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WO2016186049A1 - Mélange de dispersions aqueuses - Google Patents

Mélange de dispersions aqueuses Download PDF

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Publication number
WO2016186049A1
WO2016186049A1 PCT/JP2016/064365 JP2016064365W WO2016186049A1 WO 2016186049 A1 WO2016186049 A1 WO 2016186049A1 JP 2016064365 W JP2016064365 W JP 2016064365W WO 2016186049 A1 WO2016186049 A1 WO 2016186049A1
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Prior art keywords
aqueous dispersion
methyl
mass
polyolefin
examples
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Japanese (ja)
Inventor
中島　秀人
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Sumitomo Chemical Co Ltd
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Sumitomo Chemical Co Ltd
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/26—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes

Definitions

  • polyolefins such as propylene homopolymers and copolymers of propylene and ⁇ -olefins are excellent in mechanical properties, heat resistance, chemical resistance, water resistance and the like, and are inexpensive. It is used in a wide range of fields.
  • the surface of a base material made of polyolefins has low adhesion to substances other than polyolefins, and it is difficult to form a coating film such as an adhesive or paint. Therefore, attempts have been made to improve paintability and adhesiveness by using modified polyolefins such as chlorinated polyolefin, acid-modified chlorinated polyolefin, and acid-modified polyolefin as a component of a primer or an adhesive.
  • the modified polyolefin is usually used in the form of a solution in an organic solvent or a dispersion in an aqueous solvent, and is preferably used in the form of an aqueous dispersion in terms of safety and environment. .
  • aqueous dispersion mixture of a conventional aqueous dispersion of modified polyolefin and an aqueous dispersion such as an acrylic resin or a urethane resin in order to exert adhesion to a substrate or a coating film made of polyolefins, It was necessary to process at a relatively high temperature of ⁇ 100 ° C. For this reason, the aqueous dispersion which exhibits adhesiveness even when it processes at lower temperature from viewpoints, such as a manufacturing cost reduction and a carbon dioxide emission reduction, is desired.
  • an object of the present invention is to provide an aqueous dispersion mixture capable of exhibiting good adhesiveness.
  • the aqueous dispersion (A) is obtained by dispersing a modified polymer (a-2) which is a graft modification product of a polyolefin (a-1) with an ⁇ , ⁇ -unsaturated carboxylic acid in which a melting point peak is not substantially observed.
  • aqueous dispersion (B) contains polyurethane (b) as a dispersoid.
  • Aqueous dispersion mixture is obtained by dispersing a modified polymer (a-2) which is a graft modification product of a polyolefin (a-1) with an ⁇ , ⁇ -unsaturated carboxylic acid in which a melting point peak is not substantially observed.
  • the aqueous dispersion mixture of the present invention not only exhibits excellent adhesion to substrates made of polyolefins, but also exhibits high adhesion to substrates and coatings made of substances other than polyolefins. .
  • the aqueous dispersion mixture of the present invention can exhibit good adhesion even when treated at a low temperature of about 60 ° C. Therefore, the aqueous dispersion mixture of the present invention is suitable for a primer, a coating composition, an adhesive and the like.
  • the aqueous dispersion mixture of the present invention is an aqueous dispersion mixture containing an aqueous dispersion (A) and an aqueous dispersion (B).
  • the aqueous dispersion (A) has an ⁇ , ⁇ -unsaturation of polyolefin (a-1) (hereinafter referred to as polyolefin (a-1)) in which a melting point peak is not substantially observed by differential scanning calorimetry (DSC).
  • the said aqueous dispersion (B) is an aqueous dispersion which uses a polyurethane (b) as a dispersoid.
  • a polyolefin in which a melting point peak is not substantially observed by differential scanning calorimetry refers to a temperature range of ⁇ 100 ° C. to 200 ° C. in differential scanning calorimetry (DSC) according to JIS K 7122. This refers to a polyolefin in which a crystal melting peak with a heat of crystal melting of 1 J / g or more and a crystallization peak with a heat of crystallization of 1 J / g or more are not observed.
  • Polyolefin is a thermoplastic resin obtained by polymerizing olefin, and is a homopolymer or copolymer having at least one type of structural unit derived from olefin. The crystal melting peak and the crystallization peak can be measured, for example, by the method described in Examples described later.
  • the polyolefin (a-1) is not limited as long as the melting point peak is not substantially observed by differential scanning calorimetry (DSC), and is selected from the group consisting of ethylene and ⁇ -olefins having 3 to 20 carbon atoms.
  • a polyolefin which is a homopolymer or copolymer of at least one olefin is exemplified.
  • Examples of the ⁇ -olefin having 3 to 20 carbon atoms include linear olefins and branched olefins having 3 to 20 carbon atoms.
  • linear olefins examples include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- Examples include tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene and the like.
  • branched olefins examples include 3-methyl-1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, 2,2,4-trimethyl-1- Examples include pentene.
  • olefins selected from the group consisting of ethylene and ⁇ -olefins having 3 to 20 carbon atoms
  • ethylene / propylene ethylene / 1-butene, ethylene / 1-hexene, ethylene / 1-octene, ethylene / 4-methyl-1-pentene, ethylene / propylene / 1-butene, ethylene / propylene / 1-hexene, ethylene / 1-butene / 1-hexene, propylene / 1-butene, propylene / 1- Examples include hexene, propylene / 1-octene, propylene / 4-methyl-1-pentene, and propylene / 1-butene / 1-hexene.
  • the polyolefin (a-1) is a structural unit derived from at least one, preferably two olefins selected from the group consisting of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, and a single amount other than the olefin. It may be a polyolefin having a structural unit derived from the body. Examples of monomers other than ethylene and ⁇ -olefin include ⁇ , ⁇ -unsaturated carboxylic acids, metal salts of ⁇ , ⁇ -unsaturated carboxylic acids, vinyl esters, vinyl ester saponified products, cyclic olefins, and vinyl aromatics described below. Compounds, polyene compounds, (meth) acrylonitrile, halogenated vinyls, halogenated vinylidenes and the like. You may use these individually or in combination of 2 or more types.
