WO2023008235A1 - Dispersion de résine de polyoléfine et son procédé de fabrication - Google Patents

Dispersion de résine de polyoléfine et son procédé de fabrication Download PDF

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Publication number
WO2023008235A1
WO2023008235A1 PCT/JP2022/027882 JP2022027882W WO2023008235A1 WO 2023008235 A1 WO2023008235 A1 WO 2023008235A1 JP 2022027882 W JP2022027882 W JP 2022027882W WO 2023008235 A1 WO2023008235 A1 WO 2023008235A1
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polyolefin resin
aqueous dispersion
less
cooling
temperature
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PCT/JP2022/027882
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English (en)
Japanese (ja)
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暢康 奥村
崇嗣 杉原
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ユニチカ株式会社
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Priority to CN202280052222.0A priority Critical patent/CN117715972A/zh
Priority to KR1020237034730A priority patent/KR20240041858A/ko
Publication of WO2023008235A1 publication Critical patent/WO2023008235A1/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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • 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
    • C09D123/00—Coating compositions based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Coating compositions based on derivatives of such polymers
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to an aqueous dispersion of polyolefin resin.
  • Aqueous dispersions of polyolefin resins are used in a wide range of applications because they provide coatings with excellent adhesion to various substrates.
  • an aqueous dispersion using an acid-modified polyolefin resin containing a (meth)acrylic acid ester as a copolymer component has a high versatility of substrates that can be used, and is widely used for coating agents, adhesives, etc. ( For example, Patent Document 1).
  • the coating film obtained from the aqueous dispersion is particularly suitable for applications that are easily affected by the surrounding environment such as humidity, or applications that store contents stably for a long period of time (metal products, electronic equipment, automobile parts, packaging materials etc.), there are cases where barrier properties and rust prevention properties are required, and performance improvement is desired. That is, the technical problem of the present invention is to provide an aqueous dispersion capable of forming a coating film having few defects in appearance and having excellent barrier properties and antirust properties.
  • the present inventors have made intensive studies to solve the above problems, and as a result, the aqueous dispersion has a coarse particle size that could not be confirmed by a dynamic light scattering method, which is a conventional general method for measuring the resin particle size. Resin particles are present, and the presence of these coarse resin particles leads to defects in the appearance of the coating film (microscopic projections on the surface of the coating film, cracks in the coating film, etc.). was found to decline. That is, the present inventors have found that an aqueous dispersion containing polyolefin resin particles does not contain coarse resin particles and is uniformly dispersed in an aqueous medium when the resin particle diameter measured using a laser diffraction method is within a specific range.
  • the inventors Since it is dispersed, the inventors have found that the coating film obtained from this aqueous dispersion is free from defects in appearance and has excellent barrier properties and anti-corrosion properties, and arrived at the present invention. That is, the gist of the present invention is as follows.
  • the polyolefin resin aqueous dispersion containing polyolefin resin particles and an aqueous medium of the present invention is
  • the polyolefin resin contains 0.1 to 10% by mass of an unsaturated carboxylic acid component and 1 to 20% by mass of a (meth)acrylic acid ester component,
  • the volume average particle diameter of the polyolefin resin particles measured by the dynamic light scattering method is 0.3 ⁇ m or less, and in the volume particle size distribution measured by the laser diffraction method, the volume particle diameter integrated from the small particle diameter side A 99.9% diameter of the distribution is characterized by being 10 ⁇ m or less.
  • the coating film of the present invention is obtained from the polyolefin resin aqueous dispersion described above.
  • the method for producing a polyolefin resin aqueous dispersion of the present invention is a method for producing the above-mentioned polyolefin resin aqueous dispersion, and after the stirring step of stirring the polyolefin resin and the aqueous medium at a temperature of 110 ° C. or higher, It is characterized by including a cooling step of cooling at a rate of 1° C./min or less. According to the method for producing a polyolefin resin aqueous dispersion of the present invention, after the first cooling step of cooling from the highest temperature to a temperature of 100° C. or less and more than 40° C.
  • the stirring step preferably involves stirring at a temperature of 110° C. or higher and 20° C. or higher than the melting point of the polyolefin resin.
  • the polyolefin resin particles have a small particle size and are stably and uniformly dispersed in the aqueous medium without containing coarse particles, so that the resulting coating film has no defects in appearance. Suppressed and has excellent barrier properties and rust prevention properties.
  • aqueous dispersion contains polyolefin resin particles and an aqueous medium.
  • the olefin component that is the main component of the polyolefin resin is not particularly limited, but ethylene, propylene, isobutylene, 2-butene, 1-butene, 1-pentene, 1-hexene, 1-octene, 4-methyl-1-pentene, Examples include alkenes such as 3-methyl-1-pentene and norbornenes, and dienes such as butadiene and isoprene. A mixture of these may also be used. A copolymer obtained by copolymerizing two or more olefin components may also be used.
  • a polyolefin resin contains an unsaturated carboxylic acid component.
