WO2011118791A1 - 塗膜形成方法 - Google Patents
塗膜形成方法 Download PDFInfo
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- WO2011118791A1 WO2011118791A1 PCT/JP2011/057407 JP2011057407W WO2011118791A1 WO 2011118791 A1 WO2011118791 A1 WO 2011118791A1 JP 2011057407 W JP2011057407 W JP 2011057407W WO 2011118791 A1 WO2011118791 A1 WO 2011118791A1
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- epoxy
- aqueous
- coating film
- water
- resin
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Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
- C08G59/184—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents with amines
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- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/34—Applying different liquids or other fluent materials simultaneously
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2401/00—Form of the coating product, e.g. solution, water dispersion, powders or the like
- B05D2401/20—Aqueous dispersion or solution
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0025—Crosslinking or vulcanising agents; including accelerators
Definitions
- the present invention relates to a method for forming a coating film.
- a solvent-type paint containing an epoxy resin and a polyamine compound is used as an anticorrosion paint.
- a water-based paint for example, a water-soluble polyamine resin blended with various pigments and additives as a main agent, and further includes an epoxy resin emulsion and an acrylic silicon resin emulsion containing a glycidyl group and an alkoxysilyl group.
- An aqueous paint is mentioned (patent document 1).
- the present invention has been made to solve the above-described conventional problems, and an object of the present invention is to provide a method for forming a coating film having excellent low-temperature curability.
- the method for forming a coating film of the present invention comprises coating a base material with an aqueous coating composition to form a coating film, wherein the aqueous coating composition contains one or more primary amino groups and / or in the molecule.
- numerator are included.
- the aqueous coating composition is a two-part aqueous coating composition, the main coating liquid contains the aqueous epoxy polyamine resin (A), and the curing agent contains the compound (B).
- the said water-based epoxy-type polyamine resin (A) is a water dispersion type.
- the amino group equivalent of the aqueous epoxy polyamine resin (A) is 100 to 3000.
- the aqueous epoxy polyamine resin (A) is obtained by amine-modifying an epoxy resin, and the epoxy equivalent of the epoxy resin is 180 to 3800.
- the water-based coating composition is a water-based epoxy polyamine resin (A) obtained by amine-modifying an epoxy resin (a1) having an epoxy equivalent of 400 to 1500 as the water-based epoxy polyamine resin (A).
- an aqueous epoxy polyamine resin (A2) obtained by amine-modifying an epoxy resin (a2) having an epoxy equivalent of 2000 to 3200.
- a mass ratio a1 / a2 between the epoxy resin (a1) and the epoxy resin (a2) is 8/2 to 2/8.
- the aqueous epoxy polyamine resin (A) is obtained by neutralizing the amino group of the epoxy polyamine resin with an acid, and the neutralization rate during the neutralization is 10% to 70%. is there.
- the viscosity in 25 degreeC of the said compound (B) is 3000 mPa * s or less.
- the molecular weight of the said compound (B) is 150-2000.
- the method for forming a coating film of the present invention includes forming an overcoat layer on the coating film after the coating film is formed with the aqueous coating composition. In a preferred embodiment, the method for forming a coating film of the present invention includes forming an intermediate coating layer after forming the coating film with the aqueous coating composition and before forming the top coating layer. In a preferred embodiment, the coating film forming method of the present invention includes forming an undercoat layer on the substrate before forming a coating film with the aqueous coating composition.
- the aqueous epoxy polyamine resin (A) having one or more primary amino groups and / or second amino groups in the molecule, and one or more (meta ) By using the aqueous coating composition containing the compound (B) having an acryloyl group, a coating film exhibiting practical performance can be obtained even at a low temperature (for example, 5 ° C. or less). More specifically, the water-based coating composition uses a Michael addition reaction that is very reactive to the curing reaction, so that a cured coating film can be obtained even at a low temperature (for example, 5 ° C. or lower).
- the Michael addition reaction itself is a highly reactive reaction, but the stability of the water-based coating composition at room temperature is good. It is more workable than using a solvent-based coating composition. Furthermore, since an epoxy resin is used as a binder, a coating film having excellent corrosion resistance can be obtained.
- the coating film forming method of the present invention includes coating a base material with an aqueous coating composition to form a coating film.
- the aqueous coating composition includes an aqueous epoxy polyamine resin (A) having one or more primary amino groups and / or secondary amino groups in the molecule and one or more ( A compound (B) having a (meth) acryloyl group is included.
- the aqueous coating composition can form a coating film by mixing the aqueous epoxy polyamine resin (A) and the compound (B) to advance the curing reaction (Michael addition reaction) of these compounds. . Since the water-based epoxy polyamine resin (A) and the compound (B) can be cured at a low temperature (for example, 5 ° C.), the water-based coating composition is excellent in low-temperature curability.
- the aqueous coating composition is preferably a two-component aqueous coating composition comprising a main component coating liquid and a curing agent.
- the main agent coating liquid contains the water-based epoxy polyamine resin (A)
- the curing agent contains the compound (B).
- the aqueous coating composition comprises (1) diluting the compound (B) with an organic solvent before mixing the aqueous epoxy polyamine resin (A) and the compound (B). (2) Compound (B) An emulsifier is mixed with the compound, or the compound (B) is emulsified or dispersed in water using a dispersant, an emulsifier or an aqueous resin, or (3) the compound (B) is an aqueous epoxy polyamine resin (A). A treatment such as dispersion in a dispersion of different resins may be performed.
- the water-based epoxy polyamine resin (A) and the compound (B) can be mixed without using a special mixing apparatus, and the water-based epoxy polyamine resin (A) and the compound are excellent in dispersibility.
- An aqueous coating composition capable of efficiently reacting with (B) can be obtained.
- Examples of the organic solvent used when diluting the compound (B) with an organic solvent include ethylene glycol monobutyether and diethylene glycol monobutyl ether.
- Examples of the emulsifier used when the compound (B) is mixed with an emulsifier or when the compound (B) is emulsified or dispersed in water using a dispersant, an emulsifier, or an aqueous resin include, for example, a nonionic emulsifier and an anionic emulsifier. Etc. are used.
- Examples of the nonionic emulsifier include polyoxyethylene alkylphenol ether, polyoxyethylene styrenated phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene polyoxypropylene block polymer, sorbitan fatty acid ester and the like.
- the anionic emulsifier examples include dodecylbenzene sulfonate, dialkyl succinate sulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene styrenated phenyl ether sulfate, alkyl diphenyl ether disulfonate, and the like.
- the dispersant examples include sodium polyacrylate salt, ammonium salt of styrene maleic acid copolymer half ester, polyethylene oxide adduct of styrene maleic acid copolymer half ester, and the like.
- aqueous resin the soda salt of polyacrylic acid ester etc. are mentioned, for example.
- the curing agent may contain the above-mentioned dispersant, emulsifier, or aqueous resin.
- Examples of the dispersion when the compound (B) is dispersed in a resin dispersion different from the aqueous epoxy polyamine resin (A) include, for example, acrylic resin emulsions and dispersions, urethane resin emulsions and dispersions, Examples thereof include an aqueous epoxy polyamine resin having no primary amino group and no secondary amino group.
- the content of the aqueous epoxy polyamine resin (A) as a solid content is preferably 5 to 95 mass%, more preferably 10 to 90 mass%, based on the total solid content of the aqueous coating composition. .
- the content of the compound (B) is preferably 2 to 30% by mass, more preferably 5 to 25% by mass, based on the total solid content of the aqueous coating composition.
- the equivalent ratio ((meth) acryloyl group / amino group) of the (meth) acryloyl group of the compound (B) to the amino group of the aqueous epoxy polyamine resin (A) is preferably 0.7 to 2.5. More preferably, it is 0.8 to 2.0. When the equivalent ratio is less than 0.7, the low temperature curability of the aqueous coating composition may be lowered. When exceeding 2.5, there exists a possibility that the adhesiveness of the coating film obtained may fall.
- the aqueous coating composition may further contain a pigment.
- the viscosity of the aqueous coating composition can be increased, and the film thickness obtained by one coating can be increased.
- the number of coatings can be reduced, it is possible to obtain an aqueous coating composition that is excellent in coating workability and can form a coating film exhibiting sufficient corrosion resistance.
- the pigment examples include titanium oxide, yellow iron oxide, red iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, azo red, quinacridone red, benzimidazolone yellow, and the like; calcium carbonate, barium sulfate, kaolin, Examples include extender pigments such as clay, talc and mica; rust preventive pigments such as zinc phosphate and calcium phosphate.
- the pigment volume concentration of the pigment in the aqueous coating composition is preferably 20 to 50%, more preferably 25 to 45%, and particularly preferably 30 to 40%. When the pigment volume concentration is less than 20%, the effect of containing the pigment may not be sufficiently obtained. When the pigment volume concentration is more than 50%, the coating film appearance may be deteriorated.
- the pigment volume concentration can be obtained by calculation from the blending mass of the pigment and the specific gravity of each component in the paint.
- the water-based paint composition may contain water, a solvent or an additive.
- the solvent include glycol solvents such as ethylene glycol, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol dibutyl ether; xylene, Aromatic solvents such as Solvesso 100, Solvesso 150, Solvesso 200; hydrocarbon solvents such as mineral spirits; 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (trade name “manufactured by Chisso Corporation” CS-12 "), 2,2,4-trimethyl-1,3-pentanediol diisobutyrate (manufactured by Chisso, trade name” CS-16 "), diethyl adipate And ester solvents such as diiso
- the additive include a dispersant, a viscosity modifier, a curing catalyst, a surface modifier, an antifoaming agent, a plasticizer, a film-forming aid, an ultraviolet absorber, and an antioxidant.
- water, solvent and / or additive may be added to the main coating liquid or curing agent before mixing the main coating liquid and the curing agent.
- the main component coating liquid and the curing agent may be added after mixing. Whether water, a solvent and / or an additive is added to the main coating liquid or the curing agent can be determined depending on the expected function and properties.
- the aqueous coating composition may contain an alkoxysilane compound as an additive. By including the alkoxysilane compound, it is possible to form a coating film having excellent adhesion to the substrate.
- alkoxysilane compound examples include ⁇ -glycidoxyalkyltrialkoxysilane such as ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -glycidoxypropyltriethoxysilane, and ⁇ -glycidoxypropoxytrimethoxysilane.
