WO2010114108A1 - Emulsion aqueuse - Google Patents

Emulsion aqueuse Download PDF

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Publication number
WO2010114108A1
WO2010114108A1 PCT/JP2010/056043 JP2010056043W WO2010114108A1 WO 2010114108 A1 WO2010114108 A1 WO 2010114108A1 JP 2010056043 W JP2010056043 W JP 2010056043W WO 2010114108 A1 WO2010114108 A1 WO 2010114108A1
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WIPO (PCT)
Prior art keywords
structural unit
carboxylic acid
aqueous emulsion
unsaturated carboxylic
component
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PCT/JP2010/056043
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English (en)
Japanese (ja)
Inventor
吉田礼
肥後睦子
森本順次
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住友化学株式会社
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Publication of WO2010114108A1 publication Critical patent/WO2010114108A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/08—Homopolymers or copolymers of acrylic acid 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • 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
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/14—Monomers containing five or more carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/16—Ethene-propene or ethene-propene-diene copolymers
    • 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
    • C08J2331/00—Characterised by the use of 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 an acyloxy radical of a saturated carboxylic acid, or carbonic acid, or of a haloformic acid
    • C08J2331/02—Characterised by the use of omopolymers or copolymers of esters of monocarboxylic acids
    • C08J2331/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
    • C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C08J2333/08—Homopolymers or copolymers of acrylic acid esters
    • 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
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L31/00—Compositions of 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 an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid; Compositions of derivatives of such polymers
    • C08L31/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C08L31/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/16—Amines or polyamines

Definitions

  • the present invention relates to an aqueous emulsion.
  • Polypropylene is used for automobile parts such as bumpers because it has excellent processability and strength.
  • a paint is usually applied to automobile parts for decoration or the like.
  • a chlorinated polyolefin excellent in adhesiveness with polypropylene is applied to polypropylene, and the paint is applied thereon (for example, JP-A-5-7832).
  • the present invention ⁇ 1> An aqueous emulsion comprising the following component (A), component (B) and component (C); (A) a structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid; A structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 10 carbon atoms having an amino group which may have a substituent and an ⁇ , ⁇ -unsaturated carboxylic acid; Wherein the hydrophilic ratio of the acrylic resin is 9 to 12 (where the hydrophilic ratio of the acrylic resin is a weight average value of the hydrophilic ratio of the monomer leading to the structural unit of the acrylic resin, The hydrophilic ratio of the monomer is a value calculated by the following formula.
  • Monomer hydrophilic ratio 20 ⁇ (formula weight of monomer hydrophilic portion) / (monomer molecular weight))
  • the aqueous emulsion according to ⁇ 1> comprising a polymer obtained by graft polymerization of an ⁇ , ⁇ -unsaturated carboxylic acid anhydride to a copolymer containing a structural unit derived from a vinyl compound represented by: ⁇ 4>
  • the aqueous emulsion is an aqueous emulsion having the component (A) and the component (B) as a dispersoid and the component (C) as a dispersion medium, and the volume-based median diameter of the dispersoid is 0.01 ⁇ m.
  • the aqueous emulsion according to any one of ⁇ 1> to ⁇ 5>, which is ⁇ 3 ⁇ m; ⁇ 7> Derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 10 carbon atoms having an optionally substituted amino group and an ⁇ , ⁇ -unsaturated carboxylic acid.
  • aqueous emulsion according to any one of ⁇ 1> to ⁇ 6>, wherein the structural unit is a structural unit derived from N, N-dimethylaminoethyl methacrylate; ⁇ 8> The aqueous emulsion according to any one of ⁇ 1> to ⁇ 7>, wherein the structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid is a structural unit derived from acrylic acid or methacrylic acid; ⁇ 9> A method for producing an aqueous emulsion, wherein the component (A) and the component (B) are melt-kneaded, and the resulting molten mixture and water are mixed; (A) a structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid; A structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 10 carbon atoms having an amino group which may have a substituent and an
  • Monomer hydrophilic ratio 20 ⁇ (formula weight of monomer hydrophilic portion) / (monomer molecular weight)) (B) Thermoplastic polymer (C) Water ⁇ 10> Cured product obtained by drying the aqueous emulsion according to any one of ⁇ 1> to ⁇ 8>; ⁇ 11> A laminate having a base material layer made of at least one material selected from the group consisting of a woody material, a cellulose material, a plastic material, a ceramic material, and a metal material, and a layer made of the cured product according to ⁇ 10>; ⁇ 12> The aqueous emulsion according to any one of ⁇ 1> to ⁇ 8>, wherein the base material layer made of at least one material selected from the group consisting of a woody material, a cellulose material, a plastic material, a ceramic material, and a metal material To obtain a laminate having the base material layer and the aqueous emulsion layer, Drying the laminate obtained in
  • Monomer hydrophilic ratio 20 ⁇ (formula weight of monomer hydrophilic part) / (monomer molecular weight)); ⁇ 14> Derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 10 carbon atoms having an optionally substituted amino group and an ⁇ , ⁇ -unsaturated carboxylic acid.
  • the emulsifier according to ⁇ 13> wherein the structural unit is a structural unit derived from N, N-dimethylaminoethyl methacrylate; ⁇ 15>
  • the aqueous emulsion of the present invention comprises the following component (A), component (B) and component (C).
  • A a structural unit derived from ⁇ , ⁇ -unsaturated carboxylic acid (hereinafter abbreviated as structural unit (a1)); A structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester derived from an ⁇ , ⁇ -unsaturated carboxylic acid and an aliphatic alcohol having 1 to 10 carbon atoms having an amino group which may have a substituent (
  • structural unit (a2) wherein the hydrophilic ratio of the acrylic resin is 9 to 12 (where the hydrophilic ratio of the acrylic resin is a weight average value of the hydrophilic ratio of the monomer leading to the structural unit of the acrylic resin, The hydrophilic ratio of the monomer is a value calculated by the following formula.
  • Thermoplastic polymer (C) Water First, the component (A) will be described.
  • the component (A) is an acrylic resin containing the structural unit (a1) and the structural unit (a2).
  • the ⁇ , ⁇ -unsaturated carboxylic acid that leads the structural unit (a1) includes acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, angelic acid, sorbic acid, mesaconic acid And ⁇ , ⁇ -unsaturated carboxylic acids having 3 to 20 carbon atoms such as
  • the ⁇ , ⁇ -unsaturated carboxylic acid is preferably an ⁇ , ⁇ -unsaturated carboxylic acid having one or two carboxyl groups (—COOH).
  • the acrylic resin of the component (A) may have two or more types of structural units (a1).
  • the structural unit (a1) is preferably at least one selected from the group consisting of a structural unit derived from acrylic acid and a structural unit derived from methacrylic acid.
  • the ⁇ , ⁇ -unsaturated carboxylic acid ester leading to the structural unit (a2) is an aliphatic alcohol having 1 to 10 carbon atoms having an amino group which may have a substituent, an ⁇ , ⁇ -unsaturated carboxylic acid, Derived from. Examples of the ⁇ , ⁇ -unsaturated carboxylic acid include those described above, and acrylic acid or methacrylic acid is preferable.
