WO2012134211A2 - Microgel, son procédé de préparation, et composition de peinture soluble dans l'eau - Google Patents

Microgel, son procédé de préparation, et composition de peinture soluble dans l'eau Download PDF

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Publication number
WO2012134211A2
WO2012134211A2 PCT/KR2012/002358 KR2012002358W WO2012134211A2 WO 2012134211 A2 WO2012134211 A2 WO 2012134211A2 KR 2012002358 W KR2012002358 W KR 2012002358W WO 2012134211 A2 WO2012134211 A2 WO 2012134211A2
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shell
unsaturated monomer
microgel
acid
forming
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PCT/KR2012/002358
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English (en)
Korean (ko)
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WO2012134211A3 (fr
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문태권
이종택
이현숙
박종윤
고건혁
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주식회사 케이씨씨
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Priority to CN201280016943.2A priority Critical patent/CN103562275B/zh
Publication of WO2012134211A2 publication Critical patent/WO2012134211A2/fr
Publication of WO2012134211A3 publication Critical patent/WO2012134211A3/fr

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    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
    • C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
    • C08J3/075—Macromolecular gels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0052—Preparation of gels
    • B01J13/0065—Preparation of gels containing an organic phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • B01J13/20—After-treatment of capsule walls, e.g. hardening
    • B01J13/22—Coating
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/12—Powdering or granulating
    • C08J3/126—Polymer particles coated by polymer, e.g. core shell structures
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/02—Homopolymers or copolymers of acids; Metal or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • 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
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2205/00—Foams characterised by their properties
    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/024—Organogel, i.e. a gel containing an organic composition
    • 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
    • C08J2333/00—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or 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 of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/10—Homopolymers or copolymers of methacrylic acid esters

Definitions

  • the present invention relates to microgels and methods for their preparation, and to water-soluble coating compositions.
  • Addition of an effect pigment such as aluminum or mica to the automotive coating composition can impart a so-called glamor finish to the automotive appearance.
  • the surface coated with such an effect pigment may have a different color depending on the angle viewed by light absorption, reflection, refraction effects, and the like. This is called a metallic effect.
  • the water-soluble coating composition unlike the solvent type coating composition, most of the volatile components are composed of water, so that drying of the volatile components may be considerably delayed compared to the solvent type. As a result, the flow of the effect pigment, staining, etc. become more severe. At this time, the drying of the volatile components may be sensitively affected by the temperature and relative humidity at the time of coating the coating composition. Therefore, in the water-soluble coating composition for automobiles, it is preferable to enlarge the temperature and humidity area
  • each rheology (thixotropy) at the various coating stages of the storage, transportation, painting, holding, coating composition and drying of the coating composition should be optimized. That is, when storing the paint composition, it should maintain a suitable viscosity in order to prevent the sedimentation of the pigment, and when transporting it should be easy to transport because the viscosity is moderately low, and when painting the paint should be as low as possible, so that the paint atomization well. . After arrival, the viscosity should be rapidly restored to control the flow of the coating film and the flow of the effect pigment.
  • the present invention is to provide a microgel and a method for preparing the same, and a water-soluble coating composition capable of maximizing the plasticity properties to maximize the temperature and humidity range.
  • Method for producing a microgel according to the present invention preparing a core; Forming a first shell on the core; And forming a second shell on the first shell, and using a hydroxyl group-containing unsaturated monomer having polyalkylene glycol in at least one of forming the first shell and the second shell.
  • an acid-containing unsaturated monomer and a hydroxyl group-containing unsaturated monomer including the polyalkylene glycol may be added and reacted to form the second shell.
  • the hydroxyl group-containing unsaturated monomer having the polyalkylene glycol may be represented by the following formula.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group having 2 to 4 carbon atoms
  • n is an integer of 3 to 20
  • an acid-free or acid-containing unsaturated monomer may be added to a seed to form the core.
