SG184263A1 - Water-based coating composition and process for formation of coating film - Google Patents

Abstract

The present invention providesanaqueous coatingcomposition which is excellent in low-temperature curability and capable of forming a coating film excellent in corrosion resistance.The aqueous coating composition according to an embodiment of the present invention includes: (A) an aqueous epoxy-based polyamine resin having one or more primary amino groups and/or secondary amino groups in a molecule; (B) a compound having one or more (meth)acryloyi groups in a molecule; and (C) an alkoxysilane compound; wherein: an equivalent ratio of an amino group of the aqueous epoxy-based polyamine resin (A) and a (meth) acryloyl group of the compound (3) ((meth) acryloyl group/amino group) is 0.7 to 2.5; and a content of the alkoxysilane compound (C) in a solid content of the aqueous coating composition is 0.2 mass% to 5 mass%.No Suitable Figure

Description

F2P-NPP09201PCT

Description

Title of Invention: WATER-BASED COATING COMPOSITION AND PROCESS

FOR FORMATION OF COATING FILM

Technical Field

[0001] The present invention relates to an aqueous coating composition and a method for forming a coating film.

Background Art

[0002] In general, a solvent-type coating 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 agueous coating material.

Examples of the aqueous 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

F2P-NPP09201PCT at low temperature.

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 an aqueous coating composition which is excellent in low-temperature curability and capable of forming a coating film excellent in corrosion resistance.

Means for solving the Problems

[0006] An aqueous coating composition according to an embodiment of the present invention includes: (A) an aqueous epoxy-based polyamine resin having one or more primary amino groups and/or secondary amino groups in a molecule; (B) a compound having one or more (meth)acryloyl groups in a molecule; and (C) an alkoxysilane compound; wherein: an equivalent ratio of an amino group of the agueous epoxy-based polyamine resin (A) and a (meth)acryloyl groupof the compound (B) ((meth)acryloyl group/amino group) is 0.7 to 2.5; and a content of the alkoxysilane compound (C) in a solid content of the aqueous coating composition is 0.2

F2P-NPP09201PCT mass% to 5 mass®.

Inapreferredembodiment of the invention, the aqueous coating composition 1s a two-component aqueous coating composition comprising a base resin liquid for a coating material and a curing agent, the base resin liguid for a coating material comprising the aqueous epoxy-based polyamine resin (A) and the curing agent comprising the compound (B) and the alkoxysilane compound (C).

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 aqgueous epoxy-based polyamine resin (A) 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

F2P-NPP09201PCT aqueous epoxy-based polyamine resin (RZ) 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 2/8.

In a preferred embodiment of the invention, the aqgueous 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.

Inapreferredembodiment of the invention, the aqueous coating composition further includes a pigment, wherein the pigment has a pigment volume concentration of 20% to 50%.

According to another aspect of the present invention, a method of forming a coating film is provided. Themethod of forming a coating film includes applying the aqueous coating composition onto a substrate surface to form a coating film.

F2P-NPP0O9201PCT

In a preferred embodiment of the invention, the method of forming a coating film further includes applying a top coating material on the coating film to form a top coating layer.

Effects of the Invention

[0007] The aqueous coating composition of the present invention includes: (A) an aqueous epoxy-based polyamine resin having one or more primary amino groups and/or secondary amino groups in a molecule; (B) a compound having one or more (meth)acryloyl groups in amolecule; and (C) an alkoxysilane compound. Hence, the aqueous coating composition of the present invention exhibits excellent low-temperature curability and is capable of forming a coating film excellent in corrosion resistance.

Description of Embodiments

[0008] A. Outline of aqueous coating composition

An agueous coating composition of the present invention includes: (A) an agueous epoxy-based polyamine resin having one or more primary amino groups and/or secondary amino groups in a molecule; (B) a compound having one or more (meth)acryloyl groups in a molecule; and (C) an alkoxysilane compound. In the aqueous coating composition of the present invention, a curing reaction of the aqueous epoxy=-based polyamine resin (A) and the compound (B) is caused to proceed by mixing these compounds, to thereby allow acoatingfilmtobe formed. The agueousepoxy-basedpolyamine resin

F2P-NPP0O9201PCT (A) and the compound (B) can undergo a curing reaction even at low temperature (e.g., 5°C or less), and hence the aqueous coating composition of the present invention isexcellent in low-temperature curability. In addition, the aqueous coating composition of the present invention can form a coating film excellent in adhesive property to a substrate because the composition includes the alkoxysilane compound (C). Such excellent adhesive property can be achieved even in the case where the coating film is formed at low temperature.

[0009] The agueous coating composition of thepresent invention is preferably a two-component aqueous coating composition including a base resin liquid for a coating material and a curing agent. It ispreferred that thebase resin liquid foracoatingmaterial include the aqueous epoxy-based polyamine resin (A), and the curing agent include the compound (B) and the alkoxysilane compound (C). When the agueous coating composition of the present invention is used as the two-component aqueous coating composition, an aqueous coating compositionexcellent in low-temperature curability can be obtained because it 1s possible to select a combination of the agueous epoxy-based polyamine resin (A) and the compound {(B) such that both of them exhibit high reactivity to each other.

[0010] Beforemixing of the aqueous epoxy~basedpolyamine resin (A) and the compound (B), the aqueous coating composition of the

F2P-NPP09201PCT present invention may be treated, for example, 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) in a dispersing element of a resin different from the aqueous epoxy-based polyamine resin (A). When such treatment is 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. As a result, the agueous epoxy-based polyamine resin (A) and the compound (B) can react with each otherefficiently.

