WO2016047415A1 - Aqueous urethane resin composition, coating agent and article - Google Patents

Aqueous urethane resin composition, coating agent and article Download PDF

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Publication number
WO2016047415A1
WO2016047415A1 PCT/JP2015/075060 JP2015075060W WO2016047415A1 WO 2016047415 A1 WO2016047415 A1 WO 2016047415A1 JP 2015075060 W JP2015075060 W JP 2015075060W WO 2016047415 A1 WO2016047415 A1 WO 2016047415A1
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Prior art keywords
urethane resin
group
mass
resin composition
coating film
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PCT/JP2015/075060
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French (fr)
Japanese (ja)
Inventor
潤一 宮宅
白髪　潤
定 永浜
広義 神成
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Dic株式会社
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Priority to JP2016544491A priority Critical patent/JP6128285B2/en
Publication of WO2016047415A1 publication Critical patent/WO2016047415A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes

Definitions

  • the present invention relates to an aqueous urethane resin composition that can be used for various applications such as a coating agent and an adhesive.
  • Aqueous urethane resin compositions are generally used in various applications including coating agents and adhesives because they have good adhesion to substrates and can form flexible coatings.
  • aqueous urethane resin composition examples include an aqueous polyurethane dispersion, a) at least one organic aliphatic, alicyclic or aromatic di, tri- or polyisocyanate, b) at least one isocyanate reaction.
  • a polycarbonate diol, triol or polyol c) at least one compound comprising at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group, and d) at least one isocyanate-reactive group and At least one compound comprising at least one dispersed active group, and optionally e) at least one compound comprising at least two isocyanate-reactive groups and having a molecular weight of less than 1000 g / mol, preferably less than 500 g / mol.
  • aqueous polyurethane dispersions which the reaction product obtained is characterized by being obtained by dispersing in water are known (e.g., see Patent Document 1.).
  • aqueous urethane resin composition for example, for the surface coating of optical members such as flexible displays, etc.
  • coating films formed using the aqueous polyurethane dispersion are weather resistant. Insufficient solvent resistance may cause cracking or yellowing when the paint is used outdoors, or may peel off or dissolve when used with an industrial coating agent. Further, since the coating film formed using the aqueous polyurethane dispersion is not sufficient in terms of hardness, for example, when used for a surface coating agent such as a touch panel, the coating film is easily damaged and may cause poor appearance.
  • the problems to be solved by the present invention have excellent coating film hardness, elongation and flexibility, and excellent corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates. It is to provide an aqueous urethane resin composition capable of forming a coating film.
  • a polyol as a raw material for a urethane resin is an alkylene diol having 1 to 5 carbon atoms having two or more polymerizable unsaturated groups (a1- 1) or by using an aqueous urethane resin composition containing a urethane resin (A) using an oxyalkylene diol (a1-2) having 1 to 9 carbon atoms having two or more polymerizable unsaturated groups,
  • A aqueous urethane resin composition containing a urethane resin
  • a1-2 oxyalkylene diol having 1 to 9 carbon atoms having two or more polymerizable unsaturated groups
  • the present invention is a urethane resin (A) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group, and an aqueous urethane resin composition containing an aqueous medium (B),
  • the urethane resin (A) is an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or two or more polymerizable compounds represented by the following general formula (2) It is obtained by reacting a polyol (a1) containing an unsaturated group-containing oxyalkylenediol (a1-2), a polyisocyanate (a2), and a silane coupling agent (a3).
  • the present invention relates to an aqueous urethane resin composition.
  • R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of the linear alkylene group having 1 to 9 carbon atoms.
  • R 1 and R 3 in the general formula (2) represent a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group.
  • R 2 is an alkylene having 1 to 5 carbon atoms. Represents a group.
  • the aqueous urethane resin composition of the present invention has excellent coating film hardness, elongation and flexibility, and excellent corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates. Since a coating film can be formed, for example, acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC resin), ABS / PC resin, polystyrene resin (PS resin), polymethacrylic acid resin (PMMA resin), polyester resin It can be suitably used for a coating agent and an adhesive for a plastic substrate such as (PET resin).
  • ABS resin acrylonitrile-butadiene-styrene resin
  • PC resin polycarbonate resin
  • PS resin polystyrene resin
  • PMMA resin polymethacrylic acid resin
  • polyester resin It can be suitably used for a coating agent and an adhesive for a plastic substrate such as (PET resin).
  • the aqueous urethane resin composition of the present invention is an aqueous urethane resin composition containing a urethane resin (A) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group, and an aqueous medium (B).
  • the urethane resin (A) is an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or two represented by the following general formula (2): It is obtained by reacting the polyol (a1) containing the above oxyalkylene diol (a1-2) having a polymerizable unsaturated group, the polyisocyanate (a2), and the silane coupling agent (a3). It is characterized by that.
  • the urethane resin (A) has one or both of a hydrolyzable silyl group and a silanol group.
  • the hydrolyzable silyl group or silanol group can be hydrolyzed by contact with water or the like to form a silanol group in which a hydroxyl group is bonded to a silicon atom.
  • the hydrolyzable silyl group or silanol group can react with a self-condensation reaction or other functional group when forming a coating film. Thereby, it becomes possible to form a coating film excellent in corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates.
  • the hydrolyzable silyl group or silanol group is introduced into the urethane resin (A) by using the silane coupling agent (a3) used when the urethane resin (A) is produced.
  • urethane resin (A) among the urethane resins having a polymerizable unsaturated group, an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or the following A polyol (a1) containing an oxyalkylenediol (a1-2) having two or more polymerizable unsaturated groups represented by the general formula (2), a polyisocyanate (a2), and a silane coupling agent (a3) The one obtained by reacting with is used.
  • R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms.
  • R 1 and R 3 in the general formula (2) represent a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group.
  • R 2 is an alkylene having 1 to 5 carbon atoms. Represents a group.
  • polyol (a1) used for the production of the urethane resin (A) two or more polymerizable unsaturated groups are present in the side chain with respect to the main chain of the urethane resin (A) in which urethane bonds are mainly present.
  • the polymerizable unsaturated group derived from the alkylene diol (a1-1) and the oxyalkylene diol (a1-2) undergoes radical polymerization when forming a coating film or the like.
  • the coating film which has the outstanding coating-film hardness, elongation, and flexibility can be formed.
  • R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms.
  • pentaerythritol di (meth) acrylate has a structure in which R 1 in the general formula (1) has two atomic groups containing a polymerizable unsaturated group in the side chain of a propylene group having 3 carbon atoms.
  • alkylene diol (a1-1) those having 2 or more and 5 or less polymerizable unsaturated groups are preferably used, and those having 2 or more and 3 or less polymerizable unsaturated groups are used. It is more preferable to obtain an aqueous urethane resin composition capable of forming a coating film having excellent coating film hardness, elongation and flexibility.
  • alkylene diol (a1-1) examples include pentaerythritol di (meth) acrylate [dimethylolpropane di (meth) acrylate], dimethylolmethane di (meth) acrylate (R 1 in the general formula (1) is , Those having 3 carbon atoms and two atomic groups having a polymerizable unsaturated group), diethylolmethane di (meth) acrylate, and diethylolpropane di (meth) acrylate (general formula (1 R 1 is a group having 5 carbon atoms and having two atomic groups having a polymerizable unsaturated group.), Dipropanolmethane di (meth) acrylate, dipropanolpropanedi (meth) acrylate (formula (1) R 1 in the intended 7 carbon atoms, is an atomic group having a polymerizable unsaturated group as it has two.) Di-butanol methane di (
  • pentaerythritol di (meth) acrylate and dimethylolmethane di (meth) acrylate is an aqueous urethane resin composition capable of forming a coating film having excellent coating film hardness, elongation and flexibility. Since it is obtained, it is more preferable.
  • These alkylene diols (a1-1) can be used alone or in combination of two or more.
  • “(meth) acrylate” refers to either one or both of acrylate and methacrylate.
  • R 1 and R 3 in the general formula (2) have a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group.
  • R 1 and R 3 in the general formula (2) have a total of two or more structures having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group, preferably in the range of 2 or more and 5 or less, More preferably, it has in the range of 2 or more and 3 or less.
  • R 2 in the general formula (2) represents an alkylene group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentyl group.
  • Examples of the oxyalkylene diol (a1-2) include bis (3-acryloyloxy-2-hydroxypropoxy) methane (R 1 and R 3 in the general formula (2) are those having 2 carbon atoms and are polymerizable. One having an unsaturated group and R 2 having one carbon atom), 1,2-bis (3-acryloyloxy-2-hydroxypropoxy) ethane (general formula (2 And R 1 and R 3 are those having 2 carbon atoms and having one atomic group having a polymerizable unsaturated group, and R 2 is having 2 carbon atoms.), 1, 3-bis (3-acryloyloxy-2-hydroxypropoxy) propane (in formula (2), R 1 and R 3 have 2 carbon atoms and have one atomic group having a polymerizable unsaturated group) in and, R 2 is the number of carbon atoms Is of.), 1,4-bis (3-acryloyloxy-2-hydroxypropoxy) butane (formula (2) R 1 and R 3 in the intended 2 carbon atoms, a poly
  • bis (3-acryloyloxy-2-hydroxypropoxy) methane provides an aqueous urethane resin composition capable of forming a coating film having excellent coating hardness, elongation and flexibility. More preferable.
  • These oxyalkylene diols (a1-2) can be used alone or in combination of two or more.
  • the alkylene diol (a1-1) and the oxyalkylene diol (a1-2) are used in a total range of 0.1 to 49% by mass in the total amount of raw materials used in the production of the urethane resin (A).
  • the range of 1 to 15% by mass is more preferable.
  • the total amount of the raw material used for manufacture of the said urethane resin (A) points out the total mass containing it, when a polyol (a1), polyisocyanate (a2), and a chain extender are used.
  • polyol (a1) that can be used in the production of the urethane resin (A), in addition to the alkylene diol (a1-1) and the oxyalkylene diol (a1-2), other polyols may be used in combination as necessary. be able to.
  • Examples of the other polyol include a polyol having a hydrophilic group for the purpose of imparting excellent water dispersion stability to the urethane resin (A).
  • polyol having a hydrophilic group examples include a polyol having an anionic group, a polyol having a cationic group, and a polyol having a nonionic group. Of these, polyols having an anionic group are preferred.
  • polyol having an anionic group examples include a polyol having a carboxyl group and a polyol having a sulfonic acid group.
  • polyol having a carboxyl group examples include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like. Among them, 2,2-dimethylol is preferable. Propionic acid is preferred. Moreover, the polyester polyol which has a carboxyl group obtained by making the polyol which has the said carboxyl group, and various polycarboxylic acids react can also be used.
  • polyol having a sulfonic acid group examples include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, and salts thereof; Polyester polyols obtained by reacting low molecular polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol and the like, and the polyester polyol and ⁇ -butyrolactone And polyester polyols obtained by reacting cyclic ester compounds such as ⁇ -valerolactone and ⁇ -caprolactone.
  • dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, and
  • the anionic groups are preferably partially or wholly neutralized with a basic compound or the like because good water dispersibility can be expressed.
  • Examples of basic compounds that can be used when neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine; sodium hydroxide, water Examples thereof include metal hydroxides including potassium oxide and lithium hydroxide.
  • examples of the polyol having a cationic group include a polyol having a tertiary amino group. Specific examples include N-methyl-diethanolamine and polyols obtained by reacting a compound having two epoxies with a secondary amine.
  • the cationic group is preferably partially or completely neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, phosphoric acid or the like.
  • an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, phosphoric acid or the like.
  • the tertiary amino group as the cationic group is preferably partly or entirely quaternized.
  • the quaternizing agent include dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like, and dimethyl sulfate is preferable.
  • examples of the polyol having a nonionic group include polyalkylene glycol having a structural unit derived from ethylene oxide.
  • the polyol having a hydrophilic group is preferably used in the range of 1 to 20% by mass in the total amount of raw materials used in the production of the urethane resin (A), and further has excellent coating film hardness and elongation.
  • an aqueous urethane resin composition capable of forming a coating film having flexibility is obtained, it is more preferably used in the range of 1 to 10% by mass.
  • examples of the other polyol include polyester polyol, polycarbonate polyol, and polyether polyol.
  • polyester polyols and polycarbonate polyols are preferable because a coating film having even better coating film hardness, elongation, and flexibility can be formed.
  • polyester polyol examples include a polyester polyol obtained by reacting a low molecular weight polyol and a polycarboxylic acid; a polyester polyol obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ⁇ -caprolactone; Examples include polyester polyols obtained by polymerization.
  • low molecular weight polyol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,3-butanediol and the like having a molecular weight of about 50 to 300.
  • Aliphatic polyols such as cyclohexane dimethanol, and polyols having an aromatic structure such as bisphenol A and bisphenol F. Of these, 1,6-hexanediol and neopentyl glycol are preferable.
  • polycarboxylic acid examples include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid. And aromatic polycarboxylic acids such as anhydrides or esterified products thereof.
  • polycarbonate polyol examples include diols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and cyclohexanedimethanol, carbonate esters such as dimethyl carbonate and diethyl carbonate, and phosgene. And the like obtained by reacting with the above.
  • polyester polyol, polyether polyol and polycarbonate polyol are preferably used in the range of 1 to 70% by mass, and in the range of 15 to 45% by mass, based on the total amount of raw materials used for the production of the urethane resin (A). It is more preferable to use in the case of being able to form a coating film having even better coating film hardness, elongation and flexibility.
  • polyisocyanate (a2) used in the production of the urethane resin (A) examples include polyisocyanates having an aliphatic cyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate; 4,4′-diphenylmethane Aromatic polyisocyanates such as diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate Aliphatic polyiso, such as isocyanate Aneto and
  • polyisocyanate (a2) dicyclohexylmethane diisocyanate or isophorone diisocyanate is preferable because it can form a coating film having excellent coating film hardness, elongation and flexibility.
  • these polyisocyanates (a2) can be used alone or in combination of two or more.
  • silane coupling agent (a3) used for the production of the urethane resin (A) those having a reactive group can be used.
  • a part or all of the hydrolyzable silyl group of the silane coupling agent (a3) may be hydrolyzed to form a silanol group.
  • Examples of the reactive group include an amino group, an isocyanate group, a (meth) acrylate group, a vinyl group, a mercapto group, and an epoxy group.
  • (meth) acrylate group refers to either one or both of an acrylate group and a methacrylate group.
  • silane coupling agent (a3) examples include vinyl silanes such as vinyl tris ( ⁇ -methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, and (meth) acryl silane such as ⁇ -methacryloxypropyl trimethoxy silane.
  • N-2- (aminoethyl) -3-aminopropyltriethoxysilane is a coating film with excellent corrosion resistance, hot water resistance, chemical resistance, solvent resistance, and adhesion to various substrates. Can be formed.
  • These silane coupling agents can be used alone or in combination of two or more.
  • the silane coupling agent (a3) should be used in a range of 0.1 to 10% by mass in the total amount of raw materials used in the production of the urethane resin (A), corrosion resistance, hot water resistance, chemical resistance, It is preferable because it can form a coating film excellent in solvent resistance and adhesion to various substrates, and more preferably in the range of 2 to 7% by mass.
  • the urethane resin (A) is a step of producing a urethane resin (A ′) having an isocyanate group or a hydroxyl group at a terminal by reacting the polyol (a1) with the polyisocyanate (a2) [ 1] and the step [2] of reacting the urethane resin (A ′) with the silane coupling agent (a3).
  • the silane coupling agent (a3) is a silane coupling agent having two or more reactive groups selected from the group consisting of an amino group and an isocyanate group
  • the urethane (A) is the polyol (a1).
  • the polyisocyanate (a2) and the silane coupling agent (a3) can be mixed and reacted.
  • the reaction of the polyol (a1) and the polyisocyanate (a2) in the step [1] constituting the production process of the urethane resin (A) is performed, for example, in the absence of a solvent or in the presence of an organic solvent.
  • (A1) and the polyisocyanate (a2) can be mixed and carried out at a reaction temperature in the range of about 50 to 150 ° C.
  • the reaction between the polyol (a1) and the polyisocyanate (a2) is, for example, such that the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is 0.8 to 2.5. It is preferably carried out in the range, more preferably in the range of 0.9 to 1.5.
  • urethane resin (A ′) having an isocyanate group at the terminal manufactured in the step [1] it is possible to form a coating film having even more excellent coating film hardness, elongation and flexibility.
  • a chain extender can be used as necessary.
  • chain extender that can be used for producing the urethane resin (A ′)
  • polyamine, hydrazine compound, other active hydrogen atom-containing compounds, and the like can be used.
  • polyamine examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like. Moreover, these polyamines can be used alone or in combination of two or more.
  • hydrazine compound examples include hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; ⁇ -semicarbazide And propionic acid hydrazide.
  • these hydrazine compounds can be used alone or in combination of two or more.
  • Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, Glycols such as methylene glycol, glycerin and sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, phenol such as hydroquinone, and water
  • the urethane resin composition of the present invention can be used alone or in combination of two or more within the range in which the storage stability does not deteriorate.
  • Examples of the organic solvent that can be used when the urethane resin (A ′) is produced by the step [1] include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; ethyl acetate and butyl acetate. And nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.
  • the said organic solvent when used when manufacturing the said urethane resin (A), in order to reduce the load with respect to safety
  • the said process [2] which comprises the manufacturing process of the said urethane resin (A) mixes the said urethane resin (A ') obtained by the said process [1], and the said silane coupling agent (a3).
  • This is a reaction step.
  • the step [2] is preferably performed, for example, at a reaction temperature of 20 to 80 ° C.
  • the aqueous urethane resin composition of the present invention neutralizes part or all of the hydrophilic group of the urethane resin (A) such as the urethane resin (A-1) obtained by the above method, It can manufacture by mixing a neutralized material and an aqueous medium (B).
  • Examples of the aqueous medium (B) include water, organic solvents miscible with water, and mixtures thereof.
  • the organic solvent miscible with water include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycols And lactams such as N-methyl-2-pyrrolidone.
  • only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used.
  • the aqueous medium (B) is preferably water alone or a mixture of water and an organic solvent miscible with water, particularly water alone, from the viewpoint of safety and environmental burden.
  • the ratio of the aqueous medium (B) is preferably in the range of 10 to 90% by mass and more preferably in the range of 30 to 70% by mass with respect to the total amount of the aqueous urethane resin composition.
  • the urethane resin (A) obtained by the above method has a weight average molecular weight in the range of 10,000 to 500,000 because it can form a coating film having even better coating film hardness, elongation and flexibility. It is preferable to use those having a weight average molecular weight in the range of 20,000 to 200,000, more preferably using a weight average molecular weight in the range of 40,000 to 100,000. preferable.
  • the urethane resin (A) it is possible to form a coating film having further excellent coating film hardness, elongation and flexibility, and excellent chemical resistance and solvent resistance. It is preferable to use what has.
  • urethane resin (A) use of a resin having a urea bond equivalent in the range of 500 to 50,000 has even more excellent coating film hardness, elongation and flexibility, and chemical resistance. It is preferable because a coating film having excellent properties and solvent resistance can be formed.
  • the urethane resin (A) preferably contains the urethane resin (A) in the range of 5 to 85% by mass in the total amount of the aqueous urethane resin composition, and is in the range of 15 to 50% by mass. It is preferable that it is contained.
  • an emulsifier or the like When dispersing the urethane resin (A) in an aqueous medium, an emulsifier or the like may be used as necessary.
  • emulsifier examples include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
  • nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer.
  • Fatty acid salts such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc.
  • anionic emulsifiers such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc.
  • anionic emulsifiers such as sodium oleate, alkyl sulfate esters, alkylbenzene
  • polysiloxane (X) can be used in the aqueous urethane resin composition of the present invention.
  • polysiloxane (X) for example, condensates of various alkoxysilanes can be used.
  • alkoxysilane examples are commercially available as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, “MEK-ST” and “IPA-ST” (manufactured by Nissan Chemical Industries, Ltd.).
  • Tetraalkoxysilane methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, which are represented by organosilica sol N-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, Cycloalkenyl trimethoxysilane, trialkoxysilane such as phenyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyl dimethoxysilane, and di-alkoxysilanes such as diethyl diethoxy silane.
  • polysiloxane (X) a polymer in which a segment composed of a vinyl polymer and a segment composed of a polysiloxane are bonded can also be used.
  • Examples of the polymer include vinyl monomers such as methyl (meth) acrylate and ethyl (meth) acrylate, 3- (meth) acryloxypropyltrimethoxysilane, and (meth) acryloxypropyltriethoxysilane.
  • Examples thereof include a polymer obtained by polymerizing with a silane compound having a polymerizable unsaturated group such as a vinyl polymer having a hydrolyzable silyl group obtained by condensing the alkoxysilane with the polymer.
  • the alkoxysilane is sequentially or collectively supplied into an organic solvent solution of a vinyl polymer having a hydrolyzable silyl group and the like, and the polymer is stirred for 0.5 hour in the range of 20 to 120 ° C.
  • the reaction can be carried out for about 24 hours by subjecting the hydrolyzable silyl group of the vinyl polymer and the hydrolyzable silyl group of the alkoxysilane to a hydrolytic condensation reaction.
  • the polysiloxane (X) Since the polysiloxane (X) has a hydrolyzable silyl group or silanol group, it causes a hydrolytic condensation reaction with the hydrolyzable silyl group or silanol group of the urethane resin (A) and is strong.
  • a polysiloxane-polyurethane structure By forming a polysiloxane-polyurethane structure, it is possible to form a coating film excellent in corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates.
  • polysiloxane (X) a strong polysiloxane-polyurethane structure having a higher crosslinking density is formed, thereby providing corrosion resistance, hot water resistance, chemical resistance, solvent resistance, and adhesion to various substrates. It is preferable to use one having a polymerizable unsaturated group because a coating film excellent in the thickness can be formed.
  • the polysiloxane (X) having a polymerizable unsaturated group is, for example, a silane compound having a polymerizable unsaturated group such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane. It can be obtained by producing as a raw material for the condensate of alkoxysilane obtained using
  • the polymerizable unsaturated group is preferably contained in the polysiloxane (X) in a range of 0.2 to 3 mmol / g.
  • aqueous urethane resin composition of the present invention it is preferable to use a polymerization initiator in order to promote radical polymerization of the polymerizable unsaturated group of the urethane resin (A).
  • the polymerization initiator for example, benzophenone, benzyl, Michler ketone, thioxanthone, anthraquinone, benzoin, dialkoxyacetophenone, acyl oxime ester, benzyl ketal, hydroxyalkylphenone, halogenoketone and the like can be used.
  • the photopolymerization initiator may be used in combination with a tertiary amine such as methylamine, diethanolamine, N-methyldiethanolamine, or tributylamine as necessary.
  • polymerization initiator examples include 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 4,4′-azobis (4-cyano) valeric acid, 2,2′-azobis (2- Thermal polymerization initiators such as peroxides such as amidinopropane) dihydrochloride, benzoyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide can also be used.
  • the polymerization initiator is preferably used in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the solid content of the urethane resin (A).
  • the water-based urethane resin composition of the present invention may contain additives as necessary within a range that does not impair the object of the present invention.
  • the additive include a compound having a polymerizable unsaturated group, a film forming aid, a filler, a thixotropic agent, a tackifier, a pigment, an antibacterial agent, and the like.
  • Examples of the compound having a polymerizable unsaturated group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meta ) Acrylate, 1-adamantyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, di
  • the film forming aid examples include an anionic surfactant (dioctylsulfosuccinate ester soda salt, etc.), a hydrophobic nonionic surfactant (sorbitan monooleate, etc.), silicone oil, and the like.
  • thixotropy-imparting agent examples include fatty acid, fatty acid metal salt, fatty acid ester, paraffin, resin acid, surfactant, polyacrylic acid and the like surface-treated filler, polyvinyl chloride powder, hydrogenated castor oil, Fine powder silica, organic bentonite, sepiolite and the like can be mentioned.
  • pigment known and commonly used inorganic pigments and organic pigments can be used.
  • the inorganic pigment for example, titanium oxide, antimony red, bengara, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine blue, carbon black, graphite and the like can be used.
  • organic pigment examples include quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, phthalocyanine pigment, anthrapyrimidine pigment, ansanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, Organic pigments such as quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments can be used. Two or more kinds of these pigments can be used in combination. These pigments may be surface-treated and have a self-dispersing ability with respect to an aqueous medium.
  • antibacterial agent for example, silver chloride, trifuranide, dichlorofluanide, fluorophorpet, zinc pyrithione, methyl 2-benzimidazole carbanate, 2- (4-thiazolyl) benzimidazole and the like can be used.
  • reaction accelerators metal reaction accelerators, metal salt reaction accelerators, amine reaction accelerators, etc.
  • stabilizers ultraviolet absorbers, antioxidants, heat stabilizers, etc.
  • various additives such as moisture removing agents (4-paratoluenesulfonyl isocyanate, etc.), adsorbents (quick lime, slaked lime, zeolite, molecular sieves, etc.), adhesion-imparting agents, antifoaming agents, leveling agents and the like.
  • the aqueous urethane resin composition of the present invention is obtained by dispersing the urethane resin (A) and the acrylic resin (B) in the aqueous medium (B). At this time, it is preferable that the urethane resin (A) and the acrylic resin (B) are present as separate resin particles in the aqueous medium (B).
  • aqueous urethane resin composition of the present invention can be suitably used, for example, as a coating agent that can impart surface protection and design properties of various substrates.
  • Examples of the substrate on which the coating agent can be applied to form a coating film include a glass substrate, a metal substrate, a plastic substrate, paper, a wood substrate, and a fibrous substrate.
  • the base material of porous body structures such as a urethane foam, can also be used.
  • plastic substrates include polycarbonate substrates, polyester substrates, acrylonitrile-butadiene-styrene substrates, polyacryl substrates, polystyrene substrates, polyurethane substrates, epoxy resin substrates, polyvinyl chloride substrates, and polyamide groups. Material can be used.
  • a plated steel plate such as a galvanized steel plate or an aluminum-zinc alloy steel plate, an iron plate, an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate, or the like can be used.
  • the base material may be a planar material made of the material or may have a curved portion, or may be a base material made of fibers such as a nonwoven fabric.
  • the coating agent of the present invention has, for example, the urethane resin (A) after being applied directly to the surface of the base material or the surface of the base material on which a primer layer or the like has been previously provided and then dried.
  • a coating film can be formed by advancing radical polymerization of a polymerizable unsaturated double group.
  • a coating film is formed on the surface of the release paper by applying the coating agent on the release paper, then drying and curing, and a non-woven fabric obtained by applying an adhesive or an adhesive on the coating film.
  • a film formed using the coating agent can be laminated on the surface of a desired substrate by laminating the substrate made of such fibers and peeling the release paper.
  • Examples of the method for applying the coating agent on the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.
  • examples of the method for curing the coating agent include a heating method and a method of irradiating active energy rays such as ultraviolet rays.
  • the heating method varies depending on the type of radical polymerization initiator to be used. For example, by performing the heating at a temperature of about 100 to 150 ° C. for about 10 to 30 minutes, the radical polymerization can be advanced and cured. .
  • a method using a known lamp such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, or an LED lamp is used.
  • a known lamp such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, or an LED lamp.
  • the exposure dose of the actinic energy ray is preferably in the range of 0.05 ⁇ 5J / cm 2, more preferably in the range of 0.1 ⁇ 3J / cm 2, 0.1 ⁇ 1J / cm 2 It is particularly preferable that the range is
  • the above-mentioned ultraviolet irradiation amount is based on values measured in a wavelength range of 300 to 390 nm using a UV checker UVR-N1 (manufactured by Nippon Battery Co., Ltd.).
  • the thickness of the coating film that can be formed using the coating agent of the present invention can be appropriately adjusted according to the use of the substrate, but is preferably about 0.1 to 100 ⁇ m.
  • articles provided with a coating film formed using the coating agent on the substrate are optical members such as liquid crystal displays and flexible displays, mobile phones, various plastic products including home appliances, It can be used as metal products such as automobile exteriors and building materials.
  • a vinyl polymer (Y-1) having a trimethoxysilyl group was prepared.
  • the temperature of the reaction vessel was adjusted to 80 ° C., and 131 parts by mass of methyltrimethoxysilane (MTMS), 226 parts by mass of 3-acryloyloxypropyltrimethoxysilane (APTS), and 116 parts by mass of dimethyldimethoxysilane (DMDMS) were added.
  • MTMS methyltrimethoxysilane
  • APTS 3-acryloyloxypropyltrimethoxysilane
  • DDMS dimethyldimethoxysilane
  • Example 1 Aqueous urethane resin composition (1)
  • a heating device a stirrer, a thermometer and a reflux condenser
  • 88.8 parts by mass of methyl ethyl ketone, polycarbonate polyol (1,6-hexanediol, 1,5-pentanediol and diethyl carbonate were added.
  • aqueous urethane resin composition (1) having a nonvolatile content of 33% by mass was obtained by adding 47.5 parts by mass of an aqueous piperazine solution, causing a chain extension reaction at 40 ° C., and distillation under reduced pressure.
  • Example 2 Aqueous urethane resin composition (2)
  • a urethane resin composition (2) was obtained.
  • Example 3 Aqueous urethane resin composition (3)
  • the urethane resin (I-1) organic solvent solution 278.1 parts by mass of the polysiloxane (X-1) obtained in Production Example 1, and 8.9 parts by mass of dimethylethanolamine, 1207.1 parts by mass of exchange water was added and stirred sufficiently, 47.5 parts by mass of a 10% by mass piperazine aqueous solution was added, a chain elongation reaction was carried out at 40 ° C., and distillation under reduced pressure was carried out.
  • a urethane resin composition (3) was obtained.
  • Example 4 Aqueous urethane resin composition (4)
  • a heating device a stirrer, a thermometer and a reflux condenser
  • 89.2 parts by mass of methyl ethyl ketone, polycarbonate polyol (1,6-hexanediol, 1,5-pentanediol and diethyl carbonate were added.
  • the total amount of the organic solvent solution of the urethane resin (I-2) was mixed with 303.6 parts by mass of the polysiloxane (X-1) obtained in Production Example 1 and 8.9 parts by mass of dimethylethanolamine. Thereafter, 1368.2 parts by mass of ion-exchanged water was added, and the mixture was sufficiently stirred and distilled under reduced pressure to obtain an aqueous urethane resin composition (4) having a nonvolatile content of 45% by mass.
  • Example 5 Aqueous urethane resin composition (5)
  • Example 6 Aqueous urethane resin composition (6)
  • 836.3 parts by mass of ion-exchanged water was added and stirred sufficiently, 47.5 parts by mass of a 10% by mass piperazine aqueous solution was added, and a chain elongation reaction was performed at 40 ° C., followed by distillation under reduced pressure.
  • an aqueous urethane resin composition (6) having a nonvolatile content of 45% by mass was obtained.
  • Example 7 Aqueous urethane resin composition (7)
  • a 2-liter four-necked flask equipped with a heating device, a stirrer, a thermometer and a reflux condenser was added to 1,4-bis (3-acryloyloxy-2-hydroxypropoxy) butane (R 1 and R in the general formula (2)). 3 has 2 carbon atoms and has one atomic group having a polymerizable unsaturated group, and R 2 has 4 carbon atoms.) 35.9 parts by mass, methylhydroquinone 007 parts by mass and 0.07 parts by mass of 2,6-tert-butyl-p-cresol were charged and adjusted at 50 ° C. with stirring.
  • aqueous urethane resin composition (7) having a nonvolatile content of 33% by mass was obtained by adding 47.5 parts by mass of piperazine aqueous solution, causing chain extension reaction at 40 ° C., and distillation under reduced pressure.
  • Example 8 Aqueous urethane resin composition (8)
  • a urethane resin composition (8) was obtained.
  • Aqueous urethane resin composition (C1) Polyester polyol (number average molecular weight 2,000) obtained by reacting 1,6-hexanediol, neopentyl glycol and adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer ) 100 parts by weight, 7 parts by weight of 1,4-cyclohexanedimethanol, 5.5 parts by weight of 2,2-dimethylolpropionic acid, 1 part by weight of trimethylolpropane, and 60 parts by weight of dicyclohexylmethane diisocyanate, It mixed with 58 mass parts of methyl ethyl ketone, and was made to react on the conditions of the temperature of 80 degreeC in the said reaction container, and the organic solvent solution of the urethane prepolymer which has an isocyanate group at the terminal was obtained.
  • an organic solvent solution of the urethane prepolymer and 3 parts by mass of 2-hydroxyethyl acrylate are mixed and reacted under the conditions of a temperature of 80 ° C. in the reaction vessel, whereby the side chain has no polymerizable property.
  • An organic solvent solution of a urethane resin having a saturated bond and having an isocyanate group at the end of the main chain was obtained.
  • an organic solvent solution of the urethane resin 5 parts by mass of N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, and 163 parts by mass of methyl ethyl ketone are mixed, and the temperature in the reaction vessel is set to 50.
  • An organic solvent solution of a urethane resin (II-1) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group was obtained by adjusting the reaction to ° C.
  • aqueous urethane resin composition (C1) having a nonvolatile content of 30% by mass was obtained by adding part by mass, causing a chain elongation reaction at 40 ° C., and distillation under reduced pressure.
  • Aqueous urethane resin composition (C2) A total amount of the organic solvent solution of the urethane resin (II-1), 181 parts by mass of the polysiloxane (X-1) obtained in Production Example 1 and 4 parts by mass of dimethylethanolamine were mixed, and then ion-exchanged water 774 was used.
  • An aqueous urethane resin composition (C2) having a non-volatile content of 45% by mass is prepared by adding 46 parts by mass of a 10% by weight piperazine aqueous solution, subjecting it to chain elongation at 40 ° C., and distillation under reduced pressure. Got.
  • the obtained compounded liquid was apply
  • the hardness of the coating film constituting the article was measured by a method based on a JIS test method (JIS K-5600-5-4: 1999) scratch hardness (pencil method).
  • the measurement of the elongation of the test film was performed using “Autograph AG-Xplus 1 kN (between chucks; 50 mm, tensile speed 50 mm / min)” manufactured by Shimadzu Corporation, and was based on the elongation of the test film before the tensile test. Evaluation was performed according to the following evaluation criteria.
  • A The length of the test film after the tensile test was increased by 100% or more with respect to the length of the test film before the tensile test.
  • ⁇ The length of the test film after the tensile test was extended by 50% or more and less than 100% with respect to the length of the test film before the tensile test.
  • delta The length of the test film after a tensile test extended
  • X The length of the test film after the tensile test was elongated within a range of less than 10% with respect to the length of the test film before the tensile test.
  • the obtained compounded liquid was apply
  • the flexibility of the coating film constituting the article was measured by a method based on the JIS test method (JIS K-5600-5: 1999) flex resistance test method (mandrel diameter 2 mm), and the measurement result was In addition, the evaluation was made according to the following evaluation criteria.
  • ⁇ Cracks, wrinkles and whitening of the coating film were not observed at the bent part of the coating film. ⁇ : Some cracks in the coating film or white wrinkles were observed at the bent portion of the coating film. X: Remarkable cracks of the coating film were observed in the entire bent part of the coating film.
  • a photopolymerization initiator a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone
  • ⁇ Generation of cracks and yellowing is not observed on the coating film surface. ⁇ : Some cracks and yellowing are observed in a very small part of the coating surface. X: Generation
  • the obtained blended solution was applied to a 55% by mass aluminum-zinc alloy-plated steel sheet degreased with acetone using a bar coater so that the film thickness after drying was about 1 ⁇ m, and a dryer with an atmospheric temperature of 100 ° C.
  • the film was dried for 30 seconds and further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp to form a coating film. Then, what was cured at room temperature for 3 days was used as a test piece.
  • the surface of the coating film constituting the test piece is scratched with a cutter knife to a depth reaching the base material (cross cut part), and a salt spray test is performed with a salt spray tester manufactured by Suga Test Instruments Co., Ltd.
  • the rust generation area after 240 hours was visually evaluated and evaluated. The evaluation was performed separately for a flat portion not damaged by the cutter knife and a peripheral portion of the cross cut portion.
  • ⁇ Plane> The area where the generation
  • ⁇ The area where the occurrence of rust and the swelling or peeling of the coating film due to rust occurred was 5% or more and less than 30% with respect to the entire plane portion.
  • delta The area where the generation
  • X The area where the occurrence of rust and the swelling and peeling of the coating film due to rust occurred was 60% or more with respect to the entire plane portion.
  • the peripheral part of the crosscut part> (Double-circle): Generation
  • ⁇ A very small amount of rust was observed in the periphery of the crosscut part, but no peeling or swelling of the coating film due to it was observed.
  • ⁇ Rust was widely observed in the periphery of the crosscut portion, and although peeling or swelling of the coating film was observed due to this, no flow rust was observed.
  • Rust was widely generated in the periphery of the crosscut part, and peeling and swelling of the coating film due to the rust were observed. Further, contamination of the coating film due to flowing rust was observed.
  • the obtained blended solution was applied to a 55% by mass aluminum-zinc alloy-plated steel sheet degreased with acetone using a bar coater so that the film thickness after drying was about 1 ⁇ m, and a dryer with an atmospheric temperature of 100 ° C.
  • the film was dried for 30 seconds and further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp to form a coating film. Then, what was cured at room temperature for 3 days was used as a test piece. 1N hydrochloric acid was spotted on the surface of the coating film constituting the test piece, and the deterioration state of the coating film after standing for 180 minutes was observed.
  • the surface of the obtained coating film was rubbed 20 times back and forth on the cured coating film with a felt soaked with toluene and ethanol.
  • the state of the coating film before rubbing and after rubbing was judged by finger touch and visual observation.
  • the evaluation criteria are as follows.
  • the obtained compounded liquid was applied on each substrate shown below using a 3 mil applicator, dried at 60 ° C. for 30 minutes, further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp, and then 25 ° C.
  • a coating film cured for 2 days was prepared.
  • the surface of the obtained coating film was subjected to a cellophane (registered trademark) peeling test of 100 squares of 1 mm square according to JIS K-5400.
  • the number of grids not peeled was measured and evaluated according to the following criteria.
  • the substrate a substrate made of polyethylene terephthalate resin and a glass substrate were used.
  • A The number of grids not peeled is 90 or more.
  • ⁇ The number of grids not peeled is 60 or more and less than 90.
  • ⁇ The number of grids not peeled is 40 to less than 60.
  • X The number of grids which do not peel is less than 40.
  • Table 1 shows the compositions of the aqueous urethane resin compositions (1) to (8) obtained in Examples 1 to 8 and the above evaluation results.
  • the composition (blending amount) in Table 1 is shown as a nonvolatile content.
  • Table 2 shows the compositions and evaluation results of the aqueous urethane resin compositions (C1) and (C2) obtained in Comparative Examples 1 and 2.
  • the composition (blending amount) in Table 2 is expressed as a nonvolatile content.
  • the coating film obtained using the aqueous urethane resin composition of the present invention has excellent coating film hardness, elongation and flexibility, and It was confirmed that it was excellent in corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates.
  • Comparative Examples 1 and 2 are examples of a urethane resin using a polyol other than the polyol defined in the present invention as a polyol which is a raw material of the urethane resin.
  • the coating film obtained using the aqueous urethane resin composition of Comparative Example 1 is excellent in elongation and flexibility, the weather resistance, corrosion resistance, and adhesion to the polyethylene terephthalate substrate are insufficient, and solvent resistance It was confirmed that the property was extremely bad.
  • the coating film obtained using the aqueous urethane resin composition of Comparative Example 2 has insufficient corrosion resistance and hot water resistance, and also has extremely poor solvent resistance and adhesion to a polyethylene terephthalate substrate.
  • a coating film having both coating film hardness, elongation and flexibility, corrosion resistance, warm water resistance, chemical resistance and solvent resistance cannot be formed. It was.

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Abstract

An aqueous urethane resin composition is provided which contains an aqueous medium and a urethane resin having a hydrolyzable silyl group or a silano group and a polymerizable unsaturated group, and which is characterized in that the urethane resin is obtained by reacting polyols, polyisocyanate and a silane coupling agent, said polyols containing an alkylenediol having two or more polymerizable unsaturated groups represented by general formula (1) or an oxyalkylenediol having two or more polymerizable unsaturated groups represented by general formula (2). This aqueous urethane resin composition can form a coating film which has excellent coating film hardness, elongation and flexibility and which has excellent corrosion resistance, hot water resistance, chemical resistance, solvent resistance, and adhesion to various substrates.

Description

水性ウレタン樹脂組成物、コーティング剤及び物品Aqueous urethane resin composition, coating agent and article
　本発明は、例えば、コーティング剤、接着剤等の様々な用途に使用可能な水性ウレタン樹脂組成物に関する。 The present invention relates to an aqueous urethane resin composition that can be used for various applications such as a coating agent and an adhesive.
　水性ウレタン樹脂組成物は、一般に、基材に対して良好な密着性を有し、柔軟な塗膜を形成できることから、コーティング剤や接着剤をはじめとする様々な用途で使用されている。 Aqueous urethane resin compositions are generally used in various applications including coating agents and adhesives because they have good adhesion to substrates and can form flexible coatings.
　前記水性ウレタン樹脂組成物としては、例えば、水性ポリウレタン分散液であって、ａ）少なくとも１種の有機脂肪族、脂環式または芳香族ジ、トリまたはポリイソシアネート、ｂ）少なくとも１種のイソシアネート反応性ポリカーボネートジオール、トリオールまたはポリオール、ｃ）少なくとも１つのイソシアネート反応性基および少なくとも１つのフリーラジカル的に重合可能な不飽和基を含む少なくとも１種の化合物、およびｄ）少なくとも１つのイソシアネート反応性基および少なくとも１つの分散活性基を含む少なくとも１種の化合物、および任意選択的にｅ）少なくとも２つのイソシアネート反応性基を含み、１０００ｇ／モル未満、好ましくは５００ｇ／モル未満の分子量を有する少なくとも１種の化合物を含む混合物を反応に付し、得られた反応生成物を水に分散させることによって得られることを特徴とする水性ポリウレタン分散液が知られている（例えば、特許文献１参照。）。 Examples of the aqueous urethane resin composition include an aqueous polyurethane dispersion, a) at least one organic aliphatic, alicyclic or aromatic di, tri- or polyisocyanate, b) at least one isocyanate reaction. A polycarbonate diol, triol or polyol, c) at least one compound comprising at least one isocyanate-reactive group and at least one free-radically polymerizable unsaturated group, and d) at least one isocyanate-reactive group and At least one compound comprising at least one dispersed active group, and optionally e) at least one compound comprising at least two isocyanate-reactive groups and having a molecular weight of less than 1000 g / mol, preferably less than 500 g / mol. A mixture containing the compound Subjected to response, aqueous polyurethane dispersions which the reaction product obtained is characterized by being obtained by dispersing in water are known (e.g., see Patent Document 1.).
　しかし、水性ウレタン樹脂組成物を、例えば、フレキシブルディスプレイ等の光学部材の表面コーティング等に使用することが検討されているなかで、前記水性ポリウレタン分散液を用いて形成された塗膜は、耐候性や耐溶剤性が十分でないため、その塗装物を屋外で使用した際にワレや黄変等を引き起こす場合や、産業用のコーティング剤で使用した際に剥れや溶け出す場合があった。また、前記水性ポリウレタン分散液を用いて形成された塗膜は硬度の点で十分でないため、例えば、タッチパネル等の表面コーティング剤に使用した場合に傷つきやすく、外観不良等を引き起こす場合があった。 However, while the use of an aqueous urethane resin composition, for example, for the surface coating of optical members such as flexible displays, etc., coating films formed using the aqueous polyurethane dispersion are weather resistant. Insufficient solvent resistance may cause cracking or yellowing when the paint is used outdoors, or may peel off or dissolve when used with an industrial coating agent. Further, since the coating film formed using the aqueous polyurethane dispersion is not sufficient in terms of hardness, for example, when used for a surface coating agent such as a touch panel, the coating film is easily damaged and may cause poor appearance.
特表２００８－５３４７１０号公報JP 2008-534710 A
　本発明が解決しようとする課題は、優れた塗膜硬度、伸度及び屈曲性を有し、かつ、耐食性、耐温水性、耐薬品性、耐溶剤性及び各種基材に対する密着性に優れた塗膜を形成可能な水性ウレタン樹脂組成物を提供することである。 The problems to be solved by the present invention have excellent coating film hardness, elongation and flexibility, and excellent corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates. It is to provide an aqueous urethane resin composition capable of forming a coating film.
　本発明者らは、上記の課題を解決すべく鋭意研究した結果、ウレタン樹脂の原料であるポリオールとして、２つ以上の重合性不飽和基を有する炭素原子数１～５のアルキレンジオール（ａ１－１）または２つ以上の重合性不飽和基を有する炭素原子数１～９のオキシアルキレンジオール（ａ１－２）を使用したウレタン樹脂（Ａ）を含有した水性ウレタン樹脂組成物を用いることによって、上記課題を解決できることを見出し、本発明を完成させた。 As a result of diligent research to solve the above-mentioned problems, the present inventors have found that a polyol as a raw material for a urethane resin is an alkylene diol having 1 to 5 carbon atoms having two or more polymerizable unsaturated groups (a1- 1) or by using an aqueous urethane resin composition containing a urethane resin (A) using an oxyalkylene diol (a1-2) having 1 to 9 carbon atoms having two or more polymerizable unsaturated groups, The present inventors have found that the above problems can be solved and have completed the present invention.
　すなわち、本発明は、加水分解性シリル基またはシラノール基と、重合性不飽和基とを有するウレタン樹脂（Ａ）、及び、水性媒体（Ｂ）を含有する水性ウレタン樹脂組成物であって、前記ウレタン樹脂（Ａ）が、下記一般式（１）で示される２つ以上の重合性不飽和基を有するアルキレンジオール（ａ１－１）または下記一般式（２）で示される２つ以上の重合性不飽和基を有するオキシアルキレンジオール（ａ１－２）を含有するポリオール（ａ１）と、ポリイソシアネート（ａ２）と、シランカップリング剤（ａ３）とを反応させて得られるものであることを特徴とする水性ウレタン樹脂組成物に関するものである。 That is, the present invention is a urethane resin (A) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group, and an aqueous urethane resin composition containing an aqueous medium (B), The urethane resin (A) is an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or two or more polymerizable compounds represented by the following general formula (2) It is obtained by reacting a polyol (a1) containing an unsaturated group-containing oxyalkylenediol (a1-2), a polyisocyanate (a2), and a silane coupling agent (a3). The present invention relates to an aqueous urethane resin composition.
Figure JPOXMLDOC01-appb-C000003
Figure JPOXMLDOC01-appb-C000003
（一般式（１）中のＲ１は、炭素原子数１～９の直鎖アルキレン基のうち、その側鎖に重合性不飽和基を含む原子団を２つ以上有する構造を表す。） (R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of the linear alkylene group having 1 to 9 carbon atoms.)
Figure JPOXMLDOC01-appb-C000004
Figure JPOXMLDOC01-appb-C000004
（一般式（２）中のＲ１及びＲ３はエチレン基の側鎖に重合性不飽和基を含む原子団を有する構造を表す。Ｒ２は、炭素原子数１個～５個を有するアルキレン基を表す。） (R 1 and R 3 in the general formula (2) represent a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group. R 2 is an alkylene having 1 to 5 carbon atoms. Represents a group.)
　本発明の水性ウレタン樹脂組成物は、優れた塗膜硬度、伸度及び屈曲性を有し、かつ、耐食性、耐温水性、耐薬品性、耐溶剤性及び各種基材に対する密着性に優れた塗膜を形成できることから、例えば、アクリロニトリル－ブタジエン－スチレン樹脂（ＡＢＳ樹脂）、ポリカーボネート樹脂（ＰＣ樹脂）、ＡＢＳ／ＰＣ樹脂、ポリスチレン樹脂（ＰＳ樹脂）、ポリメタクリル酸樹脂（ＰＭＭＡ樹脂）、ポリエステル樹脂（ＰＥＴ樹脂）等のプラスチック基材のコーティング剤及び接着剤に好適に使用できる。 The aqueous urethane resin composition of the present invention has excellent coating film hardness, elongation and flexibility, and excellent corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates. Since a coating film can be formed, for example, acrylonitrile-butadiene-styrene resin (ABS resin), polycarbonate resin (PC resin), ABS / PC resin, polystyrene resin (PS resin), polymethacrylic acid resin (PMMA resin), polyester resin It can be suitably used for a coating agent and an adhesive for a plastic substrate such as (PET resin).
　本発明の水性ウレタン樹脂組成物は、加水分解性シリル基またはシラノール基と、重合性不飽和基とを有するウレタン樹脂（Ａ）、及び、水性媒体（Ｂ）を含有する水性ウレタン樹脂組成物であって、前記ウレタン樹脂（Ａ）が、下記一般式（１）で示される２つ以上の重合性不飽和基を有するアルキレンジオール（ａ１－１）または下記一般式（２）で示される２つ以上の重合性不飽和基を有するオキシアルキレンジオール（ａ１－２）を含有するポリオール（ａ１）と、ポリイソシアネート（ａ２）と、シランカップリング剤（ａ３）とを反応させて得られるものであることを特徴とする。 The aqueous urethane resin composition of the present invention is an aqueous urethane resin composition containing a urethane resin (A) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group, and an aqueous medium (B). The urethane resin (A) is an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or two represented by the following general formula (2): It is obtained by reacting the polyol (a1) containing the above oxyalkylene diol (a1-2) having a polymerizable unsaturated group, the polyisocyanate (a2), and the silane coupling agent (a3). It is characterized by that.
　前記ウレタン樹脂（Ａ）は、加水分解性シリル基またはシラノール基のいずれか一方または両方を有するものである。 The urethane resin (A) has one or both of a hydrolyzable silyl group and a silanol group.
　前記加水分解性シリル基またはシラノール基は、水等と接触することによって加水分解し、水酸基がケイ素原子に結合したシラノール基を形成しうる。 The hydrolyzable silyl group or silanol group can be hydrolyzed by contact with water or the like to form a silanol group in which a hydroxyl group is bonded to a silicon atom.
　また、前記加水分解性シリル基またはシラノール基は、塗膜を形成する際に自己縮合反応または他の官能基と反応しうる。これにより、耐食性、耐温水性、耐薬品性、耐溶剤性及び各種基材に対する密着性に優れた塗膜を形成することが可能となる。 Also, the hydrolyzable silyl group or silanol group can react with a self-condensation reaction or other functional group when forming a coating film. Thereby, it becomes possible to form a coating film excellent in corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates.
　前記加水分解性シリル基またはシラノール基は、ウレタン樹脂（Ａ）を製造する際に使用するシランカップリング剤（ａ３）を用いることにより、ウレタン樹脂（Ａ）中に導入される。 The hydrolyzable silyl group or silanol group is introduced into the urethane resin (A) by using the silane coupling agent (a3) used when the urethane resin (A) is produced.
　前記ウレタン樹脂（Ａ）としては、重合性不飽和基を有するウレタン樹脂のうち、下記一般式（１）で示される２つ以上の重合性不飽和基を有するアルキレンジオール（ａ１－１）または下記一般式（２）で示される２つ以上の重合性不飽和基を有するオキシアルキレンジオール（ａ１－２）を含有するポリオール（ａ１）と、ポリイソシアネート（ａ２）と、シランカップリング剤（ａ３）とを反応させて得られるものを使用する。 As the urethane resin (A), among the urethane resins having a polymerizable unsaturated group, an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or the following A polyol (a1) containing an oxyalkylenediol (a1-2) having two or more polymerizable unsaturated groups represented by the general formula (2), a polyisocyanate (a2), and a silane coupling agent (a3) The one obtained by reacting with is used.
Figure JPOXMLDOC01-appb-C000005
Figure JPOXMLDOC01-appb-C000005
（一般式（１）中のＲ１は、炭素原子数１～９の直鎖アルキレン基の側鎖に重合性不飽和基を含む原子団を２つ以上有する構造を表す。） (R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms.)
Figure JPOXMLDOC01-appb-C000006
Figure JPOXMLDOC01-appb-C000006
（一般式（２）中のＲ１及びＲ３はエチレン基の側鎖に重合性不飽和基を含む原子団を有する構造を表す。Ｒ２は、炭素原子数１個～５個を有するアルキレン基を表す。） (R 1 and R 3 in the general formula (2) represent a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group. R 2 is an alkylene having 1 to 5 carbon atoms. Represents a group.)
　前記ウレタン樹脂（Ａ）の製造に使用するポリオール（ａ１）としては、ウレタン結合が主として存在する、ウレタン樹脂（Ａ）の主鎖に対し、その側鎖に２つ以上の重合性不飽和基を導入することを目的として、前記一般式（１）で示される２つ以上の重合性不飽和基を有するアルキレンジオール（ａ１－１）または前記一般式（２）で示される２つ以上の重合性不飽和基を有するオキシアルキレンジオール（ａ１－２）を含有するものを使用する。前記アルキレンジオール（ａ１－１）及び前記オキシアルキレンジオール（ａ１－２）由来の重合性不飽和基は、塗膜等を形成する際にラジカル重合する。これにより、優れた塗膜硬度、伸度及び屈曲性を有する塗膜を形成することができる。 As the polyol (a1) used for the production of the urethane resin (A), two or more polymerizable unsaturated groups are present in the side chain with respect to the main chain of the urethane resin (A) in which urethane bonds are mainly present. For the purpose of introduction, an alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the general formula (1) or two or more polymerizable compounds represented by the general formula (2) Those containing an oxyalkylene diol (a1-2) having an unsaturated group are used. The polymerizable unsaturated group derived from the alkylene diol (a1-1) and the oxyalkylene diol (a1-2) undergoes radical polymerization when forming a coating film or the like. Thereby, the coating film which has the outstanding coating-film hardness, elongation, and flexibility can be formed.
　前記アルキレンジオール（ａ１－１）としては、前記一般式（１）で示される構造を有するものを使用することができる。前記一般式（１）中のＲ１は、炭素原子数１～９の直鎖アルキレン基の側鎖に重合性不飽和基を含む原子団を２つ以上有する構造を表す。例えば、ペンタエリスリトールジ（メタ）アクリレートは、一般式（１）中のＲ１は、炭素原子数３のプロピレン基の側鎖に重合性不飽和基を含む原子団を２つ有する構造である。 As the alkylene diol (a1-1), those having a structure represented by the general formula (1) can be used. R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms. For example, pentaerythritol di (meth) acrylate has a structure in which R 1 in the general formula (1) has two atomic groups containing a polymerizable unsaturated group in the side chain of a propylene group having 3 carbon atoms.
　前記アルキレンジオール（ａ１－１）としては、２つ以上５つ以下の重合性不飽和基を有するものを使用することが好ましく、２つ以上３つ以下の重合性不飽和基を有するものを使用することが、優れた塗膜硬度、伸度及び屈曲性を有する塗膜を形成可能な水性ウレタン樹脂組成物を得られることから、より好ましい。 As the alkylene diol (a1-1), those having 2 or more and 5 or less polymerizable unsaturated groups are preferably used, and those having 2 or more and 3 or less polymerizable unsaturated groups are used. It is more preferable to obtain an aqueous urethane resin composition capable of forming a coating film having excellent coating film hardness, elongation and flexibility.
　前記アルキレンジオール（ａ１－１）としては、例えば、ペンタエリスリトールジ（メタ）アクリレート〔ジメチロールプロパンジ（メタ）アクリレート〕、ジメチロールメタンジ（メタ）アクリレート（一般式（１）中のＲ１は、炭素原子数３のもので、重合性不飽和基を有する原子団を２つ有するものである。）、ジエチロールメタンジ（メタ）アクリレート、ジエチロールプロパンジ（メタ）アクリレート（一般式（１）中のＲ１は、炭素原子数５のもので、重合性不飽和基を有する原子団を２つ有するものである。）、ジプロパノールメタンジ（メタ）アクリレート、ジプロパノールプロパンジ（メタ）アクリレート（一般式（１）中のＲ１は、炭素原子数７のもので、重合性不飽和基を有する原子団を２つ有するものである。）、ジブタノールメタンジ（メタ）アクリレート、ジブタノールプロパンジ（メタ）アクリレート（一般式（１）中のＲ１は、炭素原子数９のもので、重合性不飽和基を有する原子団を２つ有するものである。）等が挙げられる。なかでも、ペンタエリスリトールジ（メタ）アクリレート、ジメチロールメタンジ（メタ）アクリレートを使用することが、優れた塗膜硬度、伸度及び屈曲性を有する塗膜を形成可能な水性ウレタン樹脂組成物を得られることから、より好ましい。これらのアルキレンジオール（ａ１－１）は、単独で用いることも２種以上を併用することもできる。なお、本発明において、「（メタ）アクリレート」とは、アクリレート及びメタクリレートのいずれか一方または両方をいう。 Examples of the alkylene diol (a1-1) include pentaerythritol di (meth) acrylate [dimethylolpropane di (meth) acrylate], dimethylolmethane di (meth) acrylate (R 1 in the general formula (1) is , Those having 3 carbon atoms and two atomic groups having a polymerizable unsaturated group), diethylolmethane di (meth) acrylate, and diethylolpropane di (meth) acrylate (general formula (1 R 1 is a group having 5 carbon atoms and having two atomic groups having a polymerizable unsaturated group.), Dipropanolmethane di (meth) acrylate, dipropanolpropanedi (meth) acrylate (formula (1) R 1 in the intended 7 carbon atoms, is an atomic group having a polymerizable unsaturated group as it has two.) Di-butanol methane di (meth) acrylate, R 1 in the di-butanol propane di (meth) acrylate (Formula (1) is of a carbon atoms 9 and has two atomic group having a polymerizable unsaturated group Etc.). Among these, the use of pentaerythritol di (meth) acrylate and dimethylolmethane di (meth) acrylate is an aqueous urethane resin composition capable of forming a coating film having excellent coating film hardness, elongation and flexibility. Since it is obtained, it is more preferable. These alkylene diols (a1-1) can be used alone or in combination of two or more. In the present invention, “(meth) acrylate” refers to either one or both of acrylate and methacrylate.
　また、前記オキシアルキレンジオール（ａ１－２）としては、前記一般式（２）で示される構造を有するものを使用することができる。前記一般式（２）中のＲ１及びＲ３は、エチレン基の側鎖に重合性不飽和基を含む原子団を有する構造である。前記一般式（２）中に、前記エチレン基の側鎖に重合性不飽和基を含む原子団を有する構造を合計２つ以上有し、好ましくは２つ以上５つ以下の範囲で有し、より好ましくは２つ以上３つ以下の範囲で有する。 As the oxyalkylene diol (a1-2), those having a structure represented by the general formula (2) can be used. R 1 and R 3 in the general formula (2) have a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group. In the general formula (2), it has a total of two or more structures having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group, preferably in the range of 2 or more and 5 or less, More preferably, it has in the range of 2 or more and 3 or less.
　また、前記一般式（２）中のＲ２は、炭素原子数１～５のアルキレン基を表し、例えば、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチル基が挙げられる。 R 2 in the general formula (2) represents an alkylene group having 1 to 5 carbon atoms, and examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group, and a pentyl group.
　前記オキシアルキレンジオール（ａ１－２）としては、例えば、ビス（３－アクリロイロキシ－２－ヒドロキシプロポキシ）メタン（一般式（２）中のＲ１及びＲ３は炭素原子数２のもので、重合性不飽和基を有する原子団を１つ有するものであり、Ｒ２は炭素原子数１のものである。）、１,２－ビス（３－アクリロイロキシ－２－ヒドロキシプロポキシ）エタン（一般式（２）中のＲ１及びＲ３は炭素原子数２のもので、重合性不飽和基を有する原子団を１つ有するものであり、Ｒ２は炭素原子数２のものである。）、１,３－ビス（３－アクリロイロキシ－２－ヒドロキシプロポキシ）プロパン（一般式（２）中のＲ１及びＲ３は炭素原子数２のもので、重合性不飽和基を有する原子団を１つ有するものであり、Ｒ２は炭素原子数３のものである。）、１,４－ビス（３－アクリロイロキシ－２－ヒドロキシプロポキシ）ブタン（一般式（２）中のＲ１及びＲ３は炭素原子数２のもので、重合性不飽和基を有する原子団を１つ有するものであり、Ｒ２は炭素原子数４のものである。）、１,５－ビス（３－アクリロイロキシ－２－ヒドロキシプロポキシ）ペンタン（一般式（２）中のＲ１及びＲ３は炭素原子数２のもので、重合性不飽和基を有する原子団を１つ有するものであり、Ｒ２は炭素原子数５のものである。）等が挙げられる。なかでも、ビス（３－アクリロイロキシ－２－ヒドロキシプロポキシ）メタンを使用することが、優れた塗膜硬度、伸度及び屈曲性を有する塗膜を形成可能な水性ウレタン樹脂組成物を得られることから、より好ましい。また、これらのオキシアルキレンジオール（ａ１－２）は、単独で用いることも２種以上を併用することもできる。 Examples of the oxyalkylene diol (a1-2) include bis (3-acryloyloxy-2-hydroxypropoxy) methane (R 1 and R 3 in the general formula (2) are those having 2 carbon atoms and are polymerizable. One having an unsaturated group and R 2 having one carbon atom), 1,2-bis (3-acryloyloxy-2-hydroxypropoxy) ethane (general formula (2 And R 1 and R 3 are those having 2 carbon atoms and having one atomic group having a polymerizable unsaturated group, and R 2 is having 2 carbon atoms.), 1, 3-bis (3-acryloyloxy-2-hydroxypropoxy) propane (in formula (2), R 1 and R 3 have 2 carbon atoms and have one atomic group having a polymerizable unsaturated group) in and, R 2 is the number of carbon atoms Is of.), 1,4-bis (3-acryloyloxy-2-hydroxypropoxy) butane (formula (2) R 1 and R 3 in the intended 2 carbon atoms, a polymerizable unsaturated group And R 2 has 4 carbon atoms.) 1,5-bis (3-acryloyloxy-2-hydroxypropoxy) pentane (in the general formula (2)) R 1 and R 3 have 2 carbon atoms, have 1 atomic group having a polymerizable unsaturated group, and R 2 has 5 carbon atoms). In particular, the use of bis (3-acryloyloxy-2-hydroxypropoxy) methane provides an aqueous urethane resin composition capable of forming a coating film having excellent coating hardness, elongation and flexibility. More preferable. These oxyalkylene diols (a1-2) can be used alone or in combination of two or more.
　前記アルキレンジオール（ａ１－１）及び前記オキシアルキレンジオール（ａ１－２）は、前記ウレタン樹脂（Ａ）の製造に使用する原料の全量中に、合計０．１～４９質量％の範囲で使用することが、優れた塗膜硬度、伸度及び屈曲性を有する塗膜を形成可能な水性ウレタン樹脂組成物を得られることから好ましく、１～１５質量％の範囲であることがより好ましい。なお、前記ウレタン樹脂（Ａ）の製造に使用する原料の全量とは、ポリオール（ａ１）とポリイソシアネート（ａ２）と、鎖伸長剤を使用した場合にはそれを含む合計質量を指す。 The alkylene diol (a1-1) and the oxyalkylene diol (a1-2) are used in a total range of 0.1 to 49% by mass in the total amount of raw materials used in the production of the urethane resin (A). In view of obtaining an aqueous urethane resin composition capable of forming a coating film having excellent coating film hardness, elongation and flexibility, the range of 1 to 15% by mass is more preferable. In addition, the total amount of the raw material used for manufacture of the said urethane resin (A) points out the total mass containing it, when a polyol (a1), polyisocyanate (a2), and a chain extender are used.
　前記ウレタン樹脂（Ａ）の製造に使用可能なポリオール（ａ１）としては、前記アルキレンジオール（ａ１－１）及び前記オキシアルキレンジオール（ａ１－２）とともに、必要に応じてその他のポリオールを組み合わせ使用することができる。 As the polyol (a1) that can be used in the production of the urethane resin (A), in addition to the alkylene diol (a1-1) and the oxyalkylene diol (a1-2), other polyols may be used in combination as necessary. be able to.
　前記その他のポリオールとしては、例えば、ウレタン樹脂（Ａ）に優れた水分散安定性を付与することを目的として、親水性基を有するポリオールが挙げられる。 Examples of the other polyol include a polyol having a hydrophilic group for the purpose of imparting excellent water dispersion stability to the urethane resin (A).
　前記親水性基を有するポリオールとしては、例えば、アニオン性基を有するポリオール、カチオン性基を有するポリオール、ノニオン性基を有するポリオールが挙げられる。なかでも、アニオン性基を有するポリオールが好ましい。 Examples of the polyol having a hydrophilic group include a polyol having an anionic group, a polyol having a cationic group, and a polyol having a nonionic group. Of these, polyols having an anionic group are preferred.
　前記アニオン性基を有するポリオールとしては、例えば、カルボキシル基を有するポリオール、スルホン酸基を有するポリオールが挙げられる。 Examples of the polyol having an anionic group include a polyol having a carboxyl group and a polyol having a sulfonic acid group.
　前記カルボキシル基を有する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－ジメチロール吉草酸等が挙げられ、なかでも、２，２－ジメチロールプロピオン酸が好ましい。また、前記カルボキシル基を有するポリオールと各種ポリカルボン酸とを反応させて得られるカルボキシル基を有するポリエステルポリオールを使用することもできる。 Examples of the polyol having a carboxyl group include 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid, 2,2-dimethylolvaleric acid and the like. Among them, 2,2-dimethylol is preferable. Propionic acid is preferred. Moreover, the polyester polyol which has a carboxyl group obtained by making the polyol which has the said carboxyl group, and various polycarboxylic acids react can also be used.
　前記スルホン酸基を有するポリオールとしては、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）イソフタル酸等のジカルボン酸またそれらの塩；前記ジカルボン酸と、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、１，６－ヘキサンジオール、ジエチレングリコール、ネオペンチルグリコール等の低分子ポリオールとを反応させて得られるポリエステルポリオール、さらに前記ポリエステルポリオールと、γ－ブチロラクトン、δ－バレロラクトン、ε－カプロラクトン等の環状エステル化合物を反応させて得られるポリエステルポリオールが挙げられる。 Examples of the polyol having a sulfonic acid group include dicarboxylic acids such as 5-sulfoisophthalic acid, sulfoterephthalic acid, 4-sulfophthalic acid, 5- (4-sulfophenoxy) isophthalic acid, and salts thereof; Polyester polyols obtained by reacting low molecular polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol and the like, and the polyester polyol and γ-butyrolactone And polyester polyols obtained by reacting cyclic ester compounds such as δ-valerolactone and ε-caprolactone.
　前記アニオン性基は、それらの一部または全部が塩基性化合物等によって中和されていることが、良好な水分散性を発現できることから好ましい。 The anionic groups are preferably partially or wholly neutralized with a basic compound or the like because good water dispersibility can be expressed.
　前記アニオン性基を中和する際に使用可能な塩基性化合物としては、例えば、アンモニア、トリエチルアミン、モルホリン、モノエタノールアミン、ジエチルエタノールアミン等の沸点が２００℃以上の有機アミン；水酸化ナトリウム、水酸化カリウム、水酸化リチウム等を含む金属水酸化物等が挙げられる。前記塩基性化合物は、得られる水性ウレタン樹脂組成物の水分散安定性を向上させる観点から、〔塩基性化合物／（カルボキシル基等の酸基の合計量）〕＝０．５～３（モル比）となる範囲で使用することが好ましく、０．７～１．５（モル比）となる範囲で使用することがより好ましい。 Examples of basic compounds that can be used when neutralizing the anionic group include organic amines having a boiling point of 200 ° C. or higher, such as ammonia, triethylamine, morpholine, monoethanolamine, diethylethanolamine; sodium hydroxide, water Examples thereof include metal hydroxides including potassium oxide and lithium hydroxide. The basic compound is [basic compound / (total amount of acid groups such as carboxyl groups)] = 0.5 to 3 (molar ratio) from the viewpoint of improving the water dispersion stability of the resulting aqueous urethane resin composition. ) Is preferably used, and more preferably in a range of 0.7 to 1.5 (molar ratio).
　また、前記カチオン性基を有するポリオールとしては、例えば、３級アミノ基を有するポリオールが挙げられる。具体的には、Ｎ－メチル－ジエタノールアミン、エポキシを２つ有する化合物と２級アミンとを反応させて得られるポリオール等が挙げられる。 In addition, examples of the polyol having a cationic group include a polyol having a tertiary amino group. Specific examples include N-methyl-diethanolamine and polyols obtained by reacting a compound having two epoxies with a secondary amine.
　前記カチオン性基は、その一部または全部が、蟻酸、酢酸、プロピオン酸、コハク酸、グルタル酸、酒石酸、アジピン酸、リン酸等の酸性化合物で中和されていることが好ましい。 The cationic group is preferably partially or completely neutralized with an acidic compound such as formic acid, acetic acid, propionic acid, succinic acid, glutaric acid, tartaric acid, adipic acid, phosphoric acid or the like.
　また、前記カチオン性基としての３級アミノ基は、その一部または全部が４級化されていることが好ましい。前記４級化剤としては、例えば、ジメチル硫酸、ジエチル硫酸、メチルクロライド、エチルクロライド等が挙げられ、ジメチル硫酸が好ましい。 The tertiary amino group as the cationic group is preferably partly or entirely quaternized. Examples of the quaternizing agent include dimethyl sulfate, diethyl sulfate, methyl chloride, ethyl chloride and the like, and dimethyl sulfate is preferable.
　また、前記ノニオン性基を有するポリオールとしては、例えば、エチレンオキサイド由来の構造単位を有するポリアルキレングリコール等が挙げられる。 In addition, examples of the polyol having a nonionic group include polyalkylene glycol having a structural unit derived from ethylene oxide.
　前記親水性基を有するポリオールは、前記ウレタン樹脂（Ａ）の製造に使用する原料の全量中に、１～２０質量％の範囲で使用することが好ましく、さらに、優れた塗膜硬度、伸度及び屈曲性を有する塗膜を形成可能な水性ウレタン樹脂組成物が得られることから１～１０質量％の範囲で使用することがより好ましい。 The polyol having a hydrophilic group is preferably used in the range of 1 to 20% by mass in the total amount of raw materials used in the production of the urethane resin (A), and further has excellent coating film hardness and elongation. In addition, since an aqueous urethane resin composition capable of forming a coating film having flexibility is obtained, it is more preferably used in the range of 1 to 10% by mass.
　また、前記その他のポリオールとしては、例えば、ポリエステルポリオール、ポリカーボネートポリオール、ポリエーテルポリオール等が挙げられる。これらの中でも、より一層優れた塗膜硬度、伸度及び屈曲性を有する塗膜を形成できることから、ポリエステルポリオール、ポリカーボネートポリオールが好ましい。 In addition, examples of the other polyol include polyester polyol, polycarbonate polyol, and polyether polyol. Among these, polyester polyols and polycarbonate polyols are preferable because a coating film having even better coating film hardness, elongation, and flexibility can be formed.
　前記ポリエステルポリオールとしては、例えば、低分子量のポリオールと、ポリカルボン酸とを反応して得られるポリエステルポリオール；ε－カプロラクトン等の環状エステル化合物を開環重合反応して得られるポリエステルポリオール；これらを共重合して得られるポリエステルポリオール等が挙げられる。 Examples of the polyester polyol include a polyester polyol obtained by reacting a low molecular weight polyol and a polycarboxylic acid; a polyester polyol obtained by a ring-opening polymerization reaction of a cyclic ester compound such as ε-caprolactone; Examples include polyester polyols obtained by polymerization.
　前記低分子量のポリオールとしては、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、１，６－ヘキサンジオール、ジエチレングリコール、ネオペンチルグリコール、１，３－ブタンジオール等の分子量が５０～３００程度である脂肪族ポリオール；シクロヘキサンジメタノール等の脂肪族環式構造を有するポリオール；ビスフェノールＡ及びビスフェノールＦ等の芳香族構造を有するポリオールが挙げられる。なかでも、１，６－ヘキサンジオール、ネオペンチルグリコールが好ましい。 Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,3-butanediol and the like having a molecular weight of about 50 to 300. Aliphatic polyols such as cyclohexane dimethanol, and polyols having an aromatic structure such as bisphenol A and bisphenol F. Of these, 1,6-hexanediol and neopentyl glycol are preferable.
　前記ポリエステルポリオールの製造に使用可能な前記ポリカルボン酸としては、例えば、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；それらの無水物またはエステル化物等が挙げられる。 Examples of the polycarboxylic acid that can be used for the production of the polyester polyol include aliphatic polycarboxylic acids such as succinic acid, adipic acid, sebacic acid, and dodecanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, and naphthalenedicarboxylic acid. And aromatic polycarboxylic acids such as anhydrides or esterified products thereof.
　また、前記ポリカーボネートポリオールとしては、例えば、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、シクロヘキサンジメタノール等のジオールと、ジメチルカーボネート、ジエチルカーボネート等の炭酸エステル、ホスゲン等とを反応させて得られたものが挙げられる。 Examples of the polycarbonate polyol include diols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, and cyclohexanedimethanol, carbonate esters such as dimethyl carbonate and diethyl carbonate, and phosgene. And the like obtained by reacting with the above.
　前記ポリエステルポリオール、ポリエーテルポリオール及びポリカーボネートポリオールは、前記ウレタン樹脂（Ａ）の製造に使用する原料の全量中に、１～７０質量％の範囲で使用することが好ましく、１５～４５質量％の範囲で使用することが、より一層優れた塗膜硬度、伸度及び屈曲性を有する塗膜を形成できることからより好ましい。 The polyester polyol, polyether polyol and polycarbonate polyol are preferably used in the range of 1 to 70% by mass, and in the range of 15 to 45% by mass, based on the total amount of raw materials used for the production of the urethane resin (A). It is more preferable to use in the case of being able to form a coating film having even better coating film hardness, elongation and flexibility.
　また、前記ウレタン樹脂（Ａ）の製造に使用するポリイソシアネート（ａ２）としては、例えば、シクロヘキサンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、イソホロンジイソシアネート等の脂肪族環式構造を有するポリイソシアネート；４，４’－ジフェニルメタンジイソシアネート、２，４’－ジフェニルメタンジイソシアネート、カルボジイミド変性ジフェニルメタンジイソシアネート、クルードジフェニルメタンジイソシアネート、フェニレンジイソシアネート、トリレンジイソシアネート、ナフタレンジイソシアネート等の芳香族ポリイソシアネート；ヘキサメチレンジイソシアネート、リジンジイソシアネート、キシリレンジイソシアネート、テトラメチルキシリレンジイソシアネート等の脂肪族ポリイソシアネートが挙げられる。なかでも、前記ポリイソシアネート（ａ２）としては、ジシクロヘキシルメタンジイソシアネートまたはイソホロンジイソシアネートが、優れた塗膜硬度、伸度及び屈曲性を有する塗膜を形成できることから好ましい。また、これらのポリイソシアネート（ａ２）は、単独で用いることも２種以上を併用することもできる。 Examples of the polyisocyanate (a2) used in the production of the urethane resin (A) include polyisocyanates having an aliphatic cyclic structure such as cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, and isophorone diisocyanate; 4,4′-diphenylmethane Aromatic polyisocyanates such as diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate; hexamethylene diisocyanate, lysine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate Aliphatic polyiso, such as isocyanate Aneto and the like. Among them, as the polyisocyanate (a2), dicyclohexylmethane diisocyanate or isophorone diisocyanate is preferable because it can form a coating film having excellent coating film hardness, elongation and flexibility. Moreover, these polyisocyanates (a2) can be used alone or in combination of two or more.
　また、前記ウレタン樹脂（Ａ）の製造に使用するシランカップラング剤（ａ３）としては、反応性基を有するものを使用することができる。前記シランカップリング剤（ａ３）が有する加水分解性シリル基の一部または全部は、加水分解しシラノール基を形成していてもよい。 Further, as the silane coupling agent (a3) used for the production of the urethane resin (A), those having a reactive group can be used. A part or all of the hydrolyzable silyl group of the silane coupling agent (a3) may be hydrolyzed to form a silanol group.
　前記反応性基としては、例えば、アミノ基、イソシアネート基、（メタ）アクリレート基、ビニル基、メルカプト基、エポキシ基等が挙げられる。なお、本発明において「（メタ）アクリレート基」とは、アクリレート基及びメタクリレート基のいずれか一方または両方をいう。 Examples of the reactive group include an amino group, an isocyanate group, a (meth) acrylate group, a vinyl group, a mercapto group, and an epoxy group. In the present invention, “(meth) acrylate group” refers to either one or both of an acrylate group and a methacrylate group.
　前記シランカップリング剤（ａ３）としては、例えば、ビニルトリス（β－メトキシエトキシ）シラン、ビニルエトキシシラン、ビニルトリメトキシシラン等のビニルシラン類、γ－メタクリロキシプロピルトリメトキシシラン等の（メタ）アクリルシラン類、β－（３，４－エポキシシクロヘキシル）エチルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）メチルトリメトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリエトキシシラン、β－（３，４－エポキシシクロヘキシル）メチルトリエトキシシラン、γ－グリシドキシプロピルトリメトキシシラン、γ－グリシドキシプロピルトリエトキシシラン等のエポキシシラン類、Ｎ－２－（アミノエチル）－３－アミノプロピルトリエトキシシラン、Ｎ－β（アミノエチル）γ－アミノプロピルトリメトキシシラン、Ｎ－β（アミノエチル）γ－アミノプロピルトリエトキシシラン、Ｎ－β（アミノエチル）γ－アミノプロピルメチルジエトキシシシラン、γ－アミノプロピルトリエトキシシラン、γ－アミノプロピルトリメトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリメトキシシラン、Ｎ－フェニル－γ－アミノプロピルトリエトキシシラン、３－アミノプロピルトリメトキシシラン等のアミノシラン類、γ－メルカプトプロピルトリメトキシシラン、γ－メルカプトプロピルトリエトキシシラン等のチオシラン類などが挙げられる。なかでも、Ｎ－２－（アミノエチル）－３－アミノプロピルトリエトキシシランを使用することが、耐食性、耐温水性、耐薬品性、耐溶剤性及び各種基材に対する密着性に優れた塗膜を形成できることから好ましい。これらのシランカップリング剤は、単独で用いることも２種以上を併用することもできる。 Examples of the silane coupling agent (a3) include vinyl silanes such as vinyl tris (β-methoxyethoxy) silane, vinyl ethoxy silane, and vinyl trimethoxy silane, and (meth) acryl silane such as γ-methacryloxypropyl trimethoxy silane. Β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- ( 3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, epoxysilanes such as γ-glycidoxypropyltriethoxysilane, N-2- (aminoethyl) -3-aminopropyl Triethoxysilane, N-β ( Minoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, aminosilanes such as γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, γ-mercaptopropyltrimethoxy And thiosilanes such as silane and γ-mercaptopropyltriethoxysilane. Of these, N-2- (aminoethyl) -3-aminopropyltriethoxysilane is a coating film with excellent corrosion resistance, hot water resistance, chemical resistance, solvent resistance, and adhesion to various substrates. Can be formed. These silane coupling agents can be used alone or in combination of two or more.
　前記シランカップリング剤（ａ３）は、前記ウレタン樹脂（Ａ）の製造に使用する原料の全量中に０．１～１０質量％の範囲で使用することが耐食性、耐温水性、耐薬品性、耐溶剤性及び各種基材に対する密着性に優れた塗膜を形成できることから好ましく、２～７質量％の範囲で使用することがより好ましい。 The silane coupling agent (a3) should be used in a range of 0.1 to 10% by mass in the total amount of raw materials used in the production of the urethane resin (A), corrosion resistance, hot water resistance, chemical resistance, It is preferable because it can form a coating film excellent in solvent resistance and adhesion to various substrates, and more preferably in the range of 2 to 7% by mass.
　前記ウレタン樹脂（Ａ）は、具体的には、前記ポリオール（ａ１）とポリイソシアネート（ａ２）とを反応させることによって、末端にイソシアネート基または水酸基を有するウレタン樹脂（Ａ’）を製造する工程〔１〕、及び、前記ウレタン樹脂（Ａ’）と、前記シランカップリング剤（ａ３）とを反応させる工程〔２〕とを経ることによって製造することができる。 Specifically, the urethane resin (A) is a step of producing a urethane resin (A ′) having an isocyanate group or a hydroxyl group at a terminal by reacting the polyol (a1) with the polyisocyanate (a2) [ 1] and the step [2] of reacting the urethane resin (A ′) with the silane coupling agent (a3).
　また、前記シランカップリング剤（ａ３）が、アミノ基及びイソシアネート基からなる群より選ばれる反応性基を２つ以上有するシランカップリング剤の場合、前記ウレタン（Ａ）は、前記ポリオール（ａ１）と、前記ポリイソシアネート（ａ２）と、前記シランカップリング剤（ａ３）とを混合し反応させることによって製造することもできる。 When the silane coupling agent (a3) is a silane coupling agent having two or more reactive groups selected from the group consisting of an amino group and an isocyanate group, the urethane (A) is the polyol (a1). And the polyisocyanate (a2) and the silane coupling agent (a3) can be mixed and reacted.
　前記ウレタン樹脂（Ａ）の製造工程を構成する前記工程〔１〕における前記ポリオール（ａ１）と前記ポリイソシアネート（ａ２）との反応は、例えば、無溶剤下または有機溶剤の存在下で、前記ポリオール（ａ１）と前記ポリイソシアネート（ａ２）とを混合し、反応温度５０～１５０℃程度の範囲で行うことができる。 The reaction of the polyol (a1) and the polyisocyanate (a2) in the step [1] constituting the production process of the urethane resin (A) is performed, for example, in the absence of a solvent or in the presence of an organic solvent. (A1) and the polyisocyanate (a2) can be mixed and carried out at a reaction temperature in the range of about 50 to 150 ° C.
　前記ポリオール（ａ１）と前記ポリイソシアネート（ａ２）との反応は、例えば、前記ポリオール（ａ１）の水酸基に対する、前記ポリイソシアネート（ａ２）のイソシアネート基の当量割合が、０．８～２．５の範囲で行うことが好ましく、０．９～１．５の範囲で行うことがより好ましい。 The reaction between the polyol (a1) and the polyisocyanate (a2) is, for example, such that the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is 0.8 to 2.5. It is preferably carried out in the range, more preferably in the range of 0.9 to 1.5.
　また、前記工程〔１〕で製造する末端にイソシアネート基を有するウレタン樹脂（Ａ’）を製造する際には、より一層優れた塗膜硬度、伸度及び屈曲性を有する塗膜を形成できることから、前記ポリオール（ａ１）及び前記ポリイソシアネート（ａ２）の他に、必要に応じて鎖伸長剤を使用することができる。 Moreover, when manufacturing the urethane resin (A ′) having an isocyanate group at the terminal manufactured in the step [1], it is possible to form a coating film having even more excellent coating film hardness, elongation and flexibility. In addition to the polyol (a1) and the polyisocyanate (a2), a chain extender can be used as necessary.
　前記ウレタン樹脂（Ａ’）を製造する際に使用できる鎖伸長剤としては、ポリアミン、ヒドラジン化合物、その他活性水素原子含有化合物等を使用することができる。 As the chain extender that can be used for producing the urethane resin (A ′), polyamine, hydrazine compound, other active hydrogen atom-containing compounds, and the like can be used.
　前記ポリアミンとしては、例えば、エチレンジアミン、１，２－プロパンジアミン、１，６－ヘキサメチレンジアミン、ピペラジン、２，５－ジメチルピペラジン、イソホロンジアミン、４，４’－ジシクロヘキシルメタンジアミン、３，３’－ジメチル－４，４’－ジシクロヘキシルメタンジアミン、１，４－シクロヘキサンジアミン等のジアミン；Ｎ－ヒドロキシメチルアミノエチルアミン、Ｎ－ヒドロキシエチルアミノエチルアミン、Ｎ－ヒドロキシプロピルアミノプロピルアミン、Ｎ－エチルアミノエチルアミン、Ｎ－メチルアミノプロピルアミン；ジエチレントリアミン、ジプロピレントリアミン、トリエチレンテトラミン等が挙げられる。また、これらのポリアミンは、単独で用いることも２種以上を併用することもできる。 Examples of the polyamine include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4′-dicyclohexylmethanediamine, 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N -Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like. Moreover, these polyamines can be used alone or in combination of two or more.
　前記ヒドラジン化合物としては、例えば、ヒドラジン、Ｎ，Ｎ’－ジメチルヒドラジン、１，６－ヘキサメチレンビスヒドラジン；コハク酸ジヒドラジッド、アジピン酸ジヒドラジド、グルタル酸ジヒドラジド、セバシン酸ジヒドラジド、イソフタル酸ジヒドラジド；β－セミカルバジドプロピオン酸ヒドラジド等が挙げられる。また、これらのヒドラジン化合物は、単独で用いることも２種以上を併用することもできる。 Examples of the hydrazine compound include hydrazine, N, N′-dimethylhydrazine, 1,6-hexamethylenebishydrazine; succinic acid dihydrazide, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide And propionic acid hydrazide. Moreover, these hydrazine compounds can be used alone or in combination of two or more.
　前記その他活性水素含有化合物としては、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、プロピレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール、ヘキサメチレングリコール、サッカロース、メチレングリコール、グリセリン、ソルビトール等のグリコール；ビスフェノールＡ、４，４’－ジヒドロキシジフェニル、４，４’－ジヒドロキシジフェニルエーテル、４，４’－ジヒドロキシジフェニルスルホン、水素添加ビスフェノールＡ、ハイドロキノン等のフェノール、及び水等が挙げられ、本発明のウレタン樹脂組成物の保存安定性が低下しない範囲内で単独で用いることも２種以上を併用することもできる。 Examples of the other active hydrogen-containing compounds include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, hexamethylene glycol, saccharose, Glycols such as methylene glycol, glycerin and sorbitol; bisphenol A, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 4,4′-dihydroxydiphenyl sulfone, hydrogenated bisphenol A, phenol such as hydroquinone, and water These can be used, and the urethane resin composition of the present invention can be used alone or in combination of two or more within the range in which the storage stability does not deteriorate.
　前記工程〔１〕によって前記ウレタン樹脂（Ａ’）を製造する際に使用可能な有機溶剤としては、例えば、アセトン、メチルエチルケトン等のケトン溶剤；テトラヒドロフラン、ジオキサン等のエーテル溶剤；酢酸エチル、酢酸ブチル等の酢酸エステル溶剤；アセトニトリル等のニトリル溶剤；ジメチルホルムアミド、Ｎ－メチルピロリドン等のアミド溶剤などが挙げられる。これらの有機溶剤は、単独で用いることも２種以上併用することもできる。 Examples of the organic solvent that can be used when the urethane resin (A ′) is produced by the step [1] include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; ethyl acetate and butyl acetate. And nitrile solvents such as acetonitrile; amide solvents such as dimethylformamide and N-methylpyrrolidone. These organic solvents can be used alone or in combination of two or more.
　また、前記有機溶剤は、前記ウレタン樹脂（Ａ）を製造する際に使用した場合は、安全性や環境に対する負荷低減を図るため、前記ウレタン樹脂（Ａ）の製造途中または製造後に、例えば、減圧留去することによって前記有機溶剤の一部または全部を除去してもよい。 Moreover, when the said organic solvent is used when manufacturing the said urethane resin (A), in order to reduce the load with respect to safety | security or an environment, in the middle of the manufacturing of the said urethane resin (A) or after manufacture, it is reduced pressure, for example You may remove a part or all of the said organic solvent by distilling off.
　また、前記ウレタン樹脂（Ａ）の製造工程を構成する前記工程〔２〕は、前記工程〔１〕で得た前記ウレタン樹脂（Ａ’）と、前記シランカップリング剤（ａ３）とを混合し反応させる工程である。前記工程〔２〕は、例えば、反応温度２０～８０℃の範囲で行うことが好ましい。 Moreover, the said process [2] which comprises the manufacturing process of the said urethane resin (A) mixes the said urethane resin (A ') obtained by the said process [1], and the said silane coupling agent (a3). This is a reaction step. The step [2] is preferably performed, for example, at a reaction temperature of 20 to 80 ° C.
　また、本発明の水性ウレタン樹脂組成物は、前記方法で得られたウレタン樹脂（Ａ－１）等のウレタン樹脂（Ａ）が有する親水性基の一部または全部を中和し、次いで、その中和物と水性媒体（Ｂ）とを混合することによって製造することができる。 In addition, the aqueous urethane resin composition of the present invention neutralizes part or all of the hydrophilic group of the urethane resin (A) such as the urethane resin (A-1) obtained by the above method, It can manufacture by mixing a neutralized material and an aqueous medium (B).
　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、例えば、メタノール、エタノール、ｎ－プロパノール及びイソプロパノール等のアルコール；アセトン、メチルエチルケトン等のケトン；エチレングリコール、ジエチレングリコール、プロピレングリコール等のポリアルキレングリコール；ポリアルキレングリコールのアルキルエーテル；Ｎ－メチル－２－ピロリドン等のラクタム等が挙げられる。本発明では、水のみを用いても良く、また水及び水と混和する有機溶剤との混合物を用いても良く、水と混和する有機溶剤のみを用いても良い。 Examples of the aqueous medium (B) include water, organic solvents miscible with water, and mixtures thereof. Examples of the organic solvent miscible with water include alcohols such as methanol, ethanol, n-propanol and isopropanol; ketones such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; alkyl ethers of polyalkylene glycols And lactams such as N-methyl-2-pyrrolidone. In the present invention, only water may be used, a mixture of water and an organic solvent miscible with water may be used, or only an organic solvent miscible with water may be used.
　また、前記水性媒体（Ｂ）としては、安全性や環境に対する負荷の点から、水のみ、または、水及び水と混和する有機溶剤との混合物が好ましく、水のみが特に好ましい。 The aqueous medium (B) is preferably water alone or a mixture of water and an organic solvent miscible with water, particularly water alone, from the viewpoint of safety and environmental burden.
　前記水性媒体（Ｂ）の割合は、前記水性ウレタン樹脂組成物の全量中に１０～９０質量％の範囲が好ましく、３０～７０質量％の範囲がより好ましい。 The ratio of the aqueous medium (B) is preferably in the range of 10 to 90% by mass and more preferably in the range of 30 to 70% by mass with respect to the total amount of the aqueous urethane resin composition.
　前記方法で得たウレタン樹脂（Ａ）は、より一層優れた塗膜硬度、伸度及び屈曲性を有する塗膜を形成できることから、１０，０００～５００，０００の範囲の重量平均分子量を有するものを使用することが好ましく、２０，０００～２００，０００の範囲の重量平均分子量を有するものを使用することがより好ましく、４０，０００～１００，０００の範囲の重量平均分子量を使用することがさらに好ましい。 The urethane resin (A) obtained by the above method has a weight average molecular weight in the range of 10,000 to 500,000 because it can form a coating film having even better coating film hardness, elongation and flexibility. It is preferable to use those having a weight average molecular weight in the range of 20,000 to 200,000, more preferably using a weight average molecular weight in the range of 40,000 to 100,000. preferable.
　また、前記ウレタン樹脂（Ａ）としては、より一層優れた塗膜硬度、伸度及び屈曲性を有し、かつ、耐薬品性及び耐溶剤性に優れた塗膜を形成できることから、ウレア結合を有するものを使用することが好ましい。 Further, as the urethane resin (A), it is possible to form a coating film having further excellent coating film hardness, elongation and flexibility, and excellent chemical resistance and solvent resistance. It is preferable to use what has.
　前記ウレタン樹脂（Ａ）としては、５００～５０，０００の範囲のウレア結合当量を有するものを使用することが、より一層優れた塗膜硬度、伸度及び屈曲性を有し、かつ、耐薬品性及び耐溶剤性に優れた塗膜を形成できることから好ましい。 As the urethane resin (A), use of a resin having a urea bond equivalent in the range of 500 to 50,000 has even more excellent coating film hardness, elongation and flexibility, and chemical resistance. It is preferable because a coating film having excellent properties and solvent resistance can be formed.
　前記ウレタン樹脂（Ａ）は、前記水性ウレタン樹脂組成物の全量中に、前記ウレタン樹脂（Ａ）を５～８５質量％の範囲で含有するものであることが好ましく、１５～５０質量％の範囲で含有するものであることが好ましい。 The urethane resin (A) preferably contains the urethane resin (A) in the range of 5 to 85% by mass in the total amount of the aqueous urethane resin composition, and is in the range of 15 to 50% by mass. It is preferable that it is contained.
　前記ウレタン樹脂（Ａ）を水性媒体中に分散する際には、必要に応じて乳化剤等を使用してもよい。 When dispersing the urethane resin (A) in an aqueous medium, an emulsifier or the like may be used as necessary.
　前記乳化剤としては、例えば、ポリオキシエチレンノニルフェニルエーテル、ポリオキシエチレンラウリルエーテル、ポリオキシエチレンスチリルフェニルエーテル、ポリオキシエチレンソルビトールテトラオレエート、ポリオキシエチレン・ポリオキシプロピレン共重合体等のノニオン系乳化剤；オレイン酸ナトリウム等の脂肪酸塩、アルキル硫酸エステル塩、アルキルベンゼンスルホン酸塩、アルキルスルホコハク酸塩、ナフタレンスルフォン酸塩、ポリオキシエチレンアルキル硫酸塩、アルカンスルフォネートナトリウム塩、アルキルジフェニルエーテルスルフォン酸ナトリウム塩等のアニオン系乳化剤などが挙げられる。 Examples of the emulsifier include nonionic emulsifiers such as polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene sorbitol tetraoleate, and polyoxyethylene / polyoxypropylene copolymer. Fatty acid salts such as sodium oleate, alkyl sulfate esters, alkylbenzene sulfonates, alkyl sulfosuccinates, naphthalene sulfonates, polyoxyethylene alkyl sulfates, alkane sulfonate sodium salts, sodium alkyl diphenyl ether sulfonates, etc. And anionic emulsifiers.
　また、本発明の水性ウレタン樹脂組成物には、ポリシロキサン（Ｘ）を使用することができる。 In addition, polysiloxane (X) can be used in the aqueous urethane resin composition of the present invention.
　前記ポリシロキサン（Ｘ）としては、例えば、各種アルコキシシランの縮合物を使用することができる。 As the polysiloxane (X), for example, condensates of various alkoxysilanes can be used.
　前記アルコキシシランとしては、例えば、テトラメトキシシラン、テトラエトキシシラン、テトラプロポキシシラン、テトライソプロポキシシラン、テトラブトキシシラン、「ＭＥＫ－ＳＴ」や「ＩＰＡ－ＳＴ」（日産化学工業株式会社製）として市販されているオルガノシリカゾル等に代表されるテトラアルコキシシラン、メチルトリメトキシシラン、メチルトリエトキシシラン、メチルトリプロポキシシラン、メチルトリブトキシシラン、エチルトリメトキシシラン、エチルトリエトキシシラン、ｎ－プロピルトリメトキシシラン、ｎ－プロピルトリエトキシシラン、イソプロピルトリメトキシシラン、イソプロピルトリエトキシシラン、３－メルカプトプロピルトリメトキシシラン、３－メルカプトプロピルトリエトキシシラン、フェニルトリメトキシシラン、フェニルトリエトキシシラン等のトリアルコキシシラン；ジメチルジメトキシシラン、ジメチルジエトキシシラン、ジエチルジメトキシシラン、ジエチルジエトキシシラン等のジアルコキシシランなどが挙げられる。 Examples of the alkoxysilane are commercially available as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, “MEK-ST” and “IPA-ST” (manufactured by Nissan Chemical Industries, Ltd.). Tetraalkoxysilane, methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, which are represented by organosilica sol N-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, Cycloalkenyl trimethoxysilane, trialkoxysilane such as phenyltriethoxysilane; dimethyldimethoxysilane, dimethyldiethoxysilane, diethyl dimethoxysilane, and di-alkoxysilanes such as diethyl diethoxy silane.
　また、前記ポリシロキサン（Ｘ）としては、ビニル重合体から構成されるセグメントとポリシロキサンから構成されるセグメントとが結合した重合体も使用することができる。 Further, as the polysiloxane (X), a polymer in which a segment composed of a vinyl polymer and a segment composed of a polysiloxane are bonded can also be used.
　前記重合体としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル等のビニル単量体と、３－（メタ）アクリロキシプロピルトリメトキシシラン、（メタ）アクリロキシプロピルトリエトキシシラン等の重合性不飽和基を有するシラン化合物とを重合することによって得られる重合体や、それに前記アルコキシシランを縮合して得られる加水分解性シリル基等を有するビニル重合体が挙げられる。 Examples of the polymer include vinyl monomers such as methyl (meth) acrylate and ethyl (meth) acrylate, 3- (meth) acryloxypropyltrimethoxysilane, and (meth) acryloxypropyltriethoxysilane. Examples thereof include a polymer obtained by polymerizing with a silane compound having a polymerizable unsaturated group such as a vinyl polymer having a hydrolyzable silyl group obtained by condensing the alkoxysilane with the polymer.
　前記重合体は、例えば、加水分解性シリル基等を有するビニル重合体の有機溶剤溶液下に、前記アルコキシシランを逐次供給または一括供給し、攪拌下で２０～１２０℃の範囲で０．５時間～２４時間程度行い、前記ビニル重合体の加水分解性シリル基等と、アルコキシシランの加水分解性シリル基等とを加水分解縮合反応させることによって製造することができる。 For example, the alkoxysilane is sequentially or collectively supplied into an organic solvent solution of a vinyl polymer having a hydrolyzable silyl group and the like, and the polymer is stirred for 0.5 hour in the range of 20 to 120 ° C. The reaction can be carried out for about 24 hours by subjecting the hydrolyzable silyl group of the vinyl polymer and the hydrolyzable silyl group of the alkoxysilane to a hydrolytic condensation reaction.
　前記ポリシロキサン（Ｘ）は、加水分解性シリル基またはシラノール基を有していることから、前記ウレタン樹脂（Ａ）が有する加水分解性シリル基またはシラノール基と加水分解縮合反応を生じ、強固なポリシロキサン－ポリウレタン構造が形成されることにより、耐食性、耐温水性、耐薬品性、耐溶剤性及び各種基材に対する密着性に優れた塗膜を形成できる。 Since the polysiloxane (X) has a hydrolyzable silyl group or silanol group, it causes a hydrolytic condensation reaction with the hydrolyzable silyl group or silanol group of the urethane resin (A) and is strong. By forming a polysiloxane-polyurethane structure, it is possible to form a coating film excellent in corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates.
　さらに、前記ポリシロキサン（Ｘ）としては、より架橋密度の高い強固なポリシロキサン－ポリウレタン構造が形成されることにより、耐食性、耐温水性、耐薬品性、耐溶剤性及び各種基材に対する密着性に優れた塗膜を形成できることから、重合性不飽和基を有するものを使用することが好ましい。重合性不飽和基を有するポリシロキサン（Ｘ）は、例えば、３－（メタ）アクリロキシプロピルトリメトキシシラン、３－（メタ）アクリロキシプロピルトリエトキシシラン等の重合性不飽和基を有するシラン化合物を使用して得られるアルコキシシランの縮合物の原料として製造することにより得られる。 Furthermore, as the polysiloxane (X), a strong polysiloxane-polyurethane structure having a higher crosslinking density is formed, thereby providing corrosion resistance, hot water resistance, chemical resistance, solvent resistance, and adhesion to various substrates. It is preferable to use one having a polymerizable unsaturated group because a coating film excellent in the thickness can be formed. The polysiloxane (X) having a polymerizable unsaturated group is, for example, a silane compound having a polymerizable unsaturated group such as 3- (meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropyltriethoxysilane. It can be obtained by producing as a raw material for the condensate of alkoxysilane obtained using
　前記重合性不飽和基は、前記ポリシロキサン（Ｘ）中に０．２～３ｍｍｏｌ／ｇの範囲で有することが好ましい。 The polymerizable unsaturated group is preferably contained in the polysiloxane (X) in a range of 0.2 to 3 mmol / g.
　本発明の水性ウレタン樹脂組成物は、前記ウレタン樹脂（Ａ）が有する重合性不飽和基のラジカル重合を進行させるうえで、重合開始剤を使用することが好ましい。 In the aqueous urethane resin composition of the present invention, it is preferable to use a polymerization initiator in order to promote radical polymerization of the polymerizable unsaturated group of the urethane resin (A).
　前記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、ハロゲノケトン等を使用することができる。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使用してもよい。 As the polymerization initiator, for example, benzophenone, benzyl, Michler ketone, thioxanthone, anthraquinone, benzoin, dialkoxyacetophenone, acyl oxime ester, benzyl ketal, hydroxyalkylphenone, halogenoketone and the like can be used. The photopolymerization initiator may be used in combination with a tertiary amine such as methylamine, diethanolamine, N-methyldiethanolamine, or tributylamine as necessary.
　また、重合開始剤としては、例えば、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、ベンゾイルパーオキサイド、ｔ－ブチルハイドロパーオキサイド、過酸化水素等の過酸化物等の熱重合開始剤を使用することもできる。 Examples of the polymerization initiator include 2,2′-azobis (2-methylpropionamidine) dihydrochloride, 4,4′-azobis (4-cyano) valeric acid, 2,2′-azobis (2- Thermal polymerization initiators such as peroxides such as amidinopropane) dihydrochloride, benzoyl peroxide, t-butyl hydroperoxide, and hydrogen peroxide can also be used.
　前記重合開始剤は、ウレタン樹脂（Ａ）の固形分１００質量部に対して、０．５～５質量部の範囲で使用することが好ましい。 The polymerization initiator is preferably used in the range of 0.5 to 5 parts by mass with respect to 100 parts by mass of the solid content of the urethane resin (A).
　本発明の水性ウレタン樹脂組成物には、本発明の目的を阻害しない範囲で必要に応じて添加剤を含有させてもよい。前記添加剤としては、例えば、重合性不飽和基を有する化合物、成膜助剤、充填材、チキソトロピー付与剤、粘着性付与剤、顔料や抗菌剤等が挙げられる。 The water-based urethane resin composition of the present invention may contain additives as necessary within a range that does not impair the object of the present invention. Examples of the additive include a compound having a polymerizable unsaturated group, a film forming aid, a filler, a thixotropic agent, a tackifier, a pigment, an antibacterial agent, and the like.
　前記重合性不飽和基を有する化合物としては、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、シクロヘキシル（メタ）アクリレート、ジシクロペンタニル（メタ）アクリレート、１－アダマンチル（メタ）アクリレート、エチレングリコールジ（メタ）アクリレート、１，３－プロパンジオールジ（メタ）アクリレート、１，４－ブタンジオールジ（メタ）アクリレート、ペンタエリスリトールトリ（メタ）アクリレート、ペンタエリスリトールテトラ（メタ）アクリレート、ジペンタエリスリトールペンタ（メタ）アクリレート、ジペンタエリスリトールヘキサ（メタ）アクリレート、トリメチロールプロパントリ（メタ）アクリレート、ジトリメチロールプロパンテトラ（メタ）アクリレート等が挙げられる。なかでも、ジペンタエリスリトールヘキサ（メタ）アクリレートを使用することが好ましい。これらを使用することによって、より一層高硬度な塗膜を形成可能なウレタン樹脂組成物を得ることができる。 Examples of the compound having a polymerizable unsaturated group include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meta ) Acrylate, 1-adamantyl (meth) acrylate, ethylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrime Trimethylolpropane tetra (meth) acrylate. Of these, dipentaerythritol hexa (meth) acrylate is preferably used. By using these, a urethane resin composition capable of forming a coating film with higher hardness can be obtained.
　前記成膜助剤としては、例えば、アニオン界面活性剤（ジオクチルスルホコハク酸エステルソーダ塩等）、疎水性ノニオン界面活性剤（ソルビタンモノオレエート等）、シリコーンオイル等が挙げられる。 Examples of the film forming aid include an anionic surfactant (dioctylsulfosuccinate ester soda salt, etc.), a hydrophobic nonionic surfactant (sorbitan monooleate, etc.), silicone oil, and the like.
　前記チキソトロピー付与剤としては、例えば、脂肪酸、脂肪酸金属塩、脂肪酸エステル、パラフィン、樹脂酸、界面活性剤、ポリアクリル酸等で表面処理された前記充填材、ポリ塩化ビニルパウダー、水添ヒマシ油、微粉末シリカ、有機ベントナイト、セピオライト等が挙げられる。 Examples of the thixotropy-imparting agent include fatty acid, fatty acid metal salt, fatty acid ester, paraffin, resin acid, surfactant, polyacrylic acid and the like surface-treated filler, polyvinyl chloride powder, hydrogenated castor oil, Fine powder silica, organic bentonite, sepiolite and the like can be mentioned.
　前記顔料としては、公知慣用の無機顔料や有機顔料を使用することができる。 As the pigment, known and commonly used inorganic pigments and organic pigments can be used.
　前記無機顔料としては、例えば、酸化チタン、アンチモンレッド、ベンガラ、カドミウムレッド、カドミウムイエロー、コバルトブルー、紺青、群青、カーボンブラック、黒鉛等を使用することができる。 As the inorganic pigment, for example, titanium oxide, antimony red, bengara, cadmium red, cadmium yellow, cobalt blue, bitumen, ultramarine blue, carbon black, graphite and the like can be used.
　前記有機顔料としては、例えば、キナクリドン顔料、キナクリドンキノン顔料、ジオキサジン顔料、フタロシアニン顔料、アントラピリミジン顔料、アンサンスロン顔料、インダンスロン顔料、フラバンスロン顔料、ペリレン顔料、ジケトピロロピロール顔料、ペリノン顔料、キノフタロン顔料、アントラキノン顔料、チオインジゴ顔料、ベンツイミダゾロン顔料、アゾ顔料等の有機顔料を使用することができる。これらの顔料は２種類以上のものを併用することができる。また、これらの顔料が表面処理されており、水性媒体に対して自己分散能を有しているものであっても良い。 Examples of the organic pigment include quinacridone pigment, quinacridone quinone pigment, dioxazine pigment, phthalocyanine pigment, anthrapyrimidine pigment, ansanthrone pigment, indanthrone pigment, flavanthrone pigment, perylene pigment, diketopyrrolopyrrole pigment, perinone pigment, Organic pigments such as quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments can be used. Two or more kinds of these pigments can be used in combination. These pigments may be surface-treated and have a self-dispersing ability with respect to an aqueous medium.
　前記抗菌剤としては、例えば、塩化銀、トリフルアニド、ジクロルフルアニド、フルオロフォルペット、ジンクピリチオン、２－ベンゾイミダゾールカルバン酸メチル、２－（４－チアゾリル）ベンゾイミダゾール等を使用することができる。 As the antibacterial agent, for example, silver chloride, trifuranide, dichlorofluanide, fluorophorpet, zinc pyrithione, methyl 2-benzimidazole carbanate, 2- (4-thiazolyl) benzimidazole and the like can be used.
　その他の添加剤としては、例えば、反応促進剤（金属系反応促進剤、金属塩系反応促進剤、アミン系反応促進剤等）、安定剤（紫外線吸収剤、酸化防止剤、耐熱安定剤等）、水分除去剤（４－パラトルエンスルフォニルイソシアネート等）、吸着剤（生石灰、消石灰、ゼオライト、モレキュラーシーブ等）、接着性付与剤、消泡剤、レベリング剤等の種々の添加剤が挙げられる。 Examples of other additives include reaction accelerators (metal reaction accelerators, metal salt reaction accelerators, amine reaction accelerators, etc.), stabilizers (ultraviolet absorbers, antioxidants, heat stabilizers, etc.). And various additives such as moisture removing agents (4-paratoluenesulfonyl isocyanate, etc.), adsorbents (quick lime, slaked lime, zeolite, molecular sieves, etc.), adhesion-imparting agents, antifoaming agents, leveling agents and the like.
　本発明の水性ウレタン樹脂組成物は、前記水性媒体（Ｂ）中に、前記ウレタン樹脂（Ａ）及び前記アクリル樹脂（Ｂ）を分散したものである。この際、前記ウレタン樹脂（Ａ）及び前記アクリル樹脂（Ｂ）とが、前記水性媒体（Ｂ）中で、別個の樹脂粒子として存在していることが好ましい。 The aqueous urethane resin composition of the present invention is obtained by dispersing the urethane resin (A) and the acrylic resin (B) in the aqueous medium (B). At this time, it is preferable that the urethane resin (A) and the acrylic resin (B) are present as separate resin particles in the aqueous medium (B).
　本発明の水性ウレタン樹脂組成物は、例えば、各種基材の表面保護や意匠性を付与しうるコーティング剤に好適に使用することができる。 The aqueous urethane resin composition of the present invention can be suitably used, for example, as a coating agent that can impart surface protection and design properties of various substrates.
　前記コーティング剤を塗布し塗膜を形成可能な基材としては、例えば、ガラス基材、金属基材、プラスチック基材、紙、木材基材、繊維質基材等が挙げられる。また、ウレタンフォーム等の多孔体構造の基材も使用することもできる。 Examples of the substrate on which the coating agent can be applied to form a coating film include a glass substrate, a metal substrate, a plastic substrate, paper, a wood substrate, and a fibrous substrate. Moreover, the base material of porous body structures, such as a urethane foam, can also be used.
　プラスチック基材としては、例えば、ポリカーボネート基材、ポリエステル基材、アクリロニトリル－ブタジエン－スチレン基材、ポリアクリル基材、ポリスチレン基材、ポリウレタン基材、エポキシ樹脂基材、ポリ塩化ビニル基材及びポリアミド基材を使用することができる。 Examples of plastic substrates include polycarbonate substrates, polyester substrates, acrylonitrile-butadiene-styrene substrates, polyacryl substrates, polystyrene substrates, polyurethane substrates, epoxy resin substrates, polyvinyl chloride substrates, and polyamide groups. Material can be used.
　前記金属基材としては、例えば、亜鉛めっき鋼板、アルミニウム－亜鉛合金鋼板等のめっき鋼板や、鉄板、アルミ板、アルミ合金板、電磁鋼板、銅板、ステンレス鋼板等を使用することができる。 As the metal substrate, for example, a plated steel plate such as a galvanized steel plate or an aluminum-zinc alloy steel plate, an iron plate, an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate, or the like can be used.
　前記基材は前記材質からなる平面状のものであっても曲部を有するものであってもよく、また、不織布のような繊維からなる基材であってもよい。 The base material may be a planar material made of the material or may have a curved portion, or may be a base material made of fibers such as a nonwoven fabric.
　本発明のコーティング剤は、例えば、それを前記基材表面に直接、または、予めプライマー層等が設けられた基材の表面に、塗布し、次いで乾燥した後、前記ウレタン樹脂（Ａ）が有する重合性不飽和二重基のラジカル重合を進行させることによって、塗膜を形成することができる。 The coating agent of the present invention has, for example, the urethane resin (A) after being applied directly to the surface of the base material or the surface of the base material on which a primer layer or the like has been previously provided and then dried. A coating film can be formed by advancing radical polymerization of a polymerizable unsaturated double group.
　また、離型紙上に前記コーティング剤を塗布し、次いで乾燥、硬化させることによって離型紙の表面に塗膜を形成し、さらに前記塗膜上に接着剤もしくは粘着剤を塗布したものを、不織布のような繊維からなる基材に貼り合わせ、離型紙を剥離することによって、所望の基材の表面に、前記コーティング剤を用いて形成される塗膜を積層することができる。 In addition, a coating film is formed on the surface of the release paper by applying the coating agent on the release paper, then drying and curing, and a non-woven fabric obtained by applying an adhesive or an adhesive on the coating film. A film formed using the coating agent can be laminated on the surface of a desired substrate by laminating the substrate made of such fibers and peeling the release paper.
　前記コーティング剤を前記基材上に塗布する方法としては、例えば、スプレー法、カーテンコーター法、フローコーター法、ロールコーター法、刷毛塗り法、浸漬法等が挙げられる。 Examples of the method for applying the coating agent on the substrate include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and a dipping method.
　また、前記コーティング剤を硬化する方法としては、加熱する方法、紫外線等の活性エネルギー線を照射する方法が挙げられる。 Also, examples of the method for curing the coating agent include a heating method and a method of irradiating active energy rays such as ultraviolet rays.
　前記加熱する方法としては、使用するラジカル重合開始剤の種類によって異なるが、例えば、１００～１５０℃程度の温度で１０分～３０分程度行うことで、前記ラジカル重合を進行させ硬化させることができる。 The heating method varies depending on the type of radical polymerization initiator to be used. For example, by performing the heating at a temperature of about 100 to 150 ° C. for about 10 to 30 minutes, the radical polymerization can be advanced and cured. .
　また、前記活性エネルギー線を照射する方法としては、例えば、紫外線であればキセノンランプ、キセノン－水銀ランプ、メタルハライドランプ、高圧水銀ランプ、低圧水銀ランプ、ＬＥＤランプ等の公知のランプを使用する方法が挙げられる。 As the method of irradiating the active energy ray, for example, a method using a known lamp such as a xenon lamp, a xenon-mercury lamp, a metal halide lamp, a high-pressure mercury lamp, a low-pressure mercury lamp, or an LED lamp is used. Can be mentioned.
　前記活性エネルギー線の照射量は、０．０５～５Ｊ／ｃｍ２の範囲であることが好ましく、０．１～３Ｊ／ｃｍ２の範囲であることがより好ましく、０．１～１Ｊ／ｃｍ２の範囲であることが特に好ましい。なお、上記の紫外線照射量は、ＵＶチェッカーＵＶＲ－Ｎ１（日本電池株式会社製）を用いて３００～３９０ｎｍの波長域において測定した値に基づく。 The exposure dose of the actinic energy ray is preferably in the range of 0.05 ~ 5J / cm 2, more preferably in the range of 0.1 ~ 3J / cm 2, 0.1 ~ 1J / cm 2 It is particularly preferable that the range is The above-mentioned ultraviolet irradiation amount is based on values measured in a wavelength range of 300 to 390 nm using a UV checker UVR-N1 (manufactured by Nippon Battery Co., Ltd.).
　本発明のコーティング剤を用いて形成可能な塗膜の厚さは、基材の使用される用途等に応じて適宜調整可能であるが、通常０．１～１００μｍ程度であることが好ましい。 The thickness of the coating film that can be formed using the coating agent of the present invention can be appropriately adjusted according to the use of the substrate, but is preferably about 0.1 to 100 μm.
　以上のように、前記基材上に前記コーティング剤を用いて形成された塗膜を設けた物品は、液晶ディスプレイ、フレキシブルディスプレイ等の光学部材、携帯電話、家電製品をはじめとする各種プラスチック製品、自動車外装、建材等の金属製品として使用することが可能である。 As described above, articles provided with a coating film formed using the coating agent on the substrate are optical members such as liquid crystal displays and flexible displays, mobile phones, various plastic products including home appliances, It can be used as metal products such as automobile exteriors and building materials.
　以下、実施例と比較例とにより、本発明を具体的に説明する。 Hereinafter, the present invention will be specifically described by way of examples and comparative examples.
〔製造例１：ポリシロキサンの製造〕
　攪拌機、温度計、滴下ロート、冷却管及び窒素ガス導入口を備えた反応容器に、フェニルトリメトキシシラン（ＰＴＭＳ）１９１質量部を仕込んで、１２０℃まで昇温した。次いで、メチルメタクリレート（ＭＭＡ）１６９質量部、３－メタクリロイルオキシプロピルトリメトキシシラン（ＭＰＴＳ）１１質量部、ｔｅｒｔ－ブチルパーオキシ－２－エチルヘキサノエート（ＴＢＰＥＨ）１８質量部からなる混合物を、前記反応容器中へ４時間かけて滴下した。その後、同温度で１６時間撹拌し、トリメトキシシリル基を有するビニル重合体（Ｙ－１）を調製した。
　次いで、前記反応容器の温度を８０℃に調整し、メチルトリメトキシシラン（ＭＴＭＳ）１３１質量部、３－アクリロイルオキシプロピルトリメトキシシラン（ＡＰＴＳ）２２６質量部、ジメチルジメトキシシラン（ＤＭＤＭＳ）１１６質量部を、前記反応容器中へ添加した。その後、ｉｓｏ－プロピルアシッドホスフェート（堺化学株式会社製「Ａ－３」）６．３質量部とイオン交換水９７質量部との混合物を、５分間で滴下し、同温度で２時間撹拌することにより、加水分解縮合反応させ、反応生成物を得た。前記反応生成物を、１Ｈ－ＮＭＲで分析したところ、前記ビニル重合体（Ｙ－１）が有するトリメトキシシリル基のほぼ１００％が加水分解していた。その後、前記反応生成物を、１０～３００ｍｍＨｇの減圧下で、４０～６０℃の条件で２時間蒸留することにより、生成したメタノール及びイオン交換水を除去することで、不揮発分が９９．４質量％であるビニル重合体セグメントとポリシロキサンセグメントとが結合したポリシロキサン（Ｘ－１）を得た。 [Production Example 1: Production of polysiloxane]
A reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, a condenser tube and a nitrogen gas inlet was charged with 191 parts by weight of phenyltrimethoxysilane (PTMS), and the temperature was raised to 120 ° C. Next, a mixture comprising 169 parts by weight of methyl methacrylate (MMA), 11 parts by weight of 3-methacryloyloxypropyltrimethoxysilane (MPTS), and 18 parts by weight of tert-butylperoxy-2-ethylhexanoate (TBPEH) The solution was dropped into the reaction vessel over 4 hours. Thereafter, the mixture was stirred at the same temperature for 16 hours to prepare a vinyl polymer (Y-1) having a trimethoxysilyl group.
Next, the temperature of the reaction vessel was adjusted to 80 ° C., and 131 parts by mass of methyltrimethoxysilane (MTMS), 226 parts by mass of 3-acryloyloxypropyltrimethoxysilane (APTS), and 116 parts by mass of dimethyldimethoxysilane (DMDMS) were added. To the reaction vessel. Thereafter, a mixture of 6.3 parts by mass of iso-propyl acid phosphate (“A-3” manufactured by Sakai Chemical Co., Ltd.) and 97 parts by mass of ion-exchanged water is added dropwise over 5 minutes and stirred at the same temperature for 2 hours. To obtain a reaction product. When the reaction product was analyzed by 1 H-NMR, almost 100% of the trimethoxysilyl group of the vinyl polymer (Y-1) was hydrolyzed. Thereafter, the reaction product is distilled under reduced pressure of 10 to 300 mmHg for 2 hours at 40 to 60 ° C. to remove the generated methanol and ion-exchanged water, so that the nonvolatile content is 99.4 mass. % Of a polysiloxane (X-1) having a vinyl polymer segment and a polysiloxane segment bonded to each other.
〔実施例１：水性ウレタン樹脂組成物（１）〕
　加熱装置、攪拌機、温度計及び還流冷却管を備えた２リットル４つ口フラスコに、メチルエチルケトン８８．８質量部、ポリカーボネートポリオール（１，６－ヘキサンジオールと１，５－ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量２０００）１００質量部、２，２－ジメチロールプロピオン酸１３．４質量部、１，６－ヘキサンジオール１２．２質量部、ペンタエリスリトールジアクリレート（一般式（１）中のＲ１は、炭素原子数３のもので、重合性不飽和基を有する原子団を２つ有するものである。）２４．３質量部、メチルヒドロキノン０．００５質量部、及び、２，６－ｔｅｒｔ－ブチル－ｐ－クレゾール０．０５質量部を仕込み、撹拌しながら５０℃に調整した。 [Example 1: Aqueous urethane resin composition (1)]
Into a 2 liter four-necked flask equipped with a heating device, a stirrer, a thermometer and a reflux condenser, 88.8 parts by mass of methyl ethyl ketone, polycarbonate polyol (1,6-hexanediol, 1,5-pentanediol and diethyl carbonate were added. Polycarbonate polyol obtained by reaction, number average molecular weight 2000) 100 parts by weight, 2,2-dimethylolpropionic acid 13.4 parts by weight, 1,6-hexanediol 12.2 parts by weight, pentaerythritol diacrylate (general formula R 1 in (1) has 3 carbon atoms and has 2 atomic groups having a polymerizable unsaturated group.) 24.3 parts by mass, 0.005 parts by mass of methylhydroquinone, and , 0.05 parts by mass of 2,6-tert-butyl-p-cresol was added and adjusted to 50 ° C. with stirring. It was.
　次に、前記４つ口フラスコにジシクロヘキシルメタンジイソシアネート１１６．５質量部を供給し、８０℃で約５時間反応させることで、側鎖に重合性不飽和結合を有し、主鎖の末端にイソシアネート基を有するウレタン樹脂の有機溶剤溶液を得た。 Next, 116.5 parts by mass of dicyclohexylmethane diisocyanate is supplied to the four-necked flask and reacted at 80 ° C. for about 5 hours to have a polymerizable unsaturated bond in the side chain and isocyanate at the end of the main chain. An organic solvent solution of a urethane resin having a group was obtained.
　次に、前記ウレタン樹脂の有機溶剤溶液を５０℃に冷却後、前記４つ口フラスコにＮ－２－（アミノエチル）―３－アミノプロピルトリエトキシシラン１１．７質量部とメチルエチルケトン２５１．１質量部を供給し、加水分解性シリル基またはシラノール基と、重合性不飽和基とを有するウレタン樹脂（Ｉ－１）の有機溶剤溶液を得た。 Next, after the organic solvent solution of the urethane resin was cooled to 50 ° C., 11.7 parts by mass of N-2- (aminoethyl) -3-aminopropyltriethoxysilane and 251.1 parts by mass of methyl ethyl ketone were added to the four-necked flask. The organic solvent solution of urethane resin (I-1) having hydrolyzable silyl group or silanol group and polymerizable unsaturated group was obtained.
　次に、前記ウレタン樹脂（Ｉ－１）の有機溶剤溶液と、ジメチルエタノールアミン８．９質量部とを混合した後、イオン交換水５４０．９質量部を加え十分に攪拌し、１０質量％のピペラジン水溶液を４７．５質量部加えて、４０℃で鎖伸長反応させ、減圧蒸留することによって、不揮発分３３質量％の水性ウレタン樹脂組成物（１）を得た。 Next, the organic solvent solution of the urethane resin (I-1) and 8.9 parts by mass of dimethylethanolamine were mixed, 540.9 parts by mass of ion-exchanged water was added, and the mixture was sufficiently stirred. An aqueous urethane resin composition (1) having a nonvolatile content of 33% by mass was obtained by adding 47.5 parts by mass of an aqueous piperazine solution, causing a chain extension reaction at 40 ° C., and distillation under reduced pressure.
〔実施例２：水性ウレタン樹脂組成物（２）〕
　前記ウレタン樹脂（Ｉ－１）の有機溶剤溶液の全量と、製造例１で得たポリシロキサン（Ｘ－１）９２．７質量部とジメチルエタノールアミン８．９質量部とを混合した後、イオン交換水５８９．１質量部を加え十分に攪拌し、１０質量％のピペラジン水溶液を４７．５質量部加えて、４０℃で鎖伸長反応させ、減圧蒸留することによって、不揮発分４５質量％の水性ウレタン樹脂組成物（２）を得た。 [Example 2: Aqueous urethane resin composition (2)]
After mixing the total amount of the organic resin solution of the urethane resin (I-1), 92.7 parts by mass of the polysiloxane (X-1) obtained in Production Example 1, and 8.9 parts by mass of dimethylethanolamine, 589.1 parts by mass of exchange water was added and sufficiently stirred, 47.5 parts by mass of a 10% by mass aqueous piperazine solution was added, a chain elongation reaction was carried out at 40 ° C., and distillation under reduced pressure was carried out. A urethane resin composition (2) was obtained.
〔実施例３：水性ウレタン樹脂組成物（３）〕
　前記ウレタン樹脂（Ｉ－１）の有機溶剤溶液の全量と、製造例１で得たポリシロキサン（Ｘ－１）２７８．１質量部とジメチルエタノールアミン８．９質量部とを混合した後、イオン交換水１２０７．１質量部を加え十分に攪拌し、１０質量％のピペラジン水溶液を４７．５質量部加えて、４０℃で鎖伸長反応させ、減圧蒸留することによって、不揮発分４５質量％の水性ウレタン樹脂組成物（３）を得た。 [Example 3: Aqueous urethane resin composition (3)]
After mixing the total amount of the urethane resin (I-1) organic solvent solution, 278.1 parts by mass of the polysiloxane (X-1) obtained in Production Example 1, and 8.9 parts by mass of dimethylethanolamine, 1207.1 parts by mass of exchange water was added and stirred sufficiently, 47.5 parts by mass of a 10% by mass piperazine aqueous solution was added, a chain elongation reaction was carried out at 40 ° C., and distillation under reduced pressure was carried out. A urethane resin composition (3) was obtained.
〔実施例４：水性ウレタン樹脂組成物（４）〕
　加熱装置、攪拌機、温度計及び還流冷却管を備えた２リットル４つ口フラスコに、メチルエチルケトン８９．２質量部、ポリカーボネートポリオール（１，６－ヘキサンジオールと１，５－ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量２０００）１００質量部、２，２－ジメチロールプロピオン酸１３．４質量部、１，６－ヘキサンジオール１１．５質量部、ペンタエリスリトールジアクリレート（一般式（１）中のＲ１は、炭素原子数３のもので、重合性不飽和基を有する原子団を２つ有するものである。）２６．１質量部、メチルヒドロキノン０．００５質量部、及び、２，６－ｔｅｒｔ－ブチル－ｐ－クレゾール０．０５質量部を仕込み、撹拌しながら５０℃に調整した。 [Example 4: Aqueous urethane resin composition (4)]
Into a 2 liter four-necked flask equipped with a heating device, a stirrer, a thermometer and a reflux condenser, 89.2 parts by mass of methyl ethyl ketone, polycarbonate polyol (1,6-hexanediol, 1,5-pentanediol and diethyl carbonate were added. Polycarbonate polyol obtained by reaction, number average molecular weight 2000) 100 parts by mass, 1,2-dimethylol propionic acid 13.4 parts by mass, 1,6-hexanediol 11.5 parts by mass, pentaerythritol diacrylate (general formula R 1 in (1) has 3 carbon atoms and has 2 atomic groups having a polymerizable unsaturated group.) 26.1 parts by mass, methyl hydroquinone 0.005 parts by mass, and , 0.05 parts by mass of 2,6-tert-butyl-p-cresol was added and adjusted to 50 ° C. with stirring. It was.
　次に、前記４つ口フラスコにジシクロヘキシルメタンジイソシアネート１１６．５質量部を供給し、８０℃で約５時間反応させることで、側鎖に重合性不飽和結合を有し、主鎖の末端にイソシアネート基を有するウレタン樹脂の有機溶剤溶液を得た。 Next, 116.5 parts by mass of dicyclohexylmethane diisocyanate is supplied to the four-necked flask and reacted at 80 ° C. for about 5 hours to have a polymerizable unsaturated bond in the side chain and isocyanate at the end of the main chain. An organic solvent solution of a urethane resin having a group was obtained.
　次に、前記ウレタン樹脂の有機溶剤溶液を５０℃に冷却後、前記４つ口フラスコにＮ－２－（アミノエチル）―３－アミノプロピルトリエトキシシラン１１．７質量部と３－アミノプロピルトリメトキシシラン２４．４質量部、メチルエチルケトン２８１．９質量部を供給し、加水分解性シリル基またはシラノール基と、重合性不飽和基とを有するウレタン樹脂（Ｉ－２）の有機溶剤溶液を得た。 Next, after the organic solvent solution of the urethane resin was cooled to 50 ° C., 11.7 parts by mass of N-2- (aminoethyl) -3-aminopropyltriethoxysilane and 3-aminopropyltriethoxysilane were added to the four-necked flask. 24.4 parts by mass of methoxysilane and 281.9 parts by mass of methyl ethyl ketone were supplied to obtain an organic solvent solution of urethane resin (I-2) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group. .
　次に、前記ウレタン樹脂（Ｉ－２）の有機溶剤溶液の全量と、製造例１で得たポリシロキサン（Ｘ－１）３０３．６質量部とジメチルエタノールアミン８．９質量部とを混合した後、イオン交換水１３６８．２質量部を加え十分に攪拌し、減圧蒸留することによって、不揮発分４５質量％の水性ウレタン樹脂組成物（４）を得た。 Next, the total amount of the organic solvent solution of the urethane resin (I-2) was mixed with 303.6 parts by mass of the polysiloxane (X-1) obtained in Production Example 1 and 8.9 parts by mass of dimethylethanolamine. Thereafter, 1368.2 parts by mass of ion-exchanged water was added, and the mixture was sufficiently stirred and distilled under reduced pressure to obtain an aqueous urethane resin composition (4) having a nonvolatile content of 45% by mass.
〔実施例５：水性ウレタン樹脂組成物（５）〕
　前記ウレタン樹脂（Ｉ－１）の有機溶剤溶液の全量と、ジペンタエリスリトールヘキサアクリレート５５．６質量部とジメチルエタノールアミン８．９質量部とを混合した後、イオン交換水７７７．６質量部を加え十分に攪拌し、１０質量％のピペラジン水溶液を４７．５質量部加えて、４０℃で鎖伸長反応させ、減圧蒸留することによって、不揮発分４５質量％の水性ウレタン樹脂組成物（５）を得た。 [Example 5: Aqueous urethane resin composition (5)]
After mixing the total amount of the organic solvent solution of the urethane resin (I-1), 55.6 parts by mass of dipentaerythritol hexaacrylate and 8.9 parts by mass of dimethylethanolamine, 777.6 parts by mass of ion-exchanged water was added. The mixture was sufficiently stirred, and 47.5 parts by mass of a 10% by mass piperazine aqueous solution was added, subjected to chain extension reaction at 40 ° C., and distilled under reduced pressure to obtain an aqueous urethane resin composition (5) having a nonvolatile content of 45% by mass. Obtained.
〔実施例６：水性ウレタン樹脂組成物（６）〕
　前記ウレタン樹脂（Ｉ－１）の有機溶剤溶液の全量と、ジペンタエリスリトールヘキサアクリレート１１１．２質量部と製造例１で得たポリシロキサン（Ｘ－１）２７８．４質量部、ジメチルエタノールアミン８．９質量部とを混合した後、イオン交換水８３６．３質量部を加え十分に攪拌し、１０質量％のピペラジン水溶液を４７．５質量部加えて、４０℃で鎖伸長反応させ、減圧蒸留することによって、不揮発分４５質量％の水性ウレタン樹脂組成物（６）を得た。 [Example 6: Aqueous urethane resin composition (6)]
Total amount of the organic resin solution of the urethane resin (I-1), 111.2 parts by mass of dipentaerythritol hexaacrylate, 278.4 parts by mass of polysiloxane (X-1) obtained in Production Example 1, dimethylethanolamine 8 After mixing with 9.9 parts by mass, 836.3 parts by mass of ion-exchanged water was added and stirred sufficiently, 47.5 parts by mass of a 10% by mass piperazine aqueous solution was added, and a chain elongation reaction was performed at 40 ° C., followed by distillation under reduced pressure. As a result, an aqueous urethane resin composition (6) having a nonvolatile content of 45% by mass was obtained.
〔実施例７：水性ウレタン樹脂組成物（７）〕
　加熱装置、攪拌機、温度計及び還流冷却管を備えた２リットル４つ口フラスコに、１,４－ビス（３－アクリロイロキシ－２－ヒドロキシプロポキシ）ブタン（一般式（２）中のＲ１及びＲ３は炭素原子数２のもので、重合性不飽和基を有する原子団を１つ有するものであり、Ｒ２は炭素原子数４のものである。）３５．９質量部、メチルヒドロキノン０．００７質量部、及び、２，６－ｔｅｒｔ－ブチル－ｐ－クレゾール０．０７質量部を仕込み、攪拌しながら５０℃で調整した。 [Example 7: Aqueous urethane resin composition (7)]
A 2-liter four-necked flask equipped with a heating device, a stirrer, a thermometer and a reflux condenser was added to 1,4-bis (3-acryloyloxy-2-hydroxypropoxy) butane (R 1 and R in the general formula (2)). 3 has 2 carbon atoms and has one atomic group having a polymerizable unsaturated group, and R 2 has 4 carbon atoms.) 35.9 parts by mass, methylhydroquinone 007 parts by mass and 0.07 parts by mass of 2,6-tert-butyl-p-cresol were charged and adjusted at 50 ° C. with stirring.
　次に前記４つ口フラスコにジシクロヘキシルメタンジイソシアネート１１６．５質量部を供給し、８０℃で約３時間反応させた後、メチルエチルケトン９１．９質量部、ポリカーボネートポリオール（１，６－ヘキサンジオールと１，５－ペンタンジオールとジエチルカーボネートとを反応させて得られるポリカーボネートポリオール、数平均分子量２０００）１００質量部、２，２－ジメチロールプロピオン酸１３．４質量部、及び、１，６－ヘキサンジオール９．９質量部を供給し、８０℃で約３時間反応させることで、側鎖に重合性不飽和結合を有し、主鎖の末端にイソシアネート基を有するウレタン樹脂の有機溶剤溶液を得た。 Next, 116.5 parts by mass of dicyclohexylmethane diisocyanate was supplied to the four-necked flask and reacted at 80 ° C. for about 3 hours, and then 91.9 parts by mass of methyl ethyl ketone, polycarbonate polyol (1,6-hexanediol and 1,1 Polycarbonate polyol obtained by reacting 5-pentanediol and diethyl carbonate, number average molecular weight 2000) 100 parts by mass, 1,2-dimethylolpropionic acid 13.4 parts by mass, and 1,6-hexanediol 9. By supplying 9 parts by mass and reacting at 80 ° C. for about 3 hours, an organic solvent solution of a urethane resin having a polymerizable unsaturated bond in the side chain and an isocyanate group at the end of the main chain was obtained.
　前記ウレタン樹脂の有機溶剤溶液を５０℃に冷却後、前記４つ口フラスコにＮ－２－（アミノエチル）―３－アミノプロピルトリエトキシシラン１１．７質量部とメチルエチルケトン２５９．３質量部を供給し、加水分解性シリル基またはシラノール基と、重合性不飽和基とを有するウレタン樹脂（Ｉ－３）の有機溶剤溶液を得た。 After cooling the organic resin solution of the urethane resin to 50 ° C., 11.7 parts by mass of N-2- (aminoethyl) -3-aminopropyltriethoxysilane and 259.3 parts by mass of methyl ethyl ketone are supplied to the four-necked flask. An organic solvent solution of urethane resin (I-3) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group was obtained.
　次に、前記ウレタン樹脂（Ｉ－３）の有機溶剤溶液と、ジメチルエタノールアミン８．９質量部とを混合した後、イオン交換水５５９．９質量部を加え十分に攪拌し、１０質量％のピペラジン水溶液を４７．５質量部加えて、４０℃で鎖伸長反応させ、減圧蒸留することによって、不揮発分３３質量％の水性ウレタン樹脂組成物（７）を得た。 Next, the organic solvent solution of the urethane resin (I-3) and 8.9 parts by mass of dimethylethanolamine were mixed, 559.9 parts by mass of ion-exchanged water was added, and the mixture was sufficiently stirred. An aqueous urethane resin composition (7) having a nonvolatile content of 33% by mass was obtained by adding 47.5 parts by mass of piperazine aqueous solution, causing chain extension reaction at 40 ° C., and distillation under reduced pressure.
〔実施例８：水性ウレタン樹脂組成物（８）〕
　前記ウレタン樹脂（Ｉ－３）の有機溶剤溶液の全量と、製造例１で得たポリシロキサン（Ｘ－１）９５．８質量部とジメチルエタノールアミン８．９質量部とを混合した後、イオン交換水６０９．８質量部を加え十分に攪拌し、１０質量％のピペラジン水溶液を４７．５質量部加えて、４０℃で鎖伸長反応させ、減圧蒸留することによって、不揮発分４５質量％の水性ウレタン樹脂組成物（８）を得た。 [Example 8: Aqueous urethane resin composition (8)]
After mixing the total amount of the organic solvent solution of the urethane resin (I-3), 95.8 parts by mass of the polysiloxane (X-1) obtained in Production Example 1, and 8.9 parts by mass of dimethylethanolamine, Add 609.8 parts by mass of exchange water, stir well, add 47.5 parts by mass of a 10% by mass piperazine aqueous solution, cause chain elongation reaction at 40 ° C., and distill under reduced pressure to obtain an aqueous solution having a non-volatile content of 45% by mass. A urethane resin composition (8) was obtained.
〔比較例１：水性ウレタン樹脂組成物（Ｃ１）〕
　温度計、窒素ガス導入管、攪拌器を備えた窒素置換された容器中で、１，６－ヘキサンジオールとネオペンチルグリコールとアジピン酸とを反応させて得られるポリエステルポリオール（数平均分子量２，０００）１００質量部と、１，４－シクロヘキサンジメタノール７質量部と、２，２－ジメチロールプロピオン酸５．５質量部と、トリメチロールプロパン１質量部と、ジシクロヘキシルメタンジイソシアネート６０質量部とを、メチルエチルケトン５８質量部に混合し、前記反応容器中の温度８０℃の条件下で反応させることによって、末端にイソシアネート基を有するウレタンプレポリマーの有機溶剤溶液を得た。 [Comparative Example 1: Aqueous urethane resin composition (C1)]
Polyester polyol (number average molecular weight 2,000) obtained by reacting 1,6-hexanediol, neopentyl glycol and adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer ) 100 parts by weight, 7 parts by weight of 1,4-cyclohexanedimethanol, 5.5 parts by weight of 2,2-dimethylolpropionic acid, 1 part by weight of trimethylolpropane, and 60 parts by weight of dicyclohexylmethane diisocyanate, It mixed with 58 mass parts of methyl ethyl ketone, and was made to react on the conditions of the temperature of 80 degreeC in the said reaction container, and the organic solvent solution of the urethane prepolymer which has an isocyanate group at the terminal was obtained.
　次に、前記ウレタンプレポリマーの有機溶剤溶液と、アクリル酸２－ヒドロキシエチル３質量部とを混合し、前記反応容器中の温度８０℃の条件下で反応させることによって、側鎖に重合性不飽和結合を有し、主鎖の末端にイソシアネート基を有するウレタン樹脂の有機溶剤溶液を得た。 Next, an organic solvent solution of the urethane prepolymer and 3 parts by mass of 2-hydroxyethyl acrylate are mixed and reacted under the conditions of a temperature of 80 ° C. in the reaction vessel, whereby the side chain has no polymerizable property. An organic solvent solution of a urethane resin having a saturated bond and having an isocyanate group at the end of the main chain was obtained.
　次に、前記ウレタン樹脂の有機溶剤溶液と、Ｎ－２－（アミノエチル）－３－アミノプロピルメチルトリエトキシシラン５質量部とメチルエチルケトン１６３質量部とを混合し、前記反応容器中の温度を５０℃に調整し反応させることによって、加水分解性シリル基またはシラノール基と、重合性不飽和基とを有するウレタン樹脂（ＩＩ－１）の有機溶剤溶液を得た。 Next, an organic solvent solution of the urethane resin, 5 parts by mass of N-2- (aminoethyl) -3-aminopropylmethyltriethoxysilane, and 163 parts by mass of methyl ethyl ketone are mixed, and the temperature in the reaction vessel is set to 50. An organic solvent solution of a urethane resin (II-1) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group was obtained by adjusting the reaction to ° C.
　次に、前記ウレタン樹脂（ＩＩ－１）の有機溶剤溶液と、ジメチルエタノールアミン４質量部とを混合した後、イオン交換水４８０質量部を加え十分に攪拌し、１０質量％のピペラジン水溶液を４６質量部加えて、４０℃で鎖伸長反応させ、減圧蒸留することによって、不揮発分３０質量％の水性ウレタン樹脂組成物（Ｃ１）を得た。 Next, the organic solvent solution of the urethane resin (II-1) and 4 parts by mass of dimethylethanolamine were mixed, 480 parts by mass of ion-exchanged water was added, and the mixture was sufficiently stirred. An aqueous urethane resin composition (C1) having a nonvolatile content of 30% by mass was obtained by adding part by mass, causing a chain elongation reaction at 40 ° C., and distillation under reduced pressure.
〔比較例２：水性ウレタン樹脂組成物（Ｃ２）〕
　前記ウレタン樹脂（ＩＩ－１）の有機溶剤溶液の全量と、製造例１で得たポリシロキサン（Ｘ－１）１８１質量部と、ジメチルエタノールアミン４質量部とを混合した後、イオン交換水７７４質量部を加え十分に攪拌し、１０質量％のピペラジン水溶液を４６質量部加えて、４０℃で鎖伸長反応させ、減圧蒸留することによって、不揮発分４５質量％の水性ウレタン樹脂組成物（Ｃ２）を得た。 [Comparative Example 2: Aqueous urethane resin composition (C2)]
A total amount of the organic solvent solution of the urethane resin (II-1), 181 parts by mass of the polysiloxane (X-1) obtained in Production Example 1 and 4 parts by mass of dimethylethanolamine were mixed, and then ion-exchanged water 774 was used. An aqueous urethane resin composition (C2) having a non-volatile content of 45% by mass is prepared by adding 46 parts by mass of a 10% by weight piperazine aqueous solution, subjecting it to chain elongation at 40 ° C., and distillation under reduced pressure. Got.
［塗膜の硬度の評価方法］
　実施例及び後述する比較例で得た水性ウレタン樹脂組成物の固形分１００質量部に対して光重合開始剤（１－ヒドロキシ－シクロヘキシル－フェニル－ケトンとベンゾフェノンの混合物）を４質量部配合して得た配合液を、塗膜の膜厚が１５μｍとなるように、それぞれガラス基材の表面に塗布した。前記塗布物を１４０℃で５分間乾燥した後、高圧水銀灯（株式会社ＧＳユアサ製）を用いて、０．５Ｊ／ｃｍ２の紫外線を１パス照射することによって、前記ガラス基材の表面に塗膜が積層した物品を得た。 [Method for evaluating hardness of coating film]
4 parts by mass of a photopolymerization initiator (a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) is blended with 100 parts by mass of the solid content of the aqueous urethane resin composition obtained in the examples and comparative examples described later. The obtained compounded liquid was apply | coated to the surface of a glass base material, respectively so that the film thickness of a coating film might be set to 15 micrometers. After the coating material is dried at 140 ° C. for 5 minutes, it is applied to the surface of the glass substrate by irradiating 0.5 J / cm 2 of ultraviolet rays for one pass using a high pressure mercury lamp (manufactured by GS Yuasa Co., Ltd.). An article with a laminated film was obtained.
　前記物品を構成する塗膜の硬度は、ＪＩＳ試験方法（ＪＩＳ　Ｋ－５６００－５－４：１９９９）引っかき硬度（鉛筆法）に準拠した方法にて測定した。 The hardness of the coating film constituting the article was measured by a method based on a JIS test method (JIS K-5600-5-4: 1999) scratch hardness (pencil method).
［塗膜の伸度の評価方法］
　実施例及び後述する比較例で得た水性ウレタン樹脂組成物の固形分１００質量部に対して光重合開始剤（１－ヒドロキシ－シクロヘキシル－フェニル－ケトンとベンゾフェノンの混合物）を４質量部配合して得た配合液を塗膜の膜厚が５０μｍとなるように、それぞれ離型フィルムの表面に塗布した。前記塗布物を２５℃の環境下で２４時間乾燥した後、高圧水銀灯（株式会社ＧＳユアサ製）を用いて、０．５Ｊ／ｃｍ２の紫外線を１パス照射し、前記離型フィルムを除去することによって、前記水性樹脂組成物からなる試験フィルム（縦４０ｍｍ、横５ｍｍ）を作製した。 [Evaluation method of film elongation]
4 parts by mass of a photopolymerization initiator (a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) is blended with 100 parts by mass of the solid content of the aqueous urethane resin composition obtained in the examples and comparative examples described later. The obtained compounded solution was applied to the surface of the release film so that the film thickness of the coating film was 50 μm. The coated material is dried for 24 hours in an environment of 25 ° C., and then, using a high-pressure mercury lamp (manufactured by GS Yuasa Co., Ltd.), one pass of 0.5 J / cm 2 of ultraviolet rays is irradiated to remove the release film. Thus, a test film (length 40 mm, width 5 mm) made of the aqueous resin composition was produced.
　前記試験フィルムの伸度の測定は、株式会社島津製作所製「オートグラフＡＧ－Ｘｐｌｕｓ１ｋＮ（チャック間；５０ｍｍ、引張速度５０ｍｍ／分）」を用いて行い、引張試験前の試験フィルムに対する伸び率に基づき、下記評価基準にしたがって評価した。 The measurement of the elongation of the test film was performed using “Autograph AG-Xplus 1 kN (between chucks; 50 mm, tensile speed 50 mm / min)” manufactured by Shimadzu Corporation, and was based on the elongation of the test film before the tensile test. Evaluation was performed according to the following evaluation criteria.
　◎：引張試験前の試験フィルムの長さに対して、引張試験後の試験フィルムの長さが１００％以上伸長した。
　○：引張試験前の試験フィルムの長さに対して、引張試験後の試験フィルムの長さが５０％以上１００％未満伸長した。
　○△：引張試験前の試験フィルムの長さに対して、引張試験後の試験フィルムの長さが３０％以上５０％未満の範囲で伸長した。
　△：引張試験前の試験フィルムの長さに対して、引張試験後の試験フィルムの長さが１０％以上３０％未満の範囲で伸長した。
　×：引張試験前の試験フィルムの長さに対して、引張試験後の試験フィルムの長さが１０％未満の範囲で伸長した。 A: The length of the test film after the tensile test was increased by 100% or more with respect to the length of the test film before the tensile test.
○: The length of the test film after the tensile test was extended by 50% or more and less than 100% with respect to the length of the test film before the tensile test.
(Circle) (triangle | delta): With respect to the length of the test film before a tensile test, the length of the test film after a tensile test was extended in the range of 30% or more and less than 50%.
(Triangle | delta): The length of the test film after a tensile test extended | stretched in 10% or more and less than 30% with respect to the length of the test film before a tensile test.
X: The length of the test film after the tensile test was elongated within a range of less than 10% with respect to the length of the test film before the tensile test.
［塗膜の屈曲性の評価方法］
　実施例及び後述する比較例で得た水性ウレタン樹脂組成物の固形分１００質量部に対して光重合開始剤（１－ヒドロキシ－シクロヘキシル－フェニル－ケトンとベンゾフェノンの混合物）を４質量部配合して得た配合液を塗膜の膜厚が２μｍとなるように、それぞれ金属板（未処理鋼板、厚さ０．８ｍｍ）の表面に塗布した。前記塗布物を１００℃で３０秒間乾燥した後、高圧水銀灯（株式会社ＧＳユアサ製）を用いて、０．５Ｊ／ｃｍ２の紫外線を１パス照射し、前記離型フィルムを除去することによって、前記金属板の表面に塗膜が積層した物品を得た。 [Method for evaluating flexibility of coating film]
4 parts by mass of a photopolymerization initiator (a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) is blended with 100 parts by mass of the solid content of the aqueous urethane resin composition obtained in the examples and comparative examples described later. The obtained compounded liquid was apply | coated to the surface of a metal plate (untreated steel plate, thickness 0.8mm) so that the film thickness of a coating film might be set to 2 micrometers. After drying the coated material at 100 ° C. for 30 seconds, using a high-pressure mercury lamp (manufactured by GS Yuasa Co., Ltd.), one pass irradiation of 0.5 J / cm 2 of ultraviolet light is performed to remove the release film, An article having a coating film laminated on the surface of the metal plate was obtained.
　前記物品を構成する塗膜の屈曲性は、ＪＩＳ試験方法（ＪＩＳ　Ｋ－５６００－５－１：１９９９）耐屈曲性試験法（マンドレル直径２ｍｍ）に準拠した方法にて測定し、測定結果をもとに、下記評価基準にしたがって評価した。 The flexibility of the coating film constituting the article was measured by a method based on the JIS test method (JIS K-5600-5: 1999) flex resistance test method (mandrel diameter 2 mm), and the measurement result was In addition, the evaluation was made according to the following evaluation criteria.
　○：塗膜の屈曲部位で、塗膜のクラック、シワ、白化が見られなかった。
　△：塗膜の屈曲部位で、塗膜の若干のクラック、または、白いスジ状のシワが見られた。
　×：塗膜の屈曲部位の全体で、塗膜の著しいクラックが見られた。 ○: Cracks, wrinkles and whitening of the coating film were not observed at the bent part of the coating film.
Δ: Some cracks in the coating film or white wrinkles were observed at the bent portion of the coating film.
X: Remarkable cracks of the coating film were observed in the entire bent part of the coating film.
［塗膜の耐候性の評価方法］
　実施例及び後述する比較例で得た水性ウレタン樹脂組成物の固形分１００質量部に対して光重合開始剤（１－ヒドロキシ－シクロヘキシル－フェニル－ケトンとベンゾフェノンの混合物）を４質量部配合して得た配合液をアセトンで脱脂した５５質量％アルミニウム－亜鉛系合金メッキ鋼板に、バーコーターを使用して乾燥後の膜厚が約１μｍになるように塗布し、雰囲気温度１００℃の乾燥機に３０秒間入れて乾燥し、さらに高圧水銀灯を用いて０．５Ｊ／ｃｍ２照射することによって、塗膜を作成した。前記塗膜をデューパネル光ウェザーメーター〔スガ試験機株式会社製、光照射時：３０Ｗ／ｍ２、７０℃、湿潤時：湿度９０％以上、５０℃、光照射／湿潤サイクル＝８時間／４時間〕を用いて１０００時間の曝露試験を行った後、該試験板の表面の塗膜の外観を下記評価基準に従って目視で評価した。 [Method for evaluating weather resistance of coating film]
4 parts by mass of a photopolymerization initiator (a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) is blended with 100 parts by mass of the solid content of the aqueous urethane resin composition obtained in the examples and comparative examples described later. The resulting blended solution was applied to a 55% by mass aluminum-zinc alloy-plated steel sheet degreased with acetone using a bar coater so that the film thickness after drying was about 1 μm. The coating film was prepared by putting in and drying for 30 seconds, and also irradiating 0.5 J / cm < 2 > using a high pressure mercury lamp. Dew panel light weather meter [manufactured by Suga Test Instruments Co., Ltd., light irradiation: 30 W / m 2 , 70 ° C., humidity: 90% humidity, 50 ° C., light irradiation / wetting cycle = 8 hours / 4 After performing an exposure test for 1000 hours, the appearance of the coating film on the surface of the test plate was visually evaluated according to the following evaluation criteria.
　○：塗膜表面にクラックおよび黄変の発生がみられない。
　△：塗膜表面のごく一部に若干のクラックおよび黄変の発生がみられる。
　×：塗膜表面全体にクラックおよび黄変の発生がみられる。 ○: Generation of cracks and yellowing is not observed on the coating film surface.
Δ: Some cracks and yellowing are observed in a very small part of the coating surface.
X: Generation | occurrence | production of a crack and yellowing is seen in the whole coating-film surface.
［塗膜の耐食性の評価方法］
　実施例及び後述する比較例で得た水性ウレタン樹脂組成物の固形分１００質量部に対して光重合開始剤（１－ヒドロキシ－シクロヘキシル－フェニル－ケトンとベンゾフェノンの混合物）を４質量部配合して得た配合液を、アセトンで脱脂した５５質量％アルミニウム－亜鉛系合金メッキ鋼板に、バーコーターを使用して乾燥後の膜厚が約１μｍになるように塗布し、雰囲気温度１００℃の乾燥機に３０秒間入れて乾燥し、さらに高圧水銀灯を用いて０．５Ｊ／ｃｍ２照射することによって、塗膜を作成した。その後、室温で３日間養生したものを試験片とした。 [Method for evaluating corrosion resistance of coating film]
4 parts by mass of a photopolymerization initiator (a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) is blended with 100 parts by mass of the solid content of the aqueous urethane resin composition obtained in the examples and comparative examples described later. The obtained blended solution was applied to a 55% by mass aluminum-zinc alloy-plated steel sheet degreased with acetone using a bar coater so that the film thickness after drying was about 1 μm, and a dryer with an atmospheric temperature of 100 ° C. The film was dried for 30 seconds and further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp to form a coating film. Then, what was cured at room temperature for 3 days was used as a test piece.
　前記試験片を構成する塗膜の表面を、基材に到達する深さまでカッターナイフで傷を付け（クロスカット部）、スガ試験機株式会社製塩水噴霧試験器にて塩水噴霧試験を実施し、２４０時間後の錆発生面積を目視により求めて評価した。評価は、カッターナイフによる傷をつけていない平面部と、クロスカット部の周辺部とに分けて行った。 The surface of the coating film constituting the test piece is scratched with a cutter knife to a depth reaching the base material (cross cut part), and a salt spray test is performed with a salt spray tester manufactured by Suga Test Instruments Co., Ltd. The rust generation area after 240 hours was visually evaluated and evaluated. The evaluation was performed separately for a flat portion not damaged by the cutter knife and a peripheral portion of the cross cut portion.
　＜平面部＞
　◎：錆の発生及び錆に起因した塗膜の膨れや剥がれの生じた面積が、平面部全体に対して５％未満であった。
　○：錆の発生及び錆に起因した塗膜の膨れや剥がれの生じた面積が、平面部全体に対して５％以上３０％未満であった。
　△：錆の発生及び錆に起因した塗膜の膨れや剥がれの生じた面積が、平面部全体に対して３０％以上６０％未満であった。
　×：錆の発生及び錆に起因した塗膜の膨れや剥がれの生じた面積が、平面部全体に対して６０％以上であった。 <Plane>
(Double-circle): The area where the generation | occurrence | production of rust and the swelling and peeling of the coating film resulting from rust were less than 5% with respect to the whole plane part.
◯: The area where the occurrence of rust and the swelling or peeling of the coating film due to rust occurred was 5% or more and less than 30% with respect to the entire plane portion.
(Triangle | delta): The area where the generation | occurrence | production of rust and the swelling and peeling of the coating film resulting from rust were 30% or more and less than 60% with respect to the whole plane part.
X: The area where the occurrence of rust and the swelling and peeling of the coating film due to rust occurred was 60% or more with respect to the entire plane portion.
　＜クロスカット部の周辺部＞
　◎：クロスカット部の周辺部に錆の発生は見られず、錆に起因した塗膜の剥離等も見られなかった。
　○：クロスカット部の周辺部に極微量の錆の発生が見られたが、それに起因した塗膜の剥離や膨れは見られなかった。
　△：クロスカット部の周辺部に広く錆の発生が見られ、それに起因した塗膜の剥離や膨れが見られたものの、流れ錆はみられなかった。
　×：クロスカット部の周辺部に広く錆の発生と、それに起因した塗膜の剥離や膨れが見られ、更に流れ錆による塗膜の汚染等が見られた。 <The peripheral part of the crosscut part>
(Double-circle): Generation | occurrence | production of rust was not seen in the peripheral part of a crosscut part, and peeling of the coating film etc. resulting from rust was not seen.
◯: A very small amount of rust was observed in the periphery of the crosscut part, but no peeling or swelling of the coating film due to it was observed.
Δ: Rust was widely observed in the periphery of the crosscut portion, and although peeling or swelling of the coating film was observed due to this, no flow rust was observed.
X: Rust was widely generated in the periphery of the crosscut part, and peeling and swelling of the coating film due to the rust were observed. Further, contamination of the coating film due to flowing rust was observed.
［耐温水性の評価方法］
　実施例及び後述する比較例で得た水性ウレタン樹脂組成物の固形分１００質量部に対して光重合開始剤（１－ヒドロキシ－シクロヘキシル－フェニル－ケトンとベンゾフェノンの混合物）を４質量部配合して得た配合液を、アセトンで脱脂した５５質量％アルミニウム－亜鉛系合金メッキ鋼板に、バーコーターを使用して乾燥後の膜厚が約１μｍになるように塗布し、雰囲気温度１００℃の乾燥機に３０秒間入れて乾燥し、さらに高圧水銀灯を用いて０．５Ｊ／ｃｍ２照射することによって、塗膜を作成した。その後、室温で３日間養生したものを試験片とした。前記試験片を６０℃の温水に浸漬し、６０分後の塗膜の劣化状態を観察した。 [Method for evaluating hot water resistance]
4 parts by mass of a photopolymerization initiator (a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) is blended with 100 parts by mass of the solid content of the aqueous urethane resin composition obtained in the examples and comparative examples described later. The obtained blended solution was applied to a 55% by mass aluminum-zinc alloy-plated steel sheet degreased with acetone using a bar coater so that the film thickness after drying was about 1 μm, and a dryer with an atmospheric temperature of 100 ° C. The film was dried for 30 seconds and further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp to form a coating film. Then, what was cured at room temperature for 3 days was used as a test piece. The said test piece was immersed in 60 degreeC warm water, and the deterioration state of the coating film 60 minutes after was observed.
　◎：塗膜の表面に全く変化が無かった。
　○：塗膜の表面に若干の変色が見られたが実用上問題ないレベルであった。
　△：塗膜全体に膨れ等が見られた。
　×：塗膜が剥離し、基材が露出した。 A: There was no change on the surface of the coating film.
○: Although slight discoloration was observed on the surface of the coating film, it was at a level where there was no practical problem.
Δ: Swelling or the like was observed in the entire coating film.
X: The coating film peeled and the base material was exposed.
［耐薬品性（耐酸性）の評価方法］
　実施例及び後述する比較例で得た水性ウレタン樹脂組成物の固形分１００質量部に対して光重合開始剤（１－ヒドロキシ－シクロヘキシル－フェニル－ケトンとベンゾフェノンの混合物）を４質量部配合して得た配合液を、アセトンで脱脂した５５質量％アルミニウム－亜鉛系合金メッキ鋼板に、バーコーターを使用して乾燥後の膜厚が約１μｍになるように塗布し、雰囲気温度１００℃の乾燥機に３０秒間入れて乾燥し、さらに高圧水銀灯を用いて０．５Ｊ／ｃｍ２照射することによって、塗膜を作成した。その後、室温で３日間養生したものを試験片とした。前記試験片を構成する塗膜の表面に１Ｎ塩酸をスポットで置き、１８０分間静置後の塗膜の劣化状態を観察した。 [Chemical resistance (acid resistance) evaluation method]
4 parts by mass of a photopolymerization initiator (a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) is blended with 100 parts by mass of the solid content of the aqueous urethane resin composition obtained in the examples and comparative examples described later. The obtained blended solution was applied to a 55% by mass aluminum-zinc alloy-plated steel sheet degreased with acetone using a bar coater so that the film thickness after drying was about 1 μm, and a dryer with an atmospheric temperature of 100 ° C. The film was dried for 30 seconds and further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp to form a coating film. Then, what was cured at room temperature for 3 days was used as a test piece. 1N hydrochloric acid was spotted on the surface of the coating film constituting the test piece, and the deterioration state of the coating film after standing for 180 minutes was observed.
　◎：塗膜の表面に全く変化が無かった。
　○：塗膜の表面に若干の黄変が見られたが実用上問題ないレベルであった。
　△：塗膜の表面が著しく変色した。
　×：塗膜が溶解し、基材が露出した。 A: There was no change on the surface of the coating film.
A: Some yellowing was observed on the surface of the coating film, but it was at a level where there was no practical problem.
(Triangle | delta): The surface of the coating film changed remarkably.
X: The coating film melt | dissolved and the base material was exposed.
［耐薬品性（耐アルカリ性）の評価方法］
　実施例及び後述する比較例で得た水性ウレタン樹脂組成物の固形分１００質量部に対して光重合開始剤（１－ヒドロキシ－シクロヘキシル－フェニル－ケトンとベンゾフェノンの混合物）を４質量部配合して得た配合液を、アセトンで脱脂した５５質量％アルミニウム－亜鉛系合金メッキ鋼板に、バーコーターを使用して乾燥後の膜厚が約１μｍになるように塗布し、雰囲気温度１００℃の乾燥機に３０秒間入れて乾燥し、さらに高圧水銀灯を用いて０．５Ｊ／ｃｍ２照射することによって、塗膜を作成した。その後、室温で３日間養生したものを試験片とした。
　前記試験片を構成する塗膜の表面に５質量％水酸化ナトリウム水溶液をスポットで置き、２０分間静置後の塗膜の劣化状態を観察した。 [Evaluation method for chemical resistance (alkali resistance)]
4 parts by mass of a photopolymerization initiator (a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) is blended with 100 parts by mass of the solid content of the aqueous urethane resin composition obtained in the examples and comparative examples described later. The obtained blended solution was applied to a 55% by mass aluminum-zinc alloy-plated steel sheet degreased with acetone using a bar coater so that the film thickness after drying was about 1 μm, and a dryer with an atmospheric temperature of 100 ° C. The film was dried for 30 seconds and further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp to form a coating film. Then, what was cured at room temperature for 3 days was used as a test piece.
A 5% by mass aqueous sodium hydroxide solution was spotted on the surface of the coating film constituting the test piece, and the deterioration state of the coating film after standing for 20 minutes was observed.
　◎：塗膜の表面に全く変化が無かった。
　○：塗膜の表面の一部に若干の変色が見られたが実用上問題ないレベルであった。
　△：塗膜の表面に変色が見られた。
　×：塗膜が溶解し、基材が露出した。 A: There was no change on the surface of the coating film.
○: Some discoloration was observed on a part of the surface of the coating film, but it was at a level where there was no practical problem.
Δ: Discoloration was observed on the surface of the coating film.
X: The coating film melt | dissolved and the base material was exposed.
［耐溶剤性の評価方法］
　実施例及び後述する比較例で得た水性ウレタン樹脂組成物の固形分１００質量部に対して光重合開始剤（１－ヒドロキシ－シクロヘキシル－フェニル－ケトンとベンゾフェノンの混合物）を４質量部配合して得た配合液を、ガラス基材上に３ｍｉｌのアプリケーターを用いて塗布し、６０℃で１０分間乾燥後、さらに高圧水銀灯を用いて０．５Ｊ／ｃｍ２照射し、その後２５℃で２日間養生した塗膜を作製した。得られた塗膜の表面に、トルエンおよびエタノールを浸み込ませたフェルトで、硬化塗膜上を往復２０回ラビングした。ラビング前とラビング後の塗膜の状態を、指触及び目視により判定した。評価基準は下記の通りである。 [Evaluation method of solvent resistance]
4 parts by mass of a photopolymerization initiator (a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) is blended with 100 parts by mass of the solid content of the aqueous urethane resin composition obtained in the examples and comparative examples described later. The obtained mixture was applied on a glass substrate using a 3 mil applicator, dried at 60 ° C. for 10 minutes, further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp, and then cured at 25 ° C. for 2 days. A coated film was prepared. The surface of the obtained coating film was rubbed 20 times back and forth on the cured coating film with a felt soaked with toluene and ethanol. The state of the coating film before rubbing and after rubbing was judged by finger touch and visual observation. The evaluation criteria are as follows.
　◎：塗膜の表面に全く変化が無かった。
　○：塗膜の表面の一部に若干の白色が見られたが実用上問題ないレベルであった。
　△：塗膜の表面に白色が見られた。
　×：塗膜が溶解し、基材が露出した。 A: There was no change on the surface of the coating film.
○: Some white color was observed on a part of the surface of the coating film, but it was at a level where there was no practical problem.
Δ: White color was observed on the surface of the coating film.
X: The coating film melt | dissolved and the base material was exposed.
［基材に対する密着性（一次密着性）］
　実施例及び後述する比較例で得た水性ウレタン樹脂組成物の固形分１００質量部に対して光重合開始剤（１－ヒドロキシ－シクロヘキシル－フェニル－ケトンとベンゾフェノンの混合物）を４質量部配合して得た配合液を、下記に示すそれぞれの基材上に３ｍｉｌのアプリケーターを用いて塗布し、６０℃で３０分間乾燥後、さらに高圧水銀灯を用いて０．５Ｊ／ｃｍ２照射し、その後２５℃で２日間養生した塗膜を作製した。得られた塗膜の表面に、ＪＩＳ　Ｋ－５４００に準じて、１ｍｍ角１００個の碁盤目のセロテープ（登録商標）剥離試験を実施した。剥離しない碁盤目数を計測し下記基準で評価した。なお、基材としては、ポリエチレンテレフタレート樹脂からなる基材及びガラス基材を使用した。 [Adhesion to substrate (primary adhesion)]
4 parts by mass of a photopolymerization initiator (a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone and benzophenone) is blended with 100 parts by mass of the solid content of the aqueous urethane resin composition obtained in the examples and comparative examples described later. The obtained compounded liquid was applied on each substrate shown below using a 3 mil applicator, dried at 60 ° C. for 30 minutes, further irradiated with 0.5 J / cm 2 using a high-pressure mercury lamp, and then 25 ° C. A coating film cured for 2 days was prepared. The surface of the obtained coating film was subjected to a cellophane (registered trademark) peeling test of 100 squares of 1 mm square according to JIS K-5400. The number of grids not peeled was measured and evaluated according to the following criteria. As the substrate, a substrate made of polyethylene terephthalate resin and a glass substrate were used.
　◎：剥離しない碁盤目数が９０以上。
　○：剥離しない碁盤目数が６０以上～９０未満。
　△：剥離しない碁盤目数が４０以上～６０未満。
　×：剥離しない碁盤目数が４０未満。 A: The number of grids not peeled is 90 or more.
○: The number of grids not peeled is 60 or more and less than 90.
Δ: The number of grids not peeled is 40 to less than 60.
X: The number of grids which do not peel is less than 40.
　実施例１～８で得られた水性ウレタン樹脂組成物（１）～（８）の組成、ならびに、上記の評価結果を表１に示す。なお、表１中の組成（配合量）は、不揮発分量で示す。 Table 1 shows the compositions of the aqueous urethane resin compositions (1) to (8) obtained in Examples 1 to 8 and the above evaluation results. In addition, the composition (blending amount) in Table 1 is shown as a nonvolatile content.
Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007
　比較例１及び２で得られた水性ウレタン樹脂組成物（Ｃ１）、（Ｃ２）の組成、ならびに評価結果を表２に示す。なお、表２中の組成（配合量）は、不揮発分量で表す。 Table 2 shows the compositions and evaluation results of the aqueous urethane resin compositions (C1) and (C2) obtained in Comparative Examples 1 and 2. In addition, the composition (blending amount) in Table 2 is expressed as a nonvolatile content.
Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008
　表１に示した実施例１～８の評価結果から、本発明の水性ウレタン樹脂組成物を用いて得られた塗膜は、優れた塗膜硬度、伸度及び屈曲性を有し、かつ、耐食性、耐温水性、耐薬品性、耐溶剤性及び各種基材に対する密着性に優れることが確認できた。 From the evaluation results of Examples 1 to 8 shown in Table 1, the coating film obtained using the aqueous urethane resin composition of the present invention has excellent coating film hardness, elongation and flexibility, and It was confirmed that it was excellent in corrosion resistance, hot water resistance, chemical resistance, solvent resistance and adhesion to various substrates.
　一方、比較例１及び２は、ウレタン樹脂の原料であるポリオールとして、本発明で規定したポリオール以外のポリオールを用いたウレタン樹脂の例である。比較性１の水性ウレタン樹脂組成物を用いて得られた塗膜は、伸度及び屈曲性に優れるものの、耐候性、耐食性及びポリエチレンテレフタレート基材に対する密着性は不十分であり、また、耐溶剤性は著しく悪いことが確認できた。 On the other hand, Comparative Examples 1 and 2 are examples of a urethane resin using a polyol other than the polyol defined in the present invention as a polyol which is a raw material of the urethane resin. Although the coating film obtained using the aqueous urethane resin composition of Comparative Example 1 is excellent in elongation and flexibility, the weather resistance, corrosion resistance, and adhesion to the polyethylene terephthalate substrate are insufficient, and solvent resistance It was confirmed that the property was extremely bad.
　比較例２の水性ウレタン樹脂組成物を用いて得られた塗膜は、耐食性及び耐温水性が不十分であり、また、耐溶剤性及びポリエチレンテレフタレート基材に対する密着性が著しく悪いことから、比較例１及び２の水性ウレタン樹脂組成物では、塗膜硬度、伸度及び屈曲性並びに耐食性、耐温水性、耐薬品性及び耐溶剤性を両立した塗膜は形成不可能であることが確認できた。 The coating film obtained using the aqueous urethane resin composition of Comparative Example 2 has insufficient corrosion resistance and hot water resistance, and also has extremely poor solvent resistance and adhesion to a polyethylene terephthalate substrate. In the aqueous urethane resin compositions of Examples 1 and 2, it can be confirmed that a coating film having both coating film hardness, elongation and flexibility, corrosion resistance, warm water resistance, chemical resistance and solvent resistance cannot be formed. It was.

Claims (9)

  1. 　加水分解性シリル基またはシラノール基と、重合性不飽和基とを有するウレタン樹脂（Ａ）、及び、水性媒体（Ｂ）を含有する水性ウレタン樹脂組成物であって、前記ウレタン樹脂（Ａ）が、下記一般式（１）で示される２つ以上の重合性不飽和基を有するアルキレンジオール（ａ１－１）または下記一般式（２）で示される２つ以上の重合性不飽和基を有するオキシアルキレンジオール（ａ１－２）を含有するポリオール（ａ１）と、ポリイソシアネート（ａ２）と、シランカップリング剤（ａ３）とを反応させて得られるものであることを特徴とする水性ウレタン樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     （一般式（１）中のＲ１は、炭素原子数１～９の直鎖アルキレン基の側鎖に重合性不飽和基を含む原子団を２つ以上有する構造を表す。）
    Figure JPOXMLDOC01-appb-C000002
     （一般式（２）中のＲ１及びＲ３はエチレン基の側鎖に重合性不飽和基を含む原子団を有する構造を表す。Ｒ２は、炭素原子数１個～５個を有するアルキレン基を表す。）     A urethane resin (A) having a hydrolyzable silyl group or silanol group and a polymerizable unsaturated group, and an aqueous urethane resin composition containing an aqueous medium (B), wherein the urethane resin (A) is An alkylene diol (a1-1) having two or more polymerizable unsaturated groups represented by the following general formula (1) or an oxy having two or more polymerizable unsaturated groups represented by the following general formula (2): An aqueous urethane resin composition obtained by reacting a polyol (a1) containing an alkylene diol (a1-2), a polyisocyanate (a2), and a silane coupling agent (a3) .
    Figure JPOXMLDOC01-appb-C000001
     (R 1 in the general formula (1) represents a structure having two or more atomic groups containing a polymerizable unsaturated group in the side chain of a linear alkylene group having 1 to 9 carbon atoms.)
    Figure JPOXMLDOC01-appb-C000002
     (R 1 and R 3 in the general formula (2) represent a structure having an atomic group containing a polymerizable unsaturated group in the side chain of the ethylene group. R 2 is an alkylene having 1 to 5 carbon atoms. Represents a group.)
  2. 　前記アルキレンジオール（ａ１－１）がペンタエリスリトールジアクリレートである請求項１記載の水性ウレタン樹脂組成物。 The aqueous urethane resin composition according to claim 1, wherein the alkylene diol (a1-1) is pentaerythritol diacrylate.
  3. 　前記アルキレンジオール（ａ１－１）及び前記オキシアルキレンジオール（ａ１－２）の合計質量が、前記ウレタン樹脂（Ａ）の製造に使用する原料の全量中に０．１～４９質量％の範囲である請求項１または２記載の水性ウレタン樹脂組成物。 The total mass of the alkylene diol (a1-1) and the oxyalkylene diol (a1-2) is in the range of 0.1 to 49% by mass with respect to the total amount of raw materials used in the production of the urethane resin (A). The aqueous urethane resin composition according to claim 1 or 2.
  4. 　前記ポリオール（ａ１）が、さらにポリエステルポリオール、ポリエーテルポリオールまたはポリカーボネートポリオールを含有するものである請求項１～３のいずれか１項記載の水性ウレタン樹脂組成物。 The aqueous urethane resin composition according to any one of claims 1 to 3, wherein the polyol (a1) further contains a polyester polyol, a polyether polyol or a polycarbonate polyol.
  5. 　前記シランカップリング剤（ａ３）が、アミノ基、イソシアネート基、（メタ）アクリレート基、ビニル基、メルカプト基、エポキシ基からなる群より選ばれる１種以上の反応性基を有するものである請求項１～４のいずれか１項記載の水性ウレタン樹脂組成物。 The silane coupling agent (a3) has one or more reactive groups selected from the group consisting of amino groups, isocyanate groups, (meth) acrylate groups, vinyl groups, mercapto groups, and epoxy groups. 5. The aqueous urethane resin composition according to any one of 1 to 4.
  6. 　前記ウレタン樹脂（Ａ）が、前記ウレタン樹脂（Ａ）の製造に使用する原料の全量中に、前記シランカップリング剤（ａ３）を０．１～１０質量％の範囲で有するものである請求項１～５のいずれか１項記載の水性ウレタン樹脂組成物。 The urethane resin (A) has the silane coupling agent (a3) in a range of 0.1 to 10% by mass in the total amount of raw materials used for the production of the urethane resin (A). 6. The aqueous urethane resin composition according to any one of 1 to 5.
  7. 　さらにポリシロキサン（Ｘ）を含有する請求項１～６のいずれか１項記載の水性ウレタン樹脂組成物。 The aqueous urethane resin composition according to any one of claims 1 to 6, further comprising polysiloxane (X).
  8. 　請求項１～７のいずれか１項記載の水性ウレタン樹脂組成物を含有することを特徴とするコーティング剤。 A coating agent comprising the aqueous urethane resin composition according to any one of claims 1 to 7.
  9. 　請求項８記載のコーティング剤の塗膜を有することを特徴とする物品。 An article comprising the coating film of the coating agent according to claim 8.
PCT/JP2015/075060 2014-09-26 2015-09-03 Aqueous urethane resin composition, coating agent and article WO2016047415A1 (en)

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