WO2021071078A1 - Procédé de préparation de latex de copolymère à base de nitrile modifié par un acide carboxylique - Google Patents

Procédé de préparation de latex de copolymère à base de nitrile modifié par un acide carboxylique Download PDF

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WO2021071078A1
WO2021071078A1 PCT/KR2020/010680 KR2020010680W WO2021071078A1 WO 2021071078 A1 WO2021071078 A1 WO 2021071078A1 KR 2020010680 W KR2020010680 W KR 2020010680W WO 2021071078 A1 WO2021071078 A1 WO 2021071078A1
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monomer
carboxylic acid
weight
based copolymer
acid
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PCT/KR2020/010680
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English (en)
Korean (ko)
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김정은
김지현
권원상
장명수
오승환
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주식회사 엘지화학
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Priority claimed from KR1020200070902A external-priority patent/KR102492405B1/ko
Application filed by 주식회사 엘지화학 filed Critical 주식회사 엘지화학
Priority to CN202080006750.3A priority Critical patent/CN113195568B/zh
Priority to JP2021531132A priority patent/JP7161054B2/ja
Priority to US17/299,571 priority patent/US11965080B2/en
Publication of WO2021071078A1 publication Critical patent/WO2021071078A1/fr

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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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/12—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/02—Direct processing of dispersions, e.g. latex, to articles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L13/00—Compositions of rubbers containing carboxyl groups
    • C08L13/02—Latex
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • C08L9/02—Copolymers with acrylonitrile
    • C08L9/04—Latex

Definitions

  • the present invention relates to a method for preparing a carboxylic acid-modified nitrile-based copolymer latex, and more particularly, a method for preparing a carboxylic acid-modified nitrile-based copolymer latex, a copolymer latex prepared thereby, a latex composition for dip molding comprising the same And it relates to a molded article prepared from the latex composition for dip molding.
  • Disposable rubber gloves which are widely used in everyday life such as housework, food industry, electronics industry, medical field, etc., are made by dip molding of natural rubber or carboxylic acid-modified nitrile-based copolymer latex. Recently, carboxylic acid-modified nitrile-based gloves are in the spotlight in the disposable gloves market due to allergies and unstable supply and demand problems caused by natural proteins of natural rubber.
  • Latex having such high strength and excellent workability at the same time is required, but in reality, the strength and workability of gloves are in a trade-off relationship. It is the film formation speed of latex that determines the strength and workability of the gloves. If the film formation speed is fast, it has high strength, but the workability is poor, and if the film formation speed is slow, the workability is excellent, but low strength gloves are made. . Accordingly, it is required to develop a carboxylic acid-modified nitrile-based copolymer latex that can secure high tensile strength even if it is made thin in a high-speed production line and has excellent workability.
  • the present invention is capable of producing a molded article having high tensile strength and elongation even at a thin thickness, and a latex composition for dip molding excellent in workability, modified with carboxylic acid. It is to provide a nitrile-based copolymer latex.
  • a water-soluble monomer and an ethylenically unsaturated acid monomer are partially polymerized in water at the beginning of polymerization.
  • a carboxylic acid-modified nitrile-based copolymer latex having a carboxylic acid pKa in a specific range was prepared, and the prepared latex composition for dip molding comprising the carboxylic acid-modified nitrile-based copolymer latex has excellent workability.
  • the molded article manufactured from the dip molding latex composition has achieved excellent tensile strength.
  • the present invention comprises the step of emulsion polymerization of a monomer mixture containing a conjugated diene monomer, an ethylenically unsaturated nitrile monomer, and an ethylenically unsaturated acid monomer in the presence of a crosslinking agent containing glyoxal. It provides a method for producing a carboxylic acid-modified nitrile-based copolymer latex.
  • the present invention includes a carboxylic acid-modified nitrile-based copolymer latex copolymer comprising a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an ethylenically unsaturated nitrile-based monomer, a repeating unit derived from an ethylenically unsaturated acid monomer, and a glyoxal-derived moiety. It provides a carboxylic acid-modified nitrile-based copolymer latex.
  • the present invention is a carboxylic acid-modified nitrile-based copolymer comprising a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an ethylenically unsaturated nitrile-based monomer, a repeating unit derived from an ethylenically unsaturated acid monomer, a repeating unit derived from a water-soluble monomer, and a glyoxal-derived moiety.
  • a carboxylic acid-modified nitrile-based copolymer latex containing a coalescence and having a pKa of 8.5 to 9.5 is provided.
  • the present invention provides a latex composition for dip molding comprising the carboxylic acid-modified nitrile-based copolymer latex according to the present invention.