- ⁇ -aminopropyltrialkoxysilane such as ⁇ -aminopropyltriethoxysilane and ⁇ -aminopropyltripropoxysilane; N-phenyl- ⁇ -aminopropyltrimethoxysilane, N-phenyl- ⁇ -aminopropyltriethoxysilane, And N-phenyl- ⁇ -aminoalkyltrialkoxysilane such as N-phenyl- ⁇ -aminopropyltripropoxysilane. These may be used alone or in combination. These may be partially hydrolyzed and / or hydrolyzed and dehydrated.
- the content thereof is preferably 0.3 to 3% by mass, more preferably 0.5 to 2% by mass, based on the total solid content of the aqueous coating composition.
- Aqueous epoxy polyamine resin (A)
- the aqueous coating composition contains an aqueous epoxy-based polyamine resin (A) having one or more primary amino groups and / or secondary amino groups in the molecule.
- the aqueous coating composition can form a coating film having excellent anticorrosion properties by including such a resin as a binder.
- “aqueous” is a concept including “water-soluble” and “water-dispersed”.
- the aqueous epoxy polyamine resin (A) is water-dispersed. If the water-dispersed water-based epoxy polyamine resin (A) is used, a coating film having excellent water resistance can be formed. Further, if the water-based epoxy polyamine resin (A) is water-dispersed, it can be easily mixed with the compound (B), and the reaction between the water-based epoxy polyamine resin (A) and the compound (B). It is possible to obtain an aqueous coating composition having a long pot life by suppressing rapid progress and adjusting the reactivity appropriately.
- the water-based epoxy polyamine resin (A) is a water-dispersed type
- the water-based paint composition before coating is difficult to contact the water-based epoxy polyamine resin (A) and the compound (B).
- the reaction is difficult to proceed even at room temperature, and the stability and coatability are good.
- the dispersion medium for example, water
- the aqueous epoxy polyamine resin (A) and the compound (B) are easily brought into contact with each other, and the curing reaction proceeds even at a low temperature. Can be formed.
- the aqueous epoxy polyamine resin (A) can be obtained, for example, by modifying an epoxy resin with an amine. Moreover, when the epoxy-type polyamine resin obtained by amine-modifying an epoxy resin is not aqueous, for example, it is made aqueous by neutralizing the amino group of the epoxy-type polyamine resin with an acid to form an aqueous epoxy-type polyamine resin ( A) can be obtained.
- the epoxy resin is preferably a bisphenol A type epoxy resin or a bisphenol F type epoxy resin, and particularly preferably a bisphenol A type epoxy resin.
- the epoxy equivalent of the epoxy resin can be determined according to the desired film properties. It is preferably 180 to 3800, more preferably 400 to 3200, and particularly preferably 700 to 3200. If the epoxy equivalent of an epoxy resin is such a range, the coating film which is excellent in water resistance, corrosion resistance, and water-resistant adhesiveness can be obtained. When the epoxy equivalent of the epoxy resin is less than 180, the initial rainfall resistance of the resulting coating film may be lowered. On the other hand, if it exceeds 3,800, the epoxy-based polyamine resin may cause phase separation without being dispersed in water, and the coating composition may not be made water-based, and an aqueous coating composition having sufficient water-resistant adhesion can be obtained. There is a risk of not.
- initial rain resistance means water resistance at the initial stage of curing of a coating film, specifically, at a stage where a coating film that is not completely cured but has no stickiness is formed. .
- initial rainfall resistance is inferior, if the coated film is exposed to rain before the coated film is completely cured, the coated film may be cracked or blistered.
- Water-based paint compositions that can form a coating with high initial rainfall resistance are particularly effective for applications to outdoor coatings that may be exposed to rainfall after application and before the coating is fully cured It is.
- the epoxy resin is an epoxy resin (a1) having an epoxy equivalent of 400 to 1500. If the aqueous epoxy polyamine resin (A1) obtained by amine-modifying such an epoxy resin (a1) is used, an aqueous coating composition capable of forming a coating film excellent in water-resistant adhesion can be obtained.
- the epoxy equivalent of the epoxy resin (a1) is more preferably 600 to 1400, and particularly preferably 800 to 1300.
- the epoxy resin is an epoxy resin (a2) having an epoxy equivalent of 2000 to 3200.
- an aqueous epoxy polyamine resin (A2) obtained by amine modification of such an epoxy resin (a2) an aqueous coating composition capable of forming a coating film excellent in initial rainfall resistance can be obtained.
- the epoxy equivalent of the epoxy resin (a2) is more preferably 2200 to 3000.
- the epoxy resin may be used in combination of two or more epoxy resins.
- the epoxy resin there may be used those obtained by chain extension by using a reaction between an active hydrogen-containing compound capable of reacting with an epoxy group and an epoxy group to increase the molecular weight or modify the molecular weight.
- an active hydrogen-containing compound capable of reacting with an epoxy group and an epoxy group to increase the molecular weight or modify the molecular weight.
- the active hydrogen-containing compound include bifunctional compounds such as dimer acid, diamine, and polyether polyol.
- the epoxy resin a resin to which a fatty acid is added before amine modification can be used.
- a resin to which a fatty acid is added before amine modification can be used.
- it is possible to reduce the reactivity by introducing a soft component into the resin or reducing the number of epoxy groups to reduce the number of amine-modified sites.
- the epoxy polyamine resin can be obtained by modifying the epoxy resin by any appropriate modification method.
- the modification method include a method of adding a first amino group-containing polyamine to an epoxy resin and a method of adding a ketiminated amino group-containing compound to an epoxy resin.
- the epoxy polyamine resin thus obtained has one or more primary amino groups and / or secondary amino groups and secondary hydroxyl groups in the molecule.
- the epoxy-based polyamine resin has a functional group such as an epoxy group, an acid anhydride group, an acid halogen group, or an isocyanate group in a part of the first amino group, the second amino group, and / or the hydroxyl group of the epoxy-based polyamine resin. It may be a resin obtained by reacting a compound.
- the physical properties of the resulting coating film are adjusted by including an aqueous product of an epoxy polyamine resin reacted with a compound having such a functional group. Can do.
- the method of adding the first amino group-containing polyamine to the epoxy resin means that the first amino group of the first amino group-containing polyamine is reacted with the epoxy group of the epoxy resin to form a second amino group, As a result, the epoxy polyamine resin having the second amino group is produced.
- Examples of the first amino group-containing polyamine include diethylenetriamine, dipropylenetriamine, dibutylenetriamine, and triethylenetetramine. These may be used alone or in combination.
- the method of adding the ketiminized amino group-containing compound to the epoxy resin means that the ketimine group is hydrolyzed after reacting the ketiminized amino group-containing compound and the epoxy resin, thereby the first amino group. As a result, the epoxy-based polyamine resin having the first amino group is produced.
- secondary amines such as diethanolamine, methylethanolamine, and diethylamine may coexist.
- the ketiminated amino group-containing compound can be obtained by reacting a first amino group-containing compound with a ketone.
- first amino group-containing compound include first amino group-containing polyamines such as diethylenetriamine, dipropylenetriamine, dibutylenetriamine, and triethylenetetramine; aminoethylethanolamine, methylaminopropylamine, ethylaminoethylamine, and the like. It is done. These may be used alone or in combination.
- the ketone include methyl ethyl ketone, acetone, and methyl isobutyl ketone.
- the epoxy-based polyamine resin may be further modified by reacting a compound having a functional group that reacts with an amino group in accordance with desired film properties.
- the functional group that reacts with an amino group include an epoxy group, a (meth) acryloyl group, an isocyanate group, and an acid anhydride group.
- the amount of amino groups contained in the epoxy polyamine resin may be any appropriate amount of amino groups depending on the properties of the desired aqueous coating composition or the physical properties of the coating film.
- the amount of the amino group is preferably 100 to 3000, more preferably 500 to 2000, and particularly preferably 800 to 2000 as the equivalent of the amino group.
- the epoxy-based polyamine resin is water-based, and the water-based epoxy-based polyamine resin (A) can be obtained. If the said water-based epoxy-type polyamine resin (A) is used, the coating film which is excellent in low-temperature curability can be obtained. If the equivalent of the amino group of the epoxy-based polyamine resin is less than 100, the resulting coating film may have low water resistance.
- the epoxy-based polyamine resin when it exceeds 3000, the epoxy-based polyamine resin does not disperse in water but causes phase separation, and the coating composition may not be water-based.
- “equivalent of amino group” means that the epoxy-based polyamine resin has a first amino group (including the case where the epoxy-based polyamine resin has a first amino group and a second amino group), When the epoxy-based polyamine resin does not have the first amino group, the molecular weight of the resin solid per one second amino group is indicated by the molecular weight of the resin solid per one amino group.
- the amino group equivalent of the epoxy-based polyamine resin can be determined from the amount of the raw material blended.
- the aqueous epoxy polyamine resin (A) can also be obtained, for example, by making the amino group of the epoxy polyamine resin (that is, the amine-modified epoxy resin) neutralized with an acid.
- the type of acid and the neutralization rate (neutralization rate with respect to the amino group of the epoxy-based polyamine resin before making it aqueous) depend on the desired state of the aqueous epoxy-based polyamine resin (A) (water-soluble to water-dispersed type). Any suitable acid type and neutralization rate may be employed. Examples of the acid include acetic acid, formic acid, lactic acid, and phosphoric acid.
- the neutralization rate (neutralization rate with respect to amino groups of the epoxy-based polyamine resin before making it aqueous) is preferably 10% to 100%, more preferably 10% to 70%, and particularly preferably 15% to 50%. %. If the neutralization rate is less than 10%, the resin does not disperse in water and phase separation may occur, and the coating composition may not be water-based. Moreover, if the neutralization rate is adjusted to 70% or less, a water-dispersed aqueous epoxy polyamine resin (A) can be obtained.
- any appropriate molecular weight can be adopted as the molecular weight (number average) of the water-based epoxy polyamine resin (A) depending on the properties of the desired water-based coating composition or the physical properties of the coating film. Preferably, it is 500 to 20000 in terms of standard polystyrene using gel permeation chromatography (GPC), and more preferably 1000 to 10,000. If the molecular weight of the aqueous epoxy polyamine resin (A) is in such a range, the aqueous epoxy polyamine resin (A) and the above compound (B) can be easily mixed, so that they can be reacted efficiently. Can do. Moreover, if the molecular weight of water-based epoxy-type polyamine resin (A) is such a range, the coating film which is excellent in corrosion resistance, water resistance, and adhesiveness can be obtained.