  • unsaturated carboxylic acid components include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, itaconic anhydride, fumaric acid, crotonic acid, etc., as well as half esters and half amides of unsaturated dicarboxylic acids. is mentioned. Among them, acrylic acid, methacrylic acid, maleic acid, and maleic anhydride are preferable, and acrylic acid and maleic anhydride are particularly preferable, from the viewpoint of obtaining a coating film having even better adhesion to the substrate.
  • the unsaturated carboxylic acid component in the polyolefin resin is contained by random copolymerization, block copolymerization, graft copolymerization (graft modification), or the like.
  • the content of the unsaturated carboxylic acid component in the polyolefin resin is required to be 0.1 to 10% by mass, preferably 1 to 8% by mass, more preferably 2 to 5% by mass. . If the content of the unsaturated carboxylic acid component in the polyolefin resin is less than 0.1% by mass, it becomes difficult to obtain resin particles having two types of particle sizes within a specific range, and the aqueous dispersion of the resin becomes difficult. It can be difficult. In addition, when the content of the unsaturated carboxylic acid component exceeds 10% by mass, the polyolefin resin loses the low water absorbency and water resistance of the olefin resin. However, the resulting coating film may be inferior in barrier properties and rust prevention properties.
  • the content of the (meth)acrylate component in the polyolefin resin must be 1 to 20% by mass, preferably 2 to 19% by mass, and more preferably 4 to 18% by mass. . If the content of the (meth)acrylic acid ester component in the polyolefin resin is outside the above range, the resulting coating film will be inferior in barrier properties and rust prevention properties even if the particle sizes of the above two types are within the specified ranges. become a thing.
  • (meth)acrylic acid ester components include (meth)acrylic acid ester components such as methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate, dimethyl maleate, diethyl maleate, Maleic acid diester components such as dibutyl maleate; alkyl vinyl ether components such as methyl vinyl ether and ethyl vinyl ether; Examples thereof include vinyl alcohol obtained by saponification with a compound, a (meth)acrylic acid amide component, and the like, and a mixture thereof may also be used.
  • (meth)acrylic acid ester component and a vinyl ester component are preferred, and a (meth)acrylic acid ester component is more preferred.
  • (meth)acrylic acid- means "acrylic acid- or methacrylic acid-”.
  • polyolefin resins include ethylene/methyl (meth)acrylate/maleic anhydride copolymer, ethylene/ethyl (meth)acrylate/maleic anhydride copolymer, ethylene/butyl (meth)acrylate/anhydride Maleic acid copolymer, propylene/1-butene/methyl (meth)acrylate/maleic anhydride copolymer, propylene/1-butene/ethyl (meth)acrylate/maleic anhydride copolymer, propylene/1- Butene/butyl (meth)acrylate/maleic anhydride copolymer, propylene/methyl (meth)acrylate/maleic anhydride copolymer, propylene/ethyl (meth)acrylate/maleic anhydride copolymer, propylene/ Butyl (meth)acrylate/maleic anhydride copolymer, ethylene/propylene/methyl (meth)acrylate/maleic anhydride
  • the polyolefin resin may be chlorinated in the range of 5-40% by mass.
  • the maleic anhydride component constituting the polyolefin resin may be imidized, and its N position is an N,N-dimethylaminoethyl group, an N,N-dimethylaminopropyl group, or an N,N-dimethylaminobutyl group. , N,N-diethylaminoethyl group, N,N-diethylaminopropyl group, N,N-diethylaminobutyl group and the like.
  • the polyolefin resin particles In the aqueous dispersion of the present invention, the polyolefin resin particles have particle sizes measured by two methods (dynamic light scattering method and laser diffraction method) that satisfy specific ranges.
  • the polyolefin resin particles in the aqueous dispersion of the present invention must have a volume average particle diameter of 0.3 ⁇ m or less measured by a dynamic light scattering method, and 0.25 ⁇ m. It is preferably 0.2 ⁇ m or less, more preferably 0.15 ⁇ m or less.
  • the volume average particle diameter of the polyolefin resin particles can be controlled by, for example, selecting the type of basic compound or organic solvent added to the aqueous medium and adjusting the amount of these added in the method for producing an aqueous polyolefin resin dispersion described later. can do.
  • the polyolefin resin particles contained in the aqueous dispersion of the present invention have a diameter of 99.9% of the volume particle size cumulative distribution integrated from the small particle size side in the volume particle size distribution obtained when measured by the laser diffraction method. (hereinafter sometimes simply referred to as “99.9% diameter”) must be 10 ⁇ m or less, preferably 7 ⁇ m or less, more preferably 5 ⁇ m or less, and 2 ⁇ m or less. is more preferable, and 1 ⁇ m or less is particularly preferable.
  • a dynamic light scattering method is generally used as a method for measuring the diameter of resin particles contained in an aqueous dispersion. This is because the measurable range of particle size based on the principle of the dynamic light scattering method is about 1 nm to several ⁇ m, which substantially covers the range necessary for performance evaluation of aqueous dispersions. On the other hand, the measurable range of the laser diffraction method is about 10 nm to 3000 ⁇ m, and it is possible to measure large particle diameters far exceeding the measurable upper limit of the dynamic light scattering method.