Further, whenthe treatment (2) ofmixinganemulsifier inthe compound (B) or emulsifying or dispersing the compound (B) with a dispersant, an emulsifier, or an aqueous resin is carried out, the compound (B) can be treated as a nonhazardous material.

[0011] Examples of the organic solvent to be used when the compound (B) 1s diluted with the organic solvent include ethylene glycol monobutyl ether and diethylene glycol moncbutyl ether.

[0012] A nonionic emulsifier or an anionic emulsifier, for example, is used as the emulsifier to be used when the emulsifier is mixed in the compound (B), or the compound (B) is emulsified or dispersed with a dispersant, an emulsifier, or an aqueous resin.

Examples of the nonionic emulsifier include a polyoxyethylene alkyl

F2P-NPP0O9201PCT 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, a dialkyl succinate sulfonic acid salt, 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 and an ammonium salt of a half ester of a styrene-maleic acid copolymer. Examples of the agueous resin include a sodium salt of polyacrylic acid ester.

[0013] Examples of thedispersingelement usedwhen the compound (B) is dispersed in a dispersing element of a resin different from the agueous epoxy-based polyamine resin (A) include an emulsion and dispersion of an acrylic resin, and an emulsion and dispersion of a urethane resin.

[0014] The content of the agueous epoxy-based polyamine resin (A) in terms of a solid content is preferably 5 mass% to 95 massy, more preferably 10mass% to 90 mass% with respect to the total solid content of the aqueous coating composition.

[0015] The content of the compound (B) is preferably 2 mass$ to 30 mass%, more preferably 5 mass% to 25 mass% with respect to

F2P-NPP09201PCT the total solid content of the aqueous coating composition.

[0016] An equivalent ratio of amino groups in the aqueous epoxy-based polyamine resin (A) and (meth)acryloyl groups in the compound (B) ((meth)acryloyl groups/amino groups) is 0.7 to 2.5, 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.

[0017] The content of the alkoxysilane compound (C) is 0.2 mass% to 5 mass%, preferably 0.3 mass% to 3 mass$%, more preferably 0.5 mass% to 2 mass% with respect to the total solid content of the agueous coating composition. As long as the content of the alkoxysilane compound (C) 1s in such range, the composition has excellent adhesive property to a substrate, resulting in obtaining an agueous coating composition capable of forming a coating film which exhibits excellent corrosion resistance. It should be noted that even 1f the content of the alkoxysilane compound (C) is set to more than 5 mass%, the adhesive property is not further improved, and the curability (in particular, low-temperature curability) of the coating film may reduce.

[0018] The aqueous coating composition of thepresent invention may further include a pigment. When the pigment is incorporated,

F2P-NPP09201PCT 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 can be reduced, and capable of forming a coating film which exhibits sufficient corrosion resistance can be obtained.

[0019] Specific examples of the pigment include: extender pigments such as precipitated barium sulfate, clay, talc, and mica; color pigments such as titanium dioxide and carbon black; and anti-rust pigments such as zinc phosphate.

[0020] The pigment volume concentration of the pigment in the agueous coating composition ispreferably 20% to 50%, morepreferably 25% to 45%, particularly preferably 30% to 40%. When the pigment volume concentrationis lessthan20%, theeffect of theincorporation of the pigment may be insufficient, while when the pigment volume concentration exceeds 50%, the outer appearance of the coating film may deteriorate. Thepigment volume concentrationcanbecalculated from the mass of the pigment blended and the specific gravity of each component in the coating material.

[0021] Water, a solvent, an additive, or the like may be blended into the aqueous coating composition of the present invention.

Specific examples of the solvent include: glycol-based solvents

F2P-NPP09201PCT such as ethylene glycol, propylene glycol, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, diethylene glycol, dipropylene glycol, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, 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-pentanediol monolscbutyrate (manufactured by CHISSO CORPORATION, trade name "Ccs-12"y, 2,2,4-trimethyl-1, 3-pentanediol diisobutyrate (manufactured by CHISSO CORPORATION, trade name "CS-16"), diethyl adipate, and diisobutyl 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 of the present invention is used as a two-component agueous 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 to may be determined based on the functions and properties expected of them.

F2P-NPP09201PCT

[0022] B. Agueous epoxy-based polyamine resin (A)

The aqueous coating composition of the present invention includes the aqueous epoxy-based polyamine resin (A) having one or more primary amino groups and/or secondary amino groups in a molecule. It should be noted that the concept of "aqueous" as used herein comprehends "water-soluble" and "water-dispersible."

[0023] The aqueous epoxy-based polyamine resin (A) is preferably water-dispersible. When a water-dispersible aqueous epoxy-based polyamine resin (A) is used, an aqueous coating composition capable of forming a coating film excellent in water resistance can be obtained. 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 along service life. Morespecifically, inthe case where the aqueous epoxy-pased polyamine resin (A) iswater-dispersible, inthe aqueous coatingcompositionbeforeapplication, thereactionhardlyproceeds even at ordinary temperature, which provides good preservation stability and application property, because the agueous epoxy-based polyamine resin (A) is hardly brought into contact with the compound (B). Ontheotherhand, afterapplication, adispersionmedium (such as water) volatilizes to facilitate the contact between the agueous

F2P-NPP09201PCT epoxy-based polyamine resin (A) and the compound (B). Therefore, the curing reaction proceeds even at low temperature, to thereby allow a coating film to be formed.

