellent in soil release properties, it can be suitably used in detergents and the like used particularly for fiber 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 an amino group-containing monomer described below and a polyalkylene glycol chain Structural unit (b) derived from, a structural unit (c) derived from a (meth) acrylic acid ester containing an optionally substituted aryl group, and the proportion of the structural unit (a) is the total structure It is a copolymer characterized by being 5 to 50% by mass with respect to 100% by mass of units. By having such a structure, the copolymer of the present disclosure is excellent in soil release properties, and also excellent in antibacterial properties and anti-soil redeposition properties.
• the structural unit (a) derived from the amino group-containing monomer of the present disclosure is a structural unit represented by general formula (1) below.
• 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 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.
• atoms contained in another structural unit of the same type means, for example, if the structural unit is represented by general formula (1), another structural unit represented by general formula (1) represents that it is an atom contained in, and "an atom contained in another heterogeneous structural unit” is, for example, if the structural unit is represented by general formula (1), it is represented by general formula (1) Represents an atom contained in a structural unit other than a structural unit.
• the structure derived from the 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 acid of a primary to tertiary amino group It can be formed by radically polymerizing a monomer having a hydrate, but is not limited to this.
• R 4 and R 5 in general formula (2) above are the same as R 4 and R 5 in general formula (1) above.
• the structural unit (a) derived from the 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-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 neutralized products thereof with acids such as hydrochloric acid and acetic acid; N,N-dimethylaminoethyl (meth)acrylate N,N-dialkylamino group-containing (meth)acrylamides such as acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide and
• a structural unit derived from the amino group-containing monomer a structural unit derived from N,N-dimethylaminoethyl (meth)acrylate represented by the following general formula (3) is particularly preferable.
• R6 in the 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 are structural units derived from N,N-dimethylaminoethyl methacrylate.
• the content of the structural unit (a) derived from the amino group-containing monomer is the structural unit derived from all the monomers constituting the copolymer of the present disclosure (hereinafter referred to as the total structure Also referred to as a unit.)
• the total structure also referred to as a unit.
• 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 It is 10% by mass or more and 30% by mass or less, and most preferably 15% by mass or more and 25% by mass or less.
• the structural unit (b) derived from a monomer having a polyalkylene glycol chain of the present disclosure is characterized by containing 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 optionally substituted alkyl group having 1 to 5 carbon atoms; Z is a hydrogen atom; 30 hydrocarbon groups or hydroxyl groups, carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups and salts thereof.
• A represents an optionally substituted alkylene group having 1 to 10 carbon atoms.
• 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 optionally substituted alkyl group having 1 to 5 carbon atoms, and the substituents are hydroxyl, carboxyl, sulfonic acid, At least one hydrophilic group selected from the group consisting of phosphate groups, amino groups and groups of salts 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.
• R 7 , R 8 and R 9 are each independently preferably a hydrogen atom or a methyl group. More preferably, R7 and R9 are hydrogen atoms, and R8 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, or 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 includes 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 the number of carbon atoms in the hydrocarbon group in the case of having a branch means the total number of carbon atoms in the main chain and the branched chains.
• 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 and stearyl group. , an icosyl group, and the like.
• 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 icosinyl 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 A phenyl group, a dibutylphenyl group, a biphenyl group, a biphenylmethyl group, a biphenylethyl group, a naphthyl group, a naphthylmethyl group, a naphthylethyl group, and the like.
• Examples of the cycloalkyl group include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.
• Examples of the cycloalkenyl group include cyclopropenyl group, cyclobutenyl group, cyclopentenyl group, cyclohexenyl group and the like.
• 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 2-20, more preferably 2-15, even more preferably 2-10, and particularly preferably 2-5.
• Z is preferably a hydrogen atom or a methyl group.
• A represents an optionally substituted alkylene group having 1 to 10 carbon atoms.
• the substituent is preferably a hydroxyl group and at least one hydrophilic group selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, a secondary or tertiary amino group, and a salt group thereof.
• All q oxyalkylene groups of AO present in the polyalkylene glycol represented by q may be the same or different.