  • the present inventors have focused on the particle size measurement results by the dynamic light scattering method and the particle size measurement results by the laser diffraction method of the polyolefin resin aqueous dispersion.
  • the volume average particle size measured by dynamic light scattering is 0.3 ⁇ m or less, and if particles larger than approximately 10 ⁇ m are not observed by laser diffraction, in other words, laser diffraction If the 99.9% diameter in the volume particle size distribution of the method is 10 ⁇ m or less, the coating film obtained from such an aqueous dispersion is suppressed in appearance defects and has excellent barrier properties and rust prevention properties.
  • the cooling rate when dispersing the polyolefin resin is specified. is preferably in the range of
  • aqueous medium In the aqueous dispersion of the present invention, polyolefin resin particles are dispersed in an aqueous medium.
  • the aqueous medium is a liquid containing water as a main component, and may contain organic solvents and basic compounds, which will be described later.
  • the aqueous medium preferably contains a hydrophilic organic solvent in order to promote the dispersion of the polyolefin resin particles, reduce the dispersed particle size, and satisfy the particle size specified in the present invention.
  • the content of the hydrophilic organic solvent is preferably 50% by mass or less with respect to the entire aqueous medium, more preferably 1 to 45% by mass, even more preferably 10 to 40% by mass, and 25 to 35% by mass is particularly preferred.
  • An aqueous medium containing more than 50% by mass of a hydrophilic organic solvent cannot be substantially regarded as an aqueous medium. Depending on the amount, the stability of the aqueous dispersion may decrease.
  • the hydrophilic organic solvent preferably has a solubility in water at 20° C. of 10 g/L or more, more preferably 20 g/L or more, from the viewpoint of obtaining an aqueous dispersion with good dispersion stability. More preferably 50 g/L or more.
  • the hydrophilic organic solvent preferably has a boiling point of 100°C or less from the viewpoint of efficiently drying and removing it in the process of forming a coating film. Hydrophilic organic solvents with a boiling point of more than 100 ° C. tend to be difficult to disperse from the coating film by drying, and in particular, the coating film dried at a low temperature has reduced water resistance and adhesion to the substrate. I have something to do.
  • Preferred hydrophilic organic solvents include, for example, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, tert-butanol, n-amyl alcohol, isoamyl alcohol, sec-amyl alcohol, tert- Alcohols such as amyl alcohol, 1-ethyl-1-propanol, 2-methyl-1-butanol, n-hexanol and cyclohexanol, ketones such as methyl ethyl ketone, methyl isobutyl ketone, ethyl butyl ketone and cyclohexanone, tetrahydrofuran, dioxane, etc.
  • ethers ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, sec-butyl acetate, 3-methoxybutyl acetate, methyl propionate, ethyl propionate, diethyl carbonate, carbonic acid Esters such as dimethyl, glycol derivatives such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol ethyl ether acetate, and 1-methoxy-2-propanol, 1 -ethoxy-2-propanol, 3-methoxy-3-methyl-1-butanol, methoxybutanol, acetonitrile, dimethylformamide, dimethylacetamide, diacetone alcohol, ethyl acetoacetate, 1,2-dimethylgly
  • polyolefin resin particles are obtained.
  • Isopropanol is particularly preferred because it is more effective in promoting dispersion.
  • the aqueous dispersion may contain a mixture of these hydrophilic organic solvents.
  • a hydrophobic organic solvent may be further contained in order to promote aqueous dispersion of the polyolefin resin.
  • the hydrophobic organic solvent is preferably an organic solvent having a solubility of less than 10 g/L in water at 20°C from the viewpoint of obtaining an aqueous dispersion with good dispersion stability. Moreover, in the process of forming a coating film, the organic solvent whose boiling point is 150 degreeC or less is preferable from a viewpoint of drying and removing efficiently.
  • hydrophobic organic solvents examples include olefinic solvents such as n-pentane, n-hexane, n-heptane, cycloheptane, cyclohexane and petroleum ether; aromatic solvents such as benzene, toluene and xylene; Halogen solvents such as carbon chloride, 1,2-dichloroethane, 1,1-dichloroethylene, trichlorethylene, 1,1,1-trichloroethane, chloroform, and the like can be mentioned.
  • the content of these hydrophobic organic solvents is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less relative to the aqueous dispersion. If the content of the hydrophobic organic solvent exceeds 15% by mass, gelation or the like may occur.
  • the organic solvent content in the aqueous dispersion can be reduced to 10% by weight or less, more preferably 5% by weight or less, and more preferably 1% by weight or less from the environmental point of view. In the stripping process, it is possible to distill off substantially all of the organic solvent used in the aqueous dispersing process.
  • the lower limit of the organic solvent content is preferably about 0.01% by mass.