  • Examples of the metal salt of ⁇ , ⁇ -unsaturated carboxylic acid include sodium salt and magnesium salt of (meth) acrylic acid.
  • vinyl ester examples include vinyl formate, vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatate and the like. Of these, vinyl acetate is preferred.
  • vinyl ester saponified product examples include vinyl alcohol which is a saponified product of a basic compound of vinyl ester or the like.
  • cyclic olefin examples include norbornene, 5-methylnorbornene, 5-ethylnorbornene, 5-propylnorbornene, 5,6-dimethylnorbornene, 1-methylnorbornene, 7-methylnorbornene, 5,5,6-trimethylnorbornene, 5 -Phenylnorbornene, 5-benzylnorbornene, 5-ethylidenenorbornene, 5-vinylnorbornene, 1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2, -Methyl-1,4,5,8-dimethano-1,2,3,4,4a, 5,8,8a-octahydronaphthalene, 2-ethyl-1,4,5,8-dimethano-1,2 , 3,4,4a, 5,8,8a-octahydronaphthalene, 2,3-dimethyl-1,
  • vinyl aromatic compounds include styrene, ⁇ -methylstyrene, p-methylstyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, fluorostyrene, p-tert-butylstyrene, ethylstyrene, vinyl And naphthalene.
  • polyene compound examples include a linear or branched aliphatic conjugated polyene compound, an alicyclic conjugated polyene compound, an aliphatic non-conjugated polyene compound, an alicyclic non-conjugated polyene compound, and an aromatic non-conjugated polyene compound.
  • a substituent such as an alkoxy group, an aryl group, an aryloxy group, an aralkyl group, and an aralkyloxy group.
  • Examples of the aliphatic conjugated polyene compound include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-propyl-1,3-butadiene, 2-isopropyl-1,3-butadiene, and 2-hexyl.
  • Examples of the alicyclic conjugated polyene compound include 2-methyl-1,3-cyclopentadiene, 2-methyl-1,3-cyclohexadiene, 2,3-dimethyl-1,3-cyclopentadiene, and 2,3-dimethyl.
  • -1,3-cyclohexadiene, 2-chloro-1,3-butadiene, 2,3-dichloro-1,3-butadiene, 1-fluoro-1,3-butadiene, 2-chloro-1,3-pentadiene examples include 2-chloro-1,3-cyclopentadiene and 2-chloro-1,3-cyclohexadiene.
  • Examples of the aliphatic non-conjugated polyene compound include 1,4-hexadiene, 1,5-hexadiene, 1,6-heptadiene, 1,6-octadiene, 1,7-octadiene, 1,8-nonadiene, 1,9- Decadiene, 1,13-tetradecadiene, 1,5,9-decatriene, 3-methyl-1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 4- Ethyl-1,4-hexadiene, 3-methyl-1,5-hexadiene, 3,3-dimethyl-1,4-hexadiene, 3,4-dimethyl-1,5-hexadiene, 5-methyl-1,4- Heptadiene, 5-ethyl-1,4-heptadiene, 5-methyl-1,5-heptadiene, 6-methyl-1,5-heptadiene, 5-ethyl-1,5
  • alicyclic non-conjugated polyene compounds include vinylcyclohexane, vinylcyclohexene, 5-vinyl-2-norbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropenyl-2-norbornene, Cyclohexadiene, dicyclopentadiene, cyclooctadiene, 2,5-norbornadiene, 2-methyl-2,5-norbornadiene, 2-ethyl-2,5-norbornadiene, 2,3-diisopropylidene-5-norbornene, 2, -Ethylidene-3-isopropylidene-5-norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 1,4-divinylcyclohexane, 1,3-divinylcyclohexane, 1,3-divinylcyclopen
  • aromatic non-conjugated polyene compound examples include divinylbenzene and vinylisopropenylbenzene.
  • the amount of the structural unit derived from ethylene contained in the polyolefin (a-1) is based on 100 mol% of all the structural units of the polyolefin (a-1) from the viewpoint of increasing the adhesive strength of the resulting aqueous dispersion mixture. Usually, it is 70 mol% or less, preferably 50 mol% or less, more preferably 20 mol% or less, and still more preferably 0 mol%.
  • the polyolefin (a-1) contains structural units derived from at least two kinds of olefins from the viewpoint of enhancing the adhesive strength of the resulting aqueous dispersion mixture, and the total number of carbon atoms of the olefins is 6 or more. It is preferable that it is the combination which becomes.
  • the polyolefin (a-1) is more preferably at least two selected from the group consisting of propylene and ⁇ -olefins having 4 to 20 carbon atoms.
  • propylene / 1-butene copolymer propylene / 1-hexene copolymer, propylene / 1-octene copolymer, propylene / 4-methyl-1-pentene copolymer, propylene / 1-butene / 1 -Hexene copolymer and the like.
  • the amount of the structural unit derived from propylene contained in the polyolefin (a-1) is based on 100 mol% of all the structural units of the polyolefin (a-1) from the viewpoint of enhancing the adhesive strength of the resulting aqueous dispersion mixture. Usually, it is 50 mol% or more, more preferably 60 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more, and most preferably 90 mol% or more.
  • the amount of the structural unit derived from propylene contained in the polyolefin (a-1) is such that all structural units of the polyolefin (a-1) are used from the viewpoint of enhancing the adhesive strength of the aqueous dispersion mixture obtained at low temperature. It is 99.9 mol% or less normally with respect to 100 mol%, Preferably it is 99 mol% or less, More preferably, it is 98.5 mol% or less, More preferably, it is 98 mol% or less.