  • the first shell may be formed by adding and reacting an acid-free or acid-containing unsaturated monomer with a hydroxyl-free or hydroxyl-containing unsaturated monomer.
  • the core may be formed by injecting a hydroxyl-free or hydroxyl-containing unsaturated monomer having a polyalkylene glycol with an acid-containing unsaturated monomer.
  • a neutralizing agent may be added to the core, and an acid-free or acid-containing unsaturated monomer may be added and reacted to form the first shell while inducing phase inversion.
  • the acid value measured after the forming of the second shell may be higher than the acid value measured after the forming of the first shell.
  • the acid value of the microgel may be 40 ⁇ 200 mgKOH / g and the hydroxyl value is 1 ⁇ 80 mgKOH / g.
  • the weight of the unsaturated monomer added in the step of preparing the core is 35 ⁇ 60, of the unsaturated monomer added in the step of forming the first shell
  • the weight part may be 20 to 40
  • the weight part of the unsaturated monomer added in the step of forming the second shell may be 10 to 30.
  • the microgel according to the present invention is prepared by the method for producing a microgel described above.
  • the water soluble coating composition according to the present invention comprises such a microgel.
  • Microgel according to the present invention the core; A first shell formed on the core; And a second shell formed on the first shell and formed by reacting an acid-containing unsaturated monomer with a hydroxyl group-containing unsaturated monomer having polyalkylene glycol.
  • the water soluble coating composition according to the present invention comprises such a microgel.
  • the present invention it is possible to stably polymerize a relatively high acid value microgel.
  • the hydroxyl group-containing unsaturated monomer having polyalkylene glycol is used in the step of forming the second shell, there is an effect that can further maximize the interaction with the adjacent factors. Thereby, a viscosity and plasticity characteristic can be improved.
  • the stability of the particles can be improved during storage, the paint atomization can be well achieved during the coating film formation, and the viscosity is increased at the low shear rate after arrival to effectively control the flow of the coating film and the like. That is, the paintable temperature and humidity application window can be maximized and the rheology in the paint step can be optimized.
  • microgel according to the present invention a manufacturing method thereof, and a water-soluble coating composition will be described in detail.
  • the method for producing a microgel according to the present invention includes preparing a core, forming a first shell on the core, and forming a second shell on the first shell. At this time, the second shell is formed by reacting an acid-containing unsaturated monomer with a hydroxyl group-containing unsaturated monomer having polyalkylene glycol.
  • an acid-free or acid-containing unsaturated monomer, a polymerization initiator, an emulsifier and ionized water are added to the seed to form a core.
  • an acid-free or acid-containing unsaturated monomer, a hydroxyl-free or hydroxyl-containing unsaturated monomer, a polymerization initiator, an emulsifier and ionized water are charged to form a first shell.
  • an acid-containing unsaturated monomer, a hydroxyl group-containing unsaturated monomer, a polymerization initiator, an emulsifier and ionized water are formed by input reaction.
  • a hydroxyl-containing unsaturated monomer having polyalkylene glycol as the hydroxyl-containing unsaturated monomer in at least one of the steps of forming the first shell and the second shell can be used.
  • the step of forming the second shell preferably includes a hydroxyl-containing unsaturated monomer having polyalkylene glycol.
  • the above-mentioned seed may be formed by input reaction of an acid-free or acid-containing unsaturated monomer, a polymerization initiator, an emulsifier, and ionized water.
  • the monomer used at the time of manufacture of a general microgel can be used.
  • at least one of a polymerizable aromatic monomer such as styrene and ⁇ -methylstyrene, or a polymerizable nitrile monomer such as
  • the acid-containing unsaturated monomer may be at least one of two carboxylic acid groups such as single carboxylic acid group, crotonic acid, itaconic acid, maleic acid, and pmaric acid, such as acrylic acid, methacrylic acid, vinylbenzene acid, and isopentyl benzene acid. It may include one.
