JP6498618B2 - Anticorrosion coating composition, anticorrosion coating, substrate with anticorrosion coating, and method for producing substrate with anticorrosion coating - Google Patents

Description

  The present invention relates to an anticorrosion coating composition that forms a coating film having excellent adhesion to a steel structure such as a ship, a bridge, and a plant, as well as excellent anticorrosion performance even at an ultra-low temperature, and the coating composition. It is related with the manufacturing method of the base material with an anticorrosion coating film and the base material with an anticorrosion coating film in which the base material was coat | covered with the said coating film.

  Conventionally, large rust steel structures such as ships, bridges, plants and the like have been coated with a primary rust preventive paint on the steel plate surface for the purpose of preventing rusting during construction. As such primary rust preventive paints, organic primary rust preventive paints such as non-zinc epoxy primer, epoxy zinc rich primer, etc., inorganic zinc primary rust preventive paints containing siloxane binder and zinc powder are known. . However, when the above-mentioned general primary anti-corrosion paint is applied to the hull shell of the LNG ship and the heat insulation structure is bonded to the formed coating film with an adhesive layer made of mastic, Adequate adhesion strength cannot be obtained for both mastics. Particularly in this case, the formed coating film is required to have sufficient adhesion strength to both the hull and the adhesive layer even at an ultra-low temperature of about −25 ° C. Such adhesion strength cannot be obtained. As the primary anticorrosive paint having the above-mentioned adhesion strength, a vinyl butyral resin-based etching primer containing zinc chromate (zinc chromate) can be mentioned. However, zinc chromate is harmful to the human body and has problems such as environmental pollution.

  Patent Document 1 (Japanese Patent No. 5367983) discloses a rust preventive pigment-containing polyfunctional epoxy resin coating composition that does not contain zinc chromate and can be applied as a primary rust preventive paint having the above-mentioned adhesion strength. . However, when water comes into contact with the coating film formed from the coating composition immediately after coating, significant whitening occurs, resulting in a decrease in corrosion resistance, coating strength, and adhesion to mastic. Since the coating film in which whitening has occurred requires surface treatment, there are problems that the number of steps increases and the construction period becomes long. In general, the primary anticorrosive paint is subjected to primary surface treatment by steel blasting by shot blasting in a shot line, and then coated by a line coating machine, and the coated steel sheets are stacked and stored. When the anticorrosive pigment-containing polyfunctional epoxy resin coating composition is applied to the same coating method, the coating composition is slow in initial curing and drying. In order to prevent the adhesion of uncured coatings to each other, it is necessary to sandwich a wood block (square material) covered with a polyethylene sheet between the coated steel sheets. There was also a problem that it was insufficient.

  Patent Document 2 (Japanese Patent Application Laid-Open No. 2005-54074) has two or more epoxy groups in one molecule, a weight average molecular weight of about 15,000 to 50,000, and a hydroxyl value of about 100 to 500. A zinc-containing one-component curable coating composition for anticorrosion of stainless steel excellent in adhesion and anticorrosion, comprising an epoxy resin and zinc powder which are less than the amount normally contained in zinc rich paint. Is disclosed. Furthermore, in the Examples, an embodiment is disclosed in which a bisphenol A type epoxy resin having a weight average molecular weight (Mw) of 20,000, zinc powder and LF bowsey (manufactured by Kikuchi Color Co., Ltd.) as rust preventive pigments are disclosed. . However, these coating compositions are not suitable for applications requiring high adhesion strength such as the hull of LNG ships.

  Patent Document 3 (Japanese Patent Laid-Open No. 2000-239570) discloses (A) an epoxy having two or more epoxy groups in one molecule, a number average molecular weight of about 350 to 3000, and an epoxy equivalent of about 100 to 1000. Resin, (B) amine-based curing agent, (C) silane coupling agent, and (D) zinc powder having a particle size of 10 to 50 μm as main components, and the silane coupling agent (C) is a resin solid content in the paint 0.5 to 20 parts by weight with respect to 100 parts by weight, and further containing 50 to 95% by weight of the zinc powder (D) in the solid content of the paint, the adhesion between the steel material and the coating film, and the corrosion resistance An anticorrosive coating composition having excellent frictional resistance is disclosed. In Examples, epoxy resin (Epicoat 1001-X-70, manufactured by Yuka Shell Epoxy Co., Ltd., bisphenol A type epoxy resin), silane coupling agent (γ-glycidoxypropyltrimethoxysilane), antirust pigment (zinc powder) ) And an amine-based curing agent (polyamideamine) are disclosed, but in the embodiment using this epoxy resin (A), initial curing and drying are slow, and coating workability on the shot line is insufficient. In addition, a coating film formed from the paint has insufficient adhesion strength with the adhesive layer.

Japanese Patent No. 5367983 JP 2005-54074 A JP 2000-239570 A

  An object of the present invention is to solve the above-described problems in the prior art, and has a curing and drying property that enables coating on a shot line even at a low temperature, for example, 5 ° C. For example, even if water contacts the surface of the coating film 5 minutes after coating, no significant whitening occurs, and the resulting coating film has excellent anticorrosion properties, and has high adhesion strength even at an ultra-low temperature of about -25 ° C. It is intended to provide a composition, as well as its use.

The anticorrosion coating composition according to the present invention (hereinafter also simply referred to as a coating composition)
(A) an epoxy resin having a weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC) method of 15,000 to 45,000,
(B) a silane coupling agent;
(C) a rust preventive pigment,
(D) It comprises an amine-based curing agent.

