WO2021065910A1 - Copolymer-containing detergent additive, soil release agent, microbial attachment inhibitor, fiber treatment agent, water treatment agent formulation, and coating formulation - Google Patents

Copolymer-containing detergent additive, soil release agent, microbial attachment inhibitor, fiber treatment agent, water treatment agent formulation, and coating formulation Download PDF

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WO2021065910A1
WO2021065910A1 PCT/JP2020/036911 JP2020036911W WO2021065910A1 WO 2021065910 A1 WO2021065910 A1 WO 2021065910A1 JP 2020036911 W JP2020036911 W JP 2020036911W WO 2021065910 A1 WO2021065910 A1 WO 2021065910A1
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group
copolymer
monomer
meth
mass
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PCT/JP2020/036911
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French (fr)
Japanese (ja)
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尊子 張替
竜佑 金尾
勇樹 牧野
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株式会社日本触媒
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers

Definitions

  • the present invention relates to detergent additives containing copolymers, soil release agents, microbial adhesion inhibitors, fiber treatment agents, water treatment agent formulations and paint formulations.
  • Patent Documents 1 and 2 disclose a copolymer of an unsaturated carboxylic acid-based monomer such as (meth) acrylic acid and a (poly) alkylene glycol-based monomer. ing.
  • Patent Document 3 describes a polymer having a predetermined structural unit (A) and a predetermined structural unit (B).
  • a recontamination inhibitor containing is disclosed.
  • Patent Document 4 describes a structural unit (A) derived from an unsaturated bond-containing monomer having at least one amino group selected from 1 to 3 secondary amino groups, and a linear or branched chain having 4 to 22 carbon atoms.
  • a fiber stain release agent consisting of 000 polymers has been disclosed.
  • Patent Document 5 discloses the use of a polymer in which a dicarboxylic acid unit, an alkylene glycol unit and a polyalkylene glycol unit are bonded via an ester bond to prevent the formation of microbial colonies on the fiber surface.
  • JP-A-2007-231260 Japanese Unexamined Patent Publication No. 2002-003551 Japanese Unexamined Patent Publication No. 2009-249743 JP-A-2007-247126 European Patent No. 2929422
  • polyester has been increasing as materials used for clothing and the like because of their excellent durability, quick drying, and less wrinkling.
  • polyester has the above-mentioned merits, since it is a hydrophobic fiber, it has a strong adsorption force with sebum stains and has a demerit that stains are hard to be removed as compared with cotton and the like.
  • stains are hard to be removed as compared with cotton and the like.
  • various polymers used for surface coating of detergents and fibers have been disclosed, but under such circumstances, various conventional polymers are not sufficient in detergency and are improved. There was room for.
  • the present invention has been made in view of the above situation, and an object of the present invention is to provide an additive for a detergent containing a copolymer having a detergency superior to that of a conventional polymer.
  • a copolymer of a monomer having a specific hydrophilic group and a monomer having an aromatic group has a structure derived from (meth) acrylic acid (salt). It was found that by setting the content ratio of the unit within a specific range, it exhibits superior detergency than the conventional polymer, and it was conceived that the above-mentioned problems can be solved brilliantly, and the present invention has been reached. Is.
  • the present invention is a monomer having at least one hydrophilic group selected from the group consisting of a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof
  • the structural unit (a) is represented by the following formula (1);
  • R 1 , R 2 and R 3 are the same or different and are selected from the group consisting of a hydrogen atom or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof.
  • Z is a hydrogen atom, a methyl group, a hydroxyl group, and a carboxyl group.
  • A is the same or different.
  • X and w represent the same or different numbers from 0 to 4.
  • y and v represent the same or different and 0. Alternatively, it is preferably represented by 1).
  • the aromatic group-containing monomer (B) preferably has a solubility parameter of 13 or less as a homopolymer.
  • the content ratio of the structural unit (a) is preferably 10 to 99% by mass with respect to 100% by mass of all the structural units.
  • the content ratio of the structural unit (b) is preferably 1 to 74% by mass with respect to 100% by mass of all the structural units.
  • the copolymer preferably contains 49% by mass or less of structural units derived from (meth) acrylic acid (salt).
  • the copolymer may have a structural unit (c) derived from a hydrophobic monomer (C) other than the structural unit (b) derived from the aromatic group-containing monomer (B), and may have a structural unit.
  • the total ratio of (b) and the structural unit (c) is preferably 1 to 90% by mass with respect to 100% by mass of all structural units.
  • the copolymer is a structural unit (e) derived from a monomer (E) other than the monomer (A), the aromatic group-containing monomer (B) and the hydrophobic monomer (C). Is preferably 0 to 30% by mass with respect to 100% by mass of all structural units.
  • the aromatic group-containing monomer (B) includes styrene, ⁇ -methylstyrene, vinyltoluene, inden, vinylnaphthalene, phenylmaleimide, vinylaniline, styrenesulfonic acid and the following formula (3);
  • R 4 , R 5 , and R 6 represent the same or different alkyl groups having a hydrogen atom or 1 to 3 carbon atoms .
  • R 7 represents an aromatic group. It is preferable that it is at least one selected from the group.
  • the hydrophobic monomer (C) has the following formula (5);
  • R 8 , R 9 , and R 10 represent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, which are the same or different.
  • R 11 is a chain hydrocarbon group and fat having 1 to 30 carbon atoms. It is preferably a compound represented by (representing a cyclic hydrocarbon group).
  • the copolymer preferably has a weight average molecular weight of 3000 to 300,000.
  • the present invention is also a detergent composition comprising the above-mentioned copolymer and a detergent additive other than the copolymer.
  • the present invention is also a soil release agent containing the above copolymer.
  • the present invention is also an antimicrobial adhesion agent containing the above copolymer.
  • the present invention is also a fiber treatment agent containing the above copolymer.
  • the present invention is also a water treatment drug formulation containing the above copolymer.
  • the present invention is also a paint formulation containing the above copolymer.
  • the present invention is also a method of using the copolymer using the above-mentioned copolymer as an additive for detergent.
  • the present invention is also a method of using a copolymer using the above-mentioned copolymer as a soil release agent.
  • the present invention is also a method of using a copolymer using the above-mentioned copolymer as a microbial adhering agent.
  • the present invention is also a method for preventing the adhesion of microorganisms by using the above-mentioned copolymer.
  • the present invention is also a method of using a copolymer using the above-mentioned copolymer as a water treatment agent.
  • the present invention is also a method of using a copolymer using the above-mentioned copolymer as a coating additive.
  • the present invention is also a fiber treatment method for treating fibers using the above-mentioned copolymer.
  • the present invention is further a method for producing a functional fiber, and the production method is also a method for producing a functional fiber including a step of treating the fiber using the copolymer.
  • the additive for detergent of the present invention has the above-mentioned structure and is superior in detergency to conventional polymers, it can be suitably used for detergents and the like for textile products such as polyester.
  • the copolymer contained in the additive for detergent of the present invention is at least one selected from the group consisting of a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof.
  • Structural unit (a) derived from the hydrophilic group-containing monomer (A) hereinafter, also referred to as hydrophilic group-containing monomer (A)
  • structure derived from the aromatic group-containing monomer (B) It has a unit (b).
  • the mechanism of action by which the detergent additive of the present invention exerts excellent detergency is presumed as follows.
  • the structural unit (b) can be obtained by washing clothes such as polyester with a detergent containing this copolymer.
  • the aromatic group in b) is adsorbed on the hydrophobic fiber such as polyester, and the state in which the copolymer is adsorbed on the fiber can be maintained even after washing. Since stains adhere to such clothing from above the adsorbed copolymer, the stains are sufficiently suppressed from penetrating into the fibers, and the action of the surfactant causes the stains together with the copolymer. It is considered that the dirt is easily removed.
  • the copolymer has a hydrophilic group, so that the permeation rate of the washing water into clothes and the like can be improved, which also makes it easier to remove stains.
  • another function of the above-mentioned copolymer of the present invention is that it can interact with a surfactant, act on stains adhering to the cloth, and bring out the stains. Since the dirt particles to which the polymer is attached have good dispersion stability, it is possible to prevent them from adhering to the cloth again. Due to these actions, the copolymer has excellent detergency.
  • the copolymer is fixed on clothes and the like to exhibit excellent antifouling property, and also sufficiently exhibits soil release property that makes it easy to remove stains. To do.
  • the above-mentioned copolymer has an aromatic group having a strong adsorption force to the fiber in the structural unit (b). Therefore, by treating the fiber with the above-mentioned copolymer, the copolymer is sufficiently applied to the fiber. It is fixed and can suppress the adhesion of microorganisms such as bacteria and fungi to fibers. Further, even if it is not a fiber, if it has a hydrophobic surface, the copolymer is adsorbed on the hydrophobic surface by the aromatic group in the structural unit (b) and is sufficiently fixed to have an effect of suppressing microbial adhesion. Therefore, it is suitably used for various applications in which antibacterial properties are required.
  • the content ratio of the structural unit (a) is preferably 10 to 99% by mass with respect to 100% by mass of all the structural units.
  • the balance between the hydrophilicity and the hydrophobicity of the copolymer becomes a more preferable range, and the detergency becomes more excellent. It is more preferably 15 to 95% by mass, further preferably 20 to 90% by mass, particularly preferably 25 to 80% by mass, still more preferably 30 to 80% by mass, and even more preferably 45 to 40% by mass. It is 75% by mass, most preferably 50 to 70% by mass.
  • the content ratio of the structural unit (b) is preferably 1 to 74% by mass with respect to 100% by mass of all the structural units.
  • the above-mentioned copolymer for detergent becomes more excellent in adsorptivity to fibers and more excellent in detergency. It is more preferably 1 to 70% by mass, further preferably 5 to 70% by mass, particularly preferably 10 to 70% by mass, still more preferably 10 to 65% by mass, and even more preferably 15 to 70% by mass. It is 60% by mass, most preferably 20 to 50% by mass.
  • the copolymer may contain structural units derived from (meth) acrylic acid (salt).
  • the content ratio of the structural unit is preferably 49% by mass or less with respect to 100% by mass of all structural units. This improves compatibility with liquid detergents and compounding stability.
  • the content ratio of the structural unit derived from (meth) acrylic acid (salt) is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and most preferably 15% by mass. % Or less.
  • the copolymer may have a structural unit (c) derived from a hydrophobic monomer (C) other than the structural unit (b) derived from the aromatic group-containing monomer (B).
  • the ratio of the structural unit (c) in the above-mentioned copolymer is such that the total ratio of the structural unit (b) and the structural unit (c) is 1 to 90% by mass with respect to 100% by mass of all the structural units. Is preferable. More preferably, the total ratio of the structural unit (b) and the structural unit (c) is 5 to 85% by mass, and even more preferably, the total ratio is 10 to 80% by mass. It is preferably 15 to 70% by mass, even more preferably 20 to 60% by mass, and most preferably 20 to 50% by mass.
  • the copolymer may have a structural unit (e) other than the structural units (a), (b) and (c).
  • the ratio of the structural unit (e) in the copolymer is preferably 0 to 30% by mass with respect to 100% by mass of all structural units. It is more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, and most preferably 0% by mass.
  • the copolymer preferably has a weight average molecular weight of 3000 to 300,000. As a result, the adsorptive power of the copolymer to the fibers is further improved. It is more preferably 5000 to 250,000, still more preferably 7000 to 220,000, particularly preferably 10000 to 200,000, even more preferably 12000 to 170000, even more preferably 15000 to 100,000, and most preferably 17,000. ⁇ 90,000.
  • the weight average molecular weight can be measured by the method described in Examples.
  • the hydrophilic group-containing monomer (A) is at least one hydrophilic group selected from the group consisting of a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a salt group thereof. It has a sex group.
  • the salt in the hydrophilic group include monovalent metal salts such as alkali metals such as sodium and potassium; divalent metal salts such as alkaline earth metals such as magnesium and calcium; ammonium salts; and organic amine salts.
  • the hydrophilic group is preferably a hydroxyl group or an oxyalkylene group.
  • the hydrophilic group-containing monomer (A) may have a plurality of the same or different hydrophilic groups.
  • a form having two or more hydroxyl groups or a form having a hydroxyl group and an oxyalkylene group may be used. , Is one of the preferred embodiments of the present invention.
  • the hydrophilic group-containing monomer (A) has the following formula (2);
  • R 1 , R 2 and R 3 are the same or different and are selected from the group consisting of a hydrogen atom or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof.
  • Z is a hydrogen atom, a methyl group, a hydroxyl group, and a carboxyl group.
  • A is the same or different.
  • X and w represent the same or different numbers from 0 to 4.
  • y and v represent the same or different and 0.
  • it preferably contains a monomer represented by 1). That is, the copolymer preferably has the structural unit (a) represented by the above formula (1).
  • R 1 , R 2 and R 3 in the above formulas (1) and (2) are the same or different from hydrogen atoms, or hydroxyl groups and carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups and salts thereof. It represents at least one hydrophilic group selected from the group consisting of groups, or an alkyl group having 1 to 3 carbon atoms which may have the hydrophilic group.
  • the alkyl group is preferably a methyl group, an ethyl group or a propyl group, which is 1 or 2, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
  • R 1 , R 2 and R 3 are preferably the same or different, and are preferably hydrogen atoms or methyl groups. More preferably, R 1 and R 2 are hydrogen atoms, and R 3 is a hydrogen atom or a methyl group. More preferably, R 1 and R 2 are hydrogen atoms, and R 3 is a methyl group.
  • Z in the above formulas (1) and (2) is at least selected from the group consisting of a hydrogen atom, a methyl group, or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof.
  • the hydrocarbon group is not particularly limited, and examples thereof include a chain hydrocarbon group such as an alkyl group, an alkenyl group, and an alkynyl group, and a cyclic hydrocarbon group such as an aryl group, a cycloalkyl group, and a cycloalkenyl group.
  • the above-mentioned hydrocarbon group may have a branch, and the number of carbon atoms of the hydrocarbon group when having a branch means the total number of carbon atoms of the main chain and the branched chain.
  • the alkyl group include an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and a stearyl group. , Icosyl group and the like.
  • alkenyl group examples include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group and an icosenyl group. And so on.
  • alkynyl group examples include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecynyl group, an octadecynyl group and an icocinyl group. And so on.
  • aryl group examples include a phenyl group, a benzyl group, a methylphenyl group, a 1-methoxy-4-methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a butylmethylphenyl group, a dimethylphenyl group and a diethyl group.
  • aryl group examples include phenyl group, dibutylphenyl group, biphenyl group, biphenylmethyl group, biphenylethyl group, naphthyl group, naphthylmethyl group, naphthylethyl and the like.
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
  • Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group and the like.
  • the hydrocarbon group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
  • the number of carbon atoms of the hydrocarbon group is preferably 2 to 20, more preferably 2 to 15, still more preferably 2 to 10, and particularly preferably 2 to 5.
  • the Z is preferably a hydrogen atom or a methyl group.
  • the above-mentioned A may have at least one hydrophilic group selected from the group consisting of a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof, which are the same or different.
  • the alkylene group represented by A is preferably having 2 to 18 carbon atoms, and more preferably 2 to 4 carbon atoms.
  • the oxyalkylene group represented by AO is, for example, a group formed by an addition reaction of an alkylene oxide and a group having a structure in which the above hydrophilic group is added thereto.
  • an alkylene oxide includes ethylene oxide and propylene oxide.
  • the oxyalkylene group represented by AO in the above formula (1) is not limited to the group formed by the addition reaction of the alkylene oxide.
  • the polyalkylene glycol is any two or more types of alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like, any of random addition, block addition, alternating addition and the like. It may be in the form.
  • an oxyethylene group as an essential component as the oxyalkylene group in the polyalkylene glycol, and more preferably 50 mol% or more is an oxyethylene group. , 90 mol% or more is more preferably an oxyethylene group.
  • n represents the average number of moles added of (AO), and is a number from 0 to 200.
  • the copolymer has excellent detergency. It is preferably 0 to 150, more preferably 0 to 100, still more preferably 0 to 80, particularly preferably 0 to 75, even more preferably 10 to 70, and even more preferably 15 to. It is 65, most preferably 20 to 50.
  • n is 1, the above A is preferably an alkylene group having a hydroxyl group.
  • x and w represent the same or different numbers from 0 to 4, and y and v represent 0 or 1.
  • the x is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.
  • w it is preferably 0 to 3, more preferably 0 to 2, still more preferably 0 or 1, and most preferably 0.
  • hydrophilic group-containing monomer (A) for example, polyalkylene glycol mono (meth) acrylate such as (poly) ethylene glycol mono (meth) acrylate and (poly) propylene glycol mono (meth) acrylate; Acrylate polyalkylene glycol mono (meth) acrylates such as methoxy (poly) ethylene glycol mono (meth) acrylates and methoxy (poly) propylene glycol mono (meth) acrylates, vinyl alcohols, (meth) allyl alcohols, 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 (Poly) alkylene glycol-based monomers such as compounds in which 10 to 100 mol of alkylene oxide is added to any of -3-buten-1-ol; glycerol mono (meth) acrylate, 2-
  • Hydroxyl-containing (meth) acrylamides such as hydroxyethyl (meth) acrylamide; unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, ⁇ -allyloxyacrylic acid and salts thereof; maleic acid, itaconic acid, mesacon Examples thereof include acids, citraconic acid, fumaric acid and the like, salts thereof, unsaturated dicarboxylic acids such as their anhydrides and the like.
  • (poly) alkylene glycol-based monomers and hydroxyl group-containing (meth) acrylates are preferable.
  • the aromatic group-containing monomer (B) in the present invention may be any monomer having an aromatic group and an ethylenically unsaturated group in the structure.
  • the aromatic-containing monomer has an aromatic group and an ethylenically unsaturated group in the structure of styrene, ⁇ -methylstyrene, vinyltoluene, inden, vinylnaphthalene, phenylmaleimide, vinylaniline, styrenesulfonic acid and the like.
  • the aromatic group-containing monomer (B) in the present invention preferably has a solubility parameter of 13 or less for the homopolymer obtained by homopolymerization.
  • a monomer is particularly excellent in adsorbing power to fibers, and can make the above-mentioned copolymer more excellent in antifouling property and soil release property.
  • the solubility parameter is preferably 12 or less, and more preferably 11 or less.
  • the solubility parameter is usually 5 or more.
  • the solubility parameter is 13 or less, at least one hydrophilic group selected from the group consisting of a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a salt group thereof. Those having a sex group are classified into a hydrophilic group-containing monomer (A).
  • the solubility parameter is a value calculated by the method described on pages 147 to 154 of "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2). The method is outlined below.
  • the aromatic group-containing monomer (B) in the present invention is preferably the following formula (3);
  • R 4 , R 5 , and R 6 represent the same or different alkyl groups having a hydrogen atom or 1 to 3 carbon atoms .
  • R 7 represents an aromatic group.
  • R 4 to R 7 are the same as those in the formula (3).
  • the structural unit may be obtained by polymerizing with a compound represented by the above formula (3).
  • it may be obtained by other methods.
  • the alkyl group in R 4 , R 5 , and R 6 is preferably a methyl group, an ethyl group, or a propyl group, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
  • R 4 , R 5 and R 6 are preferably the same or different, and are preferably hydrogen atoms or methyl groups. More preferably, R 4 and R 5 are hydrogen atoms, and R 6 is a hydrogen atom or a methyl group.
  • Examples of the aromatic group in R 7 include a group formed by removing one hydrogen atom from an aromatic compound which may have a substituent.
  • Examples of the aromatic compound include benzene, naphthalene, anthracene, biphenyl and the like.
  • Examples of the substituent that the aromatic ring may have include a hydrocarbon group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms. The substituent is preferably one having 1 to 12 carbon atoms. More preferably, it has 1 to 8 carbon atoms.
  • aromatic group-containing monomer (B) represented by the above formula (3) include, for example, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylphenyl (meth) acrylate, and propylphenyl.
  • the copolymer may have a structural unit (c) derived from a hydrophobic monomer (C) other than the aromatic group-containing monomer (B).
  • the hydrophobic monomer (C) other than the aromatic group-containing monomer (B) preferably has a solubility parameter of 13 or less with respect to the homopolymer obtained by homopolymerization.
  • Such a hydrophobic monomer can enhance the hydrophobicity in the above-mentioned copolymer and enhance the adsorptivity to the hydrophobic fiber.
  • the solubility parameter is preferably 12 or less, and more preferably 11 or less.
  • the solubility parameter is usually 5 or more.
  • the solubility parameter is 13 or less, at least one hydrophilic group selected from the group consisting of a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a salt group thereof. Those having a sex group are classified into a hydrophilic group-containing monomer (A).
  • the meaning of the solubility parameter is as described above.
  • the hydrophobic monomer (C) is preferably a monomer having an ethylenically unsaturated group and an alkyl group having 1 to 30 carbon atoms.
  • examples of the hydrophobic monomer (C) include esters of unsaturated carboxylic acids such as (meth) acrylic acid and alcohols having 1 to 12 carbon atoms which may have substituents; ethylene, propylene and the like.
  • Olefin-based monomers esters of unsaturated alcohols such as vinyl acetate with carboxylic acids having 3 to 8 carbon atoms; vinyl halides such as vinyl chloride; alkyl vinyl ethers such as methyl vinyl ethers and ethyl vinyl ethers; N-vinylpyrrolidone and the like. Cyclic vinyl-based monomer of.
  • the substituent that the alcohol may have may be a substituent other than a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a salt group thereof. Halogen atoms and the like can be mentioned.
  • the carbon number of the alcohol is preferably 2 to 22, more preferably 2 to 16, and even more preferably 4 to 8.
  • the alcohol having 1 to 30 carbon atoms is preferably an alkyl alcohol having 1 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), and tri. Decyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecil alcohol, icosyl alcohol and the like.
  • the hydrophobic monomer (C) is preferably the following formula (5);
  • R 8 , R 9 , and R 10 represent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, which are the same or different.
  • R 11 is a chain hydrocarbon group and fat having 1 to 30 carbon atoms. It is a compound represented by (representing a cyclic hydrocarbon group). That is, when the copolymer has a structural unit (c) derived from a hydrophobic monomer (C) other than the aromatic group-containing monomer (B), the following formula (6);
  • R 8 to R 11 are the same as those in the formula (5).
  • the structural unit may be obtained by polymerizing with a compound represented by the above formula (5).
  • it may be obtained by other methods.
  • the alkyl groups in R 8 , R 9 , and R 10 are the same as those in R 4 , R 5 , and R 6 in the above formula (3).
  • the number of carbon atoms in the hydrocarbon groups represented by R 7 is preferably 1-22. It is more preferably 2 to 16, still more preferably 2 to 12, particularly preferably 4 to 12, and most preferably 4 to 8.
  • Examples of the chain hydrocarbon group in R 11 include an alkyl group, an alkenyl group, an alkynyl group and the like, and examples of the alicyclic hydrocarbon group include a cycloalkyl group and a cycloalkenyl group.
  • Examples of the cycloalkyl group in R 11 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
  • Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group and the like.
  • the hydrophobic monomer (C) is 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, and tert.
  • 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 are preferable.
  • the copolymer is other than the hydrophilic group-containing monomer (A), the aromatic group-containing monomer (B), and the hydrophobic monomer (C) other than the aromatic group-containing monomer (B). It may have a structural unit (e) derived from the other monomer (E) of.