  • the hydroxyl-containing unsaturated monomer may include at least one of hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, product names PLACCEL FM1D, PLACCEL FM2D, etc. of DAICEL.
  • hydroxyl group-containing unsaturated monomer having a polyalkylene glycol may be represented by the formula (1) below.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an alkyl group having 2 to 4 carbon atoms
  • n is an integer of 3 to 20
  • hydroxyl group-containing unsaturated monomer including polyalkylene glycol, polyethylene glycol acrylate, polypropylene glycol acrylate, polybutylene glycol acrylate, etc., each of which is added with ethylene oxide, propylene oxide, butylene oxide, etc., are added.
  • Various materials can be used. In this case, a material in which ethylene oxide, propylene oxide, butylene oxide and the like are added in various amounts may be used.
  • An emulsifier can be used individually or in mixture of an anionic emulsifier, a nonionic, a reactive emulsifier, etc.
  • Anionic emulsifiers include sodium dodecyl sulfate, sodium dodecylbenzene sulfate, sodium oleic sulfate, potassium dodecyl sulfate, dioctyl sodium sulfosuccinate, sodium stearate, potassium stearate, and polyoxyethylene alkylphenyl ether ammonium sulfide Fading and so on.
  • Nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyoxyethylene fatty acid esters, and polyoxyethylene polypropylene copolymers.
  • the reactive emulsifier is an emulsifier for copolymerizing with a polymer synthesized by having an unsaturated double bond in the emulsifier component, and may have anionic or nonionic properties (for example, ADEKA brand name ADEKAREASOAP SE-1025A, DKS International company name HITENOL HS-10).
  • Polymerization initiators include oil-soluble initiators consisting of hydrogen peroxide, diisopropylene hydroperoxide, cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, lauroyl peroxide, or potassium persulfate, ammonium peroxide. Any one or more of water-soluble initiators, such as sulfate and sodium persulfate, can be selected and used.
  • a chain transfer agent may be further used to control the molecular weight when forming the seed, the core, the first shell, and the second shell.
  • Various materials may be used as the chain transfer agent, and for example, mercaptoethanol, ⁇ -methylstyrene dimer, methyl mercaptopropionate, and the like may be used.
  • the crosslinking monomer may be included in an amount of 0 to 10 parts by weight based on 100 parts by weight of the unsaturated monomer used in each of the above-described steps.
  • the amount of the crosslinking monomer exceeds 10 parts by weight, the interlayer adhesion may be lowered or the plasticity of the paint may be lowered.
  • crosslinking monomer the monomer which has 2 or more unsaturated bonds is used,
  • Allyl compounds such as vinyl compounds, such as divinyl benzene, an aryl (meth) acrylate, and a di (meth) aryl (meth) acrylamide, and ethylene Alkylenediol di (meth), such as glycol di (meth) acrylate, 1, 3- butanediol di (meth) acrylate, 1, 4- butanediol (meth) acrylate, and 1, 6- hexanediol (meth) acrylate ) At least one selected from the group consisting of an acrylate compound and the like.
  • the core is formed on the seed after forming the seed.
  • the seed is formed by input reaction of an acid-free or acid-containing unsaturated monomer, a polymerization initiator, an emulsifier, and ionized water, and an acid value may be 200 mgKOH / g or less. If the acid value exceeds 200 mgKOH / g, it is because the subsequent polymerization may not be performed smoothly.
  • the particle size of the prepared seed may be 20 ⁇ 200nm, which is an appropriate size to appropriately size the particle diameter of the core.
  • the core is formed by input reaction of an acid-free or acid-containing unsaturated monomer, a polymerization initiator, an emulsifier and ionized water, and an acid value may be 30 mgKOH / g or less. This is because if the acid value exceeds 30 mgKOH / g, the polymerization may not be performed smoothly and the core may not be smoothly formed on the seed. At this time, the acid value may be 1 ⁇ 30 mgKOH / g.
