SG184260A1

SG184260A1 - Method for forming coating film

Info

Publication number: SG184260A1
Application number: SG2012071163A
Authority: SG
Inventors: Katsuhiko Sho; Muneo Imamura; Takahiro Ujii
Original assignee: Nippon Paint Co Ltd
Priority date: 2010-03-26
Filing date: 2011-03-25
Publication date: 2012-10-30
Also published as: JPWO2011118791A1; WO2011118791A1; CN102821874A; CN102821874B; MY156874A; JP5612667B2

Abstract

The present invention provides a method for forming a coating film which is excellent in low-temperature curability.The method of forming a coating film according to an embodiment of the present invention includes coating a substrate with an aqueous coating composition to form a coating film, wherein the aqueous coating composition includes : an aqueous epoxy-based polyamine resin (A) having one or more primary amino groups and/or secondary amino groups in a molecule; and a compound (B) having one or more (meth) acryloyl groups in a molecule. No Suitable Figure

Description

NPP11067PCT

Description

Title of Invention: METHOD FOR FORMING COATING FILM

Technical Field

[0001] The present invention relates to a method for forming a coating film.

Background Art

[0002] In general, a solvent-type ccocating material including an epoxy resin and a polyamine compound is used as an anticorrosive coating material. However, in recent years, from a standpoint of environmental protection, there is a social demand for a shift from the solvent-based coating material to an aqueous coating material.

Examples of the agueous coating material include an aqueous coating material which includes: as a base resin, a mixture obtained by blending a variety of pigments and additives in a water-soluble polyamine resin; an epoxy-resin emulsion; and an acrylic silicon resin emulsion containing a glycidyl group and an alkoxysilyl group (Patent Document 1).

[0003] However, in the case of using a curing reaction of the epoxy resin and the polyamine compound, it is difficult to form a coating filmwhich exerts practical performance at low temperature (e.g., 5°C or less) because the curing reaction hardly proceeds at low temperature.

NPP11067PCT

Prior Art Document

Patent Document

[0004] [PTL 1] JP 11-166153 A

Summary of Invention

Problem to be solved by the Invention

[0005] The present invention has been made to solve the conventional problem, and an object of the present invention is to provide a method for forming a coating film which is excellent in low-temperature curability.

Means for solving the Problems

[0006] A method of forming a coating film according to an embodiment of the present invention includes coating a substrate with an aqueous coating composition to form a coating film, wherein the aqueous coating composition includes: an agueous epoxy-based polyamine resin (A) having one or more primary amino groups and/or secondary amino groups in a molecule; and a compound (B) having one or more (methj)acryloyl groups in a molecule.

Inapreferredembodiment of the invention, the aqueous coating compositionisatwo-component aqueous coatingcompositionincluding a base resin liquid for a coating material and a curing agent, the base resin liquid for a coating material comprising the aqueous

NPP11067PCT epoxy~based polyamine resin (A) and the curing agent comprising the compound (Bj).

In a preferred embodiment of the invention, the aqueous epoxy-based polyamine resin (A) is water-dispersible.

In a preferred embodiment of the invention, the aqueous epoxy-based polyamine resin (A) has an amino group equivalent of 100 to 3,000.

In a preferred embodiment of the invention, the aqueous epoxy-based polyamine resin (A) is obtained by amine-modification of an epoxy resin, and the epoxy resin has an epoxy equivalent of 180 to 3,800.

In a preferred embodiment of the invention, the aqueous epoxy-based polyamine resin (A) in the aqueous coating composition includes: an aqueous epoxy-based polyamine resin (Al) obtained by amine-modification of an epoxy resin (al) having an epoxy equivalent of 400 to 1,500; and an aqueous epoxy-based polyamine resin (A2) obtained by amine-modification of an epoxy resin (a2) having an epoxy equivalent of 2,000 to 3,200.

In a preferred embodiment of the invention, a mass ratio of the epoxy resin (al) and the epoxy resin (a2) (al/a2) is 8/2 to

NPP11067PCT 2/8.

In a preferred embodiment of the invention, the aqueous epoxy~based polyamine resin (A) is obtained by neutralization of an amino group of an epoxy-based polyamine resin with an acid, and a neutralization ratio in the neutralization is 10% to 70%.

In a preferred embodiment of the invention, the compound (B) has a viscosity at 25°C of 3,000 mPa's or less.

In a preferred embodiment of the invention, the compound (B) has a molecular weight of 150 or more and 2,000 or less.

In a preferred embodiment of the invention, the method of forming a coating film further includes forming a top coating layer on the coating film after the forming of the coating film with the agueous coating composition.

In a preferred embodiment of the invention, the method of forming a coating film further includes forming an intermediate coating layer after the forming of the coating film with the aqueous coating composition and before the forming of the top coating layer.

In a preferred embodiment of the invention, the method of forming a coating film further includes forming a undercoating layer

NPP11067PCT on substrate before the forming of the coating film with the aqueous coating composition.

Effects of the Invention

[0007] According to the method of forming a coating film according to the present invention, it is possible toobtaina coating film which exerts practical performance even at low temperature (for example, 5°C or less) by using an agueous coating composition including an aqueous epoxy-based polyamine resin (4A) having one or more primary amino groups and/or secondary amino groups in a molecule and a compound (B) having one or more (meth)acryloyl groups in a molecule. More specifically, the aqueous coating composition utilizes, for a curing reaction, a Michael addition reaction at a high reactivity, and hence a cured coating film can be obtained even at low temperature (for example, 5°C or less). Further, in the case where the aqueous epoxy-based polyamine resin (A) is water-dispersible, the aqueous coating composition has good stability at ordinary temperature in spite of very high reactivity of the Michael addition reaction itself and 1s excellent in workability compared with a solvent-based coating composition. In addition, the epoxy resin 1s used as a binder, and hence a coating film excellent in corrosion resistance can be obtained.

Description of Embodiments

[0008] A. Method of forming coating film

NPP11067PCT

A method of forming a coating film according to the present invention includes coating a substrate with an aqueous coating composition to form a coating film.

[0009] A-1. Outline of agueous coating composition

The aqueous coating composition includes: an aqueous epoxy-based polyamine resin (A) having one or more primary amino groups and/or secondary amino groups in a molecule; and a compound (B) having one or more {(meth)acryloyl groups in a molecule. In the agueous coating composition, a curing reaction (Michael addition reaction) of the aqueous epoxy-based polyamine resin (A) and the compound (B) 1s caused to proceed by mixing these compounds, to thereby allow a coating film to be formed. The curing reaction of the aqueous epoxy-based polyamine resin (A) and the compound (B) can be performed even at low temperature (for example, 5°C), and hence the aqueous «coating composition is excellent in low-temperature curability.

[0010] The aqueous coating composition 1s preferably a two-component aqueous coating composition including a base resin liguid for a coating material and a curing agent. It is preferred that the base resin liquid for a coatingmaterial include the aqueous epoxy-based polyamine resin (A), and the curing agent include the compound (B). When the aqueous coating composition is used as the two-component aqueous coating composition, an aqueous coating

NPP11067PCT composition excellent in low-temperature curability can be obtained because it 1s possible to select a combination of the aqueous epoxy-based polyamine resin (A) and the compound (B) such that both of them exhibit high reactivity to each other.

[0011] Beforemixing of the agueocus epoxy-basedpolyamine resin (A) and the compound (B), the aqueous coating composition may be treated, forexample, by (1) diluting the compound (B) with an organic solvent, (2) mixing an emulsifier in the compound (B) or emulsifying or dispersing the compound (B) with a dispersant, an emulsifier, or an aqueous resin, or (3) dispersing the compound (B) inadispersing element of a resin different from the aqueous epoxy-based polyamine resin (A). When such treatment 1s carried out, the aqueous epoxy-based polyamine resin (A) and the compound (B) can be mixed without using a special mixing device, to thereby obtain an aqueous coating composition excellent in dispersibility and capable of allowing the agueous epoxy-based polyamine resin (A) and the compound (B) to react with each other efficiently.

[0012] Examples of the organic solvent to be used when the compound (B) is diluted with the organic solvent include ethylene glycol monobutyl ether and diethylene glycol monobutyl ether.

[0013] A nonionic emulsifier or an anionic emulsifier, for example, 1s used as the emulsifier to used when the emulsifier is

NPP11067PCT mixed in the compound (B) or the compound (B) is emulsified or dispersedinwaterwiththedispersant, theemulsifier, or the aqueous resin. Examples of the nonionic emulsifier include a polyoxyethylene alkyl phenol ether, polyoxyethylene styrenated phenyl ether, a polyoxyethylene alkyl ether, a polyoxyethylene polyoxypropylene block polymer, and a sorbitan fatty acid ester.

Examples of the anionic emulsifier include a dodecylbenzenesulfonic acid salt, adialkyl succinate sulfonic acidsalt, a polyoxyethylene alkyl ether sulfuric acid ester salt, a polyoxyethylene styrenated phenyl ether sulfuric acid ester salt, and an alkyl diphenyl ether disulfonic acid salt. Examples of the dispersant include a polyacrylic acid sodium salt, an ammonium salt of a half ester of a styrene-maleic acid copolymer, and a polyethylene oxide adduct of a half ester of a styrene-maleic acid copolymer. Examples of the aqueous resin include a sodium salt of polyacrylic acid ester.

It should be noted that, in the case where the aqueous coating composition 1s a two-component composition, the dispersant, the emulsifier, or the aqueous resin may be incorporated into the curing agent.

[0014] Examples of the dispersing element to be used when the compound (B) is dispersed in the dispersing element of a resin different from the aqueous epoxy-based polyamine resin (A) include an emulsion and dispersion of an acrylic resin, an emulsion and dispersion of a urethane resin, and an aqueous epoxy-based polyamine

NPP11067PCT resin having no primary amino group and no secondary amino group.

[0015] The content of the aqueous epoxy-based polyamine resin (A) in terms of a solid content is preferably 5 to 95 mass%, more preferably 10 to 90 mass% with respect to the total solid content of the aqueous coating composition.

[0016] The content of the compound (B) is preferably 2 to 30 mass%, more preferably 5 to 25 mass% with respect to the total solid content of the agueous coating composition.

[0017] An equivalent ratio of the (meth)acryloyl group of the compound (B) and the amino group of the aqueous epoxy-based polyamine resin (A) ((meth)acryloyl group/amino group) is preferably 0.7 to 2.5, more preferably 0.8 to 2.0. When the equivalent ratio is less than 0.7, the low-temperature curability of the aqueous coating composition may reduce. When the equivalent ratio exceeds 2.5, the adhesive property of a coating film to be obtained may reduce.

[0018] The aqueous coating composition may further include a pigment. When the pigment 1s incorporated, the aqueous coating composition has an increased viscosity and can form a thick coating film by single application. As a result, an aqueous coating composition excellent in application workability can be obtained since the number of application canbe reduced, and capable of forming

NPP11067PCT a coating film which exhibits sufficient corrosion resistance can be obtained.

[0019] Specificexamplesof thepigment include: color pigments such as titanium oxide, yellow iron oxide, red iron oxide, carbon black, phthalocyanine blue, phthalocyanine green, azo red, guinacridone red, and benzimidazolone yellow; extender pigments such as calcium carbonate, barium sulfate, kaolin, clay, talc, and mica; and anti-rust pigments such as zinc phosphate and calcium phosphate.

[0020] The pigment volume concentration of the pigment in the aqueous coating composition is preferably 20 to 50%, more preferably 25to 45%, particularlypreferably 30to 40%. Whenthepigment volume concentration is less than 20%, the effect of the incorporation of the pigment may be insufficient, while when the pigment volume concentration exceeds 50%, the outer appearance of the coating film may deteriorate. It should be noted that the pigment volume concentration can be calculated from the mass of the pigment blended and the specific gravity of each component in the coating material.

[0021] The agueous coating composition may include water, a solvent, or an additive. Specific examples of the solvent include: glycol-based solvents such as ethylene glycol, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monobutyl ether,

NPP11067PCT diethylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, and diethylene glycol dibutyl ether; aromatic solvents such as xylene, Solvesso 100,

Solvesso 150, and Solvesso 200; hydrocarbon-based solvents such as mineral spirit; and ester-based solvents such as 2,2,4~trimethyl~-1,3-pentanediocl monoisobutyrate (manufactured by

CHISSO CORPORATION, trade name "cs~-12"), 2,2,4-trimethyl-1, 3-pentanediol diisobutyrate (manufactured by

CHISSQO CORPORATION, trade name "CS-16"), diethyl adipate, and diiscbutyl adipate. Specific examples of the additive include a dispersant, a viscosity adjuster, a curing catalyst, a surface conditioner, a defoamer, a plasticizer, a film forming aid, a UV absorbing agent, and an antioxidant. When the aqueous coating composition is used as a two-component aqueous coating composition, water, the solvent, and/or the additive may be added to a base resin liquid for a coating material or a curing agent before mixing of the base resin liquid for a coating material with the curing agent or may be added after mixing of the base resin liquid for a coating material with the curing agent. Which of the base resin liquid for a coating material and the curing agent water, the solvent, and/or the additive are/is added tomay be determined based on the functions and properties expected of them.

[0022] The aqueous coating composition may include an alkoxysilane compound as an additive. The aqueous coating

NPP11067PCT composition including the alkoxysilane compound can form a coating film excellent in adhesive property to the substrate.

[0023] Specificexamples of the alkoxysilane compound include: v-glycidoxyalkyltrialkoxysilanes such as vy-glycidoxypropyltrimethoxysilane, v-glycidoxypropyltriethoxysilane, and v-glycidoxypropoxytrimethoxysilane; y-—aminopropyltrialkoxysilanes such as y-aminopropyltriethoxysilane and y-amincpropyltripropoxysilane; and N-phenyl-y-amincalkyltrialkoxysilanes such as

N-phenyl-y-aminopropyltrimethoxysilane,

N-phenyl-y-aminopropyltriethoxysilane, and

N-phenyl-y-aminopropyltripropoxysilane. Theymay be used alone or incombination. Theymaybepartiallysubjectedtohydrolysisand/or hydrolysis dehydration condensation.