[0024] 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 theepoxyresinisnot agueous, the epoxy-based polyamine resin may be converted into an aqueous resin by neutralization of an amino group with an acid, to thereby obtain the aqueous epoxy-based polyamine resin (A).

[0025] As the epoxy resin, any appropriate epoxy resin may be used. The resin is preferably a bisphenol A-type epoxy resin or a bisphenol F-type epoxy resin, particularly preferably a bisphenol

A-type epoxy resin.

[0026] 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

F2P-NPP09201PCT 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 it impossible to convert the coating composition into an agueous 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 object to be coated which may be exposed to rain before the applied coating film cures completely.

[0027] In one embodiment, the epoxy resin is an epoxy resin (al) having an epoxy equivalent of 400 to 1,500. When an aqueous 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

F2P-NPP0O9201PCT epoxy resin (al) 1s more preferably 600 to 1,400, particularly preferably 800 to 1,300.

[0028] 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 aqueous 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.

[0029] As the epoxy resin, two or more kinds of epoxy resins may be used in combination.

[0030] 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 compound suchasadimeracid, diamine, or polyether polyol.

[0031] 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

F2P-NPP0O9201PCT of epoxy groups to be reduced, thereby reducing sites to be amine-modified to lower a reactivity, for example.

[0032] The epoxy-based polyamine resin can be obtained 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-containing 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, anacidanhydridegroup, anacidhalogengroup, oran isocyanate 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 aqueous epoxy-based polyamine resin (A) to be used, physical properties of the resultant coating film can be adjusted.

[0033] 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

F2P-NPP09201PCT group~containing 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.

[0034] Examples of the primary amino group-containing polyamine include diethylenetriamine, dipropylenetriamine, dibutylenetriamine, and triethylenetetramine. They may be used alone or in combination.

[0035] The method involving adding a ketiminated amino group~containing 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 formaprimary 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.

[0036] 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

F2P-NPP09201PCT triethylenetetramine; aminoethylethanclamine; methylaminopropylamine; andethylaminoethylamine. Theymaybeused aloneor incombination. Examples of the ketone includemethyl ethyl ketone, acetone, and methyl isobutyl ketone.

[0037] 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 1lsocyanate group, and an acid anhydride group.

[0038] 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 agueous epoxy-basedpolyamine resin (A). When the aqueous epoxy-basedpolyamine resin (A) is used, a coating film excellent in low-temperature curability can be obtained. 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

F2P-NPP09201PCT 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 aqueous 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 1s represented by a molecular weight of a resin solid content per secondary amino group in the case where the epoxy-based polyamine resin hasnoprimary amino group. Theaminogroupeguivalent of the epoxy~basedpolyamine resin can be determined from the blending amounts of raw materials.

[0039] 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 aqueous 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). Examplesof theacidincludeaceticacid, formicacid, lactic

F2P-NPP0O9201PCT 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) is preferably 10% to 100%, more preferably 10% to 70%, particularly preferably 15% to 50%. When the neutralization ratio is less than 10%, theresinmaynot bedispersed inwater to cause phase separation, which makes it impossible to convert the coating composition into anagueousone. Meanwhile, whentheneutralizationratioisadjusted to 70% or less, a water-dispersible aqueous epoxy-based polyamine resin (A) can be obtained.

[0040] The molecular weight (number average) of the aqueous epoxy~based polyamine resin (A) may be any appropriate molecular welght depending on desired properties of the agueous 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 measured by gel permeation chromatography (GPC). As longasthemolecular weight 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 bemixed easily with the compound.

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

F2P-NPP0O9201PCT

[0041] The aqueous coating composition of the present invention may include two or more kinds of the agueous epoxy-based polyamine resins (A).

[0042] The aqueous coating composition of thepresent invention preferably includes, as the aqueous epoxy-based polyamine resins (A), the aqueous epoxy-based polyamine resin (Al) obtained by amine-modificationof theepoxy resin (al) havinganepoxyequivalent of 400 to 1,500 and the aqueous epoxy-based polyamine resin (AZ) obtained by amine-modification of the epoxy resin (a2) having an epoxy equivalent 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) havinganepoxyeguivalentof2,000t03,200 (al/a2) ispreferably 8/2 to 2/8, more preferably 7/3 to 3/7. As long as the ratio is in such range, it ispossible to obtain an aqueous coating composition capableof formingacoatingfilmexcellentininitial rainresistance and water-resistant adhesive property.

[0043] 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.

[0044] C. Compound (B)

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

[0045] The molecular weight of the compound (B) is preferably 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 (BR) is in such range, the aqueous epoxy-based polyamine resin (A) and the compound (B) can be 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 witheachotherefficiently, 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.

[0046] The number of the (meth)acryloyl groups in the compound (B) is 1 ormore, 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.

[0047] The viscosity of the compound (B) at 25°C is preferably 3,000 mPa's or less, more preferably 50 mPa:*s to 3,000 mPa-s, particularly preferably 50 mPa*s to 2,200 mPa-s, most preferably

F2P-NPP09201PCT 50 mPa+s to 1,100 mPa*s. As long as the viscosity of the compound (B) is in such range, the aqueous 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 compound (B) can react with each other efficiently, to thereby obtain an aqueous coating composition excellent in curability.

[0048] 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,

F2P-NPP09201PCT 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 carboxyl group-containing, ethylenically unsaturated monomers 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.