  • the present invention provides a dip molded article comprising a layer derived from the latex composition for dip molding according to the present invention.
  • a carboxylic acid-modified nitrile-based copolymer latex when preparing a carboxylic acid-modified nitrile-based copolymer latex, it is subjected to emulsion polymerization in the presence of a crosslinking agent containing glyoxal to form a uniform crosslinking site in the polymer, thereby obtaining a carboxylic acid-modified nitrile-based copolymer having improved crosslinking density.
  • a crosslinking agent containing glyoxal and a specific polymerization initiator and an initiator when preparing a carboxylic acid-modified nitrile-based copolymer latex in the presence of a crosslinking agent containing glyoxal and a specific polymerization initiator and an initiator when preparing a carboxylic acid-modified nitrile-based copolymer latex, a water-soluble monomer and an ethylenically unsaturated monomer are partially polymerized in water to be water-soluble at the beginning of polymerization.
  • a carboxylic acid-modified nitrile-based copolymer latex having a low pKa of carboxylic acid was prepared, and the dip molding latex composition comprising the prepared carboxylic acid-modified nitrile-based copolymer latex is excellent in workability, and the dip Molded articles made from the latex composition for molding can implement excellent tensile strength.
  • Example 1 is a graph showing a change in pH according to the amount of KOH input in Example 1 of the present invention.
  • FIG. 2 is a differential curve of the input amount of KOH according to the pH shown in FIG. 1.
  • the terms'derived repeating unit' and'derived part' may refer to a component, structure, or the substance itself originated from a substance, and as a specific example, the'derived repeating unit' is a monomer that is introduced during polymerization of a polymer. It may mean a repeating unit formed in the polymer by participating in the polymerization reaction, and the'derived part' may refer to a chain transfer agent introduced during polymerization of the polymer to participate in the polymerization reaction to induce a chain transfer reaction of the polymer.
  • the term'latex' may mean that a polymer or copolymer polymerized by polymerization is dispersed in water, and as a specific example, fine particles of a rubber polymer or rubber copolymer polymerized by emulsion polymerization It may mean that is present in a colloidal state and dispersed in water.
  • the term'derived layer' may refer to a layer formed from a polymer or a copolymer, and as a specific example, when manufacturing a dip molded article, the polymer or copolymer is attached, fixed, and/or polymerized on a dip mold to form a polymer or It may mean a layer formed from a copolymer.
  • a method for producing a carboxylic acid-modified nitrile-based copolymer latex is provided.
  • the manufacturing method of the carboxylic acid-modified nitrile-based copolymer latex is the step of emulsion polymerization of a monomer mixture containing a conjugated diene-based monomer, an ethylenically unsaturated nitrile-based monomer, and an ethylenically unsaturated acid monomer in the presence of a crosslinking agent containing glyoxal. It may be to include.
  • the conjugated diene-based monomer is 1,3-butadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 1,3-pentadiene, and It may include at least one selected from the group consisting of isoprene, and a specific example may be 1,3-butadiene or isoprene, and a more specific example may be 1,3-butadiene.
  • the content of the conjugated diene-based monomer may be 35% to 75% by weight, 40% to 75% by weight, or 45% to 70% by weight based on the total content of the monomer mixture, and within this range, the dip molded product is flexible. And, while having excellent touch and wearing feeling, there is an effect of excellent oil resistance and tensile strength.
  • the ethylenically unsaturated nitrile-based monomer is one selected from the group consisting of acrylonitrile, methacrylonitrile, fumaronitrile, ⁇ -chloronitrile and ⁇ -cyano ethyl acrylonitrile.
  • acrylonitrile methacrylonitrile
  • fumaronitrile ⁇ -chloronitrile
  • ⁇ -cyano ethyl acrylonitrile ⁇ -cyano ethyl acrylonitrile.
  • the content of the ethylenically unsaturated nitrile-based monomer may be 20 wt% to 50 wt%, 25 wt% to 45 wt%, or 25 wt% to 40 wt% based on the total content of the monomer mixture.
  • the dip-molded product is flexible, has excellent touch and fit, and has excellent oil resistance and tensile strength.