[0024] When the alkoxysilane compound is incorporated, its content is preferably 0.3 to 3 mass%, more preferably 0.5 to 2 mass$ with respect to the total solid content of the aqueous coating composition.

[0025] A-2. Agueous epoxy-based polyamine resin (A)

The aqueous coating composition includes the aqueous epoxy—-based polyamine resin (A) having one or more primary amino

NPP11067PCT groups and/or secondary amino groups in a molecule. The agueous coating composition including such resin as a binder can form a coating filmexcellent in corrosion resistance. It shouldbe noted that the concept of "aqueous" as used herein comprehends "water-soluble" and "water-dispersible."

[0026] The aqueous epoxy-based polyamine resin (A) is preferably water-dispersible. When a water-dispersible aqueous epoxy-based polyamine resin (A) is used, a coating film excellent in water resistance can be formed. In addition, in the case where the aqueous epoxy-based polyamine resin (A) 1s water-dispersible, the resin can be easily mixed with the compound (B). Further, a rapid reaction progress of the aqueous epoxy-based polyamine resin (A) and the compound (B) can be inhibited to appropriately adjust the reactivity, thereby obtaining an aqueous coating composition with a long service life. More specifically, in the case where the agueous epoxy-based polyamine resin (A) is water-dispersible, in the aqueous coating composition before application, the reaction hardly proceeds even at ordinary temperature, which provides good stability and application property, because the aqueous epoxy~based polyamine resin (A) is hardly brought into contact with the compound (B). Ontheother hand, afterapplication, adispersionmedium (such as water) volatilizes to facilitate the contact between the aqueous epoxy-based polyamine resin (A) and the compound (B). Therefore, the curing reaction proceeds even at low temperature, to thereby

NPP11067PCT allow a coating film to be formed.

[0027] The aqueous epoxy-based polyamine resin (A) can be obtained by, for example, amine-modification of an epoxy resin.

Further, when the epoxy-based polyamine resin obtained by amine-modificationof the epoxy resin isnot aqueous, the epoxy-based polyamine resinmaybeconvertedintoanaqgueousresinby, forexample, neutralization of an amino group with an acid, to thereby obtain the aqueous epoxy-based polyamine resin (A).

[0028] The epoxy resin is preferably a bisphenol A-type epoxy resin or a bisphenol F-type epoxy resin, particularly preferably a bilsphenol A-type epoxy resin.

[0029] The epoxy equivalent of the epoxy resinmay be determined depending on desired coating film physical properties. The epoxy equivalent is preferably 180 to 3,800, more preferably 400 to 3,200, particularly preferably 700 to 3,200. When the epoxy equivalent of the epoxy resin is in such range, a coating film excellent in water resistance, corrosion resistance, and water-resistant adhesive property can be obtained. When the epoxy resin has an epoxy equivalent of less than 180, the initial rain resistance of a coating film to be obtained may reduce. Meanwhile, when the resin has an epoxy equivalent of more than 3,800, the epoxy-based polyamine resin may not be dispersed in water to cause phase separation, which makes

NPP11067PCT it impossible to convert the coating composition into an aqueous one and to obtain an aqueous coating composition having sufficient water-resistant adhesiveproperty. Itshouldbenotedthat theepoxy equivalent of the epoxy resin can be determined in accordance with

JIS K 7236. In addition, the term "initial rain resistance” as used herein refers to water resistance in an initial stage of the curing of a coating film, specifically, in a stage in which a coating film which has not completely cured but is non-sticky is formed. When the coating film is poor in initial rain resistance, the coating filmmay break or swell by exposure torainbefore the applied coating film cures completely. The aqueous coating composition capable of forming a coating film having high initial rain resistance is particularly effectively used for an outdoor cobject to be coated which may be exposed to rain before the applied coating film cures completely.

[0030] In one embodiment, the epoxy resin is an epoxy resin (al) having an epoxy equivalent of 400 to 1,500. When an agueous epoxy~based polyamine resin (Al) obtained by amine-modification of the epoxy resin (al) is used, it is possible to obtain an aqueous coating composition capable of forming a coating film excellent in water-resistant adhesive property. The epoxy equivalent of the epoxy resin (al) is more preferably 600 to 1,400, particularly preferably 800 to 1,300.

NPP11067PCT

[0031] In another embodiment, the epoxy resin is an epoxy resin (a2) having an epoxy equivalent of 2,000 to 3,200. When an aqueous epoxy-based polyamine resin (AZ) obtained by amine-modification of the epoxy resin (a2) is used, it is possible to obtain an agueous coating composition capable of forming a coating film excellent in initial rain resistance. The epoxy equivalent of the epoxy resin (a2) 1s more preferably 2,200 to 3,000.

[0032] As the epoxy resin, two or more kinds of epoxy resins may be used in combination.

[0033] As the epoxy resin, there may be used one subjected to chain elongation through utilization of a reaction of an active hydrogen-containing compound capable of reactingwith an epoxy group with an epoxy group to increase the molecular weight of the resin or tomodify the resin. Examples of the active hydrogen-containing compound include abifunctional compoundsuchasadimeracid, diamine, or polyether polyol.

[0034] As the epoxy resin, there may be used one having a fatty acid added before the amine modification. The addition allows a soft component to be introduced into the resin and allows the number of epoxy groups to be reduced, thereby reducing sites to be amine-modified to lower a reactivity, for example.

NPP11067PCT

[0035] The epoxy-based polyamine resin can be cbtained through modification of the epoxy resin by any appropriate modification method. Examples of the modification method include: a method involving adding a primary amino group-containing polyamine to an epoxy resin; and a method involving adding a ketiminated amino group~ccentaining compound to an epoxy resin. The epoxy-based polyamine resin obtained as described above has one or more primary amino groups and/or secondary amino groups, and secondary hydroxyl groups in amolecule. The epoxy-based polyamine resinmay be a resin obtained by a reaction of part of the primary amino groups, secondary amino groups, and/or hydroxyl groups in the epoxy-based polyamine resin with a compound having a functional group such as an epoxy group, anacidanhydride group, anacidhalogengroup, or anisocyanate group. When a product obtained by making an epoxy-based polyamine resin aqueous, the epoxy-based polyamine resin being obtained by areactionof acompoundhaving such functional group, is incorporated as part of the agueous epoxy-based polyamine resin (A) to be used, physical properties of the resultant coating film can be adjusted.

[0036] The method involving adding the primary amino group-containing polyamine to the epoxy resin is specifically a method involving reacting a primary amino group in the primary amino group-centalning polyamine with an epoxy group in the epoxy resin to form a secondary amino group, resulting in producing the epoxy-based polyamine resin having the secondary amino group.

NPP11067PCT

[0037] Examples of the primary amino group-containing polyamine include diethylenetriamine, dipropylenetriamine, dibutylenetriamine, and triethylenetetramine. They may be used alone or in combination.

[0038] The method involving adding a ketiminated amino group-contalning compound to the epoxy resinisspecificallyamethod involving allowing the ketiminated amino group-containing compound and the epoxy resin to react with each other and then hydrolyzing a ketimine group to forma primary amino group, resulting in producing the epoxy-based polyamine resin having a primary amino group. It should be noted that when the ketiminated amino~group containing compound and the epoxy resin are allowed to react with each other, a secondary amine such as diethanolamine, methylethanolamine, or diethylamine may coexist.

[0039] The ketiminated amino group-containing compound can be obtained by reacting a primary amino group-containing compound with a ketone. Examples of the primary amino group-containing compound include: primary amino group~containing polyamines such as diethylenetriamine, dipropylenetriamine, dibutylenetriamine, and triethylenetetramine; aminoethylethanolamine; methylaminopropylamine; andethylaminoethylamine. Theymaybe used alone or incombination. Examples of the ketone includemethyl ethyl

NPP11067PCT ketone, acetone, and methyl isobutyl ketone.

[0040] The epoxy-based polyamine resinmay further be modified by allowing the resin to react with a compound having a functional group reactive with an amino group, depending on desired coating filmphysical properties. Examplesof the functional group reactive with an amino group include an epoxy group, a {meth)acryloyl group, an isocyanate group, and an acid anhydride group.

[0041] The amount of the amino groups in the epoxy-based polyamine resin may be any appropriate amount depending on desired properties of the aqueous coating composition or desired coating film physical properties. The amount of the amino groups is, as an amino group equivalent, preferably 100 to 3,000, more preferably 500 to 2,000, particularly preferably 800 to 2,000. As long as the amino group equivalent is in such range, the epoxy-based polyamine resin is aqueous, totherebyobtain the aqueous epoxy-basedpolyamine resin (A). When the aqueous epoxy-basedpolyamine resin (A) is used, a coating film excellent in low-temperature curability can be cbtained. When the amino group equivalent of the epoxy-based polyamine resin is less than 100, water resistance of a coating film to be obtained may reduce. Meanwhile, when the amino group equivalent exceeds 3,000, the epoxy-based polyamine resin may not be dispersed in water to cause phase separation, which makes it impossible to convert the coating composition into an agueous

NPP11067PCT composition. It should be noted that the expression "amino group equivalent" as used herein is represented by a molecular weight of a resin solid content per primary amino group in the case where the epoxy-based polyamine resin has the primary amino groups (including the case where the epoxy-based polyamine resin has the primary amino groups and secondary amino groups), or is represented by a molecular weight of a resin solid content per secondary amino group in the case where the epoxy-based polyamine resin has no primary aminogroup. Theaminogroupequivalent of theepoxy-basedpolyamine resin can be determined from the blending amounts of raw materials.

[0042] For example, the aqueous epoxy-based polyamine resin (A) may be obtained by converting the epoxy-based polyamine resin {(i.e., anepoxyresinobtainedbyamine-modification) into an agueous resin by neutralization of the amino groups in the epoxy-based polyamine resin with an acid. The kind of the acid and a neutralizationratio (neutralizationratiowith respect tothe amino groups in the epoxy-based polyamine resin before conversion into an aqueous resin) may be any appropriate kind of acid and neutralization ratio depending on a desired state of the aqueous epoxy-basedpolyamine resin (A) (water-soluble towater~dispersible form). Examples of theacidincludeaceticacid, formicacid, lactic acid, and phosphoric acid. The neutralization ratio (neutralization ratio with respect to the amino groups in the epoxy-basedpolyamine resinbefore conversion into an aqueous resin)

NPP11067PCT is preferably 10% to 100%, more preferably 10% to 70%, particularly preferably 15% to 50%. When the neutralization ratio is less than 10%, the resinmaynot bedispersedinwater tocause phase separation, which makes it impossible to convert the coating composition into anagueous one. Meanwhile, whentheneutralizationraticisadjusted to 70% or less, a water-dispersible agueous epoxy-based polyamine resin (A) can be obtained.

[0043] The molecular weight (number average) of the aqueous epoxy-based polyamine resin (A) may be any appropriate molecular weight depending on desired properties of the aqueous coating composition or desired coating film physical properties. The molecular weight is preferably 500 to 20,000, more preferably 1,000 to 10,000 in terms of standardpolystyrene measuredby gel permeation chromatography (GPC). As longasthemolecularweight of the aqueous epoxy-based polyamine resin (A) is in such range, the aqueous epoxy-based polyamine resin (A) can react efficiently with the compound (B) because the resin can be mixed easily with the compound.

Inaddition, aslongasthemolecularweight of the aqueous epoxy-based polyamine resin (A) 1s in such range, a coating film excellent in corrosion resistance, water resistance, and adhesive property can be obtained.

[0044] The aqueous coating composition may include two or more kinds of the aqueous epoxy-based polyamine resins (A).

NPP11067PCT

[0045] The aqueous coating composition preferably includes, as the agueous epoxy-based polyamine resins (A), the aqueous epoxy-based polyamine resin (Al) obtained by amine-modification of the epoxy resin (al) having an epoxy equivalent of 400 to 1,500 and the aqueous epoxy-based polyamine resin (A2) obtained by amine-modificationof theepoxy resin (a2) having anepoxyequivalent of 2,000 to 3,200. A mass ratio of the epoxy resin (al) having an epoxy equivalent of 400 to 1,500 and the epoxy resin (a2) having an epoxy equivalent of 2,000 to 3,200 (al/a2) is preferably 8/2 to 2/8, more preferably 7/3 to 3/7. As long as the ratio is in such range, it ispossibletoobtainanaqueous coating composition capable of forming a ceating film excellent in initial rain resistance and water-resistant adhesive property.

[0046] The properties of the aqueous coating composition and coating film physical properties can be controlled by the molecular weight of the aqueous epoxy-based polyamine resin (A) and the amount of the amino groups therein.

[0047] A-3. Compound (B)

The compound (B) used in the aqueous coating composition has one or more (meth)acryloyl groups in a molecule.

[0048] The molecular weight of the compound (B) is preferably

NPP11067PCT 150 or more and 2,000 or less, more preferably 200 or more and 1,700 or less, particularly preferably 250 or more and 1,300 or less.

As long as the molecular weight of the compound (B) is in such range, the aqueous epoxy-based polyamine resin (A) and the compound (B) canbe easilymixed without using a special mixing device, to thereby obtain an aqueous coating composition excellent in dispersibility.

As a result, the aqueous epoxy-based polyamine resin (A) and the compound (B) can react with eachotherefficiently, to thereby obtain an aqueous coating composition excellent in curability. It should be noted that the molecular weight of the compound (B) can be calculated from its chemical formula.