  • a stripping method includes heating the aqueous dispersion under normal pressure or reduced pressure while stirring to distill off the organic solvent.
  • water is added to the aqueous dispersion in advance. good too.
  • the solid content concentration of the aqueous dispersion is not particularly limited and can be appropriately selected according to the application, etc. For example, it can be adjusted by a method of distilling off the aqueous medium or a method of diluting with water.
  • Basic compounds contained in the aqueous medium include ammonia, triethylamine, N,N-dimethylethanolamine, isopropylamine, aminoethanol, dimethylaminoethanol, diethylaminoethanol, ethylamine, diethylamine, isobutylamine, dipropylamine, 3-ethoxy Propylamine, 3-diethylaminopropylamine, sec-butylamine, propylamine, n-butylamine, 2-methoxyethylamine, 3-methoxypropylamine, 2,2-dimethoxyethylamine, monoethanolamine, morpholine, N-methylmorpholine, N - ethylmorpholine, pyrrole, pyridine and the like.
  • ammonia, triethylamine, and N,N-dimethylethanolamine are preferable from the viewpoint of accelerating the dispersion of the resin.
  • the amount of the basic compound to be added is preferably 0.5 to 10 equivalents, more preferably 0.8 to 8 equivalents, and 1.0 to 5 equivalents relative to the carboxyl groups in the polyolefin resin. Equivalent weights are particularly preferred. If the amount is less than 0.5 equivalents, dispersion becomes insufficient, and it may be difficult to obtain an aqueous dispersion having a resin particle size specified in the present invention. If the amount exceeds 10 equivalents, the drying time during coating film formation may become long, or the stability of the resulting aqueous dispersion may decrease.
  • the production method for obtaining the aqueous dispersion of the present invention is not particularly limited. , a basic compound, etc. are heated and stirred in a sealable container to disperse the resin.
  • a device used as a solid/liquid stirring device or an emulsifier can be used, and for example, it is preferable to use a device capable of applying a pressure of 0.1 MPa or more.
  • the method of stirring and the rotational speed of stirring are not particularly limited. Therefore, high-speed stirring (for example, 1000 rpm or more) is not essential, and the aqueous dispersion can be produced even with a simple apparatus.
  • aqueous dispersion it is preferable to mix raw materials such as a polyolefin resin and an aqueous medium, stir the mixture, and then cool the mixture from the stirring temperature to the lowest temperature at a cooling rate of 1°C/min or less.
  • the polyolefin resin particles can be cooled to 99.9% as measured by the above laser diffraction method.
  • the cooling rate is more preferably slow, more preferably 0.9° C./min or less, and particularly preferably 0.7° C./min or less.
  • the stirring temperature can be appropriately set from the viewpoint of pressure resistance, heating performance, energy cost, etc. of the apparatus, but it is preferably high from the viewpoint of keeping the particle size of the resin within the above range and from the viewpoint of dispersion stability. It is preferably 110° C. or higher, more preferably 120° C. or higher, and even more preferably 140° C. or higher.
  • the lowest temperature after cooling is not particularly limited, it is preferably 100°C or lower, more preferably 40°C or lower, for example.
  • the cooling may be performed in one stage at a cooling rate of 1° C./min or less, or may be performed in a plurality of stages of two or more stages with different cooling rates.
  • two-stage cooling such as cooling from the stirring temperature to a temperature of 100 ° C. or less and exceeding 40 ° C. at a cooling rate of 1 ° C./min or less and then cooling to 40 ° C. or less at a cooling rate of 3 ° C./min or less.
  • the cooling rate in the second stage is preferably 3° C./min or less, more preferably 2° C./min or less, and even more preferably 1° C./min or less.
  • the method for adjusting the cooling temperature is not particularly limited.
  • the steam, heat medium, A method of adjusting the temperature, etc. can be mentioned.
  • Non-Volatile Aqueous Agent Although the aqueous dispersion of the present invention does not exclude the inclusion of non-volatile water-improving aids, it is preferred that the dispersion contains substantially no non-volatile water-improving aids. In the present invention, it is possible to produce an aqueous dispersion in which polyolefin resin particles are excellent in dispersion stability and coarse resin particles are not present, even if substantially no non-volatile water-improving aid is contained.
  • aqueous agent refers to a drug or compound added for the purpose of promoting aqueous dispersion or stabilizing the aqueous dispersion in the production of the aqueous dispersion. , means that it has no boiling point at normal pressure or has a high boiling point (for example, 300° C. or higher) at normal pressure.
  • substantially free of non-volatile water-improving aids means that such aids are not used during production (during aqueous dispersion of the polyolefin resin), and the resulting aqueous dispersion contains this aid as a result. means not.
  • the content of the non-volatile water-improving aid is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably less than 0.5% by mass, and 0% by mass with respect to the polyolefin resin component. is most preferred.
  • non-volatile water-improving aid in the present invention examples include emulsifiers, compounds having a protective colloid action, modified waxes, acid-modified compounds with a high acid value, and water-soluble polymers.