- GPC gel permeation chromatography
- the water-based paint composition may contain two or more water-based epoxy polyamine resins (A).
- the aqueous coating composition is preferably an aqueous epoxy polyamine resin (A1) obtained by amine modification of the epoxy resin (a1) having an epoxy equivalent of 400 to 1500 as the aqueous epoxy polyamine resin (A). And an aqueous epoxy polyamine resin (A2) obtained by amine-modifying the epoxy resin (a2) having an epoxy equivalent of 2000 to 3200.
- the mass ratio a1 / a2 of the epoxy resin (a1) having an epoxy equivalent of 400 to 1500 and the epoxy resin (a2) having an epoxy equivalent of 2000 to 3200 is preferably 8/2 to 2/8, More preferably, it is 7/3 to 3/7. If it is such a range, the water-based coating composition which can form the coating film excellent in initial rainfall resistance and water-resistant adhesiveness can be obtained.
- the characteristics of the aqueous coating composition or the physical properties of the coating film can be controlled by the molecular weight and amino group amount of the aqueous epoxy polyamine resin (A).
- Compound (B) The compound (B) used for the water-based coating composition has one or more (meth) acryloyl groups in the molecule.
- the molecular weight of the compound (B) is preferably 150 or more and 2000 or less, more preferably 200 or more and 1700 or less, and particularly preferably 250 or more and 1300 or less. If the molecular weight of the compound (B) is in such a range, the aqueous epoxy polyamine resin (A) and the compound (B) can be easily mixed without using a special mixing device, and have excellent dispersibility. Water-based coating composition can be obtained. As a result, the aqueous epoxy polyamine resin (A) and the compound (B) can be efficiently reacted with each other, and an aqueous coating composition having excellent curability can be obtained. The molecular weight of the compound (B) can be calculated from the chemical formula.
- the number of (meth) acryloyl groups possessed by the compound (B) is 1 or more, preferably 2 to 4.
- the number of (meth) acryloyl groups possessed by the compound (B) can be determined according to the desired physical properties of the coating film.
- the viscosity of the compound (B) at 25 ° C. is preferably 3000 mPa ⁇ s or less, more preferably 50 to 3000 mPa ⁇ s, particularly preferably 50 to 2200 mPa ⁇ s, and most preferably 50 to 1100 mPa ⁇ s. s. If the viscosity of the compound (B) is in such a range, the aqueous epoxy polyamine resin (A) and the compound (B) can be easily mixed without using a special mixing apparatus, and the dispersibility is excellent. An aqueous coating composition can be obtained. As a result, the aqueous epoxy polyamine resin (A) and the compound (B) can be efficiently reacted with each other, and an aqueous coating composition having excellent curability can be obtained.
- Examples of the compound (B) include ethylene glycol diacrylate, ethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, 1, 3 -Butylene glycol diacrylate, 1,3-butylene glycol dimethacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, neopentyl Glycol diacrylate, neopentyl glycol dimethacrylate, 1,6-hexanediol diacrylate, 1,6-hexanediol Dimethacrylate, pentaerythritol diacrylate, pentaerythritol dimethacrylate, pentaerythritol dimethacrylate, pen
- Examples thereof include adducts of an ethylenically unsaturated monomer and a carboxyl group-containing ethylenically unsaturated monomer; and polymerizable unsaturated monocarboxylic amide compounds of polyvalent amines such as ethylenediamine diacrylate. These compounds may be used alone or in combination.
- the compound (B) can be easily mixed with the aqueous epoxy polyamine resin (A) (both can react). More preferably, the water-based epoxy polyamine resin (A) and the compound (B) are used in a non-uniform state within a range where they can be easily mixed (both can react). Particularly preferably, the compound (B) and the aqueous epoxy polyamine resin (A) are used in mutually different phase states. If it is such a state, the progress of the rapid reaction of water-based epoxy-type polyamine resin (A) and a compound (B) can be suppressed, and reactivity can be adjusted moderately.
- the water-based epoxy polyamine resin (A) and the compound (B) are in a non-uniform state, the water-based paint composition before coating is difficult to come in contact with both of these components. The reaction does not proceed easily, and the stability and coatability are good.
- the dispersion medium for example, water
- the aqueous epoxy polyamine resin (A) and the compound (B) are easily brought into contact with each other, and the curing reaction proceeds even at a low temperature.
- the compound (B) is a water-soluble compound and the aqueous epoxy polyamine resin (A) is a water-dispersed resin, the compound (B) is self-emulsifying or water-insoluble. Can be mentioned.
- any appropriate method can be adopted as the method for making the heterogeneous state depending on the solubility of the compound (B) in water.
- compound (B) when compound (B) is water-soluble, compound (B) can be used as it is.
- the aqueous epoxy polyamine resin (A) is preferably a water-dispersed resin.
- the compound (B) when the compound (B) has a self-emulsifying property, the compound (B) is used as it is, or is used by emulsifying or dispersing in water with an emulsifier, a dispersant or an aqueous resin. can do.
- the compound (B) When the compound (B) is water-insoluble, it can be used after being emulsified or dispersed in water with an emulsifier, a dispersant or an aqueous resin. In these cases, the form of the aqueous epoxy polyamine resin (A) may be water-soluble or water-dispersed, but is preferably water-dispersed. It should be noted that whether the compound (B) is “water-insoluble”, “water-soluble” or “self-emulsifying” is determined by adding 5 g of compound (B) to 100 g of water at room temperature. The state after stirring (for example, 3 minutes) and leaving still (for example, after 5 minutes) can be visually observed. After settling, it can be judged as “water-insoluble” if precipitation occurs, “water-soluble” if there is no precipitate and clear, and “self-emulsifying” if there is no precipitation and turbidity.
- the compound (B) can be modified with, for example, polyethylene oxide, and can be made water-soluble or self-emulsifiable by increasing the number of moles of ethylene oxide added to increase hydrophilicity.
- water-soluble compound (B) examples include ethoxylated bisphenol A diacrylate (EO 30 mol), ethoxylated trimethylolpropane triacrylate (EO 20 mol), ethoxylated trimethylolpropane triacrylate (EO 30 mol), and ethoxylated pentaerythritol tetra.
- examples include acrylate (EO 35 mol), ethoxylated glycerin triacrylate (EO 20 mol), and ethoxylated bisphenol A dimethacrylate (EO 30 mol). These may be used alone or in combination. In the present specification, for example, “EO 30 mol” represents that 30 ethylene oxides are contained in the molecule.
- Examples of the self-emulsifying compound (B) include polyethylene glycol # 400 diacrylate (EO 9 mol), polyethylene glycol # 600 diacrylate (EO 14 mol), polyethylene glycol # 1000 diacrylate (EO 23 mol), ethoxylated bisphenol A di Examples include acrylate (EO 10 mol), ethoxylated bisphenol A diacrylate (EO 20 mol), ethoxylated glycerin triacrylate (EO 9 mol), polyethylene glycol # 1000 dimethacrylate (EO 23 mol), and the like. These may be used alone or in combination.
- water-insoluble compound (B) examples include polyethylene glycol # 200 glycol diacrylate (EO 4 mol), ethoxylated bisphenol A diacrylate (EO 3 mol), ethoxylated bisphenol A diacrylate (EO 4 mol), propoxylated bisphenol A di Acrylate (PO 3 mol), 1,10-decanediol diacrylate, tricyclodecane dimethanol diacrylate, ethoxylated 2-methyl-1,3-propanediol diacrylate (EO 2 mol), neopentyl glycol diacrylate, 1,6- Hexanediol diacrylate, 1,9-nonanediol diacrylate, dipropylene glycol diacrylate (PO2 mol), tripropylene glycol diacrylate (P 3 mol), polypropylene glycol # 400 diacrylate (PO 7 mol), polypropylene glycol # 700 diacrylate (PO 12 mol), ethoxylated trimethylolpropan
- the compound (B) can be used as a mixture of a plurality of types of compounds (B).
- the physical property control of a water-based coating composition and the coating film obtained can be performed by combining and using the compound (B) from which a characteristic differs.
- the curability can be controlled by mixing the compound (B) having two (meth) acryloyl groups and the compound (B) having three (meth) acryloyl groups. If a mixture of the water-soluble compound (B) and the water-insoluble compound (B) is used, the water-insoluble compound (B) is easily introduced into the reaction system by the water-soluble compound (B). And a coating film having excellent low-temperature curability can be obtained.
- water-insoluble compound (B) examples include compounds that are not completely water-soluble, such as propoxylated bisphenol A diacrylate (PO4 mol).
- the mixing ratio (water-soluble / water-insoluble) of the water-soluble compound (B) and the water-insoluble compound (B) is preferably 1/9 to 9/1, more preferably 2/8 to 8 / 2.
- the aqueous coating composition can be applied to any suitable substrate.
- the substrate include metal, wood, plastics, rubber, stone, slate, concrete, mortar, fiber, paper, glass, porcelain, earthenware, film, and composites thereof.
- a sealer may be coated on the surface in advance.
- metals examples include iron, copper, tin, zinc, aluminum, and stainless steel.
- Examples of the object to be coated having metal on the surface include, for example, buildings, ships, vehicles (for example, railway vehicles, large vehicles), aircraft, bridges, offshore structures, plants, tanks (for example, oil tanks). , Pipes, steel pipes, cast iron pipes and the like.
- the coating film forming method of the present invention can also be used for buildings and civil engineering structures.
- the coating method typically includes a method in which the water-based coating composition is applied to an object to be coated and dried.
- a coating method any appropriate method can be adopted depending on the type of the object (base material) to be coated. For example, application, immersion, etc. with a brush, a roller, air spray, airless spray, a trowel, etc. are mentioned.
- the coating amount of the aqueous coating composition can be set to any appropriate coating amount depending on the application. Preferably, it is 10 to 350 g / m 2 .
- the drying method Any appropriate method can be adopted as the drying method. Natural drying or heat drying is preferred. In the case of natural drying, the drying time is preferably 2 hours or more, more preferably 24 hours or more, and particularly preferably 1 week or more. According to the method for forming a coating film of the present invention, a coating film having excellent anticorrosion properties can be formed even when dried at a low temperature (for example, 5 ° C. or less).
- the thickness of the coating film formed by applying the aqueous coating composition is preferably 20 to 150 ⁇ m, more preferably 30 to 120 ⁇ m, as the thickness of the dry coating film.
- the thickness of the dried coating film is thicker than 150 ⁇ m, there is a risk that problems such as sagging occur when forming the coating film.