  • the amino group which may have a substituent is an amino group; methylamino group, ethylamino group, propylamino group, isopropylamino group, butylamino group, isobutylamino group, sec-butylamino group, tert-butyl. 2 amino groups such as an amino group having a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms such as amino group; dimethylamino group, methylethylamino group, diethylamino group, dipropylamino group, etc.
  • an amino group having a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms; and a cyclic amino group, and two linear and branched chains having 1 to 10 carbon atoms An amino group having a linear or cyclic alkyl group is preferred, and an amino group having two linear, branched or cyclic alkyl groups having 1 to 3 carbon atoms is more preferred.
  • Examples of the aliphatic alcohol having 1 to 10 carbon atoms include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanol, 3-methylbutanol, 2,2-dimethylpropanol, 3-methyl-2-butanol, 2 -Straight chain, branched chain or cyclic aliphatic alcohols having 1 to 10 carbon atoms such as ethylhexanol, nonanol, decanol, cyclohexanol, etc., straight chain or branched chains having 1 to 4 carbon atoms Or a cyclic aliphatic alcohol is preferable.
  • Examples of the aliphatic alcohol having 1 to 10 carbon atoms having an amino group which may have a substituent include N, N-dimethylaminoethanol, N, N-diethylaminoethanol, N-methyl-N-ethylaminoethanol, Examples include N, N-dipropylaminoethanol, N-methyl-N-propylaminoethanol, N-ethyl-N-propylaminoethanol, N, N-dimethylaminopropanol and N, N-dimethylaminobutanol.
  • the ⁇ , ⁇ -unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 10 carbon atoms having an amino group which may have a substituent and an ⁇ , ⁇ -unsaturated carboxylic acid includes N, N -Diethylaminoethyl acrylate, N, N-diethylaminoethyl methacrylate, N, N-dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, N-methyl-N-ethylaminoethyl acrylate and N-methyl-N-ethylamino Examples thereof include ethyl methacrylate, and N, N-dimethylaminoethyl methacrylate is preferable.
  • the acrylic resin of the component (A) may have two or more types of structural units (a2).
  • the content of the structural unit (a1) in the acrylic resin of component (A) is usually 20 to 99 mol, preferably 50 to 99 mol, relative to 100 mol of all structural units constituting the acrylic resin. is there.
  • the content of the structural unit (a2) in the acrylic resin of the component (A) is usually 1 to 80 mol, preferably 1 to 50 mol with respect to 100 mol of all structural units constituting the acrylic resin. is there.
  • the acrylic resin of component (A) may contain two or more kinds of acrylic resins. In addition to the structural unit (a1) and the structural unit (a2), the acrylic resin of the component (A) may have another structural unit.
  • structural units include A structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 20 carbon atoms and an ⁇ , ⁇ -unsaturated carboxylic acid (hereinafter abbreviated as structural unit (b1)); A structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester derived from a polyhydric aliphatic alcohol having 1 to 10 carbon atoms and an ⁇ , ⁇ -unsaturated carboxylic acid (hereinafter abbreviated as structural unit (b2)).
  • structural unit (b3 ) A structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 10 carbon atoms having a carboxylic acid group and an ⁇ , ⁇ -unsaturated carboxylic acid (hereinafter referred to as structural unit (b3 ))), And And a structural unit derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester derived from a polyalkylene glycol and an ⁇ , ⁇ -unsaturated carboxylic acid (hereinafter abbreviated as structural unit (b4)).
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid for deriving the other structural units include those described above, and acrylic acid or methacrylic acid is preferable.
  • the ⁇ , ⁇ -unsaturated carboxylic acid ester that derives the structural unit (b1) is derived from an aliphatic alcohol having 1 to 20 carbon atoms and an ⁇ , ⁇ -unsaturated carboxylic acid.
  • Examples of the aliphatic alcohol having 1 to 20 carbon atoms include methanol, ethanol, propanol, isopropanol, butanol, tert-butanol, pentanol, 3-methylbutanol, 2,2-dimethylpropanol, 3-methyl-2-butanol, Examples thereof include linear, branched or cyclic aliphatic alcohols having 1 to 20 carbon atoms, such as 2-ethylhexanol, nonanol, decanol, dodecanol, tridecanol, hexadecanol, octadecanol, and cyclohexanol.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 20 carbon atoms and an ⁇ , ⁇ -unsaturated carboxylic acid include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, Pentyl acrylate, 3-methylbutyl acrylate, 2,2-dimethylpropyl acrylate, 3-methyl-2-butyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, dodecyl acrylate, tridecyl acrylate , Hexadecyl acrylate, octadecyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, pentyl methacrylate, 2-methyl-2-butyl me
  • the acrylic resin of component (A) may have two or more structural units (b1).
  • the ⁇ , ⁇ -unsaturated carboxylic acid ester that derives the structural unit (b2) is derived from a polyhydric aliphatic alcohol having 1 to 10 carbon atoms and an ⁇ , ⁇ -unsaturated carboxylic acid.
  • Such polyhydric aliphatic alcohols having 1 to 10 carbon atoms include hydroxymethanol, hydroxyethanol, hydroxypropanol, hydroxybutanol, hydroxypentanol and hydroxyhexanol.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester derived from a polyhydric aliphatic alcohol having 1 to 10 carbon atoms and an ⁇ , ⁇ -unsaturated carboxylic acid include hydroxymethyl acrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl Acrylate, hydroxypentyl acrylate, hydroxyhexyl acrylate, hydroxymethyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxybutyl methacrylate, hydroxypentyl methacrylate and hydroxyhexyl methacrylate.
  • the acrylic resin of component (A) may have two or more structural units (b2).
  • the structural unit (b3) is derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester derived from a C 1-10 aliphatic alcohol having a carboxylic acid group and an ⁇ , ⁇ -unsaturated carboxylic acid.
  • carboxylic acid group means an organic group having a carboxyl group (—COOH), such as carboxymethyl group, 1,2-dicarboxyethyl group, 2-carboxyphenyl group and 2,3-dicarboxyphenyl. Groups.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid ester derived from an aliphatic alcohol having 1 to 10 carbon atoms having a carboxylic acid group and an ⁇ , ⁇ -unsaturated carboxylic acid include 2-acryloyloxyethyl succinic acid, 2- Examples include acryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl succinic acid and 2-methacryloyloxyethyl phthalic acid.
  • the acrylic resin of component (A) may have two or more structural units (b3).
  • the structural unit (b4) is derived from an ⁇ , ⁇ -unsaturated carboxylic acid ester derived from a polyalkylene glycol and an ⁇ , ⁇ -unsaturated carboxylic acid.
  • polyalkylene glycol 1 to 50 alkylene groups having 1 to 4 carbon atoms such as polyethylene glycol, polypropylene glycol, polyethylene glycol polypropylene glycol, polyethylene glycol polytetramethylene glycol and methoxypolyethylene glycol are bonded via oxygen atoms.