The anticorrosion coating composition preferably has a pigment volume concentration (PVC) of 15 to 50%.
In the anticorrosion coating composition, it is preferable to contain 0.2 to 20 parts by weight of the silane coupling agent (B) with respect to 100 parts by weight of the solid content of the anticorrosion coating composition.

In the anticorrosion coating composition, the anticorrosion pigment (C) is preferably contained in an amount of 10 to 80 parts by weight with respect to 100 parts by weight of the solid content of the anticorrosion coating composition.
In the anticorrosion coating composition, the anticorrosive pigment (C) is zinc powder, scaly zinc powder, zinc alloy powder, zinc phosphate compound, calcium phosphate compound, aluminum phosphate compound, magnesium phosphate compound, Zinc phosphite compound, calcium phosphite compound, aluminum phosphite compound, strontium phosphite compound, aluminum tripolyphosphate compound, molybdate compound, cyanamide zinc compound, borate compound, nitro compound And at least one selected from the group consisting of complex oxides.

In the anticorrosion coating composition, the epoxy equivalent of the epoxy resin (A) is preferably 2,400 to 5,000 [g / eq].
The anticorrosion coating film according to the present invention is formed from the anticorrosion coating composition.

The base material with an anticorrosion coating film according to the present invention is formed by coating the surface of the base material with an anticorrosion coating film formed from the anticorrosion coating composition.
The hull with a coating film according to the present invention is formed by coating the hull of a ship with an anticorrosion coating film formed from the anticorrosion coating composition.

In the hull with a coating film, the ship is, for example, an LNG ship.
The laminated structure according to the present invention is a laminated structure in which an anticorrosive coating layer, an adhesive layer, and a heat insulating structure are laminated in this order, and the anticorrosive coating layer is formed from the anticorrosive coating composition. .

  The manufacturing method of the base material with an anticorrosion coating film according to the present invention includes a step of coating the surface of the base material with the anticorrosion coating composition, and forms the anticorrosion coating film by curing the coated anticorrosion coating composition. Process.

  The anticorrosion coating composition of the present invention has a curing and drying property that enables coating on a shot line even at a low temperature, for example, 5 ° C., and after coating, for example, 5 minutes after coating, the surface of the coating film comes into contact with water. However, no significant whitening occurs, and the coating film obtained from the anticorrosive coating composition of the present invention has excellent anticorrosion properties and has high adhesion strength even at an ultra-low temperature of about -25 ° C. The anticorrosion coating composition of the present invention can be used for various applications.

FIG. 1 is a schematic explanatory view showing the structure of a test body used in a vertical tensile test (accredited test method of GAZTRANSPORT & TECHNIIGAZ).

Hereinafter, the anticorrosion coating composition of the present invention will be described in detail including preferred embodiments.
The anticorrosive coating composition according to the present invention comprises (A) an epoxy resin having a weight average molecular weight (Mw) in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method of 15,000 to 45,000, (B) a silane coupling agent, (C) a rust preventive pigment,
(D) an amine-based curing agent.

<(A) Epoxy resin>
The epoxy resin (A) has a weight average molecular weight (Mw) in terms of standard polystyrene measured by GPC method of 15,000 to 45,000, and an epoxy equivalent of 2,400 to 5,000 [g / eq. ] Is preferable. Furthermore, it is more preferable that the weight average molecular weight (Mw) is 25,000 to 40,000 and the epoxy equivalent is 3,000 to 5,000 [g / eq]. When the weight average molecular weight of the epoxy resin (A) is in such a range, the coating composition of the present invention is excellent in curing and drying properties and is extremely suitable for shot line coating, and is formed from the coating composition. The coated film is excellent in whitening resistance and exhibits high adhesion strength even at ultra-low temperatures. The measurement of the weight average molecular weight (Mw) by GPC method can be performed, for example on the following conditions.

<GPC measurement conditions>
Equipment: 2695 Separation Module (Aliance GPC Multisystem) manufactured by Nippon Waters Co., Ltd.
Column: Tosoh Co., Ltd. TSKgel Super H4000
TSKgel Super H2000
Eluent: Tetrahydrofuran (THF)
Flow rate: 0.6 ml / min
Detector: Shodex RI-104 manufactured by Showa Denko KK
Column bath temperature: 40 ° C
Reference material: Polystyrene

  The epoxy resin (A) is not particularly limited as long as the effects of the present invention are not impaired. For example, bisphenol type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, novolac type epoxy resin (eg, phenol) Novolac type epoxy resin, cresol novolac type epoxy resin), dimer acid-modified epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, and the like. These may be used alone or in combination of two or more.

  Among these, bisphenol-type epoxy resins are preferable from the viewpoint of adhesion to the base material and corrosion resistance, bisphenol A-type epoxy resins and bisphenol F-type epoxy resins are more preferable, and bisphenol A-type epoxy resins are particularly preferable.

  As a commercial item of the epoxy resin (A), trade name “jER1010” (Mitsubishi Chemical Corporation, weight average molecular weight: 34,000), trade name “jER1009” (Mitsubishi Chemical Corporation, weight average molecular weight: 20,000).

  The epoxy resin (A) is preferably 10 to 80 parts by weight, more preferably 12 to 70 parts by weight, and particularly preferably 15 parts by weight based on 100 parts by weight of the solid content of the coating composition in the coating composition. -50 parts by weight are included. It is desirable that the content of the epoxy resin (A) is in the above range in terms of improving the curing and drying properties of the present coating composition, and the adhesion strength and anticorrosion properties of the coating film formed from the present coating composition.