  • Examples of the method for producing the polyolefin (a-1) include a method using a known Ziegler-Natta type catalyst or a known single site catalyst. From the viewpoint of further improving the scratch resistance and heat resistance of the dried product coated with the aqueous adhesive of the present invention, a method using a known single site catalyst is preferable.
  • Examples of single site catalysts include metallocene catalysts and non-metallocene complex catalysts.
  • Examples of the metallocene catalyst include, for example, JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, JP-A-60-35008. No. 1, No. 61-130314, No. 3-163088, No. 4-268307, No. 9-12790, No. 9-87313, No. 11-80233 And metallocene catalysts described in JP-A-10-508055 and the like.
  • nonmetallocene complex catalyst examples include, for example, JP-A-10-316710, JP-A-11-1000039, JP-A-11-80228, JP-A-11-80227, and JP-T-10-513289.
  • Non-metallocene complex catalysts described in JP-A-10-338706, JP-A-11-71420 and the like can be mentioned.
  • the single-site catalyst is preferably a metallocene catalyst from the viewpoint of easy availability, and more preferably has at least one cyclopentadiene-type anion skeleton and has a C1 enantiomorphic structure in Group 3 to Periodic Table. It is a catalyst obtained by using a Group 12 transition metal complex. Moreover, as an example of the manufacturing method using a metallocene catalyst, the method of European Patent Application Publication No. 12111287 and the like can be mentioned.
  • the modified polymer (a-2), which is a graft-modified product, is obtained by melting the polyolefin (a-1) and then graft-modifying it by adding ⁇ , ⁇ -unsaturated carboxylic acids.
  • Polyolefin (a-1) Is dissolved in a solvent such as toluene and xylene, and then ⁇ , ⁇ -unsaturated carboxylic acids are added to obtain a graft modification.
  • a polymerization initiator such as a peroxide can be used as necessary.
  • the ⁇ , ⁇ -unsaturated carboxylic acids include ⁇ , ⁇ -unsaturated carboxylic acids and derivatives thereof.
  • Examples include ⁇ , ⁇ -unsaturated carboxylic acids such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, crotonic acid, citraconic acid and the like; ⁇ , ⁇ -unsaturated carboxylic acid anhydrides such as anhydrous Maleic acid, itaconic anhydride, citraconic anhydride, etc .; ⁇ , ⁇ -unsaturated carboxylic acid esters such as methyl maleate, methyl itaconate, methyl citraconic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth ) Acrylate, butyl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (me
  • ⁇ -unsaturated carboxylic acids two or more of these may be used in combination. Among these, ⁇ , ⁇ -unsaturated carboxylic acid, ⁇ , ⁇ -unsaturated carboxylic acid anhydride and ⁇ , ⁇ -unsaturated carboxylic acid ester are preferable.
  • ⁇ ⁇ -unsaturated carboxylic acid
  • maleic acid is preferred.
  • ⁇ ⁇ -unsaturated carboxylic acid anhydride
  • maleic anhydride is preferred.
  • the ⁇ , ⁇ -unsaturated carboxylic acid ester is preferably an ⁇ , ⁇ -unsaturated carboxylic acid ester in which the number of carbon atoms in the R group in the ester moiety (—CO—O—R) is 4 or more.
  • An ⁇ , ⁇ -unsaturated carboxylic acid ester having 6 or more carbon atoms in the group is more preferable, and an ⁇ , ⁇ -unsaturated carboxylic acid ester having an R group having 8 or more carbon atoms in the ester moiety is more preferable.
  • the ⁇ , ⁇ -unsaturated carboxylic acid ester is preferably an ⁇ , ⁇ -unsaturated carboxylic acid ester in which the R group has 30 or less carbon atoms in the ester moiety, and the R group in the ester moiety has 20 or less carbon atoms.
  • An ⁇ , ⁇ -unsaturated carboxylic acid ester is more preferred.
  • acrylic acid and methacrylic acid are collectively referred to as (meth) acrylic acid.
  • acrylate and methacrylate are collectively referred to as (meth) acrylate.
  • the amount of structural units derived from ⁇ , ⁇ -unsaturated carboxylic acids (hereinafter referred to as unsaturated carboxylic acid units) in the modified polymer (a-2) is the structural unit derived from the polyolefin (a-1) ( Hereinafter, it is preferably 0.1 parts by mass or more, more preferably 1 part by mass or more, and still more preferably 3 parts by mass or more with respect to 100 parts by mass.
  • the amount of the unsaturated carboxylic acid unit in the modified polymer (a-2) is preferably 50 parts by mass or less, more preferably 40 parts by mass or less, and still more preferably 30 parts by mass with respect to 100 parts by mass of the olefin unit. Or less.
  • the adhesiveness to the coating film and the modified polymer (a-2) are contained in the solvent. Stability is improved when dispersed.
  • the unsaturated carboxylic acid units in the modified polymer (a-2) may be those in which an acid anhydride group is retained or those that have been ring-opened. It may be both.
  • the weight average molecular weight Mw of the modified polymer (a-2) measured by GPC (Gel Permeation Chromatography) and converted with a calibration curve of each polystyrene is preferably 20,000 or more, more preferably 25,000 or more, and further. Preferably it is 30,000 or more. Further, the weight average molecular weight Mw of the modified polymer (a-2) is preferably 200,000 or less, more preferably 150,000 or less, and still more preferably 100,000 or less. When the weight average molecular weight Mw of the modified polymer (a-2) is 20,000 or more and 200,000 or less, the adhesion to the substrate or the coating film is good.
  • the aqueous dispersion (A) is prepared by a method known in the art, for example, a post-emulsification method (for example, forced emulsification) in which a modified polymer (a-2) that is a resin to be emulsified is produced and then the resin is dispersed in an aqueous medium.
  • a post-emulsification method for example, forced emulsification
  • a-2 modified polymer
  • Method self-emulsification method, phase inversion emulsification method, etc.