  • the polyalkylene glycol and the terminal hydroxyl group of these polyalkylene glycols may be protected with an alkyl group having 1 to 20 carbon atoms, an acryl group, a methacryl group or the like.
  • Examples of ⁇ , ⁇ -unsaturated carboxylic acid ester derived from polyalkylene glycol and ⁇ , ⁇ -unsaturated carboxylic acid include polypropylene glycol acrylate, polyethylene glycol acrylate, polyethylene glycol acrylate acrylate, polyethylene glycol monoacrylate
  • the acrylic resin of component (A) preferably contains the structural unit (b1) or the structural unit (b3), and more preferably contains the structural unit (b1) and the structural unit (b3).
  • the content of the structural unit (b1) is usually 5 to 95 mol with respect to 100 mol of all the structural units constituting the acrylic resin. Preferably, it is 10 to 80 mol.
  • the content of the structural unit (b2) in the acrylic resin of component (A) is usually 0 to 50 mol, preferably 0 to 30 mol, relative to 100 mol of all structural units constituting the acrylic resin. Yes, more preferably 0 to 1 mol.
  • the content of the structural unit (b3) is usually 0.1 to 100 mol per 100 mol of all the structural units constituting the acrylic resin. 80 moles, preferably 5 to 40 moles.
  • the content of the structural unit (b4) in the acrylic resin of component (A) is usually 0 to 50 mol, preferably 0 to 30 mol, relative to 100 mol of all the structural units constituting the acrylic resin. Yes, more preferably 0 to 1 mol.
  • the content of the structural unit having an anionic group such as the structural unit (a1) or the structural unit (b3) is determined by the adhesiveness of the cured product obtained from the aqueous emulsion of the present invention to polypropylene. From the viewpoint, the amount is preferably 45 to 85 mol, more preferably 50 to 80 mol, with respect to 100 mol of all the structural units constituting the acrylic resin.
  • the acrylic resin of component (A) 5 to 80 mol of structural unit (a1), 1 to 50 mol of structural unit (a2), 10 to 10 mol per 100 mol of all structural units constituting the acrylic resin.
  • the acrylic resin of component (A) is represented by a structural unit derived from ethylene, a structural unit derived from propylene, a structural unit derived from a linear ⁇ -olefin having 4 or more carbon atoms described later, and a formula (I) described later.
  • the acrylic resin of component (A) can be produced by addition polymerization of monomers that lead each structural unit.
  • an alcohol solvent such as isopropanol, a solvent such as water, and a monomer are mixed, and the resulting mixture and a polymerization initiator such as a radical initiator are usually 70 to 100 ° C., preferably 75 to 95 ° C., more preferably 75.
  • the mixture is mixed at ⁇ 85 ° C, and the resulting mixture is usually stirred for about 1 to 24 hours to carry out the polymerization reaction, the solvent and a part of the monomer are mixed, and the resulting mixture, the polymerization initiator and the remaining mixture are mixed.
  • a method of conducting a polymerization reaction by mixing the monomer with usually 70 to 100 ° C., preferably 75 to 95 ° C., more preferably 75 to 85 ° C., and stirring the resulting mixture usually for about 1 to 24 hours. It is done.
  • a solution obtained by dissolving a polymerization initiator and the remaining monomers in an organic solvent may be used.
  • the amount of the polymerization initiator used is usually 0.01 to 5 parts by weight, preferably 2 to 3 parts by weight with respect to 100 parts by weight of the total amount of monomers.
  • a redox initiator in which a polymerization initiator and a reducing agent are used in combination can also be used as the polymerization initiator.
  • the polymer hydrophilic ratio of the acrylic resin of the component (A) is 9 to 12, preferably 9.1 to 11, and more preferably 9.1 to 10.
  • the aqueous emulsion of the present invention containing an acrylic resin having a polymer hydrophilic ratio within the above range gives a cured product having excellent adhesion to a substrate such as polypropylene by drying at, for example, about 90 ° C to 120 ° C. Furthermore, even when the drying temperature is as low as about 65 to 90 ° C., a cured product having excellent adhesion to a substrate such as polypropylene is provided.
  • the polymer hydrophilic ratio of the acrylic resin is a weight average value of the hydrophilic ratio of the monomer leading to the structural unit of the acrylic resin, and the hydrophilic ratio of the monomer is calculated by the following formula.
  • Monomer hydrophilic ratio 20 ⁇ (formula weight of monomer hydrophilic portion) / (monomer molecular weight))
  • the hydrophilic part of the monomer means a carboxyl group (—COOH), a hydroxyl group (—OH), an amino group (—NH) in the monomer. 2 ), Sulfo group (-SO 3 H), a carbonyloxy group (—CO 2 -), Dialkylamino group (-NR) 2 ) Of a nitrogen atom (N) or the like.
  • the formula weight of the carboxyl group is 45.02, the formula weight of the hydroxyl group is 17.02, the formula weight of the amino group is 16.02, the formula weight of the sulfo group is 81.07, the formula weight of the carbonyloxy group is 44.01, The formula weight of the nitrogen atom of the dialkylamino group is 14.01.
  • acrylic acid molecular weight: 72.06
  • the hydrophilic ratio of acrylic acid is 12.5.
  • 2-methacryloyloxyethyl succinic acid molecular weight: 230.21
  • the hydrophilic ratio of 2-methacryloyloxyethyl succinic acid is 11.6.
  • N, N-dimethylaminoethyl methacrylate (molecular weight: 157.21) has one carbonyloxy group and one dialkylamino group nitrogen atom as the hydrophilic portion, The hydrophilic ratio is 7.4.
  • An acrylic resin having a polymer hydrophilic ratio of 9 to 12 can be prepared.
  • Component (A) acts as an emulsifier for dispersing component (B) in component (C) in the aqueous emulsion of the present invention.
  • the emulsifier of the present invention contains the component (A), and preferably further contains water.
  • the emulsifier of the present invention may further contain an ammonium cation.
  • ammonium cation source ammonia is preferable.
  • NH of the emulsifier of the present invention 3 The degree of neutralization is preferably 50 to 300, and more preferably 100 to 200.
  • NH 3 “Neutralization degree” means the ratio (%) of the number of moles of ammonium cation contained in the emulsifier to the total number of moles of structural units derived from the monomer having an anionic group contained in component (A). Subsequently, the component (B) will be described.
  • the component (B) is a thermoplastic polymer.
  • a thermoplastic polymer containing a structural unit derived from ethylene a thermoplastic polymer containing a structural unit derived from propylene, an ester wax, and a carnauba wax.
  • thermoplastic polymers containing structural units derived from amide compounds such as Fischer-Trops wax, microcrystalline wax, paraffin wax and oxides thereof, low molecular weight polyamides and fatty acid amides.
  • a thermoplastic polymer containing a structural unit derived from ethylene and / or propylene is preferable.
  • thermoplastic polymer containing structural units derived from ethylene and / or propylene examples include polyethylene such as low density polyethylene, polyethylene wax, ethylene / vinyl acetate copolymer, ethylene / propylene / vinyl acetate copolymer, and ethylene / acrylic.