[0049] As described above, the compound (B) 1s preferably capable of being easily mixed with (capable of reacting with) the aqueous 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 agueous epoxy-based polyamine resin (A) and the compound (B) can be inhibited to appropriately adjust the reactivity. More specifically, when the aqueous epoxy-based polyamine resin (A) and the compound (B) are

F2P-NPP09201PCT in an inhomogeneous state, the aqueous coating composition before applicationhasgoodpreservationstabilityandapplicationproperty 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 tomake it easy to bring the aqueous epoxy-based polyamine resin (A) into contact with the compound (RB), and the curing reaction proceeds even at low temperature, to thereby form a coating film.

Examples thereof include: a case where the compound (B) 1s a water-soluble compound and the aqueous epoxy~based polyamine resin (A) is a water-dispersible resin; a case where the compound (B) is self-emulsifying or is converted into a water-dispersible form with a dispersant; and a case where the compound (B) is emulsified or dispersedwith the aqueous epoxy-based polyamine resin (A). 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 the mixture (e.g., for 3 minutes); allowing the mixture to stand still (e.qg., forbminutes); andthenobservingitsstatevisually.

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

F2P-NPP0O9201PCT addition, if the mixture contains no precipitate and is turbid after the same operation as above has been performed in the co-presence of a dispersant, the compound is judged to be "converted into a water-dispersible form."

[0050] In the case where the compound (B) has been modified by, for example, polyethylene oxide, the compound may be converted into a water-soluble or self-emulsifying compound by increasing the ethylene oxide addition mole number to enhance its hydrophilicity.

[0051] Examples of the compound (B) that is water-soluble include ethoxylated bisphenol Adiacrylate (EOC 30 mol), ethoxylated trimethylolpropane triacrylate (EO 20 mol), ethoxylated trimethylolpropane triacrylate (EO 30 mol), ethoxylated pentaerythritol tetraacrylate (EO 35 mol), ethoxylated glycerin triacrylate (EO 20mol), 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.

[0052] Examples of the compound (B) that is self-emulsifying or may be converted into a water-dispersible form with a dispersant include polyethylene glycol #400 diacrylate (EO 9mol), polyethylene glycol #600 diacrylate (EO 14 mol), polyethylene glycol #1000

F2P-NPP09201PCT diacrylate (EO 23 mol), ethoxylated bisphenol A diacrylate (EO 10 mol), ethoxylated bisphenol A diacrylate (EO 20 mel), ethoxylated glycerin triacrylate (EO 9 mol), and polyethylene glycol #1000 dimethacrylate (EO23mol). Theymaybeusedaloneor incombination.

[0053] Examples of the compound (B) that may be emulsified or dispersed with the aqueous epoxy-based polyamine resin (A) include polyethylene glycol #200 glycol diacrylate (EO 4 mol), ethoxylated bisphenol Adiacrylate (E0C3mol), ethoxylatedbisphenol Adiacrylate (EO 4 mol), propoxylated bisphenol A diacrylate (PO 3 mol), 1,10-decanediol diacrylate, tricyclodecanedimethanol diacrylate, ethoxylated 2-methyl-1,3-propanediol diacrylate (EO 2 mol), neopentyl glycol diacrylate, 1, 6-hexanediol diacrylate, 1,9-nonanediol diacrylate, dipropyleneglycoldiacrylate (POZ2mol), tripropylene glycol diacrylate (PO 3 mol), polypropylene glycol #400 diacrylate (PC 7 mol), polypropylene glycol #700 diacrylate (PO 12 mol), ethoxylated trimethylolpropane triacrylate (EO 3 mol), ethoxylated trimethylolpropane triacrylate (EC 9 mol), trimethylolpropane triacrylate, propoxylated trimethylolpropane triacrylate (PO 3 mol), pentaerythritol triacrylate, ethoxylated pentaerythritol tetraacrylate (EO 4 mol), ditrimethylolpropane tetraacrylate, propoxylated pentaerythritol tetraacrylate (PO 4 mol), propoxylatedbisphenol Adiacrylate (PO4mol), ethyleneglycol dimethacrylate (EO 1 mol), diethylene glycol dimethacrylate (EO 2mol), triethylene glycol dimethacrylate (EO 3 mol), tetraethylene

F2P-NPP09201PCT glycol dimethacrylate (EO 4 mol), polyethylene glycol #400 dimethacrylate (EC 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 (EC2Z2.6mol), ethoxylated bisphenol 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 (EOQO 9 mol). They may be used alone or in combination.

[0054] 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 agueous 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 (meth)acryloyl groups and a compound (B) having three (meth)acryloyl groups. Further, when a mixture of a water-soluble compound (B) and a water-insoluble compound (B) is used, the water-insoluble compound (B) canbe easily

F2P-NPP0O9201PCT introduced into a reaction system by the water-soluble compound {B). Further, the resultant coating material is excellent in low-temperature curability. Examples of the water-insoluble compound (B) include a compound which is not completely soluble in water, such as propoxylated bisphencl A diacrylate (PO 4 mol).

A mixing ratio of the water-soluble compound (B}) and the water-insoluble compound (B) (water-soluble/water-insoluble) is preferably 1/9 to 9/1, more preferably 2/8 to 8/2.

[0055] D. Alkoxysilane compound (C)

The aqueous coating composition of the present invention includes the alkoxysilane compound (C). As long as the agueous coating composition includes the alkoxysilane compound (C), a coating film excellent in adhesive property to a substrate can be obtained. The coating film formed using the aqueous coating composition of the present invention is excellent in adhesive property to a substrate even if the coating film is formed at low temperature. Such coating film which is formed using the agueous coating composition of the present invention excellent in adhesive property to a substrate exhibits excellent corrosion resistance.