- the coating film obtained from the water-based coating composition has excellent anticorrosion properties. For example, in a portion that does not require weather resistance such as the inner surface of a bridge girder, the coating film alone can sufficiently cope.
- Another coating film can be formed before and / or after the aqueous coating composition is applied to form a coating film.
- a top coating layer is formed on the coating film to form a top coating layer.
- top coat examples include epoxy / amine-based paints, two-component urethane curable paints, one-component urethane curable paints, carbodiimide curable paints, acrylic resin-based paints, alkyd resin-based paints, and silicon resin-based paints.
- the top coat may be solvent-based or water-based. Preferably, it is aqueous. This is because the environmental load can be reduced.
- the top coating is more preferably an aqueous two-component urethane curable coating, an aqueous one-component urethane curable coating, an aqueous silicon resin-based coating, or an aqueous carbodiimide curable coating.
- a water-based paint has excellent weather resistance and can achieve long-term aesthetic protection.
- top coat layer is typically formed by applying a top coat and drying (heat treatment). Any appropriate method can be adopted as the coating method depending on the type of top coat. For example, application, immersion, etc. with a brush, a roller, air spray, airless spray, a trowel, etc. are mentioned.
- the coating amount of the top coating can be set to any appropriate coating amount depending on the type of coating and the purpose of coating. Preferably, it is 30 to 400 g / m 2 .
- drying (heating) method may be employed as a method for drying (heating) the top coating material depending on the type of the top coating material. For example, natural drying, forced drying, baking, etc. are mentioned.
- the thickness of the top coat layer can be set to any appropriate thickness depending on the type of paint and the purpose of painting. Preferably, it is 10 to 150 ⁇ m.
- an undercoat layer may be formed by applying an undercoat paint on the surface of the substrate.
- an undercoat layer it is more excellent in corrosion resistance and water-resistant adhesion, and can sufficiently cope with a case where high corrosion resistance such as a bridge, a plant, and a tank is required.
- any appropriate paint can be adopted as the undercoat paint.
- an organic or inorganic zinc rich paint is mentioned. If such a paint containing zinc powder is used, an undercoat layer having extremely high anticorrosion properties can be formed. Further, since the paint has good workability, a uniform undercoat layer can be formed.
- the undercoat paint may be solvent-based or water-based. Preferably, it is aqueous. This is because the environmental load can be reduced.
- the application amount of the undercoat paint can be set to any appropriate application amount according to the type of paint and the purpose of painting. Preferably, it is 80 to 1200 g / m 2 .
- the thickness of the undercoat layer can be set to any appropriate thickness depending on the type of paint and the purpose of painting. Preferably, it is 20 to 200 ⁇ m.
- an intermediate coating layer may be formed by applying an intermediate coating on the coating film.
- an intermediate coating layer a coating film that is more excellent in corrosion resistance and water-resistant adhesion can be obtained.
- the overcoat layer is formed on the intermediate coat layer.
- any appropriate paint can be adopted as the intermediate paint.
- an epoxy / amine-based paint, a two-component urethane curable paint, a one-component urethane curable paint, and the like can be given.
- the intermediate coating may be solvent-based or water-based. Preferably, it is aqueous. This is because the environmental load can be reduced.
- the intermediate coating is more preferably a water-based epoxy / amine-based paint or a water-based two-component urethane curable paint. With such a water-based paint, the adhesiveness with the top coat layer is good and a strong multilayer coating film can be formed.
- the coating amount of the intermediate coating can be set to any appropriate coating amount depending on the type of coating and the purpose of coating. Preferably, it is 20 to 400 g / m 2 .
- the thickness of the intermediate coating layer can be set to any appropriate thickness depending on the type of paint and the purpose of coating. Preferably, it is 10 to 100 ⁇ m.
- the above-mentioned top coat, intermediate coat and undercoat can contain pigments, additives and the like.
- the pigment and additive include the pigment and additive described in the above section A-1.
- the number, type, and amount of pigments and additives to be added can be appropriately selected according to the purpose.
- the obtained coating film was subjected to a cyclic corrosion test defined in JIS K 5600 7-7, and the coating state after 120 cycles was evaluated based on the following criteria. Ratio of generated rust area to obtained coating film area A: Less than 0.05% B: 0.05% or more and less than 0.1% (initial rainfall resistance)
- the coating film was immersed in water at 5 ° C. together with the base material, pulled up after 24 hours, and allowed to stand at 5 ° C. for 24 hours. Then, the appearance of the coating film was visually observed and evaluated based on the following criteria.
- AA Appearance abnormality is not recognized.
- an epoxy polyamine resin having an amino group equivalent of 2050 was diluted with MIBK until the non-volatile content became 75% to obtain an epoxy polyamine resin having an amino group equivalent of 2050.
- Acetic acid was added thereto to achieve a neutralization rate of 40.0% (neutralization rate with respect to the amino group of the resin), and ion-exchanged water was added for dilution. Thereafter, the mixture of MIBK and water was removed under reduced pressure until the solid content became 40% by mass, to prepare an epoxy polyamine resin.
- the epoxy polyamine resin was phase-separated in water without being made aqueous.
- the characteristics of the compound (B) are as follows. At room temperature, 5 g of the compound (B) was added to 100 g of water, stirred for 3 minutes and allowed to stand. It was judged as “water-soluble”, “water-soluble” if it was clear without precipitation, and “self-emulsifying” if it was turbid without precipitation.
- a monomer mixture was prepared.
- the acid value of the obtained monomer mixed solution was 13 mgKOH / g.
- This monomer mixture is added to an aqueous emulsifier solution in which 1.2 parts of sodium alkyldiphenyl ether disulfonate (trade name “Perex SS-H” manufactured by Kao Corporation) is dissolved in 50 parts of ion-exchanged water, and emulsified using a mixer.
- a pre-emulsion To prepare a pre-emulsion.
- the former started to drip evenly over 120 minutes and the latter over 150 minutes. After completion of the dropwise addition, the reaction was continued for an additional 120 minutes at the same temperature. After cooling, the solution was neutralized with aqueous ammonia corresponding to 10 mol% of the methacrylic acid used. The neutralized product was filtered through a 200 mesh wire mesh to obtain an acrylic emulsion resin.
- emulsified epoxy resin made by ADEKA, trade name “ADEKA RESIN EM-101-50”, epoxy equivalent: 500 g / equivalent, solid content 47%), film-forming aid (made by Chisso, trade name “CS”) -12 ") 1.7 parts, 0.4 parts of a rust preventive agent, 0.2 parts of an antifoaming agent and 17 parts of the previously prepared acrylic emulsion resin were mixed to obtain a base coating liquid.
- 8.9 parts of water-soluble polyamine resin sunmide manufactured by Air Products and Chemicals, trade name “WH-910”, active hydrogen equivalent 135 g / equivalent (solid content conversion, solid content 60%)
- water 11. 2 parts were mixed to obtain a curing agent.
- curing agent were mixed, and the water-based epoxy / amine type coating material A was obtained by stirring with a disper.
- methyl isobutyl ketone and water were distilled off at 40 ° C., and the active ingredient was adjusted to 40% by mass to obtain an aqueous carbodiimide curing agent having a carbodiimide equivalent of 825 g / equivalent.
- an aqueous carbodiimide curing agent having a carbodiimide equivalent of 825 g / equivalent.
- 6.8 parts of water, 1 part of pigment dispersant (trade name “Disperbyk-190” manufactured by Big Chemie), 1 part of ethylene glycol, 0.2 part of antifoaming agent, 2 parts of barium sulfate, and 24 parts of titanium oxide were added.
- 35 parts of pigment paste obtained by mixing and dispersing with a disper 35 parts of an acrylic emulsion (acid value: 30 mgKOH / g, solid content: 55% by mass), water-soluble acrylic resin (acid value: 55 mgKOH / g, hydroxyl value: 70 mgKOH) / G, weight average molecular weight: 9000, solid content: 30% by mass) 8 parts, film forming aid (trade name “CS-12”, manufactured by Chisso Corporation), 3 parts, viscosity agent 1 part, antifoaming agent 1 part, Was added to obtain a base paint liquid.
- An aqueous carbodiimide-based paint was obtained by adding 35 parts of the previously prepared aqueous carbodiimide curing agent to the obtained main coating liquid and stirring with a disper.
- Example 1 Formation of single-layer coating film 24 hours after preparing the aqueous coating composition 1 by the method of Production Example 29 in an environment of 30 ° C., the aqueous coating composition 1 was applied to the sandblasted steel plate with a brush so that the coating amount was 200 g / m 2. Then, it was dried in an environment of 20 ° C. for 7 days to form a single layer coating film (thickness after drying: 60 ⁇ m) formed of the aqueous coating composition 1. At this time, the aqueous coating composition 1 was not gelled and could be applied with good workability. About the obtained single layer coating film, the above "corrosion resistance" was evaluated. The evaluation results are shown in Table 4.
- Example 2 to 19 Formation of single-layer coating film A single-layer coating film was obtained in the same manner as in Example 1 except that the aqueous coating composition shown in Table 4 was used instead of the aqueous coating composition 1. . In any of the examples, the aqueous coating composition 24 hours after preparation was used, but none of the aqueous coating composition was gelled. The obtained single-layer coating film was subjected to the same evaluation as in Example 1. The evaluation results are shown in Table 4.
- Aqueous coating composition 1 was prepared by the method of Production Example 29 in an environment of 5 ° C, and after 1 hour, the aqueous coating composition 1 was applied to a polished steel sheet in an amount of 200 g. / M 2 was applied with a brush and dried in an environment of 5 ° C. for 24 hours to form a single-layer coating film (thickness after drying: 60 ⁇ m) formed of the aqueous coating composition 1. At this time, the aqueous coating composition 1 was not gelled and could be applied with good workability. About the obtained coating film, the above-mentioned "initial rainfall resistance" was evaluated. The evaluation results are shown in Table 4.
- Example 21 to 38 Formation of single-layer coating film A single-layer coating film was obtained in the same manner as in Example 20, except that the aqueous coating composition shown in Table 4 was used instead of the aqueous coating composition 1. . In any of the examples, the aqueous coating composition that had passed 1 hour after preparation was used, but none of the aqueous coating compositions gelled. The obtained single-layer coating film was subjected to the same evaluation as in Example 20. The evaluation results are shown in Table 4.