  • the particle diameter of the prepared core may be 25-250 nm, which is an appropriate size to disperse the microgel in which the first shell and the second shell are formed on the core in the water-soluble coating composition to impart proper viscosity and plasticity.
  • 35 to 60 parts by weight of the unsaturated monomer can be added to 100 parts by weight of the total unsaturated monomer used in the preparation of the microgel. If the unsaturated monomer is added below 35 in the step of forming the core, the size of the core may become small and may not be suitable for forming the first shell and the second shell. If more than 60 parts by weight of the unsaturated monomer is added, the core may be too large and the thickness of the first shell and the second shell may be thin, making it difficult to have adequate viscosity and plasticity.
  • the polymerization initiator is added by 1 to 15 parts by weight, the emulsifier is added by 1 to 25 parts by weight, and the ionized water may be added by 60 to 98 parts by weight based on 100 parts by weight of the unsaturated monomer to be added during core formation. This is only an example of a suitable range required for synthesis, the present invention is not limited thereto.
  • an acid-free or acid-containing unsaturated monomer, a hydroxyl-free or hydroxyl-containing unsaturated monomer, a polymerization initiator, an emulsifier and ionized water are charged to form a first shell.
  • the acid value measured after the forming of the first shell may be 100 mgKOH / g or less and the hydroxyl value may be 80 mgKOH / g or less.
  • the acid value may be 1 ⁇ 100 mgKOH / g or less and the hydroxyl value is 0.01 ⁇ 80 mgKOH / g or less.
  • the step of forming the first shell 20 to 40 parts by weight of the unsaturated monomer may be added to and used with respect to 100 parts by weight of the total unsaturated monomer used in the preparation of the microgel.
  • the unsaturated monomer is added to less than 20 in the step of forming the first shell, the thickness of the first shell becomes thin and it is difficult to obtain the effect by forming the first shell. If more than 40 parts by weight of unsaturated monomer is added, the thickness of the first shell may be thicker than necessary, which may unnecessarily increase the cost of the material.
  • the polymerization initiator is added by 1 to 15 parts by weight, the emulsifier is added by 1 to 25 parts by weight, and the ionized water may be added by 60 to 98 parts by weight with respect to 100 parts by weight of the unsaturated monomer to be added at the time of forming the first shell. .
  • an acid-containing unsaturated monomer, a hydroxyl group-containing unsaturated monomer having polyalkylene glycol, a polymerization initiator, an emulsifier, and ionized water are added and reacted to form a second shell.
  • the unsaturated monomer in the forming of the second shell, 10 to 30 parts by weight of the unsaturated monomer may be added to and used with respect to 100 parts by weight of the total unsaturated monomer used in the preparation of the microgel.
  • the unsaturated monomer is added to less than 10 in the step of forming the first shell, the thickness of the first shell becomes thin and it is difficult to obtain the effect by forming the second shell. If more than 30 parts by weight of the unsaturated monomer is added, the thickness of the second shell having a high acid value becomes thicker than necessary, which may unnecessarily increase the cost of the material.
  • the polymerization initiator is added by 1 to 15 parts by weight, the emulsifier is added by 1 to 25 parts by weight, and the ionized water may be added by 60 to 98 parts by weight with respect to 100 parts by weight of the unsaturated monomer to be added during the formation of the second shell. .
  • the microgel thus prepared may be neutralized with a neutralizing agent consisting of a base.
  • a neutralizing agent consisting of a base.
  • inorganic bases such as ammonia, sodium hydroxide, potassium hydroxide, and inorganic bases, primary or tertiary amines such as dimethyl ethanol amine, triethyl amine, and the like can be used.
  • the microgel thus prepared comprises a core, a first shell formed on the core, a second shell formed on the first shell, and the second shell includes a hydroxyl group-containing unsaturated monomer having an acid-containing unsaturated monomer and a polyalkylene glycol. It is formed by reacting monomers.
  • the acid value of the prepared microgel may be 40 ⁇ 200 mgKOH / g and the hydroxyl value is 1 ⁇ 80 mgKOH / g.