• the alkylene group represented by A 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, oxy-2,3-butylene, oxystyrene, and oxyalkylene having 2 to 10 carbon atoms. More preferred are alkylene oxides having 2 to 4 carbon atoms such as oxyethylene, oxypropylene and oxybutylene, and more preferred are oxyethylene and oxypropylene.
• the oxyalkylene group represented by AO is not limited to a group formed by an addition reaction of alkylene oxide.
• the above q represents the average number of added moles of AO and is a number from 1 to 200. It is preferably 1-180, more preferably 2-150, even more preferably 2-100, even more preferably 2-80, and particularly preferably 2-50.
• 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, still more preferably 0.
• m is more preferably 1.
• the structural unit (b) having a polyalkylene glycol chain is formed, for example, by radically polymerizing a monomer having a polyalkylene glycol chain.
• the monomer having a polyalkylene glycol chain include polyalkylene glycol mono (meth) acrylates such as (poly) ethylene glycol mono (meth) acrylate and (poly) propylene glycol mono (meth) acrylate; methoxy (Poly) ethylene glycol mono (meth) acrylate, alkoxy polyalkylene glycol mono (meth) acrylate such as 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- A (poly)alkylene glycol-based monomer such as
• the content of the structural unit (b) having a polyalkylene glycol chain in the copolymer of the present disclosure is 5 per 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure. % by mass or more and 70% 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, it is 45% by mass or more and 60% by mass or less. Within the above range, the ratio of hydrophilic sites becomes appropriate, and the performance of the detergent additive of the present disclosure tends to be improved.
• Structural unit (c) derived from (meth) acrylic acid ester containing an aryl group optionally having a substituent of the present disclosure contains an aryl group optionally having a substituent in the structure ( It is characterized by being derived from meth)acrylate.
• the substituent is preferably a hydrophobic group, preferably a hydrocarbon group having 1 to 18 carbon atoms or an aryl group having 6 to 30 carbon atoms.
• the structural unit (c) derived from the (meth)acrylic acid ester containing an optionally substituted aryl group is, for example, a (meth)acrylic acid ester containing an optionally substituted aryl group is formed by radical polymerization of A (meth)acrylic acid ester containing an aryl group which may have a substituent in the structure is an ester of (meth)acrylic acid and an aryl alcohol having 6 to 30 carbon atoms which may have a substituent. can be given.
• aryl alcohols 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, and butylmethyl.
• phenyl 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 and the like.
• the content of structural units (c) derived from a (meth)acrylic acid ester containing an optionally substituted aryl group is all constituting the copolymer of the present disclosure 10% by mass or more and 70% by mass or less, preferably 15% by mass or more and 65% by mass or less, more preferably 15% by mass or more and 60% by mass or less with respect to 100% by mass of structural units derived from the monomer of , more preferably 15% by mass or more and 55% by mass or less, still more preferably 15% by mass or more and 50% by mass or less, particularly preferably 20% by mass or more and 45% by mass or less, most preferably It is 20 mass % or more and 40 mass % or less.
• the ratio of hydrophobic sites becomes appropriate, and the performance of the additive for detergents of the present disclosure tends to improve.
• the amino group-containing copolymer of the present disclosure has 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 substituent. may have a structural unit (d) derived from a monomer other than the structural unit (c) derived from a (meth)acrylic acid ester containing an aryl group which may be substituted.
• Other monomers are not particularly limited, but include, for example, unsaturated carboxylic acid monomers; (meth)acrylic acid esters containing no aryl group; olefinic monomers having 2 to 4 carbon atoms such as ethylene and propylene.
• vinyl halide such as vinyl chloride, methyl vinyl ether, ethyl vinyl ether, acrylonitrile and the like.
• Examples of the unsaturated carboxylic acid monomers include (meth)acrylic acid, crotonic acid, tiglic acid, 3-methylcrotonic acid, 2-methyl-2-pentenoic acid, itaconic acid, and monovalent metals thereof.
• Unsaturated carboxylic acid-based monomers such as salts, divalent metal salts, ammonium salts, and organic amine salts; Examples thereof include metal salts, ammonium salts, organic amine salts and the like, their anhydrides, and unsaturated dicarboxylic acid monomers such as half esters.