- Example 39 Formation of single-layer coating film Polished steel sheet prepared by preparing the aqueous coating composition 1 by the method of Production Example 29 in an environment of 23 ° C and defatting the aqueous coating composition 1 with xylene after 24 hours.
- a single-layer coating film (60 ⁇ m in thickness after drying) formed by the aqueous coating composition 1 is applied with a brush so that the coating amount is 200 g / m 2 and dried for 7 days in an environment of 23 ° C. Formed. At this time, the aqueous coating composition 1 was not gelled and could be applied with good workability. About the obtained coating film, said "water-resistant adhesion" was evaluated. The evaluation results are shown in Table 4.
- Example 40 to 57 Formation of a single-layer coating film A single-layer coating film was obtained in the same manner as in Example 39 except that the aqueous coating composition shown in Table 4 was used instead of the aqueous coating composition 1. . In any of the examples, the aqueous coating composition 24 hours after preparation was used, but none of the aqueous coating composition was gelled. The obtained single-layer coating film was subjected to the same evaluation as in Example 39. The evaluation results are shown in Table 4.
- Example 58 Formation of multilayer coating film (two layers) A polished steel plate degreased with xylene was used as the substrate. In an environment of 5 ° C., the aqueous coating composition 12 obtained in Production Example 40 was applied to the substrate using a brush at an application amount of 200 g / m 2 , and then dried for 24 hours in the same environment as the application. Thus, a coating film (thickness after drying: 60 ⁇ m) formed from the aqueous coating composition I was obtained. The obtained coating film had no touch feeling (specifically, no stickiness), and it was possible to apply a top coating.
- a coating amount of a solvent-type epoxy / amine-based paint A (trade name “Epotal NB-20”, manufactured by Nippon Paint Co., Ltd.) is used as a top coating paint in an environment of 5 ° C. in an environment of 5 ° C. After coating at 200 g / m 2, it was dried at 25 ° C. for 24 hours to form an overcoat layer (thickness after drying 60 ⁇ m) to obtain a multilayer coating film (two layers). The obtained “multilayer coating film (2 layers)” was evaluated for the “water adhesion”. The evaluation results are shown in Table 5.
- Example 59 to 68 Formation of multi-layer coating film (two layers) Using the substrate, aqueous coating composition and top coating composition shown in Table 5, the method described in Example 58 was carried out under the conditions shown in Table 5. A multilayer coating film (2 layers) was obtained in the same manner.
- the top coating materials shown in Table 5 used in Examples 59 to 68 are as follows.
- the polished steel plate used in Example 59 was previously degreased with xylene
- the slate plate used in Example 65 was previously provided with an aqueous sealer for inorganic materials (manufactured by Nippon Paint Co., Ltd. The name “Ultra Sealer III”) is applied.
- Example 58 None of the coating films formed from the aqueous coating composition had a touch feeling (specifically, there was no stickiness), and it was possible to apply a top coating. Further, the obtained multilayer coating film (two layers) was subjected to the same evaluation as in Example 58. The evaluation results are shown in Table 5.
- [Top coat] 1. Solvent type epoxy / amine paint A As a solvent-type epoxy / amine paint A, a product name “Epotal NB-20” manufactured by Nippon Paint Co., Ltd. was used. 2. Solvent two-component urethane paint A As the solvent two-component urethane-based paint A, Nippon Paint Co., Ltd. trade name “Hypon 50 Fine” was used. 3.
- Solvent two-component urethane paint B As the solvent two-component urethane-based paint B, Nippon Paint Co., Ltd., trade name “Nippure Top Eco” was used. 4). Water-based epoxy / amine paint A As the water-based epoxy / amine-based paint A, the water-based epoxy / amine-based paint A produced in Production Example 48 was used. 5. Aqueous two-component urethane paint A As the aqueous two-component urethane-based paint A, the aqueous two-component urethane-based paint A produced in Production Example 50 was used. 6).
- Water-based emulsion-based paint As a water-based emulsion-based paint, a product name “Odecoat G” manufactured by Nippon Paint Co., Ltd. was used. 7). Aqueous carbodiimide-based paint The aqueous carbodiimide-based paint produced in Production Example 51 was used as the aqueous carbodiimide-based paint.
- Example 69 Formation of multilayer coating film (four layers) Apply a solvent-type organic zinc rich paint (trade name “N Zinky 8000HB”, manufactured by Nippon Paint Co., Ltd.) as an undercoat on the sandblasted steel sheet to a thickness of 70 ⁇ m after drying to form an undercoat layer. It was. Thereafter, the aqueous coating composition 13 obtained in Production Example 41 was applied onto the undercoat layer with a brush so that the thickness after drying was 60 ⁇ m in an environment of 5 ° C., and then the same environment as that applied. The coating film formed with the aqueous coating composition 13 was obtained by drying for 1 day.
- a solvent-type organic zinc rich paint trade name “N Zinky 8000HB”, manufactured by Nippon Paint Co., Ltd.
- a thickness of 30 ⁇ m after drying solvent-type epoxy / amine-based paint B (made by Nippon Paint Co., Ltd., trade name “Hypon 30 Fine Intermediate Coating”) as an intermediate coating under an environment of 25 ° C. in an environment of 25 ° C.
- solvent-type epoxy / amine-based paint B made by Nippon Paint Co., Ltd., trade name “Hypon 30 Fine Intermediate Coating”
- the coating was dried for 1 day under the same environment as that for coating to obtain an intermediate coating layer.
- a solvent two-component urethane coating material A (manufactured by Nippon Paint Co., Ltd., trade name “Hypon 50 Fine”) as a top coating material is dried to a thickness of 30 ⁇ m.
- Example 70 Formation of multi-layer coating film (four layers) Multi-layer coating was carried out in the same manner as in Example 69 except that the undercoat paint, water-based paint composition, intermediate coat paint and top coat paint shown in Table 6 were used. A membrane (4 layers) was obtained. The undercoat paint, intermediate coat paint and top coat paint shown in Table 6 used in Example 70 are as follows. The obtained multilayer coating film (4 layers) was subjected to the same evaluation as in Example 69. The evaluation results are shown in Table 6. [Undercoating paint] The aqueous organic zinc rich paint obtained in Production Example 52 was used. [Intermediate paint] As the water-based epoxy / amine-based paint B, the water-based epoxy / amine-based paint B obtained in Production Example 49 was used. [Top coat] The water-based carbodiimide-based paint produced in Production Example 51 was used as the water-based carbodiimide-based paint.
- Example 1 The same procedure as in Example 58 except that solvent-based epoxy / amine-based paint A (trade name “Epotal NB-20” manufactured by Nippon Paint Co., Ltd.) was used in place of the aqueous paint composition 12 obtained in Production Example 40. Thus, a coating film formed of the solvent-type epoxy / amine-based paint A on the substrate was obtained. The obtained coating film was sticky and was not in a state where a top coating material could be applied.
- solvent-based epoxy / amine-based paint A trade name “Epotal NB-20” manufactured by Nippon Paint Co., Ltd.
- the coating film formed by the coating film forming method of the present invention exhibited sufficient curability even at low temperatures.
- the coating film formed from the conventional epoxy / amine-based paint had insufficient curability at low temperatures.
- an aqueous coating composition containing an aqueous epoxy polyamine resin (A) obtained using an epoxy resin (a1) having an epoxy equivalent of 2000 to 3200 It is possible to form a coating film that is more excellent in rainability.
- an aqueous coating composition containing an aqueous epoxy polyamine resin (A2) obtained from an epoxy resin (a2) having an epoxy equivalent of 2000 to 3200 at a specific mass ratio (a1 / a2) It is possible to form a coating film that is excellent in rainfall and water adhesion.
- the coating film forming method of the present invention was able to obtain a coating film having excellent water resistance adhesion by forming a topcoat layer.
- the coating film forming method of the present invention was able to obtain a coating film excellent in water resistance and corrosion resistance by forming an undercoat layer, an intermediate coat layer and an overcoat layer. .
- the coating-film formation method of this invention can be used suitably for an anticorrosion use, for example.
- vehicles eg, railway vehicles, large vehicles
- aircraft e.g., bridges, offshore structures, plants, tanks (eg, oil tanks), pipes, steel pipes, cast iron pipes, doors, window frames, etc. It can be suitably used for a metal part included in a building.
