WO2022138183A1 - Aqueous resin composition, coating agent, adhesive, coating film, adhesive layer and multilayer body - Google Patents

Aqueous resin composition, coating agent, adhesive, coating film, adhesive layer and multilayer body Download PDF

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Publication number
WO2022138183A1
WO2022138183A1 PCT/JP2021/045255 JP2021045255W WO2022138183A1 WO 2022138183 A1 WO2022138183 A1 WO 2022138183A1 JP 2021045255 W JP2021045255 W JP 2021045255W WO 2022138183 A1 WO2022138183 A1 WO 2022138183A1
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Prior art keywords
mass
resin composition
aqueous
parts
polyester resin
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PCT/JP2021/045255
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French (fr)
Japanese (ja)
Inventor
潤一 宮宅
辰弥 山本
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Dic株式会社
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Priority to JP2022572116A priority Critical patent/JPWO2022138183A1/ja
Publication of WO2022138183A1 publication Critical patent/WO2022138183A1/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • 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
    • C08F283/02—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonates or saturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/08—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D147/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J147/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers

Definitions

  • Aqueous resin compositions include paper coating / impregnation processing, textiles / non-woven fabrics, carpets, civil engineering and building materials, mortar cement, automobile parts, tire cords, paints, pastes, rustproof coatings, adhesives, plastic modifications, cosmetic puffs. , Electronic materials, adhesives (general, for rubber), coating / impregnation (non-woven / paper), fiber impregnation / reinforcing fiber processing (carpet, etc.), moisture-proof / water-resistant coating, cement / mortar, building material processing / wood bonding, synthetic leather , Artificial leather, gloves, contraceptives, ink acceptors, ink dispersants, etc.
  • Patent Document 1 describes an aqueous resin containing a block copolymer composed of a vinyl polymer segment and a polyurethane segment having an acid group and / or a polyurethane segment neutralized with a basic compound.
  • Patent Document 2 describes a composition containing a latex obtained by seed polymerization of a diene-based unsaturated monomer in the presence of a seed latex, and an aqueous polyurethane.
  • Patent Document 3 describes a resin composition containing a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer and another aqueous resin in the same micelle.
  • Japanese Unexamined Patent Publication No. 6-199968 Japanese Unexamined Patent Publication No. 2004-231852 Japanese Unexamined Patent Publication No. 2004-224868
  • the composite resin may be required to exhibit adhesiveness between dissimilar substrates after curing, even though it is homogeneous at the time of coating.
  • conventionally known composite resins have a main purpose of uniformly mixing different resins at the molecular level to form a coating film in a homogeneously mixed state, and the means for forming the coating film as described above is provided. unknown.
  • the present invention has been made in view of the above problems, and provides an aqueous resin composition capable of finally exhibiting adhesiveness between dissimilar substrates while being homogeneous at the time of coating. Is the subject.
  • an aqueous resin composition containing a composite resin the present inventors use a specific resin combination for the composite resin to segregate the resin by heating, although it is initially homogeneous, and finally a different type. It has been found that it is possible to form a coating film capable of exhibiting adhesiveness between the substrates of the above.
  • the present invention includes the following inventions.
  • aqueous resin composition of the present invention By using the aqueous resin composition of the present invention, it is possible to segregate the resin by heating while being homogeneous at the beginning, and finally to form a coating film capable of exhibiting adhesiveness between different types of substrates. It will be possible.
  • the aqueous resin composition of the present invention contains a composite resin (A) and an aqueous medium (B), and the composite resin (A) contains a vinyl polymer (A1) and a polyester resin (A2). ..
  • the vinyl polymer (A1) represents a polymer having a unit derived from the vinyl monomer (a).
  • the vinyl monomer (a) represents a compound having at least one polymerizable vinyl bond in one molecule.
  • the vinyl monomer (a) one kind or two or more kinds can be used, and examples thereof include a conjugated diene compound (a1) and other vinyl compounds (a2).
  • diene compound (a1) one kind or two or more kinds can be used, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1 , 3-hexadiene, 1,3-heptadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chlor-1,3-butadiene and the like. Be done.
  • the content of the conjugated diene compound (a1) is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, and the upper limit is 100, based on the total amount of the vinyl monomer (a). It is mass%.
  • the other vinyl compound (a2) one kind or two or more kinds can be used, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl.
  • the content of the other vinyl compound (a2) is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 10% by mass or more, based on the total amount of the vinyl monomer (a). It is 80% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less.
  • the total content of the conjugated diene compound (a1) and the other vinyl compound (a2) is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 80% by mass or more, based on the total amount of the vinyl monomer (a). Is 90% by mass or more, preferably 100% by mass or less.
  • the glass transition temperature of the vinyl polymer (A1) is preferably ⁇ 100 ° C. or higher, more preferably ⁇ 80 ° C. or higher, preferably 120 ° C. or lower, more preferably 100 ° C. or lower, still more preferably 50 ° C. or higher. Hereinafter, it is more preferably 25 ° C. or lower.
  • Tga represents the glass transition temperature (unit is absolute temperature) of the polymer composed of each vinyl monomer (a) used for the synthesis of the vinyl polymer (A1).
  • Wi represents the mass ratio of each vinyl monomer (a) in the raw material of the vinyl polymer (A1).
  • Tgi represents the glass transition temperature (unit: absolute temperature) of the homopolymer formed only from each vinyl monomer (a).
  • the content of the vinyl polymer (A1) is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 10% by mass or more, still more preferably 20% by mass in the composite resin (A). As described above, it is particularly preferably 30% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, still more preferably 50% by mass or less.
  • the polyester resin (A2) represents a resin in which the main chain is formed of a polyester skeleton, and is an esterification reaction product of a polyol (b1) and a polycarboxylic acid (b2); a cyclic ester compound such as ⁇ -caprolactone. Ring-opening polymers; examples thereof include copolymers thereof.
  • a low molecular weight polyol for example, a polyol having a molecular weight of 50 or more and less than 300
  • a polymer polyol polyol having a number average molecular weight of 300 or more
  • a polyol having a molecular weight of 50 or more and 300 or less can be used, and for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and the like.
  • An aliphatic polyol having 2 or more and 6 or less carbon atoms such as 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, and 1,3-butanediol; 1,4-cyclohexanediol, cyclohexanedi.
  • examples thereof include alicyclic structure-containing polyols such as methanol; bisphenol compounds such as bisphenol A and bisphenol F, and aromatic structure-containing polyols such as alkylene oxide adducts thereof.
  • polymer polyol examples include polyether polyols, polycarbonate polyols, polyolefin polyols and the like.
  • polyether polyol examples include those obtained by addition polymerization (ring-opening polymerization) of an alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator.
  • the initiator examples include ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, and 1,4-.
  • Linear diols such as butanediol and 1,6-hexanediol; Branched chain diols such as neopentyl glycol; Triols such as glycerin, trimethylolethane, trimethylolpropane and pyrogallol; polyols such as sorbitol, citrus sugar and aconit sugar.
  • Tricarboxylic acids such as aconitic acid, trimellitic acid, hemmellitic acid; phosphoric acid; polyamines such as ethylenediamine and diethylenetriamine; triisopropanolamine;phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1,2,3-propanetri Examples include thiol.
  • alkylene oxide examples include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.
  • polyether polyol it is preferable to use polyoxytetramethylene glycol obtained by addition polymerization (ring-opening polymerization) of tetrahydrofuran to the initiator.
  • polycarbonate polyol examples include a reaction product of a carbonic acid ester and a polyol; a reaction product of phosgene and bisphenol A and the like.
  • Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenylcarbonate and the like.
  • polyols examples include the polyols exemplified as the low molecular weight polyol; high molecular weight polyols such as polyether polyols (polyethylene glycol, polypropylene glycol, etc.) and polyester polyols (polyhexamethylene adipate, etc.) (for example). , Weight average molecular weight of 500 or more and 5,000 or less).
  • polystyrene polyol examples include polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, hydrogenated (hydrogenated) polyisoprene polyol, and the like.
  • polycarboxylic acid (b2) examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; Further, examples thereof include an anhydride or an ester-forming derivative of the aliphatic polycarboxylic acid and the aromatic polycarboxylic acid.
  • aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid
  • aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid
  • examples thereof include an anhydride or an ester-forming derivative of the aliphatic polycarboxylic acid and the aromatic polycarboxylic acid.
  • the polyester resin (A2) preferably has a hydrophilic group. Since the polyester resin (A2) has a hydrophilic group, the water dispersibility of the composite resin (A) can be improved.
  • hydrophilic group examples include anionic groups such as a carboxyl group and a sulfonic acid group; cationic groups such as a tertiary amino group and a quaternary ammonium group, and nonionic groups such as a polyoxyethylene group. Among them, those having an anionic group are preferable.
  • a method for imparting a hydrophilic group to the polyester resin (A2) a method using a compound having a hydrophilic group as the low molecular weight polyol or the polycarboxylic acid; esterification of the low molecular weight polyol and the polycarboxylic acid.
  • a reaction product a ring-opening polymer of a cyclic ester compound, a method of further adding a dicarboxylic acid anhydride and the like to these copolymers and the like.
  • hydrophilic low molecular weight polyol examples include hydroxy acids such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbuty acid, and 2,2-dimethylolvaleric acid; And the reaction product of the polyol having the carboxy group and the polycarboxylic acid.
  • dicarboxylic acid anhydride examples include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic acid anhydride, chlorendic acid anhydride, and methyltetrahydroanhydride.
  • examples thereof include phthalic acid, glutaric anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride and the like.
  • polycarboxylic acid having a sulfonic acid group examples include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, 5-sulfoisophthalate monoalkyl, and 5-.
  • a dicarboxylic acid having a sulfonic acid group such as dialkyl sulfoisophthalate; an alkali metal salt of the dicarboxylic acid having the sulfonic acid group and the like can be mentioned.
  • Examples of the low molecular weight polyol having a cationic group include N-methyl-diethanolamine; a polyol having a tertiary amino group such as a polyol obtained by reacting a compound having two epoxies in one molecule with a secondary amine. Can be mentioned.
  • polyol having a nonionic group examples include a polyol having a polyoxyethylene structure.
  • the polyester resin (A2) preferably contains an aromatic ring from the viewpoint of adhesion to the base material and the like. By using a raw material having an aromatic ring, the polyester resin (A2) can be made to have an aromatic ring.
  • the content of the aromatic ring in the polyester resin (A2) is, for example, preferably 0.01 mol / kg or more, more preferably 0.05 mol / kg or more, more preferably 0.1 mol / kg or more, and preferably 0.1 mol / kg or more. It is 15 mol / kg or less, more preferably 10 mol / kg or less, still more preferably 8 mol / kg or less, and even more preferably 5 mol / kg or less.
  • the acid value of the polyester resin (A2) is, for example, 0.1 mgKOH / g or more, preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, preferably 100 mgKOH / g or less, and more preferably 80 mgKOH / g or less. It is more preferably 50 mgKOH / g or less, and even more preferably 30 mgKOH / g or less.
  • the weight average molecular weight of the polyester resin (A2) is preferably 500 or more, more preferably 1,000 or more, still more preferably 3,000 or more, preferably 1,000,000 or less, and more preferably 500,000. Below, it is more preferably 100,000 or less.
  • the glass transition temperature of the polyester resin (A2) is preferably ⁇ 80 ° C. or higher, more preferably ⁇ 50 ° C. or higher, further preferably ⁇ 20 ° C. or higher, preferably 140 ° C. or lower, more preferably 120 ° C. or lower, More preferably, it is 100 ° C. or lower.
  • the motility of the polyester resin (A2) is good, and it is easy to exert the effect of the present invention.
  • the glass transition temperature of the polyester resin (A2) can be measured by a differential scanning calorimeter (DSC).
  • the content of the vinyl polymer (A1) and the polyester resin (A2) in the composite resin (A) is preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.005 or more, based on the mass. Is 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, preferably 3 or less, more preferably 2 or less, still more preferably 1 or less.
  • 1 part by mass of the vinyl polymer (A1) it is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and preferably 100 parts by mass or less. It is more preferably 10 parts by mass or less, still more preferably 3 parts by mass or less.
  • the total content of the vinyl polymer (A1) and the polyester resin (A2) is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more in the composite resin (A). Yes, the upper limit is 100% by mass.
  • the gel fraction of the composite resin (A) is preferably 0.01% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, still more preferably 10% by mass or more, and the upper limit is It may be 100% by mass, for example, 90% by mass or less, and further may be 80% by mass or less.
  • the gel fraction of the composite resin (A) can be measured by, for example, the following method.
  • the solvent-insoluble component of the sample is separated by filtering with an 80 mesh wire mesh, dried at 110 ° C. for 1 hour, and then weighed to give G2.
  • the value obtained based on the following formula is defined as the gel fraction.
  • Gel fraction (% by mass) (G2 / G1) x 100
  • the composite resin (A) it is preferable that at least a part of the surface of the vinyl polymer (A1) is covered with the polyester resin (A2), and the surface of the vinyl polymer (A1) is covered with the polyester resin (A1). It is preferable that the layer of A2) is formed.
  • the vinyl polymer (A1) is generally highly hydrophobic and difficult to disperse in water as it is, but the polyester resin (A2) covers at least a part of the surface of the vinyl polymer (A1). By doing so, the dispersibility in the aqueous medium becomes good.
  • the vinyl polymer (A1) and the polyester resin (A2) may or may not be chemically bonded.
  • the composite resin can be produced by polymerizing the vinyl monomer (a) in the aqueous medium (B) described later in the presence of the polyester resin (A2). Since the vinyl monomer (a) is hydrophobic, at least a part of the vinyl monomer (a) is made of the polyester resin (B2) by coexisting with the polyester resin (A2) in the aqueous medium (B). ), And the polymerization reaction is carried out in this state to produce the composite resin (A) of the present invention.
  • the polyester resin (A2) is subjected to polymerization of the vinyl monomer (a) in a state of being dispersed in the aqueous medium (B) (preliminary dispersion liquid).
  • the pre-dispersion liquid in which the polyester resin (A2) is dispersed in the aqueous medium (B) reacts with the polyol (b1) and the polycarboxylic acid (b2), for example, in the absence of a solvent or in the presence of an organic solvent. It can be manufactured by allowing it to be produced.
  • the organic solvent may be partially or wholly removed by distillation under reduced pressure or the like during or after the production of the polyester resin (A2).
  • the additive (C) described later may coexist or the additive (C) may be added after the polymerization reaction, if necessary.
  • a radical polymerization initiator When polymerizing the vinyl monomer (a), it is preferable to allow a radical polymerization initiator to coexist.
  • a photopolymerization initiator and a thermal polymerization initiator can be used.
  • the photopolymerization initiator include benzophenone, benzyl, Michler ketone, thioxanthone, anthraquinone, benzoin, dialkoxyacetophenone, acyloxime ester, benzylketal, hydroxyalkylphenone, and halogenoketone.
  • the photopolymerization initiator may be used in combination with a tertiary amine such as methylamine, diethanolamine, N-methyldiethanolamine or tributylamine, if necessary.
  • a tertiary amine such as methylamine, diethanolamine, N-methyldiethanolamine or tributylamine
  • thermal polymerization initiator examples include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis (2-methylpropionamidine).
  • Azo compounds such as hydrochloride, 4,4'-azobis (4-cyano) valerate, 2,2'-azobis (2-amidinopropane) dihydrochloride; benzoyl peroxide, tert-butyl hydroperoxide, tert-butyl.
  • Peroxypivalate tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide, di-tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide , Lauroyl peroxide, decanoyle peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, cumene hydroperoxide, paramentan hydroperoxide, etc.
  • Organic peroxides; thermal polymerization initiators such as inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate can be used.
  • the amount of the radical polymerization initiator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, still more preferably 0.5 part by mass or more with respect to 100 parts by mass of the total of the vinyl compound. It is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less.
  • the composite resin (A) is preferably dispersed in the aqueous medium (B).
  • the dispersed state of the composite resin (A) can be confirmed, for example, by the presence or absence of a precipitate in the aqueous resin composition.
  • the content of the composite resin (A) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 70% by mass or less in the aqueous resin composition. It is preferably 60% by mass or less, more preferably 50% by mass or less.
  • Examples of the aqueous medium (B) include water, an organic solvent miscible with water, and a mixture thereof.
  • the organic solvent to be mixed with water one kind or two or more kinds can be used, and for example, alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, 1,2-propylene glycol and 1,3-butylene glycol can be used.
  • Ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol-n-butyl ether, diethylene glycol-n-butyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene Glycol ether solvents such as glycol-n-butyl ether and tripropylene glycol methyl ether; lactam solvents such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; amide solvents such as N, N-dimethylformamide and the like. Therefore, an alcohol solvent is preferable.
  • the aqueous medium (B) is preferably water alone or a mixture of water and an organic solvent miscible with water, and more preferably only water, in consideration of safety and reduction of environmental load.
  • the content of water is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more in 100% by mass of the aqueous medium (B).
  • the content of the aqueous medium (B) is preferably 30% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 70% by mass or less, based on 100% by mass of the total amount of the aqueous resin composition.
  • the aqueous resin composition of the present invention further comprises a cross-linking agent, a surfactant, a plasticizer, an antioxidant, a wax, a light stabilizer, a flow conditioner, a dye, a leveling agent, a rhology control agent, an ultraviolet absorber, and an antioxidant.
  • a cross-linking agent e.g., a cross-linking agent, a surfactant, a plasticizer, an antioxidant, a wax, a light stabilizer, a flow conditioner, a dye, a leveling agent, a rhology control agent, an ultraviolet absorber, and an antioxidant.
  • Photocatalytic compounds, inorganic pigments, organic pigments, extender pigments, curing agents, curing catalysts, emulsifiers, dispersion stabilizers and the like may be contained.
  • the content of the additive (C) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 1 part by mass or less with respect to 100 parts by mass of the composite resin (A).
  • the water-based resin composition of the present invention is initially homogeneous, it can finally form a coating film having a hydrophobic surface, and can be used for paper coating / impregnation processing, fibers / non-woven fabrics, carpets, and civil engineering and building materials.
  • Mortal cement Mortal cement, automotive parts, tire cords, paints, pastes, rustproof coatings, adhesives, plastic modifications, cosmetic puffs, electronic materials, adhesives (general), coatings / impregnations (non-woven / paper), fiber impregnations -Suitable for reinforcing fiber processing (carpet, etc.), moisture-proof / water-resistant coating, cement / mortar, building material processing / wood adhesive, synthetic leather, artificial leather, gloves, contraception, ink accepting agent, ink dispersant tool, etc.
  • a polycondensation reaction was carried out for 12 hours until the resin (A2-1) was obtained.
  • Aqueous polyester resin composition (1) was prepared. (Acid value: 12.3 mgKOH / g Aromatic ring amount: 3.8 mol / kg)
  • Aqueous polyester resin composition (2) was prepared. (Acid value: 6.7 mgKOH / g Aromatic ring amount: 4.5 mol / kg)
  • the polymerization reaction was carried out with stirring to obtain a polyester resin (A2-3).
  • a polyester resin (A2-3) Next, while stirring and dissolving 100 parts by mass of the polyester resin (A2-3) in 200 parts by mass of methyl ethyl ketone at 60 ° C., 3 parts by mass of triethylamine was added, and then 367 parts by mass of ion-exchanged water was slowly added to carry out water solubilization. .. Then, under reduced pressure, methyl ethyl ketone was removed at 30 to 50 ° C. to prepare an aqueous polyester resin composition (3) having a non-volatile content of 25.0% by mass. (Acid value: 16.2 mgKOH / g Aromatic ring amount: 4.6 mol / kg)
  • Synthetic Example 4 Synthesis of Synthetic Rubber Latex Resin (1)
  • Newcol 261A manufactured by Nippon Embroidery Co., Ltd.
  • ion-exchanged water 200 parts by mass of ion-exchanged water as an emulsifier
  • 79 parts by mass of butadiene, 19 parts by mass of styrene, and 2 parts by mass of acrylic acid were added to 0.5 parts by mass of ammonia persulfate (APS).
  • a synthetic rubber latex having a solid content of 45% by mass (A1-1) containing a vinyl polymer (A1-1) was subjected to a reaction under the conditions of batch monomer emulsion polymerization (reaction temperature 60 ° C.) in parts by mass and then concentrated to remove unreacted monomers. 1) was obtained.
  • Example 1 Synthesis of latex composite polyester resin (1)
  • 137 parts by mass of ion-exchanged water was added to 308.9 parts by mass of the aqueous polyester resin composition (1) obtained in Synthesis Example 1, and 33.1 parts by mass of isoprene was monomerized with 0.3 parts by mass of ammonia persulfate (APS).
  • APS ammonia persulfate
  • the reaction was carried out under the conditions of batch emulsification polymerization (reaction temperature 70 ° C.), then concentration was carried out to remove unreacted monomers, and after adjusting the water content, a latex composite polyester resin (1) having a solid content of 30% by mass was obtained.
  • Example 2 Synthesis of latex composite polyester resin (2)
  • 187 parts by mass of ion-exchanged water was added to 223.8 parts by mass of the aqueous polyester resin composition (2) obtained in Synthesis Example 2, and 53.7 parts by mass of isoprene and 13.4 parts by mass of methyl methacrylate were added to ammonia persulfate (13.4 parts by mass).
  • APS Reacted under the conditions of monomer batch emulsification polymerization (reaction temperature 70 ° C.) with 0.5 parts by mass, then concentrated to remove unreacted monomers, adjusted the water content, and then made a latex composite with a solid content of 35% by mass.
  • a polyester resin (2) was obtained.
  • Example 3 Synthesis of latex composite polyester resin (3)
  • 137 parts by mass of ion-exchanged water was added to 308.9 parts by mass of the aqueous polyester resin composition (3) obtained in Synthesis Example 3, and 33.1 parts by mass of butadiene was monomerized with 0.3 parts by mass of ammonia persulfate (APS).
  • APS ammonia persulfate
  • the reaction was carried out under the conditions of batch emulsification polymerization (reaction temperature 70 ° C.), then concentration was carried out to remove unreacted monomers, and after adjusting the water content, a latex composite polyester resin (3) having a solid content of 30% by mass was obtained.
  • Example 4 Synthesis of latex composite polyester resin (4)
  • 125 parts by mass of ion-exchanged water was added to 313.5 parts by mass of the aqueous polyester resin composition (2) obtained in Synthesis Example 2, and 28.2 parts by mass of butadiene and 12.1 parts by mass of glycidyl methacrylate were added to ammonia persulfate (12.1 parts by mass).
  • APS Reacted under the conditions of monomer batch emulsification polymerization (reaction temperature 70 ° C.) with 0.3 parts by mass, then concentrated to remove unreacted monomers, adjusted the water content, and then made a latex composite with a solid content of 35% by mass.
  • a polyester resin (4) was obtained.
  • Example 5 Synthesis of latex composite polyester resin (5)
  • aqueous polyester resin composition (2) obtained in Synthesis Example 2 124.9 parts by mass of ion-exchanged water was added, and 12.1 parts by mass of isoprene and 28.2 parts by mass of methyl methacrylate were persulfated.
  • APS ammonia
  • concentration to remove unreacted monomers was performed, and after adjusting the water content, the solid content was 45% by mass.
  • a latex composite polyester resin (5) was obtained.
  • the aqueous resin composition was applied to a polyethylene terephthalate (PET) substrate and dried at 100 ° C. for 20 seconds.
  • PET polyethylene terephthalate
  • An ABS base material or a polyvinyl chloride (PVC) base material was attached to the coated surface, and after heat-treating at 100 ° C. for 3 minutes again, PET and the ABS or PVC base material were peeled off, and the state of the peeled base material was observed. .. ⁇ : PET, SBR, or PVC base material was destroyed. Or it did not come off.
  • Adhesiveness could be confirmed between PET and the SBR / PVC base material, but the adhesive layer remained only on either the PET or SBR / PVC base material.
  • X Adhesiveness could hardly be confirmed between PET and the SBR / PVC base material, and the adhesive layer remained only on either the PET or SBR / PVC base material.
  • a coating film was prepared on a polypropylene (PP) film substrate (thickness: 150 ⁇ m), dried, and a tensile test was performed using the obtained dried coating film (film). It was pulled at a tensile speed of 300 mm / min, and the elongation rate and strength with respect to its own length at break were measured.
  • PP polypropylene
  • a coating film was prepared on a PP substrate (thickness: 150 ⁇ m), dried, and the dried coating film (film) obtained by peeling was subjected to a durability test against methyl ethyl ketone (MEK). Specifically, the obtained dry coating film was immersed in methyl ethyl ketone at room temperature for one day, the weight after immersion was subtracted from the weight before immersion to obtain the elution amount, and this was divided by the weight of the coating film before immersion. , The elution rate.
  • MEK methyl ethyl ketone
  • a coating film was prepared on a PP substrate (thickness: 150 ⁇ m), dried, and the dried coating film (film) obtained by peeling was subjected to a durability test against water. Specifically, the obtained dry coating film was immersed in water at room temperature for one day, and the weight after immersion was subtracted from the weight before immersion to obtain the elution amount. The elution amount was divided by the weight of the impression coating film before immersion to obtain the elution rate. Further, the area of the dry coating film before immersion was subtracted from the area of the dry coating film after immersion to obtain the swelling area, and the swelling area was divided by the area of the dry coating film before immersion to obtain the swelling rate.
  • Examples 1 to 5 are examples of the present invention, and although they are homogeneous at the beginning, the resin is segregated by heating, and finally, a coating film capable of exhibiting adhesiveness between different types of substrates is formed. It was possible to make it.
  • Comparative Example 1 is an example in which the vinyl polymer (A1) is not contained, and the adhesiveness between different kinds of substrates is poor.
  • Comparative Example 2 is an example in which the vinyl polymer (A1) and the polyester resin (A2) are not composited, and in particular, the adhesiveness between PET and PVC was not sufficiently satisfactory.
  • Comparative Example 3 is an example in which the polyester resin (A2) is not contained, and the adhesiveness between different kinds of substrates is poor.

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Abstract

The present invention provides an aqueous resin composition which contains a composite resin (A) and an aqueous medium (B), wherein the composite resin (A) contains a vinyl polymer (A1) and a polyester resin (A2). This aqueous resin composition is capable of forming a coating film that is initially homogeneous and finally forms a hydrophobic surface; and this aqueous resin composition is suitable for paper coating/impregnation, fibers/nonwoven fabrics, carpets, civil engineering building materials, mortar cement, automobile components, tire cords, coating materials, pastes, rust preventive coating, adhesives, plastic modification, powder puffs, electronic materials, adhesives (for general use), coating/impregnation (nonwoven fabric/paper), fiber impregnation/reinforcing fiber processing (carpets and the like), moisture-proofing/water-resistant coating, cement/mortar, building material processing/wooden material bonding, synthetic leather, artificial leather, gloves, contraception, receiving agents for inks, dispersant materials for inks and the like.

Description

水性樹脂組成物、コーティング剤、接着剤、塗膜、接着層及び積層体Aqueous resin compositions, coatings, adhesives, coatings, adhesive layers and laminates
　水性樹脂組成物は、紙塗工・含浸加工、繊維・不織布、カーペット、土木建材、モルタルセメント、自動車用部品、タイヤコード、塗料、ペースト、防錆コーティング、接着剤、プラスチック改質、化粧用パフ、電子材料、接着剤（一般、ゴム用）、コーティング・含浸（不織布・紙）、繊維含浸・補強繊維加工(カーペット等）、防湿・耐水コーティング、セメント・モルタル、建材加工・木質接着、合成皮革、人工皮革、手袋、避妊具、インキ用受理剤、インキ用分散剤等の多様な用途に用いられている。 Aqueous resin compositions include paper coating / impregnation processing, textiles / non-woven fabrics, carpets, civil engineering and building materials, mortar cement, automobile parts, tire cords, paints, pastes, rustproof coatings, adhesives, plastic modifications, cosmetic puffs. , Electronic materials, adhesives (general, for rubber), coating / impregnation (non-woven / paper), fiber impregnation / reinforcing fiber processing (carpet, etc.), moisture-proof / water-resistant coating, cement / mortar, building material processing / wood bonding, synthetic leather , Artificial leather, gloves, contraceptives, ink acceptors, ink dispersants, etc.
　前記水性樹脂組成物には、用途に応じ、多様な特性が求められており、異なる樹脂を組み合わせた水性樹脂組成物が提案されている。例えば、特許文献１には、ビニル重合体セグメントと、酸基および／又は塩基性化合物で中和された酸基を有するポリウレタンセグメントとから構成されるブロック共重合体を含む水性樹脂が記載されている。また特許文献２には、ジエン系不飽和単量体をシードラテックス存在下でシード重合して得られるラテックスと、水性ポリウレタンとを含む組成物が記載されている。特許文献３には、同一ミセル内に、水酸基含有共役ジエン重合体の水素添加誘導体と、他の水性樹脂とを含有する樹脂組成物が記載されている。 The aqueous resin composition is required to have various properties depending on the intended use, and an aqueous resin composition in which different resins are combined has been proposed. For example, Patent Document 1 describes an aqueous resin containing a block copolymer composed of a vinyl polymer segment and a polyurethane segment having an acid group and / or a polyurethane segment neutralized with a basic compound. There is. Further, Patent Document 2 describes a composition containing a latex obtained by seed polymerization of a diene-based unsaturated monomer in the presence of a seed latex, and an aqueous polyurethane. Patent Document 3 describes a resin composition containing a hydrogenated derivative of a hydroxyl group-containing conjugated diene polymer and another aqueous resin in the same micelle.
特開平６－１９９９６８号公報Japanese Unexamined Patent Publication No. 6-199968 特開２００４－２３１８５２号公報Japanese Unexamined Patent Publication No. 2004-231852 特開２００４－２２４８６８号公報Japanese Unexamined Patent Publication No. 2004-224868
　前記の複合樹脂は、塗工時は、均質でありながらも、硬化後に、異種基材間の接着性を発現することを要求される場合がある。しかしながら、従来から知られる複合樹脂は、異なる樹脂を分子レベルで均質に混合し、その均質混合状態の塗膜を形成させることを主目的としており、上記のような塗膜を形成する手段については知られていない。本発明は、前記課題に鑑みてなされたものであり、塗工時は均質でありながら、最終的には異種基材間の接着性を発現することが可能な水性樹脂組成物を提供することを課題とする。 The composite resin may be required to exhibit adhesiveness between dissimilar substrates after curing, even though it is homogeneous at the time of coating. However, conventionally known composite resins have a main purpose of uniformly mixing different resins at the molecular level to form a coating film in a homogeneously mixed state, and the means for forming the coating film as described above is provided. unknown. The present invention has been made in view of the above problems, and provides an aqueous resin composition capable of finally exhibiting adhesiveness between dissimilar substrates while being homogeneous at the time of coating. Is the subject.
　本発明者らは、複合樹脂を含む水性樹脂組成物において、複合樹脂に特定の樹脂の組合せを用いることで、当初は均質でありながらも、加熱により樹脂を偏析させ、最終的には異なる種類の基材間の接着性を発現できる塗膜を形成させることが可能となることを見出した。 In an aqueous resin composition containing a composite resin, the present inventors use a specific resin combination for the composite resin to segregate the resin by heating, although it is initially homogeneous, and finally a different type. It has been found that it is possible to form a coating film capable of exhibiting adhesiveness between the substrates of the above.
　すなわち、本発明は、以下の発明を含む。
［１］複合樹脂（Ａ）及び水性媒体（Ｂ）を含み、前記複合樹脂（Ａ）が、ビニル重合体（Ａ１）とポリエステル樹脂（Ａ２）とを含むものである水性樹脂組成物。
［２］前記ポリエステル樹脂（Ａ２）の酸価が、０．１ｍｇＫＯＨ／ｇ以上１００ｍｇＫＯＨ／ｇ以下である［１］記載の水性樹脂組成物。
［３］前記ポリエステル樹脂（Ａ２）に含まれる芳香環量が、０．０１ｍｏｌ／ｋｇ以上２０ｍｏｌ／ｋｇ以下である［１］又は［２］記載の水性樹脂組成物。
［４］前記ビニル重合体（Ａ１）と、前記ポリエステル樹脂（Ａ２）との質量比（（Ａ１）／（Ａ２））が、０．００１以上３以下である［１］～［３］のいずれか１つに記載の水性樹脂組成物。
［５］［１］～［４］のいずれか１つに記載の水性樹脂組成物を含むコーティング剤。
［６］［１］～［４］のいずれか１つに記載の水性樹脂組成物を含む接着剤。
［７］［１］～［４］のいずれか１項記載の水性樹脂組成物から形成される塗膜。
［８］［１］～［４］のいずれか１項記載の水性樹脂組成物から形成される接着層。
［９］［７］記載の塗膜又は［８］記載の接着層を有する積層体。 That is, the present invention includes the following inventions.
[1] An aqueous resin composition containing a composite resin (A) and an aqueous medium (B), wherein the composite resin (A) contains a vinyl polymer (A1) and a polyester resin (A2).
[2] The aqueous resin composition according to [1], wherein the polyester resin (A2) has an acid value of 0.1 mgKOH / g or more and 100 mgKOH / g or less.
[3] The aqueous resin composition according to [1] or [2], wherein the amount of aromatic ring contained in the polyester resin (A2) is 0.01 mol / kg or more and 20 mol / kg or less.
[4] Any of [1] to [3] in which the mass ratio ((A1) / (A2)) of the vinyl polymer (A1) to the polyester resin (A2) is 0.001 or more and 3 or less. The aqueous resin composition according to one.
[5] A coating agent containing the aqueous resin composition according to any one of [1] to [4].
[6] An adhesive containing the aqueous resin composition according to any one of [1] to [4].
[7] A coating film formed from the aqueous resin composition according to any one of [1] to [4].
[8] An adhesive layer formed from the aqueous resin composition according to any one of [1] to [4].
[9] A laminate having the coating film according to [7] or the adhesive layer according to [8].
　本発明の水性樹脂組成物を用いることで、当初は均質でありながらも、加熱により樹脂を偏析させ、最終的には異なる種類の基材間の接着性を発現できる塗膜を形成させることが可能となる。 By using the aqueous resin composition of the present invention, it is possible to segregate the resin by heating while being homogeneous at the beginning, and finally to form a coating film capable of exhibiting adhesiveness between different types of substrates. It will be possible.
　本発明の水性樹脂組成物は、複合樹脂（Ａ）と水性媒体（Ｂ）とを含むものであり、前記複合樹脂（Ａ）は、ビニル重合体（Ａ１）とポリエステル樹脂（Ａ２）とを含む。 The aqueous resin composition of the present invention contains a composite resin (A) and an aqueous medium (B), and the composite resin (A) contains a vinyl polymer (A1) and a polyester resin (A2). ..
　前記ビニル重合体（Ａ１）は、ビニル単量体（ａ）に由来する単位を有する重合体を表す。前記ビニル単量体（ａ）は、１分子中に、少なくとも１つの重合性ビニル結合を有する化合物を表す。前記ビニル単量体（ａ）としては、１種又は２種以上を用いることができ、共役ジエン化合物（ａ１）、その他のビニル化合物（ａ２）などが挙げられる。 The vinyl polymer (A1) represents a polymer having a unit derived from the vinyl monomer (a). The vinyl monomer (a) represents a compound having at least one polymerizable vinyl bond in one molecule. As the vinyl monomer (a), one kind or two or more kinds can be used, and examples thereof include a conjugated diene compound (a1) and other vinyl compounds (a2).
　前記ジエン化合物（ａ１）としては、１種又は２種以上を用いることができ、例えば、１，３－ブタジエン、イソプレン、２，３－ジメチル－１，３－ブタジエン、１，３－ペンタジエン、１，３－ヘキサジエン、１，３－ヘプタジエン、２，３－ジメチルブタジエン、２－フェニル－１，３－ブタジエン、３－メチル－１，３－ペンタジエン、２－クロル－１，３－ブタジエン等が挙げられる。 As the diene compound (a1), one kind or two or more kinds can be used, for example, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1 , 3-hexadiene, 1,3-heptadiene, 2,3-dimethylbutadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, 2-chlor-1,3-butadiene and the like. Be done.
　前記共役ジエン化合物（ａ１）の含有率は、ビニル単量体（ａ）全量中、好ましくは１質量％以上、より好ましくは１０質量％以上、さらに好ましくは３０質量％以上であり、上限は１００質量％である。 The content of the conjugated diene compound (a1) is preferably 1% by mass or more, more preferably 10% by mass or more, still more preferably 30% by mass or more, and the upper limit is 100, based on the total amount of the vinyl monomer (a). It is mass%.
　前記その他のビニル化合物（ａ２）としては、１種又は２種以上を用いることができ、例えば、メチル（メタ）アクリレート、エチル（メタ）アクリレート、プロピル（メタ）アクリレート、ブチル（メタ）アクリレート、イソブチル（メタ）アクリレート、ｔｅｒｔ－ブチル（メタ）アクリレート、ペンチル（メタ）アクリレート、３－メチルブチル（メタ）アクリレート、ネオペンチル（メタ）アクリレート、イソアミル（メタ）アクリレート、ヘキシル（メタ）アクリレート、ヘプチル（メタ）アクリレート、オクチル（メタ）アクリレート、２－エチルヘキシル（メタ）アクリレート、イソオクチル（メタ）アクリレート、ノニル（メタ）アクリレート、ドデシル（メタ）アクリレート、トリデシル（メタ）アクリレート、ステアリル（メタ）アクリレート、イソステアリル（メタ）アクリレート、ヘキサデシル（メタ）アクリレート、等の炭素原子数４～２２のアルキル（メタ）アクリレート；
　シクロペンチル（メタ）アクリレート、シクロヘキシル（メタ）アクリレート、イソボルニル（メタ）アクリレート等の炭素原子数６～２０のシクロアルキル（メタ）アクリレート；
　フェニル（メタ）アクリレート等のアリル（メタ）アクリレート；
　ベンジル（メタ）アクリレート、フェネチル（メタ）アクリレート等の炭素原子数１０～２０のアラルキル（メタ）アクリレート；
　フェノキシエチル（メタ）アクリレート等のアリルオキシアルキル（メタ）アクリレート；
　クロトン酸メチル、クロトン酸エチル等のクロトン酸アルキルエステル；
　ジメチルマレート、ジブチルマレート、ジメチルフマレート、ジブチルフマレート、ジメチルイタコネート、ジブチルイタコネート等の不飽和ジカルボン酸アルキルエステル；
　スチレン、ｐ－ｔｅｒｔ－ブチルスチレン、α－メチルスチレン、ビニルトルエン、ビニルピリジン、クロロスチレン、クロロメチルスチレン等の芳香族ビニルモノマー；
　（メタ）アクリロニトリル、クロトノニトリル、（メタ）アクリルアミド、Ｎ－メチル（メタ）アクリルアミド、Ｎ－イソプロピル（メタ）アクリルアミド、Ｎ－ヒドロキシエチル（メタ）アクリルアミド、Ｎ－メチロール（メタ）アクリルアミド、Ｎ－メトキシエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチル（メタ）アクリルアミド、Ｎ，Ｎ－ジメチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジメチルアミノプロピル（メタ）アクリルアミド、Ｎ，Ｎ－ジエチルアミノエチル（メタ）アクリレート、Ｎ，Ｎ－ジエチルアミノプロピル（メタ）アクリレート、Ｎ－（メタ）アクリロイルモルホリン、Ｎ－（メタ）アクリロイルピロリジン、Ｎ－ビニルホルムアミド、Ｎ－ビニルピロリドン、Ｎ－ビニルイミダゾール、Ｎ－ビニルカルバゾール、Ｎ－ビニルキノリン、Ｎ－ビニルピペリジン等の窒素原子含有モノマー（好ましくは１置換又は２置換の（メタ）アクリルアミド（置換基が結合して環を形成しているものも含む））及び該窒素原子含有モノマーの塩化メチル塩；
　フッ化ビニル、フッ化ビニリデン、テトラフルオロエチレン、クロロトリフルオロエチエレン、ヘキサフルオロプロピレン、塩化ビニル、塩化ビニリデン等のハロゲン化オレフィン；エチレン、プロピレン、イソブチレン、１－ブテン等のα－オレフィン；
　酢酸ビニル、プロピオン酸ビニル、ピバリン酸ビニル、バーサティック酸ビニル、安息香酸ビニル、ネオデカン酸ビニル等のカルボン酸ビニルエステル；
　メチルビニルエーテル、エチルビニルエーテル、ｎ－ブチルビニルエーテル、イソブチルビニルエーテル等のアルキルビニルエーテル；シクロヘキシルビニルエーテル等のシクロアルキルビニルエーテル；
　アクロレイン、メチルビニルケトン等のカルボニル基含有モノマー；
　ポリエチレングリコール（メタ）アクリレート、メトキシポリエチレングリコール（メタ）アクリレート、ポリエチレングリコールポリプロピレングリコール共重合（メタ）アクリレート、メトキシポリエチレングリコールポリプロピレングリコール共重合（メタ）アクリレート、ポリエチレングリコールポリテトラメチレングリコール共重合（メタ）アクリレート、メトキシポリエチレングリコールポリテトラメチレングリコール共重合（メタ）アクリレート等のポリオキシエチレン基含有（メタ）アクリルモノマー；
　パーフルオロシクロヘキシル（メタ）アクリレート、ジ－パーフルオロシクロヘキシルフマレート、Ｎ－イソプロピルフルオロオクタンスルホン酸アミドエチル（メタ）アクリレート等のフルオロアルキル基含有モノマー；
　無水マレイン酸、無水シトラコン酸、無水メサコン酸、無水イタコン酸、テトラヒドロ無水フタル酸等の不飽和ジカルボン酸類無水物；
　グリシジル（メタ）アクリレート、アリルグリシジルエーテル、テトラヒドロフルフリル（メタ）アクリレート等の環状エーテル含有モノマー；
ビニリトリクロロシラン、ビニルトリエトキシシラン、ビニルトリス（β－メトキシエトキシ）シラン、γ－（メタ）アクリロキシプロピルトリメトキシシラン等のシリル基含有モノマー；
　２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、２－ヒドロキシエチルビニルエーテル、４－ヒドロキシブチルビニルエーテル、２－ヒドロキシエチルアリルエーテル等のヒドロキシ基含有モノマー；
　ビニルスルホン酸、３－アクリロキシプロパン－１－スルホン酸、３－アクリロキシオクチルオキシベンゼンスルホン酸、３－アクリロキシベンゼンジアゾスルホン酸、３－アクリロキシアゾベンゼン－４’－スルホン酸、２－アクリロイルアミノ－２－メチルプロパン－１－スルホン酸、２－アクリロイルアミド－２－メチルプロパンスルホン酸、アクリロニトリル－ｔｅｒｔ－ブチルスルホン酸等のビニル基含有スルホン酸化合物並びにそれらの塩などが挙げられる。 As the other vinyl compound (a2), one kind or two or more kinds can be used, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl. (Meta) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, 3-methylbutyl (meth) acrylate, neopentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate , Octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, dodecyl (meth) acrylate, tridecyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) Alkyl (meth) acrylates having 4 to 22 carbon atoms such as acrylates and hexadecyl (meth) acrylates;
Cycloalkyl (meth) acrylates having 6 to 20 carbon atoms such as cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, and isobornyl (meth) acrylate;
Allyl (meth) acrylates such as phenyl (meth) acrylate;
Aralkyl (meth) acrylate having 10 to 20 carbon atoms such as benzyl (meth) acrylate and phenethyl (meth) acrylate;
Allyloxyalkyl (meth) acrylates such as phenoxyethyl (meth) acrylates;
Crotonic acid alkyl esters such as methyl crotonate and ethyl crotonate;
Unsaturated dicarboxylic acid alkyl esters such as dimethylmalate, dibutylmalate, dimethylfumarate, dibutylfumarate, dimethylitaconate, dibutylitaconate;
Aromatic vinyl monomers such as styrene, p-tert-butylstyrene, α-methylstyrene, vinyltoluene, vinylpyridine, chlorostyrene, chloromethylstyrene;
(Meta) acrylonitrile, crotononitrile, (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, N-methylol (meth) acrylamide, N-methoxy Ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate, N- (meth) acryloylmorpholine, N- (meth) acryloylpyrrolidin, N-vinylformamide, N-vinylpyrrolidone, N- Nitrogen atom-containing monomers such as vinyl imidazole, N-vinylcarbazole, N-vinylquinoline, N-vinylpiperidin (preferably mono- or di-substituted (meth) acrylamides (substituents bonded to form a ring) )) And the methyl chloride salt of the nitrogen atom-containing monomer;
Halogenated olefins such as vinyl fluoride, vinylidene fluoride, tetrafluoroethylene, chlorotrifluoroethane, hexafluoropropylene, vinyl chloride and vinylidene chloride; α-olefins such as ethylene, propylene, isobutylene and 1-butene;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl versatic acid, vinyl benzoate, vinyl neodecanoate;
Alkyl vinyl ethers such as methyl vinyl ethers, ethyl vinyl ethers, n-butyl vinyl ethers and isobutyl vinyl ethers; cycloalkyl vinyl ethers such as cyclohexyl vinyl ethers;
Carbonyl group-containing monomers such as acrolein and methyl vinyl ketone;
Polyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate, polyethylene glycol polypropylene glycol copolymer (meth) acrylate, methoxypolyethylene glycol polypropylene glycol copolymer (meth) acrylate, polyethylene glycol polytetramethylene glycol copolymer (meth) acrylate , Polyoxyethylene group-containing (meth) acrylic monomer such as methoxypolyethylene glycol polytetramethylene glycol copolymer (meth) acrylate;
Fluoroalkyl group-containing monomers such as perfluorocyclohexyl (meth) acrylate, diperfluorocyclohexyl fumarate, N-isopropylfluorooctane sulfonate amide ethyl (meth) acrylate;
Unsaturated dicarboxylic acids anhydrides such as maleic anhydride, citraconic anhydride, mesaconic anhydride, itaconic anhydride, tetrahydrophthalic anhydride;
Cyclic ether-containing monomers such as glycidyl (meth) acrylate, allyl glycidyl ether, and tetrahydrofurfuryl (meth) acrylate;
Cyril group-containing monomers such as vinylitrichlorosilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, and γ- (meth) acryloxypropyltrimethoxysilane;
2-Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, 2- Hydroxy group-containing monomers such as hydroxyethyl allyl ether;
Vinyl Sulfonic Acid, 3-AcryloxyPropane-1-sulfonic Acid, 3-Acryloxyoctyloxybenzene Sulfonic Acid, 3-Acryloxybenzenediazosulfonic Acid, 3-Acryloxyazobenzene-4'-Sulfonic Acid, 2-Acryloylamino Examples thereof include vinyl group-containing sulfonic acid compounds such as -2-methylpropane-1-sulfonic acid, 2-acryloylamide-2-methylpropanesulfonic acid, and acrylonitrile-tert-butylsulfonic acid, and salts thereof.
　前記その他のビニル化合物（ａ２）の含有率は、ビニル単量体（ａ）全量中、好ましくは１質量％以上、より好ましくは５質量％以上、さらに好ましくは１０質量％以上であり、好ましくは８０質量％以下、より好ましくは６０質量％以下、さらに好ましくは５０質量％以下である。 The content of the other vinyl compound (a2) is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and preferably 10% by mass or more, based on the total amount of the vinyl monomer (a). It is 80% by mass or less, more preferably 60% by mass or less, still more preferably 50% by mass or less.
　前記共役ジエン化合物（ａ１）及び前記その他のビニル化合物（ａ２）の合計の含有率は、ビニル単量体（ａ）全量中、好ましくは７０質量％以上、より好ましくは８０質量％以上、さらに好ましくは９０質量％以上であり、好ましくは１００質量％以下である。 The total content of the conjugated diene compound (a1) and the other vinyl compound (a2) is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 80% by mass or more, based on the total amount of the vinyl monomer (a). Is 90% by mass or more, preferably 100% by mass or less.
　前記ビニル重合体（Ａ１）のガラス転移温度は、好ましくは－１００℃以上であり、より好ましくは－８０℃以上であり、好ましくは１２０℃以下、より好ましくは１００℃以下、さらに好ましくは５０℃以下、いっそう好ましくは２５℃以下である。 The glass transition temperature of the vinyl polymer (A1) is preferably −100 ° C. or higher, more preferably −80 ° C. or higher, preferably 120 ° C. or lower, more preferably 100 ° C. or lower, still more preferably 50 ° C. or higher. Hereinafter, it is more preferably 25 ° C. or lower.
　前記ビニル重合体（Ａ１）のガラス転移温度Ｔｇ（Ａ１）は、下記式（ＦＯＸ式）により求められる絶対温度でのガラス転移温度Ｔｇaを摂氏温度に換算して求められる値を表す。
　１／Ｔｇa＝Σ（Ｗi／Ｔｇi）・・・ The glass transition temperature Tg (A1) of the vinyl polymer (A1) represents a value obtained by converting the glass transition temperature Tga at the absolute temperature obtained by the following formula (FOX formula) into a temperature in degrees Celsius.
1 / Tga = Σ (Wi / Tgi) ...
　上記式中、Ｔｇaは前記ビニル重合体（Ａ１）の合成に用いる各ビニル単量体（ａ）からなる重合体のガラス転移温度（単位は絶対温度）を表す。Ｗiは、各ビニル単量体（ａ）の、前記ビニル重合体（Ａ１）の原料中における質量割合を表す。Ｔｇiは、各ビニル単量体（ａ）のみから形成される単独重合体のガラス転移温度（単位は絶対温度）を表す。 In the above formula, Tga represents the glass transition temperature (unit is absolute temperature) of the polymer composed of each vinyl monomer (a) used for the synthesis of the vinyl polymer (A1). Wi represents the mass ratio of each vinyl monomer (a) in the raw material of the vinyl polymer (A1). Tgi represents the glass transition temperature (unit: absolute temperature) of the homopolymer formed only from each vinyl monomer (a).
　前記ＦＯＸ式の詳細は、ブレティン・オブ・ジ・アメリカン・フィジカル・ソサエティ・シリーズ２（Ｂｕｌｌｅｔｉｎ ｏｆ ｔｈｅ Ａｍｅｒｉｃａｎ Ｐｈｙｓｉｃａｌ Ｓｏｃｉｅｔｙ， Ｓｅｒｉｅｓ ２）、第１巻、第３号、第１２３頁（１９５６年）に記載されている。また、ＦＯＸ式で計算するための様々な単量体の単独重合体のガラス転移温度（Ｔｇi）は、例えば、塗装と塗料（塗料出版社、１０（Ｎｏ．３５８）、１９８２）に記載されている数値等を採用することができる。 Details of the FOX formula are described in Bulletin of the American Physical Society, Series 2, Volume 1, Issue 3, page 123 (1956). Has been done. Further, the glass transition temperature (Tgi) of homopolymers of various monomers for calculation by the FOX formula is described in, for example, paints and paints (Paints Publisher, 10 (No. 358), 1982). It is possible to adopt the numerical value etc.
　前記ビニル重合体（Ａ１）の含有率は、複合樹脂（Ａ）中、好ましくは０．１質量％以上、より好ましくは１質量％以上、さらに好ましくは１０質量％以上、いっそう好ましくは２０質量％以上、特に好ましくは３０質量％以上であり、好ましくは９０質量％以下、より好ましくは７０質量％以下、さらに好ましくは６０質量％以下、いっそう好ましくは５０質量％以下である。 The content of the vinyl polymer (A1) is preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 10% by mass or more, still more preferably 20% by mass in the composite resin (A). As described above, it is particularly preferably 30% by mass or more, preferably 90% by mass or less, more preferably 70% by mass or less, still more preferably 60% by mass or less, still more preferably 50% by mass or less.
　前記ポリエステル樹脂（Ａ２）は、主鎖が、ポリエステル骨格により形成されている樹脂を表し、ポリオール（ｂ１）とポリカルボン酸（ｂ２）とのエステル化反応物；ε－カプロラクトン等の環状エステル化合物の開環重合物；これらの共重合物などが挙げられる。 The polyester resin (A2) represents a resin in which the main chain is formed of a polyester skeleton, and is an esterification reaction product of a polyol (b1) and a polycarboxylic acid (b2); a cyclic ester compound such as ε-caprolactone. Ring-opening polymers; examples thereof include copolymers thereof.
　前記ポリオール（ｂ１）としては、低分子量ポリオール（例えば、分子量５０以上３００未満のポリオール）を用いることができ、ポリマーポリオール（数平均分子量３００以上のポリオール）を含んでいてもよい。 As the polyol (b1), a low molecular weight polyol (for example, a polyol having a molecular weight of 50 or more and less than 300) can be used, and a polymer polyol (polyol having a number average molecular weight of 300 or more) may be contained.
　前記低分子量ポリオールとしては、分子量が５０以上３００以下のポリオールを用いることができ、例えば、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、３－メチル－１，５－ペンタンジオール、ジエチレングリコール、ジプロピレングリコール、ネオペンチルグリコール、１，３－ブタンジオール等の炭素原子数２以上６以下の脂肪族ポリオール；１，４－シクロヘキサンジオール、シクロヘキサンジメタノール等の脂環式構造含有ポリオール；ビスフェノールＡ、ビスフェノールＦ等のビスフェノール化合物及びそれらのアルキレンオキシド付加物等の芳香族構造含有ポリオールなどが挙げられる。 As the low molecular weight polyol, a polyol having a molecular weight of 50 or more and 300 or less can be used, and for example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and the like. An aliphatic polyol having 2 or more and 6 or less carbon atoms such as 3-methyl-1,5-pentanediol, diethylene glycol, dipropylene glycol, neopentyl glycol, and 1,3-butanediol; 1,4-cyclohexanediol, cyclohexanedi. Examples thereof include alicyclic structure-containing polyols such as methanol; bisphenol compounds such as bisphenol A and bisphenol F, and aromatic structure-containing polyols such as alkylene oxide adducts thereof.
　前記ポリマーポリオールとしては、ポリエーテルポリオール、ポリカーボネートポリオール、ポリオレフィンポリオール等が挙げられる。 Examples of the polymer polyol include polyether polyols, polycarbonate polyols, polyolefin polyols and the like.
　前記ポリエーテルポリオールとしては、活性水素原子を２個以上有する化合物の１種又は２種以上を開始剤として、アルキレンオキシドを付加重合（開環重合）させたもの等が挙げられる。 Examples of the polyether polyol include those obtained by addition polymerization (ring-opening polymerization) of an alkylene oxide using one or more compounds having two or more active hydrogen atoms as an initiator.
　前記開始剤としては、例えば、エチレングリコール、ジエチレングリコール、トリエチレングリコール、トリメチレングリコール、１，２－プロパンジオ－ル、１，３－プロパンジオ－ル、１，３－ブタンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール等の直鎖状ジオール；ネオペンチルグリコール等の分岐鎖状ジオール；グリセリン、トリメチロールエタン、トリメチロールプロパン、ピロガロール等のトリオール；ソルビトール、蔗糖、アコニット糖等のポリオール；アコニット酸、トリメリット酸、ヘミメリット酸等のトリカルボン酸；リン酸；エチレンジアミン、ジエチレントリアミン等のポリアミン；トリイソプロパノールアミン；ジヒドロキシ安息香酸、ヒドロキシフタル酸等のフェノール酸；１，２，３－プロパントリチオールなどが挙げられる。 Examples of the initiator include ethylene glycol, diethylene glycol, triethylene glycol, trimethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,3-butanediol, and 1,4-. Linear diols such as butanediol and 1,6-hexanediol; Branched chain diols such as neopentyl glycol; Triols such as glycerin, trimethylolethane, trimethylolpropane and pyrogallol; polyols such as sorbitol, citrus sugar and aconit sugar. Tricarboxylic acids such as aconitic acid, trimellitic acid, hemmellitic acid; phosphoric acid; polyamines such as ethylenediamine and diethylenetriamine; triisopropanolamine;phenolic acids such as dihydroxybenzoic acid and hydroxyphthalic acid; 1,2,3-propanetri Examples include thiol.
　前記アルキレンオキシドとしては、例えば、エチレンオキシド、プロピレンオキシド、ブチレンオキシド、スチレンオキシド、エピクロルヒドリン、テトラヒドロフラン等が挙げられる。 Examples of the alkylene oxide include ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, and tetrahydrofuran.
　前記ポリエーテルポリオールとしては、前記開始剤にテトラヒドロフランを付加重合（開環重合）させたポリオキシテトラメチレングリコールを使用することが好ましい。 As the polyether polyol, it is preferable to use polyoxytetramethylene glycol obtained by addition polymerization (ring-opening polymerization) of tetrahydrofuran to the initiator.
　前記ポリカーボネートポリオールとしては、例えば、炭酸エステルとポリオールとの反応物；ホスゲンとビスフェノールＡ等との反応物などが挙げられる。 Examples of the polycarbonate polyol include a reaction product of a carbonic acid ester and a polyol; a reaction product of phosgene and bisphenol A and the like.
　前記炭酸エステルとしては、例えば、メチルカーボネート、ジメチルカーボネート、エチルカーボネート、ジエチルカーボネート、シクロカーボネート、ジフェニルカーボネート等が挙げられる。 Examples of the carbonic acid ester include methyl carbonate, dimethyl carbonate, ethyl carbonate, diethyl carbonate, cyclocarbonate, diphenylcarbonate and the like.
　前記炭酸エステルと反応しうるポリオールとしては、例えば、上記低分子量ポリオールとして例示したポリオール；ポリエーテルポリオール（ポリエチレングリコール、ポリプロピレングリコール等）、ポリエステルポリオール（ポリヘキサメチレンアジペート等）等の高分子量ポリオール（例えば、重量平均分子量５００以上５，０００以下）などが挙げられる。 Examples of the polyol that can react with the carbonic acid ester include the polyols exemplified as the low molecular weight polyol; high molecular weight polyols such as polyether polyols (polyethylene glycol, polypropylene glycol, etc.) and polyester polyols (polyhexamethylene adipate, etc.) (for example). , Weight average molecular weight of 500 or more and 5,000 or less).
　前記ポリオレフィンポリオールとしては、例えば、ポリイソブテンポリオール、水素添加（水添）ポリブタジエンポリオール、水素添加（水添）ポリイソプレンポリオール等が挙げられる。 Examples of the polyolefin polyol include polyisobutene polyol, hydrogenated (hydrogenated) polybutadiene polyol, hydrogenated (hydrogenated) polyisoprene polyol, and the like.
　前記ポリカルボン酸（ｂ２）としては、コハク酸、アジピン酸、セバシン酸、ドデカンジカルボン酸等の脂肪族ポリカルボン酸；テレフタル酸、イソフタル酸、フタル酸、ナフタレンジカルボン酸等の芳香族ポリカルボン酸；並びに前記脂肪族ポリカルボン酸及び芳香族ポリカルボン酸の無水物又はエステル形成性誘導体などが挙げられる。 Examples of the polycarboxylic acid (b2) include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid and dodecanedicarboxylic acid; aromatic polycarboxylic acids such as terephthalic acid, isophthalic acid, phthalic acid and naphthalenedicarboxylic acid; Further, examples thereof include an anhydride or an ester-forming derivative of the aliphatic polycarboxylic acid and the aromatic polycarboxylic acid.
　前記ポリエステル樹脂（Ａ２）は、親水性基を有するものであることが好ましい。前記ポリエステル樹脂（Ａ２）が親水性基を有することで、前記複合樹脂（Ａ）の水分散性を向上することができる。 The polyester resin (A2) preferably has a hydrophilic group. Since the polyester resin (A2) has a hydrophilic group, the water dispersibility of the composite resin (A) can be improved.
　前記親水性基としては、カルボキシル基、スルホン酸基等のアニオン性基；第３級アミノ基、第４級アンモニウム基等のカチオン性基、ポリオキシエチレン基等のノニオン性基等が挙げられる。なかでも、アニオン性基を有するものであることが好ましい。 Examples of the hydrophilic group include anionic groups such as a carboxyl group and a sulfonic acid group; cationic groups such as a tertiary amino group and a quaternary ammonium group, and nonionic groups such as a polyoxyethylene group. Among them, those having an anionic group are preferable.
　前記ポリエステル樹脂（Ａ２）に親水性基を付与する方法としては、前記低分子量ポリオール又は前記ポリカルボン酸として、親水性基を有する化合物を用いる方法；前記低分子量ポリオールとポリカルボン酸とのエステル化反応物、環状エステル化合物の開環重合物、これらの共重合物等にさらにジカルボン酸無水物等を付加する方法等が挙げられる。 As a method for imparting a hydrophilic group to the polyester resin (A2), a method using a compound having a hydrophilic group as the low molecular weight polyol or the polycarboxylic acid; esterification of the low molecular weight polyol and the polycarboxylic acid. Examples thereof include a reaction product, a ring-opening polymer of a cyclic ester compound, a method of further adding a dicarboxylic acid anhydride and the like to these copolymers and the like.
　前記親水性を有する低分子量ポリオールとしては、例えば、２，２－ジメチロールプロピオン酸、２，２－ジメチロールブタン酸、２，２－ジメチロール酪酸、２，２－ジメチロール吉草酸等のヒドロキシ酸；及び前記カルボキシ基を有するポリオールと前記ポリカルボン酸との反応物などが挙げられる。 Examples of the hydrophilic low molecular weight polyol include hydroxy acids such as 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolbuty acid, and 2,2-dimethylolvaleric acid; And the reaction product of the polyol having the carboxy group and the polycarboxylic acid.
　前記ジカルボン酸無水物としては、無水マレイン酸、無水コハク酸、無水イタコン酸、無水フタル酸、無水テトラヒドロフタル酸、無水ヘキサヒドロフタル酸、無水メチルエンドメチレンテトラヒドロフタル酸、無水クロレンド酸、メチルテトラヒドロ無水フタル酸、無水グルタル酸、ｃｉｓ－４－シクロヘキセン－１，２－ジカルボン酸無水物、無水トリメリット酸等が挙げられる。 Examples of the dicarboxylic acid anhydride include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylendomethylenetetrahydrophthalic acid anhydride, chlorendic acid anhydride, and methyltetrahydroanhydride. Examples thereof include phthalic acid, glutaric anhydride, cis-4-cyclohexene-1,2-dicarboxylic acid anhydride, trimellitic anhydride and the like.
　前記スルホン酸基を有するポリカルボン酸としては、例えば、５－スルホイソフタル酸、スルホテレフタル酸、４－スルホフタル酸、５－（４－スルホフェノキシ）イソフタル酸、５－スルホイソフタル酸モノアルキル、５－スルホイソフタル酸ジアルキル等のスルホン酸基を有するジカルボン酸；前記スルホン酸基を有するジカルボン酸のアルカリ金属塩などが挙げられる。 Examples of the polycarboxylic acid having a sulfonic acid group include 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, 5-sulfoisophthalate monoalkyl, and 5-. A dicarboxylic acid having a sulfonic acid group such as dialkyl sulfoisophthalate; an alkali metal salt of the dicarboxylic acid having the sulfonic acid group and the like can be mentioned.
　前記カチオン性基を有する低分子量ポリオールとしては、Ｎ－メチル－ジエタノールアミン；１分子中にエポキシを２個有する化合物と２級アミンとを反応させて得られるポリオール等の３級アミノ基を有するポリオールなどが挙げられる。 Examples of the low molecular weight polyol having a cationic group include N-methyl-diethanolamine; a polyol having a tertiary amino group such as a polyol obtained by reacting a compound having two epoxies in one molecule with a secondary amine. Can be mentioned.
　前記ノニオン性基を有するポリオールとしては、ポリオキシエチレン構造を有するポリオール等が挙げられる。 Examples of the polyol having a nonionic group include a polyol having a polyoxyethylene structure.
　前記ポリエステル樹脂（Ａ２）は、基材との密着性等の観点から、芳香環を含むものであることが好ましい。芳香環を有する原料を用いることで、前記ポリエステル樹脂（Ａ２）が、芳香環を有するものとすることができる。 The polyester resin (A2) preferably contains an aromatic ring from the viewpoint of adhesion to the base material and the like. By using a raw material having an aromatic ring, the polyester resin (A2) can be made to have an aromatic ring.
　前記ポリエステル樹脂（Ａ２）中、芳香環の含有量は、例えば、好ましくは０．０１ｍｏｌ／ｋｇ以上、より好ましくは０．０５ｍｏｌ／ｋｇ以上、より好ましくは０．１ｍｏｌ／ｋｇ以上であり、好ましくは１５ｍｏｌ／ｋｇ以下、より好ましくは１０ｍｏｌ／ｋｇ以下、さらに好ましくは８ｍｏｌ／ｋｇ以下、いっそう好ましくは５ｍｏｌ／ｋｇ以下である。 The content of the aromatic ring in the polyester resin (A2) is, for example, preferably 0.01 mol / kg or more, more preferably 0.05 mol / kg or more, more preferably 0.1 mol / kg or more, and preferably 0.1 mol / kg or more. It is 15 mol / kg or less, more preferably 10 mol / kg or less, still more preferably 8 mol / kg or less, and even more preferably 5 mol / kg or less.
　前記ポリエステル樹脂（Ａ２）の酸価は、例えば０．１ｍｇＫＯＨ／ｇ以上、好ましくは１ｍｇＫＯＨ／ｇ以上、より好ましくは５ｍｇＫＯＨ／ｇ以上であり、好ましくは１００ｍｇＫＯＨ／ｇ以下、より好ましくは８０ｍｇＫＯＨ／ｇ以下、さらに好ましくは５０ｍｇＫＯＨ／ｇ以下、いっそう好ましくは３０ｍｇＫＯＨ／ｇ以下である。 The acid value of the polyester resin (A2) is, for example, 0.1 mgKOH / g or more, preferably 1 mgKOH / g or more, more preferably 5 mgKOH / g or more, preferably 100 mgKOH / g or less, and more preferably 80 mgKOH / g or less. It is more preferably 50 mgKOH / g or less, and even more preferably 30 mgKOH / g or less.
　前記ポリエステル樹脂（Ａ２）の重量平均分子量は、好ましくは５００以上、より好ましくは１，０００以上、さらに好ましくは３，０００以上であり、好ましくは１，０００，０００以下、より好ましくは５００，０００以下、さらに好ましくは１００，０００以下である。 The weight average molecular weight of the polyester resin (A2) is preferably 500 or more, more preferably 1,000 or more, still more preferably 3,000 or more, preferably 1,000,000 or less, and more preferably 500,000. Below, it is more preferably 100,000 or less.
　前記ポリエステル樹脂（Ａ２）のガラス転移温度は、好ましくは－８０℃以上、より好ましくは－５０℃以上、さらに好ましくは－２０℃以上であり、好ましくは１４０℃以下、より好ましくは１２０℃以下、さらに好ましくは１００℃以下である。前記ポリエステル樹脂（Ａ２）のガラス転移温度が前記範囲にあると、前記ポリエステル樹脂（Ａ２）の運動性が良好であり、本発明の効果を発揮することが容易である。 The glass transition temperature of the polyester resin (A2) is preferably −80 ° C. or higher, more preferably −50 ° C. or higher, further preferably −20 ° C. or higher, preferably 140 ° C. or lower, more preferably 120 ° C. or lower, More preferably, it is 100 ° C. or lower. When the glass transition temperature of the polyester resin (A2) is within the above range, the motility of the polyester resin (A2) is good, and it is easy to exert the effect of the present invention.
　前記ポリエステル樹脂（Ａ２）のガラス転移温度は、示差走査熱量計（ＤＳＣ）により測定することができる。 The glass transition temperature of the polyester resin (A2) can be measured by a differential scanning calorimeter (DSC).
　前記複合樹脂（Ａ）中、前記ビニル重合体（Ａ１）と、前記ポリエステル樹脂（Ａ２）との含有量は、質量基準で、好ましくは０．００１以上、より好ましくは０．００５以上、さらに好ましくは０．０１以上、いっそう好ましくは０．０５以上、よりいっそう好ましくは０．１以上であり、好ましくは３以下、より好ましくは２以下、いっそう好ましくは１以下である。
前記ビニル重合体（Ａ１）１質量部に対して、好ましくは０．１質量部以上、より好ましくは０．５質量部以上、さらに好ましくは１質量部以上であり、好ましくは１００質量部以下、より好ましくは１０質量部以下、さらに好ましくは３質量部以下である。 The content of the vinyl polymer (A1) and the polyester resin (A2) in the composite resin (A) is preferably 0.001 or more, more preferably 0.005 or more, still more preferably 0.005 or more, based on the mass. Is 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, preferably 3 or less, more preferably 2 or less, still more preferably 1 or less.
With respect to 1 part by mass of the vinyl polymer (A1), it is preferably 0.1 part by mass or more, more preferably 0.5 part by mass or more, still more preferably 1 part by mass or more, and preferably 100 parts by mass or less. It is more preferably 10 parts by mass or less, still more preferably 3 parts by mass or less.
　前記ビニル重合体（Ａ１）及びポリエステル樹脂（Ａ２）の合計の含有率は、複合樹脂（Ａ）中、好ましくは７０質量％以上、より好ましくは８０質量％以上、さらに好ましくは９０質量％以上であり、上限は１００質量％である。 The total content of the vinyl polymer (A1) and the polyester resin (A2) is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more in the composite resin (A). Yes, the upper limit is 100% by mass.
　前記複合樹脂（Ａ）のゲル分率は、好ましくは０．０１質量％以上、より好ましくは１質量％以上、さらに好ましくは３質量％以上、よりいっそう好ましくは１０質量％以上であり、上限は１００質量％であり、例えば９０質量％以下、さらには８０質量％以下であってもよい。 The gel fraction of the composite resin (A) is preferably 0.01% by mass or more, more preferably 1% by mass or more, still more preferably 3% by mass or more, still more preferably 10% by mass or more, and the upper limit is It may be 100% by mass, for example, 90% by mass or less, and further may be 80% by mass or less.
　前記複合樹脂（Ａ）のゲル分率は、例えば、以下の方法で測定することができる。まず、ガラス板上に乾燥後の膜厚が０．５ｍｍとなるように本発明の水性樹脂組成物を塗工し、８０℃で２時間乾燥した後、ガラス板から剥離し、更に１４０℃で５分間乾燥したものを直径２９ｍｍの円形に切り取って試料とする。該試料の溶剤浸漬前の重量を測定し、Ｇ１とする。次に、試料をトルエン中に常温で２４時間浸漬した後の試料の溶剤不溶解分を８０メッシュ金網で濾過することにより分離し、１１０℃で１時間乾燥した後、重量し、Ｇ２とする。以下の式に基づいて求められる値をゲル分率とする。
　　ゲル分率（質量％）＝（Ｇ２／Ｇ１）×１００ The gel fraction of the composite resin (A) can be measured by, for example, the following method. First, the aqueous resin composition of the present invention is applied onto a glass plate so that the thickness after drying is 0.5 mm, dried at 80 ° C. for 2 hours, peeled off from the glass plate, and further at 140 ° C. After drying for 5 minutes, cut into a circle with a diameter of 29 mm and use it as a sample. The weight of the sample before immersion in the solvent is measured and used as G1. Next, after immersing the sample in toluene at room temperature for 24 hours, the solvent-insoluble component of the sample is separated by filtering with an 80 mesh wire mesh, dried at 110 ° C. for 1 hour, and then weighed to give G2. The value obtained based on the following formula is defined as the gel fraction.
Gel fraction (% by mass) = (G2 / G1) x 100
　複合樹脂（Ａ）において、前記ビニル重合体（Ａ１）の表面の少なくとも一部を前記ポリエステル樹脂（Ａ２）が被覆していることが好ましく、前記ビニル重合体（Ａ１）の表面に前記ポリエステル樹脂（Ａ２）の層が形成されていることが好ましい。前記ビニル重合体（Ａ１）は、一般に疎水性が高く、そのままでは水に分散することが困難であるが、前記ポリエステル樹脂（Ａ２）が前記ビニル重合体（Ａ１）の表面の少なくとも一部を被覆していることで、水性媒体への分散性が良好となる。前記ビニル重合体（Ａ１）と前記ポリエステル樹脂（Ａ２）とは、化学的に結合していてもよく、していなくともよい。 In the composite resin (A), it is preferable that at least a part of the surface of the vinyl polymer (A1) is covered with the polyester resin (A2), and the surface of the vinyl polymer (A1) is covered with the polyester resin (A1). It is preferable that the layer of A2) is formed. The vinyl polymer (A1) is generally highly hydrophobic and difficult to disperse in water as it is, but the polyester resin (A2) covers at least a part of the surface of the vinyl polymer (A1). By doing so, the dispersibility in the aqueous medium becomes good. The vinyl polymer (A1) and the polyester resin (A2) may or may not be chemically bonded.
　前記複合樹脂は、前記ポリエステル樹脂（Ａ２）の存在下、後述する水性媒体（Ｂ）中でビニル単量体（ａ）を重合することにより製造することができる。前記ビニル単量体（ａ）は疎水性であるため、水性媒体（Ｂ）中でポリエステル樹脂（Ａ２）と共存させることで、該ビニル単量体（ａ）の少なくとも一部がポリエステル樹脂（Ｂ２）の内部に取り込まれ、この状態で重合反応を行うことで、本発明の複合樹脂（Ａ）を製造することができる。 The composite resin can be produced by polymerizing the vinyl monomer (a) in the aqueous medium (B) described later in the presence of the polyester resin (A2). Since the vinyl monomer (a) is hydrophobic, at least a part of the vinyl monomer (a) is made of the polyester resin (B2) by coexisting with the polyester resin (A2) in the aqueous medium (B). ), And the polymerization reaction is carried out in this state to produce the composite resin (A) of the present invention.
　より具体的には、前記ポリエステル樹脂（Ａ２）は、水性媒体（Ｂ）中に分散された状態（予備分散液）で、前記ビニル単量体（ａ）の重合に供されることが好ましい。前記ポリエステル樹脂（Ａ２）が水性媒体（Ｂ）中に分散された予備分散液は、例えば、無溶剤下又は有機溶剤の存在下で、前記ポリオール（ｂ１）及び前記ポリカルボン酸（ｂ２）を反応させることにより製造することができる。前記有機溶剤は、安全性や環境に対する負荷低減の観点から、前記ポリエステル樹脂（Ａ２）の製造途中または製造後に、減圧留去等によってその一部または全部を除去してもよい。 More specifically, it is preferable that the polyester resin (A2) is subjected to polymerization of the vinyl monomer (a) in a state of being dispersed in the aqueous medium (B) (preliminary dispersion liquid). The pre-dispersion liquid in which the polyester resin (A2) is dispersed in the aqueous medium (B) reacts with the polyol (b1) and the polycarboxylic acid (b2), for example, in the absence of a solvent or in the presence of an organic solvent. It can be manufactured by allowing it to be produced. From the viewpoint of safety and reduction of the load on the environment, the organic solvent may be partially or wholly removed by distillation under reduced pressure or the like during or after the production of the polyester resin (A2).
　前記重合反応の際は、必要に応じて、後述する添加剤（Ｃ）を共存させてもよく重合反応後に該添加剤（Ｃ）を添加してもよい。 At the time of the polymerization reaction, the additive (C) described later may coexist or the additive (C) may be added after the polymerization reaction, if necessary.
　前記ビニル単量体（ａ）を重合する際、ラジカル重合開始剤を共存させることが好ましい。前記重合開始剤としては、光重合開始剤、熱重合開始剤を用いることができる。前記光重合開始剤としては、例えば、ベンゾフェノン、ベンジル、ミヒラーケトン、チオキサントン、アントラキノン、ベンゾイン、ジアルコキシアセトフェノン、アシルオキシムエステル、ベンジルケタール、ヒドロキシアルキルフェノン、ハロゲノケトン等が挙げられる。前記光重合開始剤は、必要に応じてメチルアミン、ジエタノールアミン、Ｎ－メチルジエタノールアミン、トリブチルアミン等の第三アミンと組み合わせて使用してもよい。前記熱重合開始剤としては、２，２’－アゾビス（イソブチロニトリル）、２，２’－アゾビス（２－メチルブチロニトリル）、２，２’－アゾビス（２－メチルプロピオンアミジン）二塩酸塩、４，４’－アゾビス（４－シアノ）吉草酸、２，２’－アゾビス（２－アミジノプロパン）ジヒドロクロライド等のアゾ化合物；ベンゾイルパーオキサイド、ｔｅｒｔ－ブチルハイドロパーオキサイド、ｔｅｒｔ－ブチルパーオキシピバレート、ｔｅｒｔ－ブチルパーオキシベンゾエート、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート、ジ－ｔｅｒｔ－ブチルパーオキサイド、ジ－ｔｅｒｔ－ブチルハイドロパーオキサイド、クメンハイドロパーオキサイド、ベンゾイルパーオキサイド、ラウロイルパーオキサイド、デカノイルパーオキサイド、ｔｅｒｔ－ブチルクミルパーオキサイド、ジクミルパーオキサイド、ｔｅｒｔ－ブチルパーオキシラウレート、ｔｅｒｔ－ブチルパーオキシベンゾエート、クメンハイドロパーオキサイド、パラメンタンハイドロパーオキサイド、等の有機過酸化物；過酸化水素、過硫酸アンモニウム、過硫酸カリウム、過硫酸ナトリウム等の無機過酸化物などの熱重合開始剤などを使用することができる。 When polymerizing the vinyl monomer (a), it is preferable to allow a radical polymerization initiator to coexist. As the polymerization initiator, a photopolymerization initiator and a thermal polymerization initiator can be used. Examples of the photopolymerization initiator include benzophenone, benzyl, Michler ketone, thioxanthone, anthraquinone, benzoin, dialkoxyacetophenone, acyloxime ester, benzylketal, hydroxyalkylphenone, and halogenoketone. The photopolymerization initiator may be used in combination with a tertiary amine such as methylamine, diethanolamine, N-methyldiethanolamine or tributylamine, if necessary. Examples of the thermal polymerization initiator include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2-methylbutyronitrile), and 2,2'-azobis (2-methylpropionamidine). Azo compounds such as hydrochloride, 4,4'-azobis (4-cyano) valerate, 2,2'-azobis (2-amidinopropane) dihydrochloride; benzoyl peroxide, tert-butyl hydroperoxide, tert-butyl. Peroxypivalate, tert-butylperoxybenzoate, tert-butylperoxy-2-ethylhexanoate, di-tert-butyl peroxide, di-tert-butyl hydroperoxide, cumene hydroperoxide, benzoyl peroxide , Lauroyl peroxide, decanoyle peroxide, tert-butyl cumyl peroxide, dicumyl peroxide, tert-butyl peroxylaurate, tert-butyl peroxybenzoate, cumene hydroperoxide, paramentan hydroperoxide, etc. Organic peroxides; thermal polymerization initiators such as inorganic peroxides such as hydrogen peroxide, ammonium persulfate, potassium persulfate, and sodium persulfate can be used.
　前記ラジカル重合開始剤の量は、前記ビニル化合物の合計１００質量部に対して、好ましくは０．０１質量部以上、より好ましくは０．１質量部以上、さらに好ましくは０．５質量部以上であり、好ましくは２０質量部以下、より好ましくは１０質量部以下、さらに好ましくは５質量部以下である。 The amount of the radical polymerization initiator is preferably 0.01 part by mass or more, more preferably 0.1 part by mass or more, still more preferably 0.5 part by mass or more with respect to 100 parts by mass of the total of the vinyl compound. It is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 5 parts by mass or less.
　前記複合樹脂（Ａ）は、水性媒体（Ｂ）中に分散されていることが好ましい。複合樹脂（Ａ）の分散状態は、例えば、水性樹脂組成物における沈殿物の有無により確認することができる。 The composite resin (A) is preferably dispersed in the aqueous medium (B). The dispersed state of the composite resin (A) can be confirmed, for example, by the presence or absence of a precipitate in the aqueous resin composition.
　前記複合樹脂（Ａ）の含有率は、水性樹脂組成物中、好ましくは１０質量％以上、より好ましくは２０質量％以上、さらに好ましくは３０質量％以上であり、好ましくは７０質量％以下、より好ましくは６０質量％以下、さらに好ましくは５０質量％以下である。 The content of the composite resin (A) is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, and preferably 70% by mass or less in the aqueous resin composition. It is preferably 60% by mass or less, more preferably 50% by mass or less.
　前記水性媒体（Ｂ）としては、水、水と混和する有機溶剤及びこれらの混合物が挙げられる。水と混和する有機溶剤としては、１種又は２種以上を用いることができ、例えば、メタノール、エタノール、ｎ－プロパノール、イソプロピルアルコール、１，２－プロピレングリコール、１，３－ブチレングリコール等のアルコール溶剤；アセトン、メチルエチルケトン等のケトン溶剤；エチレングリコール－ｎ－ブチルエーテル、ジエチレングリコール－ｎ－ブチルエーテル、ジエチレングリコールモノエチルエーテルアセテート、ジエチレングリコールジメチルエーテル、プロピレングリコールメチルエーテル、ジプロピレングリコールメチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコール－ｎ－ブチルエーテル、トリプロピレングリコールメチルエーテル等のグリコールエーテル溶剤；Ｎ－メチル－２－ピロリドン、Ｎ－エチル－２－ピロリドン等のラクタム溶剤；Ｎ，Ｎ－ジメチルホルムアミド等のアミド溶剤などが挙げられ、アルコール溶剤が好ましい。 Examples of the aqueous medium (B) include water, an organic solvent miscible with water, and a mixture thereof. As the organic solvent to be mixed with water, one kind or two or more kinds can be used, and for example, alcohols such as methanol, ethanol, n-propanol, isopropyl alcohol, 1,2-propylene glycol and 1,3-butylene glycol can be used. Solvents: Ketone solvents such as acetone and methyl ethyl ketone; ethylene glycol-n-butyl ether, diethylene glycol-n-butyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, dipropylene glycol dimethyl ether, dipropylene Glycol ether solvents such as glycol-n-butyl ether and tripropylene glycol methyl ether; lactam solvents such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone; amide solvents such as N, N-dimethylformamide and the like. Therefore, an alcohol solvent is preferable.
　前記水性媒体（Ｂ）は、安全性や環境に対する負荷低減を考慮すると、水のみ、又は、水及び水と混和する有機溶剤との混合物が好ましく、水のみがより好ましい。水の含有率は、前記水性媒体（Ｂ）１００質量％中、好ましくは５０質量％以上、より好ましくは６０質量％以上、さらに好ましくは７０質量％以上である。 The aqueous medium (B) is preferably water alone or a mixture of water and an organic solvent miscible with water, and more preferably only water, in consideration of safety and reduction of environmental load. The content of water is preferably 50% by mass or more, more preferably 60% by mass or more, still more preferably 70% by mass or more in 100% by mass of the aqueous medium (B).
　前記水性媒体（Ｂ）の含有率は、水性樹脂組成物の全量１００質量％中、好ましくは３０質量％以上８０質量％以下、より好ましくは５０質量％以上７０質量％以下である。 The content of the aqueous medium (B) is preferably 30% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 70% by mass or less, based on 100% by mass of the total amount of the aqueous resin composition.
　本発明の水性樹脂組成物は、さらに架橋剤、界面活性剤、可塑剤、帯電防止剤、ワックス、光安定剤、流動調整剤、染料、レベリング剤、レオロジーコントロール剤、紫外線吸収剤、酸化防止剤、光触媒性化合物、無機顔料、有機顔料、体質顔料、硬化剤、硬化触媒、乳化剤、分散安定剤等の各種の添加剤（Ｃ）を含んでいてもよい。 The aqueous resin composition of the present invention further comprises a cross-linking agent, a surfactant, a plasticizer, an antioxidant, a wax, a light stabilizer, a flow conditioner, a dye, a leveling agent, a rhology control agent, an ultraviolet absorber, and an antioxidant. , Photocatalytic compounds, inorganic pigments, organic pigments, extender pigments, curing agents, curing catalysts, emulsifiers, dispersion stabilizers and the like may be contained.
　前記添加剤（Ｃ）の含有量は、前記複合樹脂（Ａ）１００質量部に対して、好ましくは２０質量部以下、より好ましくは１０質量部以下、さらに好ましくは１質量部以下である。 The content of the additive (C) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and further preferably 1 part by mass or less with respect to 100 parts by mass of the composite resin (A).
　本発明の水性樹脂組成物は、当初は均質でありながら、最終的には、疎水性表面となる塗膜を形成させることができ、紙塗工・含浸加工、繊維・不織布、カーペット、土木建材、モルタルセメント、自動車用部品、タイヤコード、塗料、ペースト、防錆コーティング、接着剤、プラスチック改質、化粧用パフ、電子材料、接着剤（一般）、コーティング・含浸（不織布・紙）、繊維含浸・補強繊維加工(カーペット等）、防湿・耐水コーティング、セメント・モルタル、建材加工・木質接着、合成皮革、人工皮革、手袋、避妊、インキ用受理剤、インキ用分散剤具等に好適である。 Although the water-based resin composition of the present invention is initially homogeneous, it can finally form a coating film having a hydrophobic surface, and can be used for paper coating / impregnation processing, fibers / non-woven fabrics, carpets, and civil engineering and building materials. , Mortal cement, automotive parts, tire cords, paints, pastes, rustproof coatings, adhesives, plastic modifications, cosmetic puffs, electronic materials, adhesives (general), coatings / impregnations (non-woven / paper), fiber impregnations -Suitable for reinforcing fiber processing (carpet, etc.), moisture-proof / water-resistant coating, cement / mortar, building material processing / wood adhesive, synthetic leather, artificial leather, gloves, contraception, ink accepting agent, ink dispersant tool, etc.
　以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited by the following examples as well as the present invention, and appropriate modifications are made to the extent that it can meet the purposes of the preceding and the following. Of course, it is possible to carry out, and all of them are included in the technical scope of the present invention.
（合成例１：水性ポリエステル樹脂組成物（１）の合成）
　温度計、窒素ガス導入管、攪拌機を備えた反応容器中で窒素ガスを導入しながら、イソフタル酸１７．１質量部、テレフタル酸３３．７質量部、ジエチレングリコール１８．１質量部、エチレングリコール２２．８質量部、５－スルホイソフタル酸ジメチルナトリウム６．５質量部、無水トリメリット酸１．９部及びテトライソプロピルチタネート０．０２質量部を仕込み、１８０～２３０℃で酸価が１０ｍｇＫＯＨ／ｇ以下になるまで１２時間重縮合反応を行い、ポリエステル樹脂（Ａ２－１）を得た。次いで、ポリエステル樹脂（Ａ２－１）１００質量部をアンモニア水０．５質量部およびイオン交換水２９０質量部に８０度で攪拌溶解しながら、水溶化を実施し、不揮発分＝２５．０質量％の水性ポリエステル樹脂組成物（１）を調製した。（酸価：１２．３ｍｇＫＯＨ／ｇ　芳香環量：３．８ｍｏｌ／ｋｇ） (Synthesis Example 1: Synthesis of Aqueous Polyester Resin Composition (1))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 17.1 parts by mass of isophthalic acid, 33.7 parts by mass of terephthalic acid, 18.1 parts by mass of diethylene glycol, and ethylene glycol 22. 8 parts by mass, 6.5 parts by mass of dimethyl sodium 5-sulfoisophthalate, 1.9 parts by weight of trimellitic anhydride and 0.02 part by mass of tetraisopropyltitanate were charged, and the acid value was reduced to 10 mgKOH / g or less at 180 to 230 ° C. A polycondensation reaction was carried out for 12 hours until the resin (A2-1) was obtained. Next, water solubilization was carried out while stirring and dissolving 100 parts by mass of the polyester resin (A2-1) in 0.5 parts by mass of ammonia water and 290 parts by mass of ion-exchanged water at 80 ° C., and the non-volatile content = 25.0% by mass. Aqueous polyester resin composition (1) was prepared. (Acid value: 12.3 mgKOH / g Aromatic ring amount: 3.8 mol / kg)
（合成例２：水性ポリエステル樹脂組成物（２）の合成）
　温度計、窒素ガス導入管、攪拌機を備えた反応容器中で窒素ガスを導入しながら、イソフタル酸２１．９質量部、テレフタル酸３９．２質量部、ジエチレングリコール１６．７質量部、エチレングリコール１４．７質量部、５－スルホイソフタル酸ジメチルナトリウム７．６質量部及びテトライソプロピルチタネート０．０２質量部を仕込み、１８０～２３０℃で酸価が３ｍｇＫＯＨ／ｇ以下になるまで１２時間重縮合反応を行い、ポリエステル樹脂（Ａ２－２）を得た。次いで、ポリエステル樹脂（Ａ２－２）１００質量部をアンモニア水０．４質量部およびイオン交換水２９０質量部に８０度で攪拌溶解しながら、水溶化を実施し、不揮発分＝２５．０質量％の水性ポリエステル樹脂組成物（２）を調製した。（酸価：６．７ｍｇＫＯＨ／ｇ　芳香環量：４．５ｍｏｌ／ｋｇ） (Synthesis Example 2: Synthesis of Aqueous Polyester Resin Composition (2))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 21.9 parts by mass of isophthalic acid, 39.2 parts by mass of terephthalic acid, 16.7 parts by mass of diethylene glycol, and 14.2 parts by mass of ethylene glycol. 7 parts by mass, 7.6 parts by mass of dimethyl sodium 5-sulfoisophthalate and 0.02 parts by mass of tetraisopropyl titanate were charged, and a polycondensation reaction was carried out at 180 to 230 ° C. for 12 hours until the acid value became 3 mgKOH / g or less. , Polyester resin (A2-2) was obtained. Next, water solubilization was carried out while stirring and dissolving 100 parts by mass of the polyester resin (A2-2) in 0.4 parts by mass of ammonia water and 290 parts by mass of ion-exchanged water at 80 ° C., and the non-volatile content = 25.0% by mass. Aqueous polyester resin composition (2) was prepared. (Acid value: 6.7 mgKOH / g Aromatic ring amount: 4.5 mol / kg)
（合成例３：水性ポリエステル樹脂組成物（３）の合成）
　温度計、窒素ガス導入管、攪拌機を備えた反応容器中で窒素ガスを導入しながら、イソフタル酸２３質量部、テレフタル酸３９．２質量部、エチレングリコール１６質量部、ネオペンチルグリコール１６．９部及びテトライソプロピルチタネート０．１質量部を仕込み１８０～２３０℃で酸価が３ｍｇＫＯＨ／ｇ以下になるまで５時間重縮合反応を行い、次に無水トリメリット酸４．９部を添加し、３時間攪拌して重合反応を行い、ポリエステル樹脂（Ａ２－３）を得た。次いで、ポリエステル樹脂（Ａ２－３）１００質量部をメチルエチルケトン２００質量部に６０度で攪拌溶解しながら、トリエチルアミン３質量部添加した後、イオン交換水３６７質量部をゆっくりと添加し水溶化を実施した。次いで減圧下、３０～５０℃にてメチルエチルケトンを除去し、不揮発分＝２５．０質量％の水性ポリエステル樹脂組成物（３）を調製した。（酸価：１６．２ｍｇＫＯＨ／ｇ　芳香環量：４．６ｍｏｌ／ｋｇ） (Synthesis Example 3: Synthesis of Aqueous Polyester Resin Composition (3))
While introducing nitrogen gas in a reaction vessel equipped with a thermometer, a nitrogen gas introduction tube, and a stirrer, 23 parts by mass of isophthalic acid, 39.2 parts by mass of terephthalic acid, 16 parts by mass of ethylene glycol, and 16.9 parts of neopentyl glycol. And 0.1 part by mass of tetraisopropyl titanate was charged, and a polycondensation reaction was carried out at 180 to 230 ° C. for 5 hours until the acid value became 3 mgKOH / g or less, and then 4.9 parts of trimellitic anhydride was added and 3 hours. The polymerization reaction was carried out with stirring to obtain a polyester resin (A2-3). Next, while stirring and dissolving 100 parts by mass of the polyester resin (A2-3) in 200 parts by mass of methyl ethyl ketone at 60 ° C., 3 parts by mass of triethylamine was added, and then 367 parts by mass of ion-exchanged water was slowly added to carry out water solubilization. .. Then, under reduced pressure, methyl ethyl ketone was removed at 30 to 50 ° C. to prepare an aqueous polyester resin composition (3) having a non-volatile content of 25.0% by mass. (Acid value: 16.2 mgKOH / g Aromatic ring amount: 4.6 mol / kg)
（合成例４：合成ゴムラテックス樹脂（１）の合成）
　乳化剤としてニューコール２６１Ａ［日本乳化剤（株）製］１部とイオン交換水２００質量部を用いてブタジエン７９質量部、スチレン１９質量部、アクリル酸２質量部を過硫酸アンモニア（ＡＰＳ）０．５質量部でモノマー一括乳化重合（反応温度６０℃）の条件下反応させて次に未反応モノマー除去の濃縮を行い、ビニル重合体（Ａ１－１）を含む固形分４５質量％の合成ゴムラテックス（１）を得た。 (Synthetic Example 4: Synthesis of Synthetic Rubber Latex Resin (1))
Using 1 part of Newcol 261A [manufactured by Nippon Embroidery Co., Ltd.] and 200 parts by mass of ion-exchanged water as an emulsifier, 79 parts by mass of butadiene, 19 parts by mass of styrene, and 2 parts by mass of acrylic acid were added to 0.5 parts by mass of ammonia persulfate (APS). A synthetic rubber latex having a solid content of 45% by mass (A1-1) containing a vinyl polymer (A1-1) was subjected to a reaction under the conditions of batch monomer emulsion polymerization (reaction temperature 60 ° C.) in parts by mass and then concentrated to remove unreacted monomers. 1) was obtained.
（実施例１：ラテックス複合ポリエステル樹脂（１）の合成）
　合成例１で得られた水性ポリエステル樹脂組成物（１）３０８．９質量部にイオン交換水１３７質量部を加え、イソプレン３３．１質量部を過硫酸アンモニア（ＡＰＳ）０．３質量部でモノマー一括乳化重合（反応温度７０℃）の条件下反応させて、次に未反応モノマー除去の濃縮を行い、水分量を調整後、固形分３０質量％のラテックス複合ポリエステル樹脂（１）を得た。 (Example 1: Synthesis of latex composite polyester resin (1))
137 parts by mass of ion-exchanged water was added to 308.9 parts by mass of the aqueous polyester resin composition (1) obtained in Synthesis Example 1, and 33.1 parts by mass of isoprene was monomerized with 0.3 parts by mass of ammonia persulfate (APS). The reaction was carried out under the conditions of batch emulsification polymerization (reaction temperature 70 ° C.), then concentration was carried out to remove unreacted monomers, and after adjusting the water content, a latex composite polyester resin (1) having a solid content of 30% by mass was obtained.
（実施例２：ラテックス複合ポリエステル樹脂（２）の合成）
　合成例２で得られた水性ポリエステル樹脂組成物（２）２２３．８質量部にイオン交換水１８７質量部を加え、イソプレン５３．７質量部、メタクリル酸メチル１３．４質量部を過硫酸アンモニア（ＡＰＳ）０．５質量部でモノマー一括乳化重合（反応温度７０℃）の条件下反応させて、次に未反応モノマー除去の濃縮を行い、水分量を調整後、固形分３５質量％のラテックス複合ポリエステル樹脂（２）を得た。 (Example 2: Synthesis of latex composite polyester resin (2))
187 parts by mass of ion-exchanged water was added to 223.8 parts by mass of the aqueous polyester resin composition (2) obtained in Synthesis Example 2, and 53.7 parts by mass of isoprene and 13.4 parts by mass of methyl methacrylate were added to ammonia persulfate (13.4 parts by mass). APS) Reacted under the conditions of monomer batch emulsification polymerization (reaction temperature 70 ° C.) with 0.5 parts by mass, then concentrated to remove unreacted monomers, adjusted the water content, and then made a latex composite with a solid content of 35% by mass. A polyester resin (2) was obtained.
（実施例３：ラテックス複合ポリエステル樹脂（３）の合成）
　合成例３で得られた水性ポリエステル樹脂組成物（３）３０８．９質量部にイオン交換水１３７質量部を加え、ブタジエン３３．１質量部を過硫酸アンモニア（ＡＰＳ）０．３質量部でモノマー一括乳化重合（反応温度７０℃）の条件下反応させて、次に未反応モノマー除去の濃縮を行い、水分量を調整後、固形分３０質量％のラテックス複合ポリエステル樹脂（３）を得た。 (Example 3: Synthesis of latex composite polyester resin (3))
137 parts by mass of ion-exchanged water was added to 308.9 parts by mass of the aqueous polyester resin composition (3) obtained in Synthesis Example 3, and 33.1 parts by mass of butadiene was monomerized with 0.3 parts by mass of ammonia persulfate (APS). The reaction was carried out under the conditions of batch emulsification polymerization (reaction temperature 70 ° C.), then concentration was carried out to remove unreacted monomers, and after adjusting the water content, a latex composite polyester resin (3) having a solid content of 30% by mass was obtained.
（実施例４：ラテックス複合ポリエステル樹脂（４）の合成）
　合成例２で得られた水性ポリエステル樹脂組成物（２）３１３．５質量部にイオン交換水１２５質量部を加え、ブタジエン２８．２質量部、メタクリル酸グリシジル１２．１質量部を過硫酸アンモニア（ＡＰＳ）０．３質量部でモノマー一括乳化重合（反応温度７０℃）の条件下反応させて、次に未反応モノマー除去の濃縮を行い、水分量を調整後、固形分３５質量％のラテックス複合ポリエステル樹脂（４）を得た。 (Example 4: Synthesis of latex composite polyester resin (4))
125 parts by mass of ion-exchanged water was added to 313.5 parts by mass of the aqueous polyester resin composition (2) obtained in Synthesis Example 2, and 28.2 parts by mass of butadiene and 12.1 parts by mass of glycidyl methacrylate were added to ammonia persulfate (12.1 parts by mass). APS) Reacted under the conditions of monomer batch emulsification polymerization (reaction temperature 70 ° C.) with 0.3 parts by mass, then concentrated to remove unreacted monomers, adjusted the water content, and then made a latex composite with a solid content of 35% by mass. A polyester resin (4) was obtained.
（実施例５：ラテックス複合ポリエステル樹脂（５）の合成）
　合成例２で得られた水性ポリエステル樹脂組成物（２）３１３．５質量部にイオン交換水１２４．９質量部を加え、イソプレン１２．１質量部、メタクリル酸メチル２８．２質量部を過硫酸アンモニア（ＡＰＳ）０．３質量部でモノマー一括乳化重合（反応温度７０℃）の条件下反応させて、次に未反応モノマー除去の濃縮を行い、水分量を調整後、固形分４５質量％のラテックス複合ポリエステル樹脂（５）を得た。 (Example 5: Synthesis of latex composite polyester resin (5))
To 313.5 parts by mass of the aqueous polyester resin composition (2) obtained in Synthesis Example 2, 124.9 parts by mass of ion-exchanged water was added, and 12.1 parts by mass of isoprene and 28.2 parts by mass of methyl methacrylate were persulfated. After reacting with 0.3 parts by mass of ammonia (APS) under the condition of monomer batch emulsification polymerization (reaction temperature 70 ° C.), then concentration to remove unreacted monomers was performed, and after adjusting the water content, the solid content was 45% by mass. A latex composite polyester resin (5) was obtained.
（比較例１）
　合成例２で得られた水性ポリエステル樹脂組成物（２）を使用した。 (Comparative Example 1)
The aqueous polyester resin composition (2) obtained in Synthesis Example 2 was used.
（比較例２：水性ポリエステル樹脂と合成ゴムラテックス樹脂のブレンド（７））
　合成例２で得られた水性ポリエステル樹脂組成物（２）１００質量部に、合成例４の合成ゴムラテックス樹脂（４）６６．７質量部を加え一定時間攪拌し、固形分３７．０質量％のブレンド品を得た。 (Comparative Example 2: Blend of water-based polyester resin and synthetic rubber latex resin (7))
To 100 parts by mass of the aqueous polyester resin composition (2) obtained in Synthesis Example 2, 66.7 parts by mass of the synthetic rubber latex resin (4) of Synthesis Example 4 was added and stirred for a certain period of time to have a solid content of 37.0% by mass. I got a blended product of.
（比較例３）
　合成例４で得られた合成ゴムラテックス樹脂（４）を使用した。 (Comparative Example 3)
The synthetic rubber latex resin (4) obtained in Synthesis Example 4 was used.
　得られた水性樹脂組成物について、それぞれ、以下の測定を行った。 The following measurements were made for each of the obtained aqueous resin compositions.
［異種基材密着性の評価方法］
　水性樹脂組成物をポリエチレンテレフタレート（ＰＥＴ）基材に塗工し、１００℃で２０秒間乾燥させた。その塗工面に、ＡＢＳ基材もしくはポリ塩化ビニル（ＰＶＣ）基材を貼り付け、再度１００℃で３分熱処理した後、ＰＥＴとＡＢＳもしくはＰＶＣ基材を剥がし、剥がれた基材の状態を観察した。
　○：ＰＥＴ、もしくはＳＢＲ，ＰＶＣ基材が材料破壊した。もしくは、剥がれなかった。
　△：ＰＥＴとＳＢＲ，ＰＶＣ基材間で接着性を確認できたが、ＰＥＴもしくはＳＢＲ，ＰＶＣ基材のどちらかの基材のみに接着層が残った。
　×：ＰＥＴとＳＢＲ，ＰＶＣ基材間でほとんど接着性を確認できず、ＰＥＴもしくはＳＢＲ，ＰＶＣ基材のどちらかの基材のみに接着層が残った。 [Evaluation method for adhesion between different types of substrates]
The aqueous resin composition was applied to a polyethylene terephthalate (PET) substrate and dried at 100 ° C. for 20 seconds. An ABS base material or a polyvinyl chloride (PVC) base material was attached to the coated surface, and after heat-treating at 100 ° C. for 3 minutes again, PET and the ABS or PVC base material were peeled off, and the state of the peeled base material was observed. ..
◯: PET, SBR, or PVC base material was destroyed. Or it did not come off.
Δ: Adhesiveness could be confirmed between PET and the SBR / PVC base material, but the adhesive layer remained only on either the PET or SBR / PVC base material.
X: Adhesiveness could hardly be confirmed between PET and the SBR / PVC base material, and the adhesive layer remained only on either the PET or SBR / PVC base material.
［フィルム物性の測定方法」
　ポリプロピレン（ＰＰ）フィルム基材上に塗膜を作製し（膜厚１５０μｍ）、乾燥させ、得られた乾燥塗膜（フィルム）を用い引張試験を行った。引張速度３００ｍｍ／分で引張り、破断時の自長に対する伸び率及び強度を測定した。 [Measuring method of film physical characteristics]
A coating film was prepared on a polypropylene (PP) film substrate (thickness: 150 μm), dried, and a tensile test was performed using the obtained dried coating film (film). It was pulled at a tensile speed of 300 mm / min, and the elongation rate and strength with respect to its own length at break were measured.
［耐溶剤性の評価方法］
　ＰＰ基材上に塗膜を作製し（膜厚１５０μｍ）、乾燥させ、剥がして得られた乾燥塗膜（フィルム）について、メチルエチルケトン（ＭＥＫ）に対する耐久性試験を実施した。詳細には、得られた乾燥塗膜を常温でメチルエチルケトン中に１日浸漬し、浸漬前の重量から、浸漬後の重量を差し引いて溶出量とし、これを浸漬前の塗膜の重量で割って、溶出率とした。 [Evaluation method of solvent resistance]
A coating film was prepared on a PP substrate (thickness: 150 μm), dried, and the dried coating film (film) obtained by peeling was subjected to a durability test against methyl ethyl ketone (MEK). Specifically, the obtained dry coating film was immersed in methyl ethyl ketone at room temperature for one day, the weight after immersion was subtracted from the weight before immersion to obtain the elution amount, and this was divided by the weight of the coating film before immersion. , The elution rate.
［耐水性、水膨潤性の評価方法］
　ＰＰ基材上に塗膜を作成し（膜厚１５０μｍ）、乾燥させ、剥がして得られた乾燥塗膜（フィルム）について、水に対する耐久性試験を実施した。詳細には、得られた乾燥塗膜を常温で水中に１日浸漬し、浸漬前の重量から、浸漬後の重量を差し引いて溶出量とした。該溶出量を、浸漬前の感想塗膜重量で割って、溶出率とした。さらに、浸漬後の乾燥塗膜の面積から、浸漬前の乾燥塗膜の面積を差し引いて膨潤面積とし、該膨潤面積を浸漬前の乾燥塗膜の面積で割って、膨潤率とした。 [Evaluation method for water resistance and water swelling]
A coating film was prepared on a PP substrate (thickness: 150 μm), dried, and the dried coating film (film) obtained by peeling was subjected to a durability test against water. Specifically, the obtained dry coating film was immersed in water at room temperature for one day, and the weight after immersion was subtracted from the weight before immersion to obtain the elution amount. The elution amount was divided by the weight of the impression coating film before immersion to obtain the elution rate. Further, the area of the dry coating film before immersion was subtracted from the area of the dry coating film after immersion to obtain the swelling area, and the swelling area was divided by the area of the dry coating film before immersion to obtain the swelling rate.
　評価結果を表１に示す。 The evaluation results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　実施例１～５は、本発明の実施例であり、当初は均質でありながらも、加熱により樹脂を偏析させ、最終的には異なる種類の基材間の接着性を発現できる塗膜を形成させることが可能であった。 Examples 1 to 5 are examples of the present invention, and although they are homogeneous at the beginning, the resin is segregated by heating, and finally, a coating film capable of exhibiting adhesiveness between different types of substrates is formed. It was possible to make it.
　比較例１は、ビニル重合体（Ａ１）を含まない例であり、異種基材間の接着性が不良であった。比較例２は、ビニル重合体（Ａ１）及びポリエステル樹脂（Ａ２）が複合化されていない例であり、特に、ＰＥＴとＰＶＣの接着性が十分に満足できるものではなかった。比較例３は、ポリエステル樹脂（Ａ２）を含まない例であり、異種基材間の接着性が不良であった。 Comparative Example 1 is an example in which the vinyl polymer (A1) is not contained, and the adhesiveness between different kinds of substrates is poor. Comparative Example 2 is an example in which the vinyl polymer (A1) and the polyester resin (A2) are not composited, and in particular, the adhesiveness between PET and PVC was not sufficiently satisfactory. Comparative Example 3 is an example in which the polyester resin (A2) is not contained, and the adhesiveness between different kinds of substrates is poor.

Claims (9)

  1. 　複合樹脂（Ａ）及び水性媒体（Ｂ）を含み、
    　前記複合樹脂（Ａ）が、ビニル重合体（Ａ１）とポリエステル樹脂（Ａ２）とを含むものである水性樹脂組成物。     Includes composite resin (A) and aqueous medium (B)
    An aqueous resin composition in which the composite resin (A) contains a vinyl polymer (A1) and a polyester resin (A2).
  2. 　前記ポリエステル樹脂（Ａ２）の酸価が、０．１ｍｇＫＯＨ／ｇ以上１００ｍｇＫＯＨ／ｇ以下である請求項１記載の水性樹脂組成物。 The aqueous resin composition according to claim 1, wherein the polyester resin (A2) has an acid value of 0.1 mgKOH / g or more and 100 mgKOH / g or less.
  3. 　前記ポリエステル樹脂（Ａ２）に含まれる芳香環量が、０．０１ｍｏｌ／ｋｇ以上２０ｍｏｌ／ｋｇ以下である請求項１又は２記載の水性樹脂組成物。 The aqueous resin composition according to claim 1 or 2, wherein the amount of aromatic ring contained in the polyester resin (A2) is 0.01 mol / kg or more and 20 mol / kg or less.
  4. 　前記ビニル重合体（Ａ１）と、前記ポリエステル樹脂（Ａ２）との質量比（（Ａ１）／（Ａ２））が、０．００１以上３以下である請求項１～３のいずれか１項記載の水性樹脂組成物。 The one according to any one of claims 1 to 3, wherein the mass ratio ((A1) / (A2)) of the vinyl polymer (A1) to the polyester resin (A2) is 0.001 or more and 3 or less. Aqueous resin composition.
  5. 　請求項１～４のいずれか１項記載の水性樹脂組成物を含むコーティング剤。 A coating agent containing the aqueous resin composition according to any one of claims 1 to 4.
  6. 　請求項１～４のいずれか１項記載の水性樹脂組成物を含む接着剤。 An adhesive containing the aqueous resin composition according to any one of claims 1 to 4.
  7. 　請求項１～４のいずれか１項記載の水性樹脂組成物から形成される塗膜。 A coating film formed from the aqueous resin composition according to any one of claims 1 to 4.
  8. 　請求項１～４のいずれか１項記載の水性樹脂組成物から形成される接着層。 An adhesive layer formed from the aqueous resin composition according to any one of claims 1 to 4.
  9. 　請求項７記載の塗膜又は請求項８記載の接着層を有する積層体。 A laminate having the coating film according to claim 7 or the adhesive layer according to claim 8.
PCT/JP2021/045255 2020-12-22 2021-12-09 Aqueous resin composition, coating agent, adhesive, coating film, adhesive layer and multilayer body WO2022138183A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07102149A (en) * 1993-09-30 1995-04-18 Taisei Kako Kk Aqueous acrylic-polyester graft resin composition and coating material or ink containing the same
JPH0939180A (en) * 1995-07-24 1997-02-10 Toyobo Co Ltd Polyamide film laminate
JPH1060219A (en) * 1996-06-27 1998-03-03 Vianova Resins Gmbh Self-crosslinkable aqueous dispersion containing polyester and vinyl polymer
JPH11269238A (en) * 1998-03-23 1999-10-05 Dainippon Ink & Chem Inc Water dispersion of fluorine composite resin, preparation thereof and product coated therewith

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07102149A (en) * 1993-09-30 1995-04-18 Taisei Kako Kk Aqueous acrylic-polyester graft resin composition and coating material or ink containing the same
JPH0939180A (en) * 1995-07-24 1997-02-10 Toyobo Co Ltd Polyamide film laminate
JPH1060219A (en) * 1996-06-27 1998-03-03 Vianova Resins Gmbh Self-crosslinkable aqueous dispersion containing polyester and vinyl polymer
JPH11269238A (en) * 1998-03-23 1999-10-05 Dainippon Ink & Chem Inc Water dispersion of fluorine composite resin, preparation thereof and product coated therewith

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