WO2017138168A1

WO2017138168A1 - Anticorrosive coating composition and method for forming dry coating film

Info

Publication number: WO2017138168A1
Application number: PCT/JP2016/073319
Authority: WO
Inventors: 弘一鍛治; 秀行近藤; 圧広山下; 愼一石原
Original assignee: 日本ペイントマリン株式会社
Priority date: 2016-02-12
Filing date: 2016-08-08
Publication date: 2017-08-17
Also published as: KR101867252B1; BR112017019321A2; DE112016002028B4; CN107960092B; DE112016002028T5; KR20170116094A; BR112017019321B1; CN107960092A; SG11201706987XA

Abstract

Provided are: a two-pack type anticorrosive coating composition configured of a first agent and a second agent, wherein the first agent comprises a bisphenol A type epoxy resin (A) and the second agent comprises an amine-based hardener (B) and a monoepoxide compound (C), the amine-based hardener (B) comprising an alicyclic amine compound (B-1) represented by formula (B-1); a coating film formed from the anticorrosive coating composition; and a ship and a marine structure which are equipped with the coating film.

Description

Anticorrosion paint composition and method of forming dry coating film

The present invention relates to epoxy-based anticorrosion paint compositions. The present invention also relates to an anticorrosion coating film formed from the anticorrosion coating composition, and a coated article such as a ship, a marine structure or the like provided with the anticorrosion coating film. Furthermore, the present invention relates to a method for forming a coating film, and a paint used therefor.

Generally, in addition to ships, marine structures such as bridges, tanks, and plants are coated with an anticorrosive coating on their surfaces for the purpose of imparting corrosion resistance to severe corrosive environments. Antifouling coatings are often applied over anticorrosion coatings. In order to impart desired properties by formation of a coating, film thickness control of the dried coating is important, and if the formed dried coating does not have a sufficient thickness, the characteristics to be imparted are also given. It tends to be inadequate.

For example, JP 2001-279167 A (patent document 1) contains an epoxy resin (a), a curing agent (b), a coumarone resin (c), and a hydroxyl group-containing terpene phenol resin (d). It is described that the anticorrosion paint composition and its application to ships and the like. As the curing agent (b), modified products of polyamines such as aliphatic polyamines, alicyclic polyamines, aromatic polyamines and the like are mentioned.

By the way, film thickness control of a coating film is not an operation which can be made easy. As a conventional film thickness control method, a wet gauge is used to confirm in advance whether or not the dry film thickness to be targeted (that can obtain a desired physical property sufficiently) can be obtained in advance. A method of measuring and confirming the dry film thickness based on the measurement of the coating film thickness in the middle of the work, ie in the wet state (before drying),
ii) In order to confirm whether or not the film thickness of the dried coating film has reached the target film thickness, there is a method of measuring the film thickness of the dried coating film directly using an electromagnetic film thickness meter etc. .

However, in any of the above methods, film thickness control has been practically difficult particularly in the following cases.
1) When the area of the to-be-coated-article surface where a coating material is applied is large like a ship etc., for example. In this case, it is extremely complicated and practically difficult to measure the film thickness using a wet gauge, an electromagnetic film thickness meter or the like over the entire surface of the object to be coated.
2) When the to-be-coated-article surface to which a coating is applied includes the surface where coating is not easy. Although coating thickness is likely to be uneven on surfaces where coating is not easy, it is often the case that the film thickness of a coating film formed on such surfaces is measured using a wet gauge, an electromagnetic film thickness meter, etc. It is difficult and complicated.
3) When the target film thickness of the coating film formed by one-time coating is large. As the thickness of the coating film to be formed by one-time coating is thicker, the frequency of measurement of the thickness of the coating film in the middle of coating tends to increase, and the film thickness control becomes complicated. In addition, "one-time coating" means that a series of operation until it coats a paint and performs a drying process is one time, therefore, the coating film formed by one-time coating means a paint. A coating film formed by performing a drying process once after applying one or more times is repeated.

As methods for solving the above-mentioned conventional problems, JP-A-10-216621 (Patent Document 2) and JP-A-2002-066445 (Patent Document 3) disclose methods for forming a coating film. As a paint, a paint called "film thickness judgment paint" can be used which enables a coating operator to visually observe the change in color difference of the wet coating during coating to determine whether or not the specified film thickness is reached. Forming a coating film is disclosed.

JP, 2001-279167, A Japanese Patent Application Laid-Open No. 10-216621 Japanese Patent Laid-Open No. 2002-066445

An epoxy resin anticorrosion coating composition is advantageous in that it has excellent adhesion to the object to be coated and corrosion resistance, but the combination of an epoxy resin and an amine curing agent has the problem that the pot life is relatively short. .

