WO2020100790A1 - Émulsion de résine aqueuse, son procédé de fabrication et composition de résine aqueuse - Google Patents

Émulsion de résine aqueuse, son procédé de fabrication et composition de résine aqueuse Download PDF

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Publication number
WO2020100790A1
WO2020100790A1 PCT/JP2019/044059 JP2019044059W WO2020100790A1 WO 2020100790 A1 WO2020100790 A1 WO 2020100790A1 JP 2019044059 W JP2019044059 W JP 2019044059W WO 2020100790 A1 WO2020100790 A1 WO 2020100790A1
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aqueous resin
resin emulsion
meth
copolymer
content
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PCT/JP2019/044059
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English (en)
Japanese (ja)
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卓也 葛谷
村田　直樹
元章 荒木
洋 高月
康宏 中川
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昭和電工株式会社
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Priority to CN201980059883.4A priority Critical patent/CN112703207B/zh
Priority to KR1020217005160A priority patent/KR20210091114A/ko
Priority to JP2020555672A priority patent/JP6937942B2/ja
Publication of WO2020100790A1 publication Critical patent/WO2020100790A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • 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
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F212/00—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 aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing

Definitions

  • the present invention relates to an aqueous resin emulsion, a method for producing the same, and an aqueous resin composition.
  • the present application claims priority based on Japanese Patent Application No. 2018-212769 filed in Japan on November 13, 2018, the contents of which are incorporated herein by reference.
  • metal products such as machine tools and transportation machines are surface-treated for the purpose of protection against impact and rust prevention.
  • anticorrosive coating is often applied to the surface of products that are expected to be used outdoors or exposed to moisture.
  • Many of the conventionally used paints contain organic solvents, and it is necessary to take measures against volatile organic compounds (VOC) to workers and the surrounding environment. Therefore, the movement from solvent-based paints to water-based paints has become active, and there is a demand for excellent water-based paints having the same performance as solvent-based paints.
  • VOC volatile organic compounds
  • Patent Document 1 describes a coating composition for thick coating containing an emulsion composition in which polymer particles are dispersed in an aqueous medium and an aggregate.
  • the polymer particles include a structural unit formed by polymerization of an alkyl (meth) acrylate monomer having an alkyl group having 4 to 14 carbon atoms, a structural unit formed by polymerization of an ethylenically unsaturated carboxylic acid monomer, and others. It is described that it is produced by emulsion-polymerizing a constitutional unit formed by polymerizing the above-mentioned monomer in the presence of a compound having at least two epoxy groups in one molecule and a basic catalyst.
  • Patent Document 2 describes a composition containing an aqueous dispersion of thermoplastic polymer particles that have absorbed a thermosetting compound having an oxirane group. It is described that the polymer particles have anti-aggregating functional groups to stabilize the latex against aggregation.
  • Patent Document 3 describes that an acrylate resin (acrylic / epoxy latex) that absorbs an epoxy compound is formed by mixing an epoxy emulsion with an emulsion of an acrylate resin.
  • Patent Document 4 describes an aqueous resin composition containing an aqueous dispersion containing an epoxy resin, a polyaddition type polyamine, and a carboxylic acid polymer. More specifically, it is described that a radical-polymerizable monomer and an epoxy resin are polymerized in water to obtain an epoxy-modified acrylic emulsion as the aqueous dispersion.
  • Patent Document 1 a carboxy group and an epoxy group react with each other by a basic catalyst. Therefore, the polymer particles contained in the emulsion composition are already crosslinked. From this, in Patent Document 1, it is necessary to precisely control the degree of crosslinking in order to maintain good dispersion stability.
  • the monomer having an anticoagulant functional group has high hydrophilicity. Therefore, the coating film formed using the composition described in this document does not have sufficient water resistance and rust resistance.
  • the epoxy compound is absorbed after the acrylic resin is synthesized.
  • the epoxy compound does not sufficiently penetrate into the particles of the acrylic resin, so that even after curing, many unreacted carboxy groups remain inside the particles, resulting in insufficient water resistance and rust resistance.
  • the epoxy compound does not sufficiently penetrate into the particles of the acrylic resin, there are some places where the acrylic resin and the epoxy resin are not in contact with each other. Therefore, when it is cured with amine or the like, it is presumed that the phase composed only of the acrylic resin having low water resistance is not protected, and the water resistance and rust resistance are insufficient.
  • composition described in Patent Document 3 is expected to have insufficient water resistance and strength of the coating film obtained by curing the composition for the above reason.
  • Patent Document 4 discloses an aqueous resin composition containing an epoxy resin-containing aqueous dispersion, a polyaddition type polyamine, and a carboxylic acid polymer.
  • Table 2 and the like raw materials for an aqueous dispersion (epoxy-modified acrylic emulsion) containing an epoxy resin are disclosed.
  • An example (Production Example 8) using a hydrophilic monomer (methyl methacrylate) other than methacrylic acid is also shown, but the amount is small.
  • gelation is suppressed by adding a carboxylic acid polymer when adding a polyamine to the aqueous dispersion.
  • a step of redispersing the particles contained in the emulsion is required in the coating step of the product (object to be coated) or in the mixing step of the emulsion and the curing agent immediately before that. If so, it will increase the cost of the product.
  • the emulsion is required to have excellent dispersion stability in order to reduce the production cost of the article to be coated.
  • the paint, or the emulsion used for the paint is often left outdoors in high temperatures, and the temperature inside the container may become high. Even when stored in such an environment, the emulsion is required to have excellent high temperature stability in order to sufficiently maintain the quality.
  • the present invention is excellent in high-temperature stability and dispersion stability, and when included in a paint, a water resistant, rust preventive and highly adherent coating film for a metal material is obtained, an aqueous resin emulsion, an aqueous resin composition, Another object of the present invention is to provide a method for producing an aqueous resin emulsion.
  • the configuration of the present invention for solving the above problems is as follows.
  • the first aspect of the present invention provides the following aqueous resin emulsion.
  • the content of the polyepoxy compound (Y) is 1 to 40% by mass based on the total amount of the copolymer (X) and the polyepoxy compound (Y).
  • the polymer (X) contains a structural unit derived from the (meth) acrylic acid ester (A) and a structural unit derived from the ethylenically unsaturated carboxylic acid (B), and contains the copolymer (X) and the polyepoxy.
  • the content of the structural unit derived from the (meth) acrylic acid ester (A) with respect to the total amount of the compound (Y) is 20 to 98% by mass, and the copolymer (X) and the polyepoxy compound (
  • the content of the structural unit derived from the ethylenically unsaturated carboxylic acid (B) with respect to the total amount with Y) is 0.1 to 10% by mass, and the structure derived from the (meth) acrylic acid ester (A) is
  • the unit includes a structural unit derived from a hydrophilic (meth) acrylic acid ester (A1) in which the alcohol-derived portion has 2 or less carbon atoms, and contains the copolymer (X) and the polyepoxy compound (Y).
  • the content of the structural unit derived from the hydrophilic (meth) acrylic acid ester (A1) is 15 to 98 mass% with respect to the total amount of the aqueous resin emulsion in the aqueous medium (Z).
  • the monomer serving as the structural unit of the polymer (X) is an emulsion obtained by emulsion polymerization in the presence of the polyepoxy compound (Y), and the content of the epoxy group in the nonvolatile content of the aqueous resin emulsion is 0.
  • the content of the carboxyl group in the nonvolatile matter of the aqueous resin emulsion is 0.10 ⁇ 10 -4 mol / g or more, an aqueous resin emulsion.
  • the aqueous resin emulsion of the first aspect of the present invention preferably includes the following features. It is also preferable to combine two or more of the following features. [2] In [1], the content of carboxy groups in the nonvolatile content of the aqueous resin emulsion is preferably 10 ⁇ 10 ⁇ 4 mol / g or less.
  • the content of the epoxy group in the nonvolatile content of the aqueous resin emulsion is preferably 50 ⁇ 10 ⁇ 4 mol / g or less.
  • the (meth) acrylic acid ester (A) is composed of a (meth) acrylic acid alkyl ester.
  • the ethylenically unsaturated carboxylic acid (B) preferably comprises a compound having a (meth) acryloyl group and a carboxy group.
  • the polyepoxy compound (Y) is a bisphenol type epoxy compound, a hydrogenated bisphenol type epoxy compound, diglycidyl ether, triglycidyl ether, tetraglycidyl ether, diglycidyl. At least one selected from an ester, a triglycidyl ester, and a tetraglycidyl ester is preferable.
  • the glass transition point of the copolymer (X) is preferably ⁇ 30 ° C. or higher and 100 ° C. or lower.
  • the copolymer (X) includes a structural unit derived from a (meth) acrylic acid ester (A) and an ethylenically unsaturated carboxylic acid (B). It is preferably composed of structural units.
  • the copolymer (X) is a structural unit (c) derived from an ethylenically unsaturated aromatic compound (C) having a benzene ring and an ethylenically unsaturated bond. ) Is preferred.
  • the ethylenically unsaturated aromatic compound (C) is preferably an aromatic vinyl compound.
  • the second aspect of the present invention provides the following aqueous resin composition.
  • the content of the functional group contained in the curing agent ( ⁇ ) is 0.01 equivalent or more and 1.0 equivalent or less with respect to the amount of the epoxy group contained in the polyepoxy compound (Y).
  • Resin composition preferably includes the following features.
  • the curing agent ( ⁇ ) has at least one selected from the group consisting of an amine group, a carboxy group, and a mercapto group.
  • the third aspect of the present invention provides the following method for producing an aqueous resin emulsion.
  • the (meth) acrylic acid ester (A) A method for producing an aqueous resin emulsion, which comprises a step of emulsion-polymerizing a monomer containing an unsaturated carboxylic acid (B) in an aqueous medium (Z) to obtain an aqueous resin emulsion,
  • the amount of the polyepoxy compound (Y) added is 1 to 40% by mass relative to the total amount of the monomer and the polyepoxy compound (Y).
  • the amount of the (meth) acrylic acid ester (A) added is 20 to 98% by mass relative to the total amount of the (Y) and the ethylenic compound based on the total amount of the monomer and the polyepoxy compound (Y).
  • the amount of the unsaturated carboxylic acid (B) added is 0.1 to 10% by mass, and the (meth) acrylic acid ester (A) is hydrophilic (meta) having a carbon number of an alcohol-derived portion of 2 or less.
  • Acrylic ester (A1) is contained, and the addition amount of the hydrophilic (meth) acrylic ester (A1) is 15 to 98% by mass with respect to the total amount of the monomer and the polyepoxy compound (Y).
  • the content of the epoxy groups in the nonvolatile content of the aqueous resin emulsion is 0.50 ⁇ 10 ⁇ 4 mol / g or more, and the content of the carboxy groups in the nonvolatile content of the aqueous resin emulsion is 0.
  • the method for producing an aqueous resin emulsion according to the third aspect of the present invention preferably includes the following features. [14] In the aqueous resin emulsion, the emulsion polymerization is preferably performed at 30 to 90 ° C.
  • a fourth aspect of the present invention is to provide a monomer containing a (meth) acrylic acid ester (A) and an ethylenically unsaturated carboxylic acid (B) in the presence of a polyepoxy compound (Y) in an aqueous medium (Z). ), Emulsion polymerization,
  • the amount of the (meth) acrylic acid ester (A) added is 20 to 98% by mass based on the total amount of the monomer and the polyepoxy compound (Y).
  • the amount of the ethylenically unsaturated carboxylic acid (B) added is 0.1 to 10% by mass with respect to the total amount of the monomer and the polyepoxy compound (Y), Provided is a method for producing an aqueous resin emulsion, wherein the amount of the polyepoxy compound (Y) added is 1 to 40% by mass based on the total amount of the monomer and the polyepoxy compound (Y).
  • an aqueous resin emulsion an aqueous resin composition which is excellent in high-temperature stability and dispersion stability and, when included in a coating composition, gives a coating film having high water resistance, rust resistance and high adhesion to metal materials.
  • a method for producing an aqueous resin emulsion can be provided.
  • 5 is a graph showing the relationship between elongation and stress of a coating film obtained from the aqueous resin composition according to Example 101. 5 is a graph showing the relationship between elongation and stress of a coating film obtained from the aqueous resin composition according to Comparative Example 104.
  • the present invention is not limited to the embodiments described below.
  • the present invention is not limited only to the following examples, and additions, omissions, substitutions and substitutions of numbers, types, positions, amounts, ratios, materials, configurations, etc. are possible without departing from the spirit of the present invention. It can be changed.
  • measuring means that molecules contained in a raw material are bonded to each other by a chemical reaction to form a polymer having a network structure.
  • (Meth) acrylate means acrylate or methacrylate
  • (meth) acrylic means acrylic or methacrylic.
  • “Ethylenically unsaturated bond” means a double bond between carbon atoms excluding carbon atoms forming an aromatic ring.
  • Weight average molecular weight is the standard polystyrene equivalent value measured by gel permeation chromatography (GPC).
  • the “coating film” means a coating film formed by coating the aqueous resin composition containing the aqueous resin emulsion according to the present embodiment, then drying the medium and curing the resin component, unless otherwise specified. ..
  • Aqueous resin composition contains an aqueous resin emulsion ( ⁇ ) and a curing agent ( ⁇ ).
  • the aqueous resin composition according to the present embodiment is produced by mixing the aqueous resin emulsion ( ⁇ ) and the curing agent ( ⁇ ) as described later.
  • the copolymer (X) has a structural unit (a) derived from a (meth) acrylic acid ester (A) and a structural unit (b) derived from an ethylenically unsaturated carboxylic acid (B).
  • the structural unit (a) derived from the (meth) acrylic acid ester (A) includes the structural unit (a1) derived from the hydrophilic (meth) acrylic acid ester (A1).
  • the copolymer (X) may be composed of the structural unit (a) and the structural unit (b) (referred to as the copolymer (X1)).
  • the copolymer (X) includes a structural unit (a), a structural unit (b), and a structural unit (c) derived from an ethylenically unsaturated aromatic compound (C) having a benzene ring and an ethylenically unsaturated bond. ) And (having a copolymer (X2)).
  • the copolymer (X) may have a structural unit (d) other than the structural units (a) to (c) (as a structural unit derived from another monomer (D)).
  • the (meth) acrylic acid ester (A) is preferably composed of (meth) acrylic acid alkyl ester.
  • the (meth) acrylic acid alkyl ester it is more preferable to have a linear, branched or cyclic alkyl group having 1 to 18 carbon atoms. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl.
  • Examples thereof include (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, and isobornyl (meth) acrylate. These may be used alone or in combination of two or more.
  • Examples of the (meth) acrylic acid ester (A) may include examples of the hydrophilic (meth) acrylic acid ester (A1) described later.
  • the (meth) acrylic acid ester having a carboxy group is not included in the (meth) acrylic acid ester (A), but is included in the ethylenically unsaturated carboxylic acid (B) described later.
  • the (meth) acrylic acid ester (A) may include a (meth) acrylic acid ester having an epoxy group.
  • Examples of the (meth) acrylic acid ester having an epoxy group include glycidyl (meth) acrylate, ⁇ -methylglycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3,4-epoxycyclohexyl. Examples thereof include methyl (meth) acrylate, 3,4-epoxycyclohexylethyl (meth) acrylate, and 3,4-epoxycyclohexylpropyl (meth) acrylate.
  • the structural unit (a) may include structural units derived from only one type of these compounds, or may include structural units derived from two or more types. Furthermore, among these compounds, the structural unit (a) preferably contains a structural unit derived from glycidyl (meth) acrylate.
  • the (meth) acrylic acid ester (A) may be a (meth) acrylic acid ester which is neither a (meth) acrylic acid alkyl ester nor a compound having an epoxy group.
  • examples of such (meth) acrylic acid ester include (meth) acrylic acid ester having a hydroxy group.
  • Examples of the (meth) acrylic acid ester having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and 2-hydroxybutyl (meth). Examples thereof include acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate and 12-hydroxylauryl (meth) acrylate.
  • mono (meth) acrylic acid esters of polyethylene glycol mono (meth) acrylic acid esters of polyalkylene glycol such as mono (meth) acrylic acid ester of polypropylene glycol, and the like can also be mentioned.
  • These (meth) acrylic acid esters having a hydroxy group may be used alone or in combination of two or more.
  • the content of the structural unit (a) derived from the (meth) acrylic acid ester (A) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 20% by mass or more. This is because the dispersion stability of the monomer of the copolymer (X) and the polyepoxy compound (Y) can be improved in the method for producing an aqueous resin emulsion described below. From this viewpoint, the content of the structural unit (a) derived from the (meth) acrylic acid ester (A) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 35% by mass or more. Is preferred, 45% by mass or more is more preferred, and 60% by mass or more is even more preferred.
  • the copolymer (X) is composed of the structural unit (a) and the structural unit (b), that is, the copolymer (X1)
  • the following ratios are used.
  • the content of the structural unit (a) derived from the (meth) acrylic acid ester (A) with respect to the total amount of the copolymer (X1) and the polyepoxy compound (Y) is 50% by mass or more. More preferably, it is particularly preferably 60% by mass or more.
  • the content of the structural unit (a) derived from the (meth) acrylic acid ester (A) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 98% by mass or less. This is because if it exceeds 98% by mass, the dispersion stability of the aqueous resin emulsion tends to decrease. From this viewpoint, the content of the structural unit (a) derived from the (meth) acrylic acid ester (A) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 92% by mass or less. Is preferred, and more preferably 87% by mass or less.
  • the copolymer (X) has the structural unit (a), the structural unit (b), and the structural unit (c), that is, when the copolymer (X) is the copolymer (X2)
  • the content of the structural unit (a) derived from the (meth) acrylic acid ester (A) in the copolymer (X2) is more preferably 75% by mass or less, and particularly preferably 65% by mass or less. preferable.
  • the structural unit derived from the (meth) acrylic acid ester (A) includes a structural unit derived from the hydrophilic (meth) acrylic acid ester (A1).
  • the hydrophilic (meth) acrylic acid ester (A1) has a (meth) acryloyloxy group (CH 2 ⁇ CR—COO—, R represents hydrogen or a methyl group), and has a portion derived from an alcohol, that is, (meth).
  • the number of carbon atoms in the portion other than the acryloyloxy group may be, for example, 1 or 2.
  • the hydrophilic (meth) acrylic acid ester (A1) include methyl (meth) acrylate, ethyl (meth) acrylate, and 2-hydroxyethyl (meth) acrylate.
  • the hydrophilic (meth) acrylic acid ester (A1) is preferably a (meth) acrylic acid alkyl ester having an alcohol-derived moiety having 2 or less carbon atoms, and more preferably methyl methacrylate.
  • the content ratio of the structural unit (a1) derived from the hydrophilic (meth) acrylic acid ester (A1) to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 15% by mass or more. This is because when the content of the hydrophilic (meth) acrylic acid ester is small as described above, gelation proceeds rapidly when the aqueous resin emulsion ( ⁇ ) is mixed with a curing agent containing polyamine.
  • the content of the structural unit (a1) derived from the hydrophilic (meth) acrylic acid ester (A1) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 15% by mass or more, 20 It is preferably at least mass%, more preferably at least 30 mass%, and even more preferably at least 40 mass%. This is because the water resistance and rust resistance of the coating film after curing are further improved.
  • the content may be 45% by mass or more or 50% by mass or more.
  • the upper limit of the content of the structural unit (a1) derived from the hydrophilic (meth) acrylic acid ester (A1) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is (meth) acrylic acid ester. It is the same as the upper limit of the content rate described in the structural unit (a) derived from (A).
  • the polyepoxy compound (Y) described below is a hydrophobic compound such as a bisphenol type epoxy compound, a hydrogenated bisphenol type epoxy compound, or a phenol novolac type epoxy compound
  • the structural unit (a1) occupies the structural unit (a1).
  • the ratio of () is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 70% by mass or less. This is to improve the affinity between the copolymer (X) and the polyepoxy compound (Y).
  • the ethylenically unsaturated carboxylic acid (B) is a compound having an ethylenically unsaturated bond and a carboxy group.
  • the ethylenically unsaturated carboxylic acid (B) is ⁇ , ⁇ -unsaturated monocarboxylic acid, ⁇ , ⁇ -unsaturated dicarboxylic acid, monoalkyl ester of ⁇ , ⁇ -unsaturated dicarboxylic acid, and vinyl containing a carboxy group. It is preferable to include at least one kind from the group consisting of compounds.
  • Examples of the ⁇ , ⁇ -unsaturated mono- or dicarboxylic acid include acrylic acid, methacrylic acid, crotonic acid, citraconic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid and the like.
  • Examples of the vinyl compound having a carboxy group include monohydroxyethyl (meth) acrylate phthalate and monohydroxypropyl (meth) acrylate oxalate.
  • the structural unit (b) may be derived from only one type of these compounds, or may include structural units derived from two or more types.
  • the ethylenically unsaturated carboxylic acid (B) is preferably a compound having a (meth) acryloyl group and a carboxy group, and further preferably contains (meth) acrylic acid. That is, the structural unit (b) is preferably a structural unit derived from a compound having a (meth) acryloyl group and a carboxy group, and further preferably a structural unit derived from (meth) acrylic acid.
  • the content of the structural unit (b) derived from the ethylenically unsaturated carboxylic acid (B) is 0.1% by mass or more based on the total amount of the copolymer (X) and the polyepoxy compound (Y). This is to improve the dispersion stability of the aqueous resin emulsion ( ⁇ ). From this viewpoint, the content of the structural unit (b) derived from the ethylenically unsaturated carboxylic acid (B) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 0.3% by mass or more. It is preferably present, and more preferably 0.5% by mass or more. The content may be 0.8% by mass or more, or 1.0% by mass or more.
  • the content of the structural unit (b) derived from the ethylenically unsaturated carboxylic acid (B) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 10% by mass or less. This is to prevent the copolymer (X) from forming a gel in a high temperature environment and improve the high temperature stability of the aqueous resin emulsion ( ⁇ ). From this viewpoint, the content of the structural unit (b) derived from the ethylenically unsaturated carboxylic acid (B) is 7% by mass or less based on the total amount of the copolymer (X) and the polyepoxy compound (Y). It is preferable that the content is 5% by mass or less. The content may be 4% by mass or less, or 3% by mass or less.
  • the ethylenically unsaturated aromatic compound (C) does not correspond to either the (meth) acrylic acid ester (A) or the ethylenically unsaturated carboxylic acid (B), and has a benzene ring and an ethylenically unsaturated bond. It is a compound.
  • the ethylenically unsaturated aromatic compound (C) is preferably an aromatic vinyl compound.
  • aromatic vinyl compound as the ethylenically unsaturated aromatic compound (C) examples include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, ⁇ -methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, tert-butoxystyrene, vinyltoluene, divinyltoluene, vinylnaphthalene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromostyrene, tribromostyrene, fluorostyrene, styrene sulfone Acid and its salt, ⁇ -methylstyrene sulfonic acid and its salt, p-hydroxystyrene, m-hydroxystyrene, o-hydroxystyrene, p-isoprop
  • the structural unit (c) may be derived from only one type of these compounds, or may include structural units derived from two or more types.
  • the structural unit (c) is more preferably a structural unit derived from a hydrocarbon, and particularly preferably a structural unit derived from styrene.
  • the copolymer (X) contains the structural unit (c) derived from the ethylenically unsaturated aromatic compound (C), that is, when the copolymer (X) is the copolymer (X2), the copolymer
  • the content of the structural unit (c) with respect to the total amount of (X2) and the polyepoxy compound (Y) is preferably 5% by mass or more. This is to improve the water resistance of the coating film. From this viewpoint, the content of the structural unit (c) with respect to the total amount of the copolymer (X2) and the polyepoxy compound (Y) is more preferably 10% by mass or more, and 15% by mass or more. Is even more preferred. The content may be 18% by mass or more, 20% by mass or more, or 23% by mass or more.
  • the content of the structural unit (c) with respect to the total amount of the copolymer (X2) and the polyepoxy compound (Y) is 50% by mass or less.
  • the content of the structural unit (c) with respect to the total amount of the copolymer (X2) and the polyepoxy compound (Y) is more preferably 40 mass% or less, and 35 mass% or less. Is more preferable.
  • the content may be 33% by mass or less, 30% by mass or less, or 28% by mass or less.
  • the other monomer (D) does not correspond to any of the (meth) acrylic acid ester (A), the ethylenically unsaturated carboxylic acid (B), and the ethylenically unsaturated aromatic compound (C), and It is a compound having an ethylenically unsaturated bond that is copolymerizable with the compound used for the synthesis of the copolymer (X).
  • the other monomer (D) include conjugated diene compounds, maleimide compounds, vinyl ether compounds, allyl ether compounds, dialkyl esters of unsaturated dicarboxylic acids, vinyl compounds having a cyano group, and the like.
  • conjugated diene compound examples include 1,3-butadiene, isoprene (2-methyl-1,3-butadiene), 2,3-dimethyl-1,3 butadiene, chloroprene (2-chloro-1,3-butadiene) Etc. These conjugated diene compounds may be used alone or in combination of two or more.
  • maleimide compound examples include maleimide, N-methylmaleimide, N-isopropylmaleimide, N-butylmaleimide, N-dodecylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4- Methylphenyl) maleimide, N- (2,6-dimethylphenyl) maleimide, N- (2,6-diethylphenyl) maleimide, N- (2-methoxyphenyl) maleimide, N-benzylmaleimide, N- (4-hydroxy) Examples thereof include phenyl) maleimide, N-naphthylmaleimide and N-cyclohexylmaleimide. These maleimide compounds may be used alone or in combination of two or more.
  • vinyl ether compound examples include alkyl vinyl ethers such as methyl vinyl ether and ethyl vinyl ether, and hydroxyl group-containing alkyl vinyl ethers in which some hydrogen atoms are substituted with hydroxyl groups.
  • allyl ether compound examples include allyl alkyl ethers such as allyl methyl ether and allyl ethyl ether, allyl alkyl ethers containing a hydroxyl group in which some hydrogen atoms are substituted with hydroxyl groups, and allyl glycidyl ether.
  • dialkyl ester of the unsaturated dicarboxylic acid for example, unsaturated dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, itaconic anhydride, citraconic acid anhydride, tetrahydrophthalic acid anhydride and the like.
  • unsaturated dicarboxylic acid such as maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, maleic anhydride, itaconic anhydride, citraconic acid anhydride, tetrahydrophthalic acid anhydride and the like.
  • the dialkyl ester of is mentioned. These dialkyl esters may be used alone or in combination of two or more. These unsaturated compounds may be used alone or in combination of two or more.
  • Examples of the vinyl compound having a cyano group include acrylonitrile, methacrylonitrile, ⁇ -ethylacrylonitrile, ⁇ -isopropylacrylonitrile, ⁇ -chloroacrylonitrile, and ⁇ -fluoroacrylonitrile. These cyano group-containing vinyl monomers may be used alone or in combination of two or more.
  • the polyepoxy compound (Y) is a compound having no ethylenically unsaturated bond and having two or more epoxy groups in one molecule.
  • the polyepoxy compound (Y) is at least 1 selected from bisphenol type epoxy compounds, hydrogenated bisphenol type epoxy compounds, diglycidyl ether, triglycidyl ether, tetraglycidyl ether, diglycidyl ester, triglycidyl ester, and tetraglycidyl ester. It is preferably a seed.
  • Examples of compounds having two or more epoxy groups in one molecule include bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, and glycerin.
  • Examples thereof include glycidyl ether and diglycidyl ester of hexahydrophthalic acid. One of these compounds may be included, or two or more of them may be included.
  • the polyepoxy compound (Y) is more preferably a bisphenol type epoxy compound or a hydrogenated bisphenol type epoxy compound, further preferably a bisphenol A type epoxy compound or a hydrogenated bisphenol A type epoxy compound. This is because the water resistance and rust resistance of the coating film after curing are further improved.
  • the weight average molecular weight of the polyepoxy compound (Y) is not particularly limited, but is preferably 1,000 or less, more preferably 800 or less, and further preferably 500 or less.
  • the compatibility of the polyepoxy compound (Y) with the copolymer (X) is improved, and an emulsion having excellent dispersion stability and storage stability can be obtained.
  • the lower limit of the molecular weight can be arbitrarily selected and may be, for example, 200 or 300, but is not limited thereto.
  • the epoxy equivalent of the polyepoxy compound (Y) (mass of the polyepoxy compound (Y) per 1 mol of the epoxy group) is preferably 500 g / mol or less, more preferably 350 g / mol or less, and 250 g / mol. The following is more preferable. This is because the strength of the coating film obtained by curing the aqueous resin composition described below becomes high.
  • the lower limit value of the epoxy equivalent can be arbitrarily selected and may be, for example, 70 g / mol or more and 120 g / mol or more, but is not limited to these examples.
  • the content of the polyepoxy compound (Y) is 1% by mass or more based on the total amount of the copolymer (X) and the polyepoxy compound (Y). This is because the aqueous resin composition is cured and a coating film having excellent rust prevention properties can be obtained. From this viewpoint, the content of the polyepoxy compound (Y) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is preferably 5% by mass or more, and 8% by mass or more. Is more preferable and 10% by mass or more is further preferable. If necessary, the amount may be 12% by mass or more, or 20% by mass or more.
  • the content of the polyepoxy compound (Y) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is 40% by mass or less. This is to obtain an aqueous resin emulsion ( ⁇ ) having high dispersion stability. From this viewpoint, the content of the polyepoxy compound (Y) with respect to the total amount of the copolymer (X) and the polyepoxy compound (Y) is preferably 35% by mass or less, and 30% by mass or less. Is more preferable.
  • the hydrophilic solvent added to water can be arbitrarily selected, and examples thereof include methanol, ethanol and N-methylpyrrolidone.
  • Aqueous resin emulsion ( ⁇ ) production method is a monomer containing a (meth) acrylic acid ester (A) and an ethylenically unsaturated carboxylic acid (B) in the presence of a polyepoxy compound (Y). (That is, the monomer for forming the copolymer (X)) is emulsion-polymerized in the aqueous medium (Z).
  • an aqueous resin emulsion ( ⁇ ) in which the polyepoxy compound (Y) is uniformly dispersed in the particles of the produced copolymer (X) is obtained.
  • “uniformly existing” does not necessarily mean that the copolymer (X) and the polyepoxy compound (Y) are compatible with each other, and the center side of the copolymer (X) particles It suffices that the domains of the polyepoxy compound (Y) exist evenly on both the surface side and the surface side.
  • a specific emulsion polymerization method a method of charging each component containing a monomer at once, a method of polymerizing while continuously supplying each component, and the like can be used. It is preferable to stir during the polymerization reaction.
  • the content of each raw material in the entire raw material used for producing the aqueous resin emulsion ( ⁇ ) is the same as the content of the structural unit derived from the raw material or the compound corresponding to the raw material in the aqueous resin emulsion ( ⁇ ). ..
  • the polymerization is preferably carried out at a temperature arbitrarily selected, for example, a temperature of 30 to 90 ° C., more preferably 40 to 80 ° C., further preferably 40 to 70 ° C. .. This is to prevent the carboxy group contained in the monomer from reacting with the epoxy group contained in the polyepoxy compound (Y).
  • the emulsifier used for emulsion polymerization can be arbitrarily selected, and examples thereof include nonionic surfactants such as polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, and alkyl sulfate ester.
  • nonionic surfactants such as polyoxyalkylene alkyl ether, polyoxyalkylene alkylphenol ether, polyoxyalkylene fatty acid ester, polyoxyalkylene sorbitan fatty acid ester, and alkyl sulfate ester.
  • anionic surfactants such as salts, alkylbenzene sulfonates, alkylsulfosuccinates, alkyldiphenyl ether disulfonates, polyoxyalkylene alkyl sulfates and polyoxyalkylene alkyl phosphates. These may be used alone or in combination of
  • a polymerization initiator for example, peroxide is preferably used.
  • peroxide peroxide is preferably used.
  • the peroxide used as the polymerization initiator include persulfates such as potassium persulfate and ammonium persulfate, hydrogen peroxide and the like.
  • a redox-based initiator which is a combination of a peroxide and a reducing agent can also be used.
  • the reducing agent include sodium sulfoxylate formaldehyde, ascorbic acid, sulfite, tartaric acid or a salt thereof.
  • the pH of the aqueous resin emulsion ( ⁇ ) is preferably 2-10, and more preferably 5-9. When the pH is within this range, the mechanical stability and chemical stability of the aqueous resin emulsion ( ⁇ ) can be improved.
  • the pH is a value measured at a liquid temperature of 25 ° C. using a pH meter with a hydrogen ion concentration indicator using a glass electrode as a standard electrode.
  • the pH can be adjusted by adding a basic substance to the aqueous resin emulsion ( ⁇ ) during the emulsion polymerization or after the completion of the emulsion polymerization.
  • a basic substance used for adjusting the pH include ammonia, triethylamine, ethanolamine, caustic soda and the like. These may be used alone or in combination of two or more.
  • the nonvolatile content concentration of the aqueous resin emulsion ( ⁇ ) is preferably 10 to 65% by mass, more preferably 15 to 60% by mass, and even more preferably 20 to 55% by mass.
  • the concentration may be 30 to 50% by mass, or 35 to 45% by mass.
  • the concentration of nonvolatile components in the aqueous resin emulsion ( ⁇ ) is different from that of the aqueous medium (Y). It can be appropriately adjusted by adjusting the addition amount.
  • the nonvolatile content was obtained after weighing 1 g of the aqueous resin emulsion ( ⁇ ) in an aluminum dish having a diameter of 5 cm and drying at 105 ° C. for 1 hour at atmospheric pressure in a dryer while circulating air. It is the ratio (mass%) of the mass of the remaining residue to the mass of the aqueous resin emulsion ( ⁇ ) before drying.
  • the viscosity of the aqueous resin emulsion ( ⁇ ) is measured at 23 ° C.
  • the viscosity of the aqueous resin emulsion ( ⁇ ) is measured by using a B-type viscometer, and is a value measured at a rotation speed of 60 rpm by selecting a rotor according to the viscosity of the aqueous resin emulsion. For example, when the viscosity of the aqueous resin emulsion ( ⁇ ) is about several mPa ⁇ s to several hundred mPa ⁇ s, the rotor No. 1 is used for measurement.
  • the viscosity may be, for example, 0.1 to 300 mPa ⁇ s, 1 to 100 mPa ⁇ s, 3 to 50 mPa ⁇ s, or 5 to 25 mPa ⁇ s. ..
  • the glass transition point Tg of the copolymer (X) is calculated based on the glass transition point of the homopolymer of each monomer used for the synthesis of the copolymer (X).
  • the glass transition point Tg of the copolymer (X) is preferably ⁇ 30 ° C. (243K) or higher. This is because the strength of the coating film is improved. From this viewpoint, the glass transition point Tg of the copolymer (X) is more preferably ⁇ 10 ° C. (263K) or higher. It is more preferable that the temperature is 0 ° C. (273 K) or higher. This is because in the case of such a range, the strength of the coating film after curing is improved.
  • the glass transition point Tg of the copolymer (X) may be 5 ° C. or higher, or 10 ° C. or higher.
  • the glass transition point Tg of the copolymer (X) is preferably 100 ° C.
  • the glass transition point Tg of the copolymer (X) is more preferably 60 ° C. (333 K) or less, and particularly preferably 50 ° C. (323 K) or less. This is because in the case of such a range, the flexibility of the coating film after curing can be improved.
  • the glass transition point Tg of the copolymer (X) may be 40 ° C. or lower, or 30 ° C. or lower.
  • the content of the epoxy group in the nonvolatile content of the aqueous resin emulsion ( ⁇ ) is 0.50 ⁇ 10 ⁇ 4 mol / g or more, preferably 3.0 ⁇ 10 ⁇ 4 mol / g or more. It is more preferably at least 0.0 ⁇ 10 ⁇ 4 mol / g. This is because it is possible to enhance the water resistance, rust resistance, and adhesion to the base material of the coating film after curing.
  • the content of epoxy groups in the nonvolatile content of the aqueous resin emulsion ( ⁇ ) may be 1.0 ⁇ 10 ⁇ 4 mol / g or more, or 6.0 ⁇ 10 ⁇ 4 mol / g or more.
  • the content of epoxy groups in the nonvolatile content of the aqueous resin emulsion ( ⁇ ) is preferably 50 ⁇ 10 ⁇ 4 mol / g or less, more preferably 30 ⁇ 10 ⁇ 4 mol / g or less, 20 More preferably, it is not more than ⁇ 10 ⁇ 4 mol / g.
  • the content of epoxy groups in the nonvolatile content of the aqueous resin emulsion ( ⁇ ) may be 15 ⁇ 10 ⁇ 4 mol / g or less, or 10 ⁇ 10 ⁇ 4 mol / g or less.
  • the epoxy group content REP [mol / g] in the nonvolatile content of ( ⁇ ) in the aqueous resin emulsion is a value determined as follows. Assuming that the nonvolatile content concentration of the aqueous resin emulsion ( ⁇ ) is C S [mass%] and the amount of epoxy groups N 1 [mol / g] contained per 1 g of the aqueous resin emulsion ( ⁇ ), the epoxy group content rate R EP Is expressed as in equation (2). The method for obtaining N 1 is as described later in the embodiment.
  • R EP N 1 / (C S /100).
  • the content of carboxy groups in the nonvolatile content of the aqueous resin emulsion ( ⁇ ) is 0.10 ⁇ 10 ⁇ 4 mol / g or more, preferably 0.50 ⁇ 10 ⁇ 4 mol / g or more, 1 It is more preferably at least 0.0 ⁇ 10 ⁇ 4 mol / g. This is because aggregation of the copolymer (X) can be suppressed during the storage of the aqueous resin emulsion ( ⁇ ) during and after the polymerization.
  • the content of carboxyl groups in the nonvolatile content of the aqueous resin emulsion (alpha) is preferably not more than 10 ⁇ 10 -4 mol / g, more preferably not more than 5.0 ⁇ 10 -4 mol / g .. It may be 3.0 ⁇ 10 ⁇ 4 mol / g or less, 2.5 ⁇ 10 ⁇ 4 mol / g or less, or 2.0 ⁇ 10 ⁇ 4 mol / g or less.
  • the carboxy group includes not only —COOH but also a structure in which a cation other than hydrogen ion and —COO ⁇ are bonded.
  • the raw materials refer to the components used in the synthesis of the aqueous resin emulsion ( ⁇ ).
  • the functional group that reacts with a carboxy group is an epoxy group, and the hydroxy group is not considered to be a functional group that reacts with a carboxy group.
  • the total amount of carboxy groups in the raw material (including the initiator, solvent, other additives, etc.) is N 3 [mol / g]
  • the total amount of epoxy groups in the raw material (including the initiator, solvent, other additives, etc.) Is N 2 [mol / g]
  • the amount of epoxy groups contained in 1 g of the aqueous resin emulsion ( ⁇ ) is N 1 [mol / g].
  • the nonvolatile content concentration of the aqueous resin emulsion ( ⁇ ) is C S [mass%].
  • the content ratio R CX of the carboxy group is represented by the formula (3). An example of how to obtain N 1 and N 2 will be described later in Examples. N 2 can be obtained by calculation.
  • the curing agent ( ⁇ ) has a functional group having reactivity with an epoxy group.
  • the curing agent ( ⁇ ) is preferably a compound having at least one selected from the group consisting of an amino group, a carboxy group and a mercapto group.
  • Examples of the curing agent ( ⁇ ) having an amino group include aliphatic polyamines, alicyclic polyamines, aromatic polyamines, polyamides, and tertiary amines.
  • Examples of the aliphatic polyamine include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and modified products thereof.
  • Examples of the alicyclic polyamine include isophoronediamine, menthanediamine, N-aminoethylpiperazine, diaminodicyclohexylmethane and modified products thereof.
  • Examples of aromatic polyamines include m-xylylenediamine, diaminodiphenylmethane, m-phenylenediamine, diaminodiphenylsulfone, and modified products thereof.
  • Examples of the polyamide include a condensation product of a dicarboxylic acid such as dimer acid and the above polyamine.
  • tertiary amine examples include tertiary amino group-containing compounds such as dimethylbenzylamine, 2,4,6-trisdimethylaminomethylphenol, modified products thereof, imidazole, 2-methylimidazole, and 2-ethyl. Examples thereof include imidazole compounds such as 4-methylimidazole and 2-phenylimidazole, and modified products thereof.
  • Other polyamines include dicyandiimide and adipic acid dihydrazide.
  • the curing agent ( ⁇ ) having a carboxy group a compound having two or more carboxy groups in the molecule is preferable.
  • Examples thereof include phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, methylhexahydrophthalic acid, pyromellitic acid, benzophenonetetracarboxylic acid, and 1,2,3,4-butanetetracarboxylic acid.
  • Examples of the curing agent ( ⁇ ) having a mercapto group include a condensate of thioglycolic acid and a polyhydric alcohol, polysulfide and the like. These curing agents may be used alone or in combination of two or more. A polyamine-based curing agent is preferable.
  • Examples of commercially available curing agents include Epi-cure 8535, 8536, 8537, 8290 and 8292; Anquamine 401; Casamid 360 and 362; Epilink 381, DP660, HZ350, 92-113 and 92-116; Beckopox EH659W, EH623W, VEH2133W; ADEKA HARDNER EH-8051; FUJI CURE FXI-919; Thomaid TXH-674-B and TXS-53-C; Epotof (Epotof). 37-680 and 37-681; RIKACID BTW; and Karenz MT BD-1.
  • the content of the functional group having reactivity with the epoxy group contained in the curing agent ( ⁇ ) is preferably 0.01 equivalent or more with respect to the amount of the epoxy group contained in the polyepoxy compound (Y), It is more preferably 0.1 equivalent or more. This is because the rustproof property of the aqueous resin composition after curing and the adhesion to the metal material are improved.
  • the content of the functional group having reactivity with the epoxy group contained in the curing agent ( ⁇ ) is preferably 1.5 equivalents or less with respect to the amount of the epoxy group contained in the polyepoxy compound (Y), It is more preferably 1.0 equivalent or less. This is because the strength of the coating film is improved. It may be 0.8 equivalents or less, or 0.5 equivalents or less.
  • the aqueous resin composition according to this embodiment may include a pigment.
  • the pigment include titanium oxide, talc, barium sulfate, carbon black, red iron oxide, calcium carbonate, silicon oxide, talc, mica, kaolin, clay, ferrite and silica sand.
  • the pigment is preferably contained in the aqueous resin composition in an amount of 0.1 to 50% by mass, more preferably 1 to 40% by mass. This is to improve the hiding power of the coating film.
  • the aqueous resin composition includes a filler, an organic or inorganic hollow balloon, a dispersant (eg, amino alcohol, polycarboxylate, etc.), a surfactant, a coupling agent (eg, silane coupling agent), a defoaming agent, Preservatives (eg biocides, fungicides, fungicides, algaecides, and combinations thereof), flow agents, leveling agents, neutralizing agents (eg hydroxides, amines, ammonia, carbonates) Etc.) and the like.
  • a dispersant eg, amino alcohol, polycarboxylate, etc.
  • a surfactant eg, silane coupling agent
  • a coupling agent eg, silane coupling agent
  • a defoaming agent eg, silane coupling agent
  • Preservatives eg biocides, fungicides, fungicides, algaecides, and combinations thereof
  • flow agents eg hydroxides, amine
  • silane coupling agent examples include epoxy silane compounds. Specific examples include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 2- (3,4-epoxycyclohex) ethyl. Examples include trimethoxysilane and the like.
  • the addition amount of the silane coupling agent is preferably 0.1 to 5 parts by mass, and more preferably 0.3 to 3 parts by mass with respect to 100 parts by mass of the aqueous resin emulsion. This is because the rustproof property of the aqueous resin composition after curing and the adhesion to the metal material are improved.
  • the method for forming a coating film comprises the steps of mixing an aqueous resin emulsion ( ⁇ ), a curing agent ( ⁇ ), and optionally other components described above to obtain an aqueous resin composition, and an aqueous resin composition.
  • the method includes a coating step of coating the article to be coated and a curing step of curing the coated coating film.
  • the aqueous resin emulsion ( ⁇ ), the curing agent ( ⁇ ) and, if necessary, other components are mixed and stirred to obtain an aqueous resin composition in which each contained component is sufficiently dispersed.
  • Stirring can be performed by, for example, Robomix (manufactured by Primix Co., Ltd.).
  • Robomix manufactured by Primix Co., Ltd.
  • the aqueous resin composition is coated on the article to be coated.
  • the object to be coated include metal materials.
  • the article to be coated may be subjected to a surface treatment such as a primer or an undercoat in advance.
  • the application method include, but are not limited to, a method using a brush or a roller.
  • the coating step is preferably performed within 1 hour after the completion of the mixing step.
  • the resin component contained in the aqueous resin composition is cured by drying and curing the article to which the aqueous resin composition is applied.
  • the curing time depends on the temperature of the atmosphere. For example, it is preferably 5 hours or longer at 20 ° C., preferably 1 hour or longer at 40 ° C., and preferably 5 minutes or longer at 60 ° C. ⁇ 3.
  • Application fields of the present invention> The aqueous resin emulsion ( ⁇ ) and the aqueous resin composition of the present invention are useful in various fields, especially in the field of metal coatings.
  • an undercoat layer and an overcoat layer if necessary. Etc. may be provided.
  • An article to which a paint containing the aqueous resin emulsion ( ⁇ ) and / or the aqueous resin composition of the present invention is applied, that is, an object to be coated can be arbitrarily selected.
  • aqueous resin emulsion ( ⁇ ) The aqueous resin emulsions ( ⁇ -1) to ( ⁇ -10) and (c ⁇ -1) to (c ⁇ -5) were evaluated as follows. In the following description, the aqueous resin emulsions ( ⁇ -1) to ( ⁇ -10) and (c ⁇ -1) to (c ⁇ -5) may be collectively referred to as the aqueous resin emulsion ( ⁇ ). .
  • the glass transition point Tg of the copolymer (X) is a value calculated by the above formula (1).
  • Dispersion stability The state of the aqueous resin emulsion ( ⁇ ) was visually observed and evaluated according to the following criteria. ⁇ (OK): Neither aggregation, precipitation, separation, nor gelation was observed. X (Not possible): At least one of aggregation, precipitation, separation, and gelation was observed.
  • the high temperature stability of the aqueous resin emulsion ( ⁇ ) was evaluated as follows. First, the aqueous resin emulsion ( ⁇ ) was placed in a 70 ml glass bottle, and the bottle was sealed and left at 60 ° C. for 7 days. Then, the state of the aqueous resin emulsion ( ⁇ ) in the glass bottle was visually observed and evaluated according to the following criteria. Good (OK): Neither aggregation, thickening, precipitation, separation, nor gelation was observed. X (Not possible): At least one of aggregation, thickening, precipitation, separation, and gelation was observed.
  • the residual ratio of the epoxy groups of the aqueous resin emulsion ( ⁇ ) was used for the synthesis of the aqueous resin emulsion ( ⁇ ) of the amount N 1 [mol / g] of the epoxy groups contained in the aqueous resin emulsion ( ⁇ ) after synthesis. It is the ratio to the total amount N 2 [mol / g] of epoxy groups contained in the components (including raw materials, initiators, solvents, and other additives).
  • the amount N 1 [mol / g] of epoxy groups in the aqueous resin emulsion ( ⁇ ) after synthesis was measured based on the total amount of epoxy groups contained in the component (raw material) used in the synthesis of the aqueous resin emulsion ( ⁇ ).
  • Excess hydrogen chloride was added to react with the epoxy group.
  • the amount of residual hydrogen chloride was confirmed by titrating unreacted hydrogen chloride with potassium hydroxide.
  • potassium hydroxide is consumed by the reaction with acidic components such as carboxylic acid contained in the aqueous resin emulsion ( ⁇ ). Therefore, the amount of acidic components was titrated in advance by blank measurement without using hydrogen chloride, and the results of this measurement were corrected.
  • the specific measurement procedure is as follows (i) to (iii).
  • the solution was titrated with a 0.1 M potassium hydroxide / ethanol solution while stirring. After dropping the potassium hydroxide / ethanol solution, the point where the purple color lasts for 30 seconds was defined as the equivalence point.
  • the amount of the potassium hydroxide / ethanol solution used for the titration is V KOH2 [mL].
  • N 1 (0.2 ⁇ V HCl / 1000 ⁇ 0.1 ⁇ V KOH 2/1000 ) / W 2 + (0.1 ⁇ V KOH 1/1000) / W 1 (4)
  • the components used in the synthesis of the aqueous resin emulsion ( ⁇ ) mean all components described in Tables 1-1 to 1-4.
  • N 2 ⁇ (m i / EP i ) / ⁇ m i (5)
  • the residual rate of epoxy groups in the aqueous resin emulsion ( ⁇ ) is represented by 100 ⁇ N 1 / N 2 [mol%].
  • N 2 0, which is the total amount of epoxy groups in the raw material, was used. Therefore, in Table 1-4, the residual rate of epoxy groups is “ ⁇ ”.
  • Epoxy group content in non-volatile matter From the nonvolatile concentration, the epoxy group content N 1 in the aqueous resin emulsion ( ⁇ ), and the total amount N 2 of epoxy groups in the raw material, which were determined by the above method, the epoxy groups in the nonvolatile content of the aqueous resin emulsion ( ⁇ ) were calculated.
  • the content rate R EP [mol / g] of was determined based on the equation (2) described above.
  • R EP N 1 / (C S /100)...(2)
  • the components used for the synthesis of the aqueous resin emulsion ( ⁇ ) mean all the components described in Table 1-1 to Table 1-4 as raw materials for the aqueous resin emulsion ( ⁇ ).
  • Examples 101 to 114 and Comparative Examples 101 to 104 (Preparation of Aqueous Resin Composition)>
  • 100 parts by mass of the aqueous resin emulsion ( ⁇ ) shown in Tables 2-1 and 2-2, 60 parts by mass of ion-exchanged water, and Tables 2-1 and 2-2 are shown.
  • the types of curing agents ( ⁇ ) were added in the amounts (parts by mass) shown in these tables and stirred for 10 minutes to prepare an aqueous resin composition.
  • “amine equivalent”, “carboxy equivalent” and “mercapto equivalent” mean mass (g) per mol of amino group, carboxy group and mercapto group, respectively. ..
  • the “equivalent amount to the epoxy group” of each curing agent is a numerical value indicating the molar ratio of the functional group contained in the curing agent ( ⁇ ) to the amount of the epoxy group based on the raw material contained in the aqueous resin emulsion ( ⁇ ). is there.
  • the coating film was taken out from the ion-exchanged water, the coating film immediately after that was weighed, and this was taken as the mass of the coating film before drying. Then, the coating film was dried at 105 ° C. for 3 hours, the coating film was weighed again, and this was taken as the mass of the dried coating film.
  • the value obtained by the following formula (7) from the mass of the coating film before drying and the mass of the coating film after drying was defined as the water swelling resistance. ⁇ (Mass of coating film before drying-mass of coating film after drying) / mass of coating film after drying ⁇ ⁇ 100 (7)
  • aqueous resin compositions prepared in Examples 101 to 114 and Comparative Examples 101 to 104 were coated on a cold-rolled steel sheet (hereinafter referred to as "base material") with a brush so that the basis weight was 50 g / m 2. Then, it was dried in a constant temperature bath at 60 ° C. for 10 minutes to form a coating film on the surface of the base material.
  • a test piece was formed by forming a notch composed of two intersecting straight lines (that is, an X shape) in the coating film so as to form a diagonal line of a 30 mm ⁇ 45 mm rectangle (this rectangle is used as a test area in this evaluation). And The notch was formed using a cutter knife so as to reach the substrate.
  • a neutral salt spray test (section 4.2.1) was performed on the test piece in which the notch was formed based on JIS Z-2371 (2000).
  • the area occupied by the swelling of the coating film in the test area [area%], the size of the swelling [mm], and the size of the flow rust from the notch [mm] were measured.
  • the size of the bulge is the longest dimension in the area occupied by one independent bulge.
  • the size of flow rust shall be the maximum value of the width of rust centered on the cross-cut portion.
  • a coating film was formed on the surface of the base material of the cold-rolled steel sheet in the same manner as the evaluation of the rust prevention property.
  • JIS K-5400 (1990) “8.5.2 Cross-cut tape method” a steel plate on which a coating film is formed is used as a test piece, and a notch at 1 mm intervals is cut with a cutter so as to penetrate the coating film. (100 squares) was put and Cellotape (registered trademark) was stuck. After 1 hour, the Cellotape (registered trademark) was peeled off, and the adhesion of the coating film to the metal material was evaluated by counting the number of masses remaining without peeling the coating film from the steel plate.
  • Example 101 The aqueous resin compositions obtained in Example 101 and Comparative Example 104 were drooled so as to spread over a 90 mm ⁇ 190 mm rectangular polyethylene film placed horizontally. This was dried at 23 ° C. for 72 hours and then cured at 50 ° C. for 24 hours to prepare a coating film. This coating film was peeled from the flat plate, and the peeled coating film was cut into a rectangle of 10 mm ⁇ 30 mm to obtain a test piece. The following tests were conducted with the longitudinal direction of this test piece as the tensile direction.
  • the thickness of the test piece was measured by using Quick Micro (registered trademark) MDQ-MX manufactured by Mitutoyo Co., Ltd., and the average value of three points was taken as the thickness t [mm] of the test piece.
  • the thickness t of the test piece is shown in Tables 3 and 4.
  • the test was performed using Autograph AG-X (manufactured by Shimadzu Corporation). At intervals (distance between chucks) of 10 mm, both sides of the test piece in the longitudinal direction were gripped by chucks. The test piece was pulled at a speed of 100 mm / min in an atmosphere of 23 ° C. and 50% RH.
  • Table 3 shows the relationship between elongation and stress of the coating film obtained from the aqueous resin composition according to Example 101.
  • Table 4 shows the relationship between the elongation and the stress of the coating film obtained from the aqueous resin composition according to Comparative Example 104.
  • the elongation is It is calculated by 100 ⁇ ⁇ L / L [%].
  • the load (measured load) applied to the test piece is F [N]
  • the width of the test piece is W [mm]
  • the thickness of the test piece is t [mm]
  • a value obtained by integrating the stress value (N / mm 2 ) with the elongation (%) value was used as a stress integral value ⁇ , and was calculated as follows based on the values shown in Tables 3 and 4.
  • the value of elongation ( ⁇ L / L [%]) at the n-th point is X n
  • the stress (N / mm 2 ) is ⁇ n .
  • the stress integral value ⁇ can be said to be the amount of work required to extend a sample having a unit cross-sectional area and unit length (distance between chucks) to fracture, that is, the energy absorption amount of the coating film until fracture. ..
  • FIG. 1 is a graph showing the relationship between elongation and stress of a coating film obtained from the aqueous resin composition according to Example 101.
  • FIG. 2 is a graph showing the relationship between elongation and stress of a coating film obtained from the aqueous resin composition according to Comparative Example 104. 1 and 2, x indicates a break point.
  • the aqueous resin emulsion (c ⁇ -1) of Comparative Example 1 containing no polyepoxy compound (Y) does not contain a crosslinking component. Therefore, as shown in Tables 2-1 and 2-2, the water resistance, the rust resistance, and the adhesion to metal materials were insufficient.
  • the aqueous resin emulsion ( ⁇ ) according to the present invention has excellent high temperature stability and dispersion stability.
  • aqueous resin composition according to the present invention when included in a paint, a coating film having excellent water resistance, anticorrosive properties and high adhesion to metal materials can be obtained.
  • an aqueous resin emulsion which is excellent in high-temperature stability and dispersion stability and, when included in a paint, provides a coating film having high water resistance, rust resistance and high adhesion to metal materials. ..

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Epoxy Resins (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymerisation Methods In General (AREA)

Abstract

L'invention concerne une émulsion de résine aqueuse qui contient un copolymère (X), un composé polyépoxy (Y) et un milieu aqueux (Z), la teneur du composé polyépoxy (Y) étant de 1 à 40 % en masse par rapport à la quantité totale du copolymère (X) et du composé polyépoxy (Y), le copolymère (X) contenant un motif structural dérivé d'un ester d'acide (méth)acrylique (A) et un motif structural dérivé d'un acide carboxylique éthyléniquement insaturé (B), la teneur du motif structural dérivé de l'ester d'acide (méth)acrylique (A) étant de 20 à 98 % en masse par rapport à la quantité totale du copolymère (X) et du composé polyépoxy (Y), la teneur du motif structural dérivé de l'acide carboxylique éthylénique insaturé (B) étant de 0,1 à 10 % en masse par rapport à la quantité totale du copolymère (X) et du composé polyépoxy (Y), le motif structural dérivé de l'ester d'acide (méth)acrylique (A) comprenant un motif structural qui est dérivé d'un ester d'acide (méth)acrylique (A1), et qui contient un groupe (méth)acryloyloxy et qui possède 2 atomes de carbone ou moins dans la partie autre que le groupe (méth)acryloyloxy, la teneur du motif structural dérivé de l'ester d'acide (méth)acrylique hydrophile (A1) étant de 15 à 98 % en masse par rapport à la quantité totale du copolymère (X) et du composé polyépoxy (Y), l'émulsion de résine aqueuse étant une émulsion obtenue par polymérisation en émulsion de monomères, qui sont les motifs structuraux du copolymère (X), dans le milieu aqueux (Z) en présence du composé polyépoxy (Y), la teneur d'un groupe époxy dans les constituants non volatils de l'émulsion de résine aqueuse étant d'au moins 0,50 × 10-4 mol/g, et la teneur d'un groupe carboxylique dans les constituants non volatils de l'émulsion de résine aqueuse étant d'au moins 0,10 × 10-4 mol/g.
PCT/JP2019/044059 2018-11-13 2019-11-11 Émulsion de résine aqueuse, son procédé de fabrication et composition de résine aqueuse WO2020100790A1 (fr)

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WO2022145228A1 (fr) * 2020-12-28 2022-07-07 昭和電工株式会社 Composition de résine aqueuse, film, procédé de fabrication de film de revêtement, ensemble de composition de résine aqueuse, et procédé de protection de métal
WO2022145227A1 (fr) * 2020-12-28 2022-07-07 昭和電工株式会社 Composition de résine aqueuse, film, procédé de fabrication de film de revêtement, ensemble de composition de résine aqueuse, et procédé de protection de métal
WO2022255272A1 (fr) * 2021-06-02 2022-12-08 昭和電工株式会社 Composition de résine aqueuse, film de revêtement, procédé de production de film de revêtement et ensemble de composition de résine aqueuse

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CN115552069A (zh) * 2020-05-13 2022-12-30 昭和电工株式会社 纤维处理剂、纤维处理组合物、纤维加工品及纤维处理剂的制造方法
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WO2022145227A1 (fr) * 2020-12-28 2022-07-07 昭和電工株式会社 Composition de résine aqueuse, film, procédé de fabrication de film de revêtement, ensemble de composition de résine aqueuse, et procédé de protection de métal
WO2022255272A1 (fr) * 2021-06-02 2022-12-08 昭和電工株式会社 Composition de résine aqueuse, film de revêtement, procédé de production de film de revêtement et ensemble de composition de résine aqueuse

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CN112703207A (zh) 2021-04-23
TW202028283A (zh) 2020-08-01

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