• (meth)acrylic acid, maleic acid and salts thereof are preferred, and (meth)acrylic acid is more preferred.
• the (meth)acrylic acid ester containing no aryl group may be an ester of an alcohol having no aryl group and (meth)acrylic acid, such as 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 , n-octyl (meth) acrylate, tridecyl (meth) acrylate, cycloalkyl (meth) acrylate such as cyclohexyl (meth) acrylate, n-lauryl (meth) acrylate, dodecyl (meth) acrylate, stearyl
• Other monomers are preferably unsaturated carboxylic acid-based monomers, and a form in which the copolymer of the present disclosure has a structural unit derived from an unsaturated carboxylic acid-based monomer is also a preferred embodiment of the present invention. is one of
• the content of structural units derived from other monomers in the copolymer of the present disclosure is 10% by mass with respect to 100% by mass of structural units derived from all monomers constituting the copolymer of the present disclosure. It is preferably 5% 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.
• the content of structural units derived from unsaturated carboxylic acid monomers 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 It is preferably 0 to 10% by mass, more preferably 0 to 6% by mass. Within the above range, the proportion of dispersing groups becomes appropriate, and the performance of the additive for detergents of the present disclosure tends to improve.
• a form in which the copolymer of the present disclosure has a structural unit derived from an unsaturated carboxylic acid-based monomer in an amount of 1 to 6% by mass with respect to 100% by mass of all structural units 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 10000 or more and 300000 or less. More preferred. Furthermore, 10000 or more and 200000 or less are especially preferable, and 10000 or more and 100000 or less are the most preferable. Within the above range, the copolymer of the present disclosure tends to have more improved soil release performance.
• the method for producing the amino group-containing copolymer of the present disclosure is not particularly limited, but it can be produced by polymerizing the monomer components, specific examples and preferred examples of the monomer components, and each monomer are as described above.
• a method for producing the amino group-containing copolymer of the present disclosure is also one aspect of the present invention.
• the method for producing the amino group-containing copolymer may have, for example, an amino group-containing monomer or a precursor thereof, a monomer having a polyalkylene glycol chain or a precursor thereof, and a substituent.
• a step of polymerizing a (meth)acrylic acid ester containing an aryl group (hereinafter referred to as a polymerization step) is included.
• Methods for initiating polymerization of the monomer components in the polymerization step include, for example, a method of adding a polymerization initiator, a method of irradiating UV, a method of applying heat, and irradiating light in the presence of a photopolymerization initiator. methods and the like. 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 -methyl propionate), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropionamidine) dihydrochloride and other azo compounds; 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, persulfates and metal salts, etc.
• persulfates such as sodium persulfate, potassium persulfate and ammonium persulfate
• 2,2′-azobis(2,4-dimethylvaleronitrile) di
• polymerization initiators may be used alone or in the form of a mixture of two or more.
• the amount of the polymerization initiator used is preferably 0.01% by mass or more and 10% by mass or less, preferably 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, still 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.
• a chain transfer agent may be used as a molecular weight modifier for the polymer.
• 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., carbon tetrachloride, methylene chloride, bromoform, halides such as bromotrichloroethane, isopropanol, secondary alcohols such as glycerin, phosphorous acid, hypophosphorous acid, hypophosphorous acid acid salts and hydrates thereof; compounds capable of generating hydrogen sulfite (salt) and hydrogen sulfite (salt) (bisulfite (salt), pyrosulfite (salt), dithionous acid (salt), sulfite (salt) etc.).
• a compound having a mercapto group is preferred, and a mercapto group-containing compound having a carboxyl group is 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 with respect to 100 mol% of the total amount of monomers constituting the structural units. , 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, most preferably 0.5 mol% or more and 5 mol% or less be.
• the solvent used in the polymerization can be selected from those capable of dissolving the monomer components, polymerization initiator, chain transfer agent, and produced copolymer as required.