  • Specific examples thereof include (1) a method of preparing an aqueous dispersion by preparing a mixture of a resin to be emulsified and water and a solvent other than water in a reactor, and then removing the solvent other than water from the mixture. (2) A method in which the resin to be emulsified is melted at a temperature equal to or higher than the temperature at which the resin to be emulsified is melted in a kneader, and water is added to form a dispersion. (3) An emulsion polymerization method or a suspension polymerization method. Moreover, when preparing a mixture, you may heat and / or stir as needed. Heating can usually be carried out at 50 to 200 ° C, preferably 60 to 150 ° C, more preferably 70 to 100 ° C. The rotation speed of the stirrer can be performed, for example, at a rotation speed of about 50 to 10,000 rpm.
  • a container preferably sealed and / or sealed
  • a heating device capable of being heated
  • a stirrer capable of applying a shearing force or the like to the contents.
  • Pressure vessel is used as the reactor.
  • examples of the kneader include a roll mill, a kneader, an extruder, an ink roll, and a Banbury mixer.
  • an extruder or a multi-screw extruder having one or more screws in the casing may be used.
  • a resin to be emulsified and a surfactant as necessary are mixed and continuously supplied from a hopper or supply port of the extruder, and this is heated, melted and kneaded. Further, there is a method in which water is supplied from at least one supply port provided in a compression zone, a metering zone, a degassing zone, and the like of the extruder, kneaded with a screw, and then continuously extruded from a die.
  • the water content in the aqueous dispersion (A) is 30% by weight or more, preferably 35% by weight or more, more preferably 40% by weight or more, and further preferably 45% by weight or more based on the total amount of the aqueous dispersion.
  • solvent other than water examples include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, alicyclic hydrocarbons such as cyclohexane and methylcyclohexane, methylene chloride, carbon tetrachloride, Halogenated hydrocarbons such as chlorobenzene, esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone, methanol, ethanol, n-propanol , Isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, alcohols such as ethylene glyco
  • a solvent that dissolves 1% by mass or more in water is preferable, and a solvent that dissolves 5% by mass or more is more preferable.
  • the ratio of the solvent other than water to water is preferably 50% or less, more preferably 20% or less, still more preferably 10% or less, still more preferably 1% or less, and particularly preferably 0%. It is.
  • the volume-based median diameter of the dispersoid contained in the aqueous dispersion (A) is preferably 1.0 ⁇ m or less, more preferably 0.9 ⁇ m or less, and even more preferably 0.8 ⁇ m or less. Further, the lower limit of the volume-based median diameter of the dispersoid contained in the aqueous dispersion (A) is not limited. In this specification, the volume-based median diameter is a particle diameter corresponding to 50% of the cumulative particle diameter distribution on a volume basis, and can be measured using, for example, a particle size distribution measuring apparatus.
  • the aqueous dispersion (A) preferably has a non-volatile content of 5% by mass or more, more preferably 15% by mass or more, still more preferably 30% by mass or more, and usually 60% by mass with respect to the entire aqueous dispersion (A). Contains below.
  • the non-volatile content is obtained by measuring the mass of the residue obtained by removing the solvent from the aqueous dispersion according to JIS K-6828-1.
  • the polyurethane (b) is a polymer containing a urethane bond in the main chain, and is, for example, a reaction product of a polyol compound and a polyisocyanate compound.
  • the polyol compound is not particularly limited, and examples thereof include water, ethylene glycol, diethylene glycol, triethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,2-propanediol, and 1,3-propane.
  • polyisocyanate compound one or a mixture of two or more known diisocyanates of aromatic, aliphatic and alicyclic can be used.
  • diisocyanates include tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 1,3-phenylene diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, isophorone diisocyanate, dimethyl diisocyanate, lysine diisocyanate.
  • diisocyanates trifunctional or higher functional polyisocyanates such as triphenylmethane triisocyanate and polymethylene polyphenyl isocyanate may be used.
  • an active hydrogen which is a compound different from the hydrophilic group-containing compound and can react with an isocyanate compound in the molecule for the purpose of chain extension, molecular weight adjustment, etc., if necessary.
  • examples of such compounds include polyvalent amine compounds such as ethylenediamine, 1,4-butanediamine, and 1,6-hexanediamine; tertiary amine-containing polyhydric alcohols such as triethanolamine, methanol, ethanol, and butanol. And monoalcohols.
  • aqueous polyurethane dispersion (B) suitable for the present invention a commercially available product can be used.
  • a commercially available aqueous dispersions of polyurethane include Adekabon titer HUX series manufactured by ADEKA Co., Ltd., Dispacol series manufactured by Sumika Covestro Urethane Co., Ltd., Superflex series manufactured by Daiichi Kogyo Seiyaku Co., Ltd., etc. Can be mentioned.
  • the volume-based median diameter of the dispersoid contained in the aqueous dispersion (B) is preferably 1.0 ⁇ m or less, more preferably 0.9 ⁇ m or less, and even more preferably 0.8 ⁇ m or less. Further, the lower limit of the volume-based median diameter of the dispersoid contained in the aqueous dispersion (B) is not limited.
  • the aqueous dispersion (B) preferably contains 15 to 70% by weight, more preferably 25 to 60% by weight of the non-volatile content with respect to the entire aqueous dispersion (B).
  • aqueous dispersion (A) or (B) in addition to the resin, water and a solvent other than water, additional resins, surfactants, basic compounds, thickeners, dispersants, curing agents, pigments, Appropriate amounts of optional components such as viscosity modifiers and additional solvents can be added at any time. These components can also be added after mixing the aqueous dispersions (A) and (B).
  • Further resins include, for example, polyolefin resins different from polyolefin (a-1), epoxy resins, acrylic resins (PMMA), polyvinyl chloride (PVC), polyvinylidene chloride, polystyrene (PS), poly Examples thereof include various polymers and copolymers such as vinyl acetate (PVAc), polytetrafluoroethylene (PTFE), acrylonitrile butadiene styrene resin (ABS resin), AS resin, and modified products thereof. These may be used alone or in combination of two or more.