  • the monomer (E) does not have a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, or a salt group thereof, has no aromatic group in the structure, and is a homopolymer.
  • the solubility parameter of is not particularly limited as long as it is larger than 13, but examples thereof include acrylonitrile.
  • the production of the above-mentioned copolymer is not particularly limited, but it can be produced by polymerizing a monomer component, and specific examples and preferable examples of the monomer component, and a preferable ratio of each monomer can be obtained.
  • the above-mentioned method for producing a copolymer is a step of polymerizing a monomer component containing a hydrophilic group-containing monomer (A) and an aromatic group-containing monomer (B) (hereinafter, also referred to as a “polymerization step”). Is preferably included.
  • a method for producing such a copolymer is also one of the present inventions.
  • the method for initiating the polymerization of the monomer component in the above polymerization step is not particularly limited, but for example, a method for adding a polymerization initiator, a method for irradiating UV, a method for applying heat, and a method in the presence of a photopolymerization initiator. There is a method of irradiating the light.
  • a polymerization initiator it is preferable to use a polymerization initiator.
  • the polymerization initiator is appropriately selected depending on the reaction solvent and the monomer species.
  • hydrogen peroxide persulfate such as sodium persulfate, potassium persulfate, ammonium persulfate; dimethyl 2,2'-azobis ( 2-Methylpropionate), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropion amidine) dihydrochloride (2,2'-azobis-2-amidinopropanedi) Hydrochloride), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] , 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azodi
  • the amount of the polymerization initiator used is the total amount of the monomer used (hydrophilic group-containing monomer (A), hydrophobic monomer (B) and other monomer (E)).
  • the amount of the polymerization initiator used is the total amount of the monomer used (hydrophilic group-containing monomer (A), hydrophobic monomer (B) and other monomer (E)).
  • 100 g it is preferably 0.1 g or more and 10 g or less, more preferably 0.2 g or more and 8 g or less, further preferably 0.25 g or more and 7 g or less, and 0.3 g. Above, 5 g or less is most preferable.
  • a chain transfer agent may be used as a molecular weight adjusting agent for the polymer, if necessary.
  • the chain transfer agent mercaptocarboxylic acids such as thioglycolic acid (mercaptoacetic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid (thiolactic acid), 4-mercaptobutanoic acid, thioapple acid and salts thereof.
  • mercaptoethanol thioglycerol, 2-mercaptoethanesulfonic acid, etc .
  • halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, etc .
  • secondary alcohols such as isopropanol, glycerin, etc .
  • Hypophosphates and their hydrates, etc . Compounds that can generate hydrogen sulfite (salt) and hydrogen sulfite (salt) (dipersulfate (salt), pyrosulfite (salt), dithioic acid (salt), sulfite (Salt) etc.); etc.
  • a compound having a mercapto group such as mercaptocarboxylic acid is preferable, and a mercapto group-containing compound having a carboxyl group (mercaptocarboxylic acid) is more preferable.
  • the amount of the chain transfer agent used in the production of the above-mentioned copolymer is preferably 0.5 mol% or more and 30 mol% or less with respect to 100 mol% of the amount of the monomer (all monomers) used, more preferably. It is preferably 0.7 mol% or more and 25 mol% or less, more preferably 0.8 mol% or more and 20 mol% or less, and most preferably 1 mol% or more and 10 mol% or less.
  • the polymerization temperature is preferably 40 ° C. or higher, and preferably 150 ° C. or lower. It is more preferably 50 ° C. or higher, and even more preferably 55 ° C. or higher. Further, it is more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.
  • the method of charging the monomer component into the reaction vessel is not particularly limited, and the method of charging the entire amount into the reaction vessel at the initial stage; the method of dividing or continuously charging the entire amount into the reaction vessel; Examples thereof include a method in which the mixture is initially charged and the rest is divided or continuously charged into the reaction vessel.
  • a radical polymerization initiator When used, it may be charged into the reaction vessel from the beginning, may be added dropwise to the reaction vessel, or these may be combined depending on the purpose.
  • the copolymer obtained as described above 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 and used.
  • the alkaline substance inorganic salts such as hydroxides and carbonates of monovalent or divalent metals; ammonia; and organic amines are suitable. Further, after the reaction is completed, the concentration can be adjusted if necessary.
  • the solvent used at the time of polymerization is timely selected from those capable of dissolving the monomer to be used, the initiator, and the polymer to be produced, and water; ethanol, 1-propanol, 2-propanol, 1-butanol, phenoxyethanol and the like having 1 to 1 carbon atoms.
  • the copolymer is preferably used for detergent applications, soil release agents, microbial adhesion inhibitors, fiber treatment agents, production of functional fibers, water treatment chemical formulations, paint formulations and the like.
  • the above detergents are used only for specific purposes such as household clothing, synthetic dishwashing detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance the function of one of its components. Also includes detergents that are used.
  • the present invention is also a detergent additive containing the above copolymer.
  • the present invention is also a method of using the above copolymer as a detergent additive.
  • the present invention is also a detergent composition containing the above-mentioned copolymer and a detergent additive other than the copolymer. Since the above-mentioned copolymer has excellent compatibility with a surfactant, it can be suitably used for liquid detergent applications.
  • the detergent composition is preferably a liquid detergent composition.
  • the present invention is further a method for producing a detergent composition, which is also a method for producing a detergent composition, which comprises a step of adding the copolymer to a detergent additive other than the copolymer. ..
  • the detergent additive other than the above-mentioned copolymer is not particularly limited as long as it is a surfactant or an additive used in ordinary detergents, and conventionally known findings in the detergent field can be appropriately referred to, and the effects of the present invention can be referred to as appropriate. Any suitable additive can be used as long as it does not impair.
  • Additives other than surfactants include, for example, anti-adhesion agents for preventing re-deposition of contaminants such as sodium carboxymethyl cellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, and colors.
  • Anti-transfer agents, fabric softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, Examples include dyes and solvents. One or more of these can be used. Further, in the case of a powder detergent composition, it is preferable to add zeolite.
  • the surfactant is preferably one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants.
  • anionic surfactant examples include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, ⁇ -olefin sulfonate, ⁇ -sulfo fatty acid or ester salt, and alkane sulfonic acid.
  • Salt saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acylamino acid type surfactant, alkyl phosphate ester or its salt, alkenyl phosphate ester Alternatively, a salt thereof or the like is suitable.
  • Alkyl groups such as methyl groups may be branched into the alkyl groups and alkenyl groups in these anionic surfactants.
  • nonionic surfactant examples include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoxide, and fatty acid glycerin. Monoesters, alkylamine oxides and the like are suitable. Alkyl groups such as methyl groups may be branched into the alkyl groups and alkenyl groups in these nonionic surfactants.
  • a quaternary ammonium salt or the like is suitable.
  • amphoteric tenside a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant and the like are suitable.
  • Alkyl groups such as methyl groups may be branched as the alkyl groups and alkenyl groups in these cationic surfactants and amphoteric surfactants.
  • the blending ratio of the surfactant is usually 10 to 80% by mass, preferably 15 to 75% by mass, more preferably 18 to 70% by mass, and particularly preferably 18 to 70% by mass, based on the total amount of the detergent composition. Is 20 to 68% by mass. If the blending ratio of the surfactant is too small, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too large, the economic efficiency may be lowered.
  • anionic surfactants and nonionic surfactants are preferable, and nonionic surfactants are particularly preferable. Since the nonionic surfactant is resistant to oil stains, the liquid detergent composition containing the copolymer and the nonionic surfactant is superior in detergency against oil stains.
  • a liquid detergent composition containing the above-mentioned copolymer and a nonionic surfactant is one of the preferred embodiments of the present invention.
  • the content ratio of the nonionic surfactant is preferably 1 to 60% by mass with respect to 100% by mass of the detergent composition. It is more preferably 3 to 60% by mass, and even more preferably 5 to 50% by mass.
  • the content ratio of the nonionic surfactant is also preferably 10 to 100% by mass with respect to 100% by mass of the total amount of the surfactant. It is more preferably 15 to 90% by mass, and even more preferably 20 to 90% by mass.
  • the detergent composition preferably contains a hydrophilic solvent.
  • the hydrophilic solvent is not particularly limited, and those usually used for liquid detergents can be used. For example, water; ethanol, 1-propanol, 2-propanol, 1-butanol, phenoxyethanol and the like have 1 to 1 to carbon atoms.
  • ethanol ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and phenoxyethanol are preferable.
  • the detergent composition preferably contains a hydrophilic solvent in a proportion of 0.1 to 30% by mass with respect to 100% by mass of the liquid detergent composition. It is more preferably 1 to 27% by mass, and even more preferably 2 to 25% by mass.
  • the detergent composition may include other detergent builders.
  • Other detergent builders include, for example, alkali builders such as carbonates, bicarbonates, silicates; tripolyphosphate, pyrophosphate, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, citrate, (meth).
  • alkali builders such as carbonates, bicarbonates, silicates
  • tripolyphosphate, pyrophosphate, bow glass nitrilotriacetate, ethylenediaminetetraacetate, citrate, (meth).
  • examples thereof include a copolymer salt of acrylic acid, a chelate builder such as an acrylic acid-maleic acid copolymer, fumarate, and zeolite; and a carboxyl derivative of a polysaccharide such as carboxymethyl cellulose.
  • the anti-salt used in the above-mentioned other detergent builders include alkali metals such as sodium and potassium, and alkaline agents such as sodium hydroxide,
  • the amount of water contained in the liquid detergent composition is usually preferably 0.1% by mass to 80% by mass with respect to the total amount of the liquid detergent composition. It is more preferably 2% by mass to 70% by mass, further preferably 3% by mass to 60% by mass, still more preferably 5% by mass to 55% by mass, and particularly preferably 5% by mass to 50% by mass. Most preferably, it is 10% by mass to 50% by mass.
  • the detergent composition may contain an enzyme.
  • an enzyme examples include protease, lipase, cellulase, amylase and the like.
  • the blending ratio of the enzyme is usually 5% by mass or less with respect to the total amount of the detergent composition.
  • the copolymer is excellent in adsorptivity to clothes and the like, and when dirt adheres to clothes to which the copolymer is adsorbed, it can exhibit soil release property that can easily remove the dirt.
  • the present invention is also a soil release agent containing the above copolymer.
  • the present invention is also a method of using the above copolymer as a soil release agent.
  • the present invention is also an antimicrobial adhesion agent containing the above.
  • the present invention is also a method of using the copolymer using the above-mentioned copolymer as a microorganism adhesion inhibitor.
  • the present invention is also a method for preventing the adhesion of microorganisms by using the above-mentioned copolymer. For example, when the above copolymer is used as an antimicrobial adhesion agent, the copolymer may be added to a detergent and used, or the copolymer may be treated into fibers in a form other than the detergent.
  • the present invention is also a fiber treatment agent containing the above copolymer.
  • the present invention is also a fiber treatment method for treating fibers using the above-mentioned copolymer.
  • various fiber processing methods such as a raw yarn modification method (kneading method, raw yarn surface modification method, etc.) and a post-processing method (absorption method, impregnation pad method, coating method, etc.) are used. Can be mentioned.
  • a post-processing method More preferably, the copolymer is adsorbed and / or immobilized on the fibers after spinning. Fibers treated with the above copolymers are also one of the present inventions.
  • the present invention is a method for producing functional fibers, and the above-mentioned production method is also a method for producing functional fibers including a step of treating the fibers with the above-mentioned copolymer.
  • the copolymer is adsorbed and / or immobilized on the fiber after the spinning step in the post-processing step.
  • the method for adsorbing and / or immobilizing the copolymer on the fiber after the spinning step is not particularly limited, but it is preferable to immerse the copolymer in the fiber and dry it.
  • the fibers after the spinning step may be fibrous or processed into a fibrous fabric.
  • the present invention is also a water treatment drug formulation containing the above copolymer.
  • the present invention is also a method of using the above copolymer as a water treatment agent.
  • Various processes such as cooling water system, cold / hot water system, dust collecting water system, paper and pulp process water system, iron making process water system, metal processing process water system, etc.
  • the present invention is also a water treatment agent containing the above-mentioned antibacterial copolymer.
  • the water treatment agent containing the copolymer is used for cooling water or treated water that passes through the RO membrane, the copolymer adheres to the heat exchanger, the RO membrane, etc., and the adhesion and proliferation of microorganisms can be prevented.
  • the heat exchange efficiency can be maintained and the permeation flow velocity of the RO membrane can be secured.
  • a polymerized phosphate, a phosphonate, an anticorrosive agent, a slime control agent, a chelating agent, and a pH adjuster may be used in the water treatment agent formulation as other compounding agents.
  • the above water treatment agent formulation is useful for preventing scale in a cooling water circulation system, a boiler water circulation system, a seawater desalination device, a pulp cooking kettle, a black liquor concentrating kettle, and the like. Further, any suitable water-soluble polymer may be contained as long as it does not affect the performance and effect.
  • the present invention is also a paint formulation containing the above copolymer.
  • the present invention is also a method of using the above copolymer as a paint additive. Due to the growing hygiene concept in recent years, fungi such as bacteria and molds in food and pharmaceutical factories, buildings such as hospitals and nursing homes, food kitchen equipment, medical equipment, medical equipment, and even general household items. Antibacterial agents, antifungal agents, antibacterial agents, disinfectants, etc. are used to prevent the spread and infection of the disease. Therefore, it is desired to impart antibacterial, antifungal, and antibacterial properties to various members not only in public facilities but also in general households, and silver is used as a general antibacterial agent. The high cost and the dispersion stability of silver-supported particles have been problems.
  • the coating composition containing the copolymer of the present invention can overcome such a problem, and by blending it in the coating material, it is possible to prevent the adhesion of bacteria on the surface of the coating film, and thus the spread of infectious diseases and the like. Can be prevented.
  • the paint formulation may contain other components other than the copolymer.
  • the other components are not particularly limited, but are, for example, highly hydrophilic polymers having ionicity such as hydroxyl groups, carboxyl groups, and amino groups, and among them, hydrophilic water-soluble such as polyvinyl alcohol type and polyvinyl alcohol / polyethylene glycol type.
  • Resin Acrylic resin, polyester resin, epoxy resin, urethane resin and the like are preferably mentioned.
  • the resin may be used alone or in combination of two or more.
  • pigments, organic solvents, curing catalysts, dispersants, desiccants, antioxidants, surfactants, defoamers, dehydrators, leveling agents, anti-settling agents, anti-sagging agents, algae-proofing agents, fungicides, Preservatives, ultraviolet absorbers, light stabilizers and the like may be appropriately added as needed.
  • the paint composition (paint composition) of the present invention can be prepared by mixing various components appropriately selected as necessary.
  • Example 1 90 g of ethanol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 70 ° C. under stirring. Next, under stirring, in a polymerization reaction system in a constant state at 70 ° C., methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23, trade name “M-230G” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., hereinafter also referred to as PGM23E).
  • methoxypolyethylene glycol monomethacrylate average number of moles of ethylene oxide added 23, trade name “M-230G” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., hereinafter also referred to as PGM23E).
  • Monomer solution 1 consisting of 91 g and 30.3 g of ion-exchanged water
  • Monomer solution 2 consisting of 39 g of benzyl methacrylate (hereinafter, also referred to as BnMA; solubility parameter: 9.8); 2,2'-azobis (2,4-dimethyl)
  • BnMA benzyl methacrylate
  • An initiator aqueous solution consisting of 15.1 g of a 5% ethanol solution of valeronitrile (trade name “V-65” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise from separate dropping nozzles.
  • the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the monomer solution 2 and the initiator aqueous solution were dropped for 180 minutes. After the completion of all dropping, the reaction solution was kept at 70 ° C. for another 60 minutes for aging to complete the polymerization, and the copolymer 1 was obtained.
  • the solid content of the obtained copolymer 1 was 49.1%, and the weight average molecular weight was 28500.
  • Example 2 In a glass reaction vessel equipped with a thermometer, agitator, and a reflux cooler, 20.0 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23 mol, product manufactured by Shin-Nakamura Chemical Industries, Ltd.) Name "M-230G”) 55.7 parts, benzyl methacrylate 23.9 parts, 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator (trade name "Fujifilm Wako Pure Chemical Industries, Ltd.” V-65 ”) 0.461 copies were charged.
  • 2-propanol methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23 mol, product manufactured by Shin-Nakamura Chemical Industries, Ltd.) Name "M-230G") 55.7 parts, benzyl methacrylate 23.9 parts, 2,2'-azobis (2,4-dimethylvaleronitrile)
  • Example 3 90 g of ethanol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 70 ° C. under stirring. Next, under stirring, 69.7 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added, trade name "M-230G” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 69.7 g, and methacrylic acid were placed in a polymerization reaction system at a constant temperature of 70 ° C.
  • M-230G trade name manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • Monomer solution 1 consisting of 14.1 g and ion-exchanged water 22.4 g; Monomer solution 2 consisting of 36 g of benzyl methacrylate 2; 2,2'-azobis (2,4-dimethylvaleronitrile) (Fuji)
  • An aqueous initiator solution consisting of 13 g of a 5% ethanol solution (trade name “V-65”) manufactured by Polymer Wako Junyaku Co., Ltd. was added dropwise from separate dropping nozzles.
  • the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the monomer solution 2 and the initiator aqueous solution were dropped for 180 minutes. After the completion of all dropping, the reaction solution was kept at 70 ° C. for another 60 minutes for aging to complete the polymerization, and the copolymer 3 was obtained. The solid content of the obtained copolymer 3 was 47.8%, and the weight average molecular weight was 77,800.
  • Example 4 90 g of ethanol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 70 ° C. under stirring. Next, under stirring, a monomer solution 1 composed of 99.6 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added, hereinafter also referred to as PGM4E) and 33.2 g of ion-exchanged water in a polymerization reaction system in a constant state at 70 ° C.
  • PGM4E methoxypolyethylene glycol monomethacrylate
  • Monomer solution 2 consisting of 20.4 g of benzyl methacrylate 2; 5% ethanol solution of 2,2'-azobis (2,4-dimethylvaleronitrile) (trade name "V-65” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 23
  • An aqueous initiator solution consisting of .7 g was added dropwise from separate dropping nozzles. Regarding the dropping time, the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the monomer solution 2 and the initiator aqueous solution were dropped for 180 minutes. After the completion of all dropping, the reaction solution was kept at 70 ° C. for another 60 minutes for aging to complete the polymerization, and a copolymer 4 was obtained. The solid content of the obtained copolymer 4 was 45.7%, and the weight average molecular weight was 18900.
  • Example 5 90 g of ethanol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 70 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 70 ° C., a monomer solution 1 consisting of 84 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added, hereinafter also referred to as PGM9E) and 28 g of ion-exchanged water; 36 g of benzyl methacrylate.
  • PGM9E methoxypolyethylene glycol monomethacrylate
  • Monomer solution 2 Initiator consisting of 18.6 g of 5% ethanol solution of 2,2'-azobis (2,4-dimethylvaleronitrile) (trade name "V-65” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
  • the aqueous solution was dropped from separate dropping nozzles. Regarding the dropping time, the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the monomer solution 2 and the initiator aqueous solution were dropped for 180 minutes. After the completion of all dropping, the reaction solution was kept at 70 ° C. for another 60 minutes for aging to complete the polymerization, and a copolymer 5 was obtained. The solid content of the obtained copolymer 5 was 47.8%, and the weight average molecular weight was 24500.
  • Comparative Example 1 480 parts of water was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, and the inside of the reaction vessel was heated to 80 ° C. while stirring at 200 rpm. 401.3 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23, trade name "M-230G” manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 78.7 parts of methacrylic acid, 120 parts of water and 3 as a chain transfer agent.
  • M-230G trade name manufactured by Shin-Nakamura Chemical Industry Co., Ltd.
  • the mixture was aged at the same temperature for 60 minutes to complete the polymerization, and after the polymerization, a 49% by mass NaOH aqueous solution: 3.69 g was added to obtain an aqueous solution of the comparative copolymer 2. ..
  • the weight average molecular weight of the obtained water-soluble copolymer was 25,700, and the solid content was 59.7% by mass.
  • ⁇ 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. 50 ⁇ L of this contaminated liquid was dropped onto the polymer-treated cloth obtained in the above pretreatment method 1, left to stand for 1 hour, and then excess oil and fat was sandwiched between filter papers and wiped off to prepare a contaminated cloth.
  • (1) -2 Preparation of hard water 1.54 g of sodium hydrogen carbonate, 10 g of 0.1N hydrogen chloride, and 200 g of the hardness mother liquor (1) -1; 200 g were placed in a beaker and diluted with ion-exchanged water to make 20000 g.
  • (1) -3 Preparation of aqueous surfactant solution Weigh 13.85 g of Perex G-65 (manufactured by Kao Corporation) and 3 g of Emargen 108 (manufactured by Kao Corporation) in a beaker, and add ion-exchanged water to make 200 g. The agent solution was adjusted.
  • Staphylococcus aureus NBRC12732 strain was used as the microbial adhesion evaluation strain. Inoculate 5 mL of Bacto (registered trademark) Brain Heart Infusion medium (Product No. 237500 manufactured by Becton Dickinson Corporation, Japan) in a culture test tube from a cryopreservation strain and stir at 37 ° C. and 300 rpm (shaking culture). Machine: After reconstructive culture while (TXY-16R-3F, manufactured by Takasaki Kagaku Kikai Co., Ltd.), subculture (20 mL) was carried out for 18 hours.
  • Bacto registered trademark
  • Brain Heart Infusion medium Product No. 237500 manufactured by Becton Dickinson Corporation, Japan
  • Machine After reconstructive culture while (TXY-16R-3F, manufactured by Takasaki Kagaku Kikai Co., Ltd.), subculture (20 mL) was carried out for 18 hours.
  • the cells were collected by centrifugation for 5 minutes with a centrifugal force of 5000 ⁇ g, and then the supernatant was removed and the cells were washed with 15 mL of PBS ( ⁇ ). This cleaning work was carried out twice in total.
  • Using the OD660-viable cell count conversion formula prepared separately prepare the bacterial solution with PBS (-) so that the bacterial solution becomes 1 ⁇ 10 9 cells / mL, and prepare a 6-well microplate (IWAKI product code 3810). -006) was added at 3 mL / well. Subsequently, a 2 ⁇ 2 cm 2 square polymer coated film was immersed in a bacterial solution in a well and allowed to stand at 37 ° C.
  • Example 6 Using a spin coater (MIKASA CO. LTD., SPIN COATER 1H-D7), 1 (w / w)% was applied to the easy-adhesion PET film (Cosmo Shine (registered trademark) A4100 # 125 manufactured by Toyo Boseki Co., Ltd.). The polymer solution of Example 1 (diluted with a 75 (w / w)% ethanol aqueous solution) was added dropwise, spin-coated, and then air-dried overnight to form a film. Microbial adhesion evaluation was carried out using the prepared film. The results are shown in Table 2 and FIG.

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Abstract

The present invention provides a detergent additive that contains a copolymer that exhibits a better detergency than conventional polymers. The present invention pertains to a detergent additive that contains a copolymer having a structural unit (a) derived from a monomer (A) that has a hydroxyl group, an oxyalkylene group, and at least one hydrophilic group selected from the group consisting of a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, and groups that are salts thereof, and having a structural unit (b) derived from an aromatic group-containing monomer (B).