  • the acid value after the second shell is made higher than the acid value after the first shell is formed, thereby increasing the acid value step by step, thereby stably polymerizing and forming a relatively high acid value microgel. Therefore, a higher acid value can be realized than when only one layer of shell is provided, and the interaction with adjacent particles can be increased, thereby improving the plasticity characteristics.
  • the hydroxyl group-containing unsaturated monomer having polyalkylene glycol is used in forming the second shell, there is an effect of maximizing the interaction with adjacent factors.
  • the stability of the particles can be improved during storage, the paint atomization can be well achieved during the coating film formation, and the viscosity is increased at the low shear rate after arrival to effectively control the flow of the coating film and the like. That is, the paintable temperature and humidity application window can be maximized and the rheology in the paint step can be optimized.
  • a core is formed by adding a hydroxyl-free or hydroxyl-containing unsaturated monomer, an acid-containing unsaturated monomer, a polymerization initiator, an emulsifier and ionized water with polyalkylene glycol.
  • the core obtained by this has an acid value of 50 mgKOH / g or less, and a hydroxyl value of 50 mgKOH / g or less.
  • the acid value may be 1-50 mgKOH / g and the hydroxyl value may be 0.01-50 mgKOH / g.
  • a neutralizing agent is added, and an acid-free or acid-containing unsaturated monomer, a polymerization initiator, an emulsifier, and ionized water are added and reacted to form a first shell while inducing phase inversion.
  • the acid value measured after the step of forming the first shell may be 30 mmKOH / g or less, and may be 1-30 mmKOH / g.
  • the neutralizing agent may be added to the amount of acid in the step of preparing the core by 0.3 to 1.5 equivalents. If the neutralizing agent is less than 0.3 equivalent, there is a problem that the degree of solubility during neutralization does not play a role of the emulsifier in the subsequent shell process. If the neutralizing agent exceeds 1.5 equivalents, it may be fully solubilized that it will not be able to act as an emulsifier in the subsequent shell process.
  • the acid-containing unsaturated monomer and the hydroxyl group-containing unsaturated monomer including polyalkylene glycol, a polymerization initiator, an emulsifier, and ionized water are formed by input reaction.
  • the acid value of the thus prepared microgel may be 40 ⁇ 200 mgKOH / g and the hydroxyl value is 1 ⁇ 80 mgKOH / g.
  • microgels may have excellent plasticity properties. This maximizes the range of paintable temperature and humidity and optimizes rheology during the painting phase.
  • the water-soluble coating composition containing the microgel as mentioned above can maximize plasticity by a microgel, and can raise the density of a coating film. As a result, properties such as stain resistance, compactness, water resistance, alkali corrosion resistance, adhesion, appearance, gloss, and flip flop can be improved. This water-soluble coating composition will be described in more detail.
  • Water-soluble coating composition is 10-30 weight% of microgels, 5-15 weight% of auxiliary resins, 1-10 weight% of amino resins, 5-15 weight% of cosolvents, 1-20 weight% of effect pigments, 0-20 weight of colored pigments %, Thickener 0-10% by weight, antifoam 1-5% by weight and the balance of other additives.
  • the auxiliary resin plays a role of forming a coating film, protecting the body, improving the appearance, and the like, and various materials such as polyurethane dispersion or polyester can be used.
  • the amino resin serves to form a network of the coating film through a curing reaction with the main resin, and methoxy melamine, butoxy melamine, melamine containing an amino group, and the like can be used.
  • the co-solvent improves the smoothness of the coating film and the storage stability of the paint, lowers the minimum film forming temperature, and contributes to the volatilization of the solvent during painting.
  • the co-solvent includes at least one of propylene glycol, N-methyl-2-pyrrolidone, n-propyl alcohol, n-butanol, propylene glycol monomethyl ether, butyl glycol, hexyl glycol, 2-ethylhexyl alcohol, butyl carbitol and the like. It may include more.