• alcohols having 1 to 8 carbon atoms such as water, ethanol, 1-propanol, 2-propanol, 1-butanol and phenoxyethanol, and glycols such as propylene glycol, butylene glycol and hexylene glycol are preferably used. be done.
• water, ethanol, ethylene glycol and propylene glycol 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. It is more preferably 45° C. or higher, and still more preferably 50° C. or higher. Also, it is more preferably 100° C. or lower, and still more preferably 90° C. or lower.
• the method of charging the monomer components, the polymerization initiator, and the chain transfer agent into the reaction vessel is not particularly limited. Examples include a method of charging, a method of charging a part into the reaction vessel at the initial stage, and a method of dividing or continuously charging the rest into the reaction vessel.
• a preferred method is to initially charge a solvent, which will be described later, and then continuously add a monomer component, a polymerization initiator, and a chain transfer agent.
• the monomer component may 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, and then polymerized.
• 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 used after being neutralized with an alkaline substance.
• a detergent additive such as an additive for liquid detergents
• an alkaline substance inorganic salts such as monovalent or divalent metal hydroxides and carbonates, ammonia, and organic amines can be used. Also, after the reaction is completed, the concentration of the copolymer can be adjusted as necessary.
• the amino group-containing copolymers of the present disclosure are used for soil release agents, antibacterial agents and anti-soil redeposition agent applications.
• Soil release agents, antimicrobial agents and anti-resoiling agents can be used as detergent additives.
• soil release agents, antimicrobial agents and anti-resoiling agents are used in detergents intended for textiles and hard surfaces.
• detergent as used herein includes household clothing, kitchen, household, textile industry and other industrial detergents.
• the present invention is also a method of using the amino group-containing copolymer as a soil release agent, antibacterial agent or anti-soil redeposition agent.
• the present invention is also a method for producing a soil release agent, the method for producing a soil release agent comprising the 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.
• the soil release property is detergency performance that can be measured by the method described in Examples below.
• the soil release agent of the present disclosure can be effective under both immersion conditions and washing conditions.
• the soil release agent of the present disclosure may be the amino group-containing copolymer of the present disclosure alone, and in addition to the amino group-containing copolymer of the present disclosure, it is not particularly limited as long as it is an additive that is usually used in detergents. can also be included.
• 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 surfactants include anti-redeposition agents such as sodium carboxymethyl cellulose, anti-color transfer agents, softeners, alkaline substances for pH adjustment, perfumes, solubilizers, fluorescent agents, coloring agents, Foaming agents, foam stabilizers, polishing agents, disinfectants, bleaching agents, bleaching auxiliaries, enzymes, dyes, solvents and the like.
• anti-redeposition agents such as sodium carboxymethyl cellulose, anti-color transfer agents, softeners, alkaline substances for pH adjustment, perfumes, solubilizers, fluorescent agents, coloring agents, Foaming agents, foam stabilizers, polishing agents, disinfectants, bleaching agents, bleaching auxiliaries, enzymes, dyes, solvents and the like.
• zeolite 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 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 the performance of sterilization (killing microorganisms), bacteriostasis (suppressing the growth of microorganisms), sterilization, disinfection, antibacterial, sterilization, antiseptic, antifungal, etc.
• the target microorganisms are , bacteria and fungi.
• bacteria examples include Gram-negative bacteria such as Escherichia coli, Pseudomonas aeruginosa, Salmonella, Moraxella, and Legionella; Gram-positive bacteria such as Staphylococcus aureus and Clostridium.
• fungi examples include yeasts such as Candida, Rhodotorula, and baker's yeast; and fungi 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 adsorbs to the surface of the microorganism having a negative charge. do.
• the hydrophobic group possessed by the amino group-containing copolymer exhibits affinity with the cell membrane portion and interacts with the cell membrane, thereby destroying the interaction between lipids constituting the cell membrane and/or binding to the membrane. It is presumed that the cells are destroyed and/or the physiological activity of the cells is inhibited by inhibiting the functions of the proteins and the like that are responsible for the death of the microorganisms.
• the antibacterial agent of the present disclosure may be the amino group-containing copolymer of the present disclosure alone, and in addition to the amino group-containing copolymer of the present disclosure, additives that are commonly used in detergent compositions are particularly Can be included without limitation.