[0049] The number of the (meth)acryloyl groups in the compound (B) is 1 crmore, preferably 2 to 4. The number of the (meth)acryloyl groups in the compound (B) may be determined depending on desired coating film physical properties.

[0050] The viscosity of the compound (B) at 25°C is preferably 3,000 mPa*s or less, more preferably 50 to 3,000 mPa-s, particularly preferably 50 to 2,200 mPa+s, most preferably 50 to 1,100 mPa-s.

As long as the viscosity of the compound (B) is in such range, the agueous epoxy-based polyamine resin (A) and the compound (B) can be easily mixed without using a special mixing device, to thereby obtain an aqueous coating composition excellent in dispersibility.

As a result, the aqueous epoxy-based polyamine resin (A) and the

NPP11067PCT compound (B) can react with eachotherefficiently, to thereby obtain an aqueous coating composition excellent in curability.

[0051] Examples of the compound (B) include: polymerizable unsaturated monocarboxylic acid ester compounds of polyhydric alcohols such as 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 triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, glycerol diacrylate, glycerol dimethacrylate, glycerol acroxy dimethacrylate, 1,1,1-trishydroxymethylethane diacrylate, 1,1,1-trishydroxymethylethane dimethacrylate, 1,1,1-trishydroxymethylethane triacrylate, 1,1,1-trishydroxymethylethane trimethacrylate, 1,1,1-trishydroxymethylpropane diacrylate, and 1,1,1-trishydroxymethylpropane dimethacrylate; adducts between epoxy group-containing, ethylenically unsaturated monomers and

NPP11067PCT carboxyl group-containing, ethylenically unsaturatedmonomers such as a reaction product between glycidyl acrylate or glycidyl methacrylate and acrylic acid, methacrylic acid, crotonic acid, or maleic acid; and polymerizable unsaturated monocarboxylic acid amide compounds of polyamines such as ethylenediamine diacrylate.

Those compounds may be used alone or in combination.

[0052] As described above, the compound (B) 1s preferably capable of being easily mixed with (capable of reacting with) the agueous epoxy-based polyamine resin (A). It is more preferred that the aqueous epoxy-based polyamine resin (A) and the compound (B) be used in an inhomogeneous state in such a range that the resin and compound can be easily mixed (can react with each other). It is particularly preferred that the compound (B) and the aqueous epoxy-based polyamine resin (A) be used in different phase states.

In such states, a rapid reaction progress of the aqueous epoxy-based polyamine resin (A) and the compound (B) can be inhibited to appropriately adjust the reactivity. More specifically, when the agueous epoxy-based polyamine resin (A) and the compound (B) are in an inhomogeneous state, the aqueous coating composition before application has good stability and application property because both the components are hardly brought into contact with each other, resulting in inhibiting the reaction at ordinary temperature. On the other hand, after application, a dispersion medium (such as water) volatizes to make it sasy to bring the aqueous epoxy-based

NPP11067PCT polyamine resin (A) into contact with the compound (B), and the curing reaction proceeds even at low temperature, to thereby form a coating film. Examples thereof include: a case where the compound (B) isawater-soluble compound and the aqueous epoxy-based polyamine resin (A) is awater-dispersible resin; and a case where the compound (B) is self-emulsifying or is water-insoluble.

[0053] As a method of providing the inhomogeneous state, any appropriate method may be employed depending on the dissolution property of the compound (B) in water. For example, in the case where the compound (B) is water-soluble, the compound (B) may be usedwithout anymodification. Inthiscase, the aqueousepoxy-based polyamine resin (A) 1s preferably a water-dispersible resin. On theother hand, inthe casewhere the compound (B) isself-emulsifying, the compound (B) may be used without any modification or may be emulsified or dispersed in water with an emulsifier, a dispersant, or an aqueous resin before use. In the case where the compound (B) is water-insoluble, the compound (B) may be emulsified or dispersed inwaterwithanemulsifier, adispersant, or an agueous resin before use. In such cases, the form of the aqueous epoxy-based polyamine resin (A) may be water-soluble or water-dispersible, and is preferably water-dispersible. It should be noted that a determination of whether the compound (B) is "water-insoluble," "water-soluble," or "self-emulsifying" can be made by: adding 5 g of the compound (B) to 100 g of water at room temperature; stirring

NPP11067PCT the mixture (e.g., for 3 minutes); allowing the mixture to stand still {(e.g., for 5 minutes); and then observing its state visually.

After allowing the mixture to stand still, if the mixture contains a precipitate, the compound is judged to be "water-insoluble," if the mixture contains no precipitate and is clear, the compound is judged to be "water-soluble," and if the mixture contains no precipitate and 1s turbid, the compound 1s Judged to be "self-emulsifying."

[0054] The compound (B) may be converted into a water-soluble or self-emulsifying compound, for example, bymodifying the compound with polyethylene oxide and increasing the ethylene oxide addition mole number to enhance its hydrophilicity.

[0055] Examples of the compound (B) that is water-soluble include ethoxylated bisphencl A diacrylate (EO 30 mol), ethoxylated trimethylolpropane triacrylate (EO 20 mol), ethoxylated trimethylolpropane triacrylate (EO 30 mol), ethoxylated pentaerythritol tetraacrylate (EO 35 mol), ethoxylated glycerin triacrylate (EO 20 mol), and ethoxylated bisphenol A dimethacrylate (EO 30 mol). They may be used alone or in combination. It should be noted that, for example, the expression "EO 30 mol" as used herein means that 30 ethylene oxide groups are contained in a molecule.

[0056] Examples of the compound (B) that is self-emulsifying

NPP11067PCT include polyethylene glycol #400 diacrylate (EO 9mol), polyethylene glycol #600 diacrylate (EO 14 mol), polyethylene glycol #1000 diacrylate (EO 23 mol), ethoxylated bisphenol A diacrylate (EO 10 mol), ethoxylated bisphenol A diacrylate (EO 20 mol), ethoxylated glycerin triacrylate (EC 9 mol), and polyethylene glycol #1000 dimethacrylate (EO2Z3mol). Theymaybeusedaloneor incombination.

[0057] Examples of the compound (B) that is water-insoluble include polyethylene glycol #200 glycol diacrylate (EO 4 mol), ethoxylated bisphenol Adiacrylate (EO3 mol), ethoxylatedbisphenol

A diacrylate (EO 4 mol), propoxylated bisphenol A diacrylate (PO 3 mol), 1,10-decanediol diacrylate, tricyclodecanedimethanocl diacrylate, ethoxylated Z2-methyl-1,3-propanediol diacrylate (EO 2 mol), neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediocldiacrylate, dipropyleneglycoldiacrylate (PO2mol), tripropylene glycol diacrylate (PO 3 mol), polypropylene glycol #400 diacrylate (PO 7 mol), polypropylene glycol #700 diacrylate (PO 12 mol), ethoxylated trimethylolpropane triacrylate (EO 3 mol), ethoxylated trimethylolpropane triacrylate (EO 9 mol), trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate (PO 3 mol), pentaerythritol triacrylate, ethoxylated pentaerythriteol tetraacrylate (EO 4 mol), ditrimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate (PO 4 mol), propoxylatedbisphenocl Adiacrylate (PO4mol), ethyleneglycol dimethacrylate (EO 1 mol), diethylene glycol dimethacrylate (EO

NPP11067PCT 2mol), triethylene glycol dimethacrylate (EO 3 mol), tetraethylene glycol dimethacrylate (EO 4 mol), polyethylene glycol #400 dimethacrylate (EO 9 mol), polyethylene glycol #600 dimethacrylate (EO 14 mol), 1,3-butanediol dimethacrylate, 1,4~-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, 1,9~-nonanediol dimethacrylate, ethoxylatedbisphenol Adimethacrylate (EO2.6mol), ethoxylated bisphencl A dimethacrylate (EO 4 mol), ethoxylated bisphenol A dimethacrylate (EO 6 mol), ethoxylated bisphenol A dimethacrylate (EO 10 mol), ethoxylated bisphenol A dimethacrylate (EO 17 mol), neopentyl glycol dimethacrylate, ethoxylated polypropylene glycol #700 dimethacrylate (PO 12 mol, EO 6 mol), glycerin dimethacrylate, tripropylene glycol dimethacrylate (PO 3 mol), polypropylene glycol #400 dimethacrylate (PO 7 mol), trimethylolpropane trimethacrylate, and ethoxylated trimethylolpropane trimethacrylate (EO 9 mol). They may be used alone or in combination.

[0058] The compound (B) may be used as a mixture of two or more kinds of the compounds (B). Through such use of the compounds (B) having different properties in combination, physical properties of the aqueous coating composition and a coating film to be obtained can be controlled. For example, the curability can be controlled by mixing a compound (B) having two (methjacryloyl groups and a compound (B) having three (meth)acryloyl groups. Further, when a mixture of a water-soluble compound (B) and a water-insoluble

NPP11067PCT compound (B) is used, the water-insoluble compound (B) can be easily introduced into a reaction system by the water-soluble compound (B), andhenceacoatingfilmexcellent in low-temperature curability can be obtained. Examples of the water-insoluble compound (B) include a compound which is not completely soluble in water, such as propoxylated bisphenol A diacrylate (PO 4 mol). A mixing ratio of the water-soluble compound (RB) and the water-insoluble compound (B) {(water-soluble/water-insoluble) is preferably 1/9 to 9/1, more preferably 2/8 to 8/2.

[0059] A-4. Method forcoatingwith aqueous coating composition

Any appropriate substrate may be coated with the aqueous coating composition. Examplesof the substrate includemetal, wood, plastics, rubber, stone, slate, concrete, mortar, fiber, paper, glass, ceramics, porcelain, afilm, andcomplexes thereof. Further, for example, when the substrate is an inorganic substrate such as slate or concrete, a sealer may be applied onto a surface of the substrate inadvance. Theaqueouscoatingcompositionispreferably applied tometal in consideration of its characteristics. Examples of themetal include iron, copper, tin, zinc, aluminum, and stainless steel.

[0060] Examples of an object to be coated having metal on its surfaces (outerandinner surfaces) includearchitectural structures, ships, vehicles (e.g., railway vehicles, large vehicles), aircraft,

NPP11067PCT bridges, marine structures, plants, tanks (e.g., petroleum tanks), pipes, steel tubes, and cast iron tubes. The method of forming a coating film according to the present invention is applicable to architectural structures and civil engineering structures as well as the foregoing.

[0061] As the coating method, there is typically given a method involving applying the aquecus coating composition onto an object to be coated, followed by drying. As an application method, any appropriate method may be adopted depending on the kind of the object to be coated (substrate) and the like. Examples thereof include application by means of a brush, a roller, an air spray, an airless spray, a trowel, or the like, and immersion.

[0062] The application amount of the aqueous coating composition may be set to any appropriate application amount depending on intended use. The application amount is preferably to 350 g/m.

[0063] As the drying method, any appropriate method may be adopted. Air drying or heat drying is preferred. In the case of the air drying, a drying time is preferably 2 hours or more, more preferably 24 hours or more, particularly preferably 1 week or more.

According to the method of forming a coating film according to the present invention, it is possible to form a coating film excellent

NPP11067PCT in corrosion resistance even when the drying is performed at low temperature (for example, 5°C or less).

[0064] The coating film to be formed through coating with the aqueous coating composition has a thickness of preferably 20 to 150 ym, more preferably 30 to 120 um in terms of thickness of a dried coating film. When the thickness of the dried coating film is more than 150 um, a problem such as the occurrence of dripping may occur at the time of the formation of the coating film.

[0065] The coating film to be obtained by using the aqueous coating composition has excellent corrosion resistance, and the use of only the coating film is sufficient for a part not requiring weatherability, such as an inner surface of a bridge girder.

[0066] B. Method of forming multilayer coating film

An additional coating film may be formed before and/or after the formation of a coating film through coating with the agueous coating composition. In an embodiment, after coating with the aqueous coating composition has been performed to form a coating film, the coating film is coated with a top coating material to form a top coating layer. The formation of the top coating laver additionally improves outer appearance, corrosion resistance, and water-resistant adhesive property.

NPP11067PCT

[0067] Any appropriate coating material may be adopted as the top coating material. Examples thereof include an epoxy/amine-basedcoatingmaterial, a two-component urethane curing type coating material, a one-component urethane curing type coating material, a carbodiimide curing type coating material, an acrylic resin-basedcoatingmaterial, analkydresin-basedcoatingmaterial, andasiliconresin-basedcoatingmaterial. Thetopcoatingmaterial may be a solvent type or an aqueous one, and is preferably an aqueous one because an environmental load may be reduced. The top coating material ismore preferably an aqueous two-component urethane curing type coating material, an aqueous one-component urethane curing type coating material, an aqueous silicon resin-based coating material, or an aqueous carbodiimide curing type coating material.

Whenthetopcoatingmaterial isanyof suchaqueouscoatingmaterials, the resultant coating film has excellent weatherability and can achieve protection of good appearance for a long period of time.

[0068] The top coating layer is typically formed by applying the topceocatingmaterial anddrying (thermally treating) thematerial.

As an application method, any appropriate method may be adopted depending on the kind of the top coating material and the like.

Examples thereof include application by means of a brush, a roller, an air spray, an airless spray, a trowel, or the like, and immersion.

[0069] The application amount of the top coating material may

NPP11067PCT be set to any appropriate application amount depending on the kind of the coating material, purposes of coating, and the like. The application amount is preferably 30 to 400 g/m?.

[0070] A method of drying (heating) the top coating material may be any appropriate drying (heating) method depending on the kind of the top coating material and the like. Examples thereof include air drying, forced drying, and baking.

[0071] The thickness of the top coating layer may be set to any appropriate thickness depending on the kind of the coating material and purposes of coating. The thickness is preferably 10 to 150 um.

