WO2023008235A1 - Polyolefin resin dispersion and method for manufacturing same - Google Patents

Polyolefin resin dispersion and method for manufacturing same 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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Prior art keywords
polyolefin resin
aqueous dispersion
less
cooling
temperature
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PCT/JP2022/027882
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French (fr)
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 KR1020237034730A priority Critical patent/KR20240041858A/en
Priority to CN202280052222.0A priority patent/CN117715972A/en
Publication of WO2023008235A1 publication Critical patent/WO2023008235A1/en

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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

The present invention is a polyolefin aqueous resin dispersion containing polyolefin resin particles and an aqueous medium. The polyolefin resin contains 0.1-10% by mass of unsaturated carboxylic acid component and 1-20% by mass of (meth)acrylic acid ester component. The volume average particle diameter measured by dynamic light scattering of the polyolefin resin particles is 0.3 μm or below, and in a volume particle size distribution measured by laser diffraction, the 99.9% diameter of the volume particle diameter integrated distribution integrated from the small particle diameter size is 10 μm or lower.

Description

ポリオレフィン樹脂水性分散体、およびその製造方法POLYOLEFIN RESIN AQUEOUS DISPERSION AND METHOD FOR PRODUCING SAME
　本発明は、ポリオレフィン樹脂の水性分散体に関する。 The present invention relates to an aqueous dispersion of polyolefin resin.
　ポリオレフィン樹脂の水性分散体は、様々な基材に対して優れた密着性を有する塗膜が得られることから、幅広い用途へ展開されている。なかでも、（メタ）アクリル酸エステルを共重合成分として含む酸変性ポリオレフィン樹脂を用いた水性分散体は、使用できる基材の汎用性が高く、コーティング剤、接着剤等に広く用いられている（例えば、特許文献１）。 Aqueous dispersions of polyolefin resins are used in a wide range of applications because they provide coatings with excellent adhesion to various substrates. Among them, 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).
特許第３６９９９３５号公報Japanese Patent No. 3699935
　前記水性分散体から得られる塗膜は、特に、湿度のような周囲環境に影響を受け易い用途、または長期間安定して内容物を保管する用途（金属製品、電子機器、自動車部品、包装材料等）においては、バリア性や防錆性が求められる場合があり、性能向上が望まれている。すなわち、本発明の技術的な課題は、外観欠点が少なく、バリア性や防錆性に優れる塗膜を形成し得る、水性分散体を提供することである。 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.
　本発明者らは、上記課題を解決するために鋭意検討した結果、前記水性分散体には、従来の一般的な樹脂粒子径の測定方法である動的光散乱法では確認できなかった粗大な樹脂粒子が存在し、この粗大樹脂粒子の存在が、塗膜における外観欠点（塗膜表面の微小な突起、塗膜の割れ等）につながり、その結果、塗膜において、バリア性や防錆性が低下することを突き止めた。
　すなわち、本発明者らは、ポリオレフィン樹脂粒子を含有する水性分散体は、レーザー回折法を用いて測定された樹脂粒子径が特定範囲であると、粗大な樹脂粒子を含まず均一に水性媒体に分散しているので、この水性分散体から得られる塗膜は、外観欠点が抑制され、バリア性、防錆性に優れることを見出し、本発明に達した。すなわち本発明の要旨は下記の通りである。 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. 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.
　本発明の、ポリオレフィン樹脂粒子および水性媒体を含有するポリオレフィン樹脂水性分散体は、
ポリオレフィン樹脂が、不飽和カルボン酸成分０．１～１０質量％と、（メタ）アクリル酸エステル成分１～２０質量％とを含み、
ポリオレフィン樹脂粒子の、動的光散乱法で測定した体積平均粒子径が、０．３μｍ以下であって、かつレーザー回折法で測定した体積粒度分布において、小粒子径側から積算した体積粒子径積算分布の９９．９％径が、１０μｍ以下であることを特徴とする。
　本発明の塗膜は、上記のポリオレフィン樹脂水性分散体から得られたものである。
　本発明のポリオレフィン樹脂水性分散体の製造方法は、上記のポリオレフィン樹脂水性分散体を製造するための方法であって、１１０℃以上の温度で、ポリオレフィン樹脂と水性媒体とを攪拌する攪拌工程後に、１℃／分以下の速度で冷却する冷却工程を含むことを特徴とするものである。
　本発明のポリオレフィン樹脂水性分散体の製造方法によれば、冷却工程が、１℃／分以下の冷却速度で最高温度から１００℃以下かつ４０℃を超える温度に冷却する第一の冷却工程後に、３℃／分以下の冷却速度で４０℃以下に冷却する第二の冷却工程を含むことが好適である。
　本発明のポリオレフィン樹脂水性分散体の製造方法によれば、攪拌工程が、１１０℃以上かつ、ポリオレフィン樹脂の融点よりも２０℃以上高い温度で攪拌するものであることが好適である。 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 μm 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 μm 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. at a cooling rate of 1° C./min or less, It is preferred to include a second cooling step of cooling to 40°C or less at a cooling rate of 3°C/min or less.
According to the method for producing the polyolefin resin aqueous dispersion of the present invention, 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.
　本発明のポリオレフィン樹脂水性分散体は、ポリオレフィン樹脂粒子が小さい粒子径で安定的に、かつ粗大な粒子を含まず均一に水性媒体に分散しているので、得られた塗膜は、外観欠点が抑制され、バリア性、防錆性に優れる。 In the polyolefin resin aqueous dispersion of the present invention, 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.
　本発明のポリオレフィン樹脂水性分散体（以下、単に「水性分散体」と称する場合がある）は、ポリオレフィン樹脂粒子および水性媒体を含む。 The polyolefin resin aqueous dispersion of the present invention (hereinafter sometimes simply referred to as "aqueous dispersion") contains polyolefin resin particles and an aqueous medium.
（ポリオレフィン樹脂）
　ポリオレフィン樹脂の主成分であるオレフィン成分は、特に限定されないが、エチレン、プロピレン、イソブチレン、２－ブテン、１－ブテン、１－ペンテン、１－ヘキセン、１－オクテン、４－メチル－１－ペンテン、３－メチル－１－ペンテン、ノルボルネン類等のアルケン類、ブタジエンやイソプレン等のジエン類等が挙げられる。これらの混合物であってもよい。また、オレフィン成分の２種類以上が共重合されたものを用いてもよい。 (polyolefin resin)
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.
　ポリオレフィン樹脂は、不飽和カルボン酸成分を含有する。不飽和カルボン酸成分としては、例えば、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸、イタコン酸、無水イタコン酸、フマル酸、クロトン酸等のほか、不飽和ジカルボン酸のハーフエステル、ハーフアミド等が挙げられる。中でも、基材との接着性がいっそう優れる塗膜が得られる観点から、アクリル酸、メタクリル酸、マレイン酸、無水マレイン酸が好ましく、特にアクリル酸、無水マレイン酸が好ましい。 A polyolefin resin contains an unsaturated carboxylic acid component. Examples of 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.
　ポリオレフィン樹脂中の不飽和カルボン酸成分は、ランダム共重合、ブロック共重合、グラフト共重合（グラフト変性）等により含有される。 The unsaturated carboxylic acid component in the polyolefin resin is contained by random copolymerization, block copolymerization, graft copolymerization (graft modification), or the like.
　ポリオレフィン樹脂における不飽和カルボン酸成分の含有量は、０．１～１０質量％であることが必要であり、１～８質量％であることが好ましく、２～５質量％であることがより好ましい。ポリオレフィン樹脂は、不飽和カルボン酸成分の含有量が０．１質量％未満であると、２種類の粒子径が特定範囲である樹脂粒子を得ることが困難となったり、樹脂の水性分散化が困難となることがある。また、ポリオレフィン樹脂は、不飽和カルボン酸成分の含有量が１０質量％を超えると、オレフィン樹脂の有する低吸水性や耐水性が失われるため、上記の２種類の粒子径が特定範囲であっても、得られる塗膜は、バリア性や防錆性に劣る場合がある。 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.
　ポリオレフィン樹脂における（メタ）アクリル酸エステル成分の含有量は、１～２０質量％であることが必要であり、２～１９質量％であることが好ましく、４～１８質量％であることがより好ましい。
　ポリオレフィン樹脂は、（メタ）アクリル酸エステル成分の含有量が上記範囲を外れると、上記の２種類の粒子径が特定範囲であっても、得られる塗膜は、バリア性や防錆性に劣るものとなる。
　（メタ）アクリル酸エステル成分としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ブチル等の（メタ）アクリル酸エステル成分、マレイン酸ジメチル、マレイン酸ジエチル、マレイン酸ジブチル等のマレイン酸ジエステル成分、メチルビニルエーテル、エチルビニルエーテル等のアルキルビニルエーテル成分、ギ酸ビニル、酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、バーサチック酸ビニル等のビニルエステル成分、ビニルエステル成分を塩基性化合物等でケン化して得られるビニルアルコール、（メタ）アクリル酸アミド成分等が挙げられ、これらの混和物であってもよい。中でも、（メタ）アクリル酸エステル成分、ビニルエステル成分が好ましく、（メタ）アクリル酸エステル成分がより好ましい。なお、「（メタ）アクリル酸～」とは、「アクリル酸～、またはメタクリル酸～」を意味する。 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.