  • the ethylenically unsaturated acid monomer may be an ethylenically unsaturated monomer containing an acidic group such as a carboxyl group, a sulfonic acid group, and an acid anhydride group, and specific examples thereof include acrylic acid, methacrylic acid, itaconic acid, maleic acid, and Ethylenically unsaturated acid monomers such as fumaric acid; Polycarboxylic anhydrides such as maleic anhydride and citraconic anhydride; Ethylenically unsaturated sulfonic acid monomers such as styrene sulfonic acid; It may be one or more selected from the group consisting of ethylenically unsaturated polycarboxylic acid partial ester monomers such as monobutyl fumarate, monobutyl maleate and mono-2-hydroxypropyl maleic acid, and more specific examples of acrylic acid and methacrylic acid , Itaconic acid, maleic
  • the content of the ethylenically unsaturated acid monomer may be 2% to 15% by weight, 3% to 9% by weight, or 4% to 7% by weight based on the total content of the monomer mixture, and within this range, the dip
  • the molded article is flexible, has excellent fit, and has excellent polymerization stability and tensile strength.
  • the monomer mixture may include a water-soluble monomer.
  • the water-soluble monomer may react with the ethylenically unsaturated acid monomer to form a water-soluble oligomer in the presence of a crosslinking agent including glyoxal and a persulfate polymerization initiator and an initiator to be described later during polymerization of the carboxylic acid-modified nitrile-based copolymer. have.
  • the water-soluble monomer may include at least one selected from the group consisting of hydroxy ethyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, dimethylaminoethyl acrylate, and diethylaminoethyl methacrylate. have.
  • the content of the water-soluble monomer may be 0.1% to 10% by weight, 0.1% to 8% by weight, or 0.3% to 5% by weight based on the total content of the monomer mixture. Within this range, there is an effect of improving workability and polymerization stability.
  • the conjugated diene monomer by emulsion polymerization of a monomer mixture comprising the conjugated diene monomer, an ethylenically unsaturated nitrile monomer, and an ethylenically unsaturated acid monomer, the conjugated diene monomer, the ethylenically unsaturated nitrile monomer, and The ethylenically unsaturated acid monomer is copolymerized, and through this, a carboxylic acid-modified nitrile-based copolymer can be prepared.
  • the conjugated diene-based monomer, ethylenically unsaturated nitrile by emulsion polymerization of a monomer mixture containing the conjugated diene-based monomer, ethylenically unsaturated nitrile-based monomer, ethylenically unsaturated acid monomer, and water-soluble monomer.
  • a system monomer, an ethylenically unsaturated acid monomer, and a water-soluble monomer are copolymerized, and through this, a carboxylic acid-modified nitrile-based copolymer can be prepared.
  • the monomer mixture may further include an ethylenically unsaturated monomer formed of the ethylenically unsaturated nitrile-based monomer and another ethylenically unsaturated monomer copolymerizable with the ethylenically unsaturated acid monomer.
  • the ethylenically unsaturated monomer is a vinyl aromatic monomer selected from the group consisting of styrene, aryl styrene, and vinyl naphthalene; Fluoroalkyl vinyl ethers such as fluoro ethyl vinyl ether; (Meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethylol (meth)acrylamide, N-methoxy methyl (meth)acrylamide, and N-propoxy methyl (meth)acrylamide Ethylenically unsaturated amide monomers selected from the group consisting of; Non-conjugated diene monomers such as vinyl pyridine, vinyl norbornene, dicyclopentadiene, and 1,4-hexadiene; Methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, trifluor
  • the content of the ethylenically unsaturated monomer may be within 20% by weight, 0.01% by weight to 20% by weight, or 0.01% by weight to 15% by weight based on the total content of the monomer mixture, and within this range, the touch of the dip-molded product And excellent wearability, and excellent tensile strength.
  • the step of emulsion polymerization of a monomer mixture including the conjugated diene monomer, an ethylenically unsaturated nitrile monomer, and an ethylenically unsaturated acid monomer is performed in the presence of a crosslinking agent containing glyoxal, By forming a uniform crosslinking site in the carboxylic acid-modified nitrile-based copolymer, it is possible to improve the crosslinking density of the copolymer.
  • the content of a crosslinking agent including glyoxal as a crosslinking agent may be added in an amount of 0.1 parts by weight to 1 part by weight based on 100 parts by weight of the total monomer mixture.
  • a crosslinking agent containing glyoxal within the above range, the degree of crosslinking between particles of the latex is improved, thereby further improving the strength of the molded article including the latex.
  • the step of emulsion polymerization of a monomer mixture including the conjugated diene-based monomer, ethylenically unsaturated nitrile-based monomer, ethylenically unsaturated acid monomer, and water-soluble monomer may include sodium persulfate, potassium persulfate, And a persulfate-based polymerization initiator comprising at least one selected from the group consisting of ammonium persulfate; It may be carried out in the presence of an initiator including at least one selected from the group consisting of hydroperoxide, ferrous sulfate, and sodium metabisulfite, and a crosslinking agent including glyoxal.