[0072] Before the formation of a coating film with the aqueous coating composition, the surface of the substrate may be coated with an undercoating material to form an undercoating layer. The formation of the undercoating layer provides additionally excellent corrosion resistance and water-resistant adhesive property, which are well applicable to a case requiring high corrosion resistance, such as a bridge, a plant, or a tank.

[0073] Any appropriate coating material may be adopted as the undercoating material. Examples thereof include an organic or inorganic zinc-rich coating material. When such coating material

NPP11067PCT containing zinc powder 1s used, an undercoating layer which has extremely high corrosion resistance can be formed. In addition, the ccating material has good workability and can form a uniform undercoating layer. The undercoatingmaterial maybe a solvent type or an aqueous one, and 1s preferably an aqueous one because an environmental load may be reduced.

[0074] As a method of forming the undercoating layer, the same method as in the case of the upper coating layer may be adopted.

The application amount of the undercoating material may be set to any appropriate application amount depending on the kind of the coatingmaterial, purposesof coating, andthelike. Theapplication amount is preferably 80 to 1,200 g/m°. The thickness of the undercoating layer may be set to any appropriate thickness depending on the kind of the coating material, purposes of coating, and the like. The thickness is preferably 20 to 200 um.

[0075] After the formation of a coating film through coating with the agueocus coating composition, the coating film may be coated withan intermediate coatingmaterial to forman intermediate coating layer. The formation of the intermediate coating layer may provide a coating film additionally excellent in corrosion resistance and water-resistant adhesive property. The top coating layer is preferably formed on the intermediate coating layer.

NPP11067PCT

[0076] Any appropriate coating material may be adopted as the intermediate coating material. Examples thereof include an epoxy/amine-basedcoatingmaterial, a two-component urethane curing type coating material, and a one-component urethane curing type coatingmaterial. Theintermediatecoatingmaterialmaybeasolvent type or an aqueous one, and is preferably an aqueous one because an environmental load may be reduced. The intermediate coating material is more preferably an aqueous epoxy/amine-based coating material or an aqueous two-component urethane curing type coating material. Such agueous coating material can form a multilayer coating film which has good adhesiveness to the top coating layer and is strong.

[0077] As a method of forming the intermediate coating layer, the same method as in the case of the upper coating layer may be adopted. The application amount of the intermediate coating material may be set to any appropriate application amount depending on the kind of the coating material, purposes of coating, and the like. The application amount is preferably 20 to 400 g/m®. The thickness of the intermediate coating layer may be set to any appropriate thickness depending on the kind of the coatingmaterial, purposes of coating, and the like. The thickness is preferably 10 to 100 um.

[0078] The top cecating material, the intermediate coating

NPP11067PCT material, and the undercoating material may each contain a pigment, an additive, and the like. Examples of the pigment and the additive include the pigments and additives described in the above-mentioned sectionA-1. Thenumber, kinds, andamountsofpigmentsandadditives to be added may be selected as appropriate depending on purposes.

Examples

[0079] Hereinafter, the present invention is described in more detail by way of examples. However, the present invention is not limited to the examples. It should be noted that, unless otherwise specified, "part (s)" and "%" in the examples are on a mass basis.

Further, evaluations in the examples were carried out for the following items.

[0080] (Corrosion resistance)

The resultant coating film was subjected to a cyclic corrosion test defined in JIS K 5600 7-7, and the state of the coating film after 120 cycles was evaluated based on the following criteria.

Ratio of area of rust generated on the coating film to the area of the resultant ccating film

A: Less than 0.05%

B: 0.05% or more and less than 0.1% (Initial rain resistance)

A coating film was immersed together with a substrate in water

NPP11067PCT at 5°C, lifted up after a lapse of 24 hours, and allowed to stand still at 5°C for 24 hours, and the outer appearance of the coating filmwas then visually observed and evaluated based on the following criteria.

BRA: No abnormality in outer appearance observed

A: Slight changes in burnish and color observed but no mark of crack or swelling observed

C: Mark of crack or swelling observed (Water-resistant adhesive property)

A coating film was immersed together with an object coated therewith in water at 20°C and lifted up after a lapse of 7 days, and then in accordance with a cross-cut method of JIS K 5600~5.6 (2006), 5x5 squares each measuring 3 mmx3 mm were formed on the coating film. A pressure-sensitive adhesive tape was attached to a surface thereof and then rapidly peeled off, and evaluation was performed based on the following criteria. points: No peeled square and no peeling along the cut part observed (peeling area: 0%) 8 points: No peeling of the squares but slight peeling along the cut part observed (peeling area: more than 0% and less than 5%) 6 points or less: Some peeled squares or significant peeling along the cut part observed (peeling area: 5% or more)

NPP11067PCT

[0081] (Production of aqueous coating composition) (Production Example 1) Production of aqueous epoxy-based polyamine resin (A) 702 parts of a raw material resin having an epoxy equivalent of 188 g/equivalent, which was synthesized from bisphenol A and epichlorohydrin, 269 parts of bisphenol A, 108 parts of a dimer acid, and 190 parts of methyl isobutyl ketone (hereinafter, referred to as "MIBK") were fed to a reactor equipped with a stirrer, a cooler, a nitrogen injection tube, and a thermometer, and the mixture was allowed to react at 117°C in the presence of 1 part of benzyldimethylamine until the epoxy equivalent reached 1,079 g/equivalent, to thereby obtain an epoxy resin. After that, 255 parts of a ketimine compound of amincethylethanolamine (73 mass$

MIBK solution) were added thereto, and the mixture was allowed to react at 117°C for 1 hour. Subsequently, the mixture was diluted with MIBK until a nonvolatile content of 75% was achieved, to thereby obtain an epoxy-based polyamine resin having an amino group equivalent of 1,184.

Rcetic acid was added thereto so that a neutralization ratio (neutralization ratio of the resin based on amino groups) of 35.0% was achieved, and the mixture was diluted with ion-exchange water.

After that, a mixture of MIBK and water was removed under reduced pressure until a solid content of 40 mass% was achieved, to thereby prepare a milky white aqueous (water-dispersible) epoxy-based

NPP11067PCT polyamine resin (A)I.

[0082] (Production Example 2) Production of aqueous epoxy-based polyamine resin (A)II 742 parts of the rawmaterial resin having an epoxy equivalent of 188 g/eguivalent, which was synthesized from bisphenol A and epichlorohydrin, 336 parts of bisphenol A, and 190 parts of MIBK were fed to a reactor equipped with a stirrer, a cooler, a nitrogen injection tube, and a thermometer, and the mixture was allowed to react at 117°C in the presence of 1 part of benzyldimethylamine until the epoxy equivalent reached 1,079 g/equivalent, to thereby obtain an epoxy resin. After that, 350 parts of a ketimine compound of diethylenetriamine (73 mass% MIBK solution) were added thereto, and themixturewasallowedtoreactat117°Cfor 1lhour. Subsequently, 27 parts of ion-exchange water and 188 parts of glycidyl neodecanocate (manufactured by Hexion Specialty Chemicals, Inc., trade name "Cardura E10-P") were fed thereto, and the mixture was allowed to react at 100°C for 2 hours. After that, the mixture was diluted with MIBK until a nonvolatile content of 75% was achieved, to thereby obtain an epoxy-based polyamine resin having an amino group equivalent of 1,093.

Acetic acid was added thereto so that a neutralization ratio (neutralization ratio of the resin based on amino groups) of 35.0% was achieved, and the mixture was diluted with ion-exchange water.

NPP11067PCT

After that, a mixture of MIBK and water was removed under reduced pressure until a solid content of 40 mass% was achieved, to thereby prepare a milky white aqueous (water-dispersible) epoxy-based polyamine resin (A)II.

[0083] (Production Example 3) Production of aqueous epoxy-based polyamine resin (A)III 525 parts of the rawmaterial resin having an epoxy equivalent of 188 g/equivalent, which was synthesized from bisphenol A and epichlorohydrin, 205 parts of bisphenol A, and 110 parts of MIBK were fed to a reactor equipped with a stirrer, a cooler, a nitrogen injection tube, and a thermometer, and the mixture was allowed to react at 117°C in the presence of 1 part of benzyldimethylamine until the epoxy equivalent reached 730 g/equivalent, to thereby obtain an epoxy resin. After that, 350 parts of a ketimine compound of diethylenetriamine (73 mass$% MIBK solution) were added thereto, andthemixturewasallowedtoreactat 117°C for lhour. Subsequently, 27 parts of ion-exchange water and 188 parts of glycidyl neodecanocate (manufactured by Hexion Specialty Chemicals, Inc., trade name "Cardura E10-P") were fed thereto, and the mixture was allowed to react at 100°C for 2 hours. After that, the mixture was diluted with MIBK until a nonvolatile content of 75% was achieved, to thereby obtain an epoxy-based polyamine resin having an amino group equivalent of 810.

NPP11067PCT

Acetic acid was added thereto so that a neutralization ratio (neutralization ratio of the resin based on amino groups) of 20.0% was achieved, and the mixture was diluted with ion-exchange water.

After that, a mixture of MIBK and water was removed under reduced pressure until a solid content of 40 mass% was achieved, to thereby prepare a milky white aqueous (water-dispersible) epoxy-based polyamine resin (A)III.

[0084] (Production Example 4) Production of aqueous epoxy-based polyamine resin (A)IV 1,%40partsoftherawmaterial resinhavinganepoxyequivalent of 188 g/equivalent, which was synthesized from bisphenol A and epichlorohydrin, 1,060 parts of bisphenol A, and 550 parts of MIBK were fed to a reactor equipped with a stirrer, a cooler, a nitrogen injection tube, and a thermometer, and the mixture was allowed to react at 117°C in the presence of 8 parts of benzyldimethylamine until the epoxy equivalent reached 3,000 g/equivalent, to thereby obtain an epoxy resin. After that, 350 parts of a ketimine compound of diethylenetriamine (73 mass$% MIBK solution) were added thereto, and themixturewasallowedtoreactat117°Cfor lhour. Subsequently, 1,060 parts of dipropylene glycol monobutyl ether (hereinafter, referred to as "DPnB") were fed thereto, and the mixture was allowed to react at 100°C for 2 hours. After that, the mixture was diluted with MIBK until a nonvolatile content of 75% was achieved, to thereby obtain an epoxy-based polyamine resin having an amino group

NPP11067PCT equivalent of 1,550.

Acetic acid was added thereto so that a neutralization ratio (neutralization ratio of the resin based on amino groups) of 40.0% was achieved, and the mixture was diluted with ion-exchange water.

After that, a mixture of MIBK and water was removed under reduced pressure until a solid content of 40 mass% was achieved, to thereby prepare a milky white aqueous (water-dispersible) epoxy-based polyamine resin (A)IV.

[0085] (Production Examples 5 to 7) Production of aqueous epoxy—-based polyamine resins (A)V to VII

Aqueous epoxy~based polyamine resins (A)Vto VII were prepared in the same manner as in Production Example 2 except that the neutralization ratio was changed as shown in Table 1 below.

[0086] (Production Example 8) Production of agueous epoxy-based polyamine resin (A)VIII 1,440 partsof therawmaterial resinhavinganepoxyequivalent of 188 g/equivalent, which was synthesized from bisphenol A and epichlorohydrin, 760 parts of bisphenol A, and 388 parts of MIBK were fed to a reactor equipped with a stirrer, a cooler, a nitrogen injection tube, and a thermometer, and the mixture was allowed to react at 117°C in the presence of 3 parts of benzyldimethylamine until the epoxy equivalent reached 2,200 g/equivalent, to thereby

NPP11067PCT obtain an epoxy resin. After that, 350 parts of a ketimine compound of diethylenetriamine (73 mass% MIBK solution) were added thereto, and the mixture was allowed to react at 117°C for 1 hour. After having been allowed to react at 100°C for an additional 2 hours, the mixture was diluted with MIBK until a nonvolatile content of 75% was achieved, to thereby obtain an epoxy-based polyamine resin having an amino group equivalent of 1,150.

After that, a mixture of MIBK and water was removed under reduced pressure until a solid content of 40 mass% was achieved, to thereby prepare a milky white aqueous (water-dispersible) epoxy-based polyamine resin (A)VIII.