Examples of (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. Among them, a (meth)acrylic acid ester component and a vinyl ester component are preferred, and a (meth)acrylic acid ester component is more preferred. Incidentally, "(meth)acrylic acid-" means "acrylic acid- or methacrylic acid-".
　ポリオレフィン樹脂の具体例としては、エチレン／（メタ）アクリル酸メチル／無水マレイン酸共重合体、エチレン／（メタ）アクリル酸エチル／無水マレイン酸共重合体、エチレン／（メタ）アクリル酸ブチル／無水マレイン酸共重合体、プロピレン／１－ブテン／（メタ）アクリル酸メチル／無水マレイン酸共重合体、プロピレン／１－ブテン／（メタ）アクリル酸エチル／無水マレイン酸共重合体、プロピレン／１－ブテン／（メタ）アクリル酸ブチル／無水マレイン酸共重合体、プロピレン／（メタ）アクリル酸メチル／無水マレイン酸共重合体、プロピレン／（メタ）アクリル酸エチル／無水マレイン酸共重合体、プロピレン／（メタ）アクリル酸ブチル／無水マレイン酸共重合体、エチレン／プロピレン／（メタ）アクリル酸メチル／無水マレイン酸共重合体、エチレン／プロピレン／（メタ）アクリル酸エチル／無水マレイン酸共重合体、エチレン／プロピレン／（メタ）アクリル酸ブチル／無水マレイン酸共重合体等が挙げられる。 Specific examples of 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 copolymer, ethylene/propylene/ethyl (meth)acrylate/maleic anhydride copolymer, Examples thereof include ethylene/propylene/butyl (meth)acrylate/maleic anhydride copolymers.
　ポリオレフィン樹脂は５～４０質量％の範囲で塩素化されていてもよい。 The polyolefin resin may be chlorinated in the range of 5-40% by mass.
　ポリオレフィン樹脂を構成する無水マレイン酸成分は、イミド化されていてもよく、そのＮ位は、Ｎ，Ｎ－ジメチルアミノエチル基、Ｎ，Ｎ－ジメチルアミノプロピル基、Ｎ，Ｎ－ジメチルアミノブチル基、Ｎ，Ｎ－ジエチルアミノエチル基、Ｎ，Ｎ－ジエチルアミノプロピル基、Ｎ，Ｎ－ジエチルアミノブチル基等で置換されていてもよい。 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.
（ポリオレフィン樹脂粒子）
　本発明の水性分散体において、ポリオレフィン樹脂粒子は、２種類の方法（動的光散乱法、およびレーザー回折法）で測定される粒子径が、何れも特定範囲を満足するものである。 (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.
　本発明の水性分散体におけるポリオレフィン樹脂粒子は、微細かつ安定に分散される観点から、動的光散乱法で測定した体積平均粒子径が０．３μｍ以下であることが必要であり、０．２５μｍ以下であることが好ましく、０．２μｍ以下であることがより好ましく、０．１５μｍ以下であることがさらに好ましい。
　ポリオレフィン樹脂粒子の体積平均粒子径は、例えば、後述のポリオレフィン樹脂水性分散体の製造方法において、水性媒体に添加する塩基性化合物や有機溶剤の種類の選択や、これらの添加量の調整により、制御することができる。 From the viewpoint of being finely and stably dispersed, the polyolefin resin particles in the aqueous dispersion of the present invention must have a volume average particle diameter of 0.3 μm or less measured by a dynamic light scattering method, and 0.25 μm. It is preferably 0.2 μm or less, more preferably 0.15 μm 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.
　さらに、本発明の水性分散体に含有されるポリオレフィン樹脂粒子は、レーザー回折法で測定した際に得られる体積粒度分布において、小粒径側から積算した体積粒子径積算分布の９９．９％径（以下、単に「９９．９％径」と称する場合がある）が１０μｍ以下であることが必要であり、７μｍ以下であることが好ましく、５μｍ以下であることがより好ましく、２μｍ以下であることがさらに好ましく、１μｍ以下であることが特に好ましい。 Furthermore, 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 μm or less, preferably 7 μm or less, more preferably 5 μm or less, and 2 μm or less. is more preferable, and 1 μm or less is particularly preferable.
　水性分散体中に含有される樹脂粒子径の測定方法としては、動的光散乱法が一般的である。動的光散乱法の原理による粒子径測定可能範囲は１ｎｍ～数μｍ程度とされており、水性分散体の性能評価に必要な範囲をほぼ網羅するからである。これに対して、レーザー回折法の測定可能範囲は１０ｎｍ～３０００μｍ程度であり、動的光散乱法の測定可能上限をはるかに超える、大きな粒子径の測定が可能である。
　本発明者らは、ポリオレフィン樹脂水性分散体の動的光散乱法による粒子径測定結果およびレーザー回折法による粒子径測定結果に着目した結果、動的光散乱法において十分に平均粒子径が小さい場合であっても、動的光散乱法の測定可能範囲上限を超える粗大粒子がレーザー回折法で観測される場合があるとの知見を得た。そして、本発明者らは、動的光散乱法で測定した体積平均粒子径が０．３μｍ以下であり、かつ、レーザー回折法により概ね１０μｍを超える粒子が観測されなければ、言い換えれば、レーザー回折法の体積粒度分布における９９．９％径が１０μｍ以下であれば、こうした水性分散体から得られる塗膜は、外観欠点が抑制され、バリア性、防錆性に優れることを見出したのである。 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 μm, 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 μm, 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. However, it was found that coarse particles exceeding the upper limit of the measurable range of the dynamic light scattering method may be observed by the laser diffraction method. The present inventors have found that the volume average particle size measured by dynamic light scattering is 0.3 μm or less, and if particles larger than approximately 10 μm 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 μm 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.
　樹脂粒子径を上記のレーザー回折法による９９．９％径を特定範囲とするための手法としては、後述する本発明の水性分散体の製造方法において、ポリオレフィン樹脂を分散させる際の冷却速度を特定の範囲とすることが好ましい。 As a method for setting the resin particle size to a specific range of 99.9% diameter by the above laser diffraction method, in the method for producing an aqueous dispersion of the present invention described later, the cooling rate when dispersing the polyolefin resin is specified. is preferably in the range of
（水性媒体）
　本発明の水性分散体は、ポリオレフィン樹脂粒子が水性媒体中に分散されている。本発明において水性媒体とは水を主成分とする液体であり、後述する有機溶剤や塩基性化合物を含有していてもよい。 (aqueous medium)
In the aqueous dispersion of the present invention, polyolefin resin particles are dispersed in an aqueous medium. In the present invention, 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.
（親水性有機溶剤）
　ポリオレフィン樹脂粒子の分散を促進し、分散粒子径を小さくし、本発明で規定する粒子径を満足するために、水性媒体は、親水性有機溶剤を含有することが好ましい。親水性有機溶剤の含有量は、水性媒体全体に対し５０質量％以下であることが好ましく、１～４５質量％であることがより好ましく、１０～４０質量％であることがさらに好ましく、２５～３５質量％であることが特に好ましい。親水性有機溶剤の含有量が５０質量％を超える水性媒体は、実質的に水性媒体と見なせなくなり、本発明の目的のひとつ（環境保護）を逸脱するだけでなく、使用する親水性有機溶剤によっては水性分散体の安定性が低下することがある。 (Hydrophilic organic solvent)
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.
　親水性有機溶剤は、分散安定性が良好な水性分散体を得るという点から、２０℃の水に対する溶解性が１０ｇ／Ｌ以上であることが好ましく、２０ｇ／Ｌ以上であることがより好ましく、５０ｇ／Ｌ以上であることがさらに好ましい。 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.
　親水性有機溶剤は、塗膜を形成する過程で、効率よく乾燥除去させる観点から、沸点が１００℃以下であることが好ましい。沸点が１００℃を超える親水性有機溶剤は、塗膜から乾燥により飛散させることが困難となる傾向にあり、特に低温で乾燥させた塗膜は、耐水性や基材との接着性等が低下することがある。 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.