  • sulfate ion radicals are converted into hydroxy radicals in the presence of water. Since the hydroxy radical is hydrophobic compared to the sulfate ion radical, polymerization proceeds in the particles, and in this case, the formation of oligomers of the ethylenic unsaturated acid monomer and the water-soluble monomer is suppressed.
  • a persulfate initiator together with an initiator including at least one selected from the group consisting of hydroperoxide, ferrous sulfate and sodium metabisulfite, and a crosslinking agent including glyoxal, hydrophilicity
  • an initiator including at least one selected from the group consisting of hydroperoxide, ferrous sulfate and sodium metabisulfite, and a crosslinking agent including glyoxal
  • hydrophilicity hydrophilicity
  • the generation of phosphorus sulfate ion radicals can be maximized, and the conversion of sulfate ion radicals into hydroxy radicals can be suppressed to promote the formation of water-soluble oligomers, which are polymers of water-soluble monomers and ethylenically unsaturated acid monomers.
  • Latex having a low pKa has excellent workability and high strength.
  • the content of the persulfate-based polymerization initiator including at least one selected from the group consisting of sodium persulfate, potassium persulfate, and ammonium persulfate is 100 weight of the total monomer mixture It may be added in an amount of 0.1 parts by weight to 5 parts by weight, 0.1 parts by weight to 3 parts by weight, or 0.1 parts by weight to 2 parts by weight based on parts. Within this range, the polymerization rate can be appropriately adjusted, the polymerization can be controlled, and the productivity of the carboxylic acid-modified nitrile-based copolymer is excellent.
  • the content of the initiator comprising at least one selected from the group consisting of hydroperoxide, ferrous sulfate, and sodium metabisulfite is a persulfate-based polymerization initiator It may be added in an amount of 1 to 100 parts by weight, 25 parts by weight to 100 parts by weight, or 30 parts by weight to 100 parts by weight based on 100 parts by weight of the total content. Within this range, there is an effect of facilitating the formation of a water-soluble oligomer by further promoting the reaction of the ethylenically unsaturated acid monomer and the water-soluble monomer.
  • the carboxylic acid-modified nitrile-based copolymer latex may be prepared by emulsion polymerization by further adding an emulsifier and a molecular weight control agent to a monomer mixture constituting the carboxylic acid-modified nitrile-based copolymer.
  • the type and content of the monomer mixture may be introduced in the monomer type and content described above, and the injection method may be selected from batch injection, continuous injection, or divided injection method.
  • an emulsifier is added to impart stability to the latex during and after the polymerization reaction, and various types of anionic emulsifiers and nonionic emulsifiers may be used.
  • alkyl benzene sulfonates such as sodium alkyl benzene sulfonate, alcohol sulfate, alcohol ether sulfonate, alkyl phenol ether sulfonate, alpha olefin sulfonate, paraffin sulfonate, ester sulfosuccinate, phosphate Esters, and the like
  • nonionic emulsifiers may include alkyl phenol ethoxylate, fethiamine ethoxylate, fatty acid ethoxylate, alkanoamide, and the like. These emulsifiers may be used alone or in combination of two or more.
  • the emulsifier may be added in an amount of 0.3 parts by weight to 10 parts by weight, 0.8 parts by weight to 8 parts by weight, or 1.5 parts by weight to 6 parts by weight based on 100 parts by weight of the total monomer mixture, and polymerization stability within this range It is excellent, and there is an effect that it is easy to manufacture a molded product due to a small amount of foaming.
  • the molecular weight modifier is, for example, a mercap such as ⁇ -methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan.
  • a mercap such as ⁇ -methylstyrene dimer, t-dodecyl mercaptan, n-dodecyl mercaptan, and octyl mercaptan.
  • Coal flow Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, and methylene bromide
  • sulfur-containing compounds such as tetraethylthiuram disulfide, dipentamethylthiuram disulfide, and diisopropylxanthogen disulfide.
  • molecular weight modifiers may be used alone or in combination of two or more.
  • the molecular weight control agent may use mercaptans, and as a more specific example, the molecular weight control agent may use t-dodecyl mercaptan.
  • the molecular weight modifier may be added in an amount of 0.1 parts by weight to 2 parts by weight, 0.2 parts by weight to 1.5 parts by weight, or 0.3 parts by weight to 1 part by weight based on 100 parts by weight of the total content of the monomer mixture, and has excellent polymerization stability within this range. , When manufacturing a molded product after polymerization, it has an excellent effect on the physical properties of the molded product.