& . So oo T ° { T © Ew | Po

T © [st © i. Eo ° = oil | To : i i i = | 318 . Po ;

TEE | | { 0 | | Elm] 1 i I a 5 LT Pj Co — t= 2 Polo Co bo ; ro <o 3 id | | i | i 2 | | : oS i T i i i t | | i i i E = v2 bo Po | Po | | Pod : = gE" . Io i : | | i fol = gc 3 5 Cod Do | | : Lr = > ~ lod i ! ; | bo Po ile = & oo a Noe Pod | | : | bod | clei o 2 13

Z = in fol | | i ! Po Pod sy N 5 1.3 = a ! | i Po Po iN Jez

ET | Poo Cl B TZ re Po FT tH } ! ! — | } - ral? i | i | i i i + i ' 8 Pod i | Po Pod Pod I : boa 0 = | 1] Po | 2 | Po Pod | of 5a Cd Pd | | Po Pod ; | | ce |=

UE | Pod T Po | ] ] ar ! ! I= ol

ERR Po _— | NE | = oi > ~ | Pod | : | bo Pe Lo ion |v & Ne Po } | ! i | Pod : oles ~ g 13 25.08) Lo — Co | els 2 7 oln i [8 | Pood _- Po | > S25

Pet | i | Pod Po > 0 £ » nN Lo Co Lo | Lal

Se {od bod Po Lo | io [od goz a Ld Pod | | P23 Eo Po ge oo Pol { 2 Pod Lo | 5 |= 5 Pod + mm | | ! lo | : 2 |g

Ew Poo bo Pod SiS | z 5 © = : i i { i ! i i fo | i k

Bi TT REEHERES : ey $2 ! Po i ; Po fo nies © a ©

Le ol { i ] Pod i | i Ad on . + 2113 | | : rent bo ! <= Sood

Lo Sl i i Po Co =a TE g Po = i | Po — i raz

S Eo Pol ; a. Po Pol | pl o } i i { { | | | | £ oui

J I Pod ! i | 3 | Po Lo — & 10 vg bold Co | LT le] | 2 |F gs” > o | ! rd | Nig = ° 3 = ° lg ! I. : i Pod Al P13 | on Q

Ey sie : Po ; : Pod i Po Sell - 2 vied HS | | i Po Eo | Sie < ~ 2 EE i | | ft bod } BB S ¢

Pal i i — Po ~ a o i ol ! | bod Lr) al = nol

Pod Pod | Pod — | I © Pod Po | | ! : HT 2 bod bo Lo | bod eg jo oo eed Pod | { |B | Po | © ° & Po Lo Po | = Pod » =

S87 = Lo — | | Cl 2 22 |” a. Co : | | 12 lo ly & Jig Po ! i ! Po | Ps io © 2 13 el fol | | | Lol i 1s] 8 Ee

RE | ! | ed | 129 Zed

Po j= | i i Pod Lo o=E ~ { ASH ial! i | i | { i i ~ © al ® i | ! Po 7 : 2 i bo i : ! | es Gor o : { i | i i | 1 | + i © 3 : Pod | i { i | } | i | i ni o : { | | i fo | i } | i ga 53 I lo | 21 i 5 © EA I. ! | © | fet Vo |= = 28° Pod [J i } | ! = 12] | = ge % ot ; bod Pod ! i | = J oa ~ lol Lo Po Po Po LOR | g oy Sg i bod ! | Po ! olelm E13

Io ai | Lo Ea | ® = 2 ® 5 : Po Po | i i | Pod oe oe © ! Po Pod joo ! Pod Io Hn)

Cw Pol Po o | ] Eo o al oo Lo Io i i | 2 bo | A = 2g, TT I. | Po Po Eo i 8 ~ gE Co Ll | | sl | 2

TX ~ Po Pol I | [=]

Ca od | io } T | [I i A] lo o ol SEE Po | I i I. bo | olels 2 8

Sigg i | i + | i i i i els oy 0 os £8 | : i Lo bod ! | 3 2 od 213 | ! | [A po ! = ° 5g i. Pod (2 | Poo | Po - 5 3E i i bod Pod oo i bo Td i | P= 4H - io bod | | i Po oid | o 1 } i ! 1 i uy 1 i i { f wi ® TT Pol Pod EE Po Po | ows © ¢ : Po | ! Por Po i ! F a . = i Po | i Pod | | gg —t ~ i | i i . + | i i { i i ih a £ iH Po Po ; i | i Poin i i |= g NB bod Po | : i Po Ph ! i © «© Be NE Pod io i f : I pod EN fo 2 = > =| 8 Pod i ! Hd - Pod Pod | 21215 « |Z 3 = 5 RLY 22 Ei

S58 Po Po | E ra — Po a 5 5% 2188 Pod | LE io 8 : Eo TT i = 4 % a I. [8 = i. Po Fol | Hale 6 —21G < ER iz 2 Tel ; hE J gHS zg ° io = 18g 15.5 Lis i 2 : g im i] PE 18x 2m Ph Po fo = hy [ iT i | iE = io Ef FRR { pw = oman gz elu Lg {0 io a 11g] { ord © x gle | i i - eo |B 8 i ie | i AY ~~ EEE PE ioe LE io - | o © al £8 | a m= iS nl 208 | |v =! w 29 Ei [Od i - 10 i tat i — PH £ o EE Ped loo iow lo 13! Loe | wo 8 2 pH igo Poa 1219 Lo= REE jor FEED fei lo of oie i X10 3 = Tz | £25 = 1g el : fa ! EC o ie : HEH EQ el i : } “Las E g | ut EL ina rr fiz El 8E = T5831 Pd TE EZ) iC ix | Tela j=) mn I Ax : iE {i | xT | ra 483 = ody | : ed il = 28/58: 2 3} LS LER vrse | Po 12 ge: Ss ule < rsex su : jo 203s ©

Ture ie 318138 8 0 rod : N 25 = rod pe fzl288 5 seq SEE IY

Axed lo I odz S19 o | a

Sizing ! a

Sozsis © 835 E 252 goizs if i ges 2

NPP11067PCT

[0088] (Production Example 9) Production of epoxy-based polyamine resin

An epoxy-based polyamine resin was prepared in the same manner as in Production Example 2 except that the neutralization ratio was changed to 5%. The epoxy~basedpolyamine resinwas not converted into an aqueous resin and caused phase separation in water.

[0089] (Production Example 10) Production of epoxy-based polyamine resin 2,560partsof therawmaterial resinhavinganepoxyequivalent of 188 g/equivalent, which was synthesized from bisphenol A and epichlorohydrin, 1,439 parts of bisphenol A, and 706 parts of MIBK were fed to a reactor equipped with a stirrer, a cooler, a nitrogen injection tube, and a thermometer, and the mixture was allowed to react at 117°C in the presence of 5 parts of benzyldimethylamine until the epoxy equivalent reached 4,000 g/equivalent, to thereby obtain an epoxy resin. After that, 350 parts of a ketimine compound of diethylenetriamine (73 mass% MIBK solution) were added thereto, and the mixture was allowed to react at 117°C for 1 hour. After having been allowed to react at 100°C for an additional 2 hours, the mixture was diluted with MIBK until a nonvolatile content of 75% was achieved, to thereby obtain an epoxy-based polyamine resin having an amino group equivalent of 2,050.

Acetic acid was added thereto so that a neutralization ratio

NPP11067PCT (neutralization ratio of the resin based on amino groups) of 40.0% was achieved, and the mixture was diluted with ion-exchange water.

After that, a mixture of MIBK and water was removed under reduced pressure until a solid content of 40 mass% was achieved, to thereby prepare an epoxy-based polyamine resin. The epoxy-based polyamine resin was not converted into an aqueous resin and caused phase separation in water.

[0080] (Production Example 11) Production of base resin liquid for coating material I 110 parts of water, 32 parts of a pigment dispersant (manufactured by BYK~Chemie, trade name "Disperbyk~190"), 4 parts of a defoamer (manufactured by BYK-Chemie, trade name "BYK-019"), 179 parts of calcium carbonate (manufactured by MARUO CALCIUM CO.,

LTD, trade name " N Ground Calcium Carbonate "), 172 parts of titanium oxide (manufactured by Du Pont, trade name "TI-PUR R706"), and 25 parts of a calcium-based anti-rust pigment (manufactured by Toho

Ganryo Kogyo Co., Ltd., trade name "EXPERT NP1007") were mixed, and the mixture was stirred with a disper for 30 minutes, to thereby produce a pigment-dispersed paste. 400 parts of the aqueous epoxy-based polyamine resin (A) I obtained in Production Example 1, 24 parts of DPnB, and 1 part of an associated thickener (manufactured by ADEKA CORPORATION, trade name "Adecanol UH-420" were added to 500 parts of the pigment paste, and the resultant wasmixed, totherebyobtainabaseresinliquidforacoatingmaterial

NPP11067PCT

I.

[0091] (Production Examples 12 to 18) Production of base resin liguids for coating material II to VIII

Baseresin liquids foracoatingmaterialIIltoVIIwereobtained in the same manner as in Production Example 11 except that aqueous epoxy-based polyamine resins (A) shown in Table 2 were used instead of the aqueous epoxy-based polyamine resin (A)I.

[0092] [Table 2]

Base resin Rgueous epoxy-based polyamine resin (A) liquid for Epoxy Amino group coating equivalent of | equivalent of material epoxy resin agueous epoxy—-based polyamine resin

Production I (Production

I 1

Production . II (Production

Production III (Production .

Production IV (Production

Example 14 tv Example 4) 3,000 1,550

Production V (Production 1

Example 15 v Example 5) 1,093

Production VI {Production ,

Production VII (Production

Production VITT VIII (Production 2,200 1,150

Example 18 Example 8)

[0093] (Production Example 19) Production of curing agent I 40 partsofwater, 10partsof DPnB, and 50partsof polyethylene glycol #400 dimethacrylate (EO 9 mol) (viscosity (25°C): 58 mPa-s, molecular weight: 508, number of functional groups: 2, acryloyl

NPP11067PCT group equivalent: 254) as the compound (B) weremixed, and themixture was stirred using a homogenizer for 10 minutes to give a curing agent TI.

[0094] (Production Examples 20 to 28) Production of curing agents II to X

Curing agents IT to X containing compounds (B) were prepared according to the method of Production Example 19 using the compounds (B) shown in Table 3 at blending ratios shown in Table 3 by mixing methods shown in Table 3. It should be noted that a nonionic emulsifier (manufactured by Nippon Nyukazai Co., Ltd., trade name "Newcol 740") was used as an emulsifier in each of the curing agents

II, V, VIII, and IX. Table 3 shows the viscosity at 25°C, molecular weight, number of functional groups, acryloyl group equivalent, and property (self-emulsifying, water-insoluble, or water-soluble) of the compound (B) used in each of Production Examples. The properties of the compound (B) were evaluated as follows. At room temperature, 5 g of the compound (B) were added to 100 g of water, and the mixture was stirred for 3 minutes and allowed to stand still, followed by visual observation. If the mixture contained a precipitate, the compound was evaluated to be "water-insoluble," if the mixture contained no precipitate and was clear, the compound was evaluated to be "water-soluble," and if the mixture contained no precipitate and was turbid, the compound was evaluated to be "self-emulsifying."”

$ = Ta Lo bol o Ww 0 — bo fm T ~ ob ! > EE os = ~ Ep] e g| I ] i = o [SR init I~1E gi £ ow 2 mimi iopnd o = © S £ £5 ol f= aN a & 3 SEESETT EY

Por lo i

Be LE Sua | Pos 5

Zz, i [I i's 1 @ 8 Pros ! N wed ig = i remand Ilo wet + ce Po LIS ahs = u |S 27 Pg EAA @ = 182 s & iol Pre | 2 kel i oo =3 Po Pon i £ oo os TTT o > 0 Ow SIN cog E| |g Ne EE

H Xo oho SIRT o! Sto gs org i a oad Sir holo ZIG = wow rr a Pod I ia i

EEE. TEE o B9E% 2

Hod | | | fo 7 Sgixima 2 {bel 4d ! jm a®= Lo Poe i oT = % o Jo oho) il 0 {od I] | 0 KS gM ooo eo I

I I | oo Cag IS wf oelR ® o ° fr | o & a © Fe joi le a. oo I< TT | £=] ee —Q oT | { FARRER

Sl |b eo ~ | Ph i Fa iZaod Cold Pie =a - Eo eT i Is Po i a bo 258% lB ” CE

SEB e iS! Pole } a [Ex To 1 EE :

TE ix dwg SB I : N Oo @ ~~ { fo [I L © Q 0° Givi ol i ed £2 0 ~~ fb i i hot a, “i | Liololn = pt © =i Polo ted .

A EEE ERT 2 Seed LE, " oc" | i o 5 Pod + o & | oie | on = DL © Po | 1

Fas | [oe 0 El a 3.02 2 ol v

LE EE Sw 0 isis mint ol 3

SINE iE - BE g

Celslz oo LE le] g 2 pls = lol foie i ow Ee] TT Ll i o

T° | nie ie << oh Io : seme Eg lo l2lla dO JS IS om Ll] £3 52% as RE 8 g5 B23 1) 113 aloo ed Pod i. 5 | ia somigTs iol io I's | I"

Hes I | | ord Cf [A Sieg! bia @ oo Plo : oO ZeEEZ 53 [Sievl lel 2 i 5 [I lm oS © o uc @ i fmt iou ini of -

PoE EE 2 ew {oho oT IRIS g col ITO Ft ] A] £2.49 i SRILA E

ON SI | Pod 1 ZRH Pod Pe i o po £ rw bis Cle g

Dol IK I I PLE £ gamit l Le ARE LE 8 ggl-ou lolol lol S | gl 18a Te CoE 2 gl 13° SRT ES ° 1 8 pe Poo bo

B ed gig o o 2.580 boro [PR fd 157 RRTm AEE EST LE ooo Pod Po io 3 3 Bi» BORD slo! | ig

I tm £ 6 © x0 fini, Sha ol Sy

PoE | 18 |& 4 osu {Tiel Ji i212 @ oo @ © I i = fo [50 2 SlEmRa REE o — el | bod ! wn 50 5= Vo Pte 2 o go» Ps 2 001s | a 03 dx rz Pd i | Plo 8 = alms Oo | I P< gos Ltd Ld i :

TE SE mim! = E ol ol 18 Oy | Cr !

Ca 2558 BiginnlE Solo! -l ir 8g 8 = io Elo I 5x 5092 Po 10 § S222 15 “oo Edw g Polo idm cl Beal CNL she 5 8lLZ ERs bole ie Poo Cd | Sais > [I . fm to © |! ol Ft | | © T > © oo |. 0 sell gl 38 Site grezil 3 bore ! 3 oR ie a 10 ir} wig Sloloio fb i i = on Lon © PE mY din o ro EE | TH t=] Toe QQ I } i S li HY

Co | i : S208 | os } of

EE | 7 Prod ; | S

Elbo | Poo fo g ob i Le 3

Li : tt =

Po i — lel | Cl NE ™ lala Co isis i ood i 0 Pod EE fe Ed i id 1208 fo Vo a. i i — . |= ols fu bb inl { ! !