　好ましい親水性有機溶剤としては、例えば、メタノール、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、イソブタノール、ｓｅｃ－ブタノール、ｔｅｒｔ－ブタノール、ｎ－アミルアルコール、イソアミルアルコール、ｓｅｃ－アミルアルコール、ｔｅｒｔ－アミルアルコール、１－エチル－１－プロパノール、２－メチル－１－ブタノール、ｎ－ヘキサノール、シクロヘキサノール等のアルコール類、メチルエチルケトン、メチルイソブチルケトン、エチルブチルケトン、シクロヘキサノン等のケトン類、テトラヒドロフラン、ジオキサン等のエーテル類、酢酸エチル、酢酸－ｎ－プロピル、酢酸イソプロピル、酢酸－ｎ－ブチル、酢酸イソブチル、酢酸－ｓｅｃ－ブチル、酢酸－３－メトキシブチル、プロピオン酸メチル、プロピオン酸エチル、炭酸ジエチル、炭酸ジメチル等のエステル類、エチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールエチルエーテルアセテート等のグリコール誘導体、さらには、１－メトキシ－２－プロパノール、１－エトキシ－２－プロパノール、３－メトキシ－３－メチル－１－ブタノール、メトキシブタノール、アセトニトリル、ジメチルホルムアミド、ジメチルアセトアミド、ジアセトンアルコール、アセト酢酸エチル、１，２－ジメチルグリセリン、１，３－ジメチルグリセリン、トリメチルグリセリン等が挙げられる。 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-dimethylglycerin, 1,3-dimethyl glycerin, trimethylglycerin and the like.
　中でも、エタノール、ｎ－プロパノール、イソプロパノール、ｎ－ブタノール、メチルエチルケトン、シクロヘキサノン、テトラヒドロフラン、ジオキサン、エチレングリコールモノエチルエーテル、エチレングリコールモノプロピルエーテル、エチレングリコールモノブチルエーテル、ジエチレングリコールモノメチルエーテルを用いると、ポリオレフィン樹脂粒子の分散促進により効果的であり好ましく、イソプロパノールが特に好ましい。 Among them, when ethanol, n-propanol, isopropanol, n-butanol, methyl ethyl ketone, cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, and diethylene glycol monomethyl ether are used, polyolefin resin particles are obtained. Isopropanol is particularly preferred because it is more effective in promoting dispersion.
（疎水性有機溶剤）
　本発明において、水性分散体は、これらの親水性有機溶剤を複数混合して含有してもよい。またポリオレフィン樹脂の水性分散化をより促進させるために、疎水性有機溶剤をさらに含有してもよい。 (hydrophobic organic solvent)
In the present invention, the aqueous dispersion may contain a mixture of these hydrophilic organic solvents. In addition, a hydrophobic organic solvent may be further contained in order to promote aqueous dispersion of the polyolefin resin.
　疎水性有機溶剤としては、分散安定性が良好な水性分散体を得るという点から、２０℃の水に対する溶解性が１０ｇ／Ｌ未満である有機溶剤が好ましい。また、塗膜を形成する過程で、効率よく乾燥除去させる観点から、沸点が１５０℃以下である有機溶剤が好ましい。このような疎水性有機溶剤としては、例えば、ｎ－ペンタン、ｎ－ヘキサン、ｎ－ヘプタン、シクロヘプタン、シクロヘキサン、石油エーテル等のオレフィン系溶剤、ベンゼン、トルエン、キシレン等の芳香族系溶剤、四塩化炭素、１，２－ジクロロエタン、１，１－ジクロロエチレン、トリクロロエチレン、１，１，１－トリクロロエタン、クロロホルム等のハロゲン系溶媒等が挙げられる。これらの疎水性有機溶剤の含有量は、水性分散体に対して１５質量％以下であることが好ましく、１０質量％以下であることがより好ましく、５質量％以下であることがさらに好ましい。疎水性有機溶剤の含有量が１５質量％を超えると、ゲル化等を引き起こすことがある。 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. Examples of such hydrophobic organic solvents 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.
　水性分散体の製造時に上記の有機溶剤を用いた場合には、ポリオレフィン樹脂の水性分散化の後に、その一部を、一般に「ストリッピング」と呼ばれる脱溶剤処理によって系外へ留去させ、有機溶剤の含有量を低減させてもよい。ストリッピングにより、水性分散体中の有機溶剤含有量は、１０質量％以下とすることができ、５質量％以下とすればより好ましく、１質量％以下とすることが、環境上より好ましい。ストリッピングの工程では、水性分散化に使用した有機溶剤を実質的に全て留去することもできるが、装置の減圧度を高めたり、操業時間を長くしたりする必要があるため、こうした生産性を考慮した場合、有機溶剤含有量の下限は０．０１質量％程度が好ましい。 When the above organic solvent is used in the production of the aqueous dispersion, after the polyolefin resin is aqueously dispersed, part of it is distilled out of the system by a solvent removal treatment generally called "stripping" to obtain the organic solvent. The solvent content may be reduced. By stripping, 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.
　ストリッピングの方法としては、常圧または減圧下で水性分散体を攪拌しながら加熱し、有機溶剤を留去する方法が挙げられる。また、水性媒体が留去されることにより、固形分濃度が高くなるので、例えば、粘度が上昇して作業性が低下するような場合には、予め水性分散体に水を添加しておいてもよい。 A stripping method includes heating the aqueous dispersion under normal pressure or reduced pressure while stirring to distill off the organic solvent. In addition, since the solid content concentration increases by distilling off the aqueous medium, for example, when the viscosity increases and the workability decreases, water is added to the aqueous dispersion in advance. good too.
　水性分散体の固形分濃度は、特に限定されず用途等に応じて適宜に選択することができ、例えば、水性媒体を留去する方法や、水で希釈する方法により調整することができる。 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.
（塩基性化合物）
　水性媒体が含有する塩基性化合物としては、アンモニア、トリエチルアミン、Ｎ，Ｎ－ジメチルエタノールアミン、イソプロピルアミン、アミノエタノール、ジメチルアミノエタノール、ジエチルアミノエタノール、エチルアミン、ジエチルアミン、イソブチルアミン、ジプロピルアミン、３－エトキシプロピルアミン、３－ジエチルアミノプロピルアミン、ｓｅｃ－ブチルアミン、プロピルアミン、ｎ－ブチルアミン、２－メトキシエチルアミン、３－メトキシプロピルアミン、２，２－ジメトキシエチルアミン、モノエタノールアミン、モルホリン、Ｎ－メチルモルホリン、Ｎ－エチルモルホリン、ピロール、ピリジン等が挙げられる。中でも、樹脂の分散促進の観点から、アンモニア、トリエチルアミン、Ｎ，Ｎ－ジメチルエタノールアミンが好ましい。 (basic compound)
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. Among them, ammonia, triethylamine, and N,N-dimethylethanolamine are preferable from the viewpoint of accelerating the dispersion of the resin.
　塩基性化合物の添加量は、ポリオレフィン樹脂中のカルボキシル基に対して０．５～１０倍当量であることが好ましく、０．８～８倍当量であることがより好ましく、１．０～５倍当量であることが特に好ましい。０．５倍当量未満では分散が不十分となり、本発明で規定する樹脂粒子径の水性分散体を得ることが難しい場合がある。１０倍当量を超えると塗膜形成時の乾燥時間が長くなったり、得られる水性分散体の安定性が低下したりする場合がある。 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.
（水性分散体の製造）
　本発明の水性分散体を得るための製造方法としては、特に限定されるものではないが、上記した各種成分、すなわち、ポリオレフィン樹脂、水性媒体、任意の各種添加剤、さらに必要に応じて有機溶剤、塩基性化合物等を、密閉可能な容器中で加熱、攪拌し、樹脂を分散させる方法を採用することができる。 (Production of aqueous dispersion)
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.
　容器としては、固／液撹拌装置や乳化機として使用されている装置を使用することができ、例えば、０．１ＭＰａ以上の加圧が可能な装置を使用することが好ましい。撹拌の方法、撹拌の回転速度は特に限定されないが、ポリオレフィン樹脂が水性媒体中で均一な状態となる程度の低速の撹拌でよい。したがって、高速撹拌（例えば１０００ｒｐｍ以上）は必須ではなく、簡便な装置でも水性分散体の製造が可能である。 As the container, 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.
　中でも、水性分散体の製造方法としては、ポリオレフィン樹脂、水性媒体等の原料を混合し、攪拌した後に、１℃／分以下の冷却速度で攪拌温度から最低温度に冷却することが好ましい。 Above all, as a method for producing an 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.
　詳細なメカニズムは分かっていないが、本発明者は様々に検討した結果、１℃／分以下の冷却速度で比較的遅く冷却することで、上記のレーザー回折法で測定したポリオレフィン樹脂粒子の９９．９％径を、特定範囲とすることができることを見出した。
　冷却速度は遅いことがより好ましく、０．９℃／分以下であることがさらに好ましく、０．７℃／分以下であることが特に好ましい。 Although the detailed mechanism is not known, as a result of various investigations by the present inventors, by cooling relatively slowly 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. We have found that a 9% diameter can be the specified range.