  • a crystalline polyolefin resin can be used as long as the content of the polyolefin (a-1) in the aqueous dispersion mixture of the present invention is not exceeded. .
  • resin which exhibits the function as an adhesive resin or a tackifier.
  • resins include rosins, terpene resins, petroleum resins obtained by polymerizing petroleum fractions having 5 carbon atoms, and hydrogenated resins, petroleum resins obtained by polymerizing petroleum fractions having 9 carbon atoms. And hydrogenated resins, other petroleum resins, coumarone resins and indene resins, polyurethane resins of a different type from polyurethane (b), and the like.
  • Rosins such as fluoride
  • terpene resins such as terpene polymers, terpene phenols, ⁇ -pinene polymers, aromatic modified terpene polymers, ⁇ -pinene polymers, terpene hydrogenated resins
  • Petroleum-based resins obtained by polymerizing components, petroleum-based resins obtained by polymerizing petroleum fractions having 9 carbon atoms, and hydrogenated resins thereof; petroleum-based resins such as maleic acid-modified products and fumaric acid-modified products
  • surfactant examples include cationic, anionic, amphoteric and nonionic surfactants. Among them, anionic or nonionic surfactants are preferable. Surfactants may be used alone or in combination of two or more.
  • anionic surfactants include higher alcohol sulfates, higher alkyl sulfonates, higher carboxylates, alkyl benzene sulfonates, polyoxyethylene alkyl sulfate salts, polyoxyethylene alkyl phenyl ether sulfate salts, vinyls. Examples include sulfosuccinate.
  • cationic surfactants include alkylammonium salts such as dodecyltrimethylammonium salt and cetyltrimethylammonium salt, alkylpyridium salts such as cetylpyridium salt and decylpyridium salt, oxyalkylenetrialkylammonium salt, dioxyalkylenedialkyl Examples include ammonium salts, allyltrialkylammonium salts, diallyldialkylammonium salts, and the like.
  • nonionic surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene propylene ether, polyoxyethylene alkyl phenyl ethers, polyethylene glycol fatty acid esters, ethylene oxide propylene oxide block copolymers, polyoxyethylene fatty acid amides, Examples thereof include compounds having a polyoxyethylene structure such as an ethylene oxide-propylene oxide copolymer, and sorbitan derivatives such as a polyoxyethylene sorbitan fatty acid ester.
  • polyoxyethylene alkyl ethers such as polyoxyethylene propylene ether, polyoxyethylene alkyl phenyl ethers, polyethylene glycol fatty acid esters, ethylene oxide propylene oxide block copolymers, polyoxyethylene fatty acid amides
  • examples thereof include compounds having a polyoxyethylene structure such as an ethylene oxide-propylene oxide copolymer, and sorbitan derivatives such as a polyoxyethylene sorbitan fatty acid ester.
  • amphoteric surfactants examples include lauryl betaine and lauryl dimethylamine oxide.
  • those capable of neutralizing carboxylic acid are preferable, and examples thereof include ammonia, organic amine compounds, metal hydroxides and the like.
  • it is ammonia or an organic amine compound.
  • organic amine compounds having a boiling point of 200 ° C. or less can be easily dispersed by ordinary drying, and maintain the water resistance and alkali resistance of the coating film when an aqueous dispersion mixture is used to form the coating film. Can be improved.
  • Examples of the organic amine compound include triethylamine, N, N-dimethylethanolamine, aminoethanolamine, N-methyl-N, N-diethanolamine, isopropylamine, iminobispropylamine, ethylamine, diethylamine, 3-ethoxypropylamine, Examples include 3-diethylaminopropylamine, sec-butylamine, propylamine, methylaminopropylamine, 3-methoxypropylamine, monoethanolamine, morpholine, N-methylmorpholine, N-ethylmorpholine and the like. Of these, N, N-dimethylethanolamine and the like are preferable.
  • Examples of the metal hydroxide include lithium hydroxide, potassium hydroxide, sodium hydroxide and the like.
  • a thickener As a thickener, it can be used to adjust the viscosity of the compound.
  • a thickener manufactured by ADEKA Corporation; Adecanol UH-140S, UH-420, UH-438, UH-450VF, UH-462, UH-472, UH-526, UH-530, UH-540, UH-541VF UH-550, UH-752, H-756VF, manufactured by San Nopco; SN thickener 920, 922, 924, 926, 929-S, A-801, A-806, A-812, A-813, A-818 621N, 636, 601, 603, 612, 613, 615, 618, 621N, 630, 634, 636, 4050 and the like.
  • a dispersant it can be used to improve the wettability of the coated substrate.
  • a dispersant manufactured by ADEKA Corporation; Adeka Coal W-193, W-287, W-288, W-304, manufactured by BYK; BYK-333, BYK-345, BYK-346, BYK-347, BYK- 348, BYK-349, BYK-378, manufactured by San Nopco; Nopco wet 50, SN wet 366, Nopco 38-C, SN disperse sand 5468, 5034, 5027, 5040, 5020 and the like.
  • an isocyanate-based and / or carbodiimide-based curing agent can be used.
  • examples thereof include diphenylmethane diisocyanate (MDI), tolylene diisocyanate (TDI), hexamethylene diisocyanate (HDI), xylene diisocyanate (XDI), and oligomers or polymers thereof, which are isocyanate-based curing agents.
  • Specific examples include Sumidur 44V20, Sumidur N3200, N3300, N3400, N3600, N3900, S-304, S-305, XP-2655, XP-2487, XP-2547 and the like made by Sumika Covestrourethane. It is done.
  • carbodiimide-based curing agent examples include a carbodilite series (manufactured by Nisshinbo Chemical Co., Ltd.).