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Abstract
Description
好ましい実施形態においては、上記水性塗料組成物が2液型水性塗料組成物であり、主剤塗料液が上記水性エポキシ系ポリアミン樹脂(A)を含み、硬化剤が上記化合物(B)を含む。
好ましい実施形態においては、上記水性エポキシ系ポリアミン樹脂(A)が水分散型である。
好ましい実施形態においては、上記水性エポキシ系ポリアミン樹脂(A)のアミノ基の当量が100~3000である。
好ましい実施形態においては、上記水性エポキシ系ポリアミン樹脂(A)が、エポキシ樹脂をアミン変性して得られ、該エポキシ樹脂のエポキシ当量が180~3800である。
好ましい実施形態においては、上記水性塗料組成物は、上記水性エポキシ系ポリアミン樹脂(A)として、エポキシ当量が400~1500であるエポキシ樹脂(a1)をアミン変成して得られる水性エポキシ系ポリアミン樹脂(A1)と、エポキシ当量が2000~3200であるエポキシ樹脂(a2)をアミン変性して得られる水性エポキシ系ポリアミン樹脂(A2)とを含む。
好ましい実施形態においては、上記前記エポキシ樹脂(a1)と前記エポキシ樹脂(a2)との質量比a1/a2が、8/2~2/8である。
好ましい実施形態においては、上記水性エポキシ系ポリアミン樹脂(A)が、エポキシ系ポリアミン樹脂のアミノ基を酸で中和して得られ、該中和の際の中和率が10%~70%である。
好ましい実施形態においては、上記化合物(B)の25℃における粘度が3000mPa・s以下である。
好ましい実施形態においては、上記化合物(B)の分子量が150以上2000以下である。
好ましい実施形態においては、本発明の塗膜形成方法は、上記水性塗料組成物による塗膜形成後、該塗膜上に、上塗り層を形成することを含む。
好ましい実施形態においては、本発明の塗膜形成方法は、上記水性塗料組成物による塗膜形成後、上記上塗り層形成前に、中塗り層を形成することを含む。
好ましい実施形態においては、本発明の塗膜形成方法は、上記水性塗料組成物による塗膜形成前に、上記基材に、下塗り層を形成することを含む。
本発明の塗膜形成方法は、基材に水性塗料組成物を塗装して塗膜を形成することを含む。
上記水性塗料組成物は、分子内に1つ以上の第1アミノ基および/または第2アミノ基を有する水性エポキシ系ポリアミン樹脂(A)および分子内に1つ以上の(メタ)アクリロイル基を有する化合物(B)を含む。上記水性塗料組成物は、水性エポキシ系ポリアミン樹脂(A)と化合物(B)とを混合することにより、これら化合物の硬化反応(マイケル付加反応)を進行させて、塗膜を形成することができる。水性エポキシ系ポリアミン樹脂(A)と化合物(B)とは、低温下(例えば、5℃)でも硬化反応し得るので、上記水性塗料組成物は低温硬化性に優れる。
上記水性塗料組成物は、分子内に1つ以上の第1アミノ基および/または第2アミノ基を有する水性エポキシ系ポリアミン樹脂(A)を含む。上記水性塗料組成物は、このような樹脂をバインダーとして含むことにより、防食性に優れた塗膜を形成することができる。なお、本明細書において「水性」とは、「水溶性」および「水分散型」を含む概念である。
上記水性塗料組成物に用いられる化合物(B)は、分子内に1以上の(メタ)アクリロイル基を有する。
上記水性塗料組成物は、任意の適切な基材に塗装され得る。基材としては、例えば、金属、木材、プラスティックス、ゴム、石材、スレート、コンクリート、モルタル、繊維、紙、ガラス、磁器、陶器、フィルム、およびこれらの複合体等が挙げられる。また、例えば、基材がスレート、コンクリート等の無機系基材の場合、予めその表面にシーラーが塗装されていてもよい。特性を考慮すると、好ましくは、金属に適用される。金属としては、例えば、鉄、銅、錫、亜鉛、アルミニウム、ステンレス等が挙げられる。
上記水性塗料組成物を塗装して塗膜を形成する前および/または後に、別の塗膜を形成することができる。一つの実施形態においては、上記水性塗料組成物を塗装して塗膜を形成した後、当該塗膜上に上塗り塗料を塗装して上塗り層を形成する。上塗り層を形成することにより、外観、防食性および耐水付着性がさらに向上する。
得られた塗膜に対し、JIS K 5600 7-7に定めるサイクル腐食試験を実施し、120サイクル後の塗膜状態を下記基準に基づいて評価した。
得られた塗膜面積に対する、生じた錆面積の割合
A:0.05%未満
B:0.05%以上0.1%未満
(初期耐降雨性)
塗膜を基材ごと5℃の水中に浸漬し、24時間経過後に引き上げ、5℃で24時間静置した後、塗膜外観を目視観察し、下記基準に基づき評価した。
AA:外観の異常が認められない
A :多少の艶・色の変化は認められるが、ワレ・フクレ跡は認められない
C :ワレ・フクレ跡が認められる
(耐水付着性)
塗膜を被塗物ごと20℃の水中に浸漬し、7日間経過後に引き上げた後、JIS K 5600-5.6(2006)クロスカット法に準じて、塗膜に3mm×3mmのマス目を5×5個作成した。その表面に粘着テープを貼付した後、急激に剥離し、下記基準に基づき評価した。
10点:1マスも剥離せず、カット部に沿った剥離も認められない(剥離面積:0%)
8点:マス目の剥離はないが、若干のカット部に沿った剥離が認められる(剥離面積:0%超えて5%未満)
6点以下:剥離したマス目が認められるか、またはカット部に沿った剥離が顕著に認められる(剥離面積:5%以上)
[製造例1]水性エポキシ系ポリアミン樹脂(A)Iの作製
撹拌機、冷却器、窒素導入管および温度計を備えた反応槽に、ビスフェノールAとエピクロルヒドリンとから合成したエポキシ当量188g/当量の原料樹脂702部、ビスフェノールA269部、ダイマー酸108部、メチルイソブチルケトン(以下「MIBK」という)190部を仕込み、ベンジルジメチルアミン1部存在下、エポキシ当量1079g/当量になるまで117℃で反応させてエポキシ樹脂を得た。その後、アミノエチルエタノールアミンのケチミン化合物(73質量%MIBK溶液)255部を加え、117℃で1時間反応させた。その後、MIBKで不揮発分75%になるまで希釈し、アミノ基の当量1184のエポキシ系ポリアミン樹脂を得た。
ここに、酢酸を加え、中和率35.0%(樹脂のアミノ基に対する中和率)となるようにし、イオン交換水を加えて希釈した。その後、固形分が40質量%となるまで減圧下でMIBKおよび水の混合物を除去し、乳白色の水性(水分散型)エポキシ系ポリアミン樹脂(A)Iを調製した。
撹拌機、冷却器、窒素導入管および温度計を備えた反応槽に、ビスフェノールAとエピクロルヒドリンとから合成したエポキシ当量188g/当量の原料樹脂742部、ビスフェノールA336部、MIBK190部を仕込み、ベンジルジメチルアミン1部存在下、エポキシ当量1079g/当量になるまで117℃で反応させてエポキシ樹脂を得た。その後、ジエチレントリアミンのケチミン化合物(73質量%MIBK溶液)350部を加え、117℃で1時間反応させた。その後、イオン交換水27部、ネオデカン酸グリシジルエステル(ヘキシオン・スペシャルティー・ケミカルズ社製、商品名「カージュラE10-P」)188部を仕込み、100℃で2時間反応させた。その後、MIBKで不揮発分75%になるまで希釈し、アミノ基の当量1093のエポキシ系ポリアミン樹脂を得た。
ここに、酢酸を加え、中和率35.0%(樹脂のアミノ基に対する中和率)となるようにし、イオン交換水を加え希釈した。その後、固形分が40質量%となるまで減圧下でMIBKおよび水の混合物を除去し、乳白色の水性(水分散型)エポキシ系ポリアミン樹脂(A)IIを調製した。
撹拌機、冷却器、窒素導入管および温度計を備えた反応槽に、ビスフェノールAとエピクロルヒドリンとから合成したエポキシ当量188g/当量の原料樹脂525部、ビスフェノールA205部、MIBK110部を仕込み、ベンジルジメチルアミン1部存在下、エポキシ当量730g/当量になるまで117℃で反応させてエポキシ樹脂を得た。その後、ジエチレントリアミンのケチミン化合物(73質量%MIBK溶液)350部を加え、117℃で1時間反応させた。その後、イオン交換水27部、ネオデカン酸グリシジルエステル(ヘキシオン・スペシャルティー・ケミカルズ社製、商品名「カージュラE10-P」)188部を仕込み、100℃で2時間反応させた。その後、MIBKで不揮発分75%になるまで希釈し、アミノ基の当量810のエポキシ系ポリアミン樹脂を得た。
ここに、酢酸を加え、中和率20.0%(樹脂のアミノ基に対する中和率)となるようにし、イオン交換水を加え希釈した。その後、固形分が40質量%となるまで減圧下でMIBKおよび水の混合物を除去し、乳白色の水性(水分散型)エポキシ系ポリアミン樹脂(A)IIIを調製した。
撹拌機、冷却器、窒素導入管および温度計を備えた反応槽に、ビスフェノールAとエピクロルヒドリンとから合成したエポキシ当量188g/当量の原料樹脂1940部、ビスフェノールA1060部、MIBK550部を仕込み、ベンジルジメチルアミン8部存在下、エポキシ当量3000g/当量になるまで117℃で反応させてエポキシ樹脂を得た。その後、ジエチレントリアミンのケチミン化合物(73質量%MIBK溶液)350部を加え、117℃で1時間反応させた。その後、ジプロピレングリコールモノブチルエーテル(以下、「DPnB」という)1060部を仕込み、100℃で2時間反応させた。その後、MIBKで不揮発分75%になるまで希釈し、アミノ基の当量1550のエポキシ系ポリアミン樹脂を得た。
ここに、酢酸を加え、中和率40.0%(樹脂のアミノ基に対する中和率)となるようにし、イオン交換水を加え希釈した。その後、固形分が40質量%となるまで減圧下でMIBKおよび水の混合物を除去し、乳白色の水性(水分散型)エポキシ系ポリアミン樹脂(A)IVを調製した。
中和率を下記表1に示す中和率とした以外は、製造例2と同様にして、水性エポキシ系ポリアミン樹脂(A)V~VIIを調整した。
撹拌機、冷却器、窒素導入管および温度計を備えた反応槽に、ビスフェノールAとエピクロルヒドリンとから合成したエポキシ当量188g/当量の原料樹脂1440部、ビスフェノールA760部、MIBK388部を仕込み、ベンジルジメチルアミン3部存在下、エポキシ当量2200g/当量になるまで117℃で反応させてエポキシ樹脂を得た。その後、ジエチレントリアミンのケチミン化合物(73質量%MIBK溶液)350部を加え、117℃で1時間反応させた。次いで、100℃でさらに2時間反応させた後、MIBKで不揮発分75%になるまで希釈し、アミノ基の当量1150のエポキシ系ポリアミン樹脂を得た。