  • Emulsifiers include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers, and amphoteric emulsifiers, and include surfactants in addition to those generally used for emulsion polymerization.
  • anionic emulsifiers include higher alcohol sulfates, higher alkylsulfonates, higher carboxylates, alkylbenzenesulfonates, polyoxyethylene alkylsulfates, polyoxyethylene alkylphenyl ether sulfates, vinyl sulfosuccinates, and the like.
  • nonionic emulsifiers include polyoxyethylene alkyl ethers, polyoxyethylene alkylphenyl ethers, polyethylene glycol fatty acid esters, ethylene oxide propylene oxide block copolymers, polyoxyethylene fatty acid amides, ethylene oxide-propylene oxide copolymers and other poly Compounds having an oxyethylene structure, sorbitan derivatives such as polyoxyethylene sorbitan fatty acid esters, and the like are included.
  • Amphoteric emulsifiers include lauryl betaine, lauryldimethylamine oxide and the like.
  • Compounds with protective colloid action, modified waxes, acid-modified compounds with high acid value, water-soluble polymers include polyvinyl alcohol, carboxyl group-modified polyvinyl alcohol, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, modified starch, polyvinylpyrrolidone.
  • polyacrylic acid and its salts carboxyl group-containing polyethylene wax, carboxyl group-containing polypropylene wax, carboxyl group-containing polyethylene-propylene wax and other acid-modified polyolefin waxes having a number average molecular weight of usually 5000 or less and salts thereof, acrylic acid-anhydride Maleic acid copolymer and its salt, styrene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid copolymer, isobutylene-maleic anhydride alternating copolymer, (meth)acrylic acid-(meth) Carboxyl group-containing polymers with an unsaturated carboxylic acid content of 10% by mass or more such as acrylic acid ester copolymers and salts thereof, polyitaconic acid and salts thereof, water-soluble acrylic copolymers having amino groups, gelatin, gum arabic and casein, which are generally used as dispersion stabilizers for fine particles.
  • the aqueous dispersion of the present invention may contain other polymers, tackifiers, inorganic particles, cross-linking agents, pigments, dyes and the like in order to further improve performance according to the purpose.
  • Other polymers and tackifiers are not particularly limited.
  • These polymers may be used as they are in solid form, but from the viewpoint of maintaining the stability of the aqueous disper
  • inorganic particles examples include metal oxides such as magnesium oxide, zinc oxide and tin oxide, inorganic compounds such as calcium carbonate and silica, layered inorganic compounds such as vermiculite, montmorillonite, hectorite, hydrotalcite and synthetic mica. .
  • the average particle size of these inorganic particles is preferably 0.005 to 10 ⁇ m from the viewpoint of the transparency of the coating film.
  • a plurality of inorganic particles may be mixed and used.
  • a cross-linking agent having self-crosslinking properties a compound having a plurality of functional groups that react with the unsaturated carboxylic acid component in the molecule, a metal having a polyvalent coordination site, or the like can be used.
  • Specific examples include oxazoline group-containing compounds, carbodiimide group-containing compounds, isocyanate group-containing compounds, epoxy group-containing compounds, melamine compounds, urea compounds, zirconium salt compounds, silane coupling agents, and the like. You can use a mixture of things. Among them, oxazoline group-containing compounds, carbodiimide group-containing compounds, isocyanate group-containing compounds, and epoxy group-containing compounds are preferable from the viewpoint of ease of handling.
  • Pigments and dyes include titanium oxide, zinc oxide, carbon black, etc. Any of disperse dyes, acid dyes, cationic dyes, reactive dyes, etc. can be used.
  • the aqueous dispersion of the present invention further contains various agents such as leveling agents, antifoaming agents, anti-popping agents, pigment dispersants, ultraviolet absorbers, thickeners, weathering agents and flame retardants. good too.
  • the coating film of the present invention is obtained from the aqueous dispersion and has excellent barrier properties.
  • the barrier properties are measured by water vapor permeability, and in the present invention, the water vapor permeability of the coating film obtained by drying at 80°C must be 150 ml/(m 2 ⁇ day ⁇ MPa) or less. is preferred, and 100 ml/(m 2 ⁇ day ⁇ MPa) or less is more preferable.
  • a method for measuring the water vapor transmission rate will be described in detail in the Examples.
  • the aqueous dispersion of the present invention is excellent in the antirust properties of the resulting coating film.
  • a coating film obtained by drying at 80° C. on a metal plate is sprayed with an aqueous NaCl solution, and after 100 hours, the rusted area ratio is preferably less than 50%.
  • a method for calculating the rusted area ratio will be described in detail in Examples.
  • the polyolefin resin particles have a small particle size and are stably and uniformly dispersed in the aqueous medium without containing coarse resin particles, thereby suppressing defects in appearance. It is possible to obtain a coating film excellent in barrier properties and rust prevention properties.
  • the aqueous dispersion of the present invention is excellent in film-forming ability.