• 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 carboxymethylcellulose, color transfer inhibitors, softeners, alkaline substances for pH adjustment, fragrances, solubilizers, and fluorescent agents. , coloring agents, foaming agents, foam stabilizers, polishing agents, disinfectants, bleaching agents, bleaching auxiliaries, enzymes, dyes, solvents and the like. In the case of a powder detergent composition, it is also preferred to incorporate zeolite.
• the anti-soil redeposition agent of the present disclosure contains the amino group-containing copolymer and exhibits excellent anti-soil redeposition ability.
• the anti-soil redeposition agent of the present disclosure preferably contains 0.1 to 100% by mass of the amino group-containing copolymer.
• the anti-soil redeposition 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 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-soil agents.
• As components contained in the detergent composition surfactants and detergent additives that are commonly used in detergent compositions can be used.
• anionic surfactants nonionic surfactants, cationic surfactants and amphoteric surfactants may be used as the surfactant, and one or more of them may 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. Salts, saturated fatty acid salts, unsaturated fatty acid salts, alkyl ether carboxylates, alkenyl ether carboxylates, amino acid type surfactants, N-acyl amino acid type surfactants, alkyl phosphates or salts thereof, alkenyl phosphates Or its salt etc. are suitable.
• the alkyl group and alkenyl group in these anionic surfactants may be branched to an alkyl group such as a methyl group.
• Nonionic surfactants include polyoxyalkylene alkyl ethers, polyoxyalkylene alkenyl ethers, polyoxyethylene alkylphenyl ethers, higher fatty acid alkanolamides or their alkylene oxide adducts, sucrose fatty acid esters, alkyl glycooxides, fatty acid glycerol mono Examples include esters, alkylamine oxides, and the like.
• the alkyl group and alkenyl group in these nonionic surfactants may be branched to an alkyl group such as a methyl group.
• Cationic surfactants include quaternary ammonium salts and the like.
• amphoteric surfactants include carboxyl-type amphoteric surfactants and sulfobetaine-type amphoteric surfactants.
• the alkyl group and alkenyl group in these cationic surfactants and amphoteric surfactants may have branched alkyl groups such as methyl groups.
• 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, with respect to the total amount of the detergent composition. It is particularly preferred that it is up to 40% by mass. When the content of the surfactant is 10 to 60% by mass with respect to the total amount of the detergent composition, it tends to be possible to achieve both detergency and economy.
• Emulgen 108 manufactured by Kao Corporation was adjusted to 1000 ppm and the content of the copolymer obtained in the example was 33 ppm.
• 360 g of the aqueous solution was stirred with a magnetic stirrer. While stirring, 6 g of the cloth was added and stirred for 10 minutes. After stirring, 360 g of ion-exchanged water was used for rinsing for 3 minutes, followed by dehydration and air drying for 1 day.
• aqueous solution of sodium hydroxide having an appropriate concentration was added to the prepared aqueous solution to adjust the pH to 7.5 to 8.5.
• (4)-3 Detergency test Set the turgot meter at 25 ° C., put 493.3 g of hard water in (1) and 5.0 g of surfactant solution in (4)-1 in the pot, and 1.7 g of a 1% copolymer aqueous solution of (4)-2 was added and mixed so that the polymer concentration was 33 ppm.
• a 16.7-g pot was put together with 5 stained cloths whose Z value was measured by a color difference observation device (Vervide: Digieye) and a bath ratio adjusting cloth (cotton white cloth), and washed by stirring at 120 rpm for 10 minutes.
• Cleaning rate calculation formula Cleaning rate (%) ((Zs-Zw)/(Zs-Zo)) x 100 Zs represents the Z value of the contaminated cloth before evaluation, Zw represents the Z value of the contaminated cloth after evaluation, and Zo represents the Z value of the white cloth before contamination.