An object of the present invention is to provide an epoxy-based anticorrosion paint composition exhibiting an improved pot life. Another object of the present invention is to provide a coating (corrosion coating) formed using the anticorrosion paint composition, and a ship and a marine structure provided with the coating.

Still another object of the present invention is to easily carry out a coating operation by using an epoxy-based anticorrosion paint composition exhibiting an improved pot life, and to easily carry out a predetermined process while suppressing a shortage of film thickness. A coating film forming method capable of forming a dried coating film having a film thickness, and a paint used therefor.

The present invention provides the anticorrosion paint composition as shown below, as well as coatings, ships and marine structures.

[1] A two-component anticorrosion paint composition comprising a first agent and a second agent,
The first agent contains bisphenol A epoxy resin (A),
The second agent contains an amine curing agent (B) and a monoepoxide compound (C),
The amine curing agent (B) has the following formula (B-1):

[In formula (B-1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, x is 1 to 3 and y is 0 to 2, and x and y The total of is 2 to 4. ]
The anticorrosive coating composition containing the alicyclic amine compound (B-1) represented by these.

[2] The amine curing agent (B) has the following formula (b-1):

The anticorrosive coating composition according to [1], comprising 2,4-di (4-aminocyclohexylmethyl) aniline represented by

[3] The corrosion prevention according to [1] or [2], wherein the content of the monoepoxide compound (C) in the second agent is 5 to 50 parts by mass with respect to 100 parts by mass of the amine curing agent (B) Paint composition.

[4] Any one of [1] to [3], wherein the equivalent ratio of the monoepoxide compound (C) contained in the second agent to the amine curing agent (B) is 1/5 to 1/40. The anticorrosion paint composition according to any of the preceding claims.

[5] The anticorrosive coating composition according to any one of [1] to [4], wherein the monoepoxide compound (C) contains a phenylglycidyl ether compound.

[6] The anticorrosive coating composition according to any one of [1] to [5], which further comprises a silane coupling agent (D).

[7] A coating film formed from the anticorrosive coating composition according to any one of [1] to [6].
[8] A ship or marine structure provided with the coating film according to [7].

The present invention also provides a method for forming a dried coating film and a colored anticorrosive paint as described below.
[1] A method for forming a dried coating on the surface of a substrate,
Following process:
[1] a step of setting a dry film thickness T;
[2] A two-component colored anticorrosion paint comprising a first agent and a second agent, which comprises the following conditions (a) to (e):
(A) The coating film formed from the colored anticorrosion paint having the dry coating thickness T conceals the surface of the object to be coated,
(B) A color difference ΔE1 between a coating formed of the colored anticorrosive paint having the dry coating thickness T and a coating formed of the colored anticorrosive coating having a dry coating thickness of 0.7 T is 2. Is 0 or more,
(C) containing a color pigment,
(D) The first agent contains a bisphenol A type epoxy resin (A), and the second agent contains an amine curing agent (B) and a monoepoxide compound (C).
(E) The amine curing agent (B) has the following formula (B-1):

[In formula (B-1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, x is 1 to 3 and y is 0 to 2, and x and y The total of is 2 to 4. ]
Containing an alicyclic amine compound (B-1) represented by
Preparing or preparing a colored anticorrosive paint satisfying
[3] a step of applying the colored anticorrosive paint to the surface until the surface of the object to be coated is covered with a coating film made of the colored anticorrosive paint;
[4] A step of drying the coated film obtained by the step of the above-mentioned [3] to obtain a dried coated film,
Method, including.

[2] The colored anticorrosive paint has the following condition (f):
(F) The color difference ΔE2 between the coating formed of the colored anticorrosive paint having the dry coating thickness T and the coating formed of the colored anticorrosive coating having a dry coating thickness of 1.3 T is less than 1 Is
The method according to [1], further satisfying

[3] The colored anticorrosive paint has the following condition (g):
(G) A color difference ΔE3 between the coating film formed from the colored anticorrosion paint having the dry coating thickness T and the surface of the article is 20 or more.
The method according to [1] or [2], further satisfying

[4] The method according to any one of [1] to [3], wherein the coating formed from the colored anticorrosion paint having the dry coating thickness T has a hiding ratio of 0.90 to 0.98. .

[5] The method according to any one of [1] to [4], wherein the content of the color pigment is 0.01 to 3% by volume in the coating film-forming component.