  • the aqueous dispersion of the present invention is uniformly applied to the surface of various substrates, set at around room temperature as necessary, and then dried or dried. and heat treatment for baking. Thereby, a uniform coating film can be adhered to various substrate surfaces.
  • aqueous dispersion to the substrate can be performed by known methods such as gravure roll coating, reverse roll coating, wire bar coating, lip coating, air knife coating, curtain flow coating, spray coating, dip coating, brush coating, and the like. can be adopted.
  • the amount of the aqueous dispersion to be applied to the base material is not particularly limited, and may be appropriately selected depending on the application. It is more preferably 1 to 50 g/m 2 and even more preferably 0.2 to 30 g/m 2 .
  • aqueous dispersion whose concentration is adjusted according to the desired thickness of the coating film. is preferred.
  • concentration of the aqueous dispersion can be adjusted by adjusting the charge composition at the time of preparation, and the once prepared aqueous dispersion may be adjusted by appropriately diluting or concentrating.
  • an ordinary hot air circulation oven, an infrared heater, or the like can be used as a heating device for the heat treatment after coating.
  • the heating temperature and heating time are appropriately selected depending on the properties of the base material or the amount of various components that can be arbitrarily added to the aqueous dispersion, but the heating temperature is low from the viewpoint of energy cost and damage to the base material. From the viewpoint of productivity, a shorter heating time is preferred.
  • the heating temperature is preferably 20 to 130°C, more preferably 30 to 120°C, even more preferably 40 to 100°C.
  • the heating time is preferably 1 second to 20 minutes, more preferably 5 seconds to 15 minutes, even more preferably 5 seconds to 10 minutes.
  • the heating temperature and time should be appropriately selected according to the type of the cross-linking agent in order to allow the reaction between the carboxyl groups in the polyolefin resin and the cross-linking agent to proceed sufficiently. is desirable.
  • the aqueous dispersion of the present invention can be suitably used as adhesives, coating agents, primers, paints, inks and the like. Since the aqueous dispersion of the present invention is even more excellent in barrier properties and rust prevention properties when it is formed into a coating film, it is particularly suitable for use in metal products, electronic devices, packaging materials, automobile parts, and the like. Specific examples of these uses include anchor coating agents for PP extrusion lamination, coating agents for secondary battery separators, primers for UV curable coating agents, primers for shoes, primers for automobile bumpers, primers for clear boxes, and PP substrates.
  • Paints adhesives for packaging materials, adhesives for paper containers, adhesives for lid materials, adhesives for in-mold transfer foils, adhesives for PP steel plates, adhesives for solar cell modules, adhesives for flocking, secondary battery electrodes adhesives for binders, secondary battery exterior adhesives, automobile belt molding adhesives, automobile member adhesives, different base material adhesives, fiber sizing agents, and the like.
  • composition and physical properties of the polyolefin resin aqueous dispersion, the properties of the coating film, and the like were measured or evaluated by the following methods.
  • composition of polyolefin resin Determined with a 1 H-NMR spectrometer (manufactured by JEOL Ltd., ECA500, 500 MHz). Measured at 120° C. using tetrachloroethane (d2) as a solvent.
  • Viscosity of Aqueous Dispersion The rotational viscosity (mPa s) of the filtered aqueous dispersion at a temperature of 20° C. was measured using a B-type viscometer (manufactured by Tokimec, DVL-BII digital viscometer). .
  • the aqueous dispersion is applied to the corona-treated surface of a nylon film (ON-15 manufactured by Unitika) using a Meyer bar so that the film thickness after drying is 10 ⁇ m, and the film is dried at 150° C. formed.
  • the water vapor transmission rate of the obtained sample was measured under the conditions of 40° C. and 100% RH using a moisture permeability meter (PERMATRAN-W3/31MW manufactured by Mocon Co., Ltd.).
  • the polyolefin resins (P-1) to (P-13) used in Examples and Comparative Examples are as follows. Table 1 shows the composition and physical properties of these polyolefin resins.
  • Polyolefin resin (P-1) Ethylene-ethyl acrylate-maleic anhydride copolymer (Bondyne HX-8290 manufactured by Arkema) was used.
  • Polyolefin resin (P-2) Ethylene-ethyl acrylate-maleic anhydride copolymer (Bondyne LX-4110 manufactured by Arkema) was used.
  • Polyolefin resins (P-3), (P-4), (P-7), (P-8), (P-12), (P-13) Based on the method described in Example 1 of JP-A-61-60709, ethylene-ethyl acrylate-maleic anhydride copolymer (P-3) was prepared so as to have the composition shown in Table 1. Obtained. Similarly, polyolefin resins (P-4), (P-7), (P-8), (P-12) and (P-13) having the compositions shown in Table 1 were obtained.
  • MFR 0.1 g/10 min-170°C, 2160 g
  • Polyolefin resin (P-9) Polyolefin resin (P-9) was obtained in the same manner as in the production of polyolefin resin (P-5), except that ethyl acrylate was not added.