[0056] The alkoxysilane compound (C) has a functional group having reactivity to or affinity for an organic substance and a functional group having reactivity to or affinity for an inorganic substance. Therefore, as the agueous coating composition of the

F2P-NPP09201PCT present invention includes the alkoxysilane compound (C), it is possible to improve the adhesive property of a formed coating film (organic substance) and a substrate (inorganic substance).

Examples of the functional group having reactivity to or affinity for an organic substance include a vinyl group, an epoxy group, a methacryl group, an amino group, and a mercapto group. On the other hand, the functional group having reactivity to or affinity for an inorganic substance is preferably a functional group which can be hydrolyzed, and examples thereof include a methoxysilane group, an ethoxysilane group, and a propoxysilane group.

[0057] Part of the alkoxysilane compound (C) may be subjected tohydrolysisand/orhydrolysisdehydrationcondensation. Specific examples thereof include: vy-glycidoxyalkyltrialkoxysilanes such as v-glycidoxypropyltrimethoxysilane, v-glycidoxypropyltriethoxysilane, and v-glycidoxypropoxytrimethoxysilane; yv-—aminopropyltrialkoxysilanes such as yv-aminopropyltriethoxysilane and y-aminopropyltripropoxysilane; and N-phenyl-y-amincalkyltrialkoxysilanes such as

N~phenyl-y~aminopropyltrimethoxysilane,

N-phenyl-y-aminopropyltriethoxysilane, and

N-phenyl-y-aminopropyltripropoxysilane. Of those, preferred are v-glycidoxyalkyltrialkoxysilanes, vy-aminopropyltrialkoxysilanes, and N-phenyl-y-aminoalkyltrialkoxysilanes, more preferred are

F2P-NPP0O9201PCT v—glycidoxyalkyltrialkoxysilanes and y-aminopropyltrialkoxysilanes, and particularly preferred are v-glycidoxyalkyltrialkoxysilanes. They may be used alone or in combination.

[0058] E. Method of forming coating film

The aqueous coating composition of the present invention can be suitably used in an inner or outer plate part of a ship and a submerged structure in seawater or freshwater. Specifically, an inner or outer plate part of a ship such as deck, hatch coaming, upper structure part, hull part, engine room, living quarter, or car hold; and a submerged structure in seawater or freshwater, such as apipingmaterial canbe usedas anobject tobe coated (substrate).

As a material for the substrate, there may be given, for example, ametalmaterial suchasaniron-based, zinc-based, or aluminum-based material.

[0059] As a method of applying the aqueous coating composition of the present invention, any appropriate application method may be employed. Examples of the application method include airless application, air spray, brush application, trowel application, and roller application. Of those, airless application is preferred.

When the composition is applied by the airless application, a thick coating film can be obtained. In addition, the coating film may be formed by applying the composition several times (e.g., two or

F2P-NPP09201PCT three times). When the composition isappliedseveral times, a thick coating film having a good outer appearance can be formed.

[0060] In application of the aqueous coating composition of thepresent invention, the thicknessof thecoatingfilmispreferably 50 um to 250 pum, more preferably 50 um to 200 um, in terms of dried coating film. When the thickness of the dried coating film is more than 250 um, a problem such as dripping may occur in formation of the coating film.

[0061] A method of drying the aqueous coating composition of the present invention may be any appropriate drying method. The method is preferably natural drying or heat drying. In the case of natural drying, the drying time is preferably 24 hours or more, more preferably 1 week or more.

[0062] After formation of the coating film using the agueous coating composition of the present invention, a top coating layer may be formed on the coating film by further applying a top coating material. According to the present invention, it is possible to provide such method of forming a multilayer coating film. When the top coating layer is formed, accating filmhaving improved corrosion resistance and outer appearance can be obtained.

[0063] Any appropriate coating material may be adopted as the

F2P-NPP09201PCT top coating material. Examples of the top coatingmaterial include an epoxy/amine-based coating material, a two-component urethane-~curable coating material, a one-component urethane-curablecoatingmaterial, andacoatingmaterial containing a carbodiimide curing agent. The top coating material may be solvent-based or aqueous. The top coating material is preferably aqueous. When the top coating material 1s aqueous, a load on the environment can be reduced in formation of the coating film.

[0064] The thickness of the top coating layer may be set to any appropriate thickness depending on the kind of the coating material and the purpose of coating. Typically, the thickness is ym to 300 um in terms of thickness of a dried coating film.

[0065] An intermediate coating layer may be formed between the coating film formed using the aqueous coating composition and the top coating layer. The intermediate coating layer may be formed by applying an intermediate coating material on the coating film formedusing the aqueous coating composition. When the intermediate coating layer is formed, a coating film having further improved corrosion resistance can be obtained.

[0066] Any appropriate coating material may be adopted as the intermediate coating material. Examples of the intermediate coating material include an epoxy/amine-based coating material,

F2P-NPP09201PCT a two-component urethane-curable coating material, and a one-component urethane-curable cocatingmaterial. The intermediate coating material may be solvent-based or aqueous. The intermediate coating material 1s preferably aqueous. When the intermediate coating material is aqueous, a load on the environment can be reduced in formation of the coating film.

[0067] The thickness of the intermediate coating layer may be set to any appropriate thickness depending on the kind of the coating material and the purpose of coating. Typically, the thickness is ym to 50 um in terms of thickness of a dried coating film.

[0068] Before formation of the coating film using the agueous coating composition, an undercoat layer may be formed by applying an underccating material on a substrate. When the undercoat layer is formed, a coating film having improved corrosion resistance can be obtained.