ここに、酢酸を加え、中和率40.0%(樹脂のアミノ基に対する中和率)となるようにし、イオン交換水を加え希釈した。その後、固形分が40質量%となるまで減圧下でMIBKおよび水の混合物を除去し、乳白色の水性(水分散型)エポキシ系ポリアミン樹脂(A)VIIIを調製した。
中和率を5%とした以外は、製造例2と同様にして、エポキシ系ポリアミン樹脂を調整した。エポキシ系ポリアミン樹脂は、水性化されずに水中で相分離した。
撹拌機、冷却器、窒素導入管および温度計を備えた反応槽に、ビスフェノールAとエピクロルヒドリンとから合成したエポキシ当量188g/当量の原料樹脂2560部、ビスフェノールA1439部、MIBK706部を仕込み、ベンジルジメチルアミン5部存在下、エポキシ当量4000g/当量になるまで117℃で反応させてエポキシ樹脂を得た。その後、ジエチレントリアミンのケチミン化合物(73質量%MIBK溶液)350部を加え、117℃で1時間反応させた。次いで、100℃でさらに2時間反応させた後、MIBKで不揮発分75%になるまで希釈し、アミノ基の当量2050のエポキシ系ポリアミン樹脂を得た。
ここに、酢酸を加え、中和率40.0%(樹脂のアミノ基に対する中和率)となるようにし、イオン交換水を加え希釈した。その後、固形分が40質量%となるまで減圧下でMIBKおよび水の混合物を除去し、エポキシ系ポリアミン樹脂を調製した。エポキシ系ポリアミン樹脂は、水性化されずに水中で相分離した。
水110部、顔料分散剤(ビックケミー社製、商品名「Disperbyk-190」)32部、消泡剤(ビックケミー社製、商品名「BYK-019」)4部、炭酸カルシウム(丸尾カルシウム社製、商品名「N重炭」)179部、酸化チタン(デュポン社製、商品名「TI-PUR R706」)172部、カルシウム系防錆顔料(東邦顔料社製、商品名「EXPERT NP1007」)25部を混合し、ディスパーで30分間攪拌することによって、顔料分散ペーストを製造した。この顔料ペースト500部に対し、製造例1で得た水性エポキシ系ポリアミン樹脂(A)I400部、DPnB24部および会合型増粘剤(アデカ社製、商品名「アデカノールUH-420」)1部を加えて混合し、主剤塗料液Iを得た。
水性エポキシ系ポリアミン樹脂(A)Iに代えて、表2に示す水性エポキシ系ポリアミン樹脂(A)を用いた以外は、製造例11と同様にして主剤塗料液II~VIIを得た。
水40部、DPnB10部および化合物(B)としてポリエチレングリコール#400ジメタクリレート(EO9mol)(粘度(25℃):58mPa・s、分子量:508、官能基数:2、アクリロイル基当量:254)50部を混合し、ホモジナイザーで10分間撹拌して、硬化剤Iを得た。
表3に示す化合物(B)、配合比および混合方法により、製造例19の方法に準じて、化合物(B)を含む硬化剤II~Xを得た。なお、硬化剤II、V、VIII、IXにおける乳化剤は、ノニオン系乳化剤(日本乳化剤社製、商品名「ニューコール740」)を用いた。各製造例で用いた化合物(B)の25℃における粘度、分子量、官能基数、アクリロイル基当量および特性(自己乳化性、非水溶性、水溶性)を表3に示す。化合物(B)の特性は、室温下において、化合物(B)5gを100gの水に加えて3分間撹拌し、静置した後の状態を目視で観察して、沈殿が生じていれば「非水溶性」、沈殿がなく透明であれば「水溶性」、沈殿がなく濁りがあれば「自己乳化性」と判断した。
製造例11~18のいずれかで得られた主剤塗料液と、製造例19~27のいずれかで得られた硬化剤とを、表4に示す配合量で混合し、それぞれディスパーで10分間撹拌することにより、水性塗料組成物1~19を得た。
[製造例48]水性エポキシ/アミン系塗料Aの製造
イオン交換水34.5部、アルキルジフェニルエーテルジスルホン酸ナトリウム(花王社製、商品名「ペレックスSS-H」)0.3部を仕込み、窒素雰囲気のもとで80℃に昇温した。次いで、モノマーとして、スチレン14部、2-エチルへキシルアクリレート58部、メチルメタクリレート22部、エチレングリコールジメタクリレート4部、およびメタクリル酸2部を含み、連鎖移動剤としてラウリルメルカプタン0.5部を含むモノマー混合液を調製した。得られたモノマー混合液の酸価は13mgKOH/gであった。このモノマー混合液を、アルキルジフェニルエーテルジスルホン酸ナトリウム(花王社製、商品名「ペレックスSS-H」)1.2部をイオン交換水50部に溶解させた乳化剤水溶液中に加え、ミキサーを用いて乳化させてプレエマルションを調製した。
このようにして得られたプレエマルションと、過硫酸アンモニウム0.3部をイオン交換水13部に溶解させた開始剤水溶液とを上記セパラブルフラスコに別個の滴下漏斗から同時に滴下した。前者は120分間、後者は150分間にわたって均等に滴下を開始した。滴下終了後、同温度でさらに120分間反応を継続した。冷却後、用いたメタクリル酸の10モル%に相当するアンモニア水で中和した。中和物を200メッシュの金網で濾過し、アクリルエマルション樹脂を得た。
続いて、顔料分散剤(ビックケミー社製、商品名「Disperbyk-190」)1.9部、消泡剤(ビックケミー社製、商品名「BYK-019」)0.3部、酸化チタン18.6部、炭酸カルシウム10.9部、タルク8.5部、防錆剤(キクチカラー社製、商品名「LFボウセイPM-303W」)2.9部、および水12.1部を混合し、ディスパーで分散した。
ここに、乳化エポキシ樹脂(ADEKA社製、商品名「アデカレジンEM-101-50」、エポキシ当量:500g/当量、固形分47%)41部、造膜助剤(チッソ社製、商品名「CS-12」)1.7部、防錆剤0.4部、消泡剤0.2部および、先に製造したアクリルエマルション樹脂17部を混合して、主剤塗料液を得た。
また、水溶性ポリアミン樹脂サンマイド(エアープロダクツ・アンド・ケミカルズ社製、商品名「WH-910」、活性水素当量 135g/当量(固形分換算)、固形分60%)8.9部と水11.2部とを混合して、硬化剤を得た。
上記主剤塗料液と硬化剤とを混合し、ディスパーで攪拌することによって、水性エポキシ/アミン系塗料Aを得た。
主剤塗料液の配合について、アクリルエマルション樹脂17部に代えて、アクリルエマルション樹脂4部とした以外は、製造例48と同様にして、水性エポキシ/アミン系塗料Bを得た。
水22部、顔料分散剤(ビックケミー社製、商品名「Disperbyk-190」)6部、酸化チタン70部、消泡剤(ビックケミー社製、商品名「BYK-011」、10%に希釈して使用)1部、ジメチルエタノールアミン水溶液(25質量%)0.4部を混合し、ディスパーで攪拌して、顔料ペーストを得た。
得られた顔料ペースト39部、水性アクリルポリオール(DIC社製、商品名「バーノックWE-306」)58部、表面調整剤(ビックケミー社製、商品名「BYK-346」)0.4部、レベリング剤(ビックケミー社製、商品名「BYK-333」)0.05部、界面活性剤(エアープロダクツ社製、商品名「ダイノール604」)0.4部、粘性調整剤(ローム&ハース社製、商品名「プライマルRM-8W」)0.5部、ジメチルエタノールアミン水溶液(25質量%)0.1部、消泡剤(サンノプコ社製、商品名「SNディフォーマー373」)2部を混合して、ディスパーで攪拌することにより主剤塗料液を得た。
上記主剤塗料液100部に対し、水分散性ポリイソシアネート(DIC社製、商品名「バーノックDNW-5000」)17部を混合し、ディスパーで攪拌して水性2液型ウレタン系塗料Aを得た。
4,4-ジシクロヘキシルメタンジイソシアネート100部を、カルボジイミド化触媒3-メチル-1-フェニル-2-ホスホレン-1-オキシド1部の存在下、170℃で8時間反応を行い、1分子中にカルボジイミド基を約3個有し、両末端にイソシアネート基を有するカルボジイミド化合物(イソシアネート当量450g/当量)を得た。
このカルボジイミド化合物をメチルイソブチルケトンで50質量%に希釈して得られた溶液360部に、ジブチル錫ラウレート0.02部および分子量2000のポリプロピレングリコール165部を加え、85℃で1時間反応させた。続いて、繰り返し単位数15のポリエチレングリコールモノメチルエーテル125部を加え、85℃で1.5時間反応させた。
赤外分光光度計でイソシアネート基の消失を確認した後、脱イオン水920部を加え、攪拌して均一化した。減圧下、40℃でメチルイソブチルケトンおよび水を留去して、有効成分が40質量%になるよう調整して、カルボジイミド当量が825g/当量の水性カルボジイミド硬化剤を得た。
次いで、水6.8部、顔料分散剤(ビックケミー社製、商品名「Disperbyk-190」)1部、エチレングリコール1部、消泡剤0.2部、硫酸バリウム2部、酸化チタン24部をディスパーで混合分散して得られた顔料ペースト35部とアクリルエマルション(酸価:30mgKOH/g、固形分:55質量%)35部、水溶性アクリル樹脂(酸価:55mgKOH/g、水酸基価:70mgKOH/g、質量平均分子量:9000、固形分:30質量%)8部、造膜助剤(チッソ社製、商品名「CS-12」)3部、粘性剤1部、消泡剤1部とを加え、主剤塗料液を得た。
得られた主剤塗料液に、先に製造した水性カルボジイミド硬化剤35部を加え、ディスパーで攪拌することにより、水性カルボジイミド系塗料を得た。
[製造例52]水性有機系ジンクリッチ塗料の製造
水溶性ポリアミン樹脂(エアープロダクツ・アンド・ケミカルズ社製、商品名「サンマイド WH-910」、活性水素当量 135g/当量(固形分換算)、固形分60%)8.8部、粘性剤1.2部、水6部を混合して硬化剤を得た。
上記硬化剤と乳化エポキシ樹脂(ADEKA社製、商品名「アデカレジンEM-101-50」、エポキシ当量 500g/当量、固形分47%)16部、亜鉛粉末68部を混合し、ディスパーで攪拌することによって、水性有機系ジンクリッチ塗料を得た。
30℃の環境下で製造例29の方法により水性塗料組成物1を調製して24時間経過後、当該水性塗料組成物1をサンドブラスト処理鋼板に塗布量200g/m2となるよう、刷毛で塗布し、20℃の環境下で7日間乾燥させて、水性塗料組成物1により形成される単層塗膜(乾燥後の厚さ60μm)を形成した。このとき、水性塗料組成物1はゲル化しておらず、作業性よく塗布することができた。得られた単層塗膜について、上記「防食性」の評価を行った。評価結果を表4に示す。
水性塗料組成物1に代えて、表4に示す水性塗料組成物を用いた以外は、実施例1と同様にして単層塗膜を得た。なお、いずれの実施例においても、調製後24時間経過した水性塗料組成物を用いたが、いずれの水性塗料組成物もゲル化することはなかった。得られた単層塗膜を実施例1と同様の評価に供した。評価結果を表4に示す。