  • the effect pigment is for imparting a metallic effect to the coating film, and may be used alone or in combination with an aqueous flake, aluminum flake, mica pigment, and the like. At this time, the effect pigment may be included in 1 to 20% by weight, preferably 1 to 15% by weight based on the water-soluble paint composition.
  • Colored pigments are those which, in combination with coating-forming materials in coating compositions, impart color and concealment effects. Generally, effect pigments and transparent or translucent colored pigments are used in combination.
  • an azo inorganic pigment, a polycyclic organic pigment containing an vat pigment, an anthraquinone organic pigment, or the like can be widely applied. Pure metallic colors may contain no colored pigments.
  • Thickeners are used to prevent flowability and to contribute to paintability and coating roughness.
  • an acrylic thickener a urethane thickener, fused silica, a cellulose thickener, a benton thickener and the like can be used alone or in combination.
  • Antifoaming agent is used in order to suppress the generation of bubbles generated in various processes such as at the time of production of coating composition, at the time of painting work and after the arrival of the paper, or to quickly remove the bubbles generated.
  • the antifoaming agent fluorine modified siloxane based, polysiloxane emulsion, organic modified siloxane based, hydrophobic silica, mineral oil and the like can be used alone or in combination.
  • CO-436 Sulfated ammonium salt of alkylphenoxypoly (5 moles of ethylene oxy) ethanol, manufactured by Rhodia
  • MAA methacrylic acid
  • BLEMMER AE-400 Polyethylene glycol acrylate (10 mol addition of ethylene oxide)
  • an acid value 81 prepared by mixing monomer 4 of Table 1 and 5 g of CO-436 in 200 g of DIW, a pre-emulsion of hydroxyl value 60, and an initiator solution having 1 g of APS dissolved in 50 g of DIW were added dropwise simultaneously for 1 hour. After aging for 1 hour, a second shell was formed.
  • the reactor was cooled to 40 ° C. and neutralized by dropwise adding an aqueous solution of 20 g of DMEA, neutralized in 40 g of DIW. Filtered with a 200 mesh filter to remove the aggregates and left for 1 day after packaging.
  • the pre-emulsion of acid value 32.6 prepared by mixing monomer 3-1 and 1.25 g of CO-436 in Table 1 to 100 g of DIW and an initiator solution of 0.5 g of APS dissolved in 50 g of DIW were added dropwise at the same time for 1 hour and then maintained for 1 hour. To form a core.
  • the reactor was cooled to 40 ° C. and filtered through a 200 mesh filter to remove aggregates and left for 1 day after packing.
  • Preparation Example 1 except that monomers 2 and 3 of Table 1 were used in forming the core, and monomers 4 of Table 1 were used in the formation of the first shell, and a second shell was not formed.
  • An emulsion was prepared by the same method as described above.
  • the solids content, acid value and hydroxyl value of the final emulsions prepared in Preparation Examples 1 and 2 and Comparative Examples 1 and 2 were measured, and the pH, particle size and viscosity were measured and shown in Table 2 below.
  • particle size was measured using an Autosizer Lo-C Model laser light scattering analyzer from Malvern. Viscosity was measured in CS mode using a 600 mm cone-plate method of the Haake RS-100 model. The measurement method of particle size and viscosity was the same below.
  • (1) Ford cup The viscosity was measured using the pod cup which is a kind of viscosity cup. That is, the cylindrical composition of a fixed volume was filled with the coating composition, and the viscosity was measured according to the time taken for all the coating composition to flow out from the hole in the bottom.
  • Coating film thickness 10-15 micrometers was defined as the coating thickness.
  • the prescribed coating film thickness was 35-45 ⁇ m.
  • WAVESCAN DOI The coating quality was measured using a wave scan which is a portable device for measuring the coating quality of the finished coating film. The better the appearance quality, the higher the LU, SH, and OP values. CF is converted from each value.