<(B) Silane coupling agent>
The silane coupling agent (B) has a reactive group contributing to a chemical bond with an organic material in the molecule, and 1-3 reactive groups as a reactive group contributing to a chemical bond with an inorganic material. The compound which has a decomposition group is mentioned. Examples of the reactive group contributing to the chemical bond with the organic material include an epoxy group, an amino group, a mercapto group, an unsaturated group, a cationic group, and a halogen group.

Such a silane coupling agent (B) is not particularly limited, and a conventionally known silane coupling agent can be used, but it has at least two hydrolyzable groups in the same molecule and adheres to the substrate. It is preferable that it is a compound which can contribute to the improvement of property, and it is more preferable that it is a compound represented by Formula: X-SiMe _n Y _3-n . In the above formula, n is 0 or 1, and X is a reactive group capable of reacting with an organic substance (for example, an amino group, a vinyl group, an epoxy group, a mercapto group, a halogen group, and a carbon group containing these groups). A hydrogen group and a group formed by substituting an ether bond for a bond between carbon atoms of the hydrocarbon group), Me is a methyl group, and Y is a hydrolyzable group (for example, a methoxy group, an ethoxy group, etc.). Indicates.

  As a commercially available product of a preferred silane coupling agent (B), specifically, a trade name “KBM-403” (γ-glycidoxypropyltrimethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd.), a trade name “Syra Ace S”. -510 "(manufactured by JNC Corporation).

  These silane coupling agents (B) are preferably 0.2 to 20 parts by weight, more preferably 0.5 to 10 parts by weight based on 100 parts by weight of the solid content of the coating composition in the coating composition. Part by weight is included. It is desirable that the content of the silane coupling agent (B) is in the above range from the viewpoint of improving the adhesion between the coating film formed from the coating composition and the steel sheet substrate and the mastic.

<(C) Antirust pigment>
Examples of the anticorrosive pigment (C) include zinc powder, scaly zinc powder, zinc alloy powder, zinc phosphate compound, calcium phosphate compound, aluminum phosphate compound, magnesium phosphate compound, zinc phosphite compound, Calcium phosphite compounds, aluminum phosphite compounds, strontium phosphite compounds, aluminum tripolyphosphate compounds, molybdate compounds, cyanamide zinc compounds, borate compounds, nitro compounds, complex oxides Can do. Specifically, for example, in the case of zinc alloy powder, conventionally known alloys such as zinc-aluminum and zinc-magnesium, and in the case of zinc phosphate compounds, the trade name “LF BOSEI P-WF” (manufactured by Kikuchi Color Co., Ltd.) In the case of a calcium zinc phosphate compound, the trade name “LF Bowsei CP-Z” (manufactured by Kikuchi Color Co., Ltd.), and in the case of a magnesium zinc phosphate compound, the trade name “LF Bousei MZP-500” (manufactured by Kikuchi Color Co., Ltd.), phosphoric acid For the magnesium magnesium compound, the trade name “LF Bowsei PMG” (manufactured by Kikuchi Color Co., Ltd.), for the calcium phosphite compound, the trade name “LF Bousei CP-200” (manufactured by Kikuchi Color Co., Ltd.), and for the aluminum phosphomolybdate zinc compound Product name "LF Bowsey PM-300C" (manufactured by Kikuchi Color Co., Ltd.), calcium zinc phosphite For compound, trade name “Protex YM-60” (produced by Taihei Chemical Industry Co., Ltd.), and for strontium zinc phosphite compound, trade name “Protex YM-92NS” (produced by Taihei Chemical Industry Co., Ltd.), dihydrogen tripolyphosphate Trade name “K White # 82” (manufactured by Teika) for aluminum compounds, trade name “K White # 94” (manufactured by Teika) for aluminum metaphosphate compounds, and trade name for molybdate compounds. “LF Bowsei M-PSN” (manufactured by Kikuchi Color Co., Ltd.) and cyanamide zinc compounds include the trade name “LF Bowsei ZK-32” (manufactured by Kikuchi Color Co., Ltd.). It can be used alone or in combination of two or more. Any of these anticorrosive pigments (C) preferably has an average particle size of 20 μm or less, more preferably 15 μm or less, and particularly preferably 10 μm or less. If the average particle size of the anticorrosive pigment (C) exceeds 20 μm, the dispersibility of these components in the coating composition becomes insufficient, and thus the denseness of the coating film is reduced, thereby adversely affecting the anticorrosion properties. May give. The average particle diameter is an average particle diameter measured by a laser scattering diffraction type particle size distribution measuring apparatus (manufactured by Shimadzu Corporation, model SALD 2200).

  Further, the rust preventive pigment (C) is preferably contained in the coating composition in an amount of 10 to 80 parts by weight, more preferably 20 to 70 parts by weight with respect to 100 parts by weight of the solid content of the coating composition. It is desirable that the content ratio of the rust preventive pigment (C) is in the above range from the viewpoint of improving the corrosion resistance of the coating film formed from the coating composition.

<(D) Amine-based curing agent>
The amine-based curing agent (D) is not particularly limited, and among them, amine-based curing agents such as aliphatic, alicyclic, aromatic, and heterocyclic are preferable.

Examples of the aliphatic amine curing agent (D) include alkylene polyamines and polyalkylene polyamines. Examples of the alkylene polyamine include a compound represented by the formula: H ₂ N—R—NH ₂ . In the above formula, R is a divalent hydrocarbon group having 1 to 30 carbon atoms and may have a branch. Specifically, methylenediamine, ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diamino Examples include heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 2-methylpentamethylenediamine, and trimethylhexamethylenediamine.