[6] The amine curing agent (B) has the following formula (b-1):

The method according to any one of [1] to [5], which comprises 2,4-di (4-aminocyclohexylmethyl) aniline represented by

[7] The content of the monoepoxide compound (C) in the second agent is 5 to 50 parts by mass with respect to 100 parts by mass of the amine curing agent (B), of [1] to [6] The method described in either.

[8] The equivalent ratio of the monoepoxide compound (C) contained in the second agent and the amine curing agent (B) is 1/5 to 1/40, in [1] to [7] The method described in either.

[9] The method according to any one of [1] to [8], wherein the monoepoxide compound (C) contains a phenyl glycidyl ether compound.

[10] The method according to any one of [1] to [9], wherein the colored anticorrosive paint further contains a silane coupling agent (D).

[11] The colored anticorrosion paint further has a scale-like pigment (F) having an average particle diameter of 10 to 300 μm, an average thickness of 2 to 50 μm, and an aspect ratio of 2 to 100 defined as an average particle diameter / average thickness. Contains
The method according to any one of [1] to [10], wherein the content of the scaly pigment (F) is 5 to 45% by volume in the coating film-forming component.

[12] The method according to [11], wherein the scaly pigment (F) is at least one pigment selected from the group consisting of talc, mica and glass flakes.

[13] A two-component colored anticorrosion paint comprising a first agent and a second agent, which is used to form a dried coating having a dry coating thickness T on the surface of a coated article,
The following conditions (a) to (e):
(A) The coating film formed from the colored anticorrosion paint having the dry coating thickness T conceals the surface of the object to be coated,
(B) A color difference ΔE1 between a coating formed of the colored anticorrosive paint having the dry coating thickness T and a coating formed of the colored anticorrosive coating having a dry coating thickness of 0.7 T is 2. Is 0 or more,
(C) containing a color pigment,
(D) The first agent contains a bisphenol A type epoxy resin (A), and the second agent contains an amine curing agent (B) and a monoepoxide compound (C).
(E) The amine curing agent (B) has the following formula (B-1):

[In formula (B-1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, x is 1 to 3 and y is 0 to 2, and x and y The total of is 2 to 4. ]
Containing an alicyclic amine compound (B-1) represented by
Meet the colored anticorrosive paint.

[14] The following condition (f):
(F) The color difference ΔE2 between the coating formed of the colored anticorrosive paint having the dry coating thickness T and the coating formed of the colored anticorrosive coating having a dry coating thickness of 1.3 T is less than 1 Is
[13] The colored anticorrosive paint according to [13], further satisfying

[15] The following condition (g):
(G) A color difference ΔE3 between the coating film formed from the colored anticorrosion paint having the dry coating thickness T and the surface of the article is 20 or more.
The colored anticorrosive paint according to [13] or [14], further satisfying

[16] The colored film according to any one of [13] to [15], wherein the coating film formed from the colored anticorrosion paint having the dry coating thickness T has a hiding ratio of 0.90 to 0.98. Anticorrosion paint.

[17] The color anticorrosive paint according to any one of [13] to [16], wherein the content of the color pigment is 0.01 to 3% by volume in the coating film-forming component.

[18] The amine curing agent (B) has the following formula (b-1):

The colored anticorrosive paint according to any one of [13] to [17], which comprises 2,4-di (4-aminocyclohexylmethyl) aniline represented by

[19] The content of the monoepoxide compound (C) in the second agent is 5 to 50 parts by mass with respect to 100 parts by mass of the amine curing agent (B), of [13] to [18] The colored anticorrosion paint as described in any one.

[20] The equivalent ratio of the monoepoxide compound (C) to the amine curing agent (B) contained in the second agent is 1/5 to 1/40, in [13] to [19] The colored anticorrosion paint as described in any one.

[21] The colored anticorrosive paint according to any one of [13] to [20], wherein the monoepoxide compound (C) contains a phenylglycidyl ether compound.

[22] The colored anticorrosive paint according to any one of [13] to [21], further comprising a silane coupling agent (D).

[23] A scaly pigment (F) having an average particle size of 10 to 300 μm, an average thickness of 2 to 50 μm, and an aspect ratio of 2 to 100 defined as an average particle size / average thickness is further contained,
The coloring and anti-corrosion paint according to any one of [13] to [22], wherein the content of the scaly pigment (F) is 5 to 45% by volume in the coating film-forming component.

[24] The colored anticorrosive paint according to [23], wherein the scale-like pigment (F) is at least one pigment selected from the group consisting of talc, mica and glass flakes.