Description

共重合体を含む洗剤用添加剤、ソイルリリース剤、微生物付着防止剤、繊維処理剤、水処理薬剤配合物及び塗料配合物Detergent additives containing copolymers, soil release agents, microbial adhesion inhibitors, fiber treatment agents, water treatment agent formulations and paint formulations
本発明は、共重合体を含む洗剤用添加剤、ソイルリリース剤、微生物付着防止剤、繊維処理剤、水処理薬剤配合物及び塗料配合物に関する。 The present invention relates to detergent additives containing copolymers, soil release agents, microbial adhesion inhibitors, fiber treatment agents, water treatment agent formulations and paint formulations.
従来、衣料類に用いられる洗剤には、洗剤の洗浄効果を向上させることを目的として、ゼオライト、カルボキシメチルセルロース、ポリエチレングリコールなどの洗剤ビルダー（洗剤助剤）を配合することが行われている。
上記の各種洗剤ビルダーに加えて、近年では、重合体が洗剤ビルダーとして洗剤組成物に配合されている。このような重合体に関して、例えば、特許文献１、２には、（メタ）アクリル酸等の不飽和カルボン酸系単量体と（ポリ）アルキレングリコール系単量体との共重合体が開示されている。また、このようなポリカルボン酸系共重合体以外にも、洗剤用途に用いられる重合体として、例えば特許文献３には、所定の構成単位（Ａ）及び所定の構成単位（Ｂ）を有するポリマーを含有する再汚染防止剤が開示されている。特許文献４には、１～３級アミノ基から選ばれる少なくとも１種のアミノ基を有する不飽和結合含有モノマー由来の構成単位（Ａ）、及び炭素数４～２２の直鎖状、分岐鎖状もしくは環状のアルキル基又はアルケニル基、あるいはアリールアルキル基又はアリール基から選ばれる少なくとも１種の疎水性基を有し、且つ、１～３級アミノ基を有しない不飽和結合含有モノマー由来の構成単位（Ｂ）を有し、ポリマー中の構成単位（Ａ）の含有量が５０～９９重量％、構成単位（Ｂ）の含有量が１～５０重量％であり、重量平均分子量２，０００～３０，０００のポリマーからなる繊維用汚れ放出剤が開示されている。 Conventionally, detergents used for clothing are blended with detergent builders (detergent aids) such as zeolite, carboxymethyl cellulose, and polyethylene glycol for the purpose of improving the cleaning effect of the detergent.
In addition to the various detergent builders described above, in recent years, polymers have been incorporated into detergent compositions as detergent builders. Regarding such a polymer, for example, Patent Documents 1 and 2 disclose a copolymer of an unsaturated carboxylic acid-based monomer such as (meth) acrylic acid and a (poly) alkylene glycol-based monomer. ing. In addition to such polycarboxylic acid-based copolymers, as polymers used for detergent applications, for example, Patent Document 3 describes a polymer having a predetermined structural unit (A) and a predetermined structural unit (B). A recontamination inhibitor containing is disclosed. Patent Document 4 describes a structural unit (A) derived from an unsaturated bond-containing monomer having at least one amino group selected from 1 to 3 secondary amino groups, and a linear or branched chain having 4 to 22 carbon atoms. Alternatively, a structural unit derived from an unsaturated bond-containing monomer having at least one hydrophobic group selected from a cyclic alkyl group or alkenyl group, or an arylalkyl group or an aryl group and having no 1st to tertiary amino group. It has (B), the content of the structural unit (A) in the polymer is 50 to 99% by weight, the content of the structural unit (B) is 1 to 50% by weight, and the weight average molecular weight is 2,000 to 30%. A fiber stain release agent consisting of 000 polymers has been disclosed.
また、衛生に対する意識の高まりから、衣料用洗剤においても、洗浄効果に加えて部屋干し等で増殖しがちな菌の増殖を防止する目的で、抗菌性や微生物付着防止能を付与した製品が上市されている。例えば特許文献５には、ジカルボン酸単位、アルキレングリコール単位およびポリアルキレングリコール単位がエステル結合を介して結合しているポリマーの、繊維表面の微生物コロニー形成を防止するための使用が開示されている。 In addition, due to heightened awareness of hygiene, products with antibacterial properties and microbial adhesion prevention ability have been launched for the purpose of preventing the growth of bacteria that tend to grow in room drying, etc., in addition to the cleaning effect, even in laundry detergents. Has been done. For example, Patent Document 5 discloses the use of a polymer in which a dicarboxylic acid unit, an alkylene glycol unit and a polyalkylene glycol unit are bonded via an ester bond to prevent the formation of microbial colonies on the fiber surface.
特開２００７－２３１２６０号公報JP-A-2007-231260 特開２００２－００３５５１号公報Japanese Unexamined Patent Publication No. 2002-003551 特開２００９－２４９７４３号公報Japanese Unexamined Patent Publication No. 2009-249743 特開２００７－２４７１２６号公報JP-A-2007-247126 欧州特許第２９２２９４２号明細書European Patent No. 2929422
ところで、近年、衣類等に用いられる素材として、耐久性に優れ、乾燥が速く、皺になりにくい等の点から、ポリエステル等の化繊が増加している。ポリエステルには上記のようなメリットがある一方で、疎水性繊維であるため皮脂汚れとの吸着力が強く、綿等に比べて汚れが落ちにくいというデメリットがある。また、近年、共働き世帯が増えていることに伴い、洗濯物をまとめて洗うことが多くなっており、洗濯物が汚れたまま長時間放置されることも、汚れが落ちにくいことの一因である。上述のとおり、洗剤や繊維の表面コートに用いられる種々の重合体が開示されているが、このような状況の中で、従来の種々の重合体は、洗浄力において充分とはいえず、改善の余地があった。 By the way, in recent years, synthetic fibers such as polyester have been increasing as materials used for clothing and the like because of their excellent durability, quick drying, and less wrinkling. While polyester has the above-mentioned merits, since it is a hydrophobic fiber, it has a strong adsorption force with sebum stains and has a demerit that stains are hard to be removed as compared with cotton and the like. In addition, as the number of double-income households has increased in recent years, it has become more common to wash laundry in bulk, and leaving the laundry dirty for a long time is one of the reasons why it is difficult to remove the dirt. is there. As described above, various polymers used for surface coating of detergents and fibers have been disclosed, but under such circumstances, various conventional polymers are not sufficient in detergency and are improved. There was room for.
本発明は、上記現状に鑑みてなされたものであり、従来の重合体よりも洗浄力に優れる共重合体を含む洗剤用添加剤を提供することを目的とする。 The present invention has been made in view of the above situation, and an object of the present invention is to provide an additive for a detergent containing a copolymer having a detergency superior to that of a conventional polymer.
本発明者は、重合体について種々検討したところ、特定の親水性基を有する単量体と芳香族基を有する単量体との共重合体において、（メタ）アクリル酸（塩）由来の構造単位の含有割合を特定の範囲とすることにより、従来の重合体よりも優れた洗浄力を発揮することを見いだし、上記課題をみごとに解決することができることに想到し、本発明に到達したものである。 As a result of various studies on the polymer, the present inventor has found that a copolymer of a monomer having a specific hydrophilic group and a monomer having an aromatic group has a structure derived from (meth) acrylic acid (salt). It was found that by setting the content ratio of the unit within a specific range, it exhibits superior detergency than the conventional polymer, and it was conceived that the above-mentioned problems can be solved brilliantly, and the present invention has been reached. Is.
すなわち本発明は、水酸基、オキシアルキレン基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有する単量体（Ａ）由来の構造単位（ａ）と、芳香族基含有単量体（Ｂ）由来の構造単位（ｂ）とを有する共重合体を含む洗剤用添加剤である。 That is, the present invention is a monomer having at least one hydrophilic group selected from the group consisting of a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof ( A detergent additive containing a copolymer having a structural unit (a) derived from A) and a structural unit (b) derived from an aromatic group-containing monomer (B).
上記構造単位（ａ）は、下記式（１）； The structural unit (a) is represented by the following formula (1);
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
（式中、Ｒ１、Ｒ２及びＲ３は、同一又は異なって、水素原子、若しくは、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基、又は、該親水性基を有していてもよい炭素数１～３のアルキル基を表す。Ｚは、水素原子、メチル基、又は、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有する炭素数２～３０の炭化水素基を表す。Ａは、同一又は異なって、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有していてもよいアルキレン基を表す。ｎは、（ＡＯ）の平均付加モル数を表し、０～２００の数である。ｘ、ｗは、同一又は異なって、０～４の数を表す。ｙ、ｖは、同一又は異なって、０又は１を表す。）で表されることが好ましい。 (In the formula, R 1 , R 2 and R 3 are the same or different and are selected from the group consisting of a hydrogen atom or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Represents at least one hydrophilic group, or an alkyl group having 1 to 3 carbon atoms which may have the hydrophilic group. Z is a hydrogen atom, a methyl group, a hydroxyl group, and a carboxyl group. Represents a hydrocarbon group having 2 to 30 carbon atoms having at least one hydrophilic group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. A is the same or different. Represents an alkylene group which may have at least one hydrophilic group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group thereof. Represents the average number of added moles of (AO) and is a number from 0 to 200. X and w represent the same or different numbers from 0 to 4. y and v represent the same or different and 0. Alternatively, it is preferably represented by 1).
上記芳香族基含有単量体（Ｂ）は、単独重合体の溶解性パラメータが１３以下であることが好ましい。 The aromatic group-containing monomer (B) preferably has a solubility parameter of 13 or less as a homopolymer.
上記共重合体は、構造単位（ａ）の含有割合が、全構造単位１００質量％に対して１０～９９質量％であることが好ましい。 In the above copolymer, the content ratio of the structural unit (a) is preferably 10 to 99% by mass with respect to 100% by mass of all the structural units.
上記共重合体は、構造単位（ｂ）の含有割合が、全構造単位１００質量％に対して１～７４質量％であることが好ましい。 In the above copolymer, the content ratio of the structural unit (b) is preferably 1 to 74% by mass with respect to 100% by mass of all the structural units.
上記共重合体は、（メタ）アクリル酸（塩）由来の構造単位の含有割合が４９質量％以下であることが好ましい。 The copolymer preferably contains 49% by mass or less of structural units derived from (meth) acrylic acid (salt).
上記共重合体は、芳香族基含有単量体（Ｂ）由来の構造単位（ｂ）以外の疎水性単量体（Ｃ）由来の構造単位（ｃ）を有していてもよく、構造単位（ｂ）と構造単位（ｃ）との合計割合が全構造単位１００質量％に対して１～９０質量％であることが好ましい。 The copolymer may have a structural unit (c) derived from a hydrophobic monomer (C) other than the structural unit (b) derived from the aromatic group-containing monomer (B), and may have a structural unit. The total ratio of (b) and the structural unit (c) is preferably 1 to 90% by mass with respect to 100% by mass of all structural units.
上記共重合体は、前記単量体（Ａ）、芳香族基含有単量体（Ｂ）及び疎水性単量体（Ｃ）以外のその他の単量体（Ｅ）由来の構造単位（ｅ）の割合が、全構造単位１００質量％に対して０～３０質量％であることが好ましい。 The copolymer is a structural unit (e) derived from a monomer (E) other than the monomer (A), the aromatic group-containing monomer (B) and the hydrophobic monomer (C). Is preferably 0 to 30% by mass with respect to 100% by mass of all structural units.
上記芳香族基含有単量体（Ｂ）は、スチレン、α－メチルスチレン、ビニルトルエン、インデン、ビニルナフタレン、フェニルマレイミド、ビニルアニリン、スチレンスルホン酸及び下記式（３）； The aromatic group-containing monomer (B) includes styrene, α-methylstyrene, vinyltoluene, inden, vinylnaphthalene, phenylmaleimide, vinylaniline, styrenesulfonic acid and the following formula (3);
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（式中、Ｒ４、Ｒ５、Ｒ６は、同一又は異なって、水素原子又は炭素数１～３のアルキル基を表す。Ｒ７は、芳香族基を表す。）で表される化合物からなる群より選択される少なくとも１種であることが好ましい。 (In the formula, R 4 , R 5 , and R 6 represent the same or different alkyl groups having a hydrogen atom or 1 to 3 carbon atoms . R 7 represents an aromatic group.) It is preferable that it is at least one selected from the group.
上記疎水性単量体（Ｃ）は、下記式（５）； The hydrophobic monomer (C) has the following formula (5);
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（式中、Ｒ８、Ｒ９、Ｒ１０は、同一又は異なって、水素原子又は炭素数１～３のアルキル基を表す。Ｒ１１は、炭素数１～３０の鎖状炭化水素基、脂環式炭化水素基を表す。）で表される化合物であることが好ましい。 (In the formula, R 8 , R 9 , and R 10 represent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, which are the same or different. R 11 is a chain hydrocarbon group and fat having 1 to 30 carbon atoms. It is preferably a compound represented by (representing a cyclic hydrocarbon group).
上記共重合体は、重量平均分子量が、３０００～３０００００であることが好ましい。 The copolymer preferably has a weight average molecular weight of 3000 to 300,000.
本発明はまた、上記共重合体と該共重合体以外の洗剤用添加剤とを含むことを特徴とする洗剤組成物でもある。 The present invention is also a detergent composition comprising the above-mentioned copolymer and a detergent additive other than the copolymer.
本発明は更に、上記共重合体を含む、ソイルリリース剤でもある。 The present invention is also a soil release agent containing the above copolymer.
本発明は更に、上記共重合体を含む微生物付着防止剤でもある。 The present invention is also an antimicrobial adhesion agent containing the above copolymer.
本発明は更に、上記共重合体を含む繊維処理剤でもある。 The present invention is also a fiber treatment agent containing the above copolymer.
本発明は更に、上記共重合体を含む、水処理薬剤配合物でもある。 The present invention is also a water treatment drug formulation containing the above copolymer.
本発明は更に、上記共重合体を含む、塗料配合物でもある。 The present invention is also a paint formulation containing the above copolymer.
本発明は更に、上記共重合体を洗剤用添加剤として使用する共重合体の使用方法でもある。 The present invention is also a method of using the copolymer using the above-mentioned copolymer as an additive for detergent.
本発明は更に、上記共重合体をソイルリリース剤として使用する共重合体の使用方法でもある。 The present invention is also a method of using a copolymer using the above-mentioned copolymer as a soil release agent.
本発明は更に、上記共重合体を微生物付着剤として使用する共重合体の使用方法でもある。 The present invention is also a method of using a copolymer using the above-mentioned copolymer as a microbial adhering agent.
本発明は更に、上記共重合体を用いて微生物の付着を防止する微生物付着防止方法でもある。 The present invention is also a method for preventing the adhesion of microorganisms by using the above-mentioned copolymer.
本発明は更に、上記共重合体を水処理剤として使用する共重合体の使用方法でもある。 The present invention is also a method of using a copolymer using the above-mentioned copolymer as a water treatment agent.
本発明は更に、上記共重合体を塗料添加剤として使用する共重合体の使用方法でもある。 The present invention is also a method of using a copolymer using the above-mentioned copolymer as a coating additive.
本発明は更に、上記共重合体を用いて繊維を処理する繊維処理方法でもある。 The present invention is also a fiber treatment method for treating fibers using the above-mentioned copolymer.
本発明は更に、機能性繊維を製造する方法であって、上記製造方法は、上記共重合体を用いて繊維を処理する工程を含む機能性繊維の製造方法でもある。 The present invention is further a method for producing a functional fiber, and the production method is also a method for producing a functional fiber including a step of treating the fiber using the copolymer.
本発明の洗剤用添加剤は、上述の構成よりなり、従来の重合体よりも洗浄力に優れるため、ポリエステル等の繊維製品に対する洗剤等に好適に用いることができる。 Since the additive for detergent of the present invention has the above-mentioned structure and is superior in detergency to conventional polymers, it can be suitably used for detergents and the like for textile products such as polyester.
実施例６、比較例４、５の微生物付着評価結果のグラフである。It is a graph of the microbial adhesion evaluation result of Example 6 and Comparative Examples 4 and 5.
以下に本発明の好ましい形態について具体的に説明するが、本発明は以下の記載のみに限定されるものではなく、本発明の要旨を変更しない範囲において適宜変更して適用することができる。なお、以下に記載される本発明の個々の好ましい形態を２又は３以上組み合わせた形態も、本発明の好ましい形態に該当する。 Hereinafter, preferred embodiments of the present invention will be specifically described, but the present invention is not limited to the following description, and can be appropriately modified and applied without changing the gist of the present invention. A form in which two or three or more of the individual preferred forms of the present invention described below are combined also falls under the preferred form of the present invention.
本発明の洗剤用添加剤に含まれる共重合体は、水酸基、オキシアルキレン基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有する単量体（Ａ）（以下、親水性基含有単量体（Ａ）ともいう。）由来の構造単位（ａ）と芳香族基含有単量体（Ｂ）由来の構造単位（ｂ）とを有するものである。
本発明の洗剤用添加剤が優れた洗浄力を発揮する作用機序は以下のように推定される。上記共重合体は、構造単位（ｂ）に繊維への吸着力が強い芳香族基を有するため、この共重合体を含む洗剤を用いてポリエステル等の衣類等を洗濯することで、構造単位（ｂ）における芳香族基がポリエステル等の疎水性繊維に対して吸着し、洗濯後においても共重合体が繊維に吸着した状態を維持することができる。このような衣類には、吸着した共重合体の上から汚れが付着することになるため、汚れが繊維の奥に浸透することが充分に抑制され、界面活性剤の作用により、共重合体とともに汚れが容易に除去されると考えられる。また、上記共重合体が親水性基を有することにより、洗濯水の衣類等への浸透速度を向上させることができ、これによっても汚れが落ちやすくなると考えられる。更に、本発明の上記共重合体のもう一つの機能は、界面活性剤と相互作用し、布に付着した汚れに働きかけ、汚れを浮かびあがらせることができるというものである。ポリマーが付着した汚れ粒子は分散安定性が良好なため、再度布に付着することを防止することができる。
これらの作用により、上記共重合体は洗浄力に優れる。また上記共重合体を用いて洗濯を繰り返すことにより、衣類等に共重合体が定着することで優れた防汚性を発揮し、また汚れを落としやすくすることができるソイルリリース性を充分に発揮する。 The copolymer contained in the additive for detergent of the present invention is at least one selected from the group consisting of a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Structural unit (a) derived from the hydrophilic group-containing monomer (A) (hereinafter, also referred to as hydrophilic group-containing monomer (A)) and structure derived from the aromatic group-containing monomer (B). It has a unit (b).
The mechanism of action by which the detergent additive of the present invention exerts excellent detergency is presumed as follows. Since the above-mentioned copolymer has an aromatic group having a strong adsorption force to fibers in the structural unit (b), the structural unit (b) can be obtained by washing clothes such as polyester with a detergent containing this copolymer. The aromatic group in b) is adsorbed on the hydrophobic fiber such as polyester, and the state in which the copolymer is adsorbed on the fiber can be maintained even after washing. Since stains adhere to such clothing from above the adsorbed copolymer, the stains are sufficiently suppressed from penetrating into the fibers, and the action of the surfactant causes the stains together with the copolymer. It is considered that the dirt is easily removed. Further, it is considered that the copolymer has a hydrophilic group, so that the permeation rate of the washing water into clothes and the like can be improved, which also makes it easier to remove stains. Furthermore, another function of the above-mentioned copolymer of the present invention is that it can interact with a surfactant, act on stains adhering to the cloth, and bring out the stains. Since the dirt particles to which the polymer is attached have good dispersion stability, it is possible to prevent them from adhering to the cloth again.
Due to these actions, the copolymer has excellent detergency. In addition, by repeating washing with the above-mentioned copolymer, the copolymer is fixed on clothes and the like to exhibit excellent antifouling property, and also sufficiently exhibits soil release property that makes it easy to remove stains. To do.
上記共重合体は、上述のとおり構造単位（ｂ）に繊維への吸着力が強い芳香族基を有するため、上記共重合体を用いて繊維を処理することにより共重合体が繊維に充分に固定され、細菌や真菌等の微生物の繊維への付着を抑制することもできる。
また、繊維以外であっても疎水性の表面を有するものであれば、構造単位（ｂ）における芳香族基により共重合体が疎水性の表面に吸着し、充分に固定されて微生物付着抑制効果を発揮することができるため、防菌性が求められる種々の用途に好適に用いられる。 As described above, the above-mentioned copolymer has an aromatic group having a strong adsorption force to the fiber in the structural unit (b). Therefore, by treating the fiber with the above-mentioned copolymer, the copolymer is sufficiently applied to the fiber. It is fixed and can suppress the adhesion of microorganisms such as bacteria and fungi to fibers.
Further, even if it is not a fiber, if it has a hydrophobic surface, the copolymer is adsorbed on the hydrophobic surface by the aromatic group in the structural unit (b) and is sufficiently fixed to have an effect of suppressing microbial adhesion. Therefore, it is suitably used for various applications in which antibacterial properties are required.
上記共重合体は、構造単位（ａ）の含有割合が、全構造単位１００質量％に対して１０～９９質量％であることが好ましい。これにより、上記共重合体の親水性と疎水性のバランスがより好適な範囲となり、洗浄力により優れることとなる。より好ましくは１５～９５質量％であり、更に好ましくは２０～９０質量％であり、特に好ましくは２５～８０質量％であり、一層好ましくは３０～８０質量％であり、より一層好ましくは４５～７５質量％であり、最も好ましくは５０～７０質量％である。 In the above copolymer, the content ratio of the structural unit (a) is preferably 10 to 99% by mass with respect to 100% by mass of all the structural units. As a result, the balance between the hydrophilicity and the hydrophobicity of the copolymer becomes a more preferable range, and the detergency becomes more excellent. It is more preferably 15 to 95% by mass, further preferably 20 to 90% by mass, particularly preferably 25 to 80% by mass, still more preferably 30 to 80% by mass, and even more preferably 45 to 40% by mass. It is 75% by mass, most preferably 50 to 70% by mass.
上記共重合体は、構造単位（ｂ）の含有割合が、全構造単位１００質量％に対して１～７４質量％であることが好ましい。これにより、上記洗剤用共重合体が繊維への吸着性により優れたものとなり、洗浄力により優れることとなる。より好ましくは１～７０質量％であり、更に好ましくは５～７０質量％であり、特に好ましくは１０～７０質量％であり、一層好ましくは１０～６５質量％であり、より一層好ましくは１５～６０質量％であり、最も好ましくは２０～５０質量％である。 In the above copolymer, the content ratio of the structural unit (b) is preferably 1 to 74% by mass with respect to 100% by mass of all the structural units. As a result, the above-mentioned copolymer for detergent becomes more excellent in adsorptivity to fibers and more excellent in detergency. It is more preferably 1 to 70% by mass, further preferably 5 to 70% by mass, particularly preferably 10 to 70% by mass, still more preferably 10 to 65% by mass, and even more preferably 15 to 70% by mass. It is 60% by mass, most preferably 20 to 50% by mass.
上記共重合体は、（メタ）アクリル酸（塩）由来の構造単位を含んでもよい。該構造単位の含有割合は、全構造単位１００質量％に対して４９質量％以下であることが好ましい。これにより、液体洗剤との相溶性や配合安定性が向上する。（メタ）アクリル酸（塩）由来の構造単位の含有割合として好ましくは４０質量％以下であり、より好ましくは３０質量％以下であり、更に好ましくは２０質量％以下であり、最も好ましくは１５質量％以下である。 The copolymer may contain structural units derived from (meth) acrylic acid (salt). The content ratio of the structural unit is preferably 49% by mass or less with respect to 100% by mass of all structural units. This improves compatibility with liquid detergents and compounding stability. The content ratio of the structural unit derived from (meth) acrylic acid (salt) is preferably 40% by mass or less, more preferably 30% by mass or less, further preferably 20% by mass or less, and most preferably 15% by mass. % Or less.