Examples of the polyalkylene polyamine include a compound represented by the formula: H ₂ N— (C _m H _2m NH) _n H. In the above formula, m is an integer of 1 to 10, and n is an integer of 2 to 10, preferably 2 to 6. Specific examples include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tripropylenetetramine, tetraethylenepentamine, tetrapropylenepentamine, pentaethylenehexamine, nonaethylenedecamine and the like.

  As other aliphatic amine curing agents (D), tetra (aminomethyl) methane, tetrakis (2-aminoethylaminomethyl) methane, 1,3-bis (2′-aminoethylamino) propane, Examples include triethylene-bis (trimethylene) hexamine, bis (3-aminoethyl) amine, bis (hexamethylene) triamine, and bis (cyanoethyl) diethylenetriamine.

  Specific examples of the alicyclic amine curing agent (D) include 1,4-cyclohexanediamine, 4,4′-methylenebiscyclohexylamine, 4,4′-isopropylidenebiscyclohexylamine, and norbornanediamine. Bis (aminomethyl) cyclohexane, diaminodicyclohexylmethane, isophoronediamine, mensendiamine (MDA) and the like.

  Examples of the aromatic amine curing agent (D) include bis (aminoalkyl) benzene, bis (aminoalkyl) naphthalene, and aromatic polyamine compounds having two or more primary amino groups bonded to the benzene ring. It is done. As this aromatic amine curing agent (D), more specifically, for example, o-xylylenediamine, m-xylylenediamine (MXDA), p-xylylenediamine, phenylenediamine, naphthylenediamine, Diaminodiphenylmethane, diaminodiethylphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylsulfone, 2,2 ' -Dimethyl-4,4'-diaminodiphenylmethane, 2,4'-diaminobiphenyl, 2,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, bis (Aminomethyl) naphthalene, bis (aminoethyl) naphthalene, etc.

  Specific examples of the heterocyclic amine curing agent (D) include N-methylpiperazine, morpholine, 1,4-bis- (3-aminopropyl) -piperazine, piperazine-1,4-diazacyclo. Heptane, 1- (2′-aminoethylpiperazine), 1- [2 ′-(2 ″ -aminoethylamino) ethyl] piperazine, 1,11-diazacycloeicosane, 1,15-diazacyclooctacosane Etc.

  Examples of the other amine curing agent (D) include diethylaminopropylamine, polyether diamine, and amines (amine compounds) described in JP-B-49-48480. Further, a modified product of the compound mentioned as the amine curing agent, for example, polyamidoamine, an amine adduct of the compound and an epoxy compound, a Mannich compound (for example, Mannich modified polyamidoamine, phenalkamine), a Michael adduct, a ketimine, an aldimine Etc.

  The amine curing agent (D) may be obtained by synthesis by a conventionally known method or may be a commercially available product. As a commercial item, for example, trade name “ACI Hardener K-39” (manufactured by PTI Japan Co., Ltd.) which is an aliphatic polyamine, trade name “PA-66”, trade name “PA-23” which is a polyamidoamine, and Trade name “PA-290 (A)” (all manufactured by Akira Otake Shin Chemical Co., Ltd.), trade name “MAD-204 (A)” (manufactured by Akira Otake Shin Chemical Co., Ltd.), Mannich, a modified polyamine Trade name “ADEKA HARDNER EH-342W3” (manufactured by ADEKA), a modified polyamidoamine, trade name “SANMIDE CX-1154” (manufactured by Sanwa Chemical Co., Ltd.), phenalkamine, a Mannich-modified aliphatic polyamine The product name “Cardlight NC556 × 80” (manufactured by Cardlight), which is an adduct, is mentioned.

As the amine curing agent (D), amine curing agents selected from these can be used alone or in combination of two or more.
The content of the amine curing agent (D) in the anticorrosion coating composition is preferably a reaction ratio calculated from the following general formula [1] or [2], preferably 0.5 to 2.0, more preferably. Is an amount of 0.8 to 1.6. It is possible to adjust the content of the amine curing agent (D) so that the reaction ratio is in the above range, and the coating composition formed from the coating composition can be cured and dried and the whitening resistance of the coating composition. This is desirable from the viewpoint of improving the anticorrosion property and adhesion strength.

  The “reactive group equivalent of the silane coupling agent (B)” in the above formulas is the mass (g) of the silane coupling agent (B) containing 1 equivalent of the reactive group. As described above, as the silane coupling agent (B), a silane coupling agent having an amino group or an epoxy group as a reactive group can be used. Depending on the type of the reactive group, the silane coupling agent (B ) Is reactive to the epoxy resin (A) or reactive to the amine curing agent (D), and an appropriate formula is selected from the above formulas [1] and [2] In addition, the reactive group equivalent of the silane coupling agent (B) must be obtained for each, and the reaction ratio must be calculated.

<Other ingredients>
In addition to the essential components, the anticorrosion coating composition may contain pigments, solvents and additives other than the anticorrosive pigment (C) as necessary from the standpoint of coating properties such as paint properties, coating workability, and hue. (For example, a dispersant, a thickener, a sagging inhibitor, an anti-settling agent, an anti-color separation agent, etc.) can be contained.

<Pigments other than rust preventive pigment (C)>
The pigment is not particularly limited as long as it is other than the anticorrosive pigment (C), and pigments that are generally widely used in coating compositions can be used, for example, calcium carbonate, clay, talc, silica, Examples include extender pigments such as mica, barium sulfate, potassium feldspar, soda feldspar, dolomite, zirconium silicate, and zinc oxide, and colored pigments such as titanium oxide, dial, iron oxide, carbon black, phthalocyanine green, and phthalocyanine blue. The said pigment can be used individually by 1 type or in combination of 2 or more types.