  • the curing agent is preferably 0.1 to 20 parts by weight, more preferably 0.1 to 10 parts by weight with respect to 100 parts by weight of the resin constituting the aqueous dispersion mixture.
  • the curing agent may be added after being dissolved in an organic solvent.
  • the pigment examples include inorganic pigments such as titanium oxide, carbon black, iron oxide, chromium oxide, bitumen, bengara, yellow lead, yellow iron oxide, azo pigments, anthracene pigments, perinone pigments, perylene pigments, and quinacridone pigments.
  • inorganic pigments such as titanium oxide, carbon black, iron oxide, chromium oxide, bitumen, bengara, yellow lead, yellow iron oxide, azo pigments, anthracene pigments, perinone pigments, perylene pigments, and quinacridone pigments.
  • Color pigments such as organic pigments such as pigments, isoindolinone pigments, indigo pigments, phthalocyanine pigments; extender pigments such as talc, calcium carbonate, clay, kaolin, silica, precipitated barium sulfate; conductive carbon, antimony-doped Examples include conductive pigments such as whiskers coated with tin oxide; non-colored or colored metallic luster such as metals or alloys such as aluminum, copper, zinc, nickel, tin, and aluminum oxide. Two or more kinds may be used in combination.
  • a pigment dispersant When using a pigment, a pigment dispersant may be used.
  • an aqueous acrylic resin such as John Kuril manufactured by BASF Japan
  • an acidic block copolymer such as BYK-190 manufactured by BYK
  • a styrene-maleic acid copolymer Surfynol manufactured by Air Products (Air Products)
  • Surfynol manufactured by Air Products Air Products
  • examples thereof include acetylenic diol derivatives such as T324; water-soluble carboxymethyl acetate butyrate such as CMCAB-641-0.5 manufactured by Eastman Chemical Co., Ltd.
  • the viscosity modifier is an agent added to properly adjust the viscosity of the aqueous dispersion, and can be used within a range that does not significantly reduce the performance of the present invention.
  • examples of the viscosity modifier (D) are not particularly limited, and examples thereof include BYK-420 and BYK-425 (manufactured by BYK).
  • solvents include, for example, aromatic hydrocarbons such as water, toluene and xylene, aliphatic hydrocarbons such as hexane, octane and decane, alicyclic aliphatic hydrocarbons such as cyclohexane and methylcyclohexane, and methylene chloride.
  • aromatic hydrocarbons such as water, toluene and xylene
  • aliphatic hydrocarbons such as hexane, octane and decane
  • alicyclic aliphatic hydrocarbons such as cyclohexane and methylcyclohexane
  • methylene chloride methylene chloride
  • Halogenated hydrocarbons such as carbon tetrachloride and chlorobenzene
  • esters such as methyl acetate, ethyl acetate, propyl acetate and butyl acetate
  • ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone and cyclohexanone
  • methanol Alcohols such as ethanol, n-propanol, isopropanol, n-butanol, 2-butanol, isobutanol, t-butanol, cyclohexanol, ethylene glycol, propylene glycol, butanediol, dipropyl ether, dibutyl ether Ethers such as tellurium and tetrahydrofuran, organic solvents having two or more functional groups such as 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-methoxypropano
  • a phenol-based stabilizer a phosphite-based stabilizer, an amine-based stabilizer, an amide-based stabilizer, and an anti-aging agent are added as necessary as long as the intended properties of the aqueous dispersion mixture of the present invention are not impaired.
  • Stabilizers such as weathering stabilizer, anti-settling agent, antioxidant, heat stabilizer, light stabilizer; thixotropic agent, thickener, dispersant, antifoaming agent, weathering agent, antistatic agent, lubricant, nucleus Additives, flame retardants, oils, dyes, curing agents, crosslinking agents, etc .; glass fibers, carbon fibers, potassium titanate fibers, wollastonite, calcium carbonate, calcium sulfate, talc, glass flakes, barium sulfate, clay, Inorganic and organic fillers such as kaolin, fine powder silica, mica, calcium silicate, aluminum hydroxide, magnesium hydroxide, aluminum oxide, magnesium oxide, alumina, celite, etc. It may contain optional components.
  • the nonvolatile content of the aqueous dispersion (B) is preferably 65 parts by mass or more, more preferably 75 parts by mass or more, with respect to 100 parts by mass of the nonvolatile content of the aqueous dispersion (A). More preferably, it contains 85 parts by mass or more.
  • the aqueous dispersion (B) preferably has a nonvolatile content of 200 parts by mass or less, more preferably 160 parts by mass or less, and still more preferably 120 parts by mass with respect to 100 parts by mass of the nonvolatile content of the aqueous dispersion (A). Contains the following.
  • the dispersoid of the aqueous dispersion (A) is preferably a self-emulsified product of the modified polymer (a-2). Therefore, the modified polymer (a-2) preferably has self-emulsifying properties. When the modified polymer (a-2) has a self-emulsifying property, it is advantageous because the aqueous dispersion (A) can be produced without using an emulsifier or a dispersant.
  • the aqueous dispersion mixture of the present invention can be obtained, for example, by mixing the aqueous dispersions (A) and (B).
  • a conventionally known method can be used as the mixing method.
  • the aqueous dispersions (A) and (B) can be charged into a container equipped with a stirrer and stirred. At this time, components other than the resin, water, and a solvent other than water may be added. Further, water may be further added.
  • the aqueous dispersion mixture of the present invention thus obtained is subjected to treatment such as drying and / or curing at a temperature of 20 ° C. to 140 ° C., preferably 40 ° C. to 120 ° C., more preferably 60 ° C. to 100 ° C. Even if it is performed, it can exhibit excellent adhesion to various substrates and various paints, and in particular, can exhibit excellent adhesion even at a relatively low temperature of 60 ° C. or less. Therefore, it is useful for various applications. For example, it can be used as it is as a water-based adhesive or primer, and it can also be used together with other components in a water-based coating composition, water-based adhesive, or primer composition.