The cooling rate is more preferably slow, more preferably 0.9° C./min or less, and particularly preferably 0.7° C./min or less.
　攪拌温度は、装置の耐圧や加熱性能、エネルギーコスト等の観点から適宜設定することが可能であるが、樹脂の粒子径を上記範囲とする観点、分散安定性の観点からは高いことが好ましく、１１０℃以上であることが好ましく、１２０℃以上であることがより好ましく、１４０℃以上であることがさらに好ましい。 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.
　なお、冷却後の最低温度は特に限定されるものではないが、例えば１００℃以下であることが好ましく、４０℃以下であることがより好ましい。 Although the lowest temperature after cooling is not particularly limited, it is preferably 100°C or lower, more preferably 40°C or lower, for example.
　冷却は、１℃／分以下の冷却速度で１段階で行ってもよいし、冷却速度の異なる２段階以上の複数段階で行ってもよい。
　例えば、１℃／分以下の冷却速度で攪拌温度から１００℃以下かつ４０℃を超える温度に冷却した後に、３℃／分以下の冷却速度で４０℃以下に冷却するような、２段階の冷却を採用してもよい。この場合、２段階目の冷却速度は３℃／分以下であることが好ましく、２℃／分以下であることがより好ましく、１℃／分以下であることがさらに好ましい。 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.
For example, 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. may be adopted. In this case, 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.
　上記の冷却温度を調整する方法は、特に限定されるものではなく、例えば、容器のヒーターの温度を調整したり、ジャケットを備えた容器を使用する場合は、ジャケット内の蒸気、熱媒、水等の温度を調整したりする方法が挙げられる。 The method for adjusting the cooling temperature is not particularly limited. For example, when adjusting the temperature of the heater of the container or using a jacketed container, the steam, heat medium, A method of adjusting the temperature, etc., can be mentioned.
（不揮発性水性化助剤）
　本発明の水性分散体は、不揮発性水性化助剤の含有を排除するものではないが、不揮発性水性化助剤を実質的に含有しないことが好ましい。本発明においては不揮発性水性化助剤を実質的に含有せずとも、ポリオレフィン樹脂粒子の分散安定性に優れ、かつ粗大な樹脂粒子が存在しない水性分散体を製造することが可能である。 (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.
　ここで、「水性化助剤」とは、水性分散体の製造において、水性分散化促進や水性分散体の安定化の目的で添加される薬剤や化合物のことであり、「不揮発性」とは、常圧での沸点を有さないか、もしくは常圧で高沸点（例えば３００℃以上）であることを指す。 Here, the term "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.
　「不揮発性水性化助剤を実質的に含有しない」とは、こうした助剤を製造時（ポリオレフィン樹脂の水性分散化時）に用いず、得られる水性分散体が結果的にこの助剤を含有しないことを意味する。不揮発性水性化助剤は、ポリオレフィン樹脂成分に対して５質量％以下であることが好ましく、より好ましくは２質量％以下、さらに好ましくは０．５質量％未満であり、０質量％であることが最も好ましい。 The phrase "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.
　本発明でいう不揮発性水性化助剤としては、例えば、乳化剤、保護コロイド作用を有する化合物、変性ワックス類、高酸価の酸変性化合物、水溶性高分子等が挙げられる。 Examples of the non-volatile water-improving aid in the present invention include emulsifiers, compounds having a protective colloid action, modified waxes, acid-modified compounds with a high acid value, and water-soluble polymers.
　乳化剤としては、カチオン性乳化剤、アニオン性乳化剤、ノニオン性乳化剤、両性乳化剤が挙げられ、一般に乳化重合に用いられるもののほか、界面活性剤類も含まれる。例えば、アニオン性乳化剤としては、高級アルコールの硫酸エステル塩、高級アルキルスルホン酸塩、高級カルボン酸塩、アルキルベンゼンスルホン酸塩、ポリオキシエチレンアルキルサルフェート塩、ポリオキシエチレンアルキルフェニルエーテルサルフェート塩、ビニルスルホサクシネート等が挙げられる。ノニオン性乳化剤としては、ポリオキシエチレンアルキルエーテル、ポリオキシエチレンアルキルフェニルエーテル、ポリエチレングリコール脂肪酸エステル、エチレンオキサイドプロピレンオキサイドブロック共重合体、ポリオキシエチレン脂肪酸アミド、エチレンオキサイド－プロピレンオキサイド共重合体等のポリオキシエチレン構造を有する化合物やポリオキシエチレンソルビタン脂肪酸エステル等のソルビタン誘導体等が挙げられる。両性乳化剤としては、ラウリルベタイン、ラウリルジメチルアミンオキサイド等が挙げられる。 Emulsifiers include cationic emulsifiers, anionic emulsifiers, nonionic emulsifiers, and amphoteric emulsifiers, and include surfactants in addition to those generally used for emulsion polymerization. For example, anionic emulsifiers include higher alcohol sulfates, higher alkylsulfonates, higher carboxylates, alkylbenzenesulfonates, polyoxyethylene alkylsulfates, polyoxyethylene alkylphenyl ether sulfates, vinyl sulfosuccinates, and the like. Examples of 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.
　保護コロイド作用を有する化合物、変性ワックス類、高酸価の酸変性化合物、水溶性高分子としては、ポリビニルアルコール、カルボキシル基変性ポリビニルアルコール、カルボキシメチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、変性デンプン、ポリビニルピロリドン、ポリアクリル酸およびその塩、カルボキシル基含有ポリエチレンワックス、カルボキシル基含有ポリプロピレンワックス、カルボキシル基含有ポリエチレン－プロピレンワックス等の数平均分子量が通常５０００以下の酸変性ポリオレフィンワックス類およびその塩、アクリル酸－無水マレイン酸共重合体およびその塩、スチレン－（メタ）アクリル酸共重合体、エチレン－（メタ）アクリル酸共重合体、イソブチレン－無水マレイン酸交互共重合体、（メタ）アクリル酸－（メタ）アクリル酸エステル共重合体等の不飽和カルボン酸含有量が１０質量％以上のカルボキシル基含有ポリマーおよびその塩、ポリイタコン酸およびその塩、アミノ基を有する水溶性アクリル系共重合体、ゼラチン、アラビアゴム、カゼイン等、一般に微粒子の分散安定剤として用いられている化合物等が挙げられる。 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.
（添加物）
　本発明の水性分散体は、目的に応じて性能をさらに向上させるために、他の重合体、粘着付与剤、無機粒子、架橋剤、顔料、染料等を含有してもよい。
　他の重合体や粘着付与剤は、特に限定されない。例えば、ポリ酢酸ビニル、エチレン－酢酸ビニル共重合体、ポリ塩化ビニル、ポリ塩化ビリニデン、エチレン－（メタ）アクリル酸共重合体、エチレン－（メタ）アクリル酸エステル－無水マレイン酸共重合体、スチレン－マレイン酸樹脂、スチレン－ブタジエン樹脂、ブタジエン樹脂、アクリロニトリル－ブタジエン樹脂、ポリウレタン樹脂、ポリ（メタ）アクリロニトリル樹脂、（メタ）アクリルアミド樹脂、塩素化ポリエチレン樹脂、塩素化ポリプロピレン樹脂、ポリエステル樹脂、変性ナイロン樹脂、ロジン、フェノール樹脂、シリコーン樹脂、エポキシ樹脂等、またはこれらを含む粘着付与剤が挙げられ、必要に応じて複数のものを混合使用してもよい。
　なお、これらの重合体は、固形状のままで使用してもよいが、水性分散体の安定性維持の点では、水性分散体に加工したものを使用することが好ましい。 (Additive)
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. For example, polyvinyl acetate, ethylene-vinyl acetate copolymer, polyvinyl chloride, polyvinylidene chloride, ethylene-(meth)acrylic acid copolymer, ethylene-(meth)acrylic acid ester-maleic anhydride copolymer, styrene -Maleic acid resin, styrene-butadiene resin, butadiene resin, acrylonitrile-butadiene resin, polyurethane resin, poly(meth)acrylonitrile resin, (meth)acrylamide resin, chlorinated polyethylene resin, chlorinated polypropylene resin, polyester resin, modified nylon resin , rosin, phenolic resins, silicone resins, epoxy resins, etc., or tackifiers containing these, and if necessary, a plurality of tackifiers may be used in combination.
These polymers may be used as they are in solid form, but from the viewpoint of maintaining the stability of the aqueous dispersion, it is preferable to use those processed into an aqueous dispersion.