[0069] Any appropriate coating material may be adopted as the undercoating material. Examples of the undercoating material include an organic or inorganic zinc-rich coating material. The undercoating material may be solvent-based or aqueous. The undercoatingmaterial is preferably aqueous. When the undercoating material 1s aqueous, a load on the environment can be reduced in formation of the coating film.

F2P-NPP09201PCT

[0070] The thickness of the undercoating layer may be set to any appropriate thickness depending on the kind of the coating material and the purpose of coating. Typically, the thickness is um to 300 um in terms of thickness of a dried coating film.

[0071] The top coating material, the intermediate coating 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 section A. The number, kinds, and amounts of pigments and additives to be added may be selected as appropriate depending on purposes.

[0072] As an application method and drying method for each of the top coating material, the intermediate coating material, and the undercoating material, any appropriate methods may be adopted depending on the kind of the coating material to be used. Examples of the application method and drying method for each of the top coating material, the intermediate coating material, and the undercoating material include the same methods described above for the application method and drying method for the aqueous coating composition.

Examples

[0073] Hereinafter, the present invention is described in more

F2P-NPP09201PCT 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.

[0074] (Production Example 1) Production of aqueous epoxy-based polyamine resin (A)I 702 parts of a raw material resin having an epoxy equivalent of 188 g/eqguivalent, 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 equlvalent reached 1,079 g/equivalent, to thereby obtain an epoxy resin. After that, 255 parts of a ketimine compound of aminoethylethanolamine (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.

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.

F2P-NPP09201PCT

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)I (specific gravity (solid content) 1.2 g/cm’) .

[0075] (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/equivalent, 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, andthemixturewasallowedtoreactat 117°C for 1hour. Subsequently, 27 parts of ion-exchange water and 188 parts of glycidyl neodecanoate (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 anonvolatile content of 75% was achieved, to thereby obtain an epoxy-based polyamine resin having an amino group equivalent of 1,093.

F2P-NPP09201PCT

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.

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 aquecus (water-dispersible) epoxy-based polyamine resin (A) II (specific gravity (solid content) 1.2 g/cm’).

[0076] {Production Example 3) Production of agueous 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, andthemixturewasallowedtoreactat117°Cfor1hour. 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

F2P-NPP09201PCT obtain an epoxy-based polyamine resin having an amino group equivalent of 810.

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 (specific gravity (solid content) 1.2 g/cm’).

[0077] (Production Example 4) Production of agueous epoxy-based polyamine resin (A)IV 1,9%940partsoftherawmaterial 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 themixturewasallowedtoreactat 117°C for 1hour. Subsequently, 1,060 parts of dipropylene glycol monobutyl ether (hereinafter, referred to as "DPnB") were fed thereto, and the mixture was allowed

F2P-NPP09201PCT 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 1,550.

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 (specific gravity (solid content) 1.2 g/cm’).

[0078] (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. The aqueous epoxy-based polyamine resins (A)V to VII were each found to have a specific gravity (solid content) of 1.2 g/cm’. [C079] (Production Example 8) Production of agueous epoxy-based polyamine resin (A)VIII 1,440 partsof the rawmaterial resinhavinganepoxyeqguivalent of 188 g/equivalent, which was synthesized from bisphenol A and

F2P-NPP09201PCT 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 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.

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) VIII (specificgravity (solidcontent) 1.2g/cm’).

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F2P-NPP09201PCT

[0081] (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.

[0082] (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

F2P-NPP0O9201PCT (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.

[0083] (Example 1) (Production of base resin liquid for coating material) 89.5 parts of talc (manufactured by FUJI TALC INDUSTRIAL CO.,

LTD., trade name "TALC SP 42," specific gravity: 2.7 g/cm’), 89.5 parts of calcium carbonate (manufactured by MARUO CALCIUM CO., LTD, tradename " NGroundCalciumCarbonate," specificgravity: 2.7 g/cm’), 172 parts of titanium oxide (manufactured by Du Pont, trade name "TI-PURR706," specific gravity: 4.3 g/cm’), 2b parts of ananti-rust pigment (manufactured by Toho Ganryo Kogyo Co., Ltd., trade name "EXPERT NP1055C, " specific gravity: 2.3 g/cm’), 4 parts of a defoamer (manufactured by SAN NOPCO LIMITED, trade name "SN Defoamer 154," specific gravity: 1.0 g/cm’), and 32 parts of a pigment dispersant (manufactured by BYK, trade name "BYK-190," specific gravity: 1.0 g/cm’) were added to 110 parts of water, 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

F2P-NPP09201PCT an associated thickener (manufactured by ADECA CORPORATION, trade name "Adecanol UH-420" were added to 500 parts of the pigment paste, and the resultant was mixed, to thereby obtain a base resin liquid for a coating material I. (Production of curing agent) 40 partsofwater, 10partsof DPnR, and 50 partsof polyethylene glycol #400 dimethacrylate (EO 9 mol) (viscosity (25°C): 58 mPa-s, molecular weight: 508, number of functional groups: 2, acryloyl group equivalent: 254) used as the compound (B) were mixed, and themixturewas stirredusinga homogenizer for 10 minutes, to thereby obtainacuringagent I. It shouldbenctedthat the specificgravity of the solid content in the curing agent I was found to be 1.2 g/cm’. (Production of aqueous coating composition) 4.8 parts of an epoxy silane coupling agent (3-glycidoxypropyltrimethoxysilane; manufactured by Shin-Etsu

Chemical Co., Ltd., trade name "KBM-403") used as the alkoxysilane compound (C) were added to 40 parts of the curing agent I, and the curing agent was then homogeneously mixed with 500 parts of the base resin liquid for a coating material I, to thereby obtain an aqueous coating composition 1.