  • polymerization in preparing the carboxylic acid-modified nitrile-based copolymer latex, polymerization may be carried out in water as a medium, for example, deionized water.
  • Additives such as a chelating agent, a dispersing agent, a pH adjusting agent, a deoxygenating agent, a particle size adjusting agent, an anti-aging agent and an oxygen scavenger may be further included.
  • the emulsifier, polymerization initiator, molecular weight modifier, additive, and the like may be added collectively or dividedly into a polymerization reactor like the monomer mixture, and may be continuously added at each input.
  • a chelating agent when the carboxylic acid-modified nitrile-based copolymer latex is polymerized, a chelating agent, a dispersant, a pH adjuster, a deoxidant, a particle size adjuster, an anti-aging agent, an oxygen scavenger, if necessary.
  • Subsidiary materials such as may be added.
  • the polymerization temperature during the emulsion polymerization may be carried out at a polymerization temperature of, for example, 10°C to 90°C, 20°C to 80°C, or 25°C to 75°C, and within this range.
  • the latex stability has an excellent effect.
  • the polymerization reaction may be terminated after the polymerization conversion rate is 90% or more, preferably 93% or more.
  • the polymerization reaction may be terminated by addition of a polymerization inhibitor, a pH adjuster, and an antioxidant. After completion of the reaction, the final obtained copolymer latex is used after removing the unreacted monomer through a conventional deodorization and concentration process.
  • the carboxylic acid-modified nitrile-based copolymer latex may have a glass transition temperature of -40°C to -15°C, -40°C to -20°C, or -35°C to -20°C.
  • the glass transition temperature of the latex satisfies the above range, the tensile strength is excellent, the stickiness of the molded article is prevented, so that the feeling of wearing is excellent, and the durability is excellent by preventing cracks.
  • the glass transition temperature can be adjusted by adjusting the content of the conjugated diene-based monomer, and can be measured by differential scanning calorimetry.
  • the average particle diameter of the carboxylic acid-modified nitrile-based copolymer may be 80 nm to 300 nm, 80 nm to 280 nm, or 100 nm to 230 nm.
  • the average particle diameter of the carboxylic acid-modified nitrile-based copolymer can be adjusted by adjusting the type or content of the emulsifier, and the average particle diameter can be measured by a laser scattering analyzer (Nicomp).
  • the carboxylic acid-modified nitrile-based copolymer latex is a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an ethylenically unsaturated nitrile-based monomer, a repeating unit derived from an ethylenically unsaturated acid monomer, and a glyoxal-derived portion. It may include a carboxylic acid-modified nitrile-based copolymer containing.
  • the crosslinking density in the copolymer is improved by appropriately controlling the crosslinking density of the copolymer, so that the tensile strength of the molded article made from the copolymer is improved and the elongation is also excellent. have.
  • the carboxylic acid-modified nitrile-based copolymer latex is a repeating unit derived from a conjugated diene-based monomer, a repeating unit derived from an ethylenically unsaturated nitrile-based monomer, a repeating unit derived from an ethylenically unsaturated acid monomer, and a repeating derived from a water-soluble monomer.
  • a carboxylic acid-modified nitrile-based copolymer including a unit and a glyoxal-derived portion may be included, and the carboxylic acid-modified nitrile-based copolymer latex may have a pKa of 8.5 to 9.5.
  • the carboxylic acid-modified nitrile-based copolymer latex according to the present invention has a low pKa, the workability of the latex composition for dip molding including the same is excellent, and the strength of the dip-molded article manufactured therefrom is improved. I can.
  • a latex composition for dip molding comprising the carboxylic acid-modified nitrile-based copolymer latex according to the present invention.
  • the dip molding latex composition is at least one selected from the group consisting of a vulcanizing agent, an ionic crosslinking agent, a pigment, a filler, a thickener, and a pH adjusting agent in the above-described carboxylic acid-modified nitrile-based copolymer latex. It can be prepared including additives.
  • the vulcanizing agent is for vulcanizing the latex composition for dip molding, and may be sulfur, and as a specific example, sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur and insoluble sulfur, etc.
  • sulfur such as powdered sulfur, precipitated sulfur, colloidal sulfur, surface-treated sulfur and insoluble sulfur, etc.
  • Can be The content of the vulcanizing agent may be 0.1 parts by weight to 10 parts by weight, or 1 part by weight to 5 parts by weight based on 100 parts by weight of the total content of the carboxylic acid-modified nitrile-based copolymer latex in the dip molding latex composition (based on solid content). And there is an effect excellent in crosslinking ability by vulcanization within this range.