　無機粒子としては、酸化マグネシウム、酸化亜鉛、酸化すず等の金属酸化物、炭酸カルシウム、シリカ等の無機化合物、バーミキュライト、モンモリロナイト、ヘクトライト、ハイドロタルサイト、合成雲母等の層状無機化合物等が挙げられる。これらの無機粒子の平均粒子径は、塗膜の透明性等の観点から、０．００５～１０μｍであることが好ましい。なお、無機粒子として複数のものを混合して使用してもよい。 Examples of inorganic particles 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 μm from the viewpoint of the transparency of the coating film. A plurality of inorganic particles may be mixed and used.
　架橋剤としては、自己架橋性を有する架橋剤、不飽和カルボン酸成分と反応する官能基を分子内に複数個有する化合物、多価の配位座を有する金属等を用いることができる。
　具体的には、オキサゾリン基含有化合物、カルボジイミド基含有化合物、イソシアネート基含有化合物、エポキシ基含有化合物、メラミン化合物、尿素化合物、ジルコニウム塩化合物、シランカップリング剤等が挙げられ、必要に応じて複数のものを混合使用してもよい。中でも、取り扱い易さの観点から、オキサゾリン基含有化合物、カルボジイミド基含有化合物、イソシアネート基含有化合物、エポキシ基含有化合物が好ましい。 As the cross-linking agent, 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.
　顔料、染料としては、酸化チタン、亜鉛華、カーボンブラック等が挙げられ、分散染料、酸性染料、カチオン染料、反応染料等いずれのものも使用することが可能である。 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.
　本発明の水性分散体は、さらに必要に応じて、レベリング剤、消泡剤、ワキ防止剤、顔料分散剤、紫外線吸収剤、増粘剤、耐候剤、難燃剤等の各種薬剤を含有してもよい。 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.
（塗膜）
　本発明の塗膜は、上記水性分散体から得られるものであり、バリア性に優れる。バリア性は、水蒸気透過度を指標とするものであり、本発明においては、８０℃で乾燥して得られた塗膜の水蒸気透過度が１５０ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）以下であることが好ましく、１００ｍｌ／（ｍ２・ｄａｙ・ＭＰａ）以下であることがより好ましい。水蒸気透過度の測定方法は、実施例において詳述する。 (Coating film)
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.
　本発明の水性分散体は、得られる塗膜の防錆性に優れるものである。本発明においては、金属板上に８０℃で乾燥して得られた塗膜に対して、ＮａＣｌ水溶液の噴霧を行い、１００時間後の発錆面積率５０％未満であることが好ましい。発錆面積率の算出方法は、実施例において詳述する。 The aqueous dispersion of the present invention is excellent in the antirust properties of the resulting coating film. In the present invention, 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.
　上記のように、本発明の水性分散体においては、ポリオレフィン樹脂粒子が小さい粒子径で安定的に、かつ粗大な樹脂粒子を含まず均一に水性媒体に分散しているので、外観欠点を抑制することができ、バリア性、防錆性に優れた塗膜を得ることができる。 As described above, in the aqueous dispersion of the present invention, 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.
（塗膜形成）
　本発明の水性分散体は、塗膜形成能に優れる。本発明の水性分散体から塗膜を形成する方法としては、例えば、本発明の水性分散体を、各種基材表面に均一に塗布し、必要に応じて室温付近でセッティングした後、乾燥または乾燥と焼き付けのための加熱処理をする方法が挙げられる。これにより、均一な塗膜を各種基材表面に接着させることができる。 (Coating film formation)
The aqueous dispersion of the present invention is excellent in film-forming ability. As a method for forming a coating film from the aqueous dispersion of the present invention, for example, 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.
　基材への水性分散体の塗布には、公知の方法、例えばグラビアロールコーティング、リバースロールコーティング、ワイヤーバーコーティング、リップコーティング、エアナイフコーティング、カーテンフローコーティング、スプレーコーティング、浸漬コーティング、はけ塗り法等が採用できる。 Application of the 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.
　基材への水性分散体の塗布量は特に限定されず、その用途によって適宜選択されるものであるが、乾燥後の塗布量として０．０１～１００ｇ／ｍ２であることが好ましく、０．１～５０ｇ／ｍ２であることがより好ましく、０．２～３０ｇ／ｍ２であることがさらに好ましい。 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 .
　なお、塗布量を調節するためには、塗布に用いる装置やその使用条件を適宜選択することに加えて、目的とする塗膜の厚さに応じて濃度調整された水性分散体を使用することが好ましい。水性分散体の濃度は、調製時の仕込み組成により調整することが可能であり、また、一旦調製した水性分散体を、適宜希釈したり、あるいは濃縮したりして調整してもよい。 In addition, in order to adjust the coating amount, in addition to appropriately selecting the equipment used for coating and its usage conditions, it is necessary to use an aqueous dispersion whose concentration is adjusted according to the desired thickness of the coating film. is preferred. The 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.
　塗布後の加熱処理のための加熱装置として、通常の熱風循環型のオーブンや赤外線ヒーター等を使用することができる。
　加熱温度や加熱時間は、基材の特性または水性分散体中に任意に配合しうる各種成分の添加量により適宜選択されるが、エネルギーコストや基材へのダメージの観点からは加熱温度は低いほうが好ましく、生産性の観点からは加熱時間は短いほうが好ましい。加熱温度としては、２０～１３０℃であることが好ましく、３０～１２０℃であることがより好ましく、４０～１００℃であることがさらに好ましい。加熱時間は、１秒～２０分であることが好ましく、５秒～１５分であることがより好ましく、５秒～１０分であることがさらに好ましい。
　なお、本発明の水性分散体に架橋剤を含有させる場合は、ポリオレフィン樹脂中のカルボキシル基と架橋剤との反応を十分進行させるために、加熱温度および時間は架橋剤の種類によって適宜選定することが望ましい。 As a heating device for the heat treatment after coating, an ordinary hot air circulation oven, an infrared heater, or the like can be used.
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.
When the aqueous dispersion of the present invention contains a cross-linking agent, 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.
（用途）
　本発明の水性分散体は、接着剤、コーティング剤、プライマー、塗料、インキ等として好適に使用できる。
　本発明の水性分散体は、塗膜とした際のバリア性、防錆性にいっそう優れるので、金属製品用途、電子機器用途、包装材料用途、自動車部品用途等に特に好適に用いられる。
　これら用途の具体例としては、ＰＰ押出ラミ用アンカーコート剤、二次電池セパレータ用コーティング剤、ＵＶ硬化型コート剤用プライマー、靴用プライマー、自動車バンパー用プライマー、クリアボックス用プライマー、ＰＰ基材用塗料、包装材料用接着剤、紙容器用接着剤、蓋材用接着剤、インモールド転写箔用接着剤、ＰＰ鋼板用接着剤、太陽電池モジュール用接着剤、植毛用接着剤、二次電池電極用バインダー用接着剤、二次電池外装用接着剤、自動車用ベルトモール用接着剤、自動車部材用接着剤、異種基材用接着剤、繊維収束剤等が挙げられる。 (Application)
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.
　以下、実施例によって本発明を具体的に説明するが、本発明はこれらに限定されるものではない。
　ポリオレフィン樹脂水性分散体の構成や物性、塗膜の特性などは、以下の方法により測定または評価した。 EXAMPLES The present invention will be specifically described below by way of examples, but the present invention is not limited to these.
The 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.
（１）ポリオレフィン樹脂の組成
　１Ｈ－ＮＭＲ分析装置（日本電子社製、ＥＣＡ５００、５００ＭＨｚ）より求めた。テトラクロロエタン（ｄ２）を溶媒とし、１２０℃で測定した。 (1) 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.
（２）ポリオレフィン樹脂の融点
　パーキンエルマー社製、ＤＳＣ７を用いてＤＳＣ法にて測定した。試料をアルミパンに詰め、１０℃／分で２００℃まで昇温し、５分間保持した後、１０℃／分で－１０℃まで降温し、次いで１０℃／分で２００℃まで昇温した際の、吸熱および発熱に伴う曲線から求めた。 (2) Melting point of polyolefin resin Measured by the DSC method using DSC7 manufactured by PerkinElmer. The sample is packed in an aluminum pan, heated to 200 ° C. at 10 ° C./min, held for 5 minutes, cooled to -10 ° C. at 10 ° C./min, and then heated to 200 ° C. at 10 ° C./min. was determined from the curve associated with the endotherm and exotherm of .
（３）ポリオレフィン樹脂のメルトフローレート（ＭＦＲ）
　ＪＩＳ　Ｋ７２１０：１９９９記載の方法に準じ、１９０℃、２１６０ｇ荷重で測定した。 (3) Melt flow rate (MFR) of polyolefin resin
Measured at 190° C. under a load of 2160 g according to the method described in JIS K7210:1999.