  • Acid copolymer ethylene / propylene / acrylic acid copolymer, ethylene / acrylic ester copolymer, ethylene / propylene / acrylic ester copolymer, ethylene / acrylic acid copolymer, ethylene / propylene / methacrylic acid copolymer , Ethylene / methacrylic ester copolymer, ethylene / propylene / methacrylic ester copolymer, polypropylene, ethylene / propylene copolymer, ethylene / hexene copolymer, propylene / hexene copolymer, ethylene / propylene / hexe Copolymers, ethylene-butene copolymer, propylene-butene copolymer, ethylene-propylene-butene copolymer and these maleic acid modified products thereof.
  • a copolymer (hereinafter abbreviated as polymer (B-1)) containing a structural unit derived from a vinyl compound (hereinafter abbreviated as vinyl compound (I)), and a polymer (B- 1) is preferably a polymer obtained by graft polymerization of an ⁇ , ⁇ -unsaturated carboxylic acid anhydride (hereinafter abbreviated as polymer (B-2)).
  • the secondary alkyl group represented by R is preferably a secondary alkyl group having 3 to 20 carbon atoms
  • the tertiary alkyl group is preferably a tertiary alkyl group having 4 to 20 carbon atoms, and an alicyclic hydrocarbon group.
  • the group is preferably a 3- to 16-membered alicyclic hydrocarbon group. Examples of the alicyclic hydrocarbon group include a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group, and a cycloalkyl group is preferable.
  • R is more preferably a 3- to 10-membered alicyclic hydrocarbon group having 3 to 20 carbon atoms and a tertiary alkyl group having 4 to 20 carbon atoms.
  • the vinyl compound (I) include 3-methyl-1-butene, 3-methyl-1-pentene, 3-methyl-1-hexene, 3-methyl-1-heptene, 3-methyl-1-octene, 3, 4-dimethyl-1-pentene, 3,4-dimethyl-1-hexene, 3,4-dimethyl-1-heptene, 3,4-dimethyl-1-octene, 3,5-dimethyl-1-hexene, 3, 5-dimethyl-1-heptene, 3,5-dimethyl-1-octene, 3,6-dimethyl-1-heptene, 3,6-dimethyl-1-octene, 3,7-dimethyl-1-octene, 3, R of 2,4-trimethyl-1-pentene, 3,4,4-trimethyl-1-hexene, 3,
  • 1-vinyladamantane, 5-vinyl-2-norbornene and 4-vinyl-1-cyclohexene are preferred, and 3-methyl-1-butene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 3,3-dimethyl-1- More preferred are butene, 3,3,4-trimethyl-1-pentene, vinylcyclohexane and vinylnorbornene,
  • the content of the structural unit derived from the vinyl compound (I) in the polymer (B-1) is usually 5 to 40 mol with respect to 100 mol of all the structural units constituting the polymer (B-1). From the viewpoint of adhesiveness of a cured product obtained by drying the aqueous emulsion of the present invention, the amount is preferably 10 to 30 mol, more preferably 10 to 20 mol.
  • the content of the structural unit derived from the vinyl compound (I) in the polymer (B-1) is the same as that of the polymer (B-1). 1 H-NMR analysis and 13 It can be determined by C-NMR analysis.
  • the polymer (B-1) may further contain a structural unit derived from a linear ⁇ -olefin having 4 to 20 carbon atoms.
  • linear ⁇ -olefin having 4 to 20 carbon atoms examples include 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene and 1-dodecene. 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene and 1-eicosene. Of these, 1-butene, 1-pentene, 1-hexene and 1-octene are preferable.
  • the total content of structural units derived from ethylene, propylene and a linear ⁇ -olefin having 4 to 20 carbon atoms in the polymer (B-1) is all the constituents of the polymer (B-1).
  • the amount is usually 95 to 60 mol, preferably 90 to 70 mol%, more preferably 90 to 80 mol, per 100 mol of the structural unit.
  • the polymer (B-1) may further have a structural unit derived from a monomer capable of addition polymerization.
  • the addition-polymerizable monomer is a monomer other than ethylene, propylene, a linear ⁇ -olefin having 4 to 20 carbon atoms and a vinyl compound (I), and includes ethylene, propylene, and a linear ⁇ having 4 to 20 carbon atoms.
  • -A monomer capable of addition polymerization with an olefin and a vinyl compound (I), and the carbon number of the monomer is usually about 3 to 20.
  • addition-polymerizable monomers include cycloolefins, formula (II) (In the formula, R ′ and R ′′ each independently represent a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms or a halogen atom.)
  • -Unsaturated carboxylic acid anhydrides In the formula, R ′ and R ′′ each independently represent a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms or a halogen atom.
  • Cycloolefins include cyclobutene, cyclopentene, cyclohexene, cyclooctene, 3-methylcyclopentene, 4-methylcyclopentene, 3-methylcyclohexene, 2-norbornene, 5-methyl-2-norbornene, 5-ethyl-2-norbornene, 5 -Butyl-2-norbornene, 5-phenyl-2-norbornene, 5-benzyl-2-norbornene, 2-tetracyclododecene, 2-tricyclodecene, 2-tricycloundecene, 2-pentacyclopentadecene, 2-pentacyclohexadecene, 8-methyl-2-tetracyclododecene, 8-ethyl-2-tetracyclododecene, 5-acetyl-2-norbornene, 5-acetyloxy-2-norbornene, 5-meth
  • Examples of the olefin represented by the formula (II) include isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, 2-methyl-1-hexene, 2-methyl-1-heptene, and 2-methyl-1. -Octene, 2,3-dimethyl-1-butene, 2,3-dimethyl-1-pentene, 2,3-dimethyl-1-hexene, 2,3-dimethyl-1-heptene, 2,3-dimethyl-1 -Octene, 2,4-dimethyl-1-pentene, 2,4,4-trimethyl-1-pentene and vinylidene chloride, isobutene, 2,3-dimethyl-1-butene and 2,4,4-trimethyl -1-pentene is preferred.
  • diene compound examples include 1,3-butadiene, 1,4-pentadiene, 1,5-hexadiene, 1,6-heptadiene, 1,7-octadiene, 1,5-cyclooctadiene, 2,5-norbornadiene, and diene.
  • cyclopentadiene 5-vinyl-2-norbornene, 5-allyl-2-norbornene, 4-vinyl-1-cyclohexene and 5-ethylidene-2-norbornene, and include 1,4-pentadiene, 1,5-hexadiene, 2,5-norbornadiene, dicyclopentadiene, 5-vinyl-2-norbornene, 4-vinyl-1-cyclohexene and 5-ethylidene-2-norbornene are preferred.
  • Aliphatic vinyl carboxylates include vinyl acetate, vinyl propionate and vinyl butyrate
  • vinyl ether compounds include methyl vinyl ether, ethyl vinyl ether and butyl vinyl ether.
  • Examples of the vinyl halide include vinyl chloride, and examples of the cyanovinyl compound include acrylonitrile and methacrylonitrile.