[0084] (Examples 2 to 22)

Aqueous coating compositions were obtained in the same manner

F2P-NPP0OS201PCT as in Example 1 except that the kinds and blending amounts of the base resin liquid for a coating material I, curing agent I, and alkoxysilane compound (C) were changed as shown in Table 2 or Table 3.

It shouldbenotedthatbaseresinliquidforacoatingmaterials

II to VIII were obtained in the same manner as in Example 1 except that aqueous epoxy-based polyamine resins (A) shown in Table 4 were used instead of the aqueous epoxy-based polyamine resin (A)I.

Curing agents II to IX containing compounds (B) were obtained according to the curing agent production method of Example 1 using the compounds (B) shown in Table 5 at blending ratios shown in Table by mixing methods shown in Table 5. 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, IV, V, VIII, and IX. Table 5 shows the viscosity at 25°C, molecular weight, number of functional groups, acryloyl group eguivalent, and properties (self-emulsifying, water-insoluble, or water-scluble) of the compound (B) used in each of 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 and allowed to stand still, followed by visual observation. If the mixture contained a precipitate, the compound was evaluated to be "water-insoluble,"

F2P-NPP09201PCT 1f 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." It should be noted that the specific gravity of the solid content in each of the curing agents II to IX was found to be 1.2 g/cm’.

As an aminosilane coupling agent used as the alkoxysilane compound (cy, N-aminoethyl-y-aminopropyltrimethoxysilane (manufacturedby Shin-Etsu Chemical Co., Ltd., trade name "KBM-603") was used.

[0085] (Comparative Examples 1 to 3)

Aqueous coating compositions were obtained in the same manner as in Example 1 except that the curing agent II was used in blending amounts shown in Table 3 instead of 40 parts of the curing agent

I, and the blending amount of the epoxy silane coupling agent (4.8 parts) was changed as shown in Table 3.

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F2P-NPP0O9201PCT

[0088] [Table 4]

Aqueous epoxy-based polyamine resin (A)

Base resin oie rent ise equivalent of liquid for Epoxy ’ aqueous coating equivalent of epoxy-based material epoxy resin . polyamine resins

I I Production Example 1,079 1,184 11 II (Production 1,079 1,093

Example 2)

IIT (Production

Tv IV (Production 3,000 1,550

Example 4) v1 VI (Production 1,079 1,093

Example 6) vIT VII (Production 1,079 1,093

Example 7)

VITT VIII (Production 2,200 1,150

Example 8)

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F2P-NPP09201PCT

[0090] <Evaluations>

The aqueous coating compositions obtained in the foregoing were evaluated by the following methods. Tables 2 and 3 show the results. (Low-temperature curability)

The aqueous coating compositions obtained in the foregoing were each applied using an applicator onto a 20 cmx30 cm grit blasted steel sheet so that a film thickness of a dried coating film of 100 ym was achieved, and then allowed to stand at 5°C in an atmosphere of a relative humidity of 50% for 16 hours, to thereby obtain a test sheet having formed thereon a coating film.

A worker with a body weight of 65 kg heeled on the surface of the resultant coating film with his safety shoe for 30 seconds, and the condition of the coating film was then evaluated visually based on the following criteria.

A: No peeled part

B: Almost no peeled part

C: Small peeled part

D: Large peeled part (Pencil hardness)

A test sheet was obtained in the same manner as intheevaluation

F2P-NPP0S201PCT of the low-temperature curability. The pencil hardness of a coating film formed on the test sheet was measured in accordance with JIS

K 5600-5-4. (Initial rain resistance)

The agueous coating compositions obtained in the foregoing were each applied onto a polished steel sheet using a brush in an application amount of 200 g/m°, and dried in an environment of 5°C for 24 hours, to thereby obtain a test sheet. The test sheet was immersed in water at 5°C, lifted up after a lapse of 24 hours, and allowed to stand still at 5°C for 24 hours. After that, the outer appearance of the coating film was visually observed and evaluated based on the following criteria.

AA: No defect in outer appearance observed

A: Slight changes in luster and color but no mark of cracking or swelling observed

C: Mark of cracking or swelling observed (Corrosion resistance evaluation A)

The aqueous coating compositions obtained in the foregoing were each spray-applied onto each of a grit blasted steel sheet, a zinc-plated steel sheet, an aluminum steel sheet, and a shop primer steel sheet, each of which had a size of 7 cmx15 cm, so that a dried film thickness of 100 um was achieved, and the sheets were allowed

F2P-NPP09201PCT to stand at 20°C for 7 days, to thereby obtain test sheets. The test sheets were tested for 200 hours with a salt spray testing machine described in JIS K 5600-7-1.

After that, X-shaped cuts were made using a cutter knife so that the cutter knife passed through the coating film on each of the test specimens and reached each of the steel sheets, and a pressure-sensitive adhesive cellophane tape was attached thereto and peeled off. The adhesive property of each of the steel sheets and the coating film was evaluated based on the same evaluation criteria as those for the low-temperature curability. (Corrosion resistance evaluation B)

The adhesive propertyofeachof the steel sheetsandthecoating film was evaluated in the same manner as in the corrosion resistance evaluation A except that the test sheets were immersed in water at 40°C for 336 hours instead of the 200-hr test using the salt spray testing machine described in JIS K 5600-7-1. (Top coating property evaluation)

The aqueous coating compositions obtained in the foregoing were each spray-applied onto a shot blasted steel sheet with a size of 7 cmx15 cm so that a dried film thickness of 95 to 105 um was achieved, and the sheet was allowed to stand at 20°C for 7 days and then exposed to an outdoor environment for 7 days.