（４）水性分散体の固形分濃度
　水性分散体を適量秤量し、これを１５０℃で残存物（固形分）の質量が恒量に達するまで加熱し、固形分濃度を求めた。 (4) Solid Content Concentration of Aqueous Dispersion An appropriate amount of the aqueous dispersion was weighed and heated at 150° C. until the mass of the residue (solid content) reached a constant weight to determine the solid content concentration.
（５）ポリオレフィン樹脂粒子の数平均粒子径、体積平均粒子径（動的光散乱法）
　日機装社製、Ｎａｎｏｔｒａｃ　Ｗａｖｅ－ＵＺ１５２粒度分布測定装置を用いて、数平均粒子径（ｍｎ）、体積平均粒子径（ｍｖ）を測定した。なお樹脂の屈折率は１．５とした。 (5) Number average particle size and volume average particle size of polyolefin resin particles (dynamic light scattering method)
The number average particle size (mn) and volume average particle size (mv) were measured using a Nanotrac Wave-UZ152 particle size distribution analyzer manufactured by Nikkiso Co., Ltd. Note that the refractive index of the resin was set to 1.5.
（６）ポリオレフィン樹脂粒子の９９．９％径（レーザー回折法）
　マルバーン社製、レーザー回折粒子径マスターサイザー３０００を用いて、粒子径を測定し、体積粒度分布において小粒径側から積算した体積粒子径積算分布の９９．９％径を確認した。 (6) 99.9% diameter of polyolefin resin particles (laser diffraction method)
The particle size was measured using a Laser Diffraction Particle Size Mastersizer 3000 manufactured by Malvern, and the 99.9% diameter of the volume particle size cumulative distribution integrated from the small particle size side in the volume particle size distribution was confirmed.
（７）水性分散体の粘度
　濾過後の水性分散体を、Ｂ型粘度計（トキメック社製、ＤＶＬ－ＢII型デジタル粘度計）を用い、温度２０℃における回転粘度（ｍＰａ・ｓ）を測定した。 (7) 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). .
（８）ｐＨ
　ＨＯＲＩＢＡ社製　ポータプル型ｐＨメーター　Ｄ－７４を用い、２０℃におけるｐＨを測定した。 (8) pH
The pH at 20° C. was measured using a portable pH meter D-74 manufactured by HORIBA.
（９）塗膜の外観欠点
　グラビヤコーターを用いて、ＰＥＴフィルム（東レ社製　ルミラー　Ｔ６０－＃５０　厚み５０μｍ　幅１ｍ）に、塗膜厚みが１μｍになるように水性分散体を塗布し、１００℃で１５秒の乾燥を行い、１０００ｍを巻き取った後、透過型欠点検出装置（ヒューテック社製）を設置したフィルムワインダーを通し（スキャン速度０．５ｍ／秒、検出感度０．５ｍｍ以上に設定）、欠点（塗膜表面の微小な突起、塗膜の割れ等）の検査を行った。検知回数から以下の基準で判断した。
〇：１０００ｍ２あたり１０回未満
△：１０００ｍ２あたり１０回以上、１００回未満
×：１０００ｍ２あたり１００回以上 (9) Appearance defects of the coating film Using a gravure coater, an aqueous dispersion is applied to a PET film (Lumirror T60-#50, thickness 50 μm, width 1 m, manufactured by Toray Industries, Inc.) so that the coating thickness is 1 μm, and the temperature is 100 ° C. After drying for 15 seconds and winding 1000 m, it is passed through a film winder equipped with a transmission type defect detection device (manufactured by Hutech) (scanning speed 0.5 m / sec, detection sensitivity set to 0.5 mm or more) , Defects (fine projections on the surface of the coating film, cracks in the coating film, etc.) were inspected. Judgment was made based on the following criteria based on the number of detections.
○: Less than 10 times per 1000m2 △ : 10 times or more and less than 100 times per 1000m2 ×: 100 times or more per 1000m2
（１０）塗膜の水蒸気透過度（バリア性）
（低温乾燥での製膜）
　ナイロンフィルム（ユニチカ社製　ＯＮ－１５）のコロナ処理面に、マイヤーバーを用いて、乾燥後の塗膜厚みが１０μｍになるように水性分散体を塗布し、８０℃で乾燥を行って塗膜を形成した。得られたサンプルの水蒸気透過度を、透湿度測定器（モコン社製　ＰＥＲＭＡＴＲＡＮ－Ｗ３／３１ＭＷ）を用いて、４０℃、１００％ＲＨの条件で測定した。 (10) Water vapor permeability of coating film (barrier property)
(Film formation by low-temperature drying)
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 μm, and dried at 80° C. to form a film. 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.).
（高温乾燥での製膜）
　ナイロンフィルム（ユニチカ社製　ＯＮ－１５）のコロナ処理面に、マイヤーバーを用いて、乾燥後の塗膜厚みが１０μｍになるように水性分散体を塗布し、１５０℃で乾燥を行って塗膜を形成した。得られたサンプルの水蒸気透過度を、透湿度測定器（モコン社製　ＰＥＲＭＡＴＲＡＮ－Ｗ３／３１ＭＷ）を用いて、４０℃、１００％ＲＨの条件で測定した。 (Film formation by high temperature drying)
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 μm, 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.).
（１１）防錆性
（低温乾燥での製膜）
　脱脂した溶融亜鉛メッキ鋼板（日本テストパネル社製、サイズ７０ｍｍ×１５０ｍｍ×０．８ｍｍｔ）に、マイヤーバーを用いて、乾燥後の塗膜厚みが２μｍになるように水性分散体を塗布し、８０℃で乾燥を行って塗膜を形成した。得られたサンプルに対して、ＪＩＳ　Ｚ－２３７１規格の塩水噴霧試験機を用いて、３５℃で５質量％のＮａＣｌ水溶液の噴霧を行い、１００時間後の塗膜表面の発錆面積状態を観察した。サンプルの全面積に対する発錆面積を算出し、以下のように評価した。
◎：発錆面積率５％未満
○：発錆面積率５％以上、１０％未満
△：発錆面積率１０％以上、５０％未満
×：発錆面積率５０％以上 (11) Rust resistance (film formation at low temperature drying)
An aqueous dispersion is applied to a degreased hot-dip galvanized steel sheet (manufactured by Nippon Test Panel Co., Ltd., size 70 mm × 150 mm × 0.8 mmt) using a Meyer bar so that the thickness of the coating after drying is 2 μm. ℃ to form a coating film. Using a JIS Z-2371 standard salt spray tester, a 5 mass% NaCl aqueous solution was sprayed on the obtained sample at 35 ° C., and the state of the rusted area on the coating film surface after 100 hours was observed. bottom. The rusted area with respect to the total area of the sample was calculated and evaluated as follows.
◎: Less than 5% rusted area rate ○: 5% or more and less than 10% rusted area rate △: 10% or more rusted area rate and less than 50% ×: 50% or more rusted area rate
（高温乾燥での製膜）
　脱脂した溶融亜鉛メッキ鋼板（日本テストパネル社製、サイズ７０ｍｍ×１５０ｍｍ×０．８ｍｍｔ）に、マイヤーバーを用いて、乾燥後の塗膜厚みが２μｍになるように水性分散体を塗布し、２００℃で乾燥を行って塗膜を形成した。得られたサンプルに対して、ＪＩＳ　Ｚ－２３７１規格の塩水噴霧試験機を用いて、３５℃で５質量％のＮａＣｌ水溶液の噴霧を行い、１００時間後の塗膜表面の発錆状態を観察した。サンプルの全面積に対する発錆面積を算出し、以下のように評価した。
◎：発錆面積率５％未満
○：発錆面積率５％以上、１０％未満
△：発錆面積率１０％以上、５０％未満
×：発錆面積率５０％以上 (Film formation by high temperature drying)
An aqueous dispersion was applied to a degreased hot-dip galvanized steel sheet (manufactured by Nippon Test Panel Co., Ltd., size 70 mm × 150 mm × 0.8 mmt) using a Meyer bar so that the coating thickness after drying was 2 μm. ℃ to form a coating film. Using a JIS Z-2371 standard salt spray tester, the obtained sample was sprayed with a 5% by mass NaCl aqueous solution at 35° C., and the state of rust on the coating film surface after 100 hours was observed. . The rusted area with respect to the total area of the sample was calculated and evaluated as follows.
◎: Less than 5% rusted area rate ○: 5% or more and less than 10% rusted area rate △: 10% or more rusted area rate and less than 50% ×: 50% or more rusted area rate
　実施例、比較例に用いたポリオレフィン樹脂（Ｐ－１）～（Ｐ－１３）は、以下の通りである。これらのポリオレフィン樹脂の組成、物性を表１に示す。 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.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
ポリオレフィン樹脂（Ｐ－１）
　エチレン－アクリル酸エチル－無水マレイン酸共重合体（アルケマ社製　ボンダインＨＸ－８２９０）を用いた。 Polyolefin resin (P-1)
Ethylene-ethyl acrylate-maleic anhydride copolymer (Bondyne HX-8290 manufactured by Arkema) was used.