ADVANTAGE OF THE INVENTION According to this invention, the epoxy-type anticorrosion coating composition which shows the improved pot life, the coating film formed using this, and the ship and marine structure provided with the said coating film can be provided. The anticorrosion paint composition of the present invention is useful, for example, as an anticorrosion paint to be applied to marine structures such as bridges, tanks, and plants, as well as ships.

According to the present invention, the coating operation can be easily performed by using the epoxy-based anticorrosion coating composition exhibiting an improved pot life, and a predetermined film thickness can be simply and conveniently suppressed while the film thickness shortage is suppressed. It is possible to provide a coating film forming method capable of forming a dried coating film, and a colored anticorrosive paint used therefor. The colored anticorrosion paint of the present invention is useful, for example, as an anticorrosion paint to be applied to marine structures such as bridges, tanks, and plants as well as ships.

FIG. 13 is a graph showing the relationship between the dry film thickness (μm) and ΔE shown in Tables 4 to 6 (Example 14 and Comparative Example 2). FIG. 16 is a graph showing the relationship between the dry film thickness (μm) and ΔE shown in Tables 4 to 6 (Examples 15 and 16). FIG. 16 is a graph showing the relationship between the dry film thickness (μm) and ΔE shown in Tables 4 to 6 (Examples 17 to 19). FIG. 16 is a graph showing the relationship between the dry film thickness (μm) and ΔE shown in Tables 4 to 6 (Examples 20 to 23). FIG. 26 is a graph showing the relationship between the dry film thickness (μm) and ΔE shown in Tables 4 to 6 (Example 24). FIG. 26 is a graph showing the relationship between the dry film thickness (μm) and ΔE shown in Tables 4 to 6 (Example 25). FIG. 26 is a graph showing the relationship between dry film thickness (μm) and ΔE shown in Tables 4 to 6 (Example 26). FIG. 27 is a graph showing the relationship between the dry film thickness (μm) and ΔE shown in Tables 4 to 6 (Examples 27 and 28).

Hereinafter, the present invention will be described in detail.
<Anticorrosion paint composition>
The anticorrosion paint composition according to the present invention is a two-pack anticorrosion paint composition comprising a first agent and a second agent. The first agent contains a bisphenol A type epoxy resin (A), and the second agent contains an amine curing agent (B) and a monoepoxide compound (C). Each component will be described in detail below.

(1) Bisphenol A type epoxy resin (A)
The first agent (main agent) of the anticorrosion paint composition contains a bisphenol A epoxy resin (A). By using the bisphenol A type epoxy resin (A), the low temperature curability of the anticorrosion coating composition can be improved, and the base material (coated object) such as a blast steel plate, shop coated steel plate, organic zinc coated steel plate etc. Adhesion can be made favorable, and thereby, good corrosion resistance can be obtained. The bisphenol A epoxy resin (A) may be used alone or in combination of two or more.

The anticorrosive coating composition can contain an epoxy resin other than the bisphenol A epoxy resin (A). However, from the viewpoint of low-temperature curability, adhesion to a base or a top coat, etc., the content of bisphenol A epoxy resin (A) in the total amount of epoxy resin is preferably 50% by mass or more, 70% by mass It is more preferable that it is more than. As epoxy resins other than bisphenol A epoxy resin (A), for example, bisphenol F epoxy resin, bisphenol AD epoxy resin, bisphenol S epoxy resin, biphenyl epoxy resin, naphthalene epoxy resin, glycidyl ester epoxy resin And glycidyl amine type epoxy resin, phenol novolac type epoxy resin, rubber modified epoxy resin and the like.

The epoxy equivalent of the bisphenol A type epoxy resin (A) is preferably 100 to 3,000, more preferably 150 to 1,000, and still more preferably 180 to 500. When the epoxy equivalent is 100 or more, good low temperature curability tends to be easily obtained, and the toughness of the obtained coating film tends to be good. If the epoxy equivalent exceeds 3000, the low temperature curability tends to be poor or the coating tends to be hard.

The number average molecular weight of the bisphenol A type epoxy resin (A) is preferably 200 to 5000, more preferably 250 to 2000, in terms of standard polystyrene measured by gel permeation chromatography (GPC). When the number average molecular weight is in the above range, an anticorrosive coating composition excellent in coating film physical properties and coating workability is easily obtained.

The epoxy resin [solid content] containing the bisphenol A type epoxy resin (A) is preferably contained in an amount of 10 to 60% by mass, and more preferably 15 to 55% by mass, in the solid content of the anticorrosion coating composition. When the content is 10% by mass or more, the corrosion resistance of the coating film tends to be good. If the content is 60% by mass or less, the coating film is not too hard, and an anticorrosion paint composition excellent in crack resistance which hardly causes defects such as cracks can be easily obtained. When the content of the bisphenol A type epoxy resin (A) exceeds 60% by mass, the adhesion to the base and the top coat tends to decrease.