上記共重合体は、芳香族基含有単量体（Ｂ）由来の構造単位（ｂ）以外の疎水性単量体（Ｃ）由来の構造単位（ｃ）を有していてもよい。
上記共重合体における構造単位（ｃ）の割合は、全構造単位１００質量％に対して構造単位（ｂ）と構造単位（ｃ）との合計割合が１～９０質量％となる割合であることが好ましい。より好ましくは、構造単位（ｂ）と構造単位（ｃ）との合計割合が５～８５質量％となる割合であり、更に好ましくは、合計割合が１０～８０質量％となる割合であり、一層好ましくは１５～７０質量％であり、より一層好ましくは２０～６０質量％であり、最も好ましくは２０～５０質量％である。 The copolymer may have a structural unit (c) derived from a hydrophobic monomer (C) other than the structural unit (b) derived from the aromatic group-containing monomer (B).
The ratio of the structural unit (c) in the above-mentioned copolymer is such that the total ratio of the structural unit (b) and the structural unit (c) is 1 to 90% by mass with respect to 100% by mass of all the structural units. Is preferable. More preferably, the total ratio of the structural unit (b) and the structural unit (c) is 5 to 85% by mass, and even more preferably, the total ratio is 10 to 80% by mass. It is preferably 15 to 70% by mass, even more preferably 20 to 60% by mass, and most preferably 20 to 50% by mass.
上記共重合体は、上記構造単位（ａ）、（ｂ）及び（ｃ）以外のその他の構造単位（ｅ）を有していてもよい。
上記共重合体における構造単位（ｅ）の割合は、全構造単位１００質量％に対して０～３０質量％であることが好ましい。
より好ましくは０～２０質量％であり、更に好ましくは０～１０質量％であり、最も好ましくは０質量％である。 The copolymer may have a structural unit (e) other than the structural units (a), (b) and (c).
The ratio of the structural unit (e) in the copolymer is preferably 0 to 30% by mass with respect to 100% by mass of all structural units.
It is more preferably 0 to 20% by mass, further preferably 0 to 10% by mass, and most preferably 0% by mass.
上記共重合体は、重量平均分子量が、３０００～３０００００であることが好ましい。これにより上記共重合体の繊維への吸着力がより向上する。より好ましくは５０００～２５００００であり、更に好ましくは７０００～２２００００であり、特に好ましくは１００００～２０００００であり、一層好ましくは１２０００～１７００００であり、より一層好ましくは１５０００～１０００００であり、最も好ましくは１７０００～９００００である。
上記重量平均分子量は、実施例に記載の方法により測定することができる。 The copolymer preferably has a weight average molecular weight of 3000 to 300,000. As a result, the adsorptive power of the copolymer to the fibers is further improved. It is more preferably 5000 to 250,000, still more preferably 7000 to 220,000, particularly preferably 10000 to 200,000, even more preferably 12000 to 170000, even more preferably 15000 to 100,000, and most preferably 17,000. ~ 90,000.
The weight average molecular weight can be measured by the method described in Examples.
＜親水性基含有単量体（Ａ）＞
上記親水性基含有単量体（Ａ）は、水酸基、オキシアルキレン基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有するものである。
上記親水性基における塩としては、ナトリウム、カリウム等のアルカリ金属等の１価金属塩；マグネシウム、カルシウム等のアルカリ土類金属等の２価金属塩；アンモニウム塩；有機アミン塩等が挙げられる。
上記親水性基として好ましくは水酸基、オキシアルキレン基である。
上記親水性基含有単量体（Ａ）は、親水性基を同一又は異なって複数有していてもよく、例えば、２以上の水酸基を有する形態や、水酸基とオキシアルキレン基とを有する形態は、本発明の好ましい実施形態の１つである。 <Hydrophilic group-containing monomer (A)>
The hydrophilic group-containing monomer (A) is at least one hydrophilic group selected from the group consisting of a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a salt group thereof. It has a sex group.
Examples of the salt in the hydrophilic group include monovalent metal salts such as alkali metals such as sodium and potassium; divalent metal salts such as alkaline earth metals such as magnesium and calcium; ammonium salts; and organic amine salts.
The hydrophilic group is preferably a hydroxyl group or an oxyalkylene group.
The hydrophilic group-containing monomer (A) may have a plurality of the same or different hydrophilic groups. For example, a form having two or more hydroxyl groups or a form having a hydroxyl group and an oxyalkylene group may be used. , Is one of the preferred embodiments of the present invention.
上記親水性基含有単量体（Ａ）は、下記式（２）； The hydrophilic group-containing monomer (A) has the following formula (2);
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（式中、Ｒ１、Ｒ２及びＲ３は、同一又は異なって、水素原子、若しくは、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基、又は、該親水性基を有していてもよい炭素数１～３のアルキル基を表す。Ｚは、水素原子、メチル基、又は、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有する炭素数２～３０の炭化水素基を表す。Ａは、同一又は異なって、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有していてもよいアルキレン基を表す。ｎは、（ＡＯ）の平均付加モル数を表し、０～２００の数である。ｘ、ｗは、同一又は異なって、０～４の数を表す。ｙ、ｖは、同一又は異なって、０又は１を表す。）で表される単量体を含むことが好ましい。すなわち、上記共重合体は、上記式（１）で表される構造単位（ａ）を有することが好ましい。 (In the formula, R 1 , R 2 and R 3 are the same or different and are selected from the group consisting of a hydrogen atom or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Represents at least one hydrophilic group, or an alkyl group having 1 to 3 carbon atoms which may have the hydrophilic group. Z is a hydrogen atom, a methyl group, a hydroxyl group, and a carboxyl group. Represents a hydrocarbon group having 2 to 30 carbon atoms having at least one hydrophilic group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. A is the same or different. Represents an alkylene group which may have at least one hydrophilic group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group thereof. Represents the average number of added moles of (AO) and is a number from 0 to 200. X and w represent the same or different numbers from 0 to 4. y and v represent the same or different and 0. Alternatively, it preferably contains a monomer represented by 1). That is, the copolymer preferably has the structural unit (a) represented by the above formula (1).
上記式（１）、（２）におけるＲ１、Ｒ２及びＲ３は、同一又は異なって、水素原子、若しくは、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基、又は、該親水性基を有していてもよい炭素数１～３のアルキル基を表す。
上記アルキル基として好ましくはメチル基、エチル基、プロピル基であり、１又は２であり、より好ましくはメチル基、エチル基であり、更に好ましくはメチル基である。
Ｒ１、Ｒ２及びＲ３は、同一又は異なって、水素原子、又は、メチル基であることが好ましい。より好ましくはＲ１、Ｒ２が水素原子であって、Ｒ３が水素原子又はメチル基である。更に好ましくは、Ｒ１、Ｒ２が水素原子であって、Ｒ３がメチル基である。 R 1 , R 2 and R 3 in the above formulas (1) and (2) are the same or different from hydrogen atoms, or hydroxyl groups and carboxyl groups, sulfonic acid groups, phosphoric acid groups, amino groups and salts thereof. It represents at least one hydrophilic group selected from the group consisting of groups, or an alkyl group having 1 to 3 carbon atoms which may have the hydrophilic group.
The alkyl group is preferably a methyl group, an ethyl group or a propyl group, which is 1 or 2, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
R 1 , R 2 and R 3 are preferably the same or different, and are preferably hydrogen atoms or methyl groups. More preferably, R 1 and R 2 are hydrogen atoms, and R 3 is a hydrogen atom or a methyl group. More preferably, R 1 and R 2 are hydrogen atoms, and R 3 is a methyl group.
上記式（１）、（２）におけるＺは、水素原子、メチル基、又は、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有する炭素数２～３０の炭化水素基を表す。
上記炭化水素基としては、特に制限されず、アルキル基、アルケニル基、アルキニル基等の鎖状炭化水素基、アリール基、シクロアルキル基、シクロアルケニル基等の環状炭化水素基が挙げられる。上記炭化水素基は、分岐を有していてもよく、分岐を有する場合の炭化水素基の炭素数は、主鎖及び分岐鎖の合計の炭素数を意味する。
上記アルキル基としては、例えば、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ヘキシル基、ヘプチル基、２－エチルへキシル基、オクチル基、ノニル基、デシル基、ドデシル基、ステアリル基、イコシル基等が挙げられる。
上記アルケニル基としては、例えば、ビニル基、アリル基、１－ブテニル基、２－ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ドデセニル基、オクタデセニル基、イコセニル基等が挙げられる。
上記アルキニル基としては、例えば、エチニル基、１－プロピニル基、２－プロピニル基、ブチニル基、ペンチニル基、ヘキシニル基、ヘプチニル基、オクチニル基、ノニニル基、デシニル基、ドデシニル基、オクタデシニル基、イコシニル基等が挙げられる。 Z in the above formulas (1) and (2) is at least selected from the group consisting of a hydrogen atom, a methyl group, or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Represents a hydrocarbon group having 2 to 30 carbon atoms having one kind of hydrophilic group.
The hydrocarbon group is not particularly limited, and examples thereof include a chain hydrocarbon group such as an alkyl group, an alkenyl group, and an alkynyl group, and a cyclic hydrocarbon group such as an aryl group, a cycloalkyl group, and a cycloalkenyl group. The above-mentioned hydrocarbon group may have a branch, and the number of carbon atoms of the hydrocarbon group when having a branch means the total number of carbon atoms of the main chain and the branched chain.
Examples of the alkyl group include an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, an octyl group, a nonyl group, a decyl group, a dodecyl group and a stearyl group. , Icosyl group and the like.
Examples of the alkenyl group include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, a dodecenyl group, an octadecenyl group and an icosenyl group. And so on.
Examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, a dodecynyl group, an octadecynyl group and an icocinyl group. And so on.
上記アリール基としては、例えば、フェニル基、ベンジル基、メチルフェニル基、１－メトキシ－４－メチルフェニル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ブチルメチルフェニル基、ジメチルフェニル基、ジエチルフェニル基、ジブチルフェニル基、ビフェニル基、ビフェニルメチル基、ビフェニルエチル基、ナフチル基、ナフチルメチル基、ナフチルエチル等が挙げられる。 Examples of the aryl group include a phenyl group, a benzyl group, a methylphenyl group, a 1-methoxy-4-methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a butylmethylphenyl group, a dimethylphenyl group and a diethyl group. Examples thereof include phenyl group, dibutylphenyl group, biphenyl group, biphenylmethyl group, biphenylethyl group, naphthyl group, naphthylmethyl group, naphthylethyl and the like.
上記シクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。
上記シクロアルケニル基としては、例えば、シクロプロペニル基、シクロブテニル基、シクロペンテニル基、シクロヘキセニル基等が挙げられる。
上記炭化水素基として、好ましくはアルキル基、アルケニル基であり、より好ましくはアルキル基である。 Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group and the like.
The hydrocarbon group is preferably an alkyl group or an alkenyl group, and more preferably an alkyl group.
上記炭化水素基の炭素数として好ましくは２～２０であり、より好ましくは２～１５であり、更に好ましくは２～１０であり、特に好ましくは２～５である。 The number of carbon atoms of the hydrocarbon group is preferably 2 to 20, more preferably 2 to 15, still more preferably 2 to 10, and particularly preferably 2 to 5.
上記Ｚとして好ましくは、水素原子、メチル基である。 The Z is preferably a hydrogen atom or a methyl group.
上記Ａは、同一又は異なって、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有していてもよいアルキレン基を表す。これは、ポリアルキレングリコール中にｎ個存在するＡＯのオキシアルキレン基が全て同一であってもよく、異なっていてもよいことを意味する。
上記Ａで表されるアルキレン基は、炭素数２～１８であることが好ましく、より好ましくは、炭素数２～４である。 The above-mentioned A may have at least one hydrophilic group selected from the group consisting of a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof, which are the same or different. Represents a good alkylene group. This means that all n oxyalkylene groups of AO present in the polyalkylene glycol may be the same or different.
The alkylene group represented by A is preferably having 2 to 18 carbon atoms, and more preferably 2 to 4 carbon atoms.
ＡＯで表されるオキシアルキレン基としては例えば、アルキレンオキシドの付加反応により形成される基及びこれに上記親水性基を付加した構造の基であり、このようなアルキレンオキシドとしては、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、イソブチレンオキシド、１－ブテンオキシド、２－ブテンオキシド、スチレンオキシド及び炭素数２～１８のアルキレンオキシド等が挙げられる。より好ましくは、エチレンオキシド、プロピレンオキシド、ブチレンオキシド等の炭素数２～４のアルキレンオキシドであり、更に好ましくは、エチレンオキシド、プロピレンオキシドである。
なお、上記式（１）におけるＡＯで表されるオキシアルキレン基は、アルキレンオキシドの付加反応により形成される基に限られない。 The oxyalkylene group represented by AO is, for example, a group formed by an addition reaction of an alkylene oxide and a group having a structure in which the above hydrophilic group is added thereto. Such an alkylene oxide includes ethylene oxide and propylene oxide. , Butylene oxide, isobutylene oxide, 1-butene oxide, 2-butene oxide, styrene oxide, alkylene oxide having 2 to 18 carbon atoms and the like. More preferably, it is an alkylene oxide having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide and butylene oxide, and even more preferably ethylene oxide and propylene oxide.
The oxyalkylene group represented by AO in the above formula (1) is not limited to the group formed by the addition reaction of the alkylene oxide.
また、上記ポリアルキレングリコールが、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、スチレンオキシド等の中から選ばれる任意の２種類以上のアルキレンオキシド付加物である場合、ランダム付加、ブロック付加、交互付加等のいずれの形態であってもよい。なお、親水性と疎水性とのバランス確保のため、ポリアルキレングリコール中のオキシアルキレン基として、オキシエチレン基を必須成分として有することが好ましく、５０モル％以上がオキシエチレン基であることがより好ましく、９０モル％以上がオキシエチレン基であることが更に好ましい。 When the polyalkylene glycol is any two or more types of alkylene oxide adducts selected from ethylene oxide, propylene oxide, butylene oxide, styrene oxide and the like, any of random addition, block addition, alternating addition and the like. It may be in the form. In order to secure a balance between hydrophilicity and hydrophobicity, it is preferable to have an oxyethylene group as an essential component as the oxyalkylene group in the polyalkylene glycol, and more preferably 50 mol% or more is an oxyethylene group. , 90 mol% or more is more preferably an oxyethylene group.
上記式（１）、（２）中、ｎは、（ＡＯ）の平均付加モル数を表し、０～２００の数である。これにより上記共重合体が洗浄力に優れることとなる。好ましくは０～１５０であり、より好ましくは０～１００であり、更に好ましくは０～８０であり、特に好ましくは０～７５であり、一層好ましくは１０～７０であり、より一層好ましくは１５～６５であり、最も好ましくは２０～５０である。
ｎが１である場合、上記Ａは、水酸基を有するアルキレン基であることが好ましい。 In the above formulas (1) and (2), n represents the average number of moles added of (AO), and is a number from 0 to 200. As a result, the copolymer has excellent detergency. It is preferably 0 to 150, more preferably 0 to 100, still more preferably 0 to 80, particularly preferably 0 to 75, even more preferably 10 to 70, and even more preferably 15 to. It is 65, most preferably 20 to 50.
When n is 1, the above A is preferably an alkylene group having a hydroxyl group.
上記式（１）、（２）中、ｘ、ｗは、同一又は異なって、０～４の数を表し、ｙ、ｖは、０又は１を表す。
ｘとして好ましくは０～３であり、より好ましくは０～２であり、更に好ましくは０又は１である。
ｗとして好ましくは０～３であり、より好ましくは０～２であり、更に好ましくは０又は１であり、最も好ましくは０である。
（ｘ，ｙ，ｖ，ｗ）の組み合わせとしては、（０，１，０，０）、（０，１，１，２）、（１，０，０，０）、（２，０，０，０）等が挙げられる。好ましくは（０，１，０，０）、（１，０，０，０）、（２，０，０，０）であり、より好ましくは（０，１，０，０）、（２，０，０，０）であり、最も好ましくは、（０，１，０，０）である。 In the above formulas (1) and (2), x and w represent the same or different numbers from 0 to 4, and y and v represent 0 or 1.
The x is preferably 0 to 3, more preferably 0 to 2, and even more preferably 0 or 1.
As w, it is preferably 0 to 3, more preferably 0 to 2, still more preferably 0 or 1, and most preferably 0.
As a combination of (x, y, v, w), (0,1,0,0), (0,1,1,2), (1,0,0,0), (2,0,0) , 0) and the like. It is preferably (0,1,0,0), (1,0,0,0), (2,0,0,0), and more preferably (0,1,0,0), (2,0). It is 0,0,0), and most preferably (0,1,0,0).
上記親水性基含有単量体（Ａ）として具体的には例えば、（ポリ）エチレングリコールモノ（メタ）アクリレート、（ポリ）プロピレングリコールモノ（メタ）アクリレート等のポリアルキレングリコールモノ（メタ）アクリレート；メトキシ（ポリ）エチレングリコールモノ（メタ）アクリレート、メトキシ（ポリ）プロピレングリコールモノ（メタ）アクリレート等のアルコキシポリアルキレングリコールモノ（メタ）アクリレート等や、ビニルアルコール、（メタ）アリルアルコール、３－メチル－３－ブテン－１－オール（イソプレノール）、３－メチル－２－ブテン－１－オール、２－メチル－３－ブテン－２－オール、２－メチル－２－ブテン－１－オール、２－メチル－３－ブテン－１－オールのいずれかにアルキレンオキシドを１０～１００モル付加した化合物等の（ポリ）アルキレングリコール系単量体；グリセロールモノ（メタ）アクリレート、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート等の水酸基含有（メタ）アクリレート；ヒドロキシメチル（メタ）アクリルアミド、ヒドロキシエチル（メタ）アクリルアミド等の水酸基含有（メタ）アクリルアミド；（メタ）アクリル酸、クロトン酸、α－アリルオキシアクリル酸及びこれらの塩等の不飽和モノカルボン酸類；マレイン酸、イタコン酸、メサコン酸、シトラコン酸、フマル酸等や、それらの塩、それらの無水物等の不飽和ジカルボン酸類等が挙げられる。これらの中でも（ポリ）アルキレングリコール系単量体や水酸基含有（メタ）アクリレートが好ましい。 Specifically, as the hydrophilic group-containing monomer (A), for example, polyalkylene glycol mono (meth) acrylate such as (poly) ethylene glycol mono (meth) acrylate and (poly) propylene glycol mono (meth) acrylate; Acrylate polyalkylene glycol mono (meth) acrylates such as methoxy (poly) ethylene glycol mono (meth) acrylates and methoxy (poly) propylene glycol mono (meth) acrylates, vinyl alcohols, (meth) allyl alcohols, 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 (Poly) alkylene glycol-based monomers such as compounds in which 10 to 100 mol of alkylene oxide is added to any of -3-buten-1-ol; glycerol mono (meth) acrylate, 2-hydroxyethyl (meth) acrylate, Hydroxyl-containing (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; hydroxymethyl (meth) acrylamide. , Hydroxyl-containing (meth) acrylamides such as hydroxyethyl (meth) acrylamide; unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-allyloxyacrylic acid and salts thereof; maleic acid, itaconic acid, mesacon Examples thereof include acids, citraconic acid, fumaric acid and the like, salts thereof, unsaturated dicarboxylic acids such as their anhydrides and the like. Among these, (poly) alkylene glycol-based monomers and hydroxyl group-containing (meth) acrylates are preferable.
＜芳香族基含有単量体（Ｂ）＞
本発明における芳香族基含有単量体（Ｂ）は、構造中に芳香族基とエチレン性不飽和基とを有する単量体であればよい。
芳香族含有単量体としては、スチレン、α－メチルスチレン、ビニルトルエン、インデン、ビニルナフタレン、フェニルマレイミド、ビニルアニリン、スチレンスルホン酸等の構造中に芳香族基とエチレン性不飽和基とを有し、エステル構造を有さない単量体や、後述する式（３）で表される単量体のような、構造中に芳香族基とエチレン性不飽和基とエステル構造とを有する単量体等が挙げられる。 <Aromatic group-containing monomer (B)>
The aromatic group-containing monomer (B) in the present invention may be any monomer having an aromatic group and an ethylenically unsaturated group in the structure.
The aromatic-containing monomer has an aromatic group and an ethylenically unsaturated group in the structure of styrene, α-methylstyrene, vinyltoluene, inden, vinylnaphthalene, phenylmaleimide, vinylaniline, styrenesulfonic acid and the like. However, a single amount having an aromatic group, an ethylenically unsaturated group, and an ester structure in the structure, such as a monomer having no ester structure or a monomer represented by the formula (3) described later. The body etc. can be mentioned.
本発明における芳香族基含有単量体（Ｂ）はさらに、単独重合を行って得られた単独重合体（ホモポリマー）の溶解性パラメータが１３以下であるものが好ましい。芳香族基含有単量体の中でも、このような単量体は、繊維への吸着力に特に優れ、上記共重合体をより防汚性やソイルリリース性に優れたものとすることができる。
上記溶解性パラメータとして好ましくは１２以下であり、より好ましくは１１以下である。上記溶解性パラメータとしては通常５以上である。
なお、溶解性パラメータが１３以下であっても、水酸基、オキシアルキレン基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有するものについては、親水性基含有単量体（Ａ）に分類する。
ここで、上記溶解性パラメータは、「ＰＯＬＹＭＥＲ　ＥＮＧＩＮＥＥＲＩＮＧ　ＡＮＤ　ＳＣＩＥＮＣＥ」（１９７４年、Ｖｏｌ．１４、Ｎｏ．２）の１４７～１５４ページに記載の方法によって計算される値である。
以下にその方法を概説する。単独重合体の溶解性パラメータ（δ）（ｃａｌ／ｃｍ３）１／２は、該重合体を形成している構成単位の蒸発エネルギー（△ｅｉ）及びモル体積（△ｖｉ）に基づいて、下記の計算法により算出される。
δ＝（△ｅｉ／△ｖｉ）１／２　　（ｃａｌ／ｃｍ３）１／２ Further, the aromatic group-containing monomer (B) in the present invention preferably has a solubility parameter of 13 or less for the homopolymer obtained by homopolymerization. Among the aromatic group-containing monomers, such a monomer is particularly excellent in adsorbing power to fibers, and can make the above-mentioned copolymer more excellent in antifouling property and soil release property.
The solubility parameter is preferably 12 or less, and more preferably 11 or less. The solubility parameter is usually 5 or more.
Even if the solubility parameter is 13 or less, at least one hydrophilic group selected from the group consisting of a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a salt group thereof. Those having a sex group are classified into a hydrophilic group-containing monomer (A).
Here, the solubility parameter is a value calculated by the method described on pages 147 to 154 of "POLYMER ENGINEERING AND SCIENCE" (1974, Vol. 14, No. 2).
The method is outlined below. The solubility parameter (δ) (cal / cm 3 ) 1/2 of the homopolymer is as follows, based on the evaporation energy (Δei) and molar volume (Δvi) of the constituent units forming the polymer. It is calculated by the calculation method of.