  • the vulcanization accelerator is 2-mercaptobenzothiazole (MBT, 2-mercaptobenzothiazole), 2,2-dithiobisbenzothiazole-2-sulfenamide (MBTS, 2,2 -dithiobisbenzothiazole-2-sulfenamide), N-cyclohexylbenzothiazole-2-sulfenamide (CBS, N-cyclohexylbenzothiasole-2-sulfenamide), 2-morpholinothiobenzothiazole (MBS, 2-morpholinothiobenzothiazole), tetra Methylthiuram monosulfide (TMTM), tetramethylthiuram disulfide (TMTD), zinc diethyldithiocarbamate (ZDEC), zinc di-n-butyldithiocarbamate (ZDBC, zinc di-n-butyldithiocarbamate), diphenylguanidine
  • MKT 2-mercaptobenzothi
  • the content of the vulcanization accelerator may be 0.1 parts by weight to 10 parts by weight, or 0.5 parts by weight to 5 parts by weight based on 100 parts by weight of the total content of the carboxylic acid-modified nitrile-based copolymer latex in the dip molding latex composition (based on solid content).
  • the zinc oxide performs ionic bonding with the carboxy group of the carboxylic acid-modified nitrile-based copolymer in the dip molding latex composition, and thus the carboxylic acid-modified nitrile-based copolymer or carboxylic acid It may be a crosslinking agent for forming a crosslinking portion through ionic bonds between the modified nitrile-based copolymers.
  • the content of zinc oxide may be 0.1 parts by weight to 5 parts by weight, or 0.5 parts by weight to 4 parts by weight based on 100 parts by weight (based on solids) of the total content of the carboxylic acid-modified nitrile-based copolymer latex in the dip molding latex composition. And, within this range, the crosslinking ability is excellent, the latex stability is excellent, and the tensile strength and flexibility of the manufactured dip molded article are excellent.
  • the latex composition for dip molding may have a solid content (concentration) of 5% to 40% by weight, 8% to 35% by weight, or 10% to 30% by weight. And, within this range, the efficiency of the latex transport is excellent, and there is an effect of excellent storage stability by preventing an increase in the viscosity of the latex.
  • the dip molding latex composition may have a pH of 9 to 12, 9 to 11.5, or 9.5 to 11, and has excellent processability and productivity when manufacturing a dip molded article within this range.
  • the pH of the latex composition for dip molding may be adjusted by the introduction of the aforementioned pH adjusting agent.
  • the pH adjusting agent may be, for example, an aqueous potassium hydroxide solution having a concentration of 1% to 5% by weight, or aqueous ammonia having a concentration of 1% to 5% by weight.
  • the latex composition for dip molding may further include additives such as pigments such as titanium dioxide, fillers such as silica, thickeners, and pH adjusters, if necessary.
  • additives such as pigments such as titanium dioxide, fillers such as silica, thickeners, and pH adjusters, if necessary.
  • the dip-molded product may be a dip-molded product manufactured by dip-molding the latex composition for dip molding, and may be a molded product including a dip-molding latex composition-derived layer formed from the dip-molding latex composition by dip molding.
  • the molded article manufacturing method for molding the molded article may include immersing the latex composition for dip molding by a direct immersion method, an anode adhesion immersion method, a Teague adhesion immersion method, etc. It can be carried out by an adhesion immersion method, and in this case, there is an advantage in that a dip-molded article having a uniform thickness can be obtained.
  • the method of manufacturing a molded article may include the steps of attaching a coagulant to a dip mold (S100); Forming a layer derived from the latex composition for dip molding, that is, a dip molding layer by immersing the dip molding mold to which the coagulant is attached to the latex composition for dip molding (S200); And heating the dip molding layer to crosslink the latex composition for dip molding (S300).
  • the step (S100) is a step of attaching a coagulant to the surface of the dip molding mold by immersing the dip molding mold in a coagulant solution to form a coagulant in the dip molding mold, and the coagulant solution is a coagulant Is dissolved in water, alcohol, or a mixture thereof, and the content of the coagulant in the coagulant solution is 5% to 75% by weight, 10% to 65% by weight, or 15% to 55% by weight based on the total content of the coagulant solution. It can be %.
  • the coagulant may be, for example, a metal halide such as barium chloride, calcium chloride, magnesium chloride, zinc chloride, and aluminum chloride; Nitrates such as barium nitrate, calcium nitrate and zinc nitrate; Acetates such as barium acetate, calcium acetate, and zinc acetate; And it may be one or more selected from the group consisting of sulfates such as calcium sulfate, magnesium sulfate, and aluminum sulfate, and a specific example may be calcium chloride or calcium nitrate.