ポリオレフィン樹脂（Ｐ－２）
　エチレン－アクリル酸エチル－無水マレイン酸共重合体（アルケマ社製　ボンダインＬＸ－４１１０）を用いた。 Polyolefin resin (P-2)
Ethylene-ethyl acrylate-maleic anhydride copolymer (Bondyne LX-4110 manufactured by Arkema) was used.
ポリオレフィン樹脂（Ｐ－３）、（Ｐ－４）、（Ｐ－７）、（Ｐ－８）、（Ｐ－１２）、（Ｐ－１３）
　特開昭６１－６０７０９号公報の実施例１に記載された方法をもとに、表１に示す組成となるように、エチレン－アクリル酸エチル－無水マレイン酸共重合体（Ｐ－３）を得た。
　同様にして、表１に示す組成となるように、ポリオレフィン樹脂（Ｐ－４）、（Ｐ－７）、（Ｐ－８）、（Ｐ－１２）、（Ｐ－１３）を得た。 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.
ポリオレフィン樹脂（Ｐ－５）
　プロピレン－ブテン共重合体（質量比：プロピレン／１－ブテン＝６５／３５）２８０ｇを４つ口フラスコ中、窒素雰囲気下でキシレン４７０ｇに加熱溶解させた後、系内温度を１４０℃に保って攪拌しつつ、無水マレイン酸４０．０ｇ、アクリル酸エチル６０．０ｇと、ジクミルパーオキサイド２８．０ｇをそれぞれ２時間かけて加え、その後６時間反応させた。反応終了後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させ、ポリオレフィン樹脂（Ｐ－５）を得た。 Polyolefin resin (P-5)
280 g of a propylene-butene copolymer (mass ratio: propylene/1-butene = 65/35) was heated and dissolved in 470 g of xylene in a four-necked flask under a nitrogen atmosphere, and then the system temperature was kept at 140°C. While stirring, 40.0 g of maleic anhydride, 60.0 g of ethyl acrylate, and 28.0 g of dicumyl peroxide were each added over 2 hours, and then reacted for 6 hours. After completion of the reaction, the obtained reactant was poured into a large amount of acetone to precipitate the resin, thereby obtaining a polyolefin resin (P-5).
ポリオレフィン樹脂（Ｐ－６）
　アイソタクチック構造のホモポリプロピレン樹脂（ＭＦＲ＝０．１ｇ／１０分－１７０℃・２１６０ｇ）を窒素ガス通気下、常圧において、３６０℃×８０分の熱減成処理を施し、得られたポリプロピレン樹脂１０００ｇをジャケット付き反応器に入れ、窒素置換した。次いで、１８０℃まで加熱昇温し溶融させた後、無水マレイン酸１２５ｇ、アクリル酸エチル１００ｇを加え、均一に混合した。そこに、ジクミルパーオキサイド６．３ｇを溶解させたキシレン１２５ｇを滴下し、１８０℃で３０分撹拌し反応させた。反応終了後、得られた反応物を多量のアセトン中に投入し、樹脂を析出させ、ポリオレフィン樹脂（Ｐ－６）を得た。 Polyolefin resin (P-6)
Polypropylene obtained by subjecting a homopolypropylene resin having an isotactic structure (MFR = 0.1 g/10 min-170°C, 2160 g) to thermal degradation treatment at normal pressure at 360°C for 80 minutes under nitrogen gas flow. 1000 g of resin was placed in a jacketed reactor and purged with nitrogen. Then, after heating to 180° C. and melting, 125 g of maleic anhydride and 100 g of ethyl acrylate were added and uniformly mixed. 125 g of xylene in which 6.3 g of dicumyl peroxide was dissolved was added dropwise thereto, and the mixture was stirred at 180° C. for 30 minutes to react. After completion of the reaction, the obtained reactant was poured into a large amount of acetone to precipitate the resin, thereby obtaining a polyolefin resin (P-6).
ポリオレフィン樹脂（Ｐ－９）
　ポリオレフィン樹脂（Ｐ－５）の製造において、アクリル酸エチルを加えなかった以外は同様の操作を行って、ポリオレフィン樹脂（Ｐ－９）を得た。 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.
ポリオレフィン樹脂（Ｐ－１０）
　ポリオレフィン樹脂（Ｐ－６）の製造において、アクリル酸エチルを加えなかった以外は同様の操作を行って、ポリオレフィン樹脂（Ｐ－１０）を得た。 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.
ポリオレフィン樹脂（Ｐ－１１）
　エチレン－メタクリル酸共重合体（三井・デュポンケミカル社製　ニュクレルＡＮ４２１１５Ｃ）を用いた。 Polyolefin resin (P-11)
An ethylene-methacrylic acid copolymer (Nucrel AN42115C manufactured by Mitsui DuPont Chemical Co., Ltd.) was used.
実施例１
　ヒーター付きの密閉できる耐圧１Ｌ容ガラス容器を備えた攪拌機を用いて、６０．０ｇのポリオレフィン樹脂（Ｐ－１）、６０．０ｇのイソプロパノール（ＩＰＡ）、３．９ｇ（樹脂中の無水マレイン酸のカルボキシル基に対して１．２倍当量）のＮ，Ｎ－ジメチルエタノールアミン（ＤＭＥＡ）および１７６．１ｇの蒸留水をガラス容器内に仕込み、攪拌翼の回転速度を３００ｒｐｍとして攪拌しながら、ヒーターの電源を入れ、１４０℃まで昇温した。１４０℃に保った状態で、６０分間攪拌を行った。その後、攪拌速度を維持したまま加熱を止め、１００℃まで６０分間かけて冷却した後、水浴につけて、４０℃まで３０分間かけて冷却した。３００メッシュのステンレス製フィルター（線径０．０３５ｍｍ、平織）で加圧濾過（空気圧０．２ＭＰａ）し、乳白色の均一な水性分散体を得た。 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.
実施例２
　実施例１において、表２に示したようにＤＭＥＡの量を変更した以外は同様の操作を行った。 Example 2
The same operation as in Example 1 was performed except that the amount of DMEA was changed as shown in Table 2.
実施例３
　実施例１において、表２に示したように攪拌温度（１４０℃）から１００℃までの冷却速度を変更した以外は同様の操作を行った。 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.
実施例４
　実施例１において、表２に示したように１００℃から４０℃までの冷却速度を変更した以外は同様の操作を行った。 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.
実施例５
　実施例１において、攪拌時の温度を１２０℃に変更した以外は同様の操作を行った。 Example 5
The same operation as in Example 1 was performed except that the temperature during stirring was changed to 120°C.
実施例６、８～１１
　実施例１において、ポリオレフィン樹脂を、表２、３に示すように、それぞれＰ－２～Ｐ－６に変更した以外は同様の操作を行った。 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.
実施例７
　実施例６において、攪拌時の温度を１２０℃に変更した以外は同様の操作を行った。 Example 7
The same operation as in Example 6 was performed except that the temperature during stirring was changed to 120°C.
実施例１２
　実施例１において、２段階で冷却せず、攪拌温度（１４０℃）から４０℃まで１００分かけて１段階で冷却した以外は同様の操作を行った。 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.
実施例１３
　実施例１において、１段階目の冷却を攪拌温度から８０℃まで９０分かけて行い、２段階目の冷却を８０℃から４０℃まで２０分かけて行った以外は、同様の操作を行った。 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. .
実施例１４
　実施例１において、有機溶剤をテトラヒドロフラン(ＴＨＦ)に変更した以外は、同様の操作を行った。 Example 14
The same operation as in Example 1 was performed except that the organic solvent was changed to tetrahydrofuran (THF).
実施例１５
　実施例１において、表３に示すようにＩＰＡの添加量を変更した以外は、同様の操作を行った。 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.
比較例１
　実施例１において、表４に示すように１４０℃から１００℃までの冷却速度を変更した以外は、同様の操作を行った。 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.
比較例２～６
　比較例１において、ポリオレフィン樹脂を、表４に示すように、それぞれＰ－２、Ｐ－４、Ｐ－５、Ｐ－６、Ｐ－７に変更した以外は、同様の操作を行った。 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.
比較例７
　実施例１において、表４に示すようにＩＰＡの添加量、ＤＭＥＡの添加量を変更した以外は、同様の操作を行った。 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.
比較例８～１４
　実施例１において、ポリオレフィン樹脂を、表５に示すように、それぞれＰ－７～Ｐ－１３に変更した以外は同様の操作を行った。 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.
