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WO2021065910A1 - Additif détergent contenant un copolymère, agent antisalissure, inhibiteur de fixation microbienne, agent de traitement de fibre, formulation d'agent de traitement de l'eau et formulation de revêtement - Google Patents

Additif détergent contenant un copolymère, agent antisalissure, inhibiteur de fixation microbienne, agent de traitement de fibre, formulation d'agent de traitement de l'eau et formulation de revêtement Download PDF

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Publication number
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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Japanese (ja)
Inventor
尊子 張替
竜佑 金尾
勇樹 牧野
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Nippon Shokubai Co Ltd
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Nippon Shokubai Co Ltd
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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

La présente invention concerne un additif détergent qui contient un copolymère qui présente un meilleur pouvoir détergent que les polymères classiques. La présente invention concerne un additif détergent qui contient un copolymère présentant un motif structural (a) dérivé d'un monomère (A) qui présente un groupe hydroxyle, un groupe oxyalkylène et au moins un groupe hydrophile choisi dans le groupe constitué par un groupe carboxyle, un groupe acide sulfonique, un groupe acide phosphorique, un groupe amino et des groupes qui sont des sels correspondants et présentant un motif structural (b) dérivé d'un monomère (B) contenant un groupe aromatique.
PCT/JP2020/036911 2019-09-30 2020-09-29 Additif détergent contenant un copolymère, agent antisalissure, inhibiteur de fixation microbienne, agent de traitement de fibre, formulation d'agent de traitement de l'eau et formulation de revêtement Ceased WO2021065910A1 (fr)

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JP2022161408A (ja) * 2021-04-09 2022-10-21 株式会社日本触媒 血液または血小板保存容器
CN115233339A (zh) * 2022-07-11 2022-10-25 东华大学 一种高亲水性聚丙烯腈纺丝原液的制备方法
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