  • a metal halide such as barium chloride, calcium chloride, magnesium chloride, zinc chloride, and aluminum chloride
  • Nitrates such as barium nitrate, calcium nitrate and zinc nitrate
  • Acetates such as barium acetate, calcium acetate, and zinc acetate
  • sulfates such as calcium sulfate, magnesium sulfate, and aluminum s
  • the step (S100) is a step of immersing the dip molding mold in a coagulant solution for at least 1 minute and then drying it at 70°C to 150°C in order to attach the coagulant to the dip molding mold. It may further include.
  • a dip molding mold to which a coagulant is attached to form a dip molding layer is immersed in the latex composition for dip molding according to the present invention, taken out, and dip molded in the dip molding mold. It may be a step of forming a layer.
  • immersion in the step (S200), in order to form a dip molding layer on the dip molding mold, during the immersion, immersion may be performed for 1 minute or more.
  • a liquid component is evaporated by heating a dip molding layer formed on a dip molding mold to obtain a dip molding product, and curing is performed by crosslinking the latex composition for dip molding. It may be a step to do.
  • vulcanization of the crosslinking agent composition included in the latex composition for dip molding and/or crosslinking by ionic bonding may be performed.
  • the heating is carried out by first heating at 70° C. to 150° C. for 1 minute to 10 minutes, and then secondary heating at 100° C. to 180° C. for 5 to 30 minutes. I can.
  • the molded article may be a glove such as a surgical glove, an examination glove, an industrial glove and a household glove, a condom, a catheter, or a health care product.
  • a monomer mixture consisting of 28% by weight of acrylonitrile, 64.2% by weight of 1,3-butadiene, 5.8% by weight of methacrylic acid, and 2% by weight of hydroxyethyl methacrylate and 100 parts by weight of the monomer mixture t -Dodecylmercaptan 0.6 parts by weight, sodium dodecyl benzenesulfonate 2 parts by weight, potassium persulfate 0.3 parts by weight, hydroperoxide 0.1 parts by weight, glyoxal 0.5 parts by weight, water 140 parts by weight and then polymerization at a temperature of 37 °C Was initiated.
  • a coagulant solution was prepared by mixing 13% by weight of calcium nitrate, 86.5% by weight of water, and 0.5% by weight of a wetting agent (manufactured by Huntsman Corporation, Australia, product name Teric 320), and a hand-shaped ceramic mold was added to the solution for 1 minute. After soaking and taking out, it was dried at 80° C. for 3 minutes to apply a coagulant to a hand-shaped mold.
  • a wetting agent manufactured by Huntsman Corporation, Australia, product name Teric 320
  • the hand-shaped mold coated with the coagulant was immersed in the obtained latex composition for dip molding for 1 minute and taken out, dried at 80° C. for 1 minute, and immersed in water for 3 minutes. Again, the mold was dried at 80° C. for 3 minutes and then crosslinked at 125° C. for 20 minutes. Thereafter, the crosslinked dip molded layer was peeled off from the hand-shaped mold to obtain a glove-shaped dip molded article.
  • Example 1 The preparation of the carboxylic acid-modified nitrile-based copolymer latex of Example 1 was carried out in the same manner as in Example 1, except that 0.1 parts by weight of glyoxal was added instead of 0.5 parts by weight.
  • Example 1 The preparation of the carboxylic acid-modified nitrile-based copolymer latex of Example 1 was carried out in the same manner as in Example 1, except that 1 part by weight of glyoxal was added instead of 0.5 part by weight.
  • Example 1 The preparation of the carboxylic acid-modified nitrile-based copolymer latex of Example 1 was carried out in the same manner as in Example 1, except that 0.05 parts by weight of glyoxal was added instead of 0.5 parts by weight.
  • Example 1 The preparation of the carboxylic acid-modified nitrile-based copolymer latex of Example 1 was carried out in the same manner as in Example 1, except that 1.5 parts by weight of glyoxal was added instead of 0.5 parts by weight.
  • Example 1 The preparation of the carboxylic acid-modified nitrile-based copolymer latex of Example 1 was carried out in the same manner as in Example 1, except that 0.5 parts by weight of glyoxal was not added.
  • Example 1 The preparation of the carboxylic acid-modified nitrile-based copolymer latex of Example 1 was carried out in the same manner as in Example 1, except that 0.1 part by weight of hydroperoxide as an initiator was not added.
  • pKa that determines the degree of ionization of the unsaturated acid monomer present in the copolymer latex.
  • the pKa of the latex was measured by the following method. After the latex obtained by polymerization was diluted to 10%, the pH was raised to 12 using a 3% aqueous potassium hydroxide solution, and then stirred at 90° C. for 2 hours.
  • Example 1 is a graph showing the pH change according to the amount of KOH input in Example 1 of the present invention.
  • the amount of carboxylic acid calculated as the amount of KOH input between the first and second inflection points of FIG. 1 is an acid present on the surface.
  • the amount of FIG. 2 is a differential curve of the input amount of KOH according to the pH shown in FIG. 1.
  • the vertex of this quadratic function is the pKa of latex. Through this, it can be seen that the pKa of the copolymer latex prepared from Example 1 has a range of 8.5 to 9.5.
  • the hand-shaped ceramic mold was immersed in the coagulant solution used in the manufacture of the dip molded product for 1 minute, taken out, and dried at 80° C. for 3 minutes, and the coagulant was applied to the hand-shaped mold. Thereafter, the hand-shaped mold to which the coagulant was applied was immersed in the latex composition for dip molding of each of Examples and Comparative Examples for 1 minute and taken out, and then the time required for droplets to fall from the hand-shaped mold was measured. If the droplet does not fall within 5 minutes, it is marked with an X.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne un procédé de préparation de latex de copolymère à base de nitrile modifié par un acide carboxylique, et concerne un procédé de préparation de latex de copolymère à base de nitrile modifié par un acide carboxylique, le procédé comprenant une étape consistant à, en présence d'un agent de réticulation comprenant du glyoxal, polymériser en émulsion un mélange de monomères comprenant un monomère à base de diène conjugué, un monomère à base de nitrile éthyléniquement insaturé et un monomère d'acide éthyléniquement insaturé.
PCT/KR2020/010680 2019-10-07 2020-08-12 Procédé de préparation de latex de copolymère à base de nitrile modifié par un acide carboxylique WO2021071078A1 (fr)

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CN202080006750.3A CN113195568B (zh) 2019-10-07 2020-08-12 制备羧酸改性的腈类共聚物胶乳的方法
JP2021531132A JP7161054B2 (ja) 2019-10-07 2020-08-12 カルボン酸変性ニトリル系共重合体ラテックスの製造方法
US17/299,571 US11965080B2 (en) 2019-10-07 2020-08-12 Method of preparing carboxylic acid-modified nitrile-based copolymer latex

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KR1020200070902A KR102492405B1 (ko) 2019-10-07 2020-06-11 카르본산 변성 니트릴계 공중합체 라텍스의 제조방법

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JP3977436B2 (ja) * 1996-09-18 2007-09-19 イーストマン ケミカル カンパニー 自己架橋性水性分散体
KR20150010221A (ko) * 2013-07-18 2015-01-28 주식회사 엘지화학 폴리알킬렌 카보네이트와 가교제를 포함하는 수지 조성물 및 이로부터 제조된 생분해성 성형품
KR20170062730A (ko) * 2015-11-30 2017-06-08 주식회사 엘지화학 딥 성형용 라텍스 조성물 및 이로부터 제조된 성형품
KR20180066819A (ko) * 2016-12-09 2018-06-19 주식회사 엘지화학 카르본산 변성 니트릴계 공중합체 라텍스 및 이를 포함하는 딥 성형용 라텍스 조성물

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JP3977436B2 (ja) * 1996-09-18 2007-09-19 イーストマン ケミカル カンパニー 自己架橋性水性分散体
JP2003342303A (ja) * 2002-03-19 2003-12-03 Nippon Zeon Co Ltd ディップ成形用ラテックス、ディップ成形用組成物およびディップ成形物
KR20150010221A (ko) * 2013-07-18 2015-01-28 주식회사 엘지화학 폴리알킬렌 카보네이트와 가교제를 포함하는 수지 조성물 및 이로부터 제조된 생분해성 성형품
KR20170062730A (ko) * 2015-11-30 2017-06-08 주식회사 엘지화학 딥 성형용 라텍스 조성물 및 이로부터 제조된 성형품
KR20180066819A (ko) * 2016-12-09 2018-06-19 주식회사 엘지화학 카르본산 변성 니트릴계 공중합체 라텍스 및 이를 포함하는 딥 성형용 라텍스 조성물

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113185624A (zh) * 2021-05-13 2021-07-30 山东星宇手套有限公司 一种环保水性胶乳凝固剂及橡胶涂层制品的制备方法

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