  • the aqueous coating composition is applied to a substrate, and the temperature is 20 ° C. to 140 ° C., preferably 40 ° C. to 120 ° C., more preferably 60 ° C. to 100 ° C. for 1 minute to 1 hour.
  • the coating film can be formed on the substrate by heating for 3 to 30 minutes.
  • a coating film of the primer and the primer composition is formed by drying and / or curing at a temperature of room temperature to 100 ° C. as necessary, and then another paint is applied on the coating film.
  • the coating composition is heated at a temperature of 20 ° C. to 140 ° C., preferably 40 ° C. to 120 ° C., more preferably 60 ° C. to 100 ° C. for 1 minute to 1 hour, preferably 3 minutes to 30 minutes.
  • the coating film can be formed.
  • the water-based adhesive is applied to one or both surfaces of the substrate, and after drying and / or curing at a temperature of room temperature to 100 ° C. as necessary, two substrates are bonded.
  • the substrate can be bonded by bonding and processing at an appropriate temperature.
  • the substrate examples include polyolefins such as olefin polymers, polyamide, unsaturated polyester, polybutylene terephthalate, polycarbonate, vinyl chloride, polyester, polyurethane, epoxy resin, paper, synthetic paper, wood, woven fabric, knitting Widely and widely made of cloth, non-woven fabric, metal components (including iron, aluminum, copper, nickel, silver, gold, platinum, various alloys, etc.), wood (including pulp, paper, etc.), stones, etc.
  • polyolefins such as olefin polymers, polyamide, unsaturated polyester, polybutylene terephthalate, polycarbonate, vinyl chloride, polyester, polyurethane, epoxy resin, paper, synthetic paper, wood, woven fabric, knitting Widely and widely made of cloth, non-woven fabric, metal components (including iron, aluminum, copper, nickel, silver, gold, platinum, various alloys, etc.), wood (including pulp, paper, etc.), stones, etc.
  • a base material is mentioned.
  • polystyrene resin examples include high-pressure polyethylene, medium-low pressure polyethylene, polypropylene, poly-4-methyl-1-pentene, poly-1-butene, ethylene / propylene copolymer, ethylene / butene copolymer, propylene / ethylene.
  • examples thereof include copolymers and propylene / butene copolymers, and polyolefins having a polypropylene crystal structure are preferred.
  • the shape of the base material is not particularly limited, such as a film, a sheet, a plate-like body and the like. Further, it may be a molded body obtained by a known molding method such as injection molding, compression molding, hollow molding, extrusion molding, or rotational molding. Moreover, the molded object may contain the inorganic filler component, the pigment, etc.
  • Examples include plate fillers such as talc, mica, and montmorillonite; fiber fillers such as short fiber glass fiber, long fiber glass fiber, carbon fiber, aramid fiber, alumina fiber, boron fiber, and zonolite; potassium titanate, magnesium Needle-shaped fillers such as oxysulfate, silicon nitride, aluminum borate, basic magnesium sulfate, zinc oxide, wollastonite, calcium carbonate, silicon carbide; precipitated calcium carbonate, heavy calcium carbonate, magnesium carbonate, etc. Examples include granular fillers; balun fillers such as glass balloons; and inorganic fillers and pigments such as zinc white, titanium white, and magnesium sulfate.
  • the substrates are bonded using the aqueous dispersion mixture of the present invention, excellent adhesion is exhibited whether the substrates are made of the same material or substrates of different materials.
  • it is suitable for lamination of a polyurethane resin film and a polyolefin resin film, lamination of a polyurethane resin film and a polyester resin film, lamination of a polyurethane resin film and a metal, and the like.
  • the paint examples include a colored base paint and a clear paint. These may be aqueous or organic solvent-based, and may contain various resins such as olefin polymers and various pigments.
  • the method for applying the aqueous dispersion mixture to the substrate is not particularly limited, and any known method can be used.
  • air spray method airless spray method, gravure roll coating, reverse roll coating, wire bar
  • coating lip coating, air knife coating, curtain flow coating, spray coating, dip coating, and brush coating.
  • Drying, curing, and heating can be performed by, for example, a conventionally used method and apparatus, for example, using nichrome wire, infrared rays, high frequency, or the like.
  • the thickness of the coating film to be formed is appropriately selected depending on the material and shape of the substrate, the composition of the paint used, etc., and is usually 0.1 ⁇ m to 500 ⁇ m, preferably 1 ⁇ m to 300 ⁇ m, more preferably Is 5 ⁇ m to 200 ⁇ m.
  • the laminate is a laminate having a dry product of an aqueous adhesive containing the aqueous dispersion mixture of the present invention.
  • a dried product is obtained by applying on a substrate and drying by the same method as the above-mentioned coating film, and the thickness thereof is also the same as that of the above-mentioned coating film.
  • Coating films, laminates and coated articles using the aqueous dispersion mixture of the present invention can be used for various industrial parts such as automobiles, home appliances, and building materials, and in particular, thin parts, highly functional parts, and large-sized parts / It has sufficient performance for practical use as a material.
  • automotive parts such as bumpers, instrument panels, trims, garnishes, TV cases, washing machine tubs, refrigerator parts, air conditioner parts, vacuum cleaner parts and other household appliance parts, toilet seats, toilet seat lids, toiletries such as water tanks, bathtubs
  • toiletries such as water tanks, bathtubs
  • bathtubs It can be used as molding materials for various industrial parts such as bathroom walls, ceilings, drain pans and other parts around the bathroom.
  • Unsaturated carboxylic acid unit content The content of the maleic anhydride unit in the modified polymer is obtained by forming a film having a thickness of 100 ⁇ m by hot-pressing the sample, and measuring the infrared absorption spectrum of the obtained film. Measured and calculated from absorption around 1780 cm ⁇ 1 .