<Solvent>
The solvent is not particularly limited as long as it is a solvent that can dissolve the epoxy resin (A). For example, coating workability on a shot line, coating after assembling a primary rust-proof treated steel plate into a block by welding. It can be appropriately selected according to each condition required for workability and the like. Examples of the solvent include alcohol solvents such as methanol, ethanol, isopropyl alcohol, and butanol; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone; ethyl acetate and butyl acetate. Ester solvents such as; and the like can be used.

The said solvent can be used individually by 1 type or in combination of 2 or more types according to the weather conditions at the time of coating.
The content of the solvent in the coating is not particularly limited, and can be appropriately determined according to each purpose such as coating workability on a shot line, and coating workability after blocking.

<Additives>
The additive is not particularly limited, and for example, additives usually used for coating applications such as a dispersant, a thickener, an anti-sagging agent, an anti-settling agent, and an anti-coloring agent can be used.
The anti-settling agent is not particularly limited, and examples thereof include a polyethylene wax thixotropic agent, specifically, trade name “DISPARON 4200-20” (manufactured by Enomoto Kasei Co., Ltd.).

<Pigment volume concentration (PVC)>
The anticorrosion coating composition according to the present invention preferably has a pigment volume concentration (PVC) of 15 to 50%, more preferably 25 to 40%. When the pigment volume concentration (PVC) is in the above range, the adhesion strength of the coating film formed from the coating composition and the adhesion to the mastic are improved. In the present invention, the pigment volume concentration (PVC) is a concentration expressed as a percentage of the total ratio (volume basis) of the pigment and the solid particles in the additive in the solid content of the coating composition of the present invention. Point to. Specifically, the pigment volume concentration (PVC) is obtained from the following general formula.

  The “solid content of the coating composition” in the present invention means a heating residue of the coating composition of the present invention under the following conditions. Usually, epoxy resin (A), amine-based curing agent (D), etc. It consists of the solid component in the said pigment component containing a coating-film formation main component, an antirust pigment (C), a silane coupling agent (B), and the said additive. The amount of heating residue of the coating composition can be measured according to the standard of JIS K5601-1-2 (heating temperature: 125 ° C., heating time: 60 minutes). Next, the pigment volume concentration (PVC) can be calculated by separating solid particles in the pigment component and additive from the heating residue and measuring the mass and true density of the separated pigment component and solid particles. it can.

<Method for producing substrate with anticorrosion coating>
The method for producing a substrate with an anticorrosive coating film according to the present invention comprises a step of painting the surface of a substrate such as a steel plate with the anticorrosion coating composition (painting step), and curing the coated coating composition to prevent corrosion. It has the process (curing process) which forms a coating film. In the above coating process, the method of coating the coating composition on the surface of the substrate that is the object to be coated is not particularly limited. For example, a conventionally known coating method can be used. A method of coating the surface of the substrate using a coating device such as a coating machine, a brush, or a roller can be given. Generally, when a paint composition is applied at a shipyard or a shipyard, an airless coater or a line coater is mainly used. The line coating machine manages the coating film thickness according to various coating conditions such as line speed, coating pressure such as air spray and airless spray installed in the coating machine, and the size (caliber) of the spray tip. The viscosity of the coating composition is appropriately adjusted using a solvent according to the coating method and the like. For example, when the coating is performed using an airless coating machine, the viscosity is appropriately adjusted to 10 to 25 seconds with Ford Cup # 4.

  The coating thickness of the anticorrosive coating composition is preferably a dry film thickness of 10 μm or more. When the dry film thickness is less than 10 μm, the anticorrosion property may be insufficient. If the dry film thickness is too thick, the amount of paint used increases, which is uneconomical, and the dryness of the coating film is inferior. The dry film thickness is more preferably about 15 to 40 μm.

  In the anticorrosion coating composition, the amine-based curing agent (D) functions as a curing agent for the epoxy resin (A). Therefore, after coating the coating composition, it can be cured at room temperature. Accordingly, curing may be promoted by preheating the base material before painting, heating the base material after painting, or the like. The curing temperature (drying temperature) in the curing step is usually 5 to 40 ° C., preferably 10 to 30 ° C., and the drying time is usually about 3 to 20 minutes, preferably 5 to 15 minutes. Usually, when line coating is performed on a shot line, the anticorrosion coating composition is applied to the surface of the base material, and the base material is loaded about 15 to 20 minutes after the coating. Therefore, when the curing and drying properties are insufficient, the base material adheres to the uncured coating film, which causes peeling of the coating film. In addition, the base material after painting may be left outdoors and left unattended, and there may be a problem that water droplets come into contact with the paint film immediately after painting due to rain or the like, and the paint film is markedly whitened. is there.

  In order to solve the above-described problems, the anticorrosive coating composition of the present invention has a coating formed by the coating composition after about 5 minutes have passed since coating even at a low temperature, for example, at 5 ° C. Even if water droplets come into contact with the film, the coating film does not whiten and is cured and dried in about 15 minutes after coating. Therefore, the anticorrosive coating composition of the present invention is extremely suitable for coating on a shot line.

  Examples of the base material include ship hulls. When the said base material is a ship's hull, the coating-coated hull is formed with the manufacturing method of the base material with an anticorrosion coating film of this invention. An example of the ship is an LNG ship.

  The substrate with the anticorrosion coating produced by the method for producing the substrate with the anticorrosion coating is subjected to long-term outdoor exposure, fusing, welding, mechanical damage, etc., and the coating has problems such as rusting. If it occurs, the coating film is subjected to secondary surface treatment with a power tool, blasting, etc., and the anticorrosion coating composition is applied using a coating device such as an airless coating machine, air spray coating machine, brush or roller. Can be painted on a substrate. In addition, when the base material is a hull of an LNG ship, the anticorrosion coating composition of the present invention is applied after the secondary surface treatment for the coating film, and the heat protection structure is mastic on the formed anticorrosion coating film. Adhesive strength similar to that obtained when the heat-resistant structure is adhered to the anti-corrosion coating film formed by coating the anti-corrosion coating composition of the present invention on the substrate on the shot line can be obtained. .

  Further, when the anticorrosion coating composition is applied to the secondary surface-treated substrate, the peripheral portion of the secondary surface treatment portion is laminated on the already formed anticorrosion coating film, so that the dry film thickness is Although it may be 40 to 120 μm in total, it is possible to maintain the same adhesion strength as that of a portion where a coating film having a thickness of 10 to 40 μm which is a normal coating thickness is formed.

<Laminated structure>
The anticorrosion coating composition is applied to the surface of the base material to form an anticorrosion coating layer, and the anticorrosion coating composition is bonded to the surface of the base material by bonding a heat insulating structure to the anticorrosion coating layer with mastic. It is possible to form a laminated structure in which an anticorrosion coating layer formed from an object, an adhesive layer formed from mastic, and a heat-resistant structure are laminated in this order. Examples of the mastic include a solvent-free amine-cured epoxy resin adhesive. Examples of the solventless amine-cured epoxy resin adhesive include “XF536M-1” (trade name, manufactured by HUNTSMAN) as a main agent and “XF537-1” (trade name, manufactured by HUNTSMAN) as a curing agent. An adhesive is mentioned. Examples of the heat-insulating structure include a panel structure made of reinforced plastic foam such as polyurethane foam and plywood. In this laminated structure, since the anticorrosion coating layer is formed between the base material and the adhesive layer made of mastic, the base material and the adhesive layer are firmly bonded via the anticorrosion coating layer. Is done. Examples of the base material include a hull of an LNG ship.

  In addition, the anticorrosion coating composition is applied to the surface of the substrate to form an anticorrosion coating layer, and the anticorrosion coating layer is coated with a top coating (for example, an epoxy resin system, for the purpose of improving design properties and coating film performance). The top coating layer formed from the top coating is applied to the anti-corrosion coating layer by repeatedly applying polyurethane resin, fluorine resin, polysiloxane resin, chlorinated rubber, acrylic resin, oil-based coating, etc. A stacked structure formed by stacking can be formed. Here, another coating layer may be appropriately provided between the anticorrosion coating layer and the top coating layer. As other coating layers, an intermediate coating formed from an intermediate coating (for example, epoxy resin, polyurethane resin, fluorine resin, polysiloxane resin, chlorinated rubber, acrylic resin, oil-based coating, etc.) Examples thereof include an undercoat coating layer formed from a coating layer and / or an undercoat paint (for example, an epoxy resin-based paint or the like).

<Use of anticorrosion coating composition>
The anticorrosive coating composition according to the present invention is used for steel structures such as ships, bridges, and plants that require anticorrosion, and for LNG ships that require high adhesion strength at ultra-low temperatures. Can be applied. In particular, by coating the hull shell that is in contact with the heat insulation structure of the cargo storage facility of the LNG ship, both the hull shell and the adhesive layer can be used together with excellent anticorrosion performance, even at ultra-low temperatures of about -25 ° C. In contrast, a coating film having sufficient adhesion strength can be obtained. In addition, there is GAZTRANSPORT & TECHNIIGAZ (France) as an organization that officially recognizes the above adhesion strength. The anticorrosion coating composition according to the present invention can form an anticorrosion coating film that satisfies the adhesion strength defined by the above-mentioned accreditation body.

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.
[Raw materials, test conditions, etc.]
・ "JER1010"
(Mitsubishi Chemical Corporation, epoxy equivalent: 4,000, weight average molecular weight: 34,000, solid content: 100% by weight, solvent content: 0% by weight, density: 1.19)
・ "JER1009"
(Mitsubishi Chemical Corporation, epoxy equivalent: 2,850, weight average molecular weight: 20,000, solid content: 100% by weight, solvent content: 0% by weight, density: 1.20)
・ "JER1007"
(Mitsubishi Chemical Corporation, epoxy equivalent: 1,975, weight average molecular weight: 10,000, solid content: 100% by weight, solvent content: 0% by weight, density: 1.15)
・ "JER1001"
(Mitsubishi Chemical Corporation, epoxy equivalent: 475, weight average molecular weight: 2,000, solid content: 100% by weight, solvent content: 0% by weight, density: 1.19)
・ "Disparon 4200-20"
(Enomoto Kasei Co., Ltd., anti-settling agent, polyethylene oxide wax, solid content: 20% by weight, solvent (xylene) content: 80% by weight, paste-like product, solid content density: 0.93)
・ "KBM-403"
(Shin-Etsu Chemical Co., Ltd., silane coupling agent, γ-glycidoxypropyltrimethoxysilane solid content: 100% by weight, solvent content: 0% by weight, epoxy equivalent: 236, density: 1.07)
・ "Talc FC-1"
(Fukuoka Talc Industrial Co., Ltd., density: 2.7)
・ "Zinc Powder F"
(Made by Hakusui Tech Co., Ltd., average particle size 4 μm, density: 7.1)
・ "LF Bow CP-Z"
(Kikuchi Color Co., Ltd., zinc phosphate compound, average particle size 3.5 μm, density: 2.9)
・ "K White # 82"
(Taika Co., Ltd., aluminum tripolyphosphate compound, average particle size 3.5 μm, density: 3.0)
・ "PROTEX YM-92NS"
(Taihei Chemical Industry Co., Ltd., zinc phosphite compound, average particle size 5 μm, density: 3.0)
・ "PA-66"
(Otake Akira Shin Chemical Co., Ltd., polyamidoamine, active hydrogen equivalent: 377, solid content: 60 wt%, solvent (xylene, butanol) content: 40 wt%, solid content density: 0.993)

[Example 1]
12.0 parts by weight of “jER1010” was dissolved in a solvent obtained by mixing 19.9 parts by weight of toluene, 19.9 parts by weight of methyl ethyl ketone, and 5.0 parts by weight of ethyl acetate to obtain a varnish shape in advance. In this varnish, 5.5 parts by weight of “Talc FC-1” as a pigment, 2.5 parts by weight of “Disparon 4200-20” as an anti-settling agent, and 1.0 weight of “KBM-403” as a silane coupling agent The ingredients were added and stirred with a high-speed rotary stirrer (Homodisper, manufactured by Primics Co., Ltd.), and further using a paint disperser (basket mill, manufactured by Asada Tekko Co., Ltd.) After the contained solid content was further finely dispersed, 25.0 parts by weight of “Zinc Powder F” was added and mixed uniformly using the high-speed rotary stirrer. The obtained mixture was used as a main agent.

Further, 2.2 parts by weight of “PA-66” was added to a solvent obtained by mixing 5.0 parts by weight of toluene and 2.0 parts by weight of isopropyl alcohol, and uniformly dispersed with a high-speed rotary stirrer. The obtained dispersion was used as a curing agent.
The coating composition of Example 1 was obtained by mixing the main agent and the curing agent thus obtained.

[Examples 2 to 13]
In Examples 2-13, the main ingredient component and the curing agent component were prepared in the same manner as in Example 1 except that the blending components and the blending ratio were changed as shown in Table 1. By mixing, a coating composition was obtained in the same manner as in Example 1.

[Comparative Examples 1-5]
In Comparative Examples 1-5, the main ingredient component and the curing agent component were prepared in the same manner as in Example 1 except that the blending components and the blending ratio were changed as shown in Table 1. By mixing, a coating composition was obtained in the same manner as in Example 1.

≪Evaluation of coating film performance≫
About the coating composition obtained by the Example and the comparative example, the coating-film performance evaluation was performed with the test method shown below. The results are shown in Table 1.

<Curing drying>
Cold-rolled steel sheet (JIS G3141, SPCC-SB, dimensions: 150 mm × 70 mm × 0.8 mm) which is a test piece of each coating composition of Examples 1 to 13 and Comparative Examples 1 to 5 in a room at 5 ° C. Further, after coating so that the dry film thickness was 20 μm, the curing and drying time was measured.

  The term “cured and dried” as used herein refers to placing a thumb on the paint surface of a test piece placed horizontally, extending the arm vertically to the test piece, pressing the thumb against the paint surface with maximum force, and simultaneously rotating 90 degrees. Sometimes, it refers to a state in which the coating film is not loosened, peeled off, wrinkled, or other signs of twisting. The time from the end of coating until reaching the above state, that is, the curing and drying time was evaluated as the curing and drying property.

<Whitening resistance>
In a room at 5 ° C., the coating compositions of Examples 1 to 13 and Comparative Examples 1 to 5 were dried on a cold-rolled steel plate (JIS G3141, SPCC-SB, dimensions: 150 mm × 70 mm × 0.8 mm). After coating to a film thickness of 20 μm and allowing to stand for 5 minutes, several drops of tap water were dropped on the surface of the coating film. After leaving still for 12 hours, the appearance of the part on the coating film on which water droplets were dropped was visually confirmed, and the degree of whitening of the part was evaluated in the following three stages.
3 points: no whitening is observed.
2 points: Slight whitening is observed.
1 point: Clear whitening is recognized.

<Anti-corrosion (salt spray resistance)>
Each coating composition of Examples 1 to 13 and Comparative Examples 1 to 5 is applied to a structural steel plate (JIS G3101, SS400, dimensions: 150 mm × 70 mm × 2.3 mm, sandblasting) so that the dry film thickness is 20 μm. Painted on. Next, the coated composition was dried for 7 days in a constant temperature and humidity room at a temperature of 23 ° C. and a relative humidity of 50% in accordance with the standard of JIS K5600-1-6 to prepare a test plate. The obtained test plate is placed in a spray cabinet having a temperature of 35 ° C. ± 2 ° C. according to JIS K5600-7-1, and a sodium chloride aqueous solution (concentration 5%) is continuously sprayed on the coating film of the test plate. The rusting state of the coating 200 hours after the start of spraying was evaluated as follows according to the standard of ASTM (American Society for Testing and Materials) standard D-610.
10 points: There is no rusting or the rusting area is 0.01% or less of the total area of the test plate.
Nine points: The rusting area exceeds 0.01% of the total area of the test plate and is 0.03% or less.
8 points: The rusting area exceeds 0.03% of the total area of the test plate and is 0.1% or less.
7 points: The rusting area exceeds 0.1% of the total area of the test plate and is 0.3% or less.
6 points: The rusting area exceeds 0.3% of the total area of the test plate and is 1% or less.
5 points: The rusting area exceeds 1% of the total area of the test plate and is 3% or less.
4 points: The rusting area exceeds 3% of the total area of the test plate and is 10% or less.
3 points: The rusting area exceeds 10% of the total area of the test plate and is 16% or less.
2 points: The rusting area exceeds 16% of the total area of the test plate and is 33% or less.
1 point: The rusting area exceeds 33% of the total area of the test plate and is 50% or less.

<Adhesiveness (Vertical Tensile Test (GAZTRANSPORT & TECHNIIGAZ Co., Ltd. Certification Test Method))>
Each coating composition of Examples 1 to 13 and Comparative Examples 1 to 5 was dried on both surfaces of a structural steel plate (JIS G3101, SS400, dimensions: diameter 56.4 mm, thickness 10 mm) so that the dry film thickness was 20 μm. Painted on. Next, the coated composition was dried for 7 days in a constant temperature and humidity room at a temperature of 23 ° C. and a relative humidity of 50% in accordance with the standard of JIS K5600-1-6. Then, using a mastic made by HUNTSMAN (main agent: trade name “XF536M-1”, curing agent: trade name “XF537-1”, mixing weight ratio: main agent / hardening agent = 100/80), GAZTRANSPORT & Adhering the support 20 to each of the two anticorrosion coating layers 30 provided on the structural steel plate 10 so as to have the structure of FIG. 1 defined in the above-mentioned certification test method of TECHNIGAZ, the temperature is 23 ° C., It was dried in a constant temperature and humidity room with a relative humidity of 50% for 7 days. In this way, a test body for a vertical tensile test in which the adhesive layer 40 was formed between the anticorrosion coating layer 30 and the support 20 was produced. Thereafter, a vertical tensile test (Tensilon universal testing machine, manufactured by Orientec Co., Ltd., tensile speed 1.3 mm / min) was performed at 23 ° C. to evaluate the adhesion of the coating film.

  Similarly, each coating composition was applied to both surfaces of the structural steel plate so that the dry film thickness was 20 μm. Next, the coated composition was dried for 7 days in a constant temperature and humidity room at a temperature of 23 ° C. and a relative humidity of 50% in accordance with the standard of JIS K5600-1-6. Thereafter, using the mastic, the support 20 is applied to each of the two anticorrosion coating layers 30 provided on the structural steel plate 10 so as to have the structure of FIG. 1 defined in the certification test method. The samples were bonded and dried for 7 days in a constant temperature and humidity room at a temperature of 23 ° C. and a relative humidity of 50% to prepare a specimen for a vertical tensile test. Then, the said vertical tension test was done at -25 degreeC, and the adhesiveness of the coating film was evaluated.

  As is clear from the description of the test results in Table 1, by using a coating composition that satisfies the various conditions specified in the present invention, a coating film excellent in curing and drying properties, whitening resistance, anticorrosion properties and adhesion properties is obtained. It is done.

DESCRIPTION OF SYMBOLS 10 ... Structural steel plate 20 ... Support body 30 ... Anticorrosion coating layer 40 ... Adhesive layer which consists of mastic

Claims (12)

(A) an epoxy resin having a weight average molecular weight (Mw) in terms of standard polystyrene measured by gel permeation chromatography (GPC) method of 15,000 to 45,000,
(B) a silane coupling agent;
(C) a rust preventive pigment,
(D) An anticorrosion coating composition comprising an amine-based curing agent.   The anticorrosive coating composition according to claim 1, wherein the pigment volume concentration (PVC) is 15 to 50%.   The anticorrosive paint composition according to claim 1 or 2, comprising 0.2 to 20 parts by weight of the silane coupling agent (B) with respect to 100 parts by weight of the solid content of the anticorrosive paint composition. .   The anticorrosive paint according to any one of claims 1 to 3, comprising 10 to 80 parts by weight of the anticorrosive pigment (C) with respect to 100 parts by weight of the solid content of the anticorrosive paint composition. Composition.   The rust preventive pigment (C) is zinc powder, scaly zinc powder, zinc alloy powder, zinc phosphate compound, calcium phosphate compound, aluminum phosphate compound, magnesium phosphate compound, zinc phosphite compound, Group consisting of calcium phosphite compound, aluminum phosphite compound, strontium phosphite compound, aluminum tripolyphosphate compound, molybdate compound, cyanamide zinc compound, borate compound, nitro compound and complex oxide The anticorrosive coating composition according to any one of claims 1 to 4, wherein the composition is one or more selected from the above.   The anticorrosion coating composition according to any one of claims 1 to 5, wherein an epoxy equivalent of the epoxy resin (A) is 2,400 to 5,000 [g / eq].   The anticorrosion coating film formed from the anticorrosion coating composition of any one of Claims 1-6.   The base material with an anticorrosion coating film by which the surface of a base material is coat | covered with the anticorrosion coating film formed from the anticorrosion coating composition of any one of Claims 1-6.   A hull with a coating film, wherein the hull of a ship is coated with an anticorrosion coating film formed from the anticorrosion coating composition according to any one of claims 1 to 6.   The ship's shell with a coating film, wherein the ship according to claim 9 is an LNG ship.   It is a laminated structure formed by laminating an anticorrosion coating layer, an adhesive layer, and a heat insulation structure in this order, and the anticorrosion coating layer is formed from the anticorrosion coating composition according to any one of claims 1 to 6. Laminated structure.   It has the process of coating the surface of a base material with the anticorrosion coating composition of any one of Claims 1-6, and the process of hardening the said coated anticorrosion coating composition and forming an anticorrosion coating film. The manufacturing method of a base material with an anticorrosion coating film.

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