  • the microgel according to the present invention uses a hydroxyl group-containing unsaturated monomer having polyalkylene glycol in the step of forming the second shell, the interaction with adjacent factors can be further maximized, thereby improving viscosity and plasticity characteristics.
  • the preparation method of the microgel it is possible to stably polymerize the microgel having a relatively high acid value, and the microgel can improve the stability of the particles during storage and to make the paint atomization well during the film formation. It is very useful industrially as a composition.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

Selon la présente invention, un procédé de préparation d'un microgel comprend une étape de préparation d'un noyau central ; une étape de formation d'une première enveloppe sur le noyau ; et une étape de formation d'une seconde enveloppe sur la première enveloppe. L'étape de formation de la première enveloppe et/ou l'étape de formation de la seconde enveloppe utilise(nt) des monomères insaturés contenant des radicaux hydroxyle et comprenant des polyalkylène glycols.
PCT/KR2012/002358 2011-03-31 2012-03-30 Microgel, son procédé de préparation, et composition de peinture soluble dans l'eau WO2012134211A2 (fr)

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EP3368204A1 (fr) * 2015-10-30 2018-09-05 Clariant International Ltd Dispersion métallique à stabilité accrue
CN108905914B (zh) * 2018-06-25 2020-10-27 浙江大学 一步法制备生物相容油核微囊及其应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990060694A (ko) * 1997-12-31 1999-07-26 김충세 알킬렌모노이소시아네이트/폴리(에틸렌 옥사이드)모노알콜 단량체가 포함된 코어/쉘형 마이크로겔 및 이를 함유한 도료 조성물
EP1693429A1 (fr) * 2005-02-22 2006-08-23 Kansai Paint Co., Ltd. Composition de revêtement intermédiaire aqueuse et procédé de formation des films de revêtement multicouche
JP2007056077A (ja) * 2005-08-22 2007-03-08 Nof Corp コア−シェル型ポリマー粒子の製造方法
KR100827464B1 (ko) * 2001-12-29 2008-05-06 주식회사 케이씨씨 역상 코어/쉘 마이크로겔의 제조방법 및 상기 역상코어/쉘 마이크로겔을 함유하는 수용성 도료조성물

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3320698B2 (ja) * 1999-12-09 2002-09-03 大日本塗料株式会社 水性塗料組成物
JP2004059622A (ja) * 2002-07-25 2004-02-26 Kansai Paint Co Ltd 水性塗料組成物
CN1282677C (zh) * 2004-09-21 2006-11-01 华南理工大学 具有微凝胶核结构的羟基丙烯酸乳液及其制备方法和应用
DE102009012455A1 (de) * 2009-03-12 2010-09-23 Follmann & Co. Gesellschaft Für Chemie-Werkstoffe Und -Verfahrenstechnik Mbh & Co. Kg Verbesserte Mikrokapseln und ihre Herstellung

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR19990060694A (ko) * 1997-12-31 1999-07-26 김충세 알킬렌모노이소시아네이트/폴리(에틸렌 옥사이드)모노알콜 단량체가 포함된 코어/쉘형 마이크로겔 및 이를 함유한 도료 조성물
KR100827464B1 (ko) * 2001-12-29 2008-05-06 주식회사 케이씨씨 역상 코어/쉘 마이크로겔의 제조방법 및 상기 역상코어/쉘 마이크로겔을 함유하는 수용성 도료조성물
EP1693429A1 (fr) * 2005-02-22 2006-08-23 Kansai Paint Co., Ltd. Composition de revêtement intermédiaire aqueuse et procédé de formation des films de revêtement multicouche
JP2007056077A (ja) * 2005-08-22 2007-03-08 Nof Corp コア−シェル型ポリマー粒子の製造方法

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WO2012134211A3 (fr) 2012-12-27
KR20120111083A (ko) 2012-10-10
CN103562275A (zh) 2014-02-05
KR101828605B1 (ko) 2018-02-13
CN103562275B (zh) 2016-01-27

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