  • Crystal melting peak and crystallization peak of polyolefin were measured under the following conditions with a differential scanning calorimeter (DSC220C: input compensation DSC manufactured by Seiko Denshi Kogyo Co., Ltd.).
  • DSC220C input compensation DSC manufactured by Seiko Denshi Kogyo Co., Ltd.
  • the temperature was decreased from 200 ° C. to ⁇ 100 ° C. at a rate of temperature decrease of 10 ° C./min, and held for 5 minutes after the temperature decrease was completed.
  • weight average molecular weight (Mw) and number average molecular weight (Mn) of a polyolefin measure a commercially available monodisperse polystyrene standard sample as a standard sample and create a calibration curve from the retention time and molecular weight of the standard sample. Went.
  • volume-based median diameter is a particle diameter corresponding to a cumulative particle diameter distribution value of 50% on a volume basis, and means a median diameter measured on a volume basis unless otherwise specified.
  • the volume-based median diameter of the dispersoid can be measured with a laser diffraction particle diameter measuring apparatus LA-950V2 manufactured by HORIBA.
  • Nonvolatile content The solvent was removed from the aqueous dispersion, and the mass of the residue was measured as the nonvolatile content (according to JIS K 6828-1).
  • the reaction was carried out for 5 hours while maintaining the system at 140 ° C., and then low-molecular volatile substances such as xylene, unreacted dodecyl methacrylate and maleic anhydride were removed while reducing the pressure in the flask with an aspirator. After completion of the decompression, the reaction product was taken out and cooled to obtain a modified polyolefin solid product.
  • the content of maleic anhydride units in the modified polyolefin was 3.9 parts by mass with respect to 100 parts by mass of the structural unit derived from the amorphous polyolefin.
  • the reaction product was taken out and cooled to obtain a modified polyolefin solid product.
  • the content of maleic anhydride units in the modified polyolefin was 1.8 parts by mass with respect to 100 parts by mass of the structural unit derived from the amorphous polyolefin.
  • ion exchange water at 80 ° C. was added little by little with vigorous stirring.
  • 400 g of ion-exchanged water was added, the contents were taken out, and volatile components other than ion-exchanged water were removed using an evaporator to obtain an aqueous dispersion (A-3) having a modified polyolefin as a dispersoid.
  • the nonvolatile content was about 30%, and the volume-based median diameter of the dispersoid was 0.6 ⁇ m.
  • Aqueous dispersion B-1 Dispacol U-54 commercially available from Sumika Covestro Urethane Co., Ltd. (non-volatile content 50% by mass, moisture 50% by mass).
  • Dispacor U-42 nonvolatile content 50% by mass, moisture 50% by mass
  • Adekabon titer HU-401 commercially available from ADEKA Co., Ltd. (non-volatile content 37% by mass, moisture 63% by mass).
  • Example 7 The aqueous dispersion mixture prepared in Example 1 above was applied to a polypropylene substrate (after degreasing treatment) with a wire bar so that the dry film thickness was about 10 ⁇ m, and dried by heating at 50 ° C. for 5 minutes. Thereafter, an acrylic urethane paint “Polynal No. 800” (manufactured by Ohashi Chemical Industry Co., Ltd.) is spray-coated on the film so as to have a dry film thickness of about 100 ⁇ m, and dried by heating at 60 ° C. for 30 minutes. Was made.
  • Examples 8 to 12 and Comparative Example 2 Instead of the aqueous dispersion mixture used in Example 7, the aqueous dispersion mixture prepared in Examples 2 to 6 and Comparative Example 1 was used. Produced.
  • aqueous dispersion mixture of the present invention exhibits high peel strength even when baked at 60 ° C. and is excellent in adhesiveness at low temperatures.
  • the aqueous dispersion mixture of the present invention not only exhibits excellent adhesion to substrates made of polyolefins, but also exhibits high adhesion to substrates and coatings made of substances other than polyolefins. .
  • the aqueous dispersion mixture of the present invention can exhibit good adhesion even when treated at a low temperature of about 60 ° C. Therefore, the aqueous dispersion mixture of the present invention can be suitably used for a primer, a coating composition, an adhesive and the like.

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  • Health & Medical Sciences (AREA)
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Abstract

La présente invention concerne un mélange de dispersions aqueuses qui comprend une dispersion aqueuse (A) et une dispersion aqueuse (B). La dispersion aqueuse (A) comprend, à titre de dispersoïde, un polymère modifié (a-2) qui est un produit de modification d'une polyoléfine (a-1) n'ayant en fait pas de pic de fusion observable par greffage à celle-ci d'un acide carboxylique α,β-unsaturé. La dispersion aqueuse (B) utilise un polyuréthane (b) à titre de dispersoïde.
PCT/JP2016/064365 2015-05-15 2016-05-13 Mélange de dispersions aqueuses Ceased WO2016186049A1 (fr)

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Publication number Priority date Publication date Assignee Title
WO2003091330A1 (fr) * 2002-04-26 2003-11-06 Mitsubishi Chemical Corporation Dispersion de polypropylene aqueuse, composition d'emulsion composite de polypropylene aqueuse et son utilisation
JP2008056914A (ja) * 2006-07-31 2008-03-13 Honda Motor Co Ltd 水性プライマー塗料組成物及び塗膜形成方法
JP2008056913A (ja) * 2006-07-31 2008-03-13 Toyota Motor Corp 自動車内装材用水性塗料組成物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003091330A1 (fr) * 2002-04-26 2003-11-06 Mitsubishi Chemical Corporation Dispersion de polypropylene aqueuse, composition d'emulsion composite de polypropylene aqueuse et son utilisation
JP2008056914A (ja) * 2006-07-31 2008-03-13 Honda Motor Co Ltd 水性プライマー塗料組成物及び塗膜形成方法
JP2008056913A (ja) * 2006-07-31 2008-03-13 Toyota Motor Corp 自動車内装材用水性塗料組成物

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