WO2019004349A1 - Urethane resin composition, steel sheet surface treatment agent, and steel sheet having coating film of same - Google Patents

Urethane resin composition, steel sheet surface treatment agent, and steel sheet having coating film of same Download PDF

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Publication number
WO2019004349A1
WO2019004349A1 PCT/JP2018/024565 JP2018024565W WO2019004349A1 WO 2019004349 A1 WO2019004349 A1 WO 2019004349A1 JP 2018024565 W JP2018024565 W JP 2018024565W WO 2019004349 A1 WO2019004349 A1 WO 2019004349A1
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Prior art keywords
mass
urethane resin
parts
resin composition
polyisocyanate
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PCT/JP2018/024565
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French (fr)
Japanese (ja)
Inventor
直人 佐竹
広義 神成
定 永浜
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Dic株式会社
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Priority to JP2019527019A priority Critical patent/JPWO2019004349A1/en
Publication of WO2019004349A1 publication Critical patent/WO2019004349A1/en

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Classifications

    • 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
    • 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
    • C08G18/08—Processes
    • 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
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols

Definitions

  • the present invention relates to a urethane resin composition, a steel sheet surface treatment agent, and a steel sheet having a coating film thereof.
  • a coating agent for surface protection of metal substrates including steel plates that is, a surface treatment agent for steel plates
  • a surface treatment agent for steel plates is increasing.
  • such a steel sheet surface treatment agent is required to have a level of corrosion resistance capable of preventing peeling and swelling of a coating film due to the corrosion of a metal substrate and a high level of chemical resistance.
  • chemical resistance in the steel industry where the coating film surface formed on the surface of a metal substrate is frequently washed using an alkaline cleaner etc., peeling or dissolution of the coating film due to the influence of the cleaning agent Is an important characteristic to prevent the deterioration of the metal base and the like.
  • a steel plate surface treatment agent having the above-mentioned properties is often required especially in the surface protection application of a metal substrate susceptible to rust.
  • the steel plate surface treatment agent is, for example, an aqueous resin composition for a metal surface treatment agent containing a carboxyl group-containing aqueous urethane resin and an aqueous vinyl-modified epoxy ester resin
  • the carboxyl group-containing aqueous urethane resin is an acid component
  • Metal surface which is a polyester urethane resin obtained by reacting a polyester polyol and a polyisocyanate compound composed of a glycol component not having a carboxyl group in the molecule and a chain extender containing a glycol component having a carboxyl group in the molecule
  • Aqueous resin compositions for treating agents are known. (See, for example, Patent Document 1).
  • the coating film formed using the aqueous resin composition for metal surface treatment is not a step beyond the point of chemical resistance and corrosion resistance in order to prevent deterioration of the metal substrate over a long period of time. There was a case that was not enough for practical use.
  • the problem to be solved by the present invention is to provide a urethane resin composition capable of forming a coating film excellent in compounding stability and excellent in corrosion resistance, chemical resistance and substrate adhesion.
  • the present inventors contain an aromatic polyester polyol having a specific range of number average molecular weight and a specific range of aromatic ring concentration, and a polyol having an anionic group.
  • a urethane resin composition containing a urethane resin that is a reaction product of a polyol and a specific polyisocyanate the inventors have found that the above problems can be solved, and completed the present invention.
  • the present invention is a urethane resin which is a reaction product of a polyol (a1) containing an aromatic polyester polyol (a1-1) and a polyol (a1-2) having an anionic group, and a polyisocyanate (a2).
  • A and a urethane resin composition containing an aqueous medium (B), wherein the aromatic ring concentration in the aromatic polyester polyol (a1-1) is 2.5 to 5 mol / kg, and the polyisocyanate (A2) contains aliphatic polyisocyanate and / or polyisocyanate having an alicyclic structure, and the acid value of the urethane resin (A) is in the range of 10 to 25 mg KOH / g.
  • the present invention relates to a urethane resin composition, a steel sheet surface treatment agent, and a steel sheet having a coating film thereof.
  • the urethane resin composition of the present invention is excellent in compounding stability, and further, because it can form a coating film excellent in corrosion resistance, chemical resistance and substrate adhesion, it can be used for surface protection of various substrates. it can.
  • a substrate to which the urethane resin composition of the present invention can be applied for example, galvanized steel sheet, aluminum-galvanized steel sheet, zinc-aluminum-magnesium alloy plated steel sheet, aluminum sheet, aluminum alloy sheet, electromagnetic steel sheet, copper sheet, stainless steel Examples include metal substrates such as steel plates, various plastics and films thereof, glass, paper, and wood.
  • the urethane resin composition of the present invention can form a coating film excellent in corrosion resistance and chemical resistance capable of preventing the deterioration of the surface of the metal base, so, for example, building members such as outer wall and roof, guardrails, It is possible to use suitably for surface coating etc. of various articles, such as civil engineering members, such as a sound barrier, a drainage ditch, household appliances, an industrial machine, an automobile exterior material, etc.
  • the urethane resin composition of the present invention is a reaction product of an aromatic polyester polyol (a1-1) and a polyol (a1) containing a polyol (a1-2) having an anionic group, and a polyisocyanate (a2).
  • a urethane resin composition comprising a certain urethane resin (A) and an aqueous medium (B), wherein the aromatic ring concentration in the aromatic polyester polyol (a1-1) is 2.5 to 5 mol / kg,
  • the polyisocyanate (a2) contains an aliphatic polyisocyanate and / or a polyisocyanate having an alicyclic structure, and the acid value of the urethane resin (A) is in the range of 10 to 25 mg KOH / g. It is characterized by
  • urethane resin (A) As the urethane resin (A), a reaction product of a polyol (a1) containing an aromatic polyester polyol (a1-1) and a polyol (a1-2) having an anionic group with a polyisocyanate (a2) Use.
  • the reactant also includes a reactant of the polyol (a1), the polyisocyanate (a2), and the other compounds.
  • polyol (a1) an aromatic polyester polyol (a1-1) and a polyol (a1-2) having an anionic group are used essentially.
  • aromatic polyester polyol (a1-1) a urethane resin composition excellent in compounding stability can be obtained, and furthermore, a coating film excellent in corrosion resistance, chemical resistance and substrate adhesion can be formed.
  • the aromatic ring concentration is in the range of 2.5 to 5 mol / kg.
  • an aromatic polyester polyol having an aromatic ring concentration in the range of 3 to 4.4 mol / kg is more preferable because a coating film having further excellent corrosion resistance, chemical resistance and substrate adhesion can be formed.
  • the urethane resin composition excellent in compounding stability can be obtained, and also the coating film excellent in corrosion resistance, chemical resistance, and base-material adhesiveness is formed.
  • the number average molecular weight is preferably in the range of 750 to 5,000, and more preferably in the range of 1,000 to 3,000. In the present specification, the number average molecular weight can be measured as a converted value using polystyrene as a standard sample, using gel permeation chromatography.
  • the aromatic polyester polyol (a1-1) can be obtained, for example, by subjecting a polyhydric carboxylic acid and a polyhydric alcohol to an esterification reaction.
  • a polyhydric carboxylic acid and a polyhydric alcohol one having an aromatic ring in at least one is used.
  • those having an aromatic ring include, for example, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, orthophthalic acid and naphthalene dicarboxylic acid, or esters thereof.
  • succinic acid for example, succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, chlorendic acid, 1,2,4- Aliphatic dicarboxylic acids such as butane-tricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid or the like, and esters thereof.
  • 1,2,4- Aliphatic dicarboxylic acids such as butane-tricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid or the like, and esters thereof.
  • These polyvalent carboxylic acids or esterification products thereof can be used alone or in combination of two or more.
  • those having an aromatic ring include, for example, aromatic diols such as benzenedimethanol, toluenedimethanol, and xylenedimethanol.
  • aromatic diols such as benzenedimethanol, toluenedimethanol, and xylenedimethanol.
  • a compound having no aromatic ring for example, ethylene glycol, propylene glycol, 1,3-propylene diol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol
  • Aliphatic polyols such as triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, neopentyl glycol ethylene glycol and the like.
  • esterification catalyst for the purpose of promoting the esterification reaction.
  • the esterification catalyst include metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, and germanium; titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, dibutyltin oxide, dibutyltin Diacetate, dibutyltin dilaurate, tin octanoate, 2-ethylhexanetin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxygermanium etc.
  • Metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafn
  • the content of the aromatic polyester polyol (a1-1) in the polyol (a1) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 99 It is at most mass%, more preferably at most 98 mass%.
  • Examples of the anionic group in the polyol (a1-2) having an anionic group include acid groups such as a carboxyl group and a sulfonic acid group, and examples of the polyol (a1-2) having an anionic group include And polyols having a carboxyl group, and polyols having a sulfonic acid group.
  • aromatic polyester polyols having an anionic group are included in the aromatic polyester polyol (a1-1).
  • polyol having a carboxyl group examples include 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol valeric acid and the like, and among them, 2,2-dimethylol Propionic acid is preferred.
  • polyester polyols having a carboxyl group obtained by reacting a polyol having a carboxyl group with various polycarboxylic acids 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 weight polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, etc., and the above-mentioned polyester polyols, ⁇ -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-sulfoph
  • the content of the polyol (a1-2) having an anionic group is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, in the polyol (a1), preferably Is 10% by mass or less, more preferably 9% by mass or less, and still more preferably 8% by mass or less.
  • the total content of the aromatic polyester polyol (a1-1) and the polyol (a1-2) having an anionic group is preferably 70% by mass or more, more preferably 80% by mass or more in the polyol (a1). More preferably, it is 90 mass% or more, Preferably it is 100 mass% or less.
  • the anionic group is preferably partially or entirely neutralized by the neutralizing agent (C) in order to express good water dispersibility.
  • a basic compound can be used as the neutralizing agent (C).
  • a basic compound having a boiling point of less than 140 ° C. is preferable, a basic compound having a boiling point of 135 ° C. or less is preferable, a basic compound having a boiling point of 90 ° C. or less is preferable, and a boiling point of 90 ° C. Less than basic compounds are more preferred.
  • the lower limit of the boiling point of the basic compound is, for example, preferably ⁇ 50 ° C., and more preferably ⁇ 40 ° C. or more. In the present specification, the boiling point represents the boiling point at 1013 hPa.
  • Examples of the basic compound include monomethylamine (boiling point: -6 ° C), dimethylamine (boiling point: 7 ° C), trimethylamine (boiling point; 3 ° C), monoethylamine (boiling point: 16.6 ° C), diethylamine (boiling point) Alkylamines such as 56 ° C), triethylamine (boiling point: 89.5 ° C), monopropylamine (boiling point: 48 ° C), dipropylamine (boiling point: 108 ° C), tripropylamine (boiling point: 156 ° C); Ethanolamine (boiling point: 170 ° C), diethanolamine (boiling point: 268 ° C), monoisopropanolamine (boiling point: 159 ° C), diisopropanolamine (boiling point: 249 ° C), N-methylethanolamine (boiling point
  • a basic compound having a boiling point of less than 140 ° C. is preferable, a basic compound having a boiling point of less than 90 ° C. is more preferable, and ammonia is more preferable because a coating film having excellent chemical resistance can be formed.
  • Ammonia may be dissolved in water and used as ammonia water.
  • the concentration of ammonia in the ammonia water is preferably 1% by mass or more, more preferably 3% by mass or more, preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass It is below.
  • the content of the neutralizing agent (C) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass with respect to 100 parts by mass in total of the polyol (a1) and the polyisocyanate (a2).
  • the amount is more preferably 0.3 parts by mass or more, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less.
  • polyol (a1) it can be used combining other polyols as needed.
  • polyester polyols other than the said aromatic polyester polyol (a1-1), and the polyol (a1-2) which has the said anionic group, polyether polyol, polycarbonate polyol, polyolefin polyol etc. Can also be used. These other polyols may be used alone or in combination of two or more.
  • polyether polyol what carried out addition polymerization of the alkylene oxide is mentioned, for example using 1 type, or 2 or more types of a compound which has 2 or more of active hydrogen atoms as an initiator.
  • the compound having two or more active hydrogen atoms include propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin and di- Glycerin, trimethylolethane, trimethylolpropane, water, hexanetriol and the like can be mentioned.
  • alkylene oxide a propylene oxide, a butylene oxide, a styrene oxide, epichlorohydrin, tetrahydrofuran etc. are mentioned, for example.
  • polyether polyols can be used alone or in combination of two or more.
  • polycarbonate polyol what was obtained by carrying out the esterification reaction of carbonic acid and carbonic acid ester, and a polyhydric alcohol is mentioned.
  • the polyhydric alcohol include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol Etc. These polycarbonate polyols may be used alone or in combination of two or more.
  • polyisocyanate (a2) used for manufacture of the said urethane resin (A) aliphatic polyisocyanate and / or polyisocyanate which has an alicyclic structure are used.
  • aliphatic polyisocyanate examples include hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate and the like. These aliphatic polyisocyanates can be used alone or in combination of two or more.
  • polyisocyanate having an alicyclic structure examples include cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and the like. These polyisocyanates having an alicyclic structure can be used alone or in combination of two or more.
  • the proportion of the aliphatic polyisocyanate and / or the polyisocyanate having the alicyclic structure in the polyisocyanate (a2) can provide a urethane resin composition excellent in compounding stability, and further, corrosion resistance, and resistance
  • the range of 10 to 100% by mass is preferable, and the range of 20 to 90% by mass is more preferable, because a coating film excellent in chemical properties and substrate adhesion can be formed.
  • polyisocyanate (a2) it can be used combining an aromatic polyisocyanate as needed.
  • aromatic polyisocyanate examples include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate and tetramethyl xylylene diisocyanate. And naphthalene diisocyanate.
  • a urethane resin (A) obtained by reacting the polyol (a1) with the polyisocyanate (a2) for example, with the polyol (a1) in the absence of a solvent or in the presence of an organic solvent
  • a method of mixing the above-mentioned polyisocyanate (a2) and reacting it at a reaction temperature of about 50 ° C. to 150 ° C. can be mentioned.
  • the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is in the range of 0.8 to 2.5. It is preferable to carry out in the range of 0.9 to 1.5, and it is particularly preferable to carry out in the range of 0.95 to 1.3.
  • the amount of urea bond in the urethane resin (A) can form a urethane resin composition excellent in compounding stability, and further, form a coating film excellent in corrosion resistance, chemical resistance and substrate adhesion.
  • it is less than 250 mmol / kg, and more preferably less than 150 mmol / kg.
  • chain extender examples include polyamines, hydrazine compounds, and other compounds containing active hydrogen atoms.
  • polyamines examples include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophorone diamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4'-dicyclohexylmethanediamine and 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like. In addition, 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, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; ⁇ -semicarbazide Propionic acid hydrazide and the like can be mentioned. Moreover, 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, sucrose, and the like.
  • 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 aqueous resin composition of the present invention may be used alone or in combination of two or more, as long as storage stability of the aqueous resin composition of the present invention does not decrease.
  • alcohol compounds such as methanol, ethanol, propanol and butanol
  • diol compounds such as ethylene glycol, 1,3-propanediol, 1,3-butanediol and 1,4-butanediol May be used as a reaction terminator.
  • the amount of the reaction terminator is preferably 0.1 parts by mass or more, preferably 1 part by mass or less, more preferably 100 parts by mass in total of the polyol (a1) and the polyisocyanate (a2). It is 0.8 parts by mass or less.
  • organic solvents examples include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetic acid ester solvents such as ethyl acetate and butyl acetate; acetonitrile and the like Nitrile solvents; amide solvents such as dimethylformamide, N-methylpyrrolidone and the like, and the like. These organic solvents can be used alone or in combination of two or more.
  • the organic solvent may be partially or entirely removed of the organic solvent, for example, by distillation under reduced pressure during or after the production of the urethane resin (A). May be
  • Examples of the aqueous medium (B) include water, an organic solvent miscible with water, and a mixture thereof.
  • the organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n-propanol and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; And alkyl ether solvents; and lactam solvents such as N-methyl-2-pyrrolidone.
  • These organic solvents miscible with water can be used alone or in combination of two or more.
  • the aqueous medium (B) is preferably water alone or a mixture of water and an organic solvent miscible with water, and more preferably only water, in consideration of safety and reduction of environmental load.
  • the content of water is preferably 80% by mass or more, more preferably 90% by mass or more, and the upper limit is 100% by mass.
  • the aqueous medium (B) is preferably contained in the range of 30 to 80% by mass, and more preferably in the range of 50 to 70% by mass, in the total amount of the urethane oil composition of the present invention.
  • a crosslinking agent if necessary, a crosslinking agent, a plasticizer, an antistatic agent, a wax, a surfactant, a light stabilizer, a flow control agent, a dye, a leveling agent, a rheology control agent, Various additives such as an ultraviolet light absorber, an antioxidant, a photocatalytic compound, an inorganic pigment, an organic pigment, and an extender pigment can be used.
  • the content thereof is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, with respect to 100 parts by mass of the urethane resin (A).
  • an amino resin an aziridine compound, a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, an isocyanate compound etc. are mentioned, for example.
  • the compounding stability of the urethane resin composition of this invention can be further improved by using the said surfactant.
  • a surfactant is used, it is preferably used in a range of 20 parts by mass or less with respect to 100 parts by mass of the urethane resin (A) because the adhesion to a substrate of the obtained coating can be maintained. It is preferred not to use.
  • a curing agent and a curing catalyst may be used in combination as needed, as long as the effects of the present invention are not impaired.
  • the curing agent examples include a compound having a silanol group and / or a hydrolyzable silyl group, a polyepoxy compound, a polyoxazoline compound, and a polyisocyanate.
  • a compound having a silanol group and / or a hydrolyzable silyl group as the curing agent in order to form a crosslinked coating film excellent in corrosion resistance.
  • the hydrolyzable silyl group or silanol group of the compound improves the adhesion to the metal of the base material, resulting in corrosion resistance. An excellent coating film can be formed.
  • an alkoxysilyl group is preferable because of its high crosslinkability and improved corrosion resistance.
  • a trimethoxysilyl group and a triethoxysilyl group are preferable because they are excellent in the crosslinkability and the corrosion resistance is improved.
  • Examples of the compound having a silanol group and / or a hydrolyzable silyl group include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, ⁇ -glycidoxypropylmethyldimethoxysilane, and ⁇ -Epoxysilane compounds such as glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, ⁇ -aminopropyltriethylsilane Examples include aminosilanes such as methoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldimethoxysilane, and ⁇ -aminopropylmethyldiethoxysilane.
  • ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane improve the crosslink density of the coating film and thus resist It is preferable because chemical properties and corrosion resistance are improved.
  • the compound having a silanol group and / or a hydrolyzable silyl group forms a coating film excellent in corrosion resistance, and a urethane resin (A) for obtaining a urethane resin composition of the present invention excellent in compounding stability. It is preferable to use in the range of 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass.
  • a curing catalyst usable for the urethane resin composition of the present invention for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate , Lead octylate, cobalt octylate, zinc octylate, calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di-n-butyltin dilaurate, Examples include di-n-butyltin maleate, p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid, dialkyl phosphorous acid and the like.
  • the urethane resin composition of the present invention may optionally contain an emulsifier, a dispersion stabilizer and a leveling agent, but from the viewpoint of suppressing the decrease in water resistance of the crosslinked coating, it may not be contained as much as possible. Preferably, it is 0.5 mass% or less with respect to the non volatile matter of the said urethane resin composition.
  • the urethane resin composition of the present invention can be used for coating of various substrates for the purpose of surface protection of various substrates and imparting of designability to various substrates.
  • the substrate examples include metal substrates such as galvanized steel plate, aluminum-galvanized steel plate, zinc-aluminum-magnesium alloy plated steel plate, aluminum plate, aluminum alloy plate, electromagnetic steel plate, copper plate, stainless steel plate, and various plastics The film, glass, paper, wood etc. are mentioned.
  • the urethane resin composition of the present invention is, for example, surface coating of various articles such as building members such as outer wall and roof, civil engineering members such as guardrails, sound barriers and drainage grooves, home appliances, industrial machines, automobile exterior materials, etc. Can be suitably used.
  • the urethane resin composition of this invention can form the coating film excellent in the corrosion resistance and chemical resistance which can prevent deterioration of the surface of the said metal base material, it can be used as a steel plate surface treatment agent.
  • the steel sheet surface treatment agent of the present invention can form a coating film excellent in chemical resistance including acid resistance, alkali resistance and the like even when the cross-linked coating film has a thickness of about 5 ⁇ m.
  • a coating film excellent in chemical resistance including acid resistance, alkali resistance and the like can be formed.
  • the steel sheet surface treatment agent of the present invention can be coated on a substrate, dried and cured to form a coating film.
  • Examples of the coating method include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and an immersion method.
  • the drying may be natural drying at normal temperature, but may be heat drying.
  • the heat drying is preferably carried out usually at 40 to 250 ° C. for about 1 to 600 seconds.
  • the steel plate having a coating of the steel plate surface treatment agent of the present invention includes, for example, galvanized steel plates used for applications such as automobiles, home appliances and building materials, plated steel plates such as aluminum-zinc alloy steel plates, zinc-aluminum-magnesium alloy A plated steel plate, an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate etc. are mentioned.
  • Synthesis Example 1 Synthesis of Aromatic Polyester Polyol (1)
  • a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer 13 parts by mass of ethylene glycol, 22 parts by mass of neopentyl glycol, 23 parts by mass of isophthalic acid, 23 parts by mass of terephthalic acid, and 10 parts by mass of adipic acid
  • the resultant was reacted with parts to obtain an aromatic polyester polyol (1) (number average molecular weight: 1,000, aromatic ring concentration: 3.5 mol / kg).
  • Synthesis Example 2 Synthesis of Aromatic Polyester Polyol (2) 12 parts by mass of ethylene glycol, 20 parts by mass of diethylene glycol, 28 parts by mass of isophthalic acid and 28 parts by mass of terephthalic acid are reacted in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe and a stirrer A polyester polyol (2) (number average molecular weight: 1,700, aromatic ring concentration: 4.5 mol / kg) was obtained.
  • Synthesis Example 3 Synthesis of Aromatic Polyester Polyol (3) 12 parts by mass of ethylene glycol, 21 parts by mass of neopentyl glycol, 27 parts by mass of isophthalic acid and 27 parts by mass of terephthalic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer An aromatic polyester polyol (3) (number average molecular weight: 1,000, aromatic ring concentration: 4.3 mol / kg) was obtained.
  • Synthesis Example 4 Synthesis of Aromatic Polyester Polyol (4) 12 parts by mass of ethylene glycol, 24 parts by mass of neopentyl glycol, 32 parts by mass of isophthalic acid and 32 parts by mass of terephthalic acid are reacted in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer. An aromatic polyester polyol (4) (number average molecular weight: 2,600, aromatic ring concentration: 3.4 mol / kg) was obtained.
  • Synthesis Example 5 Synthesis of Aromatic Polyester Polyol (5)
  • a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer 53 parts by mass of diethylene glycol and 47 parts by mass of orthophthalic acid are reacted to obtain an aromatic polyester polyol (5) [number average molecular weight; Aromatic ring concentration; 3.1 mol / kg] was obtained.
  • Synthesis Example 6 Synthesis of Aromatic Polyester Polyol (6)
  • a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer 73 parts by mass of 2,2 ′-[isopropylidenebis [(p-phenylene) (oxy)] diethanol and 2,6- 16 parts by mass of dimethyl naphthalenedicarboxylate, 9 parts by mass of terephthalic acid and 2 parts by mass of phthalic anhydride are reacted to obtain an aromatic polyester polyol (6) [number average molecular weight: 1,000, aromatic ring concentration: 6.8 mol / kg I got
  • Synthesis Example 7 Synthesis of liester polyol (7) 32 parts by mass of 1,6-hexanediol, 15 parts by mass of neopentyl glycol, and 53 parts by mass of adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer to react with polyester polyol (7) [Number average molecular weight; 2,000, aromatic ring concentration: 0 mol / kg] was obtained.
  • Example 1 Preparation of Urethane Resin Composition (1) 79.6 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1 in a reaction vessel, 3.1 parts by mass of 2,2-dimethylol propionic acid, 17.3 parts by mass of hexamethylene diisocyanate, 67 parts by mass of methyl ethyl ketone Were reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
  • Example 2 Preparation of Urethane Resin Composition (2) In a reaction vessel, 75.1 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 3.1 parts by mass of 2,2-dimethylol propionic acid, 21.8 parts by mass of isophorone diisocyanate, and 67 parts by mass of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
  • Example 3 Preparation of Urethane Resin Composition (3) 71.9 parts by mass of the aromatic polyester polyol (2) obtained in Synthesis Example 2 in a reaction vessel, 3.1 parts by mass of 2,2-dimethylol propionic acid, and 25.0 parts by mass of 4,4'-dicyclohexylmethane diisocyanate By charging 67 parts by mass of methyl ethyl ketone and reacting at 70 ° C., an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.
  • Example 4 Preparation of Urethane Resin Composition (4) 79.3 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1 in a reaction vessel, 3.1 parts by mass of 2,2-dimethylol propionic acid, 8.8 parts by mass of hexamethylene diisocyanate, and 8.8 parts by weight of toluene diisocyanate A mass part and 67 mass parts of methyl ethyl ketone were charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular terminal.
  • Example 5 Preparation of Urethane Resin Composition (5) 6. 82.7 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 4.3 parts by mass of 2,2-dimethylol propionic acid, 6.5 parts by mass of hexamethylene diisocyanate, and xylylene diisocyanate in a reaction vessel. Five parts by mass and 67 parts by mass of methyl ethyl ketone were charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular terminal.
  • Example 6 Preparation of Urethane Resin Composition (6) 74.6 parts by mass of the aromatic polyester polyol (2) obtained in Synthesis Example 2 in a reaction vessel, 4.3 parts by mass of 2,2-dimethylol propionic acid, 6.3 parts by mass of isophorone diisocyanate, and 14.7 parts of xylylene diisocyanate The mixed solution of parts by mass and 67 parts by mass of methyl ethyl ketone was charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular terminal.
  • Example 7 Preparation of Urethane Resin Composition (7) 69.8 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1 in a reaction vessel, 4.3 parts by mass of 2,2-dimethylol propionic acid, 7.8 parts by mass of 4,4'-dicyclohexylmethane diisocyanate, 18.1 parts by mass of diphenylmethane diisocyanate and 67 parts by mass of methyl ethyl ketone were charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular terminal.
  • Example 8 Preparation of Urethane Resin Composition (8) 75.0 parts by mass of the aromatic polyester polyol (3) obtained in Synthesis Example 3 in a reaction vessel, 5.5 parts by mass of 2,2-dimethylol propionic acid, and 19.5 parts by mass of hexamethylene diisocyanate, 67 parts by mass of methyl ethyl ketone Were reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
  • Example 9 Preparation of Urethane Resin Composition (9)
  • a reaction vessel 82.3 parts by mass of the aromatic polyester polyol (4) obtained in Synthesis Example 4, 5.5 parts by mass of 2,2-dimethylol propionic acid, 12.2 parts by mass of hexamethylene diisocyanate, and 67 parts by mass of methyl ethyl ketone Were reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
  • Example 10 Preparation of Urethane Resin Composition (10) In a reaction vessel, 71.5 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 3.6 parts by mass of 2,2-dimethylol propionic acid, 24.4 parts by mass of isophorone diisocyanate, and 67 parts by mass of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
  • the organic solvent solution of the urethane prepolymer is cooled to 40 ° C., and 9 parts by mass of 5% aqueous ammonia is added to neutralize some or all of the carboxyl groups of the urethane prepolymer, and further 10%.
  • An aqueous dispersion of a urethane resin is obtained by adding 5 parts by mass of an aqueous solution of piperazine and 333 parts by mass of water to obtain an aqueous dispersion of a urethane resin, and then aging and desolvation to obtain a urethane resin composition (30) I got
  • the acid value of this urethane resin composition (10) was 15 mg KOH / g, and the amount of urea bonds was 59 mmol / kg.
  • Example 11 Preparation of Urethane Resin Composition (11) In a reaction vessel, 69.3 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 3.6 parts by mass of 2,2-dimethylol propionic acid, 26.5 parts by mass of isophorone diisocyanate, and 67 parts by mass of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
  • the organic solvent solution of the urethane prepolymer is cooled to 40 ° C., and 3 parts by mass of triethylamine is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 80% aqueous hydrazine solution 0.
  • a water dispersion of a urethane resin is obtained by adding 8 parts by mass and 333 parts by mass of water and stirring sufficiently to obtain a urethane resin composition (11) having a nonvolatile content of 30% by mass by aging and desolvation.
  • the acid value of this urethane resin composition (11) was 15 mg KOH / g, and the amount of urea bonds was 210 mmol / kg.
  • Example 12 Preparation of Urethane Resin Composition (12) 84.4 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1 in a reaction vessel, 3.6 parts by mass of 2,2-dimethylol propionic acid, 1.2 parts by mass of hexamethylene diisocyanate and 10.8 parts of toluene diisocyanate A mass part and 67 mass parts of methyl ethyl ketone were charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular terminal.
  • Example 13 Preparation of Urethane Resin Composition (13) 83.2 parts by mass of the aromatic polyester polyol (5) obtained in Synthesis Example 5 in a reaction vessel, 4.3 parts by mass of 2,2-dimethylol propionic acid, 11.3 parts by mass of hexamethylene diisocyanate and 1.3 parts by weight of toluene diisocyanate A mass part and 67 mass parts of methyl ethyl ketone were charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular terminal.
  • the solution was cooled to 40 ° C., added with 0.6 parts by mass of 1,3-butanediol and reacted at 70 ° C. to completely quench the isocyanate component.
  • a part or all of the carboxyl groups possessed by the urethane prepolymer is neutralized by adding 9 parts by mass of 5% ammonia water, and 333 parts by mass of water is further added, and the aqueous dispersion of the urethane resin is sufficiently stirred.
  • the obtained resin composition was then aged and desolventized to obtain a urethane resin composition (13) having a nonvolatile content of 30% by mass.
  • the acid value of this urethane resin composition (13) was 15 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
  • Example 14 Preparation of Urethane Resin Composition (14) In a reaction vessel, 75.1 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 3.1 parts by mass of 2,2-dimethylol propionic acid, 21.8 parts by mass of isophorone diisocyanate, and 67 parts by mass of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
  • aqueous dispersion of the urethane resin was obtained by stirring to obtain a urethane resin composition (14) having a nonvolatile content of 30% by mass by aging and removing the solvent.
  • the acid value of this urethane resin composition (14) was 13 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
  • Example 15 Preparation of Urethane Resin Composition (15) In a reaction vessel, 66.6 parts by weight of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 3.6 parts by weight of 2,2-dimethylol propionic acid, 27.6 parts by weight of isophorone diisocyanate, and 67 parts by weight of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
  • aqueous dispersion of a urethane resin is obtained by adding 23 parts by mass of an aqueous solution and 333 parts by mass of water to obtain an aqueous dispersion of a urethane resin, and then aging and desolvation to obtain a urethane resin composition (15) having a nonvolatile content of 30% by mass. Obtained.
  • the acid value of this urethane resin composition (15) was 15 mg KOH / g, and the amount of urea bond was 262 mmol / kg.
  • Comparative Example 1 Preparation of Urethane Resin Composition (C1) 78.7 parts by mass of the aromatic polyester polyol (6) obtained in Synthesis Example 6 in a reaction vessel, 3.6 parts by mass of 2,2-dimethylol propionic acid, 17.7 parts by mass of hexamethylene diisocyanate, 67 parts by mass of methyl ethyl ketone Were reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
  • Comparative Example 2 Preparation of Urethane Resin Composition (C2) In a reaction vessel, 78.1 parts by mass of the aromatic polyester polyol (3) obtained in Synthesis Example 3, 3.6 parts by mass of 2,2-dimethylol propionic acid, 18.3 parts by mass of toluene diisocyanate, and 67 parts by mass of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
  • Comparative Example 4 Preparation of Urethane Resin Composition (C4) 72.7 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1 in a reaction vessel, 6.7 parts by mass of 2,2-dimethylol propionic acid, and 20.6 parts by mass of hexamethylene diisocyanate, 67 parts by mass of methyl ethyl ketone Parts were charged and reacted at 70 ° C. to obtain an organic solvent solution of urethane prepolymer having an isocyanate group at the molecular terminal.
  • the number average molecular weight of the aromatic polyester polyol represents a value obtained by measurement under the following conditions by gel permeation chromatography (GPC).
  • Measuring device High-speed GPC device ("HLC-8220GPC” manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation are connected in series and used. "TSKgel G5000" (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 4000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 "TSK gel G 3000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 This “TSKgel G2000” (7.8 mm ID ⁇ 30 cm) ⁇ 1 Detector: RI (differential refractometer) Column temperature: 40 ° C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 ⁇ L (tetrahydrofuran solution with a sample concentration of 0.4% by mass) Standard sample: Prepare a calibration curve using the following standard polystyrene.
  • Residue (aggregates) was less than 1%.
  • Residue (aggregates) was 1% or more and less than 5%.
  • Residue (aggregates) was 5% or more and less than 20%.
  • X Residue (aggregates) was 20% or more.
  • ⁇ The rusted area was less than 10% of the entire coating surface.
  • ⁇ The rusted area was 10% or more and less than 40% of the entire coating surface.
  • ⁇ The area where rust was generated was 40% or more and less than 70% of the entire coating film surface.
  • X The area in which rust occurred was 70% or more of the entire coating film surface.
  • ⁇ The area in which the blackening or browning occurred was less than 10% of the entire coating film surface.
  • Good The area in which the blackening or browning occurred was 10% or more and less than 40% of the entire coating film surface.
  • Fair The area where blackening or browning occurred was 40% or more and less than 70% of the entire coating film surface.
  • X The area in which the blackening or browning occurred was 70% or more of the entire coating film surface.
  • ⁇ no abnormality in the coating
  • ⁇ A slight (less than 5% area) floating is observed in the coating film.
  • ⁇ A slight (more than 5%, 60% or less of area) floating is observed in the coating film.
  • X Many floats (more than 60% area) are observed in the coating film.
  • Table 2 shows the compositions and evaluation results of the urethane resin compositions (C1) to (C5) produced in Comparative Examples 1 to 5.
  • the urethane resin composition of the present invention is excellent in formulation stability, and a coating film obtained using the urethane resin composition of the present invention is It was confirmed that the steel was excellent in corrosion resistance, chemical resistance and adhesion to a substrate.
  • Comparative Example 1 is an example in which the concentration of the aromatic ring in the aromatic polyester polyol was 6.8 mol / kg exceeding the range of the present invention.
  • the coating film obtained using the urethane resin composition of Comparative Example 1 is excellent in chemical resistance (ethanol resistance) and substrate adhesion, but corrosion resistance and chemical resistance (alkali resistance) are extremely insufficient. Was confirmed.
  • the comparative example 2 is an example which does not use aliphatic polyisocyanate and / or polyisocyanate which has an alicyclic structure.
  • the coating film obtained using the urethane resin composition of Comparative Example 2 is excellent in chemical resistance (ethanol resistance) and substrate adhesion as in Comparative Example 1, but the corrosion resistance and chemical resistance ( It has been confirmed that the alkali resistance is extremely insufficient.
  • the comparative example 3 is an example using the thing of 8 mgKOH / g whose acid value of a urethane resin exceeds the range of this invention. Although the coating film obtained using the urethane resin composition of this comparative example 3 is excellent in corrosion resistance and chemical resistance, it has been confirmed that the chemical resistance (alkali resistance) is extremely insufficient.
  • Comparative Example 5 is an example in which an aromatic polyester polyol is not used. Although the coating film obtained using the urethane resin composition of this comparative example 5 is excellent in the substrate adhesion, it has been confirmed that the chemical resistance is extremely insufficient.

Abstract

Provided is a urethane resin composition which has excellent blend stability and is capable of forming a coating film that has excellent corrosion resistance, chemical resistance and adhesion to a substrate. The present invention uses a urethane resin composition which contains a urethane resin (A) that is a reaction product of a polyol (a1) that contains an aromatic polyester polyol (a1-1) and a polyol (a1-2) having an anionic group and a polyisocyanate (a2) and an aqueous medium (B), and which is characterized in that: the aromatic ring concentration in the aromatic polyester polyol (a1-1) is 2.5-5 mol/kg; the polyisocyanate (a2) contains an aliphatic polyisocyanate and/or a polyisocyanate having an alicyclic structure; and the acid value of the urethane resin (A) is within the range of 10-25 mgKOH/g.

Description

ウレタン樹脂組成物、鋼板表面処理剤及びその塗膜を有する鋼板Urethane resin composition, steel sheet surface treating agent and steel sheet having coated film thereof
　本発明は、ウレタン樹脂組成物、鋼板表面処理剤及びその塗膜を有する鋼板に関する。 The present invention relates to a urethane resin composition, a steel sheet surface treatment agent, and a steel sheet having a coating film thereof.
　近年、金属需要の増加に伴って、鋼板をはじめとする金属基材の表面保護用コーティング剤、即ち鋼板表面処理剤の需要が高まっている。このような鋼板表面処理剤には、一般に、金属基材の腐食に起因した塗膜の剥がれや膨れを防止可能なレベルの耐食性や、高いレベルの耐薬品性が求められる。特に耐薬品性は、金属基材の表面に形成された塗膜表面をアルカリ性洗浄剤等を用いて洗浄することが頻繁に行われる鉄鋼業界において、該洗浄剤の影響による塗膜の剥離や溶解、金属基材の劣化等を防止するうえで重要な特性である。 In recent years, with the increase in demand for metals, the demand for a coating agent for surface protection of metal substrates including steel plates, that is, a surface treatment agent for steel plates is increasing. In general, such a steel sheet surface treatment agent is required to have a level of corrosion resistance capable of preventing peeling and swelling of a coating film due to the corrosion of a metal substrate and a high level of chemical resistance. Particularly in chemical resistance, in the steel industry where the coating film surface formed on the surface of a metal substrate is frequently washed using an alkaline cleaner etc., peeling or dissolution of the coating film due to the influence of the cleaning agent Is an important characteristic to prevent the deterioration of the metal base and the like.
　前記特性を備えた鋼板表面処理剤は、とりわけ、錆を発生しやすい金属基材の表面保護用途で求められることが多い。 A steel plate surface treatment agent having the above-mentioned properties is often required especially in the surface protection application of a metal substrate susceptible to rust.
　前記鋼板表面処理剤としては、例えば、カルボキシル基含有水性ウレタン樹脂と水性ビニル変性エポキシエステル樹脂とを含有する金属表面処理剤用水性樹脂組成物であり、前記カルボキシル基含有水性ウレタン樹脂が酸成分と分子中にカルボキシル基を含まないグリコール成分より構成されるポリエステルポリオールとポリイソシアネート化合物と、分子中にカルボキシル基を有するグリコール成分を含む鎖伸長剤とを反応させて得られるポリエステルウレタン樹脂である金属表面処理剤用水性樹脂組成物が知られている。（例えば、特許文献１参照。）。 The steel plate surface treatment agent is, for example, an aqueous resin composition for a metal surface treatment agent containing a carboxyl group-containing aqueous urethane resin and an aqueous vinyl-modified epoxy ester resin, and the carboxyl group-containing aqueous urethane resin is an acid component Metal surface which is a polyester urethane resin obtained by reacting a polyester polyol and a polyisocyanate compound composed of a glycol component not having a carboxyl group in the molecule and a chain extender containing a glycol component having a carboxyl group in the molecule Aqueous resin compositions for treating agents are known. (See, for example, Patent Document 1).
　しかし、前記金属表面処理剤用水性樹脂組成物を用いて形成された塗膜は、金属基材の劣化を長期間にわたり防止するには、耐薬品性及び耐食性の点であと一歩及ぶものではなく、実用上十分ではない場合があった。 However, the coating film formed using the aqueous resin composition for metal surface treatment is not a step beyond the point of chemical resistance and corrosion resistance in order to prevent deterioration of the metal substrate over a long period of time. There was a case that was not enough for practical use.
　そこで、耐食性、耐薬品性及び基材密着性に優れた塗膜を形成可能なウレタン樹脂組成物が求められていた。 Then, the urethane resin composition which can form the coating film excellent in corrosion resistance, chemical resistance, and base-material adhesiveness was calculated | required.
特開２００６－３２１９１１号公報JP, 2006-321911, A
　本発明が解決しようとする課題は、配合安定性に優れ、かつ、耐食性、耐薬品性及び基材密着性に優れた塗膜を形成可能なウレタン樹脂組成物を提供することである。 The problem to be solved by the present invention is to provide a urethane resin composition capable of forming a coating film excellent in compounding stability and excellent in corrosion resistance, chemical resistance and substrate adhesion.
　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、特定の範囲の数平均分子量及び特定の範囲の芳香環濃度を有する芳香族ポリエステルポリオール、及びアニオン性基を有するポリオールを含有するポリオールと、特定のポリイソシアネートとの反応物であるウレタン樹脂を含む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 intensive studies to solve the above problems, the present inventors contain an aromatic polyester polyol having a specific range of number average molecular weight and a specific range of aromatic ring concentration, and a polyol having an anionic group. By using a urethane resin composition containing a urethane resin that is a reaction product of a polyol and a specific polyisocyanate, the inventors have found that the above problems can be solved, and completed the present invention.
　すなわち、本発明は、芳香族ポリエステルポリオール（ａ１－１）、及びアニオン性基を有するポリオール（ａ１－２）を含有するポリオール（ａ１）と、ポリイソシアネート（ａ２）との反応物であるウレタン樹脂（Ａ）、及び水性媒体（Ｂ）を含むウレタン樹脂組成物であって、前記芳香族ポリエステルポリオール（ａ１－１）中の芳香環濃度が、２．５～５ｍｏｌ／ｋｇであり、前記ポリイソシアネート（ａ２）が、脂肪族ポリイソシアネート及び／または脂環式構造を有するポリイソシアネートを含むものであり、前記ウレタン樹脂（Ａ）の酸価が、１０～２５ｍｇＫＯＨ／ｇの範囲であることを特徴とするウレタン樹脂組成物、鋼板表面処理剤及びその塗膜を有する鋼板に関するものである。 That is, the present invention is a urethane resin which is a reaction product of a polyol (a1) containing an aromatic polyester polyol (a1-1) and a polyol (a1-2) having an anionic group, and a polyisocyanate (a2). (A) and a urethane resin composition containing an aqueous medium (B), wherein the aromatic ring concentration in the aromatic polyester polyol (a1-1) is 2.5 to 5 mol / kg, and the polyisocyanate (A2) contains aliphatic polyisocyanate and / or polyisocyanate having an alicyclic structure, and the acid value of the urethane resin (A) is in the range of 10 to 25 mg KOH / g. The present invention relates to a urethane resin composition, a steel sheet surface treatment agent, and a steel sheet having a coating film thereof.
　本発明のウレタン樹脂組成物は、配合安定性に優れており、さらに、耐食性、耐薬品性及び基材密着性に優れた塗膜を形成できることから、各種基材の表面保護用途に用いることができる。本発明のウレタン樹脂組成物が適用可能な基材としては、例えば、亜鉛めっき鋼板やアルミニウム－亜鉛めっき鋼板、亜鉛－アルミニウム－マグネシウム合金めっき鋼板、アルミ板、アルミ合金板、電磁鋼板、銅板、ステンレス鋼板等の金属基材、各種プラスチックやそのフィルム、ガラス、紙、木材などが挙げられる。 The urethane resin composition of the present invention is excellent in compounding stability, and further, because it can form a coating film excellent in corrosion resistance, chemical resistance and substrate adhesion, it can be used for surface protection of various substrates. it can. As a substrate to which the urethane resin composition of the present invention can be applied, for example, galvanized steel sheet, aluminum-galvanized steel sheet, zinc-aluminum-magnesium alloy plated steel sheet, aluminum sheet, aluminum alloy sheet, electromagnetic steel sheet, copper sheet, stainless steel Examples include metal substrates such as steel plates, various plastics and films thereof, glass, paper, and wood.
　また、本発明のウレタン樹脂組成物は、前記金属基材の表面の劣化を防止可能な耐食性及び耐薬品性に優れた塗膜を形成できることから、例えば、外壁、屋根等の建築部材、ガードレール、防音壁、排水溝等の土木部材、家電製品、産業機械、自動車外装材等の各種物品の表面塗装などに好適に用いることが可能である。 Further, the urethane resin composition of the present invention can form a coating film excellent in corrosion resistance and chemical resistance capable of preventing the deterioration of the surface of the metal base, so, for example, building members such as outer wall and roof, guardrails, It is possible to use suitably for surface coating etc. of various articles, such as civil engineering members, such as a sound barrier, a drainage ditch, household appliances, an industrial machine, an automobile exterior material, etc.
　本発明のウレタン樹脂組成物は、芳香族ポリエステルポリオール（ａ１－１）、及びアニオン性基を有するポリオール（ａ１－２）を含有するポリオール（ａ１）と、ポリイソシアネート（ａ２）との反応物であるウレタン樹脂（Ａ）、及び水性媒体（Ｂ）を含むウレタン樹脂組成物であって、前記芳香族ポリエステルポリオール（ａ１－１）中の芳香環濃度が、２．５～５ｍｏｌ／ｋｇであり、前記ポリイソシアネート（ａ２）が、脂肪族ポリイソシアネート及び／または脂環式構造を有するポリイソシアネートを含むものであり、前記ウレタン樹脂（Ａ）の酸価が、１０～２５ｍｇＫＯＨ／ｇの範囲であることを特徴とする。 The urethane resin composition of the present invention is a reaction product of an aromatic polyester polyol (a1-1) and a polyol (a1) containing a polyol (a1-2) having an anionic group, and a polyisocyanate (a2). A urethane resin composition comprising a certain urethane resin (A) and an aqueous medium (B), wherein the aromatic ring concentration in the aromatic polyester polyol (a1-1) is 2.5 to 5 mol / kg, The polyisocyanate (a2) contains an aliphatic polyisocyanate and / or a polyisocyanate having an alicyclic structure, and the acid value of the urethane resin (A) is in the range of 10 to 25 mg KOH / g. It is characterized by
　前記ウレタン樹脂（Ａ）としては、芳香族ポリエステルポリオール（ａ１－１）、及びアニオン性基を有するポリオール（ａ１－２）を含有するポリオール（ａ１）と、ポリイソシアネート（ａ２）との反応物を用いる。前記反応物には、前記ポリオール（ａ１）と、前記ポリイソシアネート（ａ２）と、それ以外の化合物との反応物も含むものとする。 As the urethane resin (A), a reaction product of a polyol (a1) containing an aromatic polyester polyol (a1-1) and a polyol (a1-2) having an anionic group with a polyisocyanate (a2) Use. The reactant also includes a reactant of the polyol (a1), the polyisocyanate (a2), and the other compounds.
　前記ポリオール（ａ１）としては、芳香族ポリエステルポリオール（ａ１－１）、及びアニオン性基を有するポリオール（ａ１－２）を必須として用いる。 As the polyol (a1), an aromatic polyester polyol (a1-1) and a polyol (a1-2) having an anionic group are used essentially.
　前記芳香族ポリエステルポリオール（ａ１－１）としては、配合安定性に優れたウレタン樹脂組成物を得ることができ、さらに、耐食性、耐薬品性及び基材密着性に優れた塗膜を形成できることから、芳香環濃度が２．５～５ｍｏｌ／ｋｇの範囲のものを用いる。また、より一層耐食性、耐薬品性及び基材密着性に優れた塗膜を形成できることから、芳香環濃度が３～４．４ｍｏｌ／ｋｇの範囲の芳香族ポリエステルポリオールがより好ましい。 As the aromatic polyester polyol (a1-1), a urethane resin composition excellent in compounding stability can be obtained, and furthermore, a coating film excellent in corrosion resistance, chemical resistance and substrate adhesion can be formed. The aromatic ring concentration is in the range of 2.5 to 5 mol / kg. In addition, an aromatic polyester polyol having an aromatic ring concentration in the range of 3 to 4.4 mol / kg is more preferable because a coating film having further excellent corrosion resistance, chemical resistance and substrate adhesion can be formed.
　また、前記芳香族ポリエステルポリオール（ａ１－１）としては、配合安定性に優れたウレタン樹脂組成物を得ることができ、さらに、耐食性、耐薬品性及び基材密着性に優れた塗膜を形成できることから、数平均分子量が７５０～５，０００の範囲のものが好ましく、１，０００～３，０００の範囲がより好ましい。
　本明細書において、数平均分子量は、ゲル・パーミエーション・クロマトグラフィ法を用い、ポリスチレンを標準試料とした換算値として測定することができる。 Moreover, as said aromatic polyester polyol (a1-1), the urethane resin composition excellent in compounding stability can be obtained, and also the coating film excellent in corrosion resistance, chemical resistance, and base-material adhesiveness is formed. The number average molecular weight is preferably in the range of 750 to 5,000, and more preferably in the range of 1,000 to 3,000.
In the present specification, the number average molecular weight can be measured as a converted value using polystyrene as a standard sample, using gel permeation chromatography.
　前記芳香族ポリエステルポリオール（ａ１－１）は、例えば、多価カルボン酸と多価アルコールとをエステル化反応させて得ることができる。前記多価カルボン酸と前記多価アルコールのうち、少なくとも１つに芳香環を有するものを用いる。 The aromatic polyester polyol (a1-1) can be obtained, for example, by subjecting a polyhydric carboxylic acid and a polyhydric alcohol to an esterification reaction. Among the polyvalent carboxylic acid and the polyvalent alcohol, one having an aromatic ring in at least one is used.
　前記多価カルボン酸のうち、芳香環を有するものとしては、例えば、フタル酸、イソフタル酸、テレフタル酸、オルソフタル酸、ナフタレンジカルボン酸等の芳香族ジカルボン酸又はそのエステル化物が挙げられる。また、芳香環を有さないものとしては、例えば、コハク酸、グルタル酸、アジピン酸、マレイン酸、ピメリン酸、スベリン酸、アゼライン酸、イタコン酸、セバシン酸、クロレンド酸、１，２，４－ブタン－トリカルボン酸、デカンジカルボン酸、シクロヘキサンジカルボン酸、ダイマー酸、フマル酸等の脂肪族ジカルボン酸又はそのエステル化物が挙げられる。これらの多価カルボン酸又はそのエステル化物は、単独で用いることも２種以上を併用することもできる。 Among the above polyvalent carboxylic acids, those having an aromatic ring include, for example, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, orthophthalic acid and naphthalene dicarboxylic acid, or esters thereof. Moreover, as a thing which does not have an aromatic ring, for example, succinic acid, glutaric acid, adipic acid, maleic acid, pimelic acid, suberic acid, azelaic acid, itaconic acid, sebacic acid, chlorendic acid, 1,2,4- Aliphatic dicarboxylic acids such as butane-tricarboxylic acid, decanedicarboxylic acid, cyclohexanedicarboxylic acid, dimer acid, fumaric acid or the like, and esters thereof. These polyvalent carboxylic acids or esterification products thereof can be used alone or in combination of two or more.
　前記多価アルコールのうち、芳香環を有するものとしては、例えば、ベンゼンジメタノール、トルエンジメタノール、キシレンジメタノール等の芳香族ジオールが挙げられる。また、芳香環を有さないものとしては、例えば、エチレングリコール、プロピレングリコール、１，３－プロピレンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、１，８－オクタンジオール、ジエチレングリコール、トリエチレングリコール、シクロヘキサン－１，４－ジオール、シクロヘキサン－１，４－ジメタノール、ネオペンチルグリコールエチレングリコール等の脂肪族ポリオールが挙げられる。これらの多価アルコールは、単独で用いることも２種以上を併用することもできる。 Among the polyhydric alcohols, those having an aromatic ring include, for example, aromatic diols such as benzenedimethanol, toluenedimethanol, and xylenedimethanol. Further, as a compound having no aromatic ring, for example, ethylene glycol, propylene glycol, 1,3-propylene diol, 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, diethylene glycol, Aliphatic polyols such as triethylene glycol, cyclohexane-1,4-diol, cyclohexane-1,4-dimethanol, neopentyl glycol ethylene glycol and the like. These polyhydric alcohols can be used alone or in combination of two or more.
　前記芳香族ポリエステルポリオール（ａ１－１）を製造する際のエステル化反応においては、エステル化反応を促進する目的で、エステル化触媒を用いることが好ましい。前記エステル化触媒としては、例えば、チタン、スズ、亜鉛、アルミニウム、ジルコニウム、マグネシウム、ハフニウム、ゲルマニウム等の金属；チタンテトライソプロポキシド、チタンテトラブトキシド、チタンオキシアセチルアセトナート、ジブチル錫オキサイド、ジブチル錫ジアセテート、ジブチル錫ジラウレート、オクタン酸錫、２－エチルヘキサンスズ、アセチルアセトナート亜鉛、４塩化ジルコニウム、４塩化ジルコニウムテトラヒドロフラン錯体、４塩化ハフニウム、４塩化ハフニウムテトラヒドロフラン錯体、酸化ゲルマニウム、テトラエトキシゲルマニウム等の金属化合物などが挙げられる。 In the esterification reaction for producing the aromatic polyester polyol (a1-1), it is preferable to use an esterification catalyst for the purpose of promoting the esterification reaction. Examples of the esterification catalyst include metals such as titanium, tin, zinc, aluminum, zirconium, magnesium, hafnium, and germanium; titanium tetraisopropoxide, titanium tetrabutoxide, titanium oxyacetylacetonate, dibutyltin oxide, dibutyltin Diacetate, dibutyltin dilaurate, tin octanoate, 2-ethylhexanetin, zinc acetylacetonate, zirconium tetrachloride, zirconium tetrachloride tetrahydrofuran complex, hafnium tetrachloride, hafnium tetrachloride tetrahydrofuran complex, germanium oxide, tetraethoxygermanium etc. Metal compounds and the like can be mentioned.
　前記芳香族ポリエステルポリオール（ａ１－１）の含有率は、前記ポリオール（ａ１）中、好ましくは５０質量％以上、より好ましくは８０質量％以上、さらに好ましくは９０質量％以上であり、好ましくは９９質量％以下、より好ましくは９８質量％以下である。 The content of the aromatic polyester polyol (a1-1) in the polyol (a1) is preferably 50% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 99 It is at most mass%, more preferably at most 98 mass%.
　前記アニオン性基を有するポリオール（ａ１－２）において、アニオン性基としては、カルボキシル基、スルホン酸基等の酸基が挙げられ、前記アニオン性基を有するポリオール（ａ１－２）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等が挙げられる。 Examples of the anionic group in the polyol (a1-2) having an anionic group include acid groups such as a carboxyl group and a sulfonic acid group, and examples of the polyol (a1-2) having an anionic group include And polyols having a carboxyl group, and polyols having a sulfonic acid group.
　なお、前記アニオン性基を有するポリオール（ａ１－２）のうち、アニオン性基を有する芳香族ポリエステルポリオールは、前記芳香族ポリエステルポリオール（ａ１－１）に含むものとする。 Among the polyols (a1-2) having an anionic group, aromatic polyester polyols having an anionic group are included in the aromatic polyester polyol (a1-1).
　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用いることもできる。 Examples of the polyol having a carboxyl group include 2,2-dimethylol propionic acid, 2,2-dimethylol butanoic acid, 2,2-dimethylol valeric acid and the like, and among them, 2,2-dimethylol Propionic acid is preferred. In addition, polyester polyols having a carboxyl group obtained by reacting a polyol having a carboxyl group with various polycarboxylic acids 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 weight polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, etc., and the above-mentioned polyester polyols, γ-butyrolactone And polyester polyols obtained by reacting cyclic ester compounds such as δ-valerolactone and ε-caprolactone.
　前記アニオン性基を有するポリオール（ａ１－２）の含有率は、前記ポリオール（ａ１）中、好ましくは１質量％以上、より好ましくは２質量％以上、さらに好ましくは３質量％以上であり、好ましくは１０質量％以下、より好ましくは９質量％以下、さらに好ましくは８質量％以下である。 The content of the polyol (a1-2) having an anionic group is preferably 1% by mass or more, more preferably 2% by mass or more, and still more preferably 3% by mass or more, in the polyol (a1), preferably Is 10% by mass or less, more preferably 9% by mass or less, and still more preferably 8% by mass or less.
　前記芳香族ポリエステルポリオール（ａ１－１）及びアニオン性基を有するポリオール（ａ１－２）の合計の含有率は、前記ポリオール（ａ１）中、好ましくは７０質量％以上、より好ましくは８０質量％以上、さらに好ましくは９０質量％以上であり、好ましくは１００質量％以下である。 The total content of the aromatic polyester polyol (a1-1) and the polyol (a1-2) having an anionic group is preferably 70% by mass or more, more preferably 80% by mass or more in the polyol (a1). More preferably, it is 90 mass% or more, Preferably it is 100 mass% or less.
　前記アニオン性基は、それらの一部または全部が中和剤（Ｃ）によって中和されていることが、良好な水分散性を発現するうえで好ましい。 The anionic group is preferably partially or entirely neutralized by the neutralizing agent (C) in order to express good water dispersibility.
　前記中和剤（Ｃ）としては、塩基性化合物を用いることができる。耐薬品性に優れた塗膜を形成可能できることから、沸点１４０℃未満の塩基性化合物が好ましく、沸点１３５℃以下の塩基性化合物が好ましく、沸点９０℃以下の塩基性化合物が好ましく、沸点９０℃未満の塩基性化合物がより好ましい。また、前記塩基性化合物の沸点の下限は、例えば－５０℃であることが好ましく、－４０℃以上であることがより好ましい。本明細書において、沸点は、１０１３ｈＰａにおける沸点を表すものとする。 A basic compound can be used as the neutralizing agent (C). A basic compound having a boiling point of less than 140 ° C. is preferable, a basic compound having a boiling point of 135 ° C. or less is preferable, a basic compound having a boiling point of 90 ° C. or less is preferable, and a boiling point of 90 ° C. Less than basic compounds are more preferred. The lower limit of the boiling point of the basic compound is, for example, preferably −50 ° C., and more preferably −40 ° C. or more. In the present specification, the boiling point represents the boiling point at 1013 hPa.
　前記塩基性化合物としては、例えば、モノメチルアミン（沸点；－６℃）、ジメチルアミン（沸点；７℃）、トリメチルアミン（沸点；３℃）、モノエチルアミン（沸点；１６．６℃）、ジエチルアミン（沸点；５６℃）、トリエチルアミン（沸点；８９．５℃）、モノプロピルアミン（沸点；４８℃）、ジプロピルアミン（沸点；１０８℃）、トリプロピルアミン（沸点；１５６℃）等のアルキルアミン；モノエタノールアミン（沸点；１７０℃）、ジエタノールアミン（沸点；２６８℃）、モノイソプロパノールアミン（沸点；１５９℃）、ジイソプロパノールアミン（沸点；２４９℃）、Ｎ－メチルエタノールアミン（沸点；１５９℃）、Ｎ，Ｎ－ジメチルエタノールアミン（沸点；１３５℃）、Ｎ，Ｎ－ジエチルエタノールアミン（沸点；１６２℃）、２－アミノ－２－メチル－１－プロパノール（沸点；１６６℃）、２－（ジメチルアミノ）－２－メチル－１－プロパノール（沸点；１６３℃）、Ｎ－メチルジエタノールアミン（沸点；２４５℃）、Ｎ－エチルジイソプロピルアミン（沸点；１２７℃）等のアルカノールアミン、モルホリン（沸点；１２９℃）等の有機アミンやアンモニア（沸点；－３３℃）等が挙げられる。これらの中でも、耐薬品性に優れた塗膜を形成可能できることから、沸点１４０℃未満の塩基性化合物が好ましく、沸点９０℃未満の塩基性化合物がより好ましく、アンモニアがさらに好ましい。アンモニアは、水に溶解し、アンモニア水として用いてもよい。この場合、該アンモニア水におけるアンモニアの濃度は、好ましくは１質量％以上、より好ましくは３質量％以上であり、好ましくは３０質量％以下、より好ましくは１５質量％以下、さらに好ましくは１０質量％以下である。 Examples of the basic compound include monomethylamine (boiling point: -6 ° C), dimethylamine (boiling point: 7 ° C), trimethylamine (boiling point; 3 ° C), monoethylamine (boiling point: 16.6 ° C), diethylamine (boiling point) Alkylamines such as 56 ° C), triethylamine (boiling point: 89.5 ° C), monopropylamine (boiling point: 48 ° C), dipropylamine (boiling point: 108 ° C), tripropylamine (boiling point: 156 ° C); Ethanolamine (boiling point: 170 ° C), diethanolamine (boiling point: 268 ° C), monoisopropanolamine (boiling point: 159 ° C), diisopropanolamine (boiling point: 249 ° C), N-methylethanolamine (boiling point: 159 ° C), N , N-Dimethylethanolamine (boiling point: 135 ° C), N, N-Diethylethanolamine Boiling point: 162 ° C.), 2-amino-2-methyl-1-propanol (boiling point: 166 ° C.), 2- (dimethylamino) -2-methyl-1-propanol (boiling point: 163 ° C.), N-methyldiethanolamine (boiling point: 163 ° C.) Boiling point: 245 ° C., alkanolamines such as N-ethyldiisopropylamine (boiling point: 127 ° C.), organic amines such as morpholine (boiling point: 129 ° C.), ammonia (boiling point: -33 ° C.), and the like. Among these, a basic compound having a boiling point of less than 140 ° C. is preferable, a basic compound having a boiling point of less than 90 ° C. is more preferable, and ammonia is more preferable because a coating film having excellent chemical resistance can be formed. Ammonia may be dissolved in water and used as ammonia water. In this case, the concentration of ammonia in the ammonia water is preferably 1% by mass or more, more preferably 3% by mass or more, preferably 30% by mass or less, more preferably 15% by mass or less, still more preferably 10% by mass It is below.
　前記中和剤（Ｃ）の含有量は、前記ポリオール（ａ１）及び前記ポリイソシアネート（ａ２）の合計１００質量部に対して、好ましくは０．１質量部以上、より好ましくは０．２質量部以上、さらに好ましくは０．３質量部以上であり、好ましくは１０質量部以下、より好ましくは７質量部以下、さらに好ましくは５質量部以下である。 The content of the neutralizing agent (C) is preferably 0.1 parts by mass or more, more preferably 0.2 parts by mass with respect to 100 parts by mass in total of the polyol (a1) and the polyisocyanate (a2). The amount is more preferably 0.3 parts by mass or more, preferably 10 parts by mass or less, more preferably 7 parts by mass or less, and still more preferably 5 parts by mass or less.
　また、前記ポリオール（ａ１）としては、必要に応じて、その他のポリオールを組み合わせて用いることができる。 Moreover, as said polyol (a1), it can be used combining other polyols as needed.
　また、前記その他のポリオールとしては、例えば、前記芳香族ポリエステルポリオール（ａ１－１）、及び前記アニオン性基を有するポリオール（ａ１－２）以外のポリエステルポリオール、ポリエーテルポリオール、ポリカーボネートポリオール、ポリオレフィンポリオール等を用いることもできる。これらのその他のポリオールは、単独で用いることも２種以上を併用することもできる。 Moreover, as said other polyol, polyester polyols other than the said aromatic polyester polyol (a1-1), and the polyol (a1-2) which has the said anionic group, polyether polyol, polycarbonate polyol, polyolefin polyol etc. Can also be used. These other polyols may be used alone or in combination of two or more.
　前記ポリエーテルポリオールとしては、例えば、活性水素原子を２つ以上有する化合物の１種又は２種以上を開始剤として、アルキレンオキサイドを付加重合させたものが挙げられる。前記活性水素原子を２つ以上有する化合物としては、例えば、プロピレングリコール、トリメチレングリコール、１，３－ブタンジオール、１，４－ブタンジオール、１，６－ヘキサンジオール、ネオペンチルグリコール、グリセリン、ジグリセリン、トリメチロールエタン、トリメチロールプロパン、水、ヘキサントリオール等が挙げられる。また、前記アルキレンオキサイドとしては、例えば、プロピレンオキサイド、ブチレンオキサイド、スチレンオキサイド、エピクロルヒドリン、テトラヒドロフラン等が挙げられる。これらのポリエーテルポリオールは、単独で用いることも２種以上を併用することもできる。 As said polyether polyol, what carried out addition polymerization of the alkylene oxide is mentioned, for example using 1 type, or 2 or more types of a compound which has 2 or more of active hydrogen atoms as an initiator. Examples of the compound having two or more active hydrogen atoms include propylene glycol, trimethylene glycol, 1,3-butanediol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin and di- Glycerin, trimethylolethane, trimethylolpropane, water, hexanetriol and the like can be mentioned. Moreover, as said alkylene oxide, a propylene oxide, a butylene oxide, a styrene oxide, epichlorohydrin, tetrahydrofuran etc. are mentioned, for example. These polyether polyols can be used alone or in combination of two or more.
　また、前記ポリカーボネートポリオールとしては、炭酸及び炭酸エステルと、多価アルコールとをエステル化反応させて得られたものが挙げられる。前記多価アルコールとしては、例えば、１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ジエチレングリコール、ポリエチレングリコール、ポリプロピレングリコール、ポリテトラメチレンエーテルグリコール等が挙げられる。これらのポリカーボネートポリオールは、単独で用いることも２種以上を併用することもできる。 Moreover, as said polycarbonate polyol, what was obtained by carrying out the esterification reaction of carbonic acid and carbonic acid ester, and a polyhydric alcohol is mentioned. Examples of the polyhydric alcohol include 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, diethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol Etc. These polycarbonate polyols may be used alone or in combination of two or more.
　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、脂肪族ポリイソシアネート及び／または脂環式構造を有するポリイソシアネートを用いる。 As polyisocyanate (a2) used for manufacture of the said urethane resin (A), aliphatic polyisocyanate and / or polyisocyanate which has an alicyclic structure are used.
　前記脂肪族ポリイソシアネートとしては、例えば、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、トリメチルヘキサメチレンジイソシアネート等が挙げられる。これらの脂肪族ポリイソシアネートは、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 aliphatic polyisocyanate include hexamethylene diisocyanate, lysine diisocyanate, trimethylhexamethylene diisocyanate and the like. These aliphatic polyisocyanates can be used alone or in combination of two or more.
　前記脂環式構造を有するポリイソシアネートとしては、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が挙げられる。これらの脂環式構造を有するポリイソシアネートは、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 having an alicyclic structure include cyclohexane diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate and the like. These polyisocyanates having an alicyclic structure can be used alone or in combination of two or more.
　前記脂肪族ポリイソシアネート及び／または前記脂環式構造を有するポリイソシアネートの前記ポリイソシアネート（ａ２）中の割合は、配合安定性に優れたウレタン樹脂組成物を得ることができ、さらに、耐食性、耐薬品性及び基材密着性に優れた塗膜を形成できることから、１０～１００質量％の範囲が好ましく、２０～９０質量％の範囲がより好ましい。 The proportion of the aliphatic polyisocyanate and / or the polyisocyanate having the alicyclic structure in the polyisocyanate (a2) can provide a urethane resin composition excellent in compounding stability, and further, corrosion resistance, and resistance The range of 10 to 100% by mass is preferable, and the range of 20 to 90% by mass is more preferable, because a coating film excellent in chemical properties and substrate adhesion can be formed.
　前記ポリイソシアネート（ａ２）としては、必要に応じて、芳香族ポリイソシアネートを組み合せて用いることができる。 As said polyisocyanate (a2), it can be used combining an aromatic polyisocyanate as needed.
　前記芳香族ポリイソシアネートとしては、例えば、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、トルエ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、ナフタレンジイソシアネート等が挙げられる。 Examples of the aromatic polyisocyanate include 4,4'-diphenylmethane diisocyanate, 2,4'-diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate and tetramethyl xylylene diisocyanate. And naphthalene diisocyanate.
　前記ポリオール（ａ１）と前記ポリイソシアネート（ａ２）とを反応させて得られるウレタン樹脂（Ａ）を製造する方法としては、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℃程度の範囲で反応させる方法が挙げられる。 As a method for producing a urethane resin (A) obtained by reacting the polyol (a1) with the polyisocyanate (a2), for example, with the polyol (a1) in the absence of a solvent or in the presence of an organic solvent A method of mixing the above-mentioned polyisocyanate (a2) and reacting it at a reaction temperature of about 50 ° C. to 150 ° C. can be mentioned.
　前記ポリオール（ａ１）と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く、０．９５～１．３の範囲で行うことが特に好ましい。 In the reaction of the polyol (a1) with the polyisocyanate (a2), for example, the equivalent ratio of the isocyanate group of the polyisocyanate (a2) to the hydroxyl group of the polyol (a1) is in the range of 0.8 to 2.5. It is preferable to carry out in the range of 0.9 to 1.5, and it is particularly preferable to carry out in the range of 0.95 to 1.3.
　また、前記ウレタン樹脂（Ａ）中のウレア結合量は、配合安定性に優れたウレタン樹脂組成物を得ることができ、さらに、耐食性、耐薬品性及び基材密着性に優れた塗膜を形成できることから、２５０ｍｍｏｌ／ｋｇ未満であることが好ましく、１５０ｍｍｏｌ／ｋｇ未満がより好ましい。 Further, the amount of urea bond in the urethane resin (A) can form a urethane resin composition excellent in compounding stability, and further, form a coating film excellent in corrosion resistance, chemical resistance and substrate adhesion. Preferably, it is less than 250 mmol / kg, and more preferably less than 150 mmol / kg.
　また、前記ウレタン樹脂（Ａ）を製造する際には、硬度、伸度及び屈曲性に優れた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用いることができる。 Moreover, when manufacturing the said urethane resin (A), since the coating film excellent in hardness, elongation, and flexibility can be formed, it is necessary in addition to the said polyol (a1) and the said polyisocyanate (a2). Chain extenders can be used accordingly.
　前記鎖伸長剤としては、例えば、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が挙げられる。 Examples of the chain extender include polyamines, hydrazine compounds, and other compounds containing active hydrogen atoms.
　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, isophorone diamine, 4,4'-dicyclohexylmethanediamine, 3,3'- Diamines such as dimethyl-4,4'-dicyclohexylmethanediamine and 1,4-cyclohexanediamine; N-hydroxymethylaminoethylamine, N-hydroxyethylaminoethylamine, N-hydroxypropylaminopropylamine, N-ethylaminoethylamine, N Methylaminopropylamine; diethylenetriamine, dipropylenetriamine, triethylenetetramine and the like. In addition, 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, adipic acid dihydrazide, glutaric acid dihydrazide, sebacic acid dihydrazide, isophthalic acid dihydrazide; β-semicarbazide Propionic acid hydrazide and the like can be mentioned. 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、本発明の水性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, sucrose, and the like. 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 aqueous resin composition of the present invention may be used alone or in combination of two or more, as long as storage stability of the aqueous resin composition of the present invention does not decrease.
　前記ウレタン樹脂（Ａ）を製造する際、メタノール、エタノール、プロパノール、ブタノール等のアルコール化合物；エチレングリコール、１，３－プロパンジオール、１，３－ブタンジオール、１，４－ブタンジオール等のジオール化合物を反応停止剤として用いてもよい。 In the production of the urethane resin (A), alcohol compounds such as methanol, ethanol, propanol and butanol; diol compounds such as ethylene glycol, 1,3-propanediol, 1,3-butanediol and 1,4-butanediol May be used as a reaction terminator.
　前記反応停止剤の量は、前記ポリオール（ａ１）及び前記ポリイソシアネート（ａ２）の合計１００質量部に対して、好ましくは０．１質量部以上であり、好ましくは１質量部以下、より好ましくは０．８質量部以下である。 The amount of the reaction terminator is preferably 0.1 parts by mass or more, preferably 1 part by mass or less, more preferably 100 parts by mass in total of the polyol (a1) and the polyisocyanate (a2). It is 0.8 parts by mass or less.
　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 organic solvents that can be used when producing the urethane resin (A) include ketone solvents such as acetone and methyl ethyl ketone; ether solvents such as tetrahydrofuran and dioxane; acetic acid ester solvents such as ethyl acetate and butyl acetate; acetonitrile and the like Nitrile solvents; amide solvents such as dimethylformamide, N-methylpyrrolidone and the like, and the like. These organic solvents can be used alone or in combination of two or more.
　また、前記有機溶剤は、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, in order to reduce the load on the safety and the environment, the organic solvent may be partially or entirely removed of the organic solvent, for example, by distillation under reduced pressure during or after the production of the urethane resin (A). May be
　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、イソプロパノール等のアルコール溶剤；アセトン、メチルエチルケトン等のケトン溶剤；エチレングリコール、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溶剤；Ｎ－メチル－２－ピロリドン等のラクタム溶剤などが挙げられる。これらの水と混和する有機溶剤は、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 aqueous medium (B) include water, an organic solvent miscible with water, and a mixture thereof. Examples of the organic solvent miscible with water include alcohol solvents such as methanol, ethanol, n-propanol and isopropanol; ketone solvents such as acetone and methyl ethyl ketone; polyalkylene glycols such as ethylene glycol, diethylene glycol and propylene glycol; And alkyl ether solvents; and lactam solvents such as N-methyl-2-pyrrolidone. These organic solvents miscible with water can be used alone or in combination of two or more.
　また、前記水性媒体（Ｂ）は、安全性や環境に対する負荷低減を考慮すると、水のみ、又は、水及び水と混和する有機溶剤との混合物が好ましく、水のみがより好ましい。前記水性媒体（Ｂ）中、水の含有率は、好ましくは８０質量％以上、より好ましくは９０質量％以上であり、上限は１００質量％である。 The aqueous medium (B) is preferably water alone or a mixture of water and an organic solvent miscible with water, and more preferably only water, in consideration of safety and reduction of environmental load. In the aqueous medium (B), the content of water is preferably 80% by mass or more, more preferably 90% by mass or more, and the upper limit is 100% by mass.
　前記水性媒体（Ｂ）は、本発明のウレタン脂組成物全量中に３０～８０質量％の範囲で含まれることが好ましく、５０～７０質量％の範囲で含まれることがより好ましい。 The aqueous medium (B) is preferably contained in the range of 30 to 80% by mass, and more preferably in the range of 50 to 70% by mass, in the total amount of the urethane oil composition of the present invention.
　また、本発明のウレタン樹脂組成物には、必要に応じて、架橋剤、可塑剤、帯電防止剤、ワックス、界面活性剤、光安定剤、流動調整剤、染料、レベリング剤、レオロジーコントロール剤、紫外線吸収剤、酸化防止剤、光触媒性化合物、無機顔料、有機顔料、体質顔料等の各種の添加剤等を用いることができる。前記添加剤を含む場合、その含有量は、前記ウレタン樹脂（Ａ）１００質量部に対して、好ましくは３０質量部以下、より好ましくは２０質量部以下である。 In the urethane resin composition of the present invention, if necessary, a crosslinking agent, a plasticizer, an antistatic agent, a wax, a surfactant, a light stabilizer, a flow control agent, a dye, a leveling agent, a rheology control agent, Various additives such as an ultraviolet light absorber, an antioxidant, a photocatalytic compound, an inorganic pigment, an organic pigment, and an extender pigment can be used. When the additive is contained, the content thereof is preferably 30 parts by mass or less, more preferably 20 parts by mass or less, with respect to 100 parts by mass of the urethane resin (A).
　前記架橋剤としては、例えば、アミノ樹脂、アジリジン化合物、メラミン化合物、エポキシ化合物、オキサゾリン化合物、カルボジイミド化合物、イソシアネート化合物等が挙げられる。 As said crosslinking agent, an amino resin, an aziridine compound, a melamine compound, an epoxy compound, an oxazoline compound, a carbodiimide compound, an isocyanate compound etc. are mentioned, for example.
　また、前記界面活性剤を使用することで、本発明のウレタン樹脂組成物の配合安定性をより一層向上できる。界面活性剤を使用する場合は、得られる塗膜の基材密着性を維持できることから、前記ウレタン樹脂（Ａ）１００質量部に対して、２０質量部以下の範囲で使用することが好ましく、できるだけ使用しないことが好ましい。 Moreover, the compounding stability of the urethane resin composition of this invention can be further improved by using the said surfactant. When a surfactant is used, it is preferably used in a range of 20 parts by mass or less with respect to 100 parts by mass of the urethane resin (A) because the adhesion to a substrate of the obtained coating can be maintained. It is preferred not to use.
　本発明のウレタン樹脂組成物には、本発明の効果を損なわない範囲で、必要に応じて硬化剤や硬化触媒を併用しても良い。 In the urethane resin composition of the present invention, a curing agent and a curing catalyst may be used in combination as needed, as long as the effects of the present invention are not impaired.
　前記硬化剤としては、例えば、シラノール基及び／または加水分解性シリル基を有する化合物、ポリエポキシ化合物、ポリオキサゾリン化合物、ポリイソシアネート等が挙げられる。 Examples of the curing agent include a compound having a silanol group and / or a hydrolyzable silyl group, a polyepoxy compound, a polyoxazoline compound, and a polyisocyanate.
　なかでも、前記硬化剤としては、シラノール基及び／または加水分解性シリル基を有する化合物を用いることが、耐食性に優れた架橋塗膜を形成する上で好ましい。特に、本発明のウレタン樹脂組成物を鋼板表面処理剤に用いる場合には、前記化合物の加水分解性シリル基またはシラノール基が、基材の金属との密着性を向上させ、その結果、耐食性に優れた塗膜を形成することができる。 Among them, it is preferable to use a compound having a silanol group and / or a hydrolyzable silyl group as the curing agent in order to form a crosslinked coating film excellent in corrosion resistance. In particular, when the urethane resin composition of the present invention is used as a steel sheet surface treatment agent, the hydrolyzable silyl group or silanol group of the compound improves the adhesion to the metal of the base material, resulting in corrosion resistance. An excellent coating film can be formed.
　前記加水分解性シリル基としては、例えば、アルコキシシリル基が、架橋性が高く、耐食性が向上するため好ましい。特にアルコキシシリル基としては、トリメトキシシリル基、トリエトキシシリル基が、架橋性に優れ耐食性が向上するため好ましい。 As the hydrolyzable silyl group, for example, an alkoxysilyl group is preferable because of its high crosslinkability and improved corrosion resistance. In particular, as the alkoxysilyl group, a trimethoxysilyl group and a triethoxysilyl group are preferable because they are excellent in the crosslinkability and the corrosion resistance is improved.
　前記シラノール基及び／または加水分解性シリル基を有する化合物としては、例えば、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、γ－グリシドキシプロピルメチルジメトキシシラン、γ－グリシドキシプロピルメチルジエトキシシラン、２－（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、２－（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等のエポキシシラン化合物、γ－アミノプロピルトリメトキシシラン、γ－アミノプロピルトリエトキシシラン、γ－アミノプロピルメチルジメトキシシラン、γ－アミノプロピルメチルジエトキシシラン等のアミノシランなどが挙げられる。 Examples of the compound having a silanol group and / or a hydrolyzable silyl group include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, and γ -Epoxysilane compounds such as glycidoxypropylmethyldiethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, γ-aminopropyltriethylsilane Examples include aminosilanes such as methoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropylmethyldimethoxysilane, and γ-aminopropylmethyldiethoxysilane.
　なかでも、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、及び２－（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が、塗膜の架橋密度が向上して耐薬品性や耐食性が良好となるため好ましい。 Among them, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane improve the crosslink density of the coating film and thus resist It is preferable because chemical properties and corrosion resistance are improved.
　前記シラノール基及び／または加水分解性シリル基を有する化合物は、耐食性に優れた塗膜を形成し、かつ配合安定性に優れた本発明のウレタン樹脂組成物を得るうえで、ウレタン樹脂（Ａ）１００質量部に対して０．０１質量部～１０質量部の範囲で用いることが好ましい。 The compound having a silanol group and / or a hydrolyzable silyl group forms a coating film excellent in corrosion resistance, and a urethane resin (A) for obtaining a urethane resin composition of the present invention excellent in compounding stability. It is preferable to use in the range of 0.01 parts by mass to 10 parts by mass with respect to 100 parts by mass.
　また、本発明のウレタン樹脂組成物に使用可能な硬化触媒としては、例えば、水酸化リチウム、水酸化ナトリウム、水酸カリウム、ナトリウムメチラート、テトライソプロピルチタネート、テトラ－ｎ－ブチルチタネート、オクチル酸錫、オクチル酸鉛、オクチル酸コバルト、オクチル酸亜鉛、オクチル酸カルシウム、ナフテン酸亜鉛、ナフテン酸コバルト、ジ－ｎ－ブチル錫ジアセテート、ジ－ｎ－ブチル錫ジオクトエート、ジ－ｎ－ブチル錫ジラウレート、ジ－ｎ－ブチル錫マレエート、ｐ－トルエンスルホン酸、トリクロル酢酸、燐酸、モノアルキル燐酸、ジアルキル燐酸、モノアルキル亜燐酸、ジアルキル亜燐酸等が挙げられる。 Further, as a curing catalyst usable for the urethane resin composition of the present invention, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methylate, tetraisopropyl titanate, tetra-n-butyl titanate, tin octylate , Lead octylate, cobalt octylate, zinc octylate, calcium octylate, zinc naphthenate, cobalt naphthenate, di-n-butyltin diacetate, di-n-butyltin dioctoate, di-n-butyltin dilaurate, Examples include di-n-butyltin maleate, p-toluenesulfonic acid, trichloroacetic acid, phosphoric acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, monoalkyl phosphorous acid, dialkyl phosphorous acid and the like.
　また、本発明のウレタン樹脂組成物は、必要に応じて乳化剤、分散安定剤やレベリング剤を含んでいても良いが、架橋塗膜の耐水性の低下を抑制する観点から、できるだけ含まないことが好ましく、前記ウレタン樹脂組成物の不揮発分に対して０．５質量％以下であることが好ましい。 The urethane resin composition of the present invention may optionally contain an emulsifier, a dispersion stabilizer and a leveling agent, but from the viewpoint of suppressing the decrease in water resistance of the crosslinked coating, it may not be contained as much as possible. Preferably, it is 0.5 mass% or less with respect to the non volatile matter of the said urethane resin composition.
　本発明のウレタン樹脂組成物は、各種基材の表面保護、各種基材への意匠性付与を目的として各種基材の塗装に用いることができる。 The urethane resin composition of the present invention can be used for coating of various substrates for the purpose of surface protection of various substrates and imparting of designability to various substrates.
　前記基材としては、例えば、亜鉛めっき鋼板やアルミニウム－亜鉛めっき鋼板、亜鉛－アルミニウム－マグネシウム合金めっき鋼板、アルミ板、アルミ合金板、電磁鋼板、銅板、ステンレス鋼板等の金属基材、各種プラスチックやそのフィルム、ガラス、紙、木材などが挙げられる。 Examples of the substrate include metal substrates such as galvanized steel plate, aluminum-galvanized steel plate, zinc-aluminum-magnesium alloy plated steel plate, aluminum plate, aluminum alloy plate, electromagnetic steel plate, copper plate, stainless steel plate, and various plastics The film, glass, paper, wood etc. are mentioned.
　また、本発明のウレタン樹脂組成物は、例えば、外壁、屋根等の建築部材、ガードレール、防音壁、排水溝等の土木部材、家電製品、産業機械、自動車外装材等の各種物品の表面塗装などに好適に用いることができる。 In addition, the urethane resin composition of the present invention is, for example, surface coating of various articles such as building members such as outer wall and roof, civil engineering members such as guardrails, sound barriers and drainage grooves, home appliances, industrial machines, automobile exterior materials, etc. Can be suitably used.
　また、本発明のウレタン樹脂組成物は、前記金属基材の表面の劣化を防止可能な耐食性及び耐薬品性に優れた塗膜を形成できることから、鋼板表面処理剤として用いることができる。 Moreover, since the urethane resin composition of this invention can form the coating film excellent in the corrosion resistance and chemical resistance which can prevent deterioration of the surface of the said metal base material, it can be used as a steel plate surface treatment agent.
　本発明の鋼板表面処理剤は、その架橋塗膜が５μｍ程度の膜厚であっても、耐酸性や耐アルカリ性等を含む耐薬品性に優れた塗膜を形成することができる。また、架橋塗膜が１μｍ程度の膜厚であっても、耐酸性や耐アルカリ性等を含む耐薬品性に優れた塗膜を形成することができる。 The steel sheet surface treatment agent of the present invention can form a coating film excellent in chemical resistance including acid resistance, alkali resistance and the like even when the cross-linked coating film has a thickness of about 5 μm. In addition, even if the crosslinked coating film has a thickness of about 1 μm, a coating film excellent in chemical resistance including acid resistance, alkali resistance and the like can be formed.
　本発明の鋼板表面処理剤は、基材上に塗工され、乾燥、硬化されることにより塗膜を形成することができる。 The steel sheet surface treatment agent of the present invention can be coated on a substrate, dried and cured to form a coating film.
　前記塗工方法としては、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 coating method include a spray method, a curtain coater method, a flow coater method, a roll coater method, a brush coating method, and an immersion method.
　前記乾燥は、常温下で自然乾燥でも良いが、加熱乾燥させることもできる。加熱乾燥は、通常４０～２５０℃で、１～６００秒程度の時間で行うことが好ましい。 The drying may be natural drying at normal temperature, but may be heat drying. The heat drying is preferably carried out usually at 40 to 250 ° C. for about 1 to 600 seconds.
　本発明の鋼板表面処理剤の塗膜を有する鋼板としては、例えば、自動車、家電、建材等の用途に使用される亜鉛めっき鋼板、アルミニウム－亜鉛合金鋼板等のめっき鋼板、亜鉛－アルミニウム－マグネシウム合金めっき鋼板、アルミ板、アルミ合金板、電磁鋼板、銅板、ステンレス鋼板等が挙げられる。 The steel plate having a coating of the steel plate surface treatment agent of the present invention includes, for example, galvanized steel plates used for applications such as automobiles, home appliances and building materials, plated steel plates such as aluminum-zinc alloy steel plates, zinc-aluminum-magnesium alloy A plated steel plate, an aluminum plate, an aluminum alloy plate, an electromagnetic steel plate, a copper plate, a stainless steel plate etc. are mentioned.
　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 examples and comparative examples.
（合成例１：芳香族ポリエステルポリオール（１）の合成）
　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、エチレングリコール１３質量部とネオペンチルグリコール２２質量部とイソフタル酸２３質量部とテレフタル酸２３質量部とアジピン酸１０質量部とを反応させて芳香族ポリエステルポリオール（１）〔数平均分子量；１，０００、芳香環濃度；３．５ｍｏｌ／ｋｇ〕を得た。 Synthesis Example 1: Synthesis of Aromatic Polyester Polyol (1)
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 13 parts by mass of ethylene glycol, 22 parts by mass of neopentyl glycol, 23 parts by mass of isophthalic acid, 23 parts by mass of terephthalic acid, and 10 parts by mass of adipic acid The resultant was reacted with parts to obtain an aromatic polyester polyol (1) (number average molecular weight: 1,000, aromatic ring concentration: 3.5 mol / kg).
（合成例２：芳香族ポリエステルポリオール（２）の合成）
　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、エチレングリコール１２質量部とジエチレングリコール２０質量部とイソフタル酸２８質量部とテレフタル酸２８質量部とを反応させて芳香族ポリエステルポリオール（２）〔数平均分子量；１，７００、芳香環濃度；４．５ｍｏｌ／ｋｇ〕を得た。 Synthesis Example 2 Synthesis of Aromatic Polyester Polyol (2)
12 parts by mass of ethylene glycol, 20 parts by mass of diethylene glycol, 28 parts by mass of isophthalic acid and 28 parts by mass of terephthalic acid are reacted in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe and a stirrer A polyester polyol (2) (number average molecular weight: 1,700, aromatic ring concentration: 4.5 mol / kg) was obtained.
（合成例３：芳香族ポリエステルポリオール（３）の合成）
　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、エチレングリコール１２質量部とネオペンチルグリコール２１質量部とイソフタル酸２７質量部とテレフタル酸２７質量部とを反応させて芳香族ポリエステルポリオール（３）〔数平均分子量；１，０００、芳香環濃度；４．３ｍｏｌ／ｋｇ〕を得た。 Synthesis Example 3 Synthesis of Aromatic Polyester Polyol (3)
12 parts by mass of ethylene glycol, 21 parts by mass of neopentyl glycol, 27 parts by mass of isophthalic acid and 27 parts by mass of terephthalic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer An aromatic polyester polyol (3) (number average molecular weight: 1,000, aromatic ring concentration: 4.3 mol / kg) was obtained.
（合成例４：芳香族ポリエステルポリオール（４）の合成）
　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、エチレングリコール１２質量部とネオペンチルグリコール２４質量部とイソフタル酸３２質量部とテレフタル酸３２質量部とを反応させて芳香族ポリエステルポリオール（４）〔数平均分子量；２，６００、芳香環濃度；３．４ｍｏｌ／ｋｇ〕を得た。 Synthesis Example 4 Synthesis of Aromatic Polyester Polyol (4)
12 parts by mass of ethylene glycol, 24 parts by mass of neopentyl glycol, 32 parts by mass of isophthalic acid and 32 parts by mass of terephthalic acid are reacted in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer. An aromatic polyester polyol (4) (number average molecular weight: 2,600, aromatic ring concentration: 3.4 mol / kg) was obtained.
（合成例５：芳香族ポリエステルポリオール（５）の合成）
　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、ジエチレングリコール５３質量部とオルソフタル酸４７質量部とを反応させて芳香族ポリエステルポリオール（５）〔数平均分子量；５４０、芳香環濃度；３．１ｍｏｌ／ｋｇ〕を得た。 Synthesis Example 5 Synthesis of Aromatic Polyester Polyol (5)
In a nitrogen-substituted container equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 53 parts by mass of diethylene glycol and 47 parts by mass of orthophthalic acid are reacted to obtain an aromatic polyester polyol (5) [number average molecular weight; Aromatic ring concentration; 3.1 mol / kg] was obtained.
（合成例６：芳香族ポリエステルポリオール（６）の合成）
　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、２，２’－［イソプロピリデンビス［（ｐ－フェニレン）（オキシ）］］ジエタノール７３質量部と２，６－ナフタレンジカルボン酸ジメチル１６質量部とテレフタル酸９質量部と無水フタル酸２質量部とを反応させて芳香族ポリエステルポリオール（６）〔数平均分子量；１，０００、芳香環濃度；６．８ｍｏｌ／ｋｇ〕を得た。 Synthesis Example 6: Synthesis of Aromatic Polyester Polyol (6)
In a nitrogen-substituted vessel equipped with a thermometer, a nitrogen gas inlet tube, and a stirrer, 73 parts by mass of 2,2 ′-[isopropylidenebis [(p-phenylene) (oxy)] diethanol and 2,6- 16 parts by mass of dimethyl naphthalenedicarboxylate, 9 parts by mass of terephthalic acid and 2 parts by mass of phthalic anhydride are reacted to obtain an aromatic polyester polyol (6) [number average molecular weight: 1,000, aromatic ring concentration: 6.8 mol / kg I got
（合成例７：リエステルポリオール（７）の合成）
　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３２質量部とネオペンチルグリコール１５質量部とアジピン酸５３質量部とを反応させてポリエステルポリオール（７）〔数平均分子量；２，０００、芳香環濃度；０ｍｏｌ／ｋｇ〕を得た。 Synthesis Example 7: Synthesis of liester polyol (7)
32 parts by mass of 1,6-hexanediol, 15 parts by mass of neopentyl glycol, and 53 parts by mass of adipic acid in a nitrogen-substituted container equipped with a thermometer, a nitrogen gas introduction pipe, and a stirrer to react with polyester polyol (7) [Number average molecular weight; 2,000, aromatic ring concentration: 0 mol / kg] was obtained.
（実施例１：ウレタン樹脂組成物（１）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）７９．６質量部、２，２－ジメチロールプロピオン酸３．１質量部、及びヘキサメチレンジイソシアネート１７．３質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 1 Preparation of Urethane Resin Composition (1)
79.6 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1 in a reaction vessel, 3.1 parts by mass of 2,2-dimethylol propionic acid, 17.3 parts by mass of hexamethylene diisocyanate, 67 parts by mass of methyl ethyl ketone Were reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、メタノール０．２質量部を添加し６０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水を８質量部加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（１）を得た。このウレタン樹脂組成物（１）の酸価は、１３ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.2 parts by mass of methanol was added to the organic solvent solution of the urethane prepolymer and reacted at 60 ° C. to completely quench the isocyanate component. Next, the reaction product is cooled to 40 ° C., and 8 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (1) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (1) was 13 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例２：ウレタン樹脂組成物（２）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）７５．１質量部、２，２－ジメチロールプロピオン酸３．１質量部、及びイソホロンジイソシアネート２１．８質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 2 Preparation of Urethane Resin Composition (2)
In a reaction vessel, 75.1 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 3.1 parts by mass of 2,2-dimethylol propionic acid, 21.8 parts by mass of isophorone diisocyanate, and 67 parts by mass of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、メタノール０．２質量部を添加し６０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水を８質量部加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（２）を得た。このウレタン樹脂組成物（２）の酸価は、１３ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.2 parts by mass of methanol was added to the organic solvent solution of the urethane prepolymer and reacted at 60 ° C. to completely quench the isocyanate component. Next, the reaction product is cooled to 40 ° C., and 8 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (2) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (2) was 13 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例３：ウレタン樹脂組成物（３）の調製）
　反応容器に合成例２で得た芳香族ポリエステルポリオール（２）７１．９質量部、２，２－ジメチロールプロピオン酸３．１質量部、及び４，４’－ジシクロヘキシルメタンジイソシアネート２５．０質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 3 Preparation of Urethane Resin Composition (3)
71.9 parts by mass of the aromatic polyester polyol (2) obtained in Synthesis Example 2 in a reaction vessel, 3.1 parts by mass of 2,2-dimethylol propionic acid, and 25.0 parts by mass of 4,4'-dicyclohexylmethane diisocyanate By charging 67 parts by mass of methyl ethyl ketone and reacting at 70 ° C., an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end was obtained.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、メタノール０．２質量部を添加し６０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水を８質量部加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（３）を得た。このウレタン樹脂組成物（３）の酸価は、１３ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.2 parts by mass of methanol was added to the organic solvent solution of the urethane prepolymer and reacted at 60 ° C. to completely quench the isocyanate component. Next, the reaction product is cooled to 40 ° C., and 8 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (3) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (3) was 13 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例４：ウレタン樹脂組成物（４）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）７９．３質量部、２，２－ジメチロールプロピオン酸３．１質量部、ヘキサメチレンジイソシアネート８．８質量部及びトルエンジイソシアネート８．８質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 4 Preparation of Urethane Resin Composition (4)
79.3 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1 in a reaction vessel, 3.1 parts by mass of 2,2-dimethylol propionic acid, 8.8 parts by mass of hexamethylene diisocyanate, and 8.8 parts by weight of toluene diisocyanate A mass part and 67 mass parts of methyl ethyl ketone were charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular terminal.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水を８質量部加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（４）を得た。このウレタン樹脂組成物（４）の酸価は、１３ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, the reaction product is cooled to 40 ° C., and 8 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (4) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (4) was 13 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例５：ウレタン樹脂組成物（５）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）８２．７質量部、２，２－ジメチロールプロピオン酸４．３質量部、ヘキサメチレンジイソシアネート６．５質量部及びキシリレンジイソシアネート６．５質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 5 Preparation of Urethane Resin Composition (5)
6. 82.7 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 4.3 parts by mass of 2,2-dimethylol propionic acid, 6.5 parts by mass of hexamethylene diisocyanate, and xylylene diisocyanate in a reaction vessel. Five parts by mass and 67 parts by mass of methyl ethyl ketone were charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular terminal.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水を１１質量部加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（５）を得た。このウレタン樹脂組成物（５）の酸価は、１８ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 11 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups possessed by the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (5) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (5) was 18 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例６：ウレタン樹脂組成物（６）の調製）
　反応容器に合成例２で得た芳香族ポリエステルポリオール（２）７４．６質量部、２，２－ジメチロールプロピオン酸４．３質量部、イソホロンジイソシアネート６．３質量部及びキシリレンジイソシアネート１４．７質量部、メチルエチルケトン６７質量部の混合溶液中を仕込み７０℃で反応させることによって、分子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。 Example 6 Preparation of Urethane Resin Composition (6)
74.6 parts by mass of the aromatic polyester polyol (2) obtained in Synthesis Example 2 in a reaction vessel, 4.3 parts by mass of 2,2-dimethylol propionic acid, 6.3 parts by mass of isophorone diisocyanate, and 14.7 parts of xylylene diisocyanate The mixed solution of parts by mass and 67 parts by mass of methyl ethyl ketone was charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular terminal.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水を１１質量部加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（６）を得た。このウレタン樹脂組成物（６）の酸価は、１８ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 11 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups possessed by the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (6) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (6) was 18 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例７：ウレタン樹脂組成物（７）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）６９．８質量部、２，２－ジメチロールプロピオン酸４．３質量部、４，４’－ジシクロヘキシルメタンジイソシアネート７．８質量部及びジフェニルメタンジイソシアネート１８．１質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 7 Preparation of Urethane Resin Composition (7)
69.8 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1 in a reaction vessel, 4.3 parts by mass of 2,2-dimethylol propionic acid, 7.8 parts by mass of 4,4'-dicyclohexylmethane diisocyanate, 18.1 parts by mass of diphenylmethane diisocyanate and 67 parts by mass of methyl ethyl ketone were charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular terminal.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、トリエチルアミンを３質量部加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（７）を得た。このウレタン樹脂組成物（７）の酸価は、１８ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 3 parts by mass of triethylamine is added to neutralize part or all of the carboxyl groups possessed by the urethane prepolymer, and further 333 parts by mass of water is added to sufficiently stir the urethane resin. A water dispersion was obtained, and then aging and solvent removal to obtain a urethane resin composition (7) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (7) was 18 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例８：ウレタン樹脂組成物（８）の調製）
　反応容器に合成例３で得た芳香族ポリエステルポリオール（３）７５．０質量部、２，２－ジメチロールプロピオン酸５．５質量部、及びヘキサメチレンジイソシアネート１９．５質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 8 Preparation of Urethane Resin Composition (8)
75.0 parts by mass of the aromatic polyester polyol (3) obtained in Synthesis Example 3 in a reaction vessel, 5.5 parts by mass of 2,2-dimethylol propionic acid, and 19.5 parts by mass of hexamethylene diisocyanate, 67 parts by mass of methyl ethyl ketone Were reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水を１４質量部加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分２０質量％のウレタン樹脂組成物（８）を得た。このウレタン樹脂組成物（８）の酸価は、２３ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 14 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred. A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (8) having a nonvolatile content of 20% by mass. The acid value of this urethane resin composition (8) was 23 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例９：ウレタン樹脂組成物（９）の調製）
　反応容器に合成例４で得た芳香族ポリエステルポリオール（４）８２．３質量部、２，２－ジメチロールプロピオン酸５．５質量部、及びヘキサメチレンジイソシアネート１２．２質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 9 Preparation of Urethane Resin Composition (9)
In a reaction vessel, 82.3 parts by mass of the aromatic polyester polyol (4) obtained in Synthesis Example 4, 5.5 parts by mass of 2,2-dimethylol propionic acid, 12.2 parts by mass of hexamethylene diisocyanate, and 67 parts by mass of methyl ethyl ketone Were reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水を１４質量部加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分２０質量％のウレタン樹脂組成物（９）を得た。このウレタン樹脂組成物（９）の酸価は、２３ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 14 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred. A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (9) having a nonvolatile content of 20% by mass. The acid value of this urethane resin composition (9) was 23 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例１０：ウレタン樹脂組成物（１０）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）７１．５質量部、２，２－ジメチロールプロピオン酸３．６質量部、及びイソホロンジイソシアネート２４．４質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 10 Preparation of Urethane Resin Composition (10)
In a reaction vessel, 71.5 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 3.6 parts by mass of 2,2-dimethylol propionic acid, 24.4 parts by mass of isophorone diisocyanate, and 67 parts by mass of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液を４０℃に冷却し、５％アンモニア水を９質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに１０％ピペラジン水溶液５質量部及び水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（１０）を得た。このウレタン樹脂組成物（１０）の酸価は、１５ｍｇＫＯＨ／ｇであり、ウレア結合量は、５９ｍｍｏｌ／ｋｇであった。 Then, the organic solvent solution of the urethane prepolymer is cooled to 40 ° C., and 9 parts by mass of 5% aqueous ammonia is added to neutralize some or all of the carboxyl groups of the urethane prepolymer, and further 10%. An aqueous dispersion of a urethane resin is obtained by adding 5 parts by mass of an aqueous solution of piperazine and 333 parts by mass of water to obtain an aqueous dispersion of a urethane resin, and then aging and desolvation to obtain a urethane resin composition (30) I got The acid value of this urethane resin composition (10) was 15 mg KOH / g, and the amount of urea bonds was 59 mmol / kg.
（実施例１１：ウレタン樹脂組成物（１１）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）６９．３質量部、２，２－ジメチロールプロピオン酸３．６質量部、及びイソホロンジイソシアネート２６．５質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 11 Preparation of Urethane Resin Composition (11)
In a reaction vessel, 69.3 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 3.6 parts by mass of 2,2-dimethylol propionic acid, 26.5 parts by mass of isophorone diisocyanate, and 67 parts by mass of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液を４０℃に冷却し、トリエチルアミン３質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに８０％ヒドラジン水溶液０．８質量部及び水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（１１）を得た。このウレタン樹脂組成物（１１）の酸価は、１５ｍｇＫＯＨ／ｇであり、ウレア結合量は、２１０ｍｍｏｌ／ｋｇであった。 Then, the organic solvent solution of the urethane prepolymer is cooled to 40 ° C., and 3 parts by mass of triethylamine is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 80% aqueous hydrazine solution 0. A water dispersion of a urethane resin is obtained by adding 8 parts by mass and 333 parts by mass of water and stirring sufficiently to obtain a urethane resin composition (11) having a nonvolatile content of 30% by mass by aging and desolvation. The The acid value of this urethane resin composition (11) was 15 mg KOH / g, and the amount of urea bonds was 210 mmol / kg.
（実施例１２：ウレタン樹脂組成物（１２）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）８４．４質量部、２，２－ジメチロールプロピオン酸３．６質量部、ヘキサメチレンジイソシアネート１．２質量部及びトルエンジイソシアネート１０．８質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 12 Preparation of Urethane Resin Composition (12)
84.4 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1 in a reaction vessel, 3.6 parts by mass of 2,2-dimethylol propionic acid, 1.2 parts by mass of hexamethylene diisocyanate and 10.8 parts of toluene diisocyanate A mass part and 67 mass parts of methyl ethyl ketone were charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular terminal.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水を９質量部加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（１２）を得た。このウレタン樹脂組成物（１２）の酸価は、１５ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 9 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups possessed by the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (12) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (12) was 15 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例１３：ウレタン樹脂組成物（１３）の調製）
　反応容器に合成例５で得た芳香族ポリエステルポリオール（５）８３．２質量部、２，２－ジメチロールプロピオン酸４．３質量部、ヘキサメチレンジイソシアネート１１．３質量部及びトルエンジイソシアネート１．３質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 13 Preparation of Urethane Resin Composition (13)
83.2 parts by mass of the aromatic polyester polyol (5) obtained in Synthesis Example 5 in a reaction vessel, 4.3 parts by mass of 2,2-dimethylol propionic acid, 11.3 parts by mass of hexamethylene diisocyanate and 1.3 parts by weight of toluene diisocyanate A mass part and 67 mass parts of methyl ethyl ketone were charged and reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at a molecular terminal.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、次いで４０℃に冷却し、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。５％アンモニア水９質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（１３）を得た。このウレタン樹脂組成物（１３）の酸価は、１５ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Then, the solution was cooled to 40 ° C., added with 0.6 parts by mass of 1,3-butanediol and reacted at 70 ° C. to completely quench the isocyanate component. A part or all of the carboxyl groups possessed by the urethane prepolymer is neutralized by adding 9 parts by mass of 5% ammonia water, and 333 parts by mass of water is further added, and the aqueous dispersion of the urethane resin is sufficiently stirred. The obtained resin composition was then aged and desolventized to obtain a urethane resin composition (13) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (13) was 15 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例１４：ウレタン樹脂組成物（１４）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）７５．１質量部、２，２－ジメチロールプロピオン酸３．１質量部、及びイソホロンジイソシアネート２１．８質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 14 Preparation of Urethane Resin Composition (14)
In a reaction vessel, 75.1 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 3.1 parts by mass of 2,2-dimethylol propionic acid, 21.8 parts by mass of isophorone diisocyanate, and 67 parts by mass of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、２－アミノ－２－メチル－１－プロパノール２質量部加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（１４）を得た。このウレタン樹脂組成物（１４）の酸価は、１３ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 2 parts by mass of 2-amino-2-methyl-1-propanol is added to neutralize some or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is sufficiently added The aqueous dispersion of the urethane resin was obtained by stirring to obtain a urethane resin composition (14) having a nonvolatile content of 30% by mass by aging and removing the solvent. The acid value of this urethane resin composition (14) was 13 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（実施例１５：ウレタン樹脂組成物（１５）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）６６．６量部、２，２－ジメチロールプロピオン酸３．６質量部、及びイソホロンジイソシアネート２７．６質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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。 Example 15 Preparation of Urethane Resin Composition (15)
In a reaction vessel, 66.6 parts by weight of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 3.6 parts by weight of 2,2-dimethylol propionic acid, 27.6 parts by weight of isophorone diisocyanate, and 67 parts by weight of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液を４０℃に冷却し、５％アンモニア水９質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに１０％ピペラジン水溶液２３質量部及び水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（１５）を得た。このウレタン樹脂組成物（１５）の酸価は、１５ｍｇＫＯＨ／ｇであり、ウレア結合量は、２６２ｍｍｏｌ／ｋｇであった。 Next, the organic solvent solution of the urethane prepolymer is cooled to 40 ° C., and 9 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 10% piperazine An aqueous dispersion of a urethane resin is obtained by adding 23 parts by mass of an aqueous solution and 333 parts by mass of water to obtain an aqueous dispersion of a urethane resin, and then aging and desolvation to obtain a urethane resin composition (15) having a nonvolatile content of 30% by mass. Obtained. The acid value of this urethane resin composition (15) was 15 mg KOH / g, and the amount of urea bond was 262 mmol / kg.
（比較例１：ウレタン樹脂組成物（Ｃ１）の調製）
　反応容器に合成例６で得た芳香族ポリエステルポリオール（６）７８．７質量部、２，２－ジメチロールプロピオン酸３．６質量部、及びヘキサメチレンジイソシアネート１７．７質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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: Preparation of Urethane Resin Composition (C1)
78.7 parts by mass of the aromatic polyester polyol (6) obtained in Synthesis Example 6 in a reaction vessel, 3.6 parts by mass of 2,2-dimethylol propionic acid, 17.7 parts by mass of hexamethylene diisocyanate, 67 parts by mass of methyl ethyl ketone Were reacted at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水９質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（Ｃ１）を得た。このウレタン樹脂組成物（Ｃ１）の酸価は、１５ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 9 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred. A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (C1) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (C1) was 15 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（比較例２：ウレタン樹脂組成物（Ｃ２）の調製）
　反応容器に合成例３で得た芳香族ポリエステルポリオール（３）７８．１質量部、２，２－ジメチロールプロピオン酸３．６質量部、及びトルエンジイソシアネート１８．３質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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 2: Preparation of Urethane Resin Composition (C2)
In a reaction vessel, 78.1 parts by mass of the aromatic polyester polyol (3) obtained in Synthesis Example 3, 3.6 parts by mass of 2,2-dimethylol propionic acid, 18.3 parts by mass of toluene diisocyanate, and 67 parts by mass of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水９質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（Ｃ２）を得た。このウレタン樹脂組成物（Ｃ２）の酸価は、１５ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 9 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred. A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (C2) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (C2) was 15 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（比較例３：ウレタン樹脂組成物（Ｃ３）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）８１．９質量部、２，２－ジメチロールプロピオン酸１．９質量部、及びヘキサメチレレンジイソシアネート１６．２質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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 3 Preparation of Urethane Resin Composition (C3)
In a reaction vessel, 81.9 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1, 1.9 parts by mass of 2,2-dimethylol propionic acid, 16.2 parts by mass of hexamethylene diisocyanate, and 67 parts by mass of methyl ethyl ketone Parts were charged and reacted at 70 ° C. to obtain an organic solvent solution of urethane prepolymer having an isocyanate group at the molecular terminal.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水５質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（Ｃ３）を得た。このウレタン樹脂組成物（Ｃ３）の酸価は、８ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 5 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred. A water dispersion of a urethane resin was obtained, followed by aging and solvent removal to obtain a urethane resin composition (C3) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (C3) was 8 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（比較例４：ウレタン樹脂組成物（Ｃ４）の調製）
　反応容器に合成例１で得た芳香族ポリエステルポリオール（１）７２．７質量部、２，２－ジメチロールプロピオン酸６．７質量部、及びヘキサメチレレンジイソシアネート２０．６質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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 4: Preparation of Urethane Resin Composition (C4)
72.7 parts by mass of the aromatic polyester polyol (1) obtained in Synthesis Example 1 in a reaction vessel, 6.7 parts by mass of 2,2-dimethylol propionic acid, and 20.6 parts by mass of hexamethylene diisocyanate, 67 parts by mass of methyl ethyl ketone Parts were charged and reacted at 70 ° C. to obtain an organic solvent solution of urethane prepolymer having an isocyanate group at the molecular terminal.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水１７質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分２０質量％のウレタン樹脂組成物（Ｃ４）を得た。このウレタン樹脂組成物（Ｃ４）の酸価は、２８ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 17 parts by mass of 5% ammonia water is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred. A water dispersion of a urethane resin was obtained, and then aging and solvent removal to obtain a urethane resin composition (C4) having a nonvolatile content of 20% by mass. The acid value of this urethane resin composition (C4) was 28 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
（比較例５：ウレタン樹脂組成物（Ｃ５）の調製）
　反応容器に合成例７で得たポリエステルポリオール（７）８４．８質量部、２，２－ジメチロールプロピオン酸３．６質量部、及びヘキサメチレレンジイソシアネート１１．６質量部、メチルエチルケトン６７質量部を仕込み７０℃で反応させることによって、分子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 5 Preparation of Urethane Resin Composition (C5)
In a reaction vessel, 84.8 parts by mass of the polyester polyol (7) obtained in Synthesis Example 7, 3.6 parts by mass of 2,2-dimethylol propionic acid, 11.6 parts by mass of hexamethylene diisocyanate, and 67 parts by mass of methyl ethyl ketone The reaction was carried out at 70 ° C. to obtain an organic solvent solution of a urethane prepolymer having an isocyanate group at the molecular end.
　次いで、前記ウレタンプレポリマーの有機溶剤溶液中に、１，３－ブタンジオール０．６質量部添加し７０℃で反応させ、イソシアネート成分を完全に反応停止させた。次いで４０℃に冷却し、５％アンモニア水９質量部を加えることで前記ウレタンプレポリマーが有するカルボキシル基の一部または全部を中和し、さらに水３３３質量部を加え十分に攪拌することにより、ウレタン樹脂の水分散体を得、次いでエージング・脱溶剤することによって、不揮発分３０質量％のウレタン樹脂組成物（Ｃ５）を得た。このウレタン樹脂組成物（Ｃ５）の酸価は、１５ｍｇＫＯＨ／ｇであり、ウレア結合量は、０ｍｍｏｌ／ｋｇであった。 Next, 0.6 parts by mass of 1,3-butanediol was added to the organic solvent solution of the urethane prepolymer and reacted at 70 ° C. to completely quench the isocyanate component. Next, it is cooled to 40 ° C., and 9 parts by mass of 5% aqueous ammonia is added to neutralize part or all of the carboxyl groups of the urethane prepolymer, and further 333 parts by mass of water is added and sufficiently stirred. A water dispersion of a urethane resin was obtained, followed by aging and solvent removal to obtain a urethane resin composition (C5) having a nonvolatile content of 30% by mass. The acid value of this urethane resin composition (C5) was 15 mg KOH / g, and the amount of urea bonds was 0 mmol / kg.
　上記芳香族ポリエステルポリオールの数平均分子量は、ゲル・パーミエーション・クロマトグラフィー（ＧＰＣ）法により、以下の条件で測定して得られた値を表す。 The number average molecular weight of the aromatic polyester polyol represents a value obtained by measurement under the following conditions by gel permeation chromatography (GPC).
測定装置：高速ＧＰＣ装置（東ソー株式会社製「ＨＬＣ－８２２０ＧＰＣ」）
カラム：東ソー株式会社製の下記のカラムを直列に接続して使用する。
　「ＴＳＫｇｅｌ　Ｇ５０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ４０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ３０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　「ＴＳＫｇｅｌ　Ｇ２０００」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）×１本
　　　　検出器：ＲＩ（示差屈折計）
　　　　カラム温度：４０℃
　　　　溶離液：テトラヒドロフラン（ＴＨＦ）
　　　　流速：１．０ｍＬ／分
　　　　注入量：１００μＬ（試料濃度０．４質量％のテトラヒドロフラン溶液）
標準試料：以下の標準ポリスチレンを用いて検量線を作成する。 Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation are connected in series and used.
"TSKgel G5000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 4000" (7.8 mm ID × 30 cm) × 1 "TSK gel G 3000" (7.8 mm ID × 30 cm) × 1 This “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 Detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)
Standard sample: Prepare a calibration curve using the following standard polystyrene.
（標準ポリスチレン）
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－１０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－２５００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ａ－５０００」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－４０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－８０」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－１２８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－２８８」
　東ソー株式会社製「ＴＳＫｇｅｌ　標準ポリスチレン　Ｆ－５５０」 (Standard polystyrene)
Tosoh Corporation "TSKgel standard polystyrene A-500"
Tosoh Corporation "TSKgel standard polystyrene A-1000"
Tosoh Corporation "TSKgel standard polystyrene A-2500"
Tosoh Corporation "TSKgel standard polystyrene A-5000"
Tosoh Corporation "TSKgel standard polystyrene F-1"
Tosoh Corporation "TSKgel standard polystyrene F-2"
Tosoh Corporation "TSKgel standard polystyrene F-4"
Tosoh Corporation "TSKgel standard polystyrene F-10"
Tosoh Corporation "TSKgel standard polystyrene F-20"
Tosoh Corporation "TSKgel standard polystyrene F-40"
Tosoh Corporation "TSKgel standard polystyrene F-80"
Tosoh Corporation "TSKgel standard polystyrene F-128"
Tosoh Corporation "TSKgel standard polystyrene F-288"
Tosoh Corporation "TSKgel standard polystyrene F-550"
　上記の実施例及び比較例で得られたウレタン樹脂組成物を用いて、下記の評価を行った。 The following evaluation was performed using the urethane resin composition obtained by said Example and comparative example.
［配合安定性の評価方法］
　実施例１～１５及び比較例１～５で得られたウレタン樹脂組成物１００部に、炭酸ジルコニウムアンモニウム１０質量％水溶液を２部添加し、４０℃で６時間保管した後、２００メッシュでろ過し、下記の基準で評価した。 [Method for evaluating formulation stability]
To 100 parts of the urethane resin composition obtained in Examples 1 to 15 and Comparative Examples 1 to 5, 2 parts of a 10% by mass aqueous solution of ammonium zirconium carbonate is added, stored at 40 ° C. for 6 hours, and filtered with 200 mesh. The following criteria were evaluated.
　◎：残渣（凝集物）が１％未満であった。
　○：残渣（凝集物）が１％以上５％未満であった。
　△：残渣（凝集物）が５％以上２０％未満であった。
　×：残渣（凝集物）が２０％以上であった。 ◎: Residue (aggregates) was less than 1%.
○: Residue (aggregates) was 1% or more and less than 5%.
Δ: Residue (aggregates) was 5% or more and less than 20%.
X: Residue (aggregates) was 20% or more.
［試験体の作成］
　表面処理を施していない５５質量％アルミニウム－亜鉛系合金メッキ鋼板に実施例１～１５及び比較例１～５で得られたウレタン樹脂組成物を、１μｍ厚で塗布し、２５０℃で１０秒乾燥させ、試験体を作成した。 [Create test sample]
The urethane resin compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 5 are coated to a thickness of 1 μm on a 55% by mass aluminum-zinc based alloy plated steel sheet not subjected to surface treatment and dried at 250 ° C. for 10 seconds The test body was made.
［塗膜の耐食性の評価方法］
　前記試験体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、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。ＪＩＳ試験方法（ＪＩＳ　Ｚ２３７１：２０００）に準拠した方法にて測定。 [Method of evaluating corrosion resistance of coating film]
The surface of the coating film constituting the test body is scratched with a cutter knife to a depth reaching the substrate, and a salt spray test is carried out with a salt spray tester made by Suga Test Instruments Co., Ltd. and rusted after 240 hours The occurrence area was visually determined and evaluated. Measured according to the JIS test method (JIS Z2371: 2000).
　◎：錆の生じた面積が、塗膜表面全体の１０％未満であった。
　○：錆の生じた面積が、塗膜表面全体の１０％以上４０％未満であった。
　△：錆の生じた面積が、塗膜表面全体の４０％以上７０％未満であった。
　×：錆の生じた面積が、塗膜表面全体の７０％以上であった。 ◎: The rusted area was less than 10% of the entire coating surface.
○: The rusted area was 10% or more and less than 40% of the entire coating surface.
Δ: The area where rust was generated was 40% or more and less than 70% of the entire coating film surface.
X: The area in which rust occurred was 70% or more of the entire coating film surface.
［耐薬品性（耐アルカリ性）の評価方法］
　前記試験体を使用し、１質量％濃度の水酸化ナトリウム水溶液に５時間浸漬した後の塗膜の劣化状態を、下記の基準で目視評価した。 [Method of evaluating chemical resistance (alkali resistance)]
The deterioration state of the coating film after being immersed in a 1% by mass aqueous solution of sodium hydroxide for 5 hours was visually evaluated according to the following criteria, using the test body.
　◎：黒変や茶色への変色が生じた面積が、塗膜表面全体の１０％未満であった。
　○：黒変や茶色への変色が生じた面積が、塗膜表面全体の１０％以上４０％未満であった。
　△：黒変や茶色への変色が生じた面積が、塗膜表面全体の４０％以上７０％未満であった。
　×：黒変や茶色への変色が生じた面積が、塗膜表面全体の７０％以上であった。 ◎: The area in which the blackening or browning occurred was less than 10% of the entire coating film surface.
Good: The area in which the blackening or browning occurred was 10% or more and less than 40% of the entire coating film surface.
Fair: The area where blackening or browning occurred was 40% or more and less than 70% of the entire coating film surface.
X: The area in which the blackening or browning occurred was 70% or more of the entire coating film surface.
［耐薬品性（耐エタノール性）の評価方法］
　ポリエチレンテレフタレートからなる基材の表面に、実施例１～１５及び比較例１～５で得られたウレタン樹脂組成物を、１０μｍ厚で塗布し、８０℃で５分乾燥させ、試験体を作成した。得られた試験体の皮膜形成面を、９８体積％エタノールを含浸させた脱脂綿で、１０往復ラビング試験を行い、皮膜の状態を目視で観察し、下記の基準に従って耐溶剤性を評価した。 [Method for evaluating chemical resistance (ethanol resistance)]
The urethane resin compositions obtained in Examples 1 to 15 and Comparative Examples 1 to 5 were coated to a thickness of 10 μm on the surface of a substrate made of polyethylene terephthalate and dried at 80 ° C. for 5 minutes to prepare test specimens. . The film-forming surface of the obtained test body was rubbed with cotton wool impregnated with 98% by volume of 10, and a rubbing test was performed 10 times, the state of the film was visually observed, and the solvent resistance was evaluated according to the following criteria.
　◎：皮膜に変化無し
　○：皮膜の面にラビング後が残る
　△：素地は露出しないが、皮膜が膨潤溶解した
　×：素地が露出した :: no change in the film ○: after rubbing on the surface of the film remains 皮膜: the substrate is not exposed, but the film swells and dissolves ×: the substrate is exposed
［基材密着性の評価方法］
　前記試験体を純水に２４時間浸漬した後、塗膜をクロスカットし、テープでの剥がれ具合を下記基準にて評価した。 [Method of evaluating adhesion to substrate]
After immersing the test body in pure water for 24 hours, the coating film was cross-cut and the degree of peeling with a tape was evaluated based on the following criteria.
　◎：塗膜に異常なし。
　○：塗膜にわずかに（５％以下の面積）浮きが見られる。
　△：塗膜に少し（５％超、６０％以下の面積）浮きが見られる。
　×：塗膜に多く（６０％超の面積）浮きが見られる。 ◎: no abnormality in the coating
○: A slight (less than 5% area) floating is observed in the coating film.
Δ: A slight (more than 5%, 60% or less of area) floating is observed in the coating film.
X: Many floats (more than 60% area) are observed in the coating film.
　実施例１～１５で作製したウレタン樹脂組成物（１）～（１５）の組成及び評価結果を表１に示す。 The compositions and the evaluation results of the urethane resin compositions (1) to (15) produced in Examples 1 to 15 are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　比較例１～５で作製したウレタン樹脂組成物（Ｃ１）～（Ｃ５）の組成及び評価結果を表２に示す。 Table 2 shows the compositions and evaluation results of the urethane resin compositions (C1) to (C5) produced in Comparative Examples 1 to 5.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表１に示した実施例１～１５の評価結果から、本発明のウレタン樹脂組成物は、配合安定性に優れており、また、本発明のウレタン樹脂組成物を用いて得られた塗膜は、耐食性、耐薬品性及び基材密着性に優れることが確認できた。 From the evaluation results of Examples 1 to 15 shown in Table 1, the urethane resin composition of the present invention is excellent in formulation stability, and a coating film obtained using the urethane resin composition of the present invention is It was confirmed that the steel was excellent in corrosion resistance, chemical resistance and adhesion to a substrate.
　一方、比較例１は、芳香族ポリエステルポリオール中の芳香環濃度が、本発明の範囲を上回る６．８ｍｏｌ／ｋｇのものを用いた例である。この比較例１のウレタン樹脂組成物を用いて得られた塗膜は、耐薬品性（耐エタノール性）及び基材密着性には優れるものの、耐食性及び耐薬品性（耐アルカリ性）は著しく不十分であることが確認できた。 On the other hand, Comparative Example 1 is an example in which the concentration of the aromatic ring in the aromatic polyester polyol was 6.8 mol / kg exceeding the range of the present invention. The coating film obtained using the urethane resin composition of Comparative Example 1 is excellent in chemical resistance (ethanol resistance) and substrate adhesion, but corrosion resistance and chemical resistance (alkali resistance) are extremely insufficient. Was confirmed.
　比較例２は、脂肪族ポリイソシアネート及び／または脂環式構造を有するポリイソシアネートを用いない例である。この比較例２のウレタン樹脂組成物を用いて得られた塗膜は、比較例１と同様に、耐薬品性（耐エタノール性）及び基材密着性には優れるものの、耐食性及び耐薬品性（耐アルカリ性）は著しく不十分であることが確認できた。 The comparative example 2 is an example which does not use aliphatic polyisocyanate and / or polyisocyanate which has an alicyclic structure. The coating film obtained using the urethane resin composition of Comparative Example 2 is excellent in chemical resistance (ethanol resistance) and substrate adhesion as in Comparative Example 1, but the corrosion resistance and chemical resistance ( It has been confirmed that the alkali resistance is extremely insufficient.
　比較例３は、ウレタン樹脂の酸価が本発明の範囲を上回る８ｍｇＫＯＨ／ｇのものを用いた例である。この比較例３のウレタン樹脂組成物を用いて得られた塗膜は、耐食性及び耐薬品性には優れるものの、耐薬品性（耐アルカリ性）は著しく不十分であることが確認できた。 The comparative example 3 is an example using the thing of 8 mgKOH / g whose acid value of a urethane resin exceeds the range of this invention. Although the coating film obtained using the urethane resin composition of this comparative example 3 is excellent in corrosion resistance and chemical resistance, it has been confirmed that the chemical resistance (alkali resistance) is extremely insufficient.
　比較例５は、芳香族ポリエステルポリオールを用いない例である。この比較例５のウレタン樹脂組成物を用いて得られた塗膜は、基材密着性には優れるものの、耐薬品性が著しく不十分であることが確認できた。 Comparative Example 5 is an example in which an aromatic polyester polyol is not used. Although the coating film obtained using the urethane resin composition of this comparative example 5 is excellent in the substrate adhesion, it has been confirmed that the chemical resistance is extremely insufficient.

Claims (7)

  1. 　芳香族ポリエステルポリオール（ａ１－１）、及びアニオン性基を有するポリオール（ａ１－２）を含有するポリオール（ａ１）と、ポリイソシアネート（ａ２）との反応物であるウレタン樹脂（Ａ）、及び水性媒体（Ｂ）を含むウレタン樹脂組成物であって、
    　前記芳香族ポリエステルポリオール（ａ１－１）中の芳香環濃度が、２．５～５ｍｏｌ／ｋｇであり、
    　前記ポリイソシアネート（ａ２）が、脂肪族ポリイソシアネート及び／または脂環式構造を有するポリイソシアネートを含むものであり、
    　前記ウレタン樹脂（Ａ）の酸価が、１０～２５ｍｇＫＯＨ／ｇの範囲であることを特徴とするウレタン樹脂組成物。     Urethane resin (A) which is a reaction product of aromatic polyester polyol (a1-1) and polyol (a1) containing polyol (a1-2) having an anionic group, and polyisocyanate (a2), and aqueous resin It is a urethane resin composition containing a medium (B),
    The aromatic ring concentration in the aromatic polyester polyol (a1-1) is 2.5 to 5 mol / kg,
    The polyisocyanate (a2) includes an aliphatic polyisocyanate and / or a polyisocyanate having an alicyclic structure,
    A urethane resin composition characterized in that the acid value of the urethane resin (A) is in the range of 10 to 25 mg KOH / g.
  2. 　前記脂肪族ポリイソシアネート及び／または前記脂環式構造を有するポリイソシアネートの前記ポリイソシアネート（ａ２）中の割合が、１０～１００質量％の範囲である請求項１記載のウレタン樹脂組成物。 The urethane resin composition according to claim 1, wherein the proportion of the aliphatic polyisocyanate and / or the polyisocyanate having the alicyclic structure in the polyisocyanate (a2) is in the range of 10 to 100% by mass.
  3. 　前記ウレタン樹脂（Ａ）中のウレア結合量が、２５０ｍｍｏｌ／ｋｇ未満である請求項１又は２記載のウレタン樹脂組成物。 The urethane resin composition according to claim 1 or 2, wherein the amount of urea bond in the urethane resin (A) is less than 250 mmol / kg.
  4. 　前記ウレタン樹脂組成物が、さらに、中和剤（Ｃ）を含有する請求項１～３のいずれか１項記載のウレタン樹脂組成物。 The urethane resin composition according to any one of claims 1 to 3, wherein the urethane resin composition further contains a neutralizing agent (C).
  5. 　前記中和剤（Ｃ）が、沸点１４０℃未満の塩基性化合物である請求項４記載のウレタン樹脂組成物。 The urethane resin composition according to claim 4, wherein the neutralizing agent (C) is a basic compound having a boiling point of less than 140 ° C.
  6. 　請求項１～５のいずれか１項記載のウレタン樹脂組成物を含有することを特徴とする鋼板表面処理剤。 A steel plate surface treatment agent comprising the urethane resin composition according to any one of claims 1 to 5.
  7. 　請求項６記載の鋼板表面処理剤の塗膜を有することを特徴とする鋼板。 A steel plate having a coating of the steel plate surface treatment agent according to claim 6.
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