  • Polyolefin resin (P-10) Polyolefin resin (P-10) was obtained in the same manner as in the production of polyolefin resin (P-6), except that ethyl acrylate was not added.
  • Polyolefin resin (P-11) An ethylene-methacrylic acid copolymer (Nucrel AN42115C manufactured by Mitsui DuPont Chemical Co., Ltd.) was used.
  • Example 1 60.0 g of polyolefin resin (P-1), 60.0 g of isopropanol (IPA), 3.9 g (maleic anhydride N,N-Dimethylethanolamine (DMEA) of 1.2 equivalents to the carboxyl group) and 176.1 g of distilled water were charged in a glass container, and the rotation speed of the stirring blade was set to 300 rpm while stirring, and the heater was turned on. The power was turned on and the temperature was raised to 140°C. Stirring was performed for 60 minutes while maintaining the temperature at 140°C. Thereafter, the heating was stopped while the stirring speed was maintained, and the mixture was cooled to 100°C over 60 minutes, then placed in a water bath and cooled to 40°C over 30 minutes. Pressure filtration (air pressure 0.2 MPa) was performed through a 300-mesh stainless steel filter (wire diameter 0.035 mm, plain weave) to obtain a milky white uniform aqueous dispersion.
  • P-1 polyolefin resin
  • IPA isoprop
  • Example 2 The same operation as in Example 1 was performed except that the amount of DMEA was changed as shown in Table 2.
  • Example 3 The same operation as in Example 1 was performed except that the cooling rate from the stirring temperature (140° C.) to 100° C. was changed as shown in Table 2.
  • Example 4 The same operation as in Example 1 was performed except that the cooling rate from 100° C. to 40° C. was changed as shown in Table 2.
  • Example 5 The same operation as in Example 1 was performed except that the temperature during stirring was changed to 120°C.
  • Examples 6, 8-11 The same operation as in Example 1 was performed except that the polyolefin resin was changed to P-2 to P-6, respectively, as shown in Tables 2 and 3.
  • Example 7 The same operation as in Example 6 was performed except that the temperature during stirring was changed to 120°C.
  • Example 12 The same operation as in Example 1 was performed except that cooling was not performed in two steps, but cooling was performed in one step from the stirring temperature (140° C.) to 40° C. over 100 minutes.
  • Example 13 In Example 1, the same operation was performed except that the first stage cooling was performed from the stirring temperature to 80 ° C. over 90 minutes, and the second stage cooling was performed from 80 ° C. to 40 ° C. over 20 minutes. .
  • Example 14 The same operation as in Example 1 was performed except that the organic solvent was changed to tetrahydrofuran (THF).
  • Example 15 The same operation as in Example 1 was performed, except that the amount of IPA added was changed as shown in Table 3.
  • Comparative example 1 The same operation as in Example 1 was performed, except that the cooling rate from 140° C. to 100° C. was changed as shown in Table 4.
  • Comparative Examples 2-6 The same procedure as in Comparative Example 1 was performed except that the polyolefin resin was changed to P-2, P-4, P-5, P-6 and P-7 as shown in Table 4.
  • Comparative example 7 The same operation as in Example 1 was performed, except that the amount of IPA added and the amount of DMEA added were changed as shown in Table 4.
  • Comparative Examples 8-14 The same operation as in Example 1 was performed except that the polyolefin resin was changed to P-7 to P-13, respectively, as shown in Table 5.
  • Tables 2 to 5 summarize the manufacturing conditions of the aqueous dispersions in Examples and Comparative Examples, the compositions of the resulting aqueous dispersions and coating films made of them, and the evaluation results.
  • an aqueous dispersion was obtained using an organic solvent or a basic compound through a high-temperature stirring process and filtration using a filter.
  • the cooling rate is fast as in Comparative Examples 1 to 7, even if an organic solvent or a basic compound is used, and even after stirring and filtration, only an aqueous dispersion in which the 99.9% diameter of the polyolefin resin particles exceeds 10 ⁇ m.
  • the coating film had many defects in appearance and was inferior in barrier properties and rust prevention properties.
  • Example 15 when the aqueous dispersion of the present invention was used as a coating film, defects in appearance were suppressed, and it was possible to obtain a coating film having excellent barrier properties and rust prevention properties. Further, even if the amount of the basic compound added during aqueous dispersion is reduced as in Example 2, or the amount of the organic solvent added is reduced as in Example 15, the aqueous dispersion of the present invention can be obtained. It was possible to obtain a coating film excellent in each performance. Furthermore, the cooling rate during aqueous dispersion was increased as in Example 3 or 4, the stirring temperature during aqueous dispersion was decreased as in Example 5, and the temperature was reduced to 1 stage instead of 2 stages as in Example 12.
  • aqueous dispersion of the present invention it is possible to obtain the aqueous dispersion of the present invention even by cooling in stages or changing the temperature in the first stage of cooling as in Example 13, and it is possible to obtain a coating film excellent in each performance.