Q S Eat Ie PB [i = isi ia Poe i i . A= sh ; Pood Le i j= SEE {x — i | Pio fo i at win tel 91 {oh | wn } Pde] tn i cla E2502 { RE f= lO i [] i

S15 aa Revel Ie loi alalg ; joie 5g in i

EE Sih srdEs 2 PELE IR he ZiEi2ig 8 3 245 op) ie fm lmiZiEinio [9o|8l 18 wig E085 I~ fa o [B $10 HS TE gl 2 ole ol E slo hp 1ol ol fond 1 TH E f= 1 lal oie l= i Ee) 5 Sig =e gid E205 Hamye tw OS Lo Lng [sib I> sibiBe 5188 RIE — 3 aigioix 212)8 a © Sicielel® BERS uy o gig ETE jo; oo HESS Pele! 8) © on I Pl Ela © 81d & Lal Qin oid [R12 = <O ! Eo RIRG io] BILE bell {01 Olu) | ! 10

Por pH ; | | St Veins fed d 1 el o> Po to) fred | e 1 Oo! > em Mi

P13 i i= | | E = Boi % 3 EE Sear 8 — Pood Pet | = S i=l tot Ll BS fort

PoE i i ja i ig | & wid polo : i INR prt { = wi 0 x [I [I i [I Lol PE Siig

Po PoE | [RE bat 1] n= i Poo : HE Lol i i ol ! | Vo 2 im {BE

Pol ER TT

Polo Pod i Poi {ot i { end Pro | Eb : : :

LN — BERN B ¢ punod meee | Polo prmodieD RERREEERE be ob io { { eer Pol | i ddd ; ! g punod et od {

WoD i i

NPP11067PCT

[0096] (Production Examples 29 to 47) Production of aqueous coating compositions 1 to 19

The base resin liquid for a coating material obtained in

Production Examples 11 to 18 and the curing agents obtained in

Production Examples 19 to 27 were mixed in blending amounts shown in Table 4, and the mixtures were stirred for 10 minutes with a disper to give aqueous coating compositions 1 to 19.

[0097] (Production of top coating material and intermediate coating material) (Production Example 48) Production of aqueous epoxy/amine-based coating material A 34.5 parts of ion~exchange water and 0.3 part of a sodiumalkyl diphenyl ether disulfonate (manufactured by Kao Corporation, trade name "PELEX S5S-H") were lcaded and heated in a nitrogen atmosphere to 80°C. Next, a monomer mixed solution including, as monomers, 14 parts of styrene, 58 parts of 2-ethylhexyl acrylate, 22 parts of methyl methacrylate, 4 parts of ethylene glycol dimethacrylate, and 2 parts of methacrylic acid, and as a chain transfer agent, 0.5 part of lauryl mercaptan was prepared. The resultant monomer mixed solution had an acid value of 13 mgKOH/g. The monomer mixed solution was added to an emulsifier aqueous solution of 1.2 parts of a sodium alkyl diphenyl ether disulfonate {manufactured by Kao

Corporation, trade name "PELEX SS-H") in 50 parts of ion-exchange water, and the mixture was emulsified with a mixer to prepare a

NPP11067PCT pre-emulsion.

The thus-obtained pre-emulsion and an initiator aqueous solutionof 0.3 partofammoniumpersulfateinl3partsof ion-exchange water were added dropwise into the separable flask from different dropping funnels simultaneously. Dropwise addition at constant rates over 120 minutes for the former and over 150 minutes for the latter was started. After the completion of the dropwise addition, a reaction was continued at the same temperature as above for an additional 120 minutes. The resultant was cooled and then neutralized with aqueous ammonia corresponding to 10 mol% of the methacrylicacidused. Theneutralizationproductwas filteredwith a 200-mesh metal screen to give an acrylic emulsion resin.

Subsequently, 1.9 parts of a pigment dispersant (manufactured by BYK~Chemie, trade name "Disperbyk-190"), 0.3 part of a defoamer (manufactured by BYK-Chemie, trade name "BYK-019"), 18.6 parts of titanium oxide, 10.9 parts of calcium carbonate, 8.5 parts of talc, 2.9 parts of an anti-rust agent (manufactured by KIKUCHI COLOR &

CHEMICALS CORPORATION, trade name "LF BOUSEI PM-303W"™), and 12.1 parts of water weremixed with each other and dispersedwith a disper.

To the dispersion were added 41 parts of an emulsified epoxy resin (manufactured by ADEKA CORPORATION, trade name "ADEKA RESIN

EM-101-50, "epoxyeqguivalent: 500g/equivalent, solidcontent: 47%),

NPP11067PCT 1.7 parts of a film forming aid (manufactured by CHISSO CORPORATION, "Cs~-12"), 0.4 part of an anti~-rust agent, 0.2 part of a defoamer, and 17 parts of the acrylic emulsion resin produced in the foregoing to give a base resin liquid for a coating material.

Further, 8.9 parts of a water-soluble polyamine resin Sunmide (manufactured by Ailr Products and Chemicals, Inc., trade name "WH-910," active hydrogen equivalent: 135 g/equivalent (in terms of solid content), solid content: 60%) and 11.2 parts of water were mixed with each other to give a curing agent.

The base resin liquid for a coating material and the curing agent were mixed with each other and stirred with a disper to give an aqueous epoxy/amine-based coating material A.

[0098] (Production Example 49) Production of aqueous epoxy/amine-based coating material B

An aqueous epoxy/amine-based coating material B was obtained in the same manner as in Production Example 48 except that the blend of the base resin liguid for a coating material was changed by using 4 parts of the acrylic emulsion resin instead of 17 parts of the acrylic emulsion resin.

[0099] (Production Example 50) Production of aqueous two-component urethane-based coating material A

NPP11067PCT 22partsofwater, 6partsofapigment dispersant (manufactured by BYK-Chemie, trade name "Disperbyk-190"), 70 parts of titanium oxide, 1 part of a defoamer (manufactured by BYK-Chemie, trade name "BYK-011," diluted to 10% before use), and 0.4 part of a dimethylethanolamine agueous solution (25 mass%) were mixed with each other and stirred with a disper to give a pigment paste. 39 parts of the resultant pigment paste, 58 parts of an aqueous acrylicpolyol (manufacturedby DIC Corporation, trade name "BURNOCK

WE-306"), 0.4 part of a surface conditioner (manufactured by

BYK~Chemie, trade name "BYK-346"), 0.05 part of a leveling agent (manufactured by BYK-Chemie, trade name "BYK-333"), 0.4 part of a surfactant (manufactured by Air Products and Chemicals, Inc., trade name "DYNOL 604"), 0.5 part of a viscosity adjuster (manufactured by Rohm and Haas Company, trade name "Primal RM-8W"), 0.1 part of a dimethylethanolamine aqueous solution (25 mass$%), and 2 parts of a defoamer (manufactured by SAN NOPCO LIMITED, trade name "SN-Defoamer 373") were mixed with each other and stirred with a disper to give a base resin liquid for a coating material. 100 parts of the base resin liquid for a coating material were mixed with 17 parts of a water dispersible polyisocyanate (manufactured by DIC Corporation, trade name "BURNOCK DNW-5000"), and the mixture was stirred with a disper to give an aqueous two-component urethane-based coating material A.

NPP11067PCT

[0100] (Production Example 51) Production of aqueous carbodiimide-based coating material 100 parts of 4,4-dicyclohexylmethane diisocyanate were subjected to a reaction in the presence of 1 part of 3-methyl-l-phenyl-2-phospholene-l-oxide as a carbodiimidation catalyst at 170°C for 8 hours to give a carbodiimide compound having about 3 carbodiimide groups permolecule and having isocyanate groups at both terminals (isocyanate equivalent: 450 g/equivalent).

To 360partsofasolutionobtainedbydilutingthecarbodiimide compound with methyl isobutyl ketone to 50 mass% were added 0.02 part of dibutyltin laurate and 165 parts of polypropylene glycol having a molecular weight of 2,000, and the mixture was subjected to a reaction at 85°C for 1 hour. Subsequently, 125 parts of polyethylene glycol monomethyl ether having 15 repeat units were added thereto, and the resultant mixture was subjected to a reaction at 85°C for 1.5 hours.

After the confirmation of disappearance of the isocyanate groups with an infrared spectrophotometer, 920 parts of deionized water were added, and themixture was stirred to homogeneity. Methyl isobutyl ketone and water were distilled off at 40°C under reduced pressure so that an effective component was adjusted to 40 mass% to give an aqueous carbodiimide curing agent having a carbodiimide

NPP11067PCT equivalent of 825 g/eqguivalent.

Next, to 35 parts of a pigment paste obtained by mixing and dispersing, with a disper, 6.8 parts of water, 1 part of a pigment dispersant (manufacturedbyBYK-Chemie, trade name "Disperbyk-190"), 1 part of ethylene glycol, 0.2 part of a defoamer, 2 parts of barium sulfate, and 24 parts of titanium oxide were added 35 parts of an acrylic emulsion (acid value: 30 mgKOH/g, solid content: 55 mass%), 8 parts of a water-soluble acrylic resin (acid value: 55 mgKOH/g, hydroxyl value: 70 mgKOH/g, mass average molecular weight: 9,000, solid content: 30 mass%), 3partsof a film forming aid (manufactured by CHISSO CORPORATION, trade name "CS-12"), 1 part of a viscosity agent, and 1 part of a defoamer to give a base resin liquid for a coating material.

To the resultant base resin liquid for a coating material were added 35 parts of the aqueous carbodiimide curing agent produced previously, and the mixture was stirred with a disper to give an agueous carbodiimide-based coating material.

[0101] (Production of underccating material) (Production Example 52) Production of aqueous organic zinc-rich coating material 8.8 parts of a water-soluble polyamine resin (manufactured by Air Products and Chemicals, Inc., trade name "Sunmide WH-910,"

NPP11067PCT active hydrogen equivalent: 135 g/equivalent (in terms of solid content), solid content: 60%), 1.2 parts of a viscosity agent, and 6 parts of water were mixed with each other to give a curing agent.

The curing agent, 16 parts of an emulsified epoxy resin (manufactured by ADEKA CORPORATION, trade name "ADEKA RESIN

EM-101-50, " epoxyequivalent: 500 g/equivalent, solidcontent: 47%), and 68 parts of zinc powder were mixed, and the mixture was stirred with a disper to give an aqueous organic zinc-rich coating material.

[0102] (Example 1) Formation of single-layer coating film

An aqueous coating composition 1 was prepared under an environment of 30°C by the method of Production Example 29, and 24 hours after the preparation, the aqueous coating composition 1 was applied onto a sandblasted steel sheet with a brush in an application amount of 200 g/m’ and dried under an environment of 20°C for 7 days to form a single-layer coating film (thickness after drying: 60 um) formed with the aqueous coating composition 1. At that time, the aqueous coating composition 1 did not gelate and was able to be applied with good workability. The resultant single-layer coating filmsubjected to theevaluation for "corrosion resistance." Table 4 shows the evaluation results.

[0103] (Examples 2 to 19) Formation of single-layer coating film

NPP11067PCT

Single-layer coating films were obtained in the same manner as in Example 1 except that the aqueous coating compositions shown in Table 4 were used instead of the aqueous coating composition 1. Itshouldbenotedthat, althoughtheagueouscoatingcompositions were used 24 hours after the preparation in all Examples, none of the aqueous coating compositions gelated. The resultant single-layer coating films were subjected to the same evaluation as in Example 1. Table 4 shows the evaluation results.

[0104] (Example 20) Formation of single-layer coating film

The aqueous coating composition 1 was prepared under an environment of 5°C by the method of Production Example 29, and 1 hour after the preparation, the aqueous coating composition 1 was applied onto a polished steel sheet with a brush in an application amount of 200 g/m? and dried under an environment of 5°C for 24 hours to form a single-layer coating film (thickness after drying: 60 um) formed with the aqueous coating composition 1. At that time, the aqueous coating composition 1 did not gelate and was able to be applied with good workability. The resultant coating film was subjected to the evaluation for "initial rain resistance." Table 4 shows the evaluation results.

[0105] (Examples 21 to 38) Formation of single-layer coating film

Single-layer coating films were obtained in the same manner

NPP11067PCT as in Example 20 except that the aqueous coating compositions shown in Table 4 were used instead of the aqueous coating composition 1. Itshouldbenotedthat, althoughtheagueouscoatingcompositions were used 1 hour after the preparation in all Examples, none of the aqueous coating compositions gelated. The resultant single-layer coating films were subjected to the same evaluation as in Example 20. Table 4 shows the evaluation results.

[0106] (Example 39) Formation of single-layer coating film

The aqueous coating composition 1 was prepared under an environment of 23°C by the method of Production Example 29, and 24 hours after the preparation, the aqueous coating composition 1 was applied onto a polished steel sheet degreased with xylene with a brush in an application amount of 200 g/m? and dried under an environment of 23°C for 7 days to form a single-layer coating film (thickness after drying: 60 um) formed with the aqueous coating composition 1. At that time, the aqueous coating composition 1 did not gelate and was able to be applied with good workability. The resultant coating film was subjected to the evaluation for "water-resistant adhesive property." Table 4 shows the evaluation results.

[0107] (Examples 40 to 57) Formation of single-layer coating film

Single-layer coating films were obtained in the same manner

NPP11067PCT as in Example 39 except that the agueous coating compositions shown in Table 4 were used instead of the aqueous coating composition 1. Itshouldbenotedthat, althoughtheaqgueouscoatingcompositions were used 24 hours after the preparation in all Examples, none of the aqueous coating compositions gelated.

The resultant single-layer coating films were subjected to the same evaluation as in Example 39. Table 4 shows the evaluation results.