• ⁇ cleaning rate of 90% or more
• ⁇ cleaning rate of 60% or more and less than 90%
• ⁇ cleaning rate of less than 60%
• (2)-2 Detergency test Set the turgot meter at 25 ° C., put 498.8 g of hard water in (1)-2 and 0.85 g of the surfactant solution in (1)-3 in the pot, and 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 the soiled cloth whose Z value was measured in advance with a spectral color difference meter (SE6000 manufactured by Nippon Denshoku Industries Co., Ltd.) and the bath ratio adjusting cloth were placed in a pot and washed by stirring at 120 rpm for 10 minutes. After the pot was drained and one rinse was performed for 3 minutes, the fabric was dehydrated and air dried for 1 day.
• SE6000 spectral color difference meter
• Emulgen 108 As a surfactant solution, Emulgen 108 (PAE manufactured by Kao Corporation) was diluted with deionized water to prepare 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 deionized water was added to make 100 g.
• Redeposition prevention rate (%) [(whiteness after washing) / (whiteness of original white cloth)] x 100
• the ability to prevent redeposition was determined according to the following criteria.
• Anti-soil redeposition rate is +1.0% or more against polymer-free conditions: ⁇
• Anti-soil redeposition rate for polymer non-addition conditions is +0.5% or more and less than 1.0%: ⁇
• Anti-soil redeposition rate for non-polymer added conditions is less than +0.5%: ⁇
• Antibacterial activity value ⁇ log (control sample/viable count after culture) -log (control sample/viable count immediately after inoculation) ⁇ - ⁇ log (test sample/viable count after culture)-log (test sample/viable count immediately after inoculation number) ⁇ Antibacterial evaluation was determined according to the following criteria. Antibacterial activity value of 2.5 or more: ⁇ Antibacterial activity value of 2.0 or more and less than 2.5: ⁇ Antibacterial activity value less than 2.0: ⁇
• PGM23E 78.3 g, dimethylaminoethyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd., hereinafter also referred to as DAM) 20.3 g, ethanol (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) 42.2 g, acetic acid (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) Monomer solution 1 consisting of 7.4 g; benzyl methacrylate (manufactured by Fuji Film Wako Pure Chemical Industries, hereinafter also referred to as BnMA.) An aqueous initiator solution consisting of 50.4 g of a 3% ethanol solution of azobis(2,4-dimethylvaleronitrile) (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
• V-65 a copolymer 1 was obtained.
• the monomer solution and the aqueous initiator solution started dropping at the same time, the monomer solutions 1 and 2 were dropped for 180 minutes, and the aqueous initiator solution was dropped for 240 minutes. After all dropping was completed, the reaction solution was kept at 70° C. for an additional 60 minutes for aging to complete the polymerization, and a copolymer 7 was obtained.
• ⁇ Production Example 12> A separable glass flask equipped with a thermometer, a reflux condenser, and a stirrer was charged with 62.3 g of ethanol, and the mixture was heated to 70° C. after flowing nitrogen at 100 ml/min for 60 minutes while stirring. After setting the nitrogen flow to 50 ml/min, a monomer solution 1 consisting of DAM 20.3 g, ethanol 11.8 g, acetic acid 7.3 g; PGM23E 72.2 g, methacrylic acid ( 6.0 g of MAA, 33.5 g of ethanol; monomer solution 3 of 36.5 g of BnMA; 50.1 g of a 3.5% ethanol solution of V-65. Each was dropped from separate dropping nozzles.
• the dropping of the monomer solution and the aqueous initiator solution was started at the same time, and the monomer solutions 1, 2 and 3 were dropped for 180 minutes, and the aqueous initiator solution was dropped for 240 minutes. After all dropping was completed, the reaction solution was kept at 70° C. for an additional 60 minutes for aging to complete the polymerization, and a copolymer 12 was obtained.
• Table 2 shows the results of soil release property evaluation 1 for Examples 1 to 9 using the copolymers 1 to 9 produced in Production Examples 1 to 9 and Comparative Example 1 for a system that does not use a polymer. .
• Table 6 shows the results of antibacterial evaluation of Examples 48 to 56 using the copolymers produced in Production Examples and Comparative Example 5, which does not use a polymer.
• the copolymer of the present disclosure is also excellent in anti-soil redeposition and antibacterial properties.

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