  • the content of the structural unit derived from the addition-polymerizable monomer in the polymer (B-1) may be an amount that does not impair the adhesion of the cured product obtained by drying the aqueous emulsion of the present invention. 5 mol or less is preferable with respect to 100 mol of all the structural units constituting the combination (B-1), and 1 mol or less is more preferable.
  • the polymer (B-1) can be produced, for example, by polymerizing a corresponding monomer using a transition metal compound having a group having an indenyl anion skeleton or a crosslinked cyclopentadienyl anion skeleton as a catalyst. .
  • a transition metal compound having a group having an indenyl anion skeleton or a crosslinked cyclopentadienyl anion skeleton as a catalyst.
  • the methods described in JP-A No. 2003-82028, JP-A No. 2003-160621 and JP-A No. 2000-128932 are preferable.
  • an ethylene homopolymer, a propylene homopolymer and / or a vinylcyclohexane single A polymer may form.
  • the polymer (B-1) can be easily taken out by performing solvent extraction using a Soxhlet extractor or the like.
  • a vinylcyclohexane homopolymer can be removed as an insoluble component.
  • chloroform is used as the solvent, olefin homopolymers such as ethylene homopolymer and propylene homopolymer can be removed as insoluble components.
  • the polymer (B-1) can be separated as a soluble component in these solvents.
  • the polymer (B-1) containing the by-product as described above may be used.
  • the weight average molecular weight (Mw) of the polymer (B-1) is usually about 5,000 to 1,000,000, and the mechanical strength of the cured product obtained by drying the aqueous emulsion of the present invention and the polymer From the viewpoint of the fluidity of (B-1), it is preferably about 10,000 to 500,000, more preferably about 15,000 to 400,000.
  • the molecular weight distribution of the polymer (B-1) can be determined by gel permeation chromatography (GPC).
  • the intrinsic viscosity [ ⁇ ] of the polymer (B-1) is usually about 0.25 to 10 dl / g, preferably from the viewpoint of the mechanical strength of the cured product obtained by drying the aqueous emulsion of the present invention. It is about 0.3 to 3 dl / g.
  • the melt flow rate (MFR) of the polymer (B-1) measured under the conditions of 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven Co.) in accordance with JIS K 7210.
  • the polymer (B-2) is a polymer obtained by graft polymerizing an ⁇ , ⁇ -unsaturated carboxylic acid anhydride to the polymer (B-1).
  • the graft polymerization amount of the ⁇ , ⁇ -unsaturated carboxylic acid anhydride is usually about 0.01 to 20 parts by weight, preferably about 0.05 to 10 parts by weight with respect to 100 parts by weight of the polymer (B-2). More preferably, it is about 0.1 to 5 parts by weight.
  • the aqueous emulsion of the present invention containing a polymer (B-2) having a graft polymerization amount of ⁇ , ⁇ -unsaturated carboxylic acid anhydride of 0.01 part by weight or more is preferred because its adhesiveness tends to be improved.
  • the aqueous emulsion of the present invention containing a polymer (B-2) having a graft polymerization amount of ⁇ , ⁇ -unsaturated carboxylic acid anhydride of 20% by weight or less is preferred because its thermal stability tends to be improved.
  • Examples of the ⁇ , ⁇ -unsaturated carboxylic acid anhydride include ⁇ , ⁇ -unsaturated carboxylic acid anhydrides having 4 to 20 carbon atoms such as maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. preferable. Two or more ⁇ , ⁇ -unsaturated carboxylic acid anhydrides may be used in combination.
  • the polymer (B-2) is graft-polymerized by adding an ⁇ , ⁇ -unsaturated carboxylic acid anhydride to the melt polymer (B-1) obtained by melting the polymer (B-1).
  • the polymer (B-1) is dissolved in a solvent such as toluene and xylene, and ⁇ , ⁇ -unsaturated carboxylic acid anhydride is added to the resulting solution for graft polymerization. It can. Graft polymerization is usually performed in the presence of a radical initiator. When the amount of the radical initiator used is small, the amount of graft polymerization of the ⁇ , ⁇ -unsaturated carboxylic acid anhydride is reduced, and the adhesiveness of the cured product obtained by drying the aqueous emulsion of the present invention is improved.
  • the amount of the unreacted radical initiator contained in the polymer (B-2) tends to increase if the amount is too much, the amount of the polymer (B-1) is 100 parts by weight.
  • the amount is usually 0.01 to 10 parts by weight, preferably 0.01 to 1 part by weight.
  • the radical initiator an organic peroxide is usually used, and an organic peroxide having a decomposition temperature of 50 to 210 ° C. with a half-life of 1 minute is preferable. When an organic peroxide having a decomposition temperature of 50 ° C.
  • the amount of graft polymerization of ⁇ , ⁇ -unsaturated carboxylic acid anhydride tends to be improved, and an organic peroxide having a decomposition temperature of 210 ° C. or lower is preferred.
  • an oxide is used, decomposition of the polymer (B-1) in graft polymerization tends to be reduced.
  • An organic peroxide having a function of extracting protons from the polymer (B-1) after generating radicals by decomposition is preferred. Examples of the organic peroxide having a decomposition temperature of 50 to 210 ° C.
  • diacyl peroxide compounds with a half-life of 1 minute include diacyl peroxide compounds, dialkyl peroxide compounds, peroxyketal compounds, alkyl perester compounds, and percarbonate compounds. Dialkyl peroxide compounds, diacyl peroxide compounds, percarbonate compounds and alkyl perester compounds are preferred.
  • the addition amount of the organic peroxide is usually 0.01 to 20 parts by weight, preferably 0.01 to 10 parts by weight with respect to 100 parts by weight of the polymer (B-1).
  • the polymer (B) can be melt kneaded using an extruder, and various polymers or various known methods for mixing polymers and solid or liquid additives can be used.
  • a method of graft polymerization by adding an ⁇ , ⁇ -unsaturated carboxylic acid anhydride to the molten polymer (B-1) obtained by melting -1). It is more preferable to combine all or some of the components for graft polymerization and separately mix them with a Henschel mixer, ribbon blender, blender or the like to obtain a uniform mixture, and then melt and knead the mixture.
  • melt-kneading means known kneading means such as a Banbury mixer, a plast mill, a Brabender plastograph, a uniaxial or biaxial extruder can be widely employed.
  • the polymer (B-2) can be continuously produced and the productivity is improved, the polymer (B-1), the ⁇ , ⁇ -unsaturated carboxylic acid anhydride and the radical initiator are sufficiently sufficient in advance.
  • a method is preferred in which the mixture obtained by mixing is fed from the feed port of a single-screw or twin-screw extruder and kneaded.
  • the temperature of the portion where the melt kneading of the extruder is performed (for example, the cylinder temperature of the extruder) is usually 50 to 300 ° C., preferably 80 to 270 ° C.
  • the melt kneading is preferably performed in two stages, and the temperature of the second stage melt kneading is preferably higher than the temperature of the first stage melt kneading.
  • the melt kneading time is usually 0.1 to 30 minutes, preferably 0.1 to 5 minutes.