9 2s © . . 3 222.5% 1 Ot g ~ goomgl2- Za 3 } © STA XM wy 8

A go BFA “ <0E X oc =“ ce © a m9 & g22 $2 ou 0 mn; —~ = Ea® Lew § ZED 8 & wlzw aly PR 2B xm A = x gece" gE

Re) [IS on

S & -= et i oc © oy ooo a 2 £85 274

Cu Ow © ~~ >, Eo Send 5 EG 3 & Tag eT xo a x ro Sa o «Ls oo. sg 2 i oc © © © aol he

FARE: E-P . ~ —_ 8 ewl3Tiw"3ESL 2 g Y¥izelaeB xo a % go ZT Cw © i <0 E KH 8 oo g 2 o © - © wo] "g 3 2 c+ 0, : ac o 5 i

Sonz$58° 38s & 2 : § Nsw al a ? E 2 Rog Rm — un 2 8 2 ggg g* “ :

Oo a pod 8g = = e g - 8 3 °o © ° nop a" y ® : sc a emlBEHn GEL g 2

E wv eo 2 58m hn] 2 2

EVvaeihong = 3 2 28aFoi™ ES © g ? i «CE MX @ 6 oo o= = = = = f

A

2 228 £4

CH g ~~

Eemal8f BT 28S g 5 sw egxm H © & gog g*° - 8 & a g = so © oom 8 5 225 Ba o PO mm ~~

Em J Fee 3 253 3

E 290.8 2 ct 8 a8 xm = 2 go "0 © = 0g g&° . ! 8 oo °F

EET o . . 5 g82 #73 o. = ©

Eagles Bao o 7 sm Eero & &

Eggert do. g & 3 22 © un] oo = lses te & ocolfiue"zER b=

Xo = ~~ ~ & < ™~ = 2 S148 5c lolo | mo]: 5181809 £88 > > o > < « < oN Mow

Eo | oe | : 5 5 SE las} i — —t oN eG le 02 ol2 ls pl Gol 0 _ © olf el” ul? ol ICI = la jee — i Oe p Zz 2 ol2 = g EE EERE ESfolfefeZezg o © Lalli ml al gla alg g 537408151352 2 So lgRshshsheaennet Sl. asssBsBalE : Sil © gzizrEae 2 gle gle 8 CERES Ballas g 95 2% Un Qs 3 gle rR ol* ol¥ ol old o > Sls iE iw 2x 8 Mlowm rs Os mw © s | 8s fs GHEE EET oN . pm fu

Oo by = pi > — = — 5 = g Siege ofl wm | Zl > =o

EERE

Ll

Terzsaew HUTIR0D 307 PTNDTIT x w HuTIBCT 307 PINDIT UTSEI esey ausbe butang

: f Ee = e © I pl

S C= 8 - - ol ° i - i ! co © © ! He vo ot wn 2 ZED 6 °o ] o, 0 gE & l + oco~lg he 3 BT & c o t = Emmis 0 T wow 0 oO = ~ on <let o ® To grown

By ~N g o | = « “98 a. r~ - | oO —-

SS i ~t | i i

Pol s — . pod 20 : Vy A “+d ~ 3 z 26-722 gE 3

By | = Bormw ll um IED 0 ~ o i = “mniER oS TES on pi] Z nf i [© = 2c 8 3 > cjg] © 5% go 2° Cd

Z - = = = Cs 2g © t i © © bl | a no od 2 2 12 E80. -

[2] |Erssifitiifs 2 2 ” “ gM 8 Bxe iH ° 3 iis) ge » ro 2% OQ = = od =9s ou o = t hd :

I | °c o = i ft i « @ © wold O03 o i E850 D o © = Bows T um 304 3 2 "lelel 2 frmwifh oD 2 =< © Pl ! % ro &% = - “= 8 id «CE Hog ou 112] cs = A ~i } ! o

S Sw - i Pa moon oe 43 112] 2. .85328% ¢ = |s eo wn | 2 [Bos mele~ 255 c wn n > I A I ig Mm se Exe £ ~

SSE EF FREE) of ) © | gS Ze e ] ! 4 rT © o &

J w s

I 0 | a. ir . by 5 2 Es sg = o o | & CoemunlOd GT 8 E = So

Saale] E RERIEESEE S ° - a x [58280 ~ - i <0 Eg &_ i — | 0 ~ : ; ; boi | o ou @ @ 522 oe i + 3 j=% = : = Bm Sm HCE ~ = © ~ i et £ im mew 4 =a in 0 > LIGETI g "OPIS Te LT xe - m

A ° i a x 1&0 &% 0% - i i <0E 2 | 8 mg

Ll 2 i 7

A] i © 5 —- | oO - = co © © 5 izes P23 ° - Jou o alow a o ~ ETS Siow @ = 8 on © c IRI © rn © T xm Wy 3 od a a 2% aco - x ico BF 0

Ong a fold Zi t > 1 es ~ le l~leoxns 12 |¥ioll eg | ~

Np TIE. IE Lol 81S - awd nie £20 ie foie mr ul oe clo |o|o

Cg, |8 =p Xe irc |~clold ~~~

SE=z D> EL ! tcoceilololim|d|loclocieo 52 lo (Ei dls 2 oe ~ “| ~ . - . .

PRPREREEER EE EEE

SE ulE og old lm wl E Yiz ™ i ult ol 0% olT 20lo

TT SSB = Belin Sig Alm Sime l= 8g

LB LElLalle TaiEACR, 0 $ 1TRITQTRTR" TT E “Sim Bie Sis 060g gifs ow o LaLa Lala + Fe) Po fo , or 3i5isra RTRs ELE EEE ELE tr o Yim CSR Malin nie E wu te © © Qig W

Tmo |S [ume i 1H {> joiHle | | : 23s |B (EEE oma ae | TET d ! SIE ae] ey po —— vn

Z ge = 38] | butzecs zoz pInbIT ulssx sseg

E= © S s lelal

Z | | 2 i —

Ll

Le i i a o “ © a < - ~ Lf o - | 3 = ~ |< = a | | E ot i — - | i i © : : i a, = o 43 ! py rs o | = 3 “ | pe ~ . O £ “ So <El eg © I

I © on | -

I i ! + I i T 0 i J f a ~™m tf ef 0

Sl x [ose = — i 2 © : = ~ pe 2 S - =i] © : S - ge i «© i — 7 7 T — > oO =ls o £0 ee coi oz 10 w of frst § 0) 0 {0B Qe oc of - © om od FOloie - > 8 i o = °o “oll

SHS lelelzislielnleinfis lo [58

HPN alm Ne ae BEE IOD

Oo i wae gE lulors a- | pe VE lajmjo~ o |B TL |B foie Te

Lig | SEE 5 lgge

S oY al k= : 22 Tim Gldi-le

I ALERTED

0 [OL SR [I] « ~~ im wom [LJ bab joie om fot © 5 ove Elf ol ¢lB OE ig gle eB. Sielaic me 2 IEEE ol elE uf eB EE eS of olf T55 R0IE @

PAL So Taam Tada nara Siogiglliieo wl GY SL RG Bl Bla 2H SNe BIB ns BIND mRI9 gi8inl8 oP ELSES Sy Sle Zig BY FA EN Roped oH Oa de Ble Ble Gla Bimal Flo dle BIR ZS om ET vine BE gel » lg dleomolsorolonr ele Es gs pHigin dg = 2 By iE |= Eom wom [EE wo {0 Jeg) x : 1 “on nt hol mi i °c,e or Hale = = (oc 5 —t gis 3 ‘ oe > 1G $4

Clg mialE E25 EE RE 2 Sle > | > EET IEE i i | Wo wio|E 229 2 |B 1 at i 1 auebe Butany 252 S12

NPP11067PCT

[0109] (Example 58) Formation of multilayer coating film (two layers)

As a substrate, a polished steel sheet degreased with xylene was used. The aqueous coating composition 12 obtained in Production

Example 40 was applied under an environment of 5°C onto the substrate with a brush in an application amount of 200 g/m? and then dried for 24 hours at the same environment as in application to give a coating film (thickness after drying: 60 um) formed with the aqueous coating composition I. The resultant coating film had no finger feeling (specifically, no sticky feeling) and a top coatingmaterial was able to be applied thereonto.

A solvent type epoxy/amine-based coating material A (manufactured by NIPPON PAINT Co., Ltd., trade name "Epotal NB-20") was applied as the top coating material onto the resultant coating film under an environment of 5°C with a brush in an application amount of 200 g/m? and then dried at 25°C for 24 hours to form a topcoatinglayer (thicknessafterdrying: 60um). Thus, amultilayer coating film (two layers) was obtained.

The resultant multilayer coating film (two layers) was subjectedtotheevaluation for "water-resistant adhesiveproperty."”

Table 5 shows the evaluation results.

[0110] (Examples 59 to 68) Formationofmultilayer coating film

NPP11067PCT (two layers)

Multilayer coating films (two layers) were obtained using the substrates, aqueous coating compositions, and top coatingmaterials shown in Table 5 under the conditions shown in Table 5 in accordance with the method described in Example 58. The top coating materials used in Examples 59 to 68 and shown in Table 5 are as follows. It should be noted that the polished steel sheet used in Example 59 had been degreased with xylene in advance, and the slate sheet used in Example 65 had had an aqueous sealer for an inorganic material (manufactured by NIPPON PAINT CO., LTD., trade name "Ultra Sealer

III") applied onto its surface in advance.

Any of the coating films formed with the aqueous coating compositions hadno finger feeling (specifically, nosticky feeling) and the top coating materials were able to be applied thereonto.

In addition, the resultant multilayer coating films (two layers) were subjected to the same evaluation as in Example 58.

Table 5 shows the evaluation results. (Top coating material) 1. Solvent type epoxy/amine-based coating material A

As the solvent type epoxy/amine-based coating material BA, "Epotal NB-20" (trade name) manufactured by NIPPON PAINT Co., Ltd. was used.

NPP11067PCT 2. Solvent two-component urethane-based coating material A

As the solvent two-component urethane-based coatingmaterial

A, "HI-PON 50 FINE" (trade name) manufactured by NIPPON PAINT Co.,

Ltd. was used. 3. Solvent two-component urethane-based coating material B

As the solvent two-component urethane-based coating material

B, "NIPPE URETOP ECO" (trade name) manufactured by NIPPON PAINT

Co., Ltd. was used. 4. Aqueous epoxy/amine-based coating material A

As the aqueous epoxy/amine-based coating material A, the aqueous epoxy/amine-based coatingmaterial A produced in Production

Example 48 was used. 5. Aqueous two-component urethane-based coating material A

As the aqueous two-component urethane-based coating material

A, the aqueous two-component urethane-based coating material A produced in Production Example 50 was used. 6. Aqueous emulsion-based coating material

As the aqueous emulsicn-based coating material, "ODE COAT G" (trade name) manufactured by NIPPON PAINT Co., Ltd. was used. 7. Aqueous carbodiimide-based coating material

As the aqueous carbodiimide-based coating material, the agueous carbodiimide-based coating material produced in Production

Example 51 was used.

—t 2 On| . mo gm | . . old gal Tl ot Pn Hod | i | ' 2 osgid Lo Lo a E oH ] i on

Be a5 2 8.050% 5) mE A © g2zle oo < ! -- | T 58S a | IT! 0 | | i > E12 89 & & on (E oH | ! i — og | ol 22a | Po = 5 1385 SPE ol lz [aM g3 be I — | ° ERIE { Pow oN o | l=15)° 0

Zz. | Po 5 > fla 5d ! } i i od 43 — : i { i Oo X [ ~N ood | _ I§ = © oo : | ! 35 5 51g 13] 4 ~lY & My i | 280% | 5 5 i ol + a | T Fago | ! S20 Qo @ ool | TT ® Eg | i { EO a 25 u[2 8 Co | — a2

HEHE Qe | i | { : mE 3 ol PD | = Lg | i i i = a 2 FIPS EES 28 | | | j i © 5 Ef i L258 Soa 0 & Of i ER £ x E < © | | Le | zo < 0550 w | io i i i a> SEED | oO wm ; J ; | > — : j = x 0 9

T ! i { 0 J ra 1 oO og o | 7 i i i = 0 oo i Lolo of He ol | ; ; | G hl i 12128 0 o wl? Eo | i i | << “wm | A HO On elo bh” solo gl | ! i &% E | | | | | 28D oral Co Co 2 = AE

A : ! i ; ' ©

Bie. gly)! = 1 Lo 5°50

Bart ie zg] | E coo | | i | ! Sw 43 Qa mo | = |= ooo | i i | i g 9

Sele El } 15 =. | } i ! 8 2108 s8c ! ! | ] 7 ol i Sle 0. = PO o~ [I oo SEzilz |e oie EF wo i A EE 0 o i i | 5S EE Io 51°] ie] B ~ 2 i | i ClEEEL | - | 154 © c on | 1 i { S00 gid] - 0 lon] | ! Ea d ] 8122 0 o 21% |= : ! : 88 } Se i? o 23

Bl AA Cc 5°

Z 9 oe elu £8 lois] 81?® i i | i oe 5g ° el | i o i | ! Lo | S = | RES w ° : | | : | 588% SED isl © ol 9 i | | | £920 | Loa oo 5) 3 ol © © Oo yl | i B18T | IPN RE Bx 0 ojo zo ; ! 0 2 © ! 13108 0 © nlS gl i i 182584 | Poof od 1g = — — o 2 | | i 50 | : Pin | 288 lo] LT 8 | i | | P& © = Qo elo 28g) | i i 0 | | ! po El 25 2, 29 7 | Dey oo | Sug i | | | x =“ oe ae = | L5E : ; ; | EE gla ied ES o8 | i 7 i | oe ali 1 §3 | — : i) | 2 i | i | i £

Zz 0 | | ¢ 4 FR I ! Pod En SEE 0 i | PN 53 a | So | o : t i | i Se "a i i IE IE} + } + i | > i oH Poet = Oo rt | | i ! x “| Pm Pe 1 © © ot i i | ; ~ 0 o | | ol 5 Ba s — Re c oi : i ; ! oc & oi ! Sos 0 ol £