5℃の環境下で製造例29の方法により水性塗料組成物1を調製して1時間経過後、当該水性塗料組成物1を磨き鋼板に塗布量200g/m2となるよう、刷毛で塗布し、5℃の環境下で24時間乾燥させて、水性塗料組成物1により形成される単層塗膜(乾燥後の厚さ60μm)を形成した。このとき、水性塗料組成物1はゲル化しておらず、作業性よく塗布することができた。得られた塗膜について、上記「初期耐降雨性」の評価を行った。評価結果を表4に示す。
水性塗料組成物1に代えて、表4に示す水性塗料組成物を用いた以外は、実施例20と同様にして単層塗膜を得た。なお、いずれの実施例においても、調製後1時間経過した水性塗料組成物を用いたが、いずれの水性塗料組成物もゲル化することはなかった。得られた単層塗膜を実施例20と同様の評価に供した。評価結果を表4に示す。
23℃の環境下で製造例29の方法により水性塗料組成物1を調製して24時間経過後、当該水性塗料組成物1をキシレンで脱脂した磨き鋼板に塗布量200g/m2となるよう、刷毛で塗布し、23℃の環境下で7日間乾燥させて、水性塗料組成物1により形成される単層塗膜(乾燥後の厚さ60μm)を形成した。このとき、水性塗料組成物1はゲル化しておらず、作業性よく塗布することができた。得られた塗膜について、上記「耐水付着性」の評価を行った。評価結果を表4に示す。
水性塗料組成物1に代えて、表4に示す水性塗料組成物を用いた以外は、実施例39と同様にして単層塗膜を得た。なお、いずれの実施例においても、調製後24時間経過した水性塗料組成物を用いたが、いずれの水性塗料組成物もゲル化することはなかった。得られた単層塗膜を実施例39と同様の評価に供した。評価結果を表4に示す。
基材として、キシレンで脱脂した磨き鋼板を用いた。5℃の環境下で、当該基板に、刷毛を用いて、塗布量200g/m2で製造例40で得られた水性塗料組成物12を塗布した後、塗布時と同じ環境下で24時間乾燥させて、水性塗料組成物Iにより形成される塗膜(乾燥後の厚さ60μm)を得た。得られた塗膜は、指触感がなく(具体的には、べたつきがなく)、上塗り塗料を塗布することが可能であった。
得られた塗膜の上に、5℃の環境下で、上塗り塗料として溶剤型エポキシ/アミン系塗料A(日本ペイント社製、商品名「エポタールNB-20」)を刷毛を用いて、塗布量200g/m2で塗布した後、25℃で24時間乾燥させて、上塗り層(乾燥後の厚さ60μm)を形成し、複層塗膜(2層)を得た。
得られた複層塗膜(2層)について、上記「耐水付着性」の評価を行った。評価結果を表5に示す。
表5に示す基材、水性塗料組成物および上塗り塗料を用いて、表5に示す条件下、実施例58に記載の方法に準じて複層塗膜(2層)を得た。実施例59~68で用いた表5に示す上塗り塗料は、以下のとおりである。なお、実施例59で用いた磨き鋼板は、予め、キシレンで脱脂したものであり、実施例65で用いたスレート板は、予め、その表面に、無機質材用水性シーラー(日本ペイント社製、商品名「ウルトラシーラーIII」)を塗布したものである。
水性塗料組成物により形成された塗膜は、いずれも指触感がなく(具体的には、べたつきがなく)、上塗り塗料を塗布することが可能であった。
また、得られた複層塗膜(2層)を実施例58と同様の評価に供した。評価結果を表5に示す。
[上塗り塗料]
1.溶剤型エポキシ/アミン系塗料A
溶剤型エポキシ/アミン系塗料Aとして、日本ペイント社製、商品名「エポタールNB-20」を用いた。
2.溶剤2液型ウレタン系塗料A
溶剤2液型ウレタン系塗料Aとして、日本ペイント社製、商品名「ハイポン50ファイン」を用いた。
3.溶剤2液型ウレタン系塗料B
溶剤2液型ウレタン系塗料Bとして、日本ペイント社製、商品名「ニッペウレトップエコ」を用いた。
4.水性エポキシ/アミン系塗料A
水性エポキシ/アミン系塗料Aとして、製造例48で製造した水性エポキシ/アミン系塗料Aを用いた。
5.水性2液型ウレタン系塗料A
水性2液型ウレタン系塗料Aとして、製造例50で製造した水性2液型ウレタン系塗料Aを用いた。
6.水性エマルション系塗料
水性エマルション系塗料として、日本ペイント社製、商品名「オーデコートG」を用いた。
7.水性カルボジイミド系塗料
水性カルボジイミド系塗料として、製造例51で製造した水性カルボジイミド系塗料を用いた。
サンドブラスト鋼板に、下塗り塗料として溶剤型有機系ジンクリッチ塗料(日本ペイント社製、商品名「Nジンキー8000HB」)を、乾燥後の厚さが70μmとなるように塗装して、下塗り層を形成させた。
その後、当該下塗り層上に、5℃の環境下で、製造例41で得られた水性塗料組成物13を乾燥後の厚さが60μmとなるように刷毛で塗布した後、塗布時と同じ環境下で1日間乾燥させて、水性塗料組成物13により形成された塗膜を得た。
得られた塗膜上に、25℃の環境下で、中塗り塗料として溶剤型エポキシ/アミン系塗料B(日本ペイント社製、商品名「ハイポン30ファイン中塗」)を乾燥後の厚さが30μmになるように刷毛で塗布した後、塗布時と同じ環境下で1日間乾燥させて、中塗り層を得た。
当該中塗り層上に、25℃の環境下で、上塗り塗料として溶剤2液型ウレタン系塗料A(日本ペイント社製、商品名「ハイポン50ファイン」)を乾燥後の厚さが30μmとなるようにエアスプレーで塗布した後、塗布時と同じ環境下で7日間乾燥させて、上塗り層を形成し、複層塗膜(4層)を得た。
得られた複層塗膜(4層)について、上記「耐水付着性」および「防食性」の評価を行った。評価結果を表6に示す。
表6に示す下塗り塗料、水性塗料組成物、中塗り塗料および上塗り塗料を用いた以外は、実施例69と同様にして、複層塗膜(4層)を得た。なお、実施例70で用いた表6に示す下塗り塗料、中塗り塗料および上塗り塗料は、以下のとおりである。
得られた複層塗膜(4層)を実施例69と同様の評価に供した。評価結果を表6に示す。
[下塗り塗料]
製造例52で得られた水性有機系ジンクリッチ塗料を用いた。
[中塗り塗料]
水性エポキシ/アミン系塗料Bとして、製造例49で得られた水性エポキシ/アミン系塗料Bを用いた。
[上塗り塗料]
水性カルボジイミド系塗料として、製造例51で製造した水性カルボジイミド系塗料を用いた。
製造例40で得られた水性塗料組成物12に代えて、溶剤型エポキシ/アミン系塗料A(日本ペイント社製、商品名「エポタールNB-20」)を用いた以外は、実施例58と同様にして、基材上に、溶剤型エポキシ/アミン系塗料Aにより形成される塗膜を得た。得られた塗膜は、べたついており、上塗り塗料を塗装できる状態ではなかった。
Claims (13)
- 基材に、水性塗料組成物を塗装して塗膜を形成することを含み、
該水性塗料組成物が、
分子内に1つ以上の第1アミノ基および/または第2アミノ基を有する水性エポキシ系ポリアミン樹脂(A)と、
分子内に1つ以上の(メタ)アクリロイル基を有する化合物(B)とを含む、
塗膜形成方法。 - 前記水性塗料組成物が2液型水性塗料組成物であり、
主剤塗料液が前記水性エポキシ系ポリアミン樹脂(A)を含み、硬化剤が前記化合物(B)を含む、請求項1に記載の塗膜形成方法。 - 前記水性エポキシ系ポリアミン樹脂(A)が、水分散型である、請求項1または2に記載の塗膜形成方法。
- 前記水性エポキシ系ポリアミン樹脂(A)のアミノ基の当量が、100~3000である、請求項1から3のいずれかに記載の塗膜形成方法。
- 前記水性エポキシ系ポリアミン樹脂(A)が、エポキシ樹脂をアミン変性して得られ、該エポキシ樹脂のエポキシ当量が180~3800である、請求項1から4のいずれかに記載の塗膜形成方法。
- 前記水性塗料組成物が、前記水性エポキシ系ポリアミン樹脂(A)として、エポキシ当量が400~1500であるエポキシ樹脂(a1)をアミン変成して得られる水性エポキシ系ポリアミン樹脂(A1)と、エポキシ当量が2000~3200であるエポキシ樹脂(a2)をアミン変性して得られる水性エポキシ系ポリアミン樹脂(A2)とを含む、請求項1から4のいずれかに記載の塗膜形成方法。
- 前記エポキシ樹脂(a1)と前記エポキシ樹脂(a2)との質量比a1/a2が、8/2~2/8である、請求項6に記載の塗膜形成方法。
- 前記水性エポキシ系ポリアミン樹脂(A)が、エポキシ系ポリアミン樹脂のアミノ基を酸で中和して得られ、該中和の際の中和率が10%~70%である、請求項1から7のいずれかに記載の塗膜形成方法。
- 前記化合物(B)の25℃における粘度が、3000mPa・s以下である、請求項1から8のいずれかに記載の塗膜形成方法。
- 前記化合物(B)の分子量が、150以上2000以下である、請求項1から9のいずれかに記載の塗膜形成方法。
- 前記水性塗料組成物による塗膜形成後、該塗膜上に、上塗り層を形成することを含む、請求項1から10のいずれかに記載の塗膜形成方法。
- 前記水性塗料組成物による塗膜形成後、前記上塗り層形成前に、中塗り層を形成することを含む、請求項11に記載の塗膜形成方法。
- 前記水性塗料組成物による塗膜形成前に、前記基材に、下塗り層を形成することを含む、請求項1から12のいずれかに記載の塗膜形成方法。
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CN113307918B (zh) * | 2021-06-07 | 2022-04-15 | 东莞长联新材料科技股份有限公司 | 一种植物油基聚丙烯酸酯非离子乳液及其制备方法和应用 |
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EP3492507A1 (en) * | 2017-11-29 | 2019-06-05 | ALLNEX AUSTRIA GmbH | Hardener composition for aqueous epoxy resin based coating compositions, process for their preparation, and use thereof |
CN112725941A (zh) * | 2020-12-27 | 2021-04-30 | 中复神鹰碳纤维股份有限公司 | 一种可以承受高倍蒸汽牵伸的碳纤维原丝油剂 |
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SG184260A1 (en) | 2012-10-30 |
JP5612667B2 (ja) | 2014-10-22 |
MY156874A (en) | 2016-04-15 |
JPWO2011118791A1 (ja) | 2013-07-04 |
CN102821874B (zh) | 2015-07-15 |
CN102821874A (zh) | 2012-12-12 |
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