F2P-NPP09201PCT

Five steel sheets each thus having formed thereon a coating film were prepared. An clil-based coating material (manufactured by NIPPON PAINT MARINE COATINGS Co., Ltd., trade name "CR Marine

Finish"), a solvent-type urethane-based «coating material (manufactured by NIPPON PAINT MARINE COATINGS Co., Ltd., trade name "Polyuremytilac M"), a solvent-type epoxy-based coating material (manufactured by NIPPON PAINT MARINE COATINGS Co., Ltd., trade name "Epoxy Finish M"), an aqueous epoxy-based coating material (manufactured by NIPPON PAINT MARINE COATINGS Co., Ltd., trade name "ODEMARINE PF"), or an aqueous urethane-based coating material (manufactured by NIPPON PAINT Co., Ltd., trade name "ODE URE TOP") was spray-applied onto each of the prepared steel sheets so that a dried film thickness of 35 to 45 um was achieved, and the sheets were allowed to stand at 20°C for 7 days, to thereby obtain test sheets.

The adhesivepropertyofeachof the steel sheetsandthecoating film formed using the aqueous coating composition obtained above was evaluated in the same manner as in the corrosion resistance evaluation A except that the test sheets were obtained as described above.

[0091] As clear fromthe results of Examples 1 to 22, the aqueous coating composition of the present invention exhibits excellent

F2P-NPP09201PCT low-temperature curability by containing the agueous epoxy-based polyamine resin (A) and the compound (B). Meanwhile, as clear from a comparison between Examples 1 to 21 and Comparative Example 1, the aqueous coating composition of the present invention can form a coating film excellent in corrosion resistance by containing the alkoxysilane compound (C).

[0092] Inaddition, as clear froma comparison between Examples 1 to 22 and Comparative Example 3, when the content ratio of the alkoxysilane compound (C) is in a specific range, excellent low-temperature curabilityandcorrosionresistancecanbeachieved.

Further, as clear from a comparison between Examples 1 to 21 and

Comparative Example 2, when the equivalent ratio of the aqueous epoxy-based polyamine resin (A) and the compound (B) is in a specific range, excellent low-temperature curability and corrosion resistance can be achieved.

[0083] Further, as clear from the results of Examples 12 to l16and 20 to 22, 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 can form a coating film significantly excellent in initial rain resistance.

Industrial Applicability

[0094] The agueous coating composition of the present invention

F2P-NPP09201PCT can be suitably used as an anticorrosive coating material in an inner or outer plate part of a ship and a submerged structure in seawater or freshwater.

Specifically, the composition can be suitably used in: an inner or outer plate part of a ship such as deck, hatch coaming, upper structure part, hull part, engine room, living quarter, or car hold; a submerged structure in seawater ox freshwater, such as a piping material; and the like.

Claims (12)

1. F2P-NPP0O9201PCT Claims
2. [Claim 1] An aqueous coating composition, comprising: (A) an aqueous epoxy-based polyamine resin having one or more primary amino groups and/or secondary amino groups in a molecule; (B) a compound having one or more (meth)acryloyl groups in a molecule; and (C) an alkoxysilane compound; wherein: anequivalentratioof anamino group of the aqueous epoxy—-based polyamine resin (A) and a {(meth)acryloyl group of the compcund (B) {({meth)acryloyl group/amino group} is 0.7 to 2.5; and a content of the alkoxysilane compound (C) in a solid content of the aqueous coating composition is 0.2 mass% to 5 mass%. [Claim?2] Anaquecus coating compositionaccordingtoclaiml, wherein the aqueous coating composition is a two-component agueous 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 agueous epoxy-based polyamine resin (A) and the curing agent comprising the compound (B) and the alkoxysilane compound (C).
3. [Claim 3] An agueous coating composition according to claim 1 or 2, wherein the aqueous epoxy-based polyamine resin (A) is

   F2P-NPP09201PCT water-dispersible.
4. [Claim 4] An aqueous coating composition 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.
5. [Claim 5] An aqueous coating composition according to any one 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.
6. [Claim 6] An aqueous coating composition according to any one of claims 1 to 4, wherein the aqueous epoxy-based polyamine resin (A) 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.
7. [Claim 7] Anaqueous coating compositionaccordingtoclaim6, wherein amass ratio of the epoxy resin (al) and the epoxy resin (a2) (al/a2) is 8/2 to 2/8.

   F2P-NPP0O9201PCT
8. [Claim 8] An aqueous coating composition 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%.
9. [Claim 9] An aqueous coating composition according to any one of claims 1 to 8, wherein the compound (B) has a viscosity at 25°C of 3,000 mPa‘s or less.
10. [Claim 10] An agueous coating composition according to any one of claims 1 to 9, further comprising a pigment, wherein the pigment has a pigment volume concentration of 20% to 50%.
11. [Claim 11] A method of forming a coating film, comprising applying the aqueous coating composition according to any one of claims 1 to 10 onto a substrate surface to form a coating film.
12. [Claim 12] A method of forming a coating film according to claim 11, further comprising applying a top coatingmaterial on the coating film to form a top coating layer.