  • the structural unit derived from the ⁇ , ⁇ -unsaturated carboxylic acid anhydride in the polymer (B-2) may be a structural unit in which the acid anhydride structure is retained, or the acid anhydride structure is ring-opened.
  • the molecular weight distribution (Mw / Mn) of the polymer (B-2) is usually 1.5 to 10, preferably 1.5 to 7, and more preferably 1.5 to 5.
  • the molecular weight distribution of the polymer (B-2) can be measured by the same method as the molecular weight distribution of the polymer (B-1).
  • the value of the intrinsic viscosity [ ⁇ ] of the polymer (B-2) is usually about 0.25 to 10 dl / g, and from the viewpoint of the mechanical strength of a cured product obtained by drying the aqueous emulsion of the present invention, About 0.3 to 3 dl / g is preferable.
  • the melt flow rate (MFR) of the polymer (B-2) measured under the conditions of 190 ° C. and 2.16 kgf using a melt indexer (L217-E14011, manufactured by Techno Seven) in accordance with JIS K 7210.
  • the aqueous emulsion of the present invention contains water as the component (C) in addition to the component (A) and the component (B), the component (A) and the component (B) are dispersoids, and the component (C) is dispersed. It is an emulsion used as a medium.
  • the volume-based median diameter of the dispersoid is usually 0.01 to 3 ⁇ m, preferably 0.1 to 2 ⁇ m, and more preferably 0.5 to 1.7 ⁇ m.
  • the volume-based median diameter is 0.01 ⁇ m or more, it is easy to produce an aqueous emulsion, and when it is 3 ⁇ m or less, the stationary stability of the aqueous emulsion and the adhesiveness of a cured product obtained by drying the aqueous emulsion There is a tendency to improve.
  • “Standing stability” refers to the property that the aqueous emulsion is homogeneous when the aqueous emulsion is stored for 3 days without stirring, that is, the layer rich in component (B) and / or component (C) in the aqueous emulsion. This means that a layer rich in is difficult to form.
  • “Volume-based median diameter” means a particle diameter corresponding to 50% of the cumulative particle diameter distribution on a volume basis.
  • the content of the component (A) in the aqueous emulsion of the present invention is usually 1 to 30 parts by weight, preferably 2 to 10 parts by weight with respect to 100 parts by weight of (B).
  • the total content of component (A) and component (B) in the aqueous emulsion of the present invention is usually 10 to 90 parts by weight, preferably 30 to 70 parts by weight, more preferably 100 parts by weight of the aqueous emulsion. 40 to 60 parts by weight.
  • the content of (C) in the aqueous emulsion of the present invention is usually 90 to 10 parts by weight, preferably 70 to 30 parts by weight, more preferably 60 to 40 parts by weight with respect to 100 parts by weight of the aqueous emulsion.
  • the aqueous emulsion of the present invention is a method in which component (A) and component (B) are melt-kneaded, and the resulting molten mixture and water are mixed; the step of mixing component (A) with heated component (B)
  • a method comprising: heating and kneading component (A) and component (B), and dispersing the obtained kneaded mixture in component (C); and dissolving component (B) in an organic solvent such as toluene,
  • the method of mixing the obtained solution and component (A) and including the process of removing the said organic solvent from the obtained mixture is mentioned.
  • a chemical emulsification method such as self-emulsification can also be used.
  • a method comprising melting and kneading the component (A) and the component (B), mixing the obtained molten mixture and water, and a method including the step of mixing the component (A) with the heated component (B) are preferable. It is.
  • a twin screw extruder As an apparatus used for the process of melt kneading component (A) and component (B), a twin screw extruder, Labo Plast Mill (manufactured by Toyo Seiki Seisakusho Co., Ltd.), Labo Plast Mill Micro (manufactured by Toyo Seiki Seisakusho Co., Ltd.) Multi-screw extruder, homogenizer, T. et al.
  • K-Filmics (Primics Co., Ltd.) and other equipment with barrels (cylinders), stirring tanks, chemical stirrers, vortex mixers, flow jet mixers, colloid mills, ultrasonic generators, high-pressure homogenizers, Dispersion (registered by Fujikin Co., Ltd.) Trademarks), static mixers, micro mixers, and other devices that do not have a barrel (cylinder).
  • the shear rate of equipment with a barrel is usually 200 to 100,000 seconds -1 Degree, preferably 1000 to 2500 seconds -1 Degree.
  • Shear rate is 200 seconds -1 When it is above, the adhesiveness of the cured product obtained by drying the aqueous emulsion tends to be improved, and 100,000 seconds -1 When it is below, it tends to be easy to industrially produce an aqueous emulsion.
  • “Shear rate” means a numerical value obtained by dividing the peripheral speed [mm / sec] of the outermost periphery of the screw element by the clearance [mm] between the screw and the barrel.
  • the component (A) is pressurized and supplied from at least one supply port provided in the compression zone, metering zone or degassing zone of the extruder, and the component (A) and the component (B) are kneaded with a screw. Subsequently, a method of continuously producing an aqueous emulsion from a die by supplying component (C) from at least one supply port provided in the compression zone of the extruder can be mentioned. As a method including the step of mixing the component (A) with the heated component (B), after heating the cylinder of the kneader, the component (B) is put into the cylinder and rotated while rotating the component (B).
  • the component (A) and the component (B) are mixed while the component (A) and the component (B) are mixed while rotating, and the resulting mixture is poured into warm water.
  • a method using a multi-screw extruder is suitable for the method including the step of mixing the component (A) with the heated component (B).
  • component (B) is supplied from a hopper of a multi-screw extruder having two or more screws in the casing, and component (B) is heated and melt-kneaded, and then the extruder
  • the component (A) is supplied from at least one liquid supply port provided in the compression zone or / and the metering zone, and the component (A) and the component (B) are kneaded and dispersed in the component (C).
  • the emulsion of the present invention is an aqueous polyurethane emulsion, other aqueous emulsion such as ethylene-vinyl acetate copolymer aqueous emulsion, thermosetting resin such as urea resin, melamine resin, phenol resin, clay, kaolin, talc, calcium carbonate, etc. Fillers, antiseptics, rust inhibitors, antifoaming agents, foaming agents, polyacrylic acid, polyether, methylcellulose, carboxymethylcellulose, polyvinyl alcohol, starch and other thickeners, viscosity modifiers, flame retardants, titanium oxide, etc.
  • other aqueous emulsion such as ethylene-vinyl acetate copolymer aqueous emulsion
  • thermosetting resin such as urea resin, melamine resin, phenol resin, clay, kaolin, talc, calcium carbonate, etc.
  • a cured product having excellent adhesion to a base material such as a wood material, a cellulose material, a plastic material, a ceramic material, or a metal material can be obtained.
  • the drying temperature is usually 30 to 180 ° C, preferably 60 to 150 ° C.
  • the drying time is usually about 1 minute to 12 hours, preferably about 10 minutes to 6 hours. Drying may be performed under ventilation or under reduced pressure.
  • the cured product of the present invention is excellent in adhesiveness with a substrate even at a low drying temperature of about 65 to 90 ° C.