  • Met Furthermore, even if the type of polyolefin resin used is changed as in Examples 6 to 11, or the type of organic solvent to be added is changed as in Example 14, the aqueous dispersion of the present invention can be obtained. It was possible to obtain a coating film excellent in each performance.
  • Comparative Example 6 uses a polyolefin resin in which the content of the (meth)acrylic acid ester component is below the specified range of the present invention, and the cooling rate during cooling during aqueous dispersion is set to a high condition.
  • the obtained aqueous dispersion had a volume particle size distribution of 99.9% exceeding 10 ⁇ m in volume particle size distribution measured by a laser diffraction method.
  • the results were inferior in terms of durability and rust resistance.
  • the aqueous dispersion of Comparative Example 8 uses a polyolefin resin having a (meth)acrylic acid ester component content below the specified range of the present invention.
  • the 99.9% diameter and volume average particle diameter of this aqueous dispersion were within the range of the present invention, but the resulting coating film was inferior in barrier properties and rust prevention properties.
  • the aqueous dispersion of Comparative Example 9 uses a polyolefin resin in which the content of the (meth)acrylic acid ester component exceeds the specified range of the present invention.
  • the 99.9% diameter and volume average particle diameter of this aqueous dispersion were within the range of the present invention, but the resulting coating film was inferior in barrier properties and rust prevention properties.
  • the aqueous dispersions of Comparative Examples 10 to 12 used polyolefin resins containing no (meth)acrylate component.
  • the 99.9% diameter and volume average particle diameter of this aqueous dispersion were within the range of the present invention, but the resulting coating film was inferior in barrier properties and rust prevention properties.
  • Comparative Example 13 uses a polyolefin resin having an unsaturated carboxylic acid content below the specified range of the present invention.
  • the polyolefin resin only swelled with the solvent and did not disperse, and an aqueous dispersion could not be obtained.
  • the aqueous dispersion of Comparative Example 14 uses a polyolefin resin having an unsaturated carboxylic acid content exceeding the specified range of the present invention. This aqueous dispersion had a 99.9% diameter and a volume average particle diameter within the range of the present invention, but the resulting coating film was inferior in barrier properties and rust prevention properties.

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Abstract

La présente invention concerne une dispersion de résine aqueuse de polyoléfine contenant des particules de résine de polyoléfine et un milieu aqueux. La résine de polyoléfine contient 0,1-10 % en masse d'un composant d'acide carboxylique insaturé et 1-20 % en masse d'un composant ester d'acide (méth) acrylique. Le diamètre de particule moyen en volume mesuré par diffusion de lumière dynamique des particules de résine de polyoléfine est de 0,3 µm ou moins, et dans une distribution de taille de particule volumique mesurée par diffraction laser, le diamètre de 99,9 % de la distribution intégrée de diamètre de particule volumique intégré à partir de la taille de petit diamètre de particule est de 10 µm ou moins.
PCT/JP2022/027882 2021-07-30 2022-07-15 Dispersion de résine de polyoléfine et son procédé de fabrication WO2023008235A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3026209B1 (ja) * 1998-10-27 2000-03-27 京都大学長 高分子樹脂の結晶化方法
JP2003171512A (ja) * 2001-12-05 2003-06-20 Unitika Ltd ポリオレフィン樹脂水性分散体、及びその製造方法
WO2004104090A1 (fr) * 2003-05-22 2004-12-02 Unitika Ltd. Dispersion de resine polyolefinique aqueuse, procede de production correspondant et materiau de revetement diluable a l'eau comprenant ladite dispersion
JP2006045295A (ja) * 2004-08-03 2006-02-16 Sumitomo Seika Chem Co Ltd ポリオレフィン系樹脂粒子の製造方法
JP2011144220A (ja) * 2010-01-12 2011-07-28 Dic Corp ポリプロピレンワックス分散体の製造方法
WO2017195828A1 (fr) * 2016-05-13 2017-11-16 住友化学株式会社 Dispersion aqueuse, film de revêtement, et stratifié

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3026209B1 (ja) * 1998-10-27 2000-03-27 京都大学長 高分子樹脂の結晶化方法
JP2003171512A (ja) * 2001-12-05 2003-06-20 Unitika Ltd ポリオレフィン樹脂水性分散体、及びその製造方法
WO2004104090A1 (fr) * 2003-05-22 2004-12-02 Unitika Ltd. Dispersion de resine polyolefinique aqueuse, procede de production correspondant et materiau de revetement diluable a l'eau comprenant ladite dispersion
JP2006045295A (ja) * 2004-08-03 2006-02-16 Sumitomo Seika Chem Co Ltd ポリオレフィン系樹脂粒子の製造方法
JP2011144220A (ja) * 2010-01-12 2011-07-28 Dic Corp ポリプロピレンワックス分散体の製造方法
WO2017195828A1 (fr) * 2016-05-13 2017-11-16 住友化学株式会社 Dispersion aqueuse, film de revêtement, et stratifié

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