Ly 0 HY i | f ! gag | Pas 1o 0, — ug nl i i 7 Eg | ! Pin | a. @ "eT 8 | | i ! | i ! Pa o E ® © 02283 : | | i © ; i ! | | i glo = Slo 810 5) bo PL] Bog : : | | i n 2 2 3iiee 3% a Co Po Al = © JpELE0 22 | S55 | Co | a = fei.20 DCs i i | i : wd 5 of Pog = i rt ~ 3 ai =) —- ge | i | i 0 gg ! el Eo | : i

S 58 1812828 ed ga | od <5 82 "

FS S213 Lae <« ; | | i : > wt Pg ! lg] = LD = : ; ! | EEE a Pm D3] 0 © 2 | + Lo 29 ‘RE. Fr 3 ¢ la . | ! ! ! } oo : io 0 —i ss cue | | : 0avT | | Pat 1S Q, —- = i J <8 §iS fe i og | | 2 o a @ = sTifigs iz CT 2 3 ! pred | — 1 : i + ! © © Sale im si Cogtd c | : | | x =

I: nei pi oo da {ed LH . = | 1 i i { a STi 2 3558 5 SEIS eo 2 |g Bio SE oi 57 eT i £8 1% Poo ig <6 assis Sq Sigs SL i |< LT ZIE o = HEE { { i Em fie} feet Lo cig El Po {| o Tg io ai0 S18 EN Eioc 8 v i { oc i : ier i i _ uotatsod 1] F staf 358%u8 buta 1 TSOqUo x JC HE |e 5521800 ° raeo > Oi ig Sn a o o snoenb | SOs EE 5 © 2 r } : ! jE v | or | LO MO S [eTIS] ! : LE o new BUT | Ho =

Tae go a

Tieod d ¢ 5

CL oo a

ET oO

Ry b~

O

2 ri

Z on 7 a

So i

Les 1 5g ol 5 | ed gE | i 8] io | , 1% | i 58 123k 21% | Co i fgg 552 | :

ZR S55 3 — o - Seti 5 Co 1 | ape mm

EL | | O | LE + | i | Ese preg

Se | | : 05 pS gO | o> 82 i 55 ” 27 | Loo | | gue } 2 co 18 3

LH Co HS a 3004 2, 51g E oF 3g 8 07% ve E — = 28g ig 7 ! | 2 o£ | FN j L © ; i | | o 56 | | © | ERE BT ! ; | : — go Ez lkE SE gd E82 oo

CELT £Q : ! | { 2 Se iil] BE i 2 | 7 iE Co i o | [a Pog £5 : | | ; Sz | | LE o Lo j | Jig) i 5d | | CE 55 | Po iE S13

ST | | 28% 305d 35), 15)8 | Sa fg) iH] fen . = PE.

EE a — 2" 2 | ZC | i i | | i 28 | 2 18 v | | | LT << Si ° 0 | 2 5 To | | ! ; 2 | | | ; ] Tl EA |] Co o i | 9 woo io 2c | i : ile £2 ! i i } Spe © | : 1 { i Sait:

Slo | | | 0% | HE 1e5%) Co £08: 1515153 5 | S82

RE i 5 | a | i PQ og | oo | oo : ; i o o { Po iE @ ! | j = g8 Lo | = oh | | :

Oi ; 20 8 | | : :

Co LC Ea | | fi

Pea 7d ; i j | | | i oi Lo oq Hen : i i i -r i | Le 0 | | a | Fg

SE | | | 823 | ES 8S | | ! ‘ BE : - | | 0

Sa | | i BET 305 oo i | ES | | Digs

SL eo i | | oo i 5 5 e533 Po] | Sglk

Cat — | 0 of

H t ! i f r 3g B55] ge] | | - 58 | HHH: 23% | _ ] = < | 22 SER 2 o® EEN |]

A E- } 18 . PS RIE 1233875 i : PEL | Pou |S

EE = i 5208 Lo on | 0 758k Pp ic | 23% | a Sigs ~ 518 5) ir : ul 8 : = El 5 38 5i5 So3is 4 = 0 | | g 2 A 8 ©g 5185i8 Lio 8d << = ol 8 525i wi © SiS A i | i {no He 8. 2 21 vi aid Eig w ! | | 8

I sis Si 0 c.5 £28 : ; i — < i< SEE go 3 8 — uo < | ZiE EEE ER bu Fat i 8% 13 5i3 gis oi

T rsod T 9 oO Dw 2 rae oa L & 2824 LL Blo oo wo ER slo 2

Ss ° FSS 55 N ne |g Bi Eater s i Sia = dG 2 nb Le La, Zenit i ! 0! DO Py £|5 9 {=< SEE:

Tet el i Simla

TI | =] io

P13 CEE: eu 6 i El

UtaE LTE 0s do 5

L va 68 Sg 5

T

©

NPP11067PCT

[0112] (Example 69) Formation of multilayer coating film (four layers)

A sandblasted steel sheet was coatedwithasolvent typeorganic zinc-rich coating material (manufactured by NIPPON PAINT Co., Ltd., trade name "N Zinky 8000 NB") as an undercoating material so that a thickness after drying of 70 uymwas achieved to form an undercoating layer.

After that, the aqueous coating composition 13 obtained in

Production Example 41 was applied under an environment of 5°C with a brush onto the undercoating layer so that a thickness after drying of 60 um was achieved, and then dried under the same environment as in its application for 1 day to give a coating film formed with the aqueous coating composition 13.

A solvent type epoxy/amine-based coating material B (manufactured by NIPPON PAINT Co., Ltd., trade name "HI-PON 30 FINE

Intermediate coating") was applied as an intermediate coating material under an environment of 25°C with a brush onto the resultant coating film so that a thickness after drying of 30 um was achieved, and then dried under the same environment as in its application for 1 day to give an intermediate coating layer.

A solvent two-component urethane-based coating material A (manufactured by NIPPON PAINT Co., Ltd., trade name "HI-PON 50 FINE")

NPP11067PCT was applied as a top coating material under an environment of 25°C with an air spray onto the intermediate coating layer so that a thickness after drying of 30 um was achieved, and then dried under the same environment as in its application for 7 days to form a top coating layer. Thus, a multilayer coating film (four layers).

The resultant multilayer coating film (four layers) was subjectedtotheevaluations for "water-resistant adhesiveproperty"” and "corrosion resistance." Table 6 shows the evaluation results.

[0113] (Example 70) Formation of multilayer coating film (four layers)

A multilayer coating film (four layers) was obtained in the same manner as in Example 69 except that the undercoating material, agueous coating composition, intermediate coating material, and top coating material shown in Table 6 were used. It should be noted that the undercoating material, intermediate coating material, and top coating material shown in Table 6 and used in Example 70 are as follows.

The resultant multilayer coating film (four layers) was subjected to the same evaluations as in Example 69. Table 6 shows the evaluation results. (Undercoating material)

NPP11067PCT

The aqueous organic zinc-rich coating material obtained in

Production Example 52 was used. (Intermediate coating material)

As the aqueous epoxy/amine-based coating material B, the aqueous epoxy/amine-based coatingmaterial Bobtained in Production

Example 49 was used. (Top coating material)

As an aqueous carbodiimide-basedcoatingmaterial, the aqueous carbodiimide-based coating material produced in Production Example 51 was used.

[0114] [Table 6] ] Example 69 Example 70

Undercoating Solvent type organic Agueous organic material zinc-rich coating zinc-rich coating material material

Aqueous coating Aqueous coating Aqueous coating composition composition 13 composition 13

Intermediate coating Solvent type Aqueous material epoxy/amine-based epoxy/amine-based coating material B coating material B

Top cecating material | Solvent Agueous two-component carbodiimide-based urethane-based coating material coating material A

Water-resistant 10 points 10 points adhesive property

[0115] (Comparative Example 1)

NPP11067PCT

A coating film formed with the solvent type epoxy/amine-based coating material A on a substrate was obtained in the same manner as in Example 58 except that the solvent type epoxy/amine-based coating material A (manufactured by NIPPON PAINT Co., Ltd., trade name "Epotal NB-20") was used instead of the agueous coating composition 12 obtained in Production Example 40. The resultant coating film was sticky, and hence it was impossible to apply a top coating material.

[0116] As shown in each of Examples 1 to 19, according to the method of forming a coating film according to the present invention, it was possible to give a coating film excellent in corrosion resistance.

[0117] As shown in each of Examples 1 to 19 and 39 to 57, in the case of using the water-dispersible aqueous epoxy-based polyamine resin (A), the agueous coating composition which had been stored for a long period of time did not gelate, was excellent in workability, and allowed a coating film excellent in corrosion resistance to be formed.

[0118] As shown in each of Examples 20 to 38, 58, 60, and 62, the coating film formed by the method of forming a coating film according to the present invention exhibited sufficient curability even at low temperature. On the other hand, as shown in Comparative

NPP11067PCT

Example 1, the coating film formed with the conventional epoxy/amine-based coating material had insufficient curability at low temperature.

[0119] As shown in each of Examples 31 to 35, when the aqueous coating composition including the aqueous epoxy-based polyamine resin (A) obtained using the epoxy resin (al) having an epoxy equivalent of 2,000 to 3,200 is used, a coating film excellent in initial rain resistance can be formed. Meanwhile, as shown in each of Examples 31, 32, 34, 35, 50, 51, 53, and 54, when the aqueous coating composition including the aqueous epoxy-based polyamine resin (Al) obtained using an epoxy resin (al) having an epoxy equivalent of 400 to 1,500 and an aqueous epoxy-based polyamine resin (AZ) obtained using an epoxy resin (a2) having an epoxy equivalent of 2,000 to 3,200 at a specific mass ratio (al/a2) is used, a coating film excellent in initial rain resistance and water-resistant adhesive property can be formed.

[0120] As shown in each of Examples 58 to 68, a coating film excellent in water-resistant adhesive property was able to be obtained according to the method of forming a coating film according to the present invention by forming the top coating layer.

[0121] As shown in each of Examples 69 and 70, a coating film excellent in water-resistant adhesive property and corrosion

NPP11067PCT resistance was able to be obtained according to the method of forming a coating film according to the present invention by forming the undercoating layer, the intermediate coating layer, and the top coating layer.

Industrial Applicability

[0122] The method of forming a coating film according to the present invention can be suitably used in, for example, an anticorrosive application. Specifically, the method can be suitably applied to, for example, ships, vehicles (e.g., railway vehicles, large vehicles), aircraft, bridges, marine structures, plants, tanks (e.g., petroleum tanks), pipes, steel tubes, and cast irontubesaswellasmetal parts includedinarchitectural structures, such as doors and window frames.

Claims

NPP11067PCT Claims

[Claim 1] A method of forming a coating film, comprising coating a substrate with an aqueous coating composition to form a coating film, wherein the aqueous coating composition comprises: an aqueous epoxy-based polyamine resin (A) having one or more primary amino groups and/or secondary amino groups in a molecule; and a compound (B) having one or more {(meth)acryloyl groups in a molecule.

[Claim 2] A method of forming a coating film according to claim 1, wherein the agueous coating composition is a two-component aqueous coating composition comprising a base resin liquid for a coating material and a curing agent, the base resin liquid for a coating material comprising the aqueous epoxy-based polyamine resin (A) and the curing agent comprising the compound (B).

[Claim 3] A method of forming a coating film according to claim 1 or 2, wherein the aqueous epoxy-based polyamine resin (A) is water-dispersible.

[Claim 4] A method of forming a coating film according to any one of claims 1 to 3, wherein the aqueous epoxy-based polyamine resin (A) has an amino group equivalent of 100 to 3,000.

[Claim 5] A method of forming a coating film according to any one

NPP11067PCT of claims 1 to 4, wherein the aqueous epoxy-based polyamine resin (A) is obtained by amine-modification of an epoxy resin, and the epoxy resin has an epoxy equivalent of 180 to 3,800.

[Claim 6] A method of forming a coating film according to any one of claims 1 to 4, wherein the aqueous epoxy-based polyamine resin (A) in the aqueous coating composition comprises: an aqueous epoxy-based polyamine resin (Al) obtained by amine-modification of an epoxy resin (al) having an epoxy equivalent of 400 to 1,500; and an aqueous epoxy-based polyamine resin (AZ) obtained by amine-modification of an epoxy resin (a2) having an epoxy equivalent of 2,000 to 3,200.

[Claim 7] A method of forming a coating film according to claim 6, wherein a mass ratio of the epoxy resin (al) and the epoxy resin (a2) (al/a2) is 8/2 to 2/8.

[Claim 8] A method of forming a coating film according to any one of claims 1 to 7, wherein the aqueous epoxy-based polyamine resin (A) is obtained by neutralization of an amino group of an epoxy-based polyamine resin with an acid, and a neutralization ratio in the neutralization is 10% to 70%.

[Claim 8] A method of forming a coating film according to any one

NPP11067PCT of claims 1 to 8, wherein the compound (B) has a viscosity at 25°C of 3,000 mPa's or less.

[Claim 10] A method of forming a coating film according to any one of claims 1 to 9, wherein the compound (B) has a molecular weight of 150 or more and 2,000 or less.

[Claim 11] A method of forming a coating film according to any one of claims 1 to 10, further comprising forming a top coating layer on the coating film after the forming of the coating film with the aqueous coating composition.

[Claim 12] A method of forming a coating film according to claim 11, further comprising forming an intermediate coating layer after the forming of the coating film with the aqueous coating composition and before the forming of the top coating layer.

[Claim 13] A method of forming a coating film according to any one of claims 1 to 12, further comprising forming a undercoating layer on substrate before the forming of the coating film with the aqueous coating composition.