　実施例、比較例における水性分散体の製造条件と、得られた水性分散体、およびそれらからなる塗膜の構成、評価結果を表２～５にまとめて示す。 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.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　実施例および比較例の何れにおいても、有機溶剤や塩基性化合物を用い、高温度での攪拌工程やフィルターを用いた濾過を経て、水性分散体が得られた。しかし、比較例１～７のように冷却速度が速い場合は、有機溶剤や塩基性化合物を用い、攪拌や濾過を経ても、ポリオレフィン樹脂粒子の９９．９％径が１０μｍを超える水性分散体しか得られず、実施例と比較すると、塗膜とした際に外観欠点が多く、バリア性や防錆性に劣るものとなった。 In both Examples and Comparative Examples, an aqueous dispersion was obtained using an organic solvent or a basic compound through a high-temperature stirring process and filtration using a filter. However, when 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 μm. When compared with the examples, the coating film had many defects in appearance and was inferior in barrier properties and rust prevention properties.
　すなわち、実施例１～１５のように、本発明の水性分散体は、塗膜とした場合の外観欠点が抑制され、バリア性、防錆性に優れる塗膜を得ることが可能であった。
　また、実施例２のように水性分散時の塩基性化合物の添加量を少なくしたり、実施例１５のように有機溶剤の添加量を少なくしたりしても、本発明の水性分散体を得ることができ、各性能に優れる塗膜を得ることが可能であった。
　さらにまた、実施例３または４のように水性分散時の冷却速度を早くしたり、実施例５のように水性分散時の攪拌温度を低くしたり、実施例１２のように２段階ではなく１段階で冷却したり、実施例１３のように１段階目の冷却における温度を変更したりしても、本発明の水性分散体を得ることができ、各性能に優れる塗膜を得ることが可能であった。
　さらにまた、実施例６～１１のように用いるポリオレフィン樹脂の種類を変更したり、実施例１４のように添加する有機溶剤の種類を変更したりしても、本発明の水性分散体を得ることができ、各性能に優れる塗膜を得ることが可能であった。 That is, as in Examples 1 to 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. 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.
　比較例１～５では、水性分散時における冷却時の冷却速度が速かったことから、得られた水性分散体においては、レーザー回折法で測定した体積粒度分布において９９．９％径が１０μｍを超えた。この水性分散体から得られた塗膜は、外観欠点が多く、バリア性、防錆性に劣る結果となった。 In Comparative Examples 1 to 5, the cooling rate during cooling during the aqueous dispersion was fast, so in the obtained aqueous dispersion, 99.9% diameter exceeded 10 μm in the volume particle size distribution measured by the laser diffraction method. rice field. The coating film obtained from this aqueous dispersion had many defects in appearance and was inferior in barrier properties and rust prevention properties.
　比較例６は、（メタ）アクリル酸エステル成分の含有量が本発明の規定範囲を下回るポリオレフィン樹脂中を用いて、水性分散時における冷却時の冷却速度を速い条件としたものである。得られた水性分散体は、レーザー回折法で測定した体積粒度分布において９９．９％径が１０μｍを超えており、また、この水性分散体から得られた塗膜は、外観欠点が多く、バリア性、防錆性に劣る結果となった。 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 μm in volume particle size distribution measured by a laser diffraction method. The results were inferior in terms of durability and rust resistance.
　比較例７では、水性分散時における有機溶剤、塩基性化合物の添加量が少なかったため、動的光散乱法で測定される体積平均粒子径が０．３μｍを超える水性分散体が得られた。この水性分散体から得られた塗膜は、外観欠点が多く、バリア性、防錆性に劣る結果となった。 In Comparative Example 7, since the amounts of the organic solvent and basic compound added during aqueous dispersion were small, an aqueous dispersion with a volume average particle size exceeding 0.3 μm as measured by the dynamic light scattering method was obtained. The coating film obtained from this aqueous dispersion had many defects in appearance and was inferior in barrier properties and rust prevention properties.
　比較例８の水性分散体は、（メタ）アクリル酸エステル成分の含有量が本発明の規定範囲を下回るポリオレフィン樹脂を用いたものである。この水性分散体の９９．９％径、体積平均粒子径は本発明の範囲であったが、得られた塗膜は、バリア性、防錆性に劣る結果となった。
　比較例９の水性分散体は、（メタ）アクリル酸エステル成分の含有量が本発明の規定範囲を上回るポリオレフィン樹脂を用いたものである。この水性分散体の９９．９％径、体積平均粒子径は本発明の範囲であったが、得られた塗膜は、バリア性、防錆性に劣る結果となった。
　比較例１０～１２の水性分散体は、（メタ）アクリル酸エステル成分を含まないポリオレフィン樹脂を用いたものである。この水性分散体の９９．９％径、体積平均粒子径は本発明の範囲であったが、得られた塗膜は、バリア性、防錆性に劣る結果となった。 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.
　比較例１３は、不飽和カルボン酸成分の含有量が本発明の規定範囲を下回るポリオレフィン樹脂を用いたものである。ポリオレフィン樹脂が溶媒によって膨潤するのみで分散せず、水性分散体を得ることができなかった。
　比較例１４の水性分散体は、不飽和カルボン酸成分の含有量が本発明の規定範囲を上回るポリオレフィン樹脂を用いたものである。この水性分散体は、９９．９％径、体積平均粒子径は本発明の範囲であったが、得られた塗膜は、バリア性、防錆性に劣る結果となった。 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.

Claims (5)

  1. ポリオレフィン樹脂粒子および水性媒体を含有するポリオレフィン樹脂水性分散体であって、ポリオレフィン樹脂が不飽和カルボン酸成分０．１～１０質量％と（メタ）アクリル酸エステル成分１～２０質量％とを含み、ポリオレフィン樹脂粒子の動的光散乱法で測定した体積平均粒子径が０．３μｍ以下であって、かつレーザー回折法で測定した体積粒度分布において、小粒子径側から積算した体積粒子径積算分布の９９．９％径が１０μｍ以下である、ポリオレフィン樹脂水性分散体。 A polyolefin resin aqueous dispersion containing polyolefin resin particles and an aqueous medium, wherein 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)acrylate component, The volume average particle diameter of the polyolefin resin particles measured by the dynamic light scattering method is 0.3 μm or less, and in the volume particle size distribution measured by the laser diffraction method, the volume particle size cumulative distribution integrated from the small particle size side. A polyolefin resin aqueous dispersion having a 99.9% diameter of 10 μm or less.
  2. 請求項１に記載のポリオレフィン樹脂水性分散体から得られた塗膜。 A coating film obtained from the polyolefin resin aqueous dispersion according to claim 1 .
  3. 請求項１に記載のポリオレフィン樹脂水性分散体を製造する方法であって、１１０℃以上の温度で、ポリオレフィン樹脂と水性媒体とを攪拌する攪拌工程後に、１℃／分以下の速度で１００℃以下に冷却する冷却工程を含む、ポリオレフィン樹脂水性分散体の製造方法。 2. A method for producing the polyolefin resin aqueous dispersion according to claim 1, wherein after the stirring step of stirring the polyolefin resin and the aqueous medium at a temperature of 110° C. or higher, the temperature is 100° C. or lower at a rate of 1° C./min or lower. A method for producing a polyolefin resin aqueous dispersion, comprising a cooling step of cooling to
  4. 冷却工程が、１℃／分以下の冷却速度で最高温度から１００℃以下かつ４０℃を超える温度に冷却する第一の冷却工程後に、３℃／分以下の冷却速度で４０℃以下に冷却する第二の冷却工程を含む、請求項３に記載のポリオレフィン樹脂水性分散体の製造方法。 After a first cooling step where the cooling step cools from the maximum temperature to a temperature of 100°C or less and above 40°C at a cooling rate of 1°C/min or less, cooling to 40°C or less at a cooling rate of 3°C/min or less. 4. The method for producing a polyolefin resin aqueous dispersion according to claim 3, comprising a second cooling step.
  5. 攪拌工程が、１１０℃以上かつ、ポリオレフィン樹脂の融点よりも２０℃以上高い温度で攪拌するものである、請求項３または４に記載のポリオレフィン樹脂水性分散体の製造方法。 5. The method for producing an aqueous polyolefin resin dispersion according to claim 3 or 4, wherein the stirring step is performed at a temperature of 110°C or higher and 20°C or higher than the melting point of the polyolefin resin.
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JP3026209B1 (en) * 1998-10-27 2000-03-27 京都大学長 Crystallization method of polymer resin
JP2003171512A (en) * 2001-12-05 2003-06-20 Unitika Ltd Polyolefin resin aqueous dispersion, and its production method
WO2004104090A1 (en) * 2003-05-22 2004-12-02 Unitika Ltd. Aqueous polyolefin resin dispersion, process for producing the same, and water-based coating material comprising the same
JP2006045295A (en) * 2004-08-03 2006-02-16 Sumitomo Seika Chem Co Ltd Manufacturing method of polyolefin resin particle
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