  • the cured product obtained by drying the aqueous emulsion of the present invention has excellent adhesion to polyolefins (for example, polypropylene and the like) to which other materials such as paint are difficult to adhere.
  • polyolefins for example, polypropylene and the like
  • a laminate in which the aqueous emulsion layer is laminated on the substrate is obtained, and by drying the laminate, the substrate layer and the cured product are obtained. It is possible to form a laminate having a layer made of Such a layer formed of a cured product can be used as a paint, a primer, a base material, an adhesive, or the like.
  • Base materials include wood materials such as wood, plywood, MDF, particleboard, fiberboard; paper materials such as wallpaper and wrapping paper: cellulose materials such as cotton, linen, rayon; polyethylene (mainly structural units derived from ethylene) Polyolefin as component, the same applies hereinafter), polypropylene (polyolefin having a structural unit derived from propylene as a main component, the same applies hereinafter), polyolefin such as polystyrene, polycarbonate, acrylonitrile / butadiene / styrene copolymer (ABS resin), (meta ) Acrylic resin Polyester, polyether, polyvinyl chloride, polyurethane, foamed urethane and other plastic materials; glass, ceramics and other ceramic materials; and metal materials such as iron, stainless steel, copper and aluminum.
  • Base materials include wood materials such as wood, plywood, MDF, particleboard, fiberboard; paper materials such as wallpaper and wrapping paper: cellulose materials such as cotton, linen, rayon; polyethylene (mainly structural
  • Such a substrate may be a composite material composed of a plurality of materials.
  • an inorganic filler such as talc, silica, activated carbon, or a kneaded molded product of carbon fiber and a plastic material may be used.
  • polyurethane is a polymer crosslinked by a urethane bond, and is usually obtained by reaction of alcohol (compound having —OH) and isocyanate (compound having —NCO).
  • the foamed polyurethane is a polyurethane foamed with a volatile solvent such as carbon dioxide or freon produced by a reaction between isocyanate and water as a crosslinking agent.
  • Semi-rigid polyurethane is usually used for automobile interior members, and hard polyurethane is usually used for paints.
  • polypropylene, polystyrene, polycarbonate, acrylonitrile / butadiene / styrene copolymer (ABS resin), polyethylene terephthalate, polyvinyl chloride, (meth) acrylic resin, glass, aluminum and polyurethane are preferable, and polypropylene, More preferred are polyvinyl chloride, glass, aluminum and polyurethane.
  • ABS resin acrylonitrile / butadiene / styrene copolymer
  • polyvinyl chloride (meth) acrylic resin, glass, aluminum and polyurethane
  • polypropylene More preferred are polyvinyl chloride, glass, aluminum and polyurethane.
  • cured material obtained from the emulsion of this invention can be used as an adhesive layer which adhere
  • one of the substrates is a water-absorbing substrate such as a woody material, a paper-based material, or a cellulose material
  • aqueous emulsion of the present invention when applied onto the water-absorbing substrate, components contained in the aqueous emulsion ( C) is absorbed by the water-absorbing substrate, and an adhesive layer containing the component (A) and the component (B) is formed on the water-absorbing substrate. Therefore, a laminated body in which the water-absorbing base material, the adhesive layer, and the other base material are laminated in this order is obtained by pasting the other base material on the adhesive layer.
  • the aqueous emulsion of the present invention is applied on the non-water-absorbing substrate and then heated to cure on the non-water-absorbing substrate. After the product is formed, the other substrate is bonded onto the cured product and further heated to obtain a laminate.
  • the heating temperature is usually 60 to 200 ° C.
  • the aqueous emulsion of the present invention gives a cured product having excellent adhesiveness even when the heating temperature is 60 to 90 ° C, and further, cured product having excellent adhesiveness even when the heating temperature is a low temperature of 65 to 80 ° C. give.
  • a liquid material may be further applied as a paint to the cured product of the present invention. Examples of the coating material include materials for the base material such as polyurethane. When the material is a liquid material, the adhesiveness to the cured product is excellent.
  • a sample solution is prepared by dissolving 1.0 g of a sample in 20 ml of xylene.
  • the prepared solution is dropped into 300 ml of methanol while stirring.
  • the precipitate deposited in methanol is collected and dried at 80 ° C. for 8 hours.
  • a film having a thickness of 100 ⁇ m is prepared by hot pressing.
  • V The infrared absorption spectrum of the produced film was measured, and the amount of maleic acid graft was quantified based on the absorption peak near 1780 cm ⁇ 1 .
  • the intrinsic viscosity ([ ⁇ ], unit: dl / g) of component (B) was measured at 135 ° C. using tetralin as a solvent using an Ubbelohde viscometer.
  • [Glass transition temperature and melting point] The glass transition temperature ([Tg], unit: ° C) and melting point ([Tm], unit: ° C) of the component (B) are as follows using a differential scanning calorimeter (SSC-5200 manufactured by Seiko Denshi Kogyo Co., Ltd.). The differential scanning calorimetry curve was measured by using the differential scanning calorimetry curve obtained in step (c). ⁇ Measurement conditions> (A) The sample is heated from 20 ° C.
  • Acrylic acid manufactured by Mitsubishi Chemical Corporation, hereinafter abbreviated as AA
  • AA Acrylic acid
  • N, N-dimethylaminoethyl methacrylate (monomer for deriving the structural unit (a2) is used as the monomer for deriving the structural unit (a1).
  • DMA Sanyo Chemical Industries, Ltd.
  • MMA methyl methacrylate
  • lauryl methacrylate lauryl methacrylate.
  • -Component (A) was produced using -methacryloyloxyethyl succinic acid (manufactured by Kyoeisha Chemical Co., Ltd., hereinafter abbreviated as HO-MS).
  • HO-MS -methacryloyloxyethyl succinic acid
  • the “molar ratio” represents the number of moles of each monomer when the total number of moles of the monomer is 100.
  • a 1 L reactor equipped with a cooler, a nitrogen introducing tube, a stirrer, and a dropping funnel and having a heating jacket was charged with 150 parts of isopropanol and 100 parts of ion-exchanged water. While stirring the resulting solution, its internal temperature was adjusted to 80 ° C. After replacing the gas in the reaction vessel with nitrogen, 20 parts of the monomer mixture prepared above was charged all at once. Further, 2 parts of 2,2′-azobisisobutyronitrile was added as a polymerization initiator, and the resulting mixture was stirred at 80 ° C. Next, 80 parts of the monomer mixture was added dropwise to the resulting mixture at 80 ° C. with stirring for 4 hours.
  • the obtained emulsifier is referred to as (A-1).
  • the results are shown in Table 1.
  • ⁇ Production Examples 2 to 4 of component (A)> A viscous emulsifier containing an acrylic resin is obtained in the same manner as in Production Example 1 of the above component (A) except that the type and amount of monomer used and the amount of ammonia used are changed to those shown in Table 1. It was.
  • the obtained emulsifiers are referred to as (A-2), (A-3), and (A-4), respectively.
  • the results are shown in Table 1.