(2) Amine curing agent (B)
The amine curing agent (B) contained in the second agent has the following formula (B-1):

And an alicyclic amine compound (B-1) represented by In formula (B-1), R ¹ , R ² and R ³ each independently represent a hydrogen atom or a methyl group, x is 1 to 3, y is 0 to 2, and x and y The total is 2 to 4. By using an amine-based curing agent (B) containing an alicyclic amine compound (B-1), it is possible to form a corrosion resistant coating film having good chemical resistance, mechanical strength and corrosion resistance, and a two-pack type anticorrosion paint The pot life of the composition can be extended moderately. On the other hand, when a general aliphatic polyamine or the like is used as a curing agent for epoxy resin, the pot life is short, and the gelation of the anticorrosive coating composition after mixing the two solutions is quick.

R ¹ , R ² and R ³ are preferably hydrogen atoms. x is preferably 1 or 2 and y is preferably 1 or 2.

The alicyclic amine compound (B-1) may contain only one kind of alicyclic amine compound satisfying the above formula (B-1), or an alicyclic amine satisfying the above formula (B-1) It may be a mixture of two or more of the compounds. The amine curing agent (B) is a mixture of one or more of the alicyclic amine compound (B-1) satisfying the above formula (B-1) and one or more of other amine compounds, It is also good. In the present specification, “alicyclic amine compound” means an amine compound having one or more alicyclic rings in the molecule.

Among them, the amine curing agent (B) has the following formula (b-1) from the viewpoint of extending the pot life:

It is preferable to contain 2,4-di (4-aminocyclohexylmethyl) aniline represented by 2,4-di (4-aminocyclohexylmethyl) aniline is a kind of alicyclic amine compound (B-1), and in the above formula (B-1), x is 1 and y is 1 It is a compound.

From the viewpoint of pot life extension, the content of the alicyclic amine compound (B-1) (preferably, 2,4-di (4-aminocyclohexylmethyl) aniline) in the amine curing agent (B) is 50 mass % Or more, preferably 60% by mass or more, and more preferably 65% by mass or more (e.g., 70% by mass or more, 80% by mass or more, or 90% by mass or more).

As the above-mentioned other amine compounds, those conventionally known as curing agents for epoxy resins can be used. Specific examples of other amine compounds include polyamine curing agents, modified polyamine curing agents, polyamide curing agents, modified polyamide curing agents, and the like. The other amine compounds may be used alone or in combination of two or more.

Examples of polyamine-based curing agents include aliphatic polyamines (meta-xylene diamine, isophorone diamine, diethylene triamine, triethylene tetramine, diamino diphenyl methane etc.); alicyclic polyamines other than alicyclic amine compounds (B-1); Polyamine etc. are mentioned. The modified polyamine-based curing agent is a modified product of the above-mentioned polyamine, and is, for example, an aliphatic, alicyclic or aromatic polyamine modified by epoxide addition, Michael addition, Mannich addition, thiourea addition, acrylonitrile addition, ketone blocking, etc. Etc.

Examples of the polyamide-based curing agent include polyamidoamines which are produced by condensation of dimer acid and polyamine and have reactive primary and secondary amino groups in the molecule. The polyamine forming the polyamidoamine can be the above-mentioned aliphatic polyamine, alicyclic polyamine, aromatic polyamine and the like.

The modified polyamide-based curing agent is a modified polyamide, and examples thereof include an epoxy adduct formed by adding an epoxy compound to polyamide, a Mannich modified polyamide, and the like.

A commercial item may be used as an amine curing agent (B). As the amine-based curing agent (B) containing 2,4-di (4-aminocyclohexylmethyl) aniline as a main component, for example, a trade name “Ancamine 2280” manufactured by Air Products Inc. can be suitably used.

The amine equivalent of the amine curing agent (B) is usually 50 to 1000, preferably 60 to 800, more preferably 100 to 600, and still more preferably 100 to 500. When the amine equivalent of the amine curing agent (B) is in the above range, the anticorrosion coating film is excellent in the anticorrosion properties of the anticorrosion coating film and the adhesion to the substrate and the top coat film, and an anticorrosion coating composition having a long pot life can be easily obtained.

The amine-based curing agent (B) [solid content] is preferably contained in an amount of 5 to 40% by mass, and more preferably 7 to 30% by mass, in the solid content of the anticorrosion coating composition. When the content of the amine curing agent (B) is within the above range, it is advantageous in terms of corrosion resistance of the anticorrosion coating, crack resistance, adhesion to the base and top coat, coating workability, etc. It is advantageous also in extending the pot life of the anticorrosion paint composition. From the same viewpoint, the content ratio of the amine-based curing agent (B) (solid content) to the epoxy (solid content) in the anticorrosion coating composition is equivalent to the equivalent ratio [active hydrogen / epoxy in amine-based curing agent (B) Epoxy group], preferably 0.65 to 2, more preferably 0.7 to 1.7, and still more preferably 0.8 to 1.3. The term "epoxy" as used herein is a generic term for an epoxy resin containing a bisphenol A type epoxy resin (A) and a compound having an epoxy group other than an epoxy resin such as a monoepoxide compound (C) described later.

(3) Monoepoxide compound (C)
The monoepoxide compound (C) contained in the second agent refers to a compound having one epoxy group in the molecule. Including the monoepoxide compound (C) in the second agent together with the amine curing agent (B) is advantageous for appropriately prolonging the pot life. As the monoepoxide compound (C), only one type may be used, or two or more types may be used in combination.

Preferred examples of monoepoxide compounds (C) are monoglycidyl ethers, and specific examples thereof include alkyl glycidyl ether and phenyl glycidyl ether (alkyl phenyl glycidyl ether and the like). The carbon number of the alkyl moiety of the alkyl glycidyl ether and the alkyl phenyl glycidyl ether is usually 1 to 20, preferably 5 to 18, and more preferably 10 to 16. The epoxy equivalent of the monoepoxide compound (C) is usually 50 to 1000, preferably 100 to 600, and more preferably 150 to 500. Among the above, the monoepoxide compound (C) is preferably a phenyl glycidyl ether from the viewpoint of extending the pot life.

The first agent may further contain a monoepoxide compound (C). This is advantageous in reducing the viscosity of the first agent.

The content of monoepoxide compound (C) [solid content] in the second agent is preferably 5 to 50 parts by mass, and more preferably 100 parts by mass of the amine curing agent (B) [solid content]. 6 to 50 parts by mass (eg, 10 to 48 parts by mass). When the content of the monoepoxide compound (C) is within the above range, the pot life extending effect can be easily obtained. When the content of the monoepoxide compound (C) exceeds 50 parts by mass, the corrosion resistance and hardness of the coating may be lowered.

From the same viewpoint, the content ratio of the monoepoxide compound (C) [solid content] to the amine curing agent (B) [solid content] in the second agent is equivalent to the equivalent ratio [epoxy group in the monoepoxide compound (C) [Active hydrogen in amine-based curing agent (B)], preferably 1 / 1.5 to 1/50, more preferably 1/2 to 1/45, still more preferably 1/5 to 1 / 40.

From the same viewpoint, when the first agent contains the monoepoxide compound (C), the content of the monoepoxide compound (C) [solid content] and the amine curing agent (B) [solid content] in the anticorrosive coating composition The ratio is preferably 1 / 1.5 to 1/50, more preferably 1/50, as the equivalent ratio [epoxy group in monoepoxide compound (C) / active hydrogen in amine curing agent (B)]. It is 2 to 1/40, more preferably 1/3 to 1/30.

When the first agent contains the monoepoxide compound (C), the content of the monoepoxide compound (C) [solid content] in the first agent is an epoxy resin containing the bisphenol A type epoxy resin (A) [solid content] The amount is usually 0.1 to 100 parts by mass, preferably 5 to 50 parts by mass, and more preferably 10 to 50 parts by mass with respect to 100 parts by mass.

The monoepoxide compound (C) [solid content] is preferably contained in an amount of 0.1 to 30% by mass, and more preferably 0.5 to 20% by mass, in the solid content of the anticorrosion coating composition. When the content of the monoepoxide compound (C) is in the above range, it is advantageous for prolonging the pot life.

(4) Silane coupling agent (D)
The anticorrosion paint composition can contain a silane coupling agent (D) as required. By containing the silane coupling agent (D), adhesion to the base and the top coat, corrosion resistance, curability and the like can be enhanced. As the silane coupling agent (D), only one type may be used, or two or more types may be used in combination.

Preferred examples of the silane coupling agent (D) are alkoxysilane compounds. Examples of alkoxysilane compounds include γ-glycidyloxyalkyltrialkoxysilanes such as γ-glycidyloxypropyltrimethoxysilane and γ-glycidyloxypropyltriethoxysilane; γ-aminopropyltriethoxysilane, γ-aminopropyltripropoxy Γ-aminoalkyltrialkoxysilanes such as silane; N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, N- such as N-phenyl-γ-aminopropyltripropoxysilane And phenyl-γ-aminoalkyltrialkoxysilane and the like.

The silane coupling agent (D) [solid content] is preferably contained in an amount of 0.1 to 15% by mass in the solid content of the anticorrosion coating composition, and 0.2 to 10% by mass (for example, 1 to 5% by mass) More preferably, it is included. When the content of the silane coupling agent (F) is in the above range, it is advantageous in enhancing the adhesion to the base and the top coat, the corrosion resistance, the curability, and the like.

(5) (meth) acrylate compound (E)
The anticorrosion paint composition can contain a (meth) acrylate compound (E) as required. The (meth) acrylate compound (E) refers to a compound having one or more (meth) acryloyl groups in the molecule. By containing the (meth) acrylate compound (E), the adhesion to the base and the top coat, the corrosion resistance, the curability and the like can be enhanced. As the (meth) acrylate compound (E), only one type may be used, or two or more types may be used in combination. In the present specification, “(meth) acryloyl group” represents at least one selected from methacryloyl and acryloyl. The same applies to “(meth) acrylic”.

An example of (meth) acrylate compound (E) is (meth) acrylic acid alkyl ester such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate and the like . The carbon number of the alkyl moiety is preferably 1 to 10, more preferably 1 to 5.

Other examples of the (meth) acrylate compound (E) are ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, nona ethylene glycol Di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, hexanediol di (meth) acrylate, butanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, Trimethylolpropane ethylene oxide adduct tri (meth) acrylate, trimethylolpropane propylene oxide adduct tri (meth) acrylate, glycerin tri (meth) Crylates, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (2- (meth) acryloyloxyethyl) isodianurate, pentaerythritol tri (meth) acrylate and tolylene di Multifunctional (meth) acrylic compounds such as 2: 1 adducts with isocyanates.

Still another example of the (meth) acrylate compound (E) is a vinyl ester resin (epoxy (meth) acrylate) obtained by the reaction of an epoxy resin and (meth) acrylic acid. The epoxy resin may be other epoxy resin as described above in the paragraph of “(1) Bisphenol A type epoxy resin (A)” besides bisphenol A type epoxy resin, but preferably bisphenol A type epoxy resin It is.

Among the above, the (meth) acrylate compound (E) is preferably a vinyl ester resin, and is a bisphenol A type vinyl ester resin, from the viewpoints of adhesion to a base and a top coat, corrosion resistance, curability, etc. Is more preferred. The number average molecular weight of the vinyl ester resin is preferably 1000 to 5000, more preferably 1000 to 3000, in terms of standard polystyrene conversion value by GPC measurement. When the number average molecular weight of the vinyl ester resin is in the above range, it is advantageous for enhancing the adhesion to the base and the top coat, the corrosion resistance, the curability and the like.

The (meth) acrylate compound (E) [solid content] is preferably contained in an amount of 0.2 to 15% by mass in the solid content of the anticorrosion coating composition, and 0.5 to 10% by mass (e.g. 1 to 6% by mass) More preferably included. When the content of the (meth) acrylate compound (E) is in the above range, it is advantageous for enhancing the adhesion to the base and the top coat, the corrosion resistance, the curability, and the like. For the same reason, the content of the (meth) acrylate compound (E) (solid content) in the anticorrosion coating composition is 100 parts by mass of the epoxy resin (solid content) containing bisphenol A type epoxy resin (A), The amount is preferably 5 to 25 parts by mass, more preferably 10 to 20 parts by mass (eg, 10 to 16 parts by mass).

(6) Other formulation components The anticorrosion paint composition can contain one or more other formulation components, as necessary. As other blending components, for example, thermoplastic resin, solvent, pigment, anti-sagging agent (anti-settling agent), anti-coloring agent, anti-foaming / anti-abrasive agent, film-forming aid, UV absorber, anti-oxidant Agents, leveling agents, matting agents, curing accelerators, dispersing agents, viscosity modifiers, surface conditioners, plasticizers, preservatives, reactive diluents, non-reactive diluents and the like. As a thermoplastic resin, petroleum-based resin, (meth) acrylic resin, polyester resin etc. can be used, for example. By containing a thermoplastic resin, there are cases where the physical properties of the coating can be improved.

As the solvent, those commonly used in the relevant field can be used, and examples thereof include toluene, xylene, isobutanol, methyl ethyl ketone, methyl isobutyl ketone, benzyl alcohol and the like. Two or more mixed solvents may be used.

As a pigment, a color pigment, an extender pigment, a rust preventive pigment etc. are mentioned. Specific examples of coloring pigments are titanium oxide, carbon black, lead white, graphite, zinc sulfide, zinc oxide (zinc white), chromium oxide, yellow nickel titanium, yellow chromium titanium, yellow iron oxide, red iron oxide, black iron oxide And phthalocyanine blue, phthalocyanine green, ultramarine blue, benzimidazolone yellow, quinacridone red, azo red / yellow pigments and the like. Two or more color pigments may be used.

Specific examples of the extender pigment are talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, silicic acid, silicate, alumina, calcium sulfate, mica-like iron oxide (MIO), glass flakes, mica (szolite mica, clarite)・ Including mica etc. Two or more extender pigments may be used.

Specific examples of anticorrosive pigments are zinc molybdate, aluminum molybdate, lead cyanamide, red lead, lead suboxide, zinc chromate, zinc powder (Zn), zinc oxide (zinc white), basic lead chromate, basic It includes lead sulfate, calcium leadate, aluminum tripolyphosphate, zinc phosphate, calcium phosphate, aluminum powder (Al), hemihydrate gypsum and the like. Two or more rust preventive pigments may be used.

(7) Preparation of anticorrosion paint composition The anticorrosion paint composition according to the present invention can be prepared in the same manner as a general anticorrosion paint using an epoxy resin. The anticorrosive coating composition according to the present invention is a two-component type, and comprises a first agent (main agent) containing at least a bisphenol A epoxy resin (A), an alicyclic amine curing agent (B) and a monoepoxide compound ( It consists of the 2nd agent (hardening agent) which contains C) at least. Both the first and second agents can contain a solvent. Usually, the first agent and the second agent are mixed and coated on a substrate just before use.

In the two-component anticorrosion paint composition, the silane coupling agent (D), the (meth) acrylate compound (E), and the other components may be blended in any of the first agent and the second agent. Or you may mix | blend with both. Usually, a silane coupling agent (D) and a (meth) acrylate compound (E) are mix | blended with a 1st agent.

(8) Coating of Anticorrosion Paint Composition Coating of the anticorrosion paint composition onto a substrate can be carried out by a general method such as brushing, roller, spray and the like. Specifically, the coating composition obtained by mixing the first agent and the second agent immediately before use is applied using the above method. The coating of the coating composition obtained by mixing the first and second agents onto a substrate is carried out within the pot life (useful time) after mixing the first and second agents. According to the anticorrosive coating composition according to the present invention, since the pot life is long, coating workability can be improved. After coating, it can be dried to form an anticorrosive coating. The drying temperature is usually normal temperature (about 20 to 35 ° C.), but can be performed at a temperature lower than this.

The object to be coated (target to which the anticorrosion coating composition is to be applied) is not particularly limited as long as it requires anticorrosion, but, for example, a ship (the inner surface of a ballast tank of a ship or the bottom of a ship) In addition to outer plates, etc., it can be bridges, tanks, plants (petroleum plants etc.), marine structures such as pipes, etc. The material of the surface of the substrate to be coated with the anticorrosion coating composition can be, for example, a coating film made of a coating material such as iron-based metal such as steel, non-ferrous metal, concrete, and old coating film. The old coating film refers to a coating film or a part thereof which has been previously formed and used.

The anticorrosive coating composition according to the present invention is suitably applied to a coating method (method for producing a composite coating film) on which an undercoating film is formed on a surface of a substrate and then a top coating film is formed thereon. it can. In this method, the anticorrosion paint composition according to the present invention can be used to form an undercoat film. The undercoating film may be a laminated structure of a plurality of coating films, and in this case, the anticorrosion coating composition according to the present invention is used, for example, for forming an undercoating film (contacting the topcoat film) on the outermost surface. .

Examples of the base of the undercoating film made of the anticorrosion coating composition according to the present invention include a rustproof coating, a shop coating, an organic or inorganic zinc primer coated coating, and the like. The surface of the substrate may be blasted.

The film thickness of the anticorrosion coating film formed from the anticorrosion paint composition according to the present invention can be appropriately selected according to the type of the object to be coated, the application and the like, but in general, the dry film thickness is 10 to 500 μm. It is an extent. In addition, the anticorrosive coating film formed from the anticorrosive coating composition according to the present invention may be a dried coating film having a desired film thickness by coating the composition several times. There is no particular limitation on the amount applied once, and the coating is usually applied so that the dