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WO2019004349A1 - Composition de résine uréthane, agent de traitement de surface pour plaque d'acier, et plaque d'acier ayant un film de revêtement de celui-ci - Google Patents

Composition de résine uréthane, agent de traitement de surface pour plaque d'acier, et plaque d'acier ayant un film de revêtement de celui-ci 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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WO
WIPO (PCT)
Prior art keywords
mass
urethane resin
parts
resin composition
polyisocyanate
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2018/024565
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English (en)
Japanese (ja)
Inventor
直人 佐竹
広義 神成
定 永浜
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
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Filing date
Publication date
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Priority to JP2019527019A priority Critical patent/JPWO2019004349A1/ja
Publication of WO2019004349A1 publication Critical patent/WO2019004349A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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.

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Abstract

L'invention fournit une composition de résine uréthane qui présente une excellente stabilité de mélange, et qui permet de former un film de revêtement excellent en termes de résistance à la corrosion, de résistance aux produits chimiques et d'adhérence de matériau de base. Plus précisément, l'invention concerne une composition de résine uréthane qui contient: une résine uréthane (A) qui est un produit de réaction entre un polyol (a1) comprenant un polyol de polyester aromatique (a1-1) et un polyol (a1-2) ayant un groupe anionique, et un polyisocyanate (a2); et un milieu aqueux (B). Cette composition de résine uréthane est caractéristique en ce que la concentration en cycle aromatique dans ledit polyol de polyester aromatique (a1-1), est comprise entre ２,５ et ５ｍｏｌ／ｋｇ. Ledit polyisocyanate (a2) contient un polyisocyanate aliphatique et/ou un polyisocyanate de structure type alicyclique. L'indice d'acide de la résine uréthane (A) se trouve dans une plage de １０ à ２５ｍｇＫＯＨ／ｇ.
PCT/JP2018/024565 2017-06-29 2018-06-28 Composition de résine uréthane, agent de traitement de surface pour plaque d'acier, et plaque d'acier ayant un film de revêtement de celui-ci Ceased WO2019004349A1 (fr)

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JP2020200430A (ja) * 2019-06-13 2020-12-17 三井化学株式会社 ポリウレタンディスパージョンおよびその製造方法
CN112227083A (zh) * 2020-09-30 2021-01-15 京准化工技术(上海)有限公司 一种织物耐水压提升剂及其制备方法
CN113574129A (zh) * 2019-03-26 2021-10-29 第一工业制药株式会社 聚氨酯水分散体以及涂布剂
WO2023176841A1 (fr) * 2022-03-15 2023-09-21 三井化学株式会社 Dispersion de polyuréthane et composition d'encre
WO2023195297A1 (fr) * 2022-04-04 2023-10-12 第一工業製薬株式会社 Adhésif pour film optique, revêtement et film optique
JP2023152588A (ja) * 2022-04-04 2023-10-17 第一工業製薬株式会社 光学フィルム用接着剤、皮膜及び光学フィルム
WO2024135512A1 (fr) * 2022-12-22 2024-06-27 Dic株式会社 Composition aqueuse de résine uréthane, corps multicouche et article

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0656953A (ja) * 1992-07-03 1994-03-01 Bayer Ag 水溶性もしくは水分散性ポリイソシアネート混合物および焼付組成物におけるその使用
JPH09504564A (ja) * 1993-11-06 1997-05-06 ビーエーエスエフ ラッケ ウント ファルベン アクチエンゲゼルシャフト 水性ラッカー及び自動車塗装における充填層を製造するためのその使用
JP2000026798A (ja) * 1998-07-09 2000-01-25 Dainippon Ink & Chem Inc プライマーコート剤
JP2002128853A (ja) * 2000-10-23 2002-05-09 Asahi Denka Kogyo Kk 水分散性ポリウレタン組成物
JP2003041186A (ja) * 2001-07-30 2003-02-13 Asahi Denka Kogyo Kk ノンクロム処理金属材塗料用水分散型ポリウレタン組成物及びその製造方法。
US20050143531A1 (en) * 2003-12-30 2005-06-30 Ju-Kil Lee Urethane-modified polyester resin composition
WO2009107325A1 (fr) * 2008-02-27 2009-09-03 株式会社Adeka Composition aqueuse de résine de polyuréthane et article recouvert par celle-ci
JP2012092311A (ja) * 2010-09-28 2012-05-17 Dic Corp プライマーコート剤及び積層体
WO2012063450A1 (fr) * 2010-11-09 2012-05-18 株式会社Adeka Composition de résine de polyuréthane à base d'eau, matériau de revêtement utilisant ladite composition et article revêtu
JP2015218267A (ja) * 2014-05-19 2015-12-07 Dic株式会社 水性樹脂組成物、それを用いた積層体及び物品
JP2016028110A (ja) * 2014-07-11 2016-02-25 ジャパンコーティングレジン株式会社 ポリウレタン及びウレタン−（メタ）アクリル複合樹脂

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0656953A (ja) * 1992-07-03 1994-03-01 Bayer Ag 水溶性もしくは水分散性ポリイソシアネート混合物および焼付組成物におけるその使用
JPH09504564A (ja) * 1993-11-06 1997-05-06 ビーエーエスエフ ラッケ ウント ファルベン アクチエンゲゼルシャフト 水性ラッカー及び自動車塗装における充填層を製造するためのその使用
JP2000026798A (ja) * 1998-07-09 2000-01-25 Dainippon Ink & Chem Inc プライマーコート剤
JP2002128853A (ja) * 2000-10-23 2002-05-09 Asahi Denka Kogyo Kk 水分散性ポリウレタン組成物
JP2003041186A (ja) * 2001-07-30 2003-02-13 Asahi Denka Kogyo Kk ノンクロム処理金属材塗料用水分散型ポリウレタン組成物及びその製造方法。
US20050143531A1 (en) * 2003-12-30 2005-06-30 Ju-Kil Lee Urethane-modified polyester resin composition
WO2009107325A1 (fr) * 2008-02-27 2009-09-03 株式会社Adeka Composition aqueuse de résine de polyuréthane et article recouvert par celle-ci
JP2009203316A (ja) * 2008-02-27 2009-09-10 Adeka Corp 水系ポリウレタン樹脂組成物及びそれを塗布してなる被塗物
JP2012092311A (ja) * 2010-09-28 2012-05-17 Dic Corp プライマーコート剤及び積層体
WO2012063450A1 (fr) * 2010-11-09 2012-05-18 株式会社Adeka Composition de résine de polyuréthane à base d'eau, matériau de revêtement utilisant ladite composition et article revêtu
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JP2020200430A (ja) * 2019-06-13 2020-12-17 三井化学株式会社 ポリウレタンディスパージョンおよびその製造方法
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WO2023176841A1 (fr) * 2022-03-15 2023-09-21 三井化学株式会社 Dispersion de polyuréthane et composition d'encre
JPWO2023176841A1 (fr) * 2022-03-15 2023-09-21
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JP2023152588A (ja) * 2022-04-04 2023-10-17 第一工業製薬株式会社 光学フィルム用接着剤、皮膜及び光学フィルム
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