  • ⁇ Production Example 1 of Component (B)> After replacing the gas inside the stainless steel reactor with argon gas, 386 parts of vinylcyclohexane and 3640 parts of toluene were added.
  • This copolymer is referred to as (B-1b).
  • (B-1b) ⁇ Production Example 4 of Component (B)>
  • (B-1b) is used instead of (B-1a)
  • propylene A polymer obtained by graft polymerization of maleic anhydride to a vinylcyclohexane copolymer can be obtained. This polymer is referred to as (B-2b).
  • Example 1 After setting the cylinder temperature of the table type kneader PBV-0.3 (purchased from Irie Shokai) to 97 ° C, put 110 parts of (B-2a) into the cylinder and rotate it forward at 10 revolutions per minute. (B-2a) was melted for 10 minutes. Thereafter, (A-1) was added so that the solid content was 10 parts, and the cover glass was occasionally opened at 60 revolutions per minute to carry out kneading and emulsification for 3 minutes. Next, 110 parts of warm water at 90 ° C. was added to obtain an aqueous emulsion. The volume-based median diameter of the dispersoid in the obtained aqueous emulsion was 1.3 ⁇ m.
  • the volume-based median diameter was measured with a laser diffraction / scattering particle size distribution analyzer (manufactured by Horiba, Ltd.).
  • the adhesiveness of the cured product obtained from the aqueous emulsion was evaluated by the following test method (cross cut tape method). The results are shown in Table 2. Moreover, when the obtained aqueous emulsion was stored for 3 days without stirring, its appearance and uniformity did not change, and its stationary stability was also good.
  • ⁇ Adhesion test method> After washing the surface of the 3 mm thick polypropylene plate with isopropanol, the aqueous emulsion was applied onto the polypropylene plate using a bar coater so that the cured product obtained by drying had a thickness of 10 ⁇ m.
  • the obtained coating film was dried with a hot air dryer at 80 ° C. for 5 minutes, and further dried by heating in an oven at 70 ° C. for 30 minutes to obtain a cured product.
  • the aqueous emulsion was applied onto the polypropylene plate using a bar coater so that the cured product obtained by drying had a thickness of 10 ⁇ m.
  • the obtained coating film was dried at 80 ° C. for 5 minutes with a hot air dryer, and further heated and dried in an oven at 90 ° C. for 30 minutes to obtain a cured product.
  • each cured product was cut with a grid-like cut with a gap interval of 1 mm, and then a cellophane tape was affixed thereon. After 1 to 2 minutes, the tape was held at one end and peeled off at a right angle, and the adhesion was evaluated based on the following evaluation criteria.
  • X Peeling of the cured product is observed, and the peeling area is 40% or more of the square area.
  • Example 3 In Example 1, except having replaced (A-1) with (A-2), it implemented similarly to Example 1 and obtained the milky white aqueous emulsion. When the obtained aqueous emulsion was stored for 3 days without stirring, the appearance and uniformity did not change, and the standing stability was also good.
  • Table 2 shows the volume-based median diameter of the dispersoid in the obtained aqueous emulsion and the evaluation results of the adhesiveness of the cured product obtained from the aqueous emulsion.
  • Example 4 In Example 1, except having replaced (A-1) with (A-3), it implemented similarly to Example 1 and obtained the milky-white aqueous emulsion. When the obtained aqueous emulsion was stored for 3 days without stirring, the appearance and uniformity did not change, and the standing stability was also good.
  • Table 2 shows the volume-based median diameter of the dispersoid in the obtained aqueous emulsion and the evaluation results of the adhesiveness of the cured product obtained from the aqueous emulsion.
  • Example 5 In Example 1, except having replaced (A-1) with (A-4), it implemented similarly to Example 1 and obtained the milky white aqueous emulsion. When the obtained aqueous emulsion was stored for 3 days without stirring, the appearance and uniformity did not change, and the standing stability was also good. Table 2 shows the volume-based median diameter of the dispersoid in the obtained aqueous emulsion and the evaluation results of the adhesiveness of the cured product obtained from the aqueous emulsion.
  • Example 6 In Example 2, an aqueous emulsion can be obtained by carrying out similarly to Example 2 except using (B-1a) instead of (B-2a).
  • Example 7 an aqueous emulsion can be obtained by carrying out similarly to Example 2 except using (B-1b) instead of (B-2a).
  • Example 8 an aqueous emulsion can be obtained by carrying out similarly to Example 2 except using (B-2b) instead of (B-2a).
  • the aqueous emulsion of the present invention can give a cured product having excellent adhesion to a substrate to which other materials such as paint such as polypropylene are difficult to adhere.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Dispersion Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne une émulsion aqueuse contenant le composant (A), le composant (B) et le composant (C) suivants : (A) résine acrylique contenant un motif structural dérivé d'un acide carboxylique α,β-insaturé et un motif structural dérivé d'un ester d'acide carboxylique α,β-insaturé dérivé d'un alcool aliphatique contenant 1 à 10 atomes de carbone et un groupe amino qui peut porter un substituant et un acide carboxylique α,β-insaturé, et dont le taux d'hydrophilie est de 9 à 12 (le taux d'hydrophilie de la résine acrylique est le poids unitaire moyen des taux d'hydrophilie de monomères dont dérivent les motifs structuraux de la résine acrylique et le taux d'hydrophilie d'un monomère est une valeur calculée par l'équation suivante : (taux d'hydrophilie du monomère)= 20 x(poids formulaire des parties hydrophiles du monomère)/(poids moléculaire du monomère)) ; (B) un polymère thermoplastique ; et (C) de l'eau.
PCT/JP2010/056043 2009-03-31 2010-03-26 Emulsion aqueuse WO2010114108A1 (fr)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109312122A (zh) * 2016-06-08 2019-02-05 三菱化学株式会社 水性树脂分散体

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008024755A (ja) * 2006-07-18 2008-02-07 Chuo Rika Kogyo Corp 熱可塑性樹脂水性分散液
JP2008063557A (ja) * 2006-04-21 2008-03-21 Sumitomo Chemical Co Ltd オレフィン系共重合体またはその変性物の水性エマルジョン
JP2009172503A (ja) * 2008-01-23 2009-08-06 Chuo Rika Kogyo Corp 高分子乳化剤、及びこれを用いたポリオレフィン系樹脂エマルジョン

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008063557A (ja) * 2006-04-21 2008-03-21 Sumitomo Chemical Co Ltd オレフィン系共重合体またはその変性物の水性エマルジョン
JP2008024755A (ja) * 2006-07-18 2008-02-07 Chuo Rika Kogyo Corp 熱可塑性樹脂水性分散液
JP2009172503A (ja) * 2008-01-23 2009-08-06 Chuo Rika Kogyo Corp 高分子乳化剤、及びこれを用いたポリオレフィン系樹脂エマルジョン

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109312122A (zh) * 2016-06-08 2019-02-05 三菱化学株式会社 水性树脂分散体
CN109312122B (zh) * 2016-06-08 2021-10-29 三菱化学株式会社 水性树脂分散体

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JP2010254988A (ja) 2010-11-11

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