δ = (Δei / Δvi) 1/2 (cal / cm 3 ) 1/2
本発明における芳香族基含有単量体（Ｂ）として好ましくは、下記式（３）； The aromatic group-containing monomer (B) in the present invention is preferably the following formula (3);
Figure JPOXMLDOC01-appb-C000007
Figure JPOXMLDOC01-appb-C000007
（式中、Ｒ４、Ｒ５、Ｒ６は、同一又は異なって、水素原子又は炭素数１～３のアルキル基を表す。Ｒ７は、芳香族基を表す。）で表される化合物である。
すなわち、上記共重合体は、下記式（４）； (In the formula, R 4 , R 5 , and R 6 represent the same or different alkyl groups having a hydrogen atom or 1 to 3 carbon atoms . R 7 represents an aromatic group.) is there.
That is, the above-mentioned copolymer has the following formula (4);
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
（式中、Ｒ４～Ｒ７は、式（３）と同じである。）で表される構造単位を有することが好ましい。
なお、上記共重合体が上記式（４）で表される構造単位を有する場合、当該構造単位は上記式（３）で表される化合物を用いて重合することで得られるものであってもよく、その他の方法で得られるものであってもよい。 (In the formula, R 4 to R 7 are the same as those in the formula (3).) It is preferable to have a structural unit represented by the formula (3).
When the copolymer has a structural unit represented by the above formula (4), the structural unit may be obtained by polymerizing with a compound represented by the above formula (3). Well, it may be obtained by other methods.
上記Ｒ４、Ｒ５、Ｒ６におけるアルキル基として好ましくはメチル基、エチル基、プロピル基であり、より好ましくはメチル基、エチル基であり、更に好ましくはメチル基である。
Ｒ４、Ｒ５及びＲ６は、同一又は異なって、水素原子、又は、メチル基であることが好ましい。より好ましくはＲ４、Ｒ５が水素原子であって、Ｒ６が水素原子又はメチル基である。 The alkyl group in R 4 , R 5 , and R 6 is preferably a methyl group, an ethyl group, or a propyl group, more preferably a methyl group or an ethyl group, and further preferably a methyl group.
R 4 , R 5 and R 6 are preferably the same or different, and are preferably hydrogen atoms or methyl groups. More preferably, R 4 and R 5 are hydrogen atoms, and R 6 is a hydrogen atom or a methyl group.
上記Ｒ７における芳香族基としては、置換基を有していてもよい芳香族化合物から水素原子を１つ除いてできる基が挙げられる。
芳香族化合物としては、ベンゼン、ナフタレン、アントラセン、ビフェニル等が挙げられる。
芳香環が有していてもよい置換基としては、炭素数１～２０の炭化水素基、炭素数１～２０のアルコキシ基が挙げられる。置換基は、炭素数１～１２のものが好ましい。より好ましくは、炭素数１～８のものである。 Examples of the aromatic group in R 7 include a group formed by removing one hydrogen atom from an aromatic compound which may have a substituent.
Examples of the aromatic compound include benzene, naphthalene, anthracene, biphenyl and the like.
Examples of the substituent that the aromatic ring may have include a hydrocarbon group having 1 to 20 carbon atoms and an alkoxy group having 1 to 20 carbon atoms. The substituent is preferably one having 1 to 12 carbon atoms. More preferably, it has 1 to 8 carbon atoms.
上記Ｒ７における芳香族基としては、例えば、フェニル基、ベンジル基、メチルフェニル基、１－メトキシ－４－メチルフェニル基、エチルフェニル基、プロピルフェニル基、ブチルフェニル基、ブチルメチルフェニル基、ジメチルフェニル基、ジエチルフェニル基、ジブチルフェニル基、２－（２－メチルフェニル）エチル基、２－（３－メチルフェニル）エチル基、２－（４－メチルフェニル）エチル基、２－（４－プロピルフェニル）エチル基、ビフェニル基、ビフェニルメチル基、ビフェニルエチル基、ナフチル基、ナフチルメチル基、ナフチルエチル基等が挙げられる。 The aromatic group in the above R 7, for example, a phenyl group, a benzyl group, methylphenyl group, 1-methoxy-4-methylphenyl group, ethylphenyl group, propylphenyl group, butylphenyl group, butyl methylphenyl group, dimethyl Phenyl group, diethylphenyl group, dibutylphenyl group, 2- (2-methylphenyl) ethyl group, 2- (3-methylphenyl) ethyl group, 2- (4-methylphenyl) ethyl group, 2- (4-propyl) Phenyl) Ethyl group, biphenyl group, biphenylmethyl group, biphenylethyl group, naphthyl group, naphthylmethyl group, naphthylethyl group and the like can be mentioned.
上記式（３）で表される芳香族基含有単量体（Ｂ）の具体例としては、例えば、フェニル（メタ）アクリレート、ベンジル（メタ）アクリレート、２－エチルフェニル（メタ）アクリレート、プロピルフェニル（メタ）アクリレート、ブチルフェニル（メタ）アクリレート、ペンチルフェニル（メタ）アクリレート、ヘキシルフェニル（メタ）アクリレート、ブチルメチルフェニル（メタ）アクリレート、ジメチルフェニル（メタ）アクリレート、ジエチルフェニル（メタ）アクリレート、ジブチルフェニル（メタ）アクリレート、２－フェニルエチル（メタ）アクリレート、４－メチルフェニル（メタ）アクリレート、４－メチルベンジル（メタ）アクリレート、１－メトキシ－４－メチルフェニル（メタ）アクリレート、２－（２－メチルフェニル）エチル（メタ）アクリレート、２－（３－メチルフェニル）エチル（メタ）アクリレート、２－（４－メチルフェニル）エチル（メタ）アクリレート、２－（４－プロピルフェニル）エチル（メタ）アクリレート、ビフェニルメチル（メタ）アクリレート、ビフェニルエチル（メタ）アクリレート、ナフチル（メタ）アクリレート、ナフチルメチル（メタ）アクリレート、ナフチルエチル（メタ）アクリレート等が挙げられる。中でも好ましくはフェニル（メタ）アクリレート、ベンジル（メタ）アクリレートである。 Specific examples of the aromatic group-containing monomer (B) represented by the above formula (3) include, for example, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-ethylphenyl (meth) acrylate, and propylphenyl. (Meta) acrylate, butylphenyl (meth) acrylate, pentylphenyl (meth) acrylate, hexylphenyl (meth) acrylate, butylmethylphenyl (meth) acrylate, dimethylphenyl (meth) acrylate, diethylphenyl (meth) acrylate, dibutylphenyl (Meta) acrylate, 2-phenylethyl (meth) acrylate, 4-methylphenyl (meth) acrylate, 4-methylbenzyl (meth) acrylate, 1-methoxy-4-methylphenyl (meth) acrylate, 2- (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, naphthylmethyl (meth) acrylate, naphthylethyl (meth) acrylate and the like. Of these, phenyl (meth) acrylate and benzyl (meth) acrylate are preferable.
上記共重合体は、芳香族基含有単量体（Ｂ）以外の疎水性単量体（Ｃ）由来の構造単位（ｃ）を有していてもよい。
芳香族基含有単量体（Ｂ）以外の疎水性単量体（Ｃ）は、単独重合を行って得られた単独重合体（ホモポリマー）に対する溶解性パラメータが１３以下であるものが好ましい。このような疎水性単量体は、上記共重合体における疎水性を高め、疎水性の繊維への吸着性を高めることができる。上記溶解性パラメータとして好ましくは１２以下であり、より好ましくは１１以下である。上記溶解性パラメータとしては通常５以上である。
なお、溶解性パラメータが１３以下であっても、水酸基、オキシアルキレン基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有するものについては、親水性基含有単量体（Ａ）に分類する。
溶解性パラメータの意味は上述のとおりである。 The copolymer may have a structural unit (c) derived from a hydrophobic monomer (C) other than the aromatic group-containing monomer (B).
The hydrophobic monomer (C) other than the aromatic group-containing monomer (B) preferably has a solubility parameter of 13 or less with respect to the homopolymer obtained by homopolymerization. Such a hydrophobic monomer can enhance the hydrophobicity in the above-mentioned copolymer and enhance the adsorptivity to the hydrophobic fiber. The solubility parameter is preferably 12 or less, and more preferably 11 or less. The solubility parameter is usually 5 or more.
Even if the solubility parameter is 13 or less, at least one hydrophilic group selected from the group consisting of a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a salt group thereof. Those having a sex group are classified into a hydrophilic group-containing monomer (A).
The meaning of the solubility parameter is as described above.
上記疎水性単量体（Ｃ）としては、エチレン性不飽和基と炭素数１～３０のアルキル基を有する単量体であることが好ましい。
疎水性単量体（Ｃ）としては、例えば（メタ）アクリル酸等の不飽和カルボン酸と置換基を有していてもよい炭素数１～１２のアルコールとのエステル類；エチレン、プロピレン等のオレフィン系単量体；酢酸ビニル等の不飽和アルコールと炭素数３～８のカルボン酸とのエステル；塩化ビニル等のハロゲン化ビニル；メチルビニルエーテル、エチルビニルエーテル等のアルキルビニルエーテル類；Ｎ－ビニルピロリドン等の環状ビニル系単量体が挙げられる。 The hydrophobic monomer (C) is preferably a monomer having an ethylenically unsaturated group and an alkyl group having 1 to 30 carbon atoms.
Examples of the hydrophobic monomer (C) include esters of unsaturated carboxylic acids such as (meth) acrylic acid and alcohols having 1 to 12 carbon atoms which may have substituents; ethylene, propylene and the like. Olefin-based monomers; esters of unsaturated alcohols such as vinyl acetate with carboxylic acids having 3 to 8 carbon atoms; vinyl halides such as vinyl chloride; alkyl vinyl ethers such as methyl vinyl ethers and ethyl vinyl ethers; N-vinylpyrrolidone and the like. Cyclic vinyl-based monomer of.
上記アルコールが有していてもよい置換基は、水酸基、オキシアルキレン基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基以外の置換基であればよいが、例えば、ハロゲン原子等が挙げられる。
上記アルコールの炭素数として好ましくは２～２２であり、より好ましくは２～１６であり、更に好ましくは４～８である。
上記炭素数１～３０のアルコールとして好ましくは、炭素数１～３０のアルキルアルコール等が挙げられる。 The substituent that the alcohol may have may be a substituent other than a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a salt group thereof. Halogen atoms and the like can be mentioned.
The carbon number of the alcohol is preferably 2 to 22, more preferably 2 to 16, and even more preferably 4 to 8.
The alcohol having 1 to 30 carbon atoms is preferably an alkyl alcohol having 1 to 30 carbon atoms.
上記炭素数１～３０のアルキルアルコールとしては、メタノール、エタノール、プロパノール、ブタノール、ペンチルアルコール、ヘキシルアルコール、ヘプチルアルコール、オクチルアルコール、ノニルアルコール、デシルアルコール、ウンデシルアルコール、ドデシルアルコール（ラウリルアルコール）、トリデシルアルコール、テトラデシルアルコール、ペンタデシルアルコール、ヘキサデシルアルコール、ヘプタデシルアルコール、オクタデシルアルコール、ノナデシルアルコール及びイコシルアルコール等である。 Examples of the alkyl alcohol having 1 to 30 carbon atoms include methanol, ethanol, propanol, butanol, pentyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol (lauryl alcohol), and tri. Decyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecil alcohol, icosyl alcohol and the like.
上記疎水性単量体（Ｃ）として好ましくは、下記式（５）； The hydrophobic monomer (C) is preferably the following formula (5);
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
（式中、Ｒ８、Ｒ９、Ｒ１０は、同一又は異なって、水素原子又は炭素数１～３のアルキル基を表す。Ｒ１１は、炭素数１～３０の鎖状炭化水素基、脂環式炭化水素基を表す。）で表される化合物である。
すなわち、上記共重合体が芳香族基含有単量体（Ｂ）以外の疎水性単量体（Ｃ）由来の構造単位（ｃ）を有する場合、下記式（６）； (In the formula, R 8 , R 9 , and R 10 represent hydrogen atoms or alkyl groups having 1 to 3 carbon atoms, which are the same or different. R 11 is a chain hydrocarbon group and fat having 1 to 30 carbon atoms. It is a compound represented by (representing a cyclic hydrocarbon group).
That is, when the copolymer has a structural unit (c) derived from a hydrophobic monomer (C) other than the aromatic group-containing monomer (B), the following formula (6);
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
（式中、Ｒ８～Ｒ１１は、式（５）と同じである。）で表される構造単位を有することが好ましい。
なお、上記共重合体が上記式（６）で表される構造単位を有する場合、当該構造単位は上記式（５）で表される化合物を用いて重合することで得られるものであってもよく、その他の方法で得られるものであってもよい。 (In the formula, R 8 to R 11 are the same as those in the formula (5).) It is preferable to have a structural unit represented by the formula (5).
When the copolymer has a structural unit represented by the above formula (6), the structural unit may be obtained by polymerizing with a compound represented by the above formula (5). Well, it may be obtained by other methods.
上記Ｒ８、Ｒ９、Ｒ１０におけるアルキル基は、上記式（３）におけるＲ４、Ｒ５、Ｒ６と同様である。
上記Ｒ７における炭化水素基の炭素数は、１～２２であることが好ましい。より好ましくは２～１６であり、更に好ましくは２～１２であり、特に好ましくは４～１２であり、最も好ましくは４～８である。 The alkyl groups in R 8 , R 9 , and R 10 are the same as those in R 4 , R 5 , and R 6 in the above formula (3).
The number of carbon atoms in the hydrocarbon groups represented by R 7 is preferably 1-22. It is more preferably 2 to 16, still more preferably 2 to 12, particularly preferably 4 to 12, and most preferably 4 to 8.
上記Ｒ１１における鎖状炭化水素基としては、アルキル基、アルケニル基、アルキニル基等が挙げられ、脂環式炭化水素基としては、シクロアルキル基、シクロアルケニル基等が挙げられる。 Examples of the chain hydrocarbon group in R 11 include an alkyl group, an alkenyl group, an alkynyl group and the like, and examples of the alicyclic hydrocarbon group include a cycloalkyl group and a cycloalkenyl group.
上記Ｒ１１におけるアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、ヘキシル基、ヘプチル基、２－エチルへキシル基、オクチル基、ノニル基、デシル基、ドデシル基、ステアリル基、イコシル基等が挙げられる。
上記Ｒ７におけるアルケニル基としては、例えば、ビニル基、アリル基、１－ブテニル基、２－ブテニル基、ペンテニル基、ヘキセニル基、ヘプテニル基、オクテニル基、ノネニル基、デセニル基、ドデセニル基、オクタデセニル基、イコセニル基等が挙げられる。
上記Ｒ７におけるアルキニル基としては、例えば、エチニル基、１－プロピニル基、２－プロピニル基、ブチニル基、ペンチニル基、ヘキシニル基、ヘプチニル基、オクチニル基、ノニニル基、デシニル基、ドデシニル基、オクタデシニル基、イコシニル基等が挙げられる。 The alkyl group in the R 11, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a hexyl group, a heptyl group, a 2-ethylhexyl group, octyl group, nonyl group, decyl group , Dodecyl group, stearyl group, icosyl group and the like.
The alkenyl group represented by R 7, for example, vinyl, allyl, 1-butenyl, 2-butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, dodecenyl, octadecenyl , Icosenyl group and the like.
The alkynyl group represented by R 7, for example, ethynyl, 1-propynyl, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, dodecynyl group, octadecynyl group , Icosinyl group and the like.
上記Ｒ１１におけるシクロアルキル基としては、例えば、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基等が挙げられる。
上記シクロアルケニル基としては、例えば、シクロプロペニル基、シクロブテニル基、シクロペンテニル基、シクロヘキセニル基等が挙げられる。 Examples of the cycloalkyl group in R 11 include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group and the like.
Examples of the cycloalkenyl group include a cyclopropenyl group, a cyclobutenyl group, a cyclopentenyl group, a cyclohexenyl group and the like.
上記疎水性単量体（Ｃ）として好ましくは、アルキル（メタ）アクリレートである。
アルキル（メタ）アクリレートとしては、例えばメチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレート、ノニル（メタ）アクリレート、デシル（メタ）アクリレート、ドデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イコシル（メタ）アクリレート等が挙げられる。中でも好ましくはメチル（メタ）アクリレート、エチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、ｎ－オクチル（メタ）アクリレートであり、より好ましくはエチル（メタ）アクリレート、ｎ－プロピル（メタ）アクリレート、イソプロピル（メタ）アクリレート、ｎ－ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ｓｅｃ－ブチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート等が挙げられる。 The hydrophobic monomer (C) is preferably an alkyl (meth) acrylate.
Examples of the alkyl (meth) acrylate include 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, sec-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, stearyl Examples thereof include (meth) acrylate and icosyl (meth) acrylate. Of these, 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 are preferable. , Se-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, more preferably ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, Examples thereof include n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.
上記共重合体は、親水性基含有単量体（Ａ）、芳香族基含有単量体（Ｂ）、芳香族基含有単量体（Ｂ）以外の疎水性単量体（Ｃ）、以外のその他の単量体（Ｅ）由来の構造単位（ｅ）を有していてもよい。
単量体（Ｅ）は、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基を有さず、構造中に芳香族基を有さず、かつ、単独重合体の溶解性パラメータが１３より大きいものであれば特に制限されないが、例えばアクリロニトリル等が挙げられる。 The copolymer is other than the hydrophilic group-containing monomer (A), the aromatic group-containing monomer (B), and the hydrophobic monomer (C) other than the aromatic group-containing monomer (B). It may have a structural unit (e) derived from the other monomer (E) of.
The monomer (E) does not have a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, or a salt group thereof, has no aromatic group in the structure, and is a homopolymer. The solubility parameter of is not particularly limited as long as it is larger than 13, but examples thereof include acrylonitrile.
＜共重合体の製造方法＞
上記共重合体の製造は、特に制限されないが、単量体成分を重合することにより製造することができ、単量体成分の具体例及び好ましい例、並びに、各単量体の好ましい割合は、上述のとおりである。
上記共重合体の製造方法は、親水性基含有単量体（Ａ）及び芳香族基含有単量体（Ｂ）を含む単量体成分を重合する工程（以下、「重合工程」ともいう）を含むことが好ましい。
このような共重合体の製造方法もまた、本発明の１つである。 <Method for producing copolymer>
The production of the above-mentioned copolymer is not particularly limited, but it can be produced by polymerizing a monomer component, and specific examples and preferable examples of the monomer component, and a preferable ratio of each monomer can be obtained. As described above.
The above-mentioned method for producing a copolymer is a step of polymerizing a monomer component containing a hydrophilic group-containing monomer (A) and an aromatic group-containing monomer (B) (hereinafter, also referred to as a “polymerization step”). Is preferably included.
A method for producing such a copolymer is also one of the present inventions.
上記重合工程における、単量体成分の重合を開始する方法としては、特に制限されないが、例えば、重合開始剤を添加する方法、ＵＶを照射する方法、熱を加える方法、光重合開始剤存在下に光を照射する方法等が挙げられる。
上記重合工程では、重合開始剤を用いることが好ましい。
上記重合開始剤としては、反応溶媒やモノマー種によって、適時選択されるが、例えば、過酸化水素；過硫酸ナトリウム、過硫酸カリウム、過硫酸アンモニウム等の過硫酸塩；ジメチル２，２’－アゾビス（２－メチルプロピオネート）、２，２’－アゾビス（イソブチロニトリル）、２，２’－アゾビス（２－メチルプロピオンアミジン）二塩酸塩（２，２’－アゾビス－２－アミジノプロパン二塩酸塩）、２，２’－アゾビス［Ｎ－（２－カルボキシエチル）－２－メチルプロピオンアミジン］水和物、２，２’－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］、２，２’－アゾビス［２－（２－イミダゾリン－２－イル）プロパン］二塩酸塩、２，２’－アゾビス（１－イミノ－１－ピロリジノ－２－メチルプロパン）二塩酸塩、２，２’－アゾビス（２，４－ジメチルバレロニトリル）、２，２’－アゾジイソブチロニトリル、２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）、ジメチル２，２’－アゾビス（２－メチルプロピオネート）、２，２’－アゾビス（２－メチルブチロニトリル）のアゾ系化合物；過酸化ベンゾイル、過酸化ラウロイル、過酢酸、ジ－ｔ－ブチルパーオキサイド、クメンヒドロパーオキサイド等の有機過酸化物；アスコルビン酸と過酸化水素、過硫酸塩と金属塩等の、酸化剤と還元剤とを組み合わせてラジカルを発生させる酸化還元型開始剤等が好適である。これらの重合開始剤のうち、残存単量体が減少する傾向にあることから、過酸化水素、過硫酸塩、アゾ系化合物が好ましい。これらの重合開始剤は、単独で使用されてもよく、２種以上の混合物の形態で使用されてもよい。 The method for initiating the polymerization of the monomer component in the above polymerization step is not particularly limited, but for example, a method for adding a polymerization initiator, a method for irradiating UV, a method for applying heat, and a method in the presence of a photopolymerization initiator. There is a method of irradiating the light.
In the above polymerization step, it is preferable to use a polymerization initiator.
The polymerization initiator is appropriately selected depending on the reaction solvent and the monomer species. For example, hydrogen peroxide; persulfate such as sodium persulfate, potassium persulfate, ammonium persulfate; dimethyl 2,2'-azobis ( 2-Methylpropionate), 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylpropion amidine) dihydrochloride (2,2'-azobis-2-amidinopropanedi) Hydrochloride), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropionamidine] hydrate, 2,2'-azobis [2- (2-imidazolin-2-yl) propane] , 2,2'-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis (1-imino-1-pyrrolidino-2-methylpropane) dihydrochloride, 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azodiisobutyronitrile, 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2' -Azobis (2-methylpropionate), 2,2'-azobis (2-methylbutyronitrile) azo compounds; benzobis peroxide, lauroyl peroxide, peracetic acid, di-t-butyl peroxide, cumene Organic peroxides such as hydroperoxide; oxidation-reduction initiators that generate radicals by combining an oxidizing agent and a reducing agent, such as ascorbic acid and hydrogen peroxide, persulfate and metal salt, and the like are suitable. Among these polymerization initiators, hydrogen peroxide, persulfate, and azo compounds are preferable because the residual monomer tends to decrease. These polymerization initiators may be used alone or in the form of a mixture of two or more.
上記重合開始剤の使用量としては、単量体の使用量（親水性基含有単量体（Ａ）、疎水性単量体（Ｂ）及びその他の単量体（Ｅ）の合計の使用量）１００ｇに対して、０．１ｇ以上、１０ｇ以下であることが好ましく、０．２ｇ以上、８ｇ以下であることがより好ましく、０．２５ｇ以上、７ｇ以下であることが更に好ましく、０．３ｇ以上、５ｇ以下が最も好ましい。 The amount of the polymerization initiator used is the total amount of the monomer used (hydrophilic group-containing monomer (A), hydrophobic monomer (B) and other monomer (E)). ) With respect to 100 g, it is preferably 0.1 g or more and 10 g or less, more preferably 0.2 g or more and 8 g or less, further preferably 0.25 g or more and 7 g or less, and 0.3 g. Above, 5 g or less is most preferable.
上記重合工程では、必要に応じ重合体の分子量調整剤として連鎖移動剤を用いてもよい。連鎖移動剤として具体的には、チオグリコール酸（メルカプト酢酸）、３－メルカプトプロピオン酸、２－メルカプトプロピオン酸（チオ乳酸）、４－メルカプトブタン酸、チオリンゴ酸及びこれらの塩等のメルカプトカルボン酸やメルカプトエタノール、チオグリセロール、２－メルカプトエタンスルホン酸等；四塩化炭素、塩化メチレン、ブロモホルム、ブロモトリクロロエタン等のハロゲン化物；イソプロパノール、グリセリン等の第２級アルコール；亜リン酸、次亜リン酸、次亜リン酸塩及びこれらの水和物等；亜硫酸水素（塩）や亜硫酸水素（塩）を発生し得る化合物（重亜硫酸（塩）、ピロ亜硫酸（塩）、亜ジチオン酸（塩）、亜硫酸（塩）等）；等が挙げられる。中でもメルカプトカルボン酸等のメルカプト基を有する化合物が好ましく、より好ましくはカルボキシル基を有するメルカプト基含有化合物（メルカプトカルボン酸）である。 In the above polymerization step, a chain transfer agent may be used as a molecular weight adjusting agent for the polymer, if necessary. Specifically, as the chain transfer agent, mercaptocarboxylic acids such as thioglycolic acid (mercaptoacetic acid), 3-mercaptopropionic acid, 2-mercaptopropionic acid (thiolactic acid), 4-mercaptobutanoic acid, thioapple acid and salts thereof. And mercaptoethanol, thioglycerol, 2-mercaptoethanesulfonic acid, etc .; halides such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, etc .; secondary alcohols such as isopropanol, glycerin, etc .; Hypophosphates and their hydrates, etc .; Compounds that can generate hydrogen sulfite (salt) and hydrogen sulfite (salt) (dipersulfate (salt), pyrosulfite (salt), dithioic acid (salt), sulfite (Salt) etc.); etc. Among them, a compound having a mercapto group such as mercaptocarboxylic acid is preferable, and a mercapto group-containing compound having a carboxyl group (mercaptocarboxylic acid) is more preferable.
上記共重合体の製造における連鎖移動剤の使用量としては、単量体（全単量体）の使用量１００モル％に対して、０．５モル％以上、３０モル％以下が好ましく、より好ましくは０．７モル％以上、２５モル％以下であり、更に好ましくは０．８モル％以上、２０モル％以下であり、最も好ましくは１モル％以上、１０モル％以下である。 The amount of the chain transfer agent used in the production of the above-mentioned copolymer is preferably 0.5 mol% or more and 30 mol% or less with respect to 100 mol% of the amount of the monomer (all monomers) used, more preferably. It is preferably 0.7 mol% or more and 25 mol% or less, more preferably 0.8 mol% or more and 20 mol% or less, and most preferably 1 mol% or more and 10 mol% or less.
上記重合工程において、重合温度としては、４０℃以上であることが好ましく、また、１５０℃以下であることが好ましい。より好ましくは５０℃以上であり、更に好ましくは５５℃以上である。また、より好ましくは１２０℃以下であり、更に好ましくは１１０℃以下である。 In the above polymerization step, the polymerization temperature is preferably 40 ° C. or higher, and preferably 150 ° C. or lower. It is more preferably 50 ° C. or higher, and even more preferably 55 ° C. or higher. Further, it is more preferably 120 ° C. or lower, and further preferably 110 ° C. or lower.
上記重合工程において単量体成分の反応容器への投入方法は特に限定されず、全量を反応容器に初期に一括投入する方法；全量を反応容器に分割又は連続投入する方法；一部を反応容器に初期に投入し、残りを反応容器に分割又は連続投入する方法等が挙げられる。なお、ラジカル重合開始剤を使用する場合、反応容器に初めから仕込んでもよく、反応容器へ滴下してもよく、また目的に応じてこれらを組み合わせてもよい。
上記のようにして得られた共重合体は、そのままでも液体洗剤用添加剤等の洗剤添加剤として用いることができるが、必要に応じて、更にアルカリ性物質で中和して用いてもよい。アルカリ性物質としては、一価金属又は二価金属の水酸化物や炭酸塩等の無機塩；アンモニア；有機アミンが好適である。また、反応終了後、必要ならば濃度調整を行うこともできる。 In the above polymerization step, the method of charging the monomer component into the reaction vessel is not particularly limited, and the method of charging the entire amount into the reaction vessel at the initial stage; the method of dividing or continuously charging the entire amount into the reaction vessel; Examples thereof include a method in which the mixture is initially charged and the rest is divided or continuously charged into the reaction vessel. When a radical polymerization initiator is used, it may be charged into the reaction vessel from the beginning, may be added dropwise to the reaction vessel, or these may be combined depending on the purpose.
The copolymer obtained as described above 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 and used. As the alkaline substance, inorganic salts such as hydroxides and carbonates of monovalent or divalent metals; ammonia; and organic amines are suitable. Further, after the reaction is completed, the concentration can be adjusted if necessary.
重合時に使用される溶媒は、使用するモノマーや開始剤、製造するポリマーを溶解できるものから適時選択され、水；エタノール、１－プロパノール、２－プロパノール、１－ブタノール、フェノキシエタノール等の炭素数１～８のアルコール類；プロピレングリコール、ブチレングリコール、ヘキシレングリコールなどのグリコール類；ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコール等のポリアルキレングリコール類；ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノブチルエーテル等のアルキルエーテル類；スルホン、ジエチルスルホン、ビス（２－ヒドロキシエチル）スルホンなどのスルホキシド（ジメチルスルホキシド等）等；環状エーテル（テトラヒドロフラン及びテトラヒドロピラン等）；ニトリル（アセトニトリル、プロピオニトリル、ブチロニトリル、アクリロニトリル及びメタクリルニトリル等）；カーボネート（エチレンカーボネート及びプロピオンカーボネート等）；ケトン（アセトン、ジエチルケトン、アセトフェノン、メチルエチルケトン、シクロヘキサノン、シクロペンタノン及びジアセトンアルコール等）が挙げられ、これらの１種又は２種以上を用いることができる。中でも好ましくは水、エタノール、エチレングリコール、プロピレングリコール、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、フェノキシエタノールである。 The solvent used at the time of polymerization is timely selected from those capable of dissolving the monomer to be used, the initiator, and the polymer to be produced, and water; ethanol, 1-propanol, 2-propanol, 1-butanol, phenoxyethanol and the like having 1 to 1 carbon atoms. Alcohols of 8; glycols such as propylene glycol, butylene glycol, hexylene glycol; polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol; diethylene glycol monomethyl ether , Alkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol monobutyl ether; sulfoxides such as sulfone, diethylsulfone, bis (2-hydroxyethyl) sulfone (dimethylsulfoxide, etc.); cyclic ethers (tetrahydropyrane, etc.); Propionitrile, butyronitrile, acrylonitrile, methacrylnitrile, etc.); carbonates (ethylene carbonate, propion carbonate, etc.); ketones (acetone, diethyl ketone, acetophenone, methyl ethyl ketone, cyclohexanone, cyclopentanone, diacetone alcohol, etc.). One or more of the above can be used. Of these, water, ethanol, ethylene glycol, propylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and phenoxyethanol are preferable.
＜共重合体の用途＞
上記共重合体は、洗剤用途、ソイルリリース剤、微生物付着防止剤、繊維処理剤、機能性繊維の製造、水処理薬剤配合物、塗料配合物等に用いられることが好ましい。 <Use of copolymer>
The copolymer is preferably used for detergent applications, soil release agents, microbial adhesion inhibitors, fiber treatment agents, production of functional fibers, water treatment chemical formulations, paint formulations and the like.
（洗剤用途）
上記洗剤とは、家庭用の衣料用、食器用合成洗剤、繊維工業その他の工業用洗剤、硬質表面洗浄剤のほか、その成分の１つの働きを高めた漂白洗剤等の特定の用途にのみ用いられる洗剤も含まれる。
本発明は、上記共重合体を含む洗剤用添加剤でもある。
本発明は更に、上記共重合体を洗剤用添加剤として使用する方法でもある。
本発明はまた、上記共重合体と該共重合体以外の洗剤用添加剤とを含む洗剤組成物でもある。
上記共重合体は、界面活性剤との相溶性に優れるため、液体洗剤用途に好適に用いることができる。上記洗剤組成物は、液体洗剤組成物であることが好ましい。
本発明は更に、洗剤組成物を製造する方法であって、上記製造方法は、上記共重合体を該共重合体以外の洗剤用添加剤に添加する工程を含む洗剤組成物の製造方法でもある。
上記共重合体以外の洗剤添加剤としては、界面活性剤や通常洗剤に用いられる添加剤であれば特に制限されず、洗剤分野において従来公知の知見を適宜参照することができ、本発明の効果を損なわない範囲で、任意の適切な添加剤を用いることができる。 (For detergent use)
The above detergents are used only for specific purposes such as household clothing, synthetic dishwashing detergents, textile industry and other industrial detergents, hard surface cleaners, and bleaching detergents that enhance the function of one of its components. Also includes detergents that are used.
The present invention is also a detergent additive containing the above copolymer.
The present invention is also a method of using the above copolymer as a detergent additive.
The present invention is also a detergent composition containing the above-mentioned copolymer and a detergent additive other than the copolymer.
Since the above-mentioned copolymer has excellent compatibility with a surfactant, it can be suitably used for liquid detergent applications. The detergent composition is preferably a liquid detergent composition.
The present invention is further a method for producing a detergent composition, which is also a method for producing a detergent composition, which comprises a step of adding the copolymer to a detergent additive other than the copolymer. ..
The detergent additive other than the above-mentioned copolymer is not particularly limited as long as it is a surfactant or an additive used in ordinary detergents, and conventionally known findings in the detergent field can be appropriately referred to, and the effects of the present invention can be referred to as appropriate. Any suitable additive can be used as long as it does not impair.
界面活性剤以外の添加剤としては、例えば、カルボキシメチルセルロースナトリウム等の汚染物質の再沈着を防止するための再付着防止剤、ベンゾトリアゾールやエチレン－チオ尿素等の汚れ抑制剤、ソイルリリース剤、色移り防止剤、柔軟剤、ｐＨ調節のためのアルカリ性物質、香料、可溶化剤、蛍光剤、着色剤、起泡剤、泡安定剤、つや出し剤、殺菌剤、漂白剤、漂白助剤、酵素、染料、溶媒等が挙げられる。これらの１種又は２種以上を用いることができる。また、粉末洗剤組成物の場合には、ゼオライトを配合することが好ましい。 Additives other than surfactants include, for example, anti-adhesion agents for preventing re-deposition of contaminants such as sodium carboxymethyl cellulose, stain inhibitors such as benzotriazole and ethylene-thiourea, soil release agents, and colors. Anti-transfer agents, fabric softeners, alkaline substances for pH adjustment, fragrances, solubilizers, fluorescent agents, colorants, foaming agents, foam stabilizers, polishes, bactericides, bleaching agents, bleaching aids, enzymes, Examples include dyes and solvents. One or more of these can be used. Further, in the case of a powder detergent composition, it is preferable to add zeolite.
上記界面活性剤は、アニオン性界面活性剤、ノニオン性界面活性剤、カチオン性界面活性剤及び両性界面活性剤からなる群から選択される１種又は２種以上であることが好ましい。 The surfactant is preferably one or more selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants and amphoteric surfactants.
上記アニオン性界面活性剤としては、アルキルベンゼンスルホン酸塩、アルキルエーテル硫酸塩、アルケニルエーテル硫酸塩、アルキル硫酸塩、アルケニル硫酸塩、α－オレフィンスルホン酸塩、α－スルホ脂肪酸又はエステル塩、アルカンスルホン酸塩、飽和脂肪酸塩、不飽和脂肪酸塩、アルキルエーテルカルボン酸塩、アルケニルエーテルカルボン酸塩、アミノ酸型界面活性剤、Ｎ－アシルアミノ酸型界面活性剤、アルキルリン酸エステル又はその塩、アルケニルリン酸エステル又はその塩等が好適である。これらのアニオン性界面活性剤におけるアルキル基、アルケニル基には、メチル基等のアルキル基が分岐していてもよい。 Examples of the anionic surfactant include alkylbenzene sulfonate, alkyl ether sulfate, alkenyl ether sulfate, alkyl sulfate, alkenyl sulfate, α-olefin sulfonate, α-sulfo fatty acid or ester salt, and alkane sulfonic acid. Salt, saturated fatty acid salt, unsaturated fatty acid salt, alkyl ether carboxylate, alkenyl ether carboxylate, amino acid type surfactant, N-acylamino acid type surfactant, alkyl phosphate ester or its salt, alkenyl phosphate ester Alternatively, a salt thereof or the like is suitable. Alkyl groups such as methyl groups may be branched into the alkyl groups and alkenyl groups in these anionic surfactants.
上記ノニオン性界面活性剤としては、ポリオキシアルキレンアルキルエーテル、ポリオキシアルキレンアルケニルエーテル、ポリオキシエチレンアルキルフェニルエーテル、高級脂肪酸アルカノールアミド又はそのアルキレンオキサイド付加物、ショ糖脂肪酸エステル、アルキルグリコキシド、脂肪酸グリセリンモノエステル、アルキルアミンオキサイド等が好適である。これらのノニオン性界面活性剤におけるアルキル基、アルケニル基には、メチル基等のアルキル基が分岐していてもよい。 Examples of the nonionic surfactant include polyoxyalkylene alkyl ether, polyoxyalkylene alkenyl ether, polyoxyethylene alkyl phenyl ether, higher fatty acid alkanolamide or an alkylene oxide adduct thereof, sucrose fatty acid ester, alkyl glycoxide, and fatty acid glycerin. Monoesters, alkylamine oxides and the like are suitable. Alkyl groups such as methyl groups may be branched into the alkyl groups and alkenyl groups in these nonionic surfactants.
上記カチオン性界面活性剤としては、第４級アンモニウム塩等が好適である。また、両性界面活性剤としては、カルボキシル型両性界面活性剤、スルホベタイン型両性界面活性剤等が好適である。これらのカチオン性界面活性剤、両性界面活性剤におけるアルキル基、アルケニル基は、メチル基等のアルキル基が分岐していてもよい。 As the cationic surfactant, a quaternary ammonium salt or the like is suitable. Further, as the amphoteric tenside, a carboxyl type amphoteric surfactant, a sulfobetaine type amphoteric surfactant and the like are suitable. Alkyl groups such as methyl groups may be branched as the alkyl groups and alkenyl groups in these cationic surfactants and amphoteric surfactants.
上記界面活性剤の配合割合は、通常、洗剤組成物の全量に対して１０～８０質量％であり、好ましくは１５～７５質量％であり、更に好ましくは１８～７０質量％であり、特に好ましくは２０～６８質量％である。界面活性剤の配合割合が少なすぎると、十分な洗浄力を発揮できなくなる虞があり、界面活性剤の配合割合が多すぎると、経済性が低下する虞がある。 The blending ratio of the surfactant is usually 10 to 80% by mass, preferably 15 to 75% by mass, more preferably 18 to 70% by mass, and particularly preferably 18 to 70% by mass, based on the total amount of the detergent composition. Is 20 to 68% by mass. If the blending ratio of the surfactant is too small, sufficient detergency may not be exhibited, and if the blending ratio of the surfactant is too large, the economic efficiency may be lowered.
上記界面活性剤の中でも好ましくはアニオン性界面活性剤とノニオン性界面活性剤であり、特に好ましくはノニオン界面活性剤である。ノニオン性系界面活性剤は油汚れに強いため、上記共重合体とノニオン性系界面活性剤とを含む液体洗剤組成物は、油汚れに対する洗浄力により優れることとなる。上記共重合体とノニオン性系界面活性剤とを含む液体洗剤組成物は本発明の好適な実施形態の１つである。 Among the above-mentioned surfactants, anionic surfactants and nonionic surfactants are preferable, and nonionic surfactants are particularly preferable. Since the nonionic surfactant is resistant to oil stains, the liquid detergent composition containing the copolymer and the nonionic surfactant is superior in detergency against oil stains. A liquid detergent composition containing the above-mentioned copolymer and a nonionic surfactant is one of the preferred embodiments of the present invention.
上記ノニオン性界面活性剤の含有割合は、洗剤組成物１００質量％に対して１～６０質量％であることが好ましい。より好ましくは３～６０質量％であり、更に好ましくは５～５０質量％である。
上記ノニオン性界面活性剤の含有割合はまた、界面活性剤の全量１００質量％に対して、１０～１００質量％であることが好ましい。より好ましくは１５～９０質量％であり、更に好ましくは２０～９０質量％である。 The content ratio of the nonionic surfactant is preferably 1 to 60% by mass with respect to 100% by mass of the detergent composition. It is more preferably 3 to 60% by mass, and even more preferably 5 to 50% by mass.
The content ratio of the nonionic surfactant is also preferably 10 to 100% by mass with respect to 100% by mass of the total amount of the surfactant. It is more preferably 15 to 90% by mass, and even more preferably 20 to 90% by mass.
上記洗剤組成物は、親水性溶剤を含むことが好ましい。
親水性溶剤としては特に制限されず、液体洗剤に通常用いられるものを使用することができるが、例えば、水；エタノール、１－プロパノール、２－プロパノール、１－ブタノール、フェノキシエタノール等の炭素数１～８のアルコール類；プロピレングリコール、ブチレングリコール、ヘキシレングリコールなどのグリコール類；ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール、テトラプロピレングリコール等のポリアルキレングリコール類；ジエチレングリコールモノメチルエーテル、ジエチレングリコールジメチルエーテル、ジエチレングリコールモノブチルエーテル等のアルキルエーテル類；スルホン、ジエチルスルホン、ビス（２－ヒドロキシエチル）スルホンなどのスルホキシド（ジメチルスルホキシド等）等；環状エーテル（テトラヒドロフラン及びテトラヒドロピラン等）；ニトリル（アセトニトリル、プロピオニトリル、ブチロニトリル、アクリロニトリル及びメタクリルニトリル等）；カーボネート（エチレンカーボネート及びプロピオンカーボネート等）；ケトン（アセトン、ジエチルケトン、アセトフェノン、メチルエチルケトン、シクロヘキサノン、シクロペンタノン及びジアセトンアルコール等）が挙げられ、これらの１種又は２種以上を用いることができる。中でも好ましくはエタノール、エチレングリコール、プロピレングリコール、ジエチレングリコール、ジプロピレングリコール、ジエチレングリコールモノブチルエーテル、ジエチレングリコールモノエチルエーテル、フェノキシエタノールである。 The detergent composition preferably contains a hydrophilic solvent.
The hydrophilic solvent is not particularly limited, and those usually used for liquid detergents can be used. For example, water; ethanol, 1-propanol, 2-propanol, 1-butanol, phenoxyethanol and the like have 1 to 1 to carbon atoms. Alcohols of 8; glycols such as propylene glycol, butylene glycol, hexylene glycol; polyalkylene glycols such as diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol; diethylene glycol monomethyl ether , Alkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol monobutyl ether; sulfoxides (dimethylsulfoxide, etc.) such as sulfone, diethylsulfone, bis (2-hydroxyethyl) sulfone; cyclic ethers (tetrahydropyrane, etc.); Propionitrile, butyronitrile, acrylonitrile, methacrylnitrile, etc.); Carbonate (ethylene carbonate, propion carbonate, etc.); Ketone (acetone, diethylketone, acetophenone, methylethylketone, cyclohexanone, cyclopentanone, diacetone alcohol, etc.). One or more of the above can be used. Of these, ethanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, and phenoxyethanol are preferable.
上記洗剤組成物は、親水性溶剤を液体洗剤組成物１００質量％に対して０．１～３０質量％の割合で含むことが好ましい。より好ましくは１～２７質量％であり、更に好ましくは２～２５質量％である。 The detergent composition preferably contains a hydrophilic solvent in a proportion of 0.1 to 30% by mass with respect to 100% by mass of the liquid detergent composition. It is more preferably 1 to 27% by mass, and even more preferably 2 to 25% by mass.
上記洗剤組成物は、他の洗剤ビルダーを含んでもよい。他の洗剤ビルダーとしては、例えば、炭酸塩、炭酸水素塩、珪酸塩などのアルカリビルダー；トリポリリン酸塩、ピロリン酸塩、ボウ硝、ニトリロトリ酢酸塩、エチレンジアミンテトラ酢酸塩、クエン酸塩、（メタ）アクリル酸の共重合体塩、アクリル酸－マレイン酸共重合体、フマル酸塩、ゼオライト等のキレートビルダー；カルボキシメチルセルロース等の多糖類のカルボキシル誘導体；等が挙げられる。上記の他の洗剤ビルダーに用いられる対塩としては、ナトリウム、カリウム等のアルカリ金属、水酸化ナトリウム、アンモニウム、アミン等のアルカリ剤が挙げられる。 The detergent composition may include other detergent builders. Other detergent builders include, for example, alkali builders such as carbonates, bicarbonates, silicates; tripolyphosphate, pyrophosphate, bow glass, nitrilotriacetate, ethylenediaminetetraacetate, citrate, (meth). Examples thereof include a copolymer salt of acrylic acid, a chelate builder such as an acrylic acid-maleic acid copolymer, fumarate, and zeolite; and a carboxyl derivative of a polysaccharide such as carboxymethyl cellulose. Examples of the anti-salt used in the above-mentioned other detergent builders include alkali metals such as sodium and potassium, and alkaline agents such as sodium hydroxide, ammonium and amines.
上記洗剤組成物が液体洗剤組成物である場合、液体洗剤組成物に含まれる水分量は、通常、液体洗剤組成物の全量に対して、好ましくは０．１質量％～８０質量％であり、より好ましくは２質量％～７０質量％であり、更に好ましくは３質量％～６０質量％であり、一層好ましくは５質量％～５５質量％であり、特に好ましくは５質量％～５０質量％であり、最も好ましくは１０質量％～５０質量％である。 When the detergent composition is a liquid detergent composition, the amount of water contained in the liquid detergent composition is usually preferably 0.1% by mass to 80% by mass with respect to the total amount of the liquid detergent composition. It is more preferably 2% by mass to 70% by mass, further preferably 3% by mass to 60% by mass, still more preferably 5% by mass to 55% by mass, and particularly preferably 5% by mass to 50% by mass. Most preferably, it is 10% by mass to 50% by mass.
上記洗剤組成物は酵素を含んでいてもよい。このような酵素としては、例えば、プロテアーゼ、リパーゼ、セルラーゼ、アミラーゼなどが挙げられる。
上記酵素の配合割合は、通常、洗剤組成物の全量に対して、好ましくは５質量％以下である。 The detergent composition may contain an enzyme. Examples of such an enzyme include protease, lipase, cellulase, amylase and the like.
The blending ratio of the enzyme is usually 5% by mass or less with respect to the total amount of the detergent composition.
（ソイルリリース剤）
上記共重合体は、衣類等への吸着性に優れ、上記共重合体が吸着した衣類に汚れが付着した場合に、汚れを落としやすくすることができるソイルリリース性を発揮することができる。
本発明はまた、上記共重合体を含むソイルリリース剤でもある。
本発明は更に、上記共重合体をソイルリリース剤として使用する方法でもある。 (Soil release agent)
The copolymer is excellent in adsorptivity to clothes and the like, and when dirt adheres to clothes to which the copolymer is adsorbed, it can exhibit soil release property that can easily remove the dirt.
The present invention is also a soil release agent containing the above copolymer.
The present invention is also a method of using the above copolymer as a soil release agent.
（微生物付着防止剤、繊維処理剤）
上記共重合体は、共重合体を繊維に処理することにより、繊維に充分に吸着及び／又は固定され、細菌や真菌等の微生物の繊維への付着を抑制することもできる。
本発明は、上記を含む微生物付着防止剤でもある。
本発明は更に、上記共重合体を微生物付着防止剤として使用する共重合体の使用方法でもある。
本発明は更に、上記共重合体を用いて微生物の付着を防止する微生物付着防止方法でもある。
例えば上記共重合体を微生物付着防止剤として使用する際、共重合体を洗剤に添加して用いてもよく、洗剤以外の形態で共重合体を繊維に処理することもできる。 (Microbial adhesion inhibitor, fiber treatment agent)
By treating the copolymer into fibers, the copolymer can be sufficiently adsorbed and / or fixed to the fibers, and the adhesion of microorganisms such as bacteria and fungi to the fibers can be suppressed.
The present invention is also an antimicrobial adhesion agent containing the above.
The present invention is also a method of using the copolymer using the above-mentioned copolymer as a microorganism adhesion inhibitor.
The present invention is also a method for preventing the adhesion of microorganisms by using the above-mentioned copolymer.
For example, when the above copolymer is used as an antimicrobial adhesion agent, the copolymer may be added to a detergent and used, or the copolymer may be treated into fibers in a form other than the detergent.
本発明は、上記共重合体を含む繊維処理剤でもある。
本発明は更に、上記共重合体を用いて繊維を処理する繊維処理方法でもある。
上記繊維処理方法としては、原糸改質法（練り込み法・原糸表面改質法等）及び後加工法（吸尽法、含浸パッド法及び塗布法等）といった種々の繊維の加工方法が挙げられる。繊維の表面に共重合体をコーティングする観点から、後加工法により繊維を処理することが好ましい。より好ましくは紡糸後の繊維に共重合体を吸着及び／又は固定化することである。
上記共重合体を用いて処理された繊維もまた、本発明の１つである。 The present invention is also a fiber treatment agent containing the above copolymer.
The present invention is also a fiber treatment method for treating fibers using the above-mentioned copolymer.
As the above fiber treatment method, various fiber processing methods such as a raw yarn modification method (kneading method, raw yarn surface modification method, etc.) and a post-processing method (absorption method, impregnation pad method, coating method, etc.) are used. Can be mentioned. From the viewpoint of coating the surface of the fiber with the copolymer, it is preferable to treat the fiber by a post-processing method. More preferably, the copolymer is adsorbed and / or immobilized on the fibers after spinning.
Fibers treated with the above copolymers are also one of the present inventions.
（機能性繊維の製造方法）
上記共重合体は、繊維に防汚性や微生物付着防止能を付与することができるため、このような機能を有する機能性繊維の製造に好適に用いられる。
すなわち、本発明は、機能性繊維を製造する方法であって、上記製造方法は、上記共重合体を用いて繊維を処理する工程を含む機能性繊維の製造方法でもある。
上記製造方法は、後加工工程において、上記共重合体を紡糸工程後の繊維に吸着及び／又は固定化することが好ましい。
紡糸工程後の繊維に共重合体を吸着及び／又は固定化する方法は特に制限されないが、繊維に共重合体を浸漬させて乾燥させることが好ましい。
紡糸工程後の繊維は、繊維状であっても、繊維生地に加工されたものであってもよい。 (Manufacturing method of functional fiber)
Since the above-mentioned copolymer can impart antifouling property and microbial adhesion prevention ability to the fiber, it is suitably used for producing a functional fiber having such a function.
That is, the present invention is a method for producing functional fibers, and the above-mentioned production method is also a method for producing functional fibers including a step of treating the fibers with the above-mentioned copolymer.
In the above-mentioned production method, it is preferable that the copolymer is adsorbed and / or immobilized on the fiber after the spinning step in the post-processing step.
The method for adsorbing and / or immobilizing the copolymer on the fiber after the spinning step is not particularly limited, but it is preferable to immerse the copolymer in the fiber and dry it.
The fibers after the spinning step may be fibrous or processed into a fibrous fabric.
（水処理剤、塗料）
上記共重合体は、細菌や真菌等の微生物の付着を抑制することができるため、水処理剤、塗料等の抗菌性が求められる用途にも好適に用いることができる。
 
本発明はまた、上記共重合体を含む水処理薬剤配合物でもある。
本発明は更に、上記共重合体を水処理剤として使用する方法でもある。
冷却水系、冷温水系、集塵水系、紙パルプ工程水系、製鉄工程水系、金属加工工程水系等の各種工程水中に生育する微生物は、系内で増殖してスライムやバイオファウリングと呼ばれる微生物性の付着物を形成し、熱交換器の伝熱効率低下、逆浸透膜の流路の閉塞及び嫌気性菌による微生物腐食などの微生物障害を引き起こす原因となる。本発明は、上記防菌性を有する共重合体を含む水処理薬剤でもある。上記共重合体を含む水処理薬剤を冷却水やＲＯ膜に通水する処理水に用いると、共重合体が熱交換器やＲＯ膜等に付着し、微生物の付着・増殖を防止できることから、熱交換効率を維持できたり、ＲＯ膜の透過流速を確保できる。
上記水処理剤配合物には、必要に応じて、他の配合剤として、重合リン酸塩、ホスホン酸塩、防食剤、スライムコントロール剤、キレート剤、ｐＨ調整剤を用いてもよい。
上記水処理剤配合物は、冷却水循環系、ボイラー水循環系、海水淡水化装置、パルプ蒸解釜、黒液濃縮釜等でのスケール防止に有用である。また、性能、効果に影響しない範囲で、任意の適切な水溶性重合体を含んでもよい。 (Water treatment agent, paint)
Since the above-mentioned copolymer can suppress the adhesion of microorganisms such as bacteria and fungi, it can be suitably used for applications requiring antibacterial properties such as water treatment agents and paints.

The present invention is also a water treatment drug formulation containing the above copolymer.
The present invention is also a method of using the above copolymer as a water treatment agent.
Various processes such as cooling water system, cold / hot water system, dust collecting water system, paper and pulp process water system, iron making process water system, metal processing process water system, etc. It forms deposits and causes microbial damage such as a decrease in heat transfer efficiency of the heat exchanger, blockage of the flow path of the back-penetrating membrane, and microbial corrosion by anaerobic bacteria. The present invention is also a water treatment agent containing the above-mentioned antibacterial copolymer. When the water treatment agent containing the copolymer is used for cooling water or treated water that passes through the RO membrane, the copolymer adheres to the heat exchanger, the RO membrane, etc., and the adhesion and proliferation of microorganisms can be prevented. The heat exchange efficiency can be maintained and the permeation flow velocity of the RO membrane can be secured.
If necessary, a polymerized phosphate, a phosphonate, an anticorrosive agent, a slime control agent, a chelating agent, and a pH adjuster may be used in the water treatment agent formulation as other compounding agents.
The above water treatment agent formulation is useful for preventing scale in a cooling water circulation system, a boiler water circulation system, a seawater desalination device, a pulp cooking kettle, a black liquor concentrating kettle, and the like. Further, any suitable water-soluble polymer may be contained as long as it does not affect the performance and effect.
本発明は更に、上記共重合体を含む塗料配合物でもある。
本発明は更に、上記共重合体を塗料添加剤として使用する方法でもある。
近年の衛生思想の高まりによって、食品や医薬品の工場、病院や養護施設等の建物、食品厨房器具、医療器具、医療機器等の装置において、又は一般家庭用品においてまでも、細菌、かび等の真菌の拡大・感染防止のため、抗菌剤、抗カビ剤、防菌剤、消毒剤等が使用されている。
そのため、公共施設のみならず一般家庭においても、様々な部材に抗菌性や抗カビ性、防菌性を付与することが望まれており、一般的な抗菌剤としては銀が使用されているが、コストが高いことや銀を担持させた粒子の分散安定性が課題となっていた。本発明の共重合体を含む塗料組成物はそのような課題を克服することが可能であり、塗料中に配合することで、塗膜表面の菌の付着を防止できることから、感染症などの拡大を防止可能である。
上記塗料配合物は、上記共重合体以外のその他の成分を含んでいてもよい。
その他の成分としては特に制限されないが、例えば、水酸基、カルボキシル基、アミノ基等のイオン性を有する親水性の高い高分子、中でも、ポリビニルアルコール系、ポリビニルアルコール／ポリエチレングリコール系などの親水性水溶性樹脂；アクリル樹脂、ポリエステル樹脂、エポキシ樹脂、ウレタン樹脂等が好適に挙げられる。また、樹脂は、一種単独で用いてもよく、二種以上を組み合わせて用いてもよい。また、顔料、有機溶剤、硬化触媒、分散剤、乾燥剤、酸化防止剤、界面活性剤、消泡剤、脱水剤、レベリング剤、沈降防止剤、ダレ止め剤、防藻剤、防カビ剤、防腐剤、紫外線吸収剤、光安定剤等を必要に応じて適宜配合してもよい。本発明の塗料配合物（塗料組成物）は、必要に応じて適宜選択される各種成分を混合することによって調製できる。 The present invention is also a paint formulation containing the above copolymer.
The present invention is also a method of using the above copolymer as a paint additive.
Due to the growing hygiene concept in recent years, fungi such as bacteria and molds in food and pharmaceutical factories, buildings such as hospitals and nursing homes, food kitchen equipment, medical equipment, medical equipment, and even general household items. Antibacterial agents, antifungal agents, antibacterial agents, disinfectants, etc. are used to prevent the spread and infection of the disease.
Therefore, it is desired to impart antibacterial, antifungal, and antibacterial properties to various members not only in public facilities but also in general households, and silver is used as a general antibacterial agent. The high cost and the dispersion stability of silver-supported particles have been problems. The coating composition containing the copolymer of the present invention can overcome such a problem, and by blending it in the coating material, it is possible to prevent the adhesion of bacteria on the surface of the coating film, and thus the spread of infectious diseases and the like. Can be prevented.
The paint formulation may contain other components other than the copolymer.
The other components are not particularly limited, but are, for example, highly hydrophilic polymers having ionicity such as hydroxyl groups, carboxyl groups, and amino groups, and among them, hydrophilic water-soluble such as polyvinyl alcohol type and polyvinyl alcohol / polyethylene glycol type. Resin: Acrylic resin, polyester resin, epoxy resin, urethane resin and the like are preferably mentioned. Further, the resin may be used alone or in combination of two or more. In addition, pigments, organic solvents, curing catalysts, dispersants, desiccants, antioxidants, surfactants, defoamers, dehydrators, leveling agents, anti-settling agents, anti-sagging agents, algae-proofing agents, fungicides, Preservatives, ultraviolet absorbers, light stabilizers and the like may be appropriately added as needed. The paint composition (paint composition) of the present invention can be prepared by mixing various components appropriately selected as necessary.
以下に実施例を掲げて本発明を更に詳細に説明するが、本発明はこれらの実施例のみに限定されるものではない。なお、特に断りのない限り、「部」は「質量部」を、「％」は「質量％」を意味するものとする。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass".
＜共重合体の重量平均分子量測定＞
共重合体の重量平均分子量（Ｍｗ）は、ＧＰＣ（ゲルパーミュエーションクロマトグラフィー）により測定した。
測定条件、装置などは以下の通りである。
装置：東ソー社製　ＥｃｏＳＥＣ　ＨＬＣ－８３２０ＧＰＣ
検出器：示差屈折率計（ＲＩ）検出器
カラム：東ソー社製　ＴＳＫｇｅｌ　α－Ｍ、α－２５００
カラム温度：４０℃
流速：０．４ｍＬ／ｍｉｎ
注入量：２０μＬ（試料濃度０．４ｗｔ％の溶離液調製溶液）
検量線：ジーエルサイエンス社製　ポリエチレングリコール
ＧＰＣソフト：東ソー社製　ＥｃｏＳＥＣ－ＷＳ
溶離液：０．５Ｍ酢酸＋０．２Ｍ硝酸Ｎａ／アセトニトリル＝５０／５０（ｖ／ｖ） <Measurement of weight average molecular weight of copolymer>
The weight average molecular weight (Mw) of the copolymer was measured by GPC (gel permeation chromatography).
The measurement conditions, equipment, etc. are as follows.
Equipment: Tosoh EcoSEC HLC-8320GPC
Detector: Differential Refractometer (RI) Detector Column: Tosoh TSKgel α-M, α-2500
Column temperature: 40 ° C
Flow velocity: 0.4 mL / min
Injection volume: 20 μL (sample concentration 0.4 wt% eluent preparation solution)
Calibration curve: Polyethylene glycol GPC software manufactured by GL Sciences: EcoSEC-WS manufactured by Tosoh Corporation
Eluent: 0.5M acetic acid + 0.2M Na nitrate / acetonitrile = 50/50 (v / v)
実施例１
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、エタノール９０ｇを仕込み、攪拌下、７０℃に昇温した。次いで攪拌下、７０℃一定状態の重合反応系中に、メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数２３、新中村化学工業社製の商品名「Ｍ－２３０Ｇ」、以下、ＰＧＭ２３Ｅともいう）９１ｇ、イオン交換水３０．３ｇからなるモノマー溶液１；ベンジルメタクリレート（以下、ＢｎＭＡともいう。溶解性パラメータ：９．８）３９ｇからなるモノマー溶液２；２，２’－アゾビス（２，４－ジメチルバレロニトリル）（富士フイルム和光純薬社製の商品名「Ｖ－６５」）の５％エタノール溶液１５．１ｇからなる開始剤水溶液をそれぞれ別々の滴下ノズルより滴下した。滴下時間に関して、モノマー溶液１と開始剤水溶液は同時に滴下を開始し、モノマー溶液１は１２０分間、モノマー溶液２と開始剤水溶液は１８０分間滴下した。
全滴下終了後、さらに６０分間反応溶液を７０℃に保持して熟成し、重合を完結させ、共重合体１を得た。
得られた共重合体１の固形分は４９．１％、重量平均分子量は２８５００であった。 Example 1
90 g of ethanol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 70 ° C. under stirring. Next, under stirring, in a polymerization reaction system in a constant state at 70 ° C., methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23, trade name “M-230G” manufactured by Shin-Nakamura Chemical Industry Co., Ltd., hereinafter also referred to as PGM23E). Monomer solution 1 consisting of 91 g and 30.3 g of ion-exchanged water; Monomer solution 2 consisting of 39 g of benzyl methacrylate (hereinafter, also referred to as BnMA; solubility parameter: 9.8); 2,2'-azobis (2,4-dimethyl) An initiator aqueous solution consisting of 15.1 g of a 5% ethanol solution of valeronitrile (trade name “V-65” manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added dropwise from separate dropping nozzles. Regarding the dropping time, the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the monomer solution 2 and the initiator aqueous solution were dropped for 180 minutes.
After the completion of all dropping, the reaction solution was kept at 70 ° C. for another 60 minutes for aging to complete the polymerization, and the copolymer 1 was obtained.
The solid content of the obtained copolymer 1 was 49.1%, and the weight average molecular weight was 28500.
実施例２
温度計、攪拌機、還流冷却器を備えたガラス製反応容器に、溶媒として２－プロパノール２０．０部、メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数２３モル、新中村化学工業社製の商品名「Ｍ－２３０Ｇ」）５５．７部、ベンジルメタクリレート２３．９部、重合開始剤として２，２’－アゾビス（２，４－ジメチルバレロニトリル）（富士フイルム和光純薬社製の商品名「Ｖ－６５」）０．４６１部を仕込んだ。攪拌下、反応容器内を５００ｍＬ／分で３０分間窒素置換した後、７０℃に昇温し、５時間引き続いて７０℃に温度を維持し、重合反応を完結させた。途中、２時間３０分、３時間、３時間３０分、４時間経過時において２，２’－アゾビス（４－メトキシ－２，４－ジメチルバレロニトリル）（富士フイルム和光純薬社製の商品名「Ｖ－７０」）０．５７２部ずつを添加した。重合反応完結後に室温まで冷却し、重量平均分子量（Ｍｗ）１５２２００の重合体の溶液を得た。エバポレーターで溶媒を除き、水で１０倍に希釈することで共重合体２の水溶液を得た。 Example 2
In a glass reaction vessel equipped with a thermometer, agitator, and a reflux cooler, 20.0 parts of 2-propanol as a solvent, methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23 mol, product manufactured by Shin-Nakamura Chemical Industries, Ltd.) Name "M-230G") 55.7 parts, benzyl methacrylate 23.9 parts, 2,2'-azobis (2,4-dimethylvaleronitrile) as a polymerization initiator (trade name "Fujifilm Wako Pure Chemical Industries, Ltd." V-65 ") 0.461 copies were charged. After stirring, the inside of the reaction vessel was replaced with nitrogen at 500 mL / min for 30 minutes, the temperature was raised to 70 ° C., and the temperature was maintained at 70 ° C. for 5 hours thereafter to complete the polymerization reaction. 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile) (trade name manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) after 2 hours 30 minutes, 3 hours, 3 hours 30 minutes, and 4 hours on the way. "V-70") 0.572 parts each was added. After the polymerization reaction was completed, the mixture was cooled to room temperature to obtain a solution of a polymer having a weight average molecular weight (Mw) of 152200. The solvent was removed with an evaporator, and the mixture was diluted 10-fold with water to obtain an aqueous solution of the copolymer 2.
実施例３
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、エタノール９０ｇを仕込み、攪拌下、７０℃に昇温した。次いで攪拌下、７０℃一定状態の重合反応系中に、メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数２３、新中村化学工業社製の商品名「Ｍ－２３０Ｇ」）６９．７ｇ、メタクリル酸（以下、ＭＡＡともいう。）１４．１ｇ、イオン交換水２２．４ｇからなるモノマー溶液１；ベンジルメタクリレート３６ｇからなるモノマー溶液２；２，２’－アゾビス（２，４－ジメチルバレロニトリル）（富士フイルム和光純薬社製の商品名「Ｖ－６５」）の５％エタノール溶液１３ｇからなる開始剤水溶液をそれぞれ別々の滴下ノズルより滴下した。滴下時間に関して、モノマー溶液１と開始剤水溶液は同時に滴下を開始し、モノマー溶液１は１２０分間、モノマー溶液２と開始剤水溶液は１８０分間滴下した。
全滴下終了後、さらに６０分間反応溶液を７０℃に保持して熟成し、重合を完結させ、共重合体３を得た。
得られた共重合体３の固形分は４７．８％、重量平均分子量は７７８００であった。 Example 3
90 g of ethanol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 70 ° C. under stirring. Next, under stirring, 69.7 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added, trade name "M-230G" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 69.7 g, and methacrylic acid were placed in a polymerization reaction system at a constant temperature of 70 ° C. (Hereinafter, also referred to as MAA) Monomer solution 1 consisting of 14.1 g and ion-exchanged water 22.4 g; Monomer solution 2 consisting of 36 g of benzyl methacrylate 2; 2,2'-azobis (2,4-dimethylvaleronitrile) (Fuji) An aqueous initiator solution consisting of 13 g of a 5% ethanol solution (trade name “V-65”) manufactured by Polymer Wako Junyaku Co., Ltd. was added dropwise from separate dropping nozzles. Regarding the dropping time, the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the monomer solution 2 and the initiator aqueous solution were dropped for 180 minutes.
After the completion of all dropping, the reaction solution was kept at 70 ° C. for another 60 minutes for aging to complete the polymerization, and the copolymer 3 was obtained.
The solid content of the obtained copolymer 3 was 47.8%, and the weight average molecular weight was 77,800.
実施例４
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、エタノール９０ｇを仕込み、攪拌下、７０℃に昇温した。次いで攪拌下、７０℃一定状態の重合反応系中に、メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数４、以下、ＰＧＭ４Ｅともいう）９９．６ｇ、イオン交換水３３．２ｇからなるモノマー溶液１；ベンジルメタクリレート２０．４ｇからなるモノマー溶液２；２，２’－アゾビス（２，４－ジメチルバレロニトリル）（富士フイルム和光純薬社製の商品名「Ｖ－６５」）の５％エタノール溶液２３．７ｇからなる開始剤水溶液をそれぞれ別々の滴下ノズルより滴下した。滴下時間に関して、モノマー溶液１と開始剤水溶液は同時に滴下を開始し、モノマー溶液１は１２０分間、モノマー溶液２と開始剤水溶液は１８０分間滴下した。
全滴下終了後、さらに６０分間反応溶液を７０℃に保持して熟成し、重合を完結させ、共重合体４を得た。
得られた共重合体４の固形分は４５．７％、重量平均分子量は１８９００であった。 Example 4
90 g of ethanol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 70 ° C. under stirring. Next, under stirring, a monomer solution 1 composed of 99.6 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added, hereinafter also referred to as PGM4E) and 33.2 g of ion-exchanged water in a polymerization reaction system in a constant state at 70 ° C. Monomer solution 2 consisting of 20.4 g of benzyl methacrylate 2; 5% ethanol solution of 2,2'-azobis (2,4-dimethylvaleronitrile) (trade name "V-65" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 23 An aqueous initiator solution consisting of .7 g was added dropwise from separate dropping nozzles. Regarding the dropping time, the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the monomer solution 2 and the initiator aqueous solution were dropped for 180 minutes.
After the completion of all dropping, the reaction solution was kept at 70 ° C. for another 60 minutes for aging to complete the polymerization, and a copolymer 4 was obtained.
The solid content of the obtained copolymer 4 was 45.7%, and the weight average molecular weight was 18900.
実施例５
温度計、還流冷却器、攪拌機を備えたガラス製のセパラブルフラスコに、エタノール９０ｇを仕込み、攪拌下、７０℃に昇温した。次いで攪拌下、７０℃一定状態の重合反応系中に、メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数９、以下、ＰＧＭ９Ｅともいう）８４ｇ、イオン交換水２８ｇからなるモノマー溶液１；ベンジルメタクリレート３６ｇからなるモノマー溶液２；２，２’－アゾビス（２，４－ジメチルバレロニトリル）（富士フイルム和光純薬社製の商品名「Ｖ－６５」）の５％エタノール溶液１８．６ｇからなる開始剤水溶液をそれぞれ別々の滴下ノズルより滴下した。滴下時間に関して、モノマー溶液１と開始剤水溶液は同時に滴下を開始し、モノマー溶液１は１２０分間、モノマー溶液２と開始剤水溶液は１８０分間滴下した。
全滴下終了後、さらに６０分間反応溶液を７０℃に保持して熟成し、重合を完結させ、共重合体５を得た。
得られた共重合体５の固形分は４７．８％、重量平均分子量は２４５００であった。 Example 5
90 g of ethanol was placed in a glass separable flask equipped with a thermometer, a reflux condenser, and a stirrer, and the temperature was raised to 70 ° C. under stirring. Then, under stirring, in a polymerization reaction system in a constant state at 70 ° C., a monomer solution 1 consisting of 84 g of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added, hereinafter also referred to as PGM9E) and 28 g of ion-exchanged water; 36 g of benzyl methacrylate. Monomer solution 2; Initiator consisting of 18.6 g of 5% ethanol solution of 2,2'-azobis (2,4-dimethylvaleronitrile) (trade name "V-65" manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) The aqueous solution was dropped from separate dropping nozzles. Regarding the dropping time, the monomer solution 1 and the initiator aqueous solution started dropping at the same time, the monomer solution 1 was dropped for 120 minutes, and the monomer solution 2 and the initiator aqueous solution were dropped for 180 minutes.
After the completion of all dropping, the reaction solution was kept at 70 ° C. for another 60 minutes for aging to complete the polymerization, and a copolymer 5 was obtained.
The solid content of the obtained copolymer 5 was 47.8%, and the weight average molecular weight was 24500.
比較例１
温度計、攪拌機、滴下装置、窒素導入管及び還流冷却装置を備えたガラス製反応装置に水４８０部を仕込み、２００ｒｐｍで攪拌下、反応容器内を窒素置換しながら８０℃まで加熱した。メトキシポリエチレングリコールモノメタクリレート（エチレンオキシドの平均付加モル数２３、新中村化学工業社製の商品名「Ｍ－２３０Ｇ」）４０１．３部、メタクリル酸７８．７部、水１２０部及び連鎖移動剤として３－メルカプトプロピオン酸（以下、ＭＰＡともいう）５．４７部を混合したモノマー水溶液を４時間、過硫酸アンモニウム（以下、ＡＰＳともいう）５．５２部及び水１１０．６部を混合した水溶液を５時間かけて同時刻から滴下した。滴下終了後、１時間引き続いて８０℃に温度を維持し、重合反応を完結させ、重量平均分子量１７０００の比較共重合体１の水溶液を得た。 Comparative Example 1
480 parts of water was charged into a glass reactor equipped with a thermometer, a stirrer, a dropping device, a nitrogen introduction tube and a reflux cooling device, and the inside of the reaction vessel was heated to 80 ° C. while stirring at 200 rpm. 401.3 parts of methoxypolyethylene glycol monomethacrylate (average number of moles of ethylene oxide added 23, trade name "M-230G" manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), 78.7 parts of methacrylic acid, 120 parts of water and 3 as a chain transfer agent. -A monomer aqueous solution containing 5.47 parts of mercaptopropionic acid (hereinafter, also referred to as MPA) for 4 hours, and an aqueous solution containing 5.52 parts of ammonium persulfate (hereinafter, also referred to as APS) and 110.6 parts of water for 5 hours. It was dropped from the same time. After completion of the dropping, the temperature was continuously maintained at 80 ° C. for 1 hour to complete the polymerization reaction, and an aqueous solution of the comparative copolymer 1 having a weight average molecular weight of 17,000 was obtained.
比較例２
攪拌機、冷却管、温度計、窒素導入管、滴下ロートを備えた、５００ｍｌセパラブルフラスコに、８０質量％の３－メチル－３－ブテン－１－オールにエチレンオキシドを平均５０モル付加した不飽和ポリアルキレングリコールエーテル（以下、ＭＢ－５０ともいう。）ＭＢ－５０水溶液：２６０．２ｇ、イオン交換水：６６．６ｇを仕込み、窒素置換後、攪拌しながら５８℃まで昇温した。所定の温度になった時点で、３５質量％の過酸化水素水（Ｈ２Ｏ２）：０．５７ｇを一括で投入した。その後、１００質量％のアクリル酸（以下、ＡＡともいう。）：１４．８ｇ、１．６質量％のＬ－アスコルビン酸（以下、Ｌ－Ａｓともいう。）水溶液：１６．７ｇ、３．５質量％のＭＰＡ水溶液：１７．４ｇをそれぞれ滴下した。ただし、ＡＡは１８０分かけて滴下し、Ｌ－Ａｓ水溶液とＭＰＡ水溶液は２１０分かけて滴下した。Ｌ－Ａｓ水溶液の滴下終了後、同温度で６０分間熟成し、重合を完結させ、重合後、４９質量％のＮａＯＨ水溶液：３．６９ｇを加えることで、比較共重合体２の水溶液を得た。得られた水溶性共重合体の重量平均分子量は２５７００、固形分は５９．７質量％であった。 Comparative Example 2
Unsaturated poly with an average of 50 mol of ethylene oxide added to 80% by mass of 3-methyl-3-butene-1-ol in a 500 ml separable flask equipped with a stirrer, a cooling tube, a thermometer, a nitrogen introduction tube, and a dropping funnel. An alkylene glycol ether (hereinafter, also referred to as MB-50) MB-50 aqueous solution: 260.2 g and ion-exchanged water: 66.6 g were charged, and after nitrogen substitution, the temperature was raised to 58 ° C. with stirring. When the temperature reached a predetermined temperature, 0.57 g of 35% by mass hydrogen peroxide solution (H 2 O 2 ) was added all at once. Then, 100% by mass acrylic acid (hereinafter, also referred to as AA): 14.8 g, 1.6% by mass L-ascorbic acid (hereinafter, also referred to as LAs) aqueous solution: 16.7 g, 3.5. 17.4 g of a mass% MPA aqueous solution was added dropwise. However, AA was added dropwise over 180 minutes, and the L'As aqueous solution and the MPA aqueous solution were added dropwise over 210 minutes. After completion of dropping the L—As aqueous solution, the mixture was aged at the same temperature for 60 minutes to complete the polymerization, and after the polymerization, a 49% by mass NaOH aqueous solution: 3.69 g was added to obtain an aqueous solution of the comparative copolymer 2. .. The weight average molecular weight of the obtained water-soluble copolymer was 25,700, and the solid content was 59.7% by mass.
洗浄力評価
実施例１～５、比較例１、２で製造した共重合体１～５、比較共重合体１、２及び比較例３としてブランクについて、以下の方法により洗浄力評価を行った。結果を表１に示す。
＜布の前処理方法＞
Ｔｅｓｔｆａｂｉｒｉｃ社製　Ｓｔｙｌｅ７０３（ポリエステル繊維）を５×５ｃｍに裁断したものを用意した。実施例、比較例で得られた共重合体を２５ｐｐｍに調整した水溶液３００ｇを準備し、マグネティックスターラーで撹拌しながら、上記布５ｇを添加し、１０分間撹拌した。１０分後、布の重量の３倍になるように脱水し、１日間風乾した。
＜汚染布の作成＞
オリーブオイル６１．５ｇ、オレイン酸３７ｇ、酸化鉄（ＩＩＩ）１ｇ、オイルレッド０．５ｇを混合し、油脂汚染液を作成した。この汚染液を５０μＬ、上記前処理方法１で得られたポリマー処理布に滴下し、１時間放置した後、余計な油脂を濾紙で挟んでふき取り、汚染布を作成した。
＜洗浄力評価＞
（１）－１：硬度母液の調製
塩化カルシウム２水和物８．３９ｇ、塩化マグネシウム６水和物２．９ｇをビーカーにはかりとり、イオン交換水を加え１０００ｇとした。
（１）－２：硬水の調製
炭酸水素ナトリウム１．５４ｇ、０．１Ｎ塩化水素１０ｇ、硬度母液（１）－１；２００ｇをビーカーに入れてイオン交換水で希釈して２００００ｇとした。
（１）－３：界面活性剤水溶液の作成
ペレックスＧ－６５（花王社製）１３．８５ｇとエマルゲン１０８（花王社製）３ｇをビーカーに測りとり、イオン交換水を加えて２００ｇとし、界面活性剤溶液を調整した。
（２）：洗浄力試験
（１）－３の界面活性剤水溶液１６．６７ｇと（１）－２の硬水を混合し、４０００ｇの洗浄液を作成した。ターゴットメーターを２５℃にセットし、洗浄液５００ｇをポットにいれた。予め色差計（日本電色工業社製：ＳＥ－６０００）で反射率を測定した汚染布５枚、浴比調整布とを合わせて１６．６７ｇポットに入れて、１２０ｒｐｍで１０分間撹拌して洗浄した。ポットの水を捨て、すすぎ１回を行った後、布を脱水し１日間風乾させた。
風乾後、色差計にて再度、白布の反射率を測定し、下記式により洗浄率を求めた。得られた洗浄率に基づき、以下の判定基準で洗浄力を評価した。結果を表１に示す。
◎：洗浄率９０％以上
〇：洗浄率５０％以上、９０％未満
×：洗浄率５０％未満 Detergency Evaluation The detergency of the copolymers 1 to 5, Comparative Copolymers 1 and 2, and the blanks produced in Comparative Examples 1 and 2 and Comparative Example 3 were evaluated by the following methods. The results are shown in Table 1.
<Cloth pretreatment method>
A style 703 (polyester fiber) manufactured by Testfabric was cut into 5 x 5 cm and prepared. 300 g of an aqueous solution prepared by adjusting the copolymers obtained in Examples and Comparative Examples to 25 ppm was prepared, 5 g of the above cloth was added while stirring with a magnetic stirrer, and the mixture was stirred for 10 minutes. After 10 minutes, it was dehydrated to 3 times the weight of the cloth and air-dried for 1 day.
<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. 50 μL of this contaminated liquid was dropped onto the polymer-treated cloth obtained in the above pretreatment method 1, left to stand for 1 hour, and then excess oil and fat was sandwiched between filter papers and wiped off to prepare a contaminated cloth.
<Detergency evaluation>
(1) -1: Preparation of hardness mother liquor 8.39 g of calcium chloride dihydrate and 2.9 g of magnesium chloride hexahydrate were weighed in a beaker, and ion-exchanged water was added to make 1000 g.
(1) -2: Preparation of hard water 1.54 g of sodium hydrogen carbonate, 10 g of 0.1N hydrogen chloride, and 200 g of the hardness mother liquor (1) -1; 200 g were placed in a beaker and diluted with ion-exchanged water to make 20000 g.
(1) -3: Preparation of aqueous surfactant solution Weigh 13.85 g of Perex G-65 (manufactured by Kao Corporation) and 3 g of Emargen 108 (manufactured by Kao Corporation) in a beaker, and add ion-exchanged water to make 200 g. The agent solution was adjusted.
(2): Detergency test 16.67 g of the surfactant aqueous solution of (1) -3 and the hard water of (1) -2 were mixed to prepare 4000 g of a cleaning solution. The turgot meter was set at 25 ° C., and 500 g of the cleaning liquid was put into a pot. Put 5 contaminated cloths whose reflectance was measured in advance with a color difference meter (manufactured by Nippon Denshoku Kogyo Co., Ltd .: SE-6000) and a bath ratio adjusting cloth in a 16.67 g pot, and stir at 120 rpm for 10 minutes to wash. did. After discarding the water in the pot and rinsing once, the cloth was dehydrated and air-dried for 1 day.
After air-drying, the reflectance of the white cloth was measured again with a color difference meter, and the cleaning rate was calculated by the following formula. Based on the obtained cleaning rate, the cleaning power was evaluated according to the following criteria. The results are shown in Table 1.
⊚: Cleaning rate 90% or more 〇: Cleaning rate 50% or more, less than 90% ×: Cleaning rate less than 50%
Figure JPOXMLDOC01-appb-M000011
Figure JPOXMLDOC01-appb-M000011
Figure JPOXMLDOC01-appb-T000012
Figure JPOXMLDOC01-appb-T000012
微生物付着評価
菌株はＳｔａｐｈｙｌｏｃｏｃｃｕｓ　ａｕｒｅｕｓ　ＮＢＲＣ１２７３２株を用いた。培養試験管に入れたＢａｃｔｏ（登録商標）Ｂｒａｉｎ　Ｈｅａｒｔ　Ｉｎｆｕｓｉｏｎ培地（日本ベクトン・ディッキンソン株式会社製　製品番号２３７５００）５ｍＬに対して、凍結保存株から植菌して３７℃、３００ｒｐｍで撹拌（振とう培養機：高崎科学器械株式会社製、ＴＸＹ－１６Ｒ－３Ｆ）しながら復元培養したのち、継代培養（２０ｍＬ）を１８時間実施した。その後、５０００×ｇの遠心力で、５分間遠心して菌体を回収したのち、上清を除きＰＢＳ（－）１５ｍＬで洗浄を行なった。この洗浄作業を計２回実施した。別途作成しておいたＯＤ６６０－生菌数の換算式を用いて、菌液が１×１０９ｃｅｌｌｓ／ｍＬとなるようＰＢＳ（－）で調製し、６穴マイクロプレート（ＩＷＡＫＩ社製　製品コード３８１０－００６）に３ｍＬ／ウェルで添加した。続いて、２×２ｃｍ２四方のポリマーコートフィルムをウェルに入れた菌液に浸漬し、３７℃、３．５時間静置した。その後、フィルムをピンセットでゆっくりと取り出し、別途用意しておいたＰＢＳ（－）３０ｍＬにゆっくりとディッピングを５回行った。別途用意した６穴マイクロプレートに洗浄したフィルムを移し、２．５％グルタルアルデヒド水溶液（富士フイルム和光純薬社製、販売元コード０７２－０２２６２、ＰＢＳ（－）で希釈）を３ｍＬ／ウェルでゆっくりと添加し、２時間常温静置することで固定化処理を実施した。続いてフィルムをＰＢＳ（－）３０ｍＬにゆっくりとディッピングを１回行った。その後、凍結乾燥を実施して脱水処理を実施した。フィルム中央部分０．７５×０．７５ｃｍ２四方分を裁断してＳＥＭ台に乗せて金蒸着（ＪＥＯＬ社製、Ｓｍａｒｔ　ｃｏａｔｅｒ）したのち、ＳＥＭ（日本電子社製、ＪＳＭ７６００Ｆ）でフィルム全体を観察後、平均的な５箇所の撮影を実施した。得られたＳＥＭ写真に対してＩｍａｇｅＪソフトウェアを用いて細菌の表面被覆率を算出し、ｔ検定を実施した。 As the microbial adhesion evaluation strain, Staphylococcus aureus NBRC12732 strain was used. Inoculate 5 mL of Bacto (registered trademark) Brain Heart Infusion medium (Product No. 237500 manufactured by Becton Dickinson Corporation, Japan) in a culture test tube from a cryopreservation strain and stir at 37 ° C. and 300 rpm (shaking culture). Machine: After reconstructive culture while (TXY-16R-3F, manufactured by Takasaki Kagaku Kikai Co., Ltd.), subculture (20 mL) was carried out for 18 hours. Then, the cells were collected by centrifugation for 5 minutes with a centrifugal force of 5000 × g, and then the supernatant was removed and the cells were washed with 15 mL of PBS (−). This cleaning work was carried out twice in total. Using the OD660-viable cell count conversion formula prepared separately, prepare the bacterial solution with PBS (-) so that the bacterial solution becomes 1 × 10 9 cells / mL, and prepare a 6-well microplate (IWAKI product code 3810). -006) was added at 3 mL / well. Subsequently, a 2 × 2 cm 2 square polymer coated film was immersed in a bacterial solution in a well and allowed to stand at 37 ° C. for 3.5 hours. Then, the film was slowly taken out with tweezers, and dipping was slowly performed 5 times in 30 mL of PBS (−) prepared separately. Transfer the washed film to a separately prepared 6-well microplate, and slowly dilute a 2.5% glutaraldehyde aqueous solution (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., distributor code 072-02262, diluted with PBS (-)) at 3 mL / well. Was added, and the film was allowed to stand at room temperature for 2 hours to carry out the immobilization treatment. The film was then slowly dip into 30 mL of PBS (−) once. Then, freeze-drying was carried out to carry out dehydration treatment. After cutting two squares of 0.75 x 0.75 cm in the center of the film and placing them on an SEM stand for gold deposition (Smart coater manufactured by JEOL Ltd.), and then observing the entire film with SEM (JSM7600F manufactured by JEOL Ltd.). , An average of 5 places were photographed. The surface coverage of bacteria was calculated for the obtained SEM photographs using ImageJ software, and t-test was performed.
＜実施例６＞
スピンコーター（ＭＩＫＡＳＡ　ＣＯ．ＬＴＤ．、ＳＰＩＮ　ＣＯＡＴＥＲ　１Ｈ－Ｄ７）を用いて、易接着ＰＥＴフィルム（東洋紡株式会社製　コスモシャイン（登録商標）Ａ４１００　♯１２５）に対して、１（ｗ／ｗ）％実施例１のポリマー溶液（７５（ｗ／ｗ）％エタノール水溶液で希釈）を滴下、スピンコート後、一晩風乾して成膜した。作製したフィルムを用いて、微生物付着評価を実施した。その結果を表２及び図１に示す。 <Example 6>
Using a spin coater (MIKASA CO. LTD., SPIN COATER 1H-D7), 1 (w / w)% was applied to the easy-adhesion PET film (Cosmo Shine (registered trademark) A4100 # 125 manufactured by Toyo Boseki Co., Ltd.). The polymer solution of Example 1 (diluted with a 75 (w / w)% ethanol aqueous solution) was added dropwise, spin-coated, and then air-dried overnight to form a film. Microbial adhesion evaluation was carried out using the prepared film. The results are shown in Table 2 and FIG.
＜比較例４＞
易接着ＰＥＴフィルム（東洋紡株式会社製　コスモシャイン（登録商標）Ａ４１００　♯１２５）を用いた。作製したフィルムを用いて、微生物付着評価を実施した。その結果を表２及び図１に示す。 <Comparative example 4>
An easy-adhesive PET film (Cosmo Shine (registered trademark) A4100 # 125 manufactured by Toyobo Co., Ltd.) was used. Microbial adhesion evaluation was carried out using the prepared film. The results are shown in Table 2 and FIG.
＜比較例５＞
スピンコーター（ＭＩＫＡＳＡ　ＣＯ．ＬＴＤ．、ＳＰＩＮ　ＣＯＡＴＥＲ　１Ｈ－Ｄ７）を用いて、易接着ＰＥＴフィルム（東洋紡株式会社製　コスモシャイン（登録商標）Ａ４１００　♯１２５）に対して、１（ｗ／ｗ）％に希釈したＴｅｘｃａｒｅ（登録商標）２６０（クラリアントジャパン株式会社製）溶液（７５（ｗ／ｗ）％エタノール水溶液で希釈）を滴下、スピンコート後、一晩風乾して成膜した。作製したフィルムを用いて、微生物付着評価を実施した。その結果を表２及び図１に示す。 <Comparative example 5>
Using a spin coater (MIKASA CO. LTD., SPIN COATER 1H-D7), 1 (w / w)% of the easy-adhesive PET film (Cosmo Shine (registered trademark) A4100 # 125 manufactured by Toyo Boseki Co., Ltd.) A diluted Texas (registered trademark) 260 (manufactured by Clariant Japan Co., Ltd.) solution (diluted with a 75 (w / w)% ethanol aqueous solution) was added dropwise, spin-coated, and then air-dried overnight to form a film. Microbial adhesion evaluation was carried out using the prepared film. The results are shown in Table 2 and FIG.
Figure JPOXMLDOC01-appb-T000013
Figure JPOXMLDOC01-appb-T000013

Claims (8)

  1. 水酸基、オキシアルキレン基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有する単量体（Ａ）由来の構造単位（ａ）と、芳香族基含有単量体（Ｂ）由来の構造単位（ｂ）とを有する共重合体を含む、洗剤用添加剤。 A structure derived from a monomer (A) having at least one hydrophilic group selected from the group consisting of a hydroxyl group, an oxyalkylene group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group thereof. An additive for detergents, which comprises a copolymer having a unit (a) and a structural unit (b) derived from an aromatic group-containing monomer (B).
  2. 前記共重合体は、構造単位（ａ）が、下記式（１）；
    Figure JPOXMLDOC01-appb-C000001
     （式中、Ｒ１、Ｒ２及びＲ３は、同一又は異なって、水素原子、若しくは、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基、又は、該親水性基を有していてもよい炭素数１～３のアルキル基を表す。Ｚは、水素原子、メチル基、又は、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有する炭素数２～３０の炭化水素基を表す。Ａは、同一又は異なって、水酸基並びにカルボキシル基、スルホン酸基、リン酸基、アミノ基及びこれらの塩の基からなる群より選択される少なくとも１種の親水性基を有していてもよいアルキレン基を表す。ｎは、（ＡＯ）の平均付加モル数を表し、０～２００である。ｘ、ｗは、同一又は異なって、０～４の数を表す。ｙ、ｖは、同一又は異なって、０又は１を表す。）で表される、請求項１に記載の洗剤用添加剤。     The structural unit (a) of the copolymer is the following formula (1);
    Figure JPOXMLDOC01-appb-C000001
     (In the formula, R 1 , R 2 and R 3 are the same or different and are selected from the group consisting of a hydrogen atom or a hydroxyl group and a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. Represents at least one hydrophilic group, or an alkyl group having 1 to 3 carbon atoms which may have the hydrophilic group. Z is a hydrogen atom, a methyl group, a hydroxyl group, and a carboxyl group. Represents a hydrocarbon group having 2 to 30 carbon atoms having at least one hydrophilic group selected from the group consisting of a sulfonic acid group, a phosphoric acid group, an amino group and a group of salts thereof. A is the same or different. Represents an alkylene group which may have at least one hydrophilic group selected from the group consisting of a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group and a group thereof. Represents the average number of added moles of (AO) and is 0 to 200. X and w represent the same or different numbers 0 to 4. y and v represent the same or different, 0 or 1 The detergent additive according to claim 1, which is represented by (1).
  3. 前記芳香族基含有単量体（Ｂ）は、スチレン、α－メチルスチレン、ビニルトルエン、インデン、ビニルナフタレン、フェニルマレイミド、ビニルアニリン、スチレンスルホン酸及び下記式（３）；
    Figure JPOXMLDOC01-appb-C000002
     （式中、Ｒ４、Ｒ５、Ｒ６は、同一又は異なって、水素原子又は炭素数１～３のアルキル基を表す。Ｒ７は、芳香族基を表す。）で表される化合物からなる群より選択される少なくとも１種である、請求項１又は２に記載の洗剤用添加剤。     The aromatic group-containing monomer (B) includes styrene, α-methylstyrene, vinyltoluene, inden, vinylnaphthalene, phenylmaleimide, vinylaniline, styrenesulfonic acid and the following formula (3);
    Figure JPOXMLDOC01-appb-C000002
     (In the formula, R 4 , R 5 , and R 6 represent the same or different alkyl groups having a hydrogen atom or 1 to 3 carbon atoms . R 7 represents an aromatic group.) The detergent additive according to claim 1 or 2, which is at least one selected from the group.
  4. 請求項１～３のいずれかに記載の共重合体を含む、ソイルリリース剤。 A soil release agent containing the copolymer according to any one of claims 1 to 3.
  5. 請求項１～３のいずれかに記載の共重合体を含む、微生物付着防止剤。 An antimicrobial adhesion agent comprising the copolymer according to any one of claims 1 to 3.
  6. 請求項１～３のいずれかに記載の共重合体を含む、繊維処理剤。 A fiber treatment agent containing the copolymer according to any one of claims 1 to 3.
  7. 請求項１～３のいずれかに記載の共重合体を含む、水処理薬剤配合物。 A water treatment drug formulation containing the copolymer according to any one of claims 1 to 3.
  8. 請求項１～３のいずれかに記載の共重合体を含む、塗料配合物。 A paint formulation comprising the copolymer according to any one of claims 1 to 3.
PCT/JP2020/036911 2019-09-30 2020-09-29 Copolymer-containing detergent additive, soil release agent, microbial attachment inhibitor, fiber treatment agent, water treatment agent formulation, and coating formulation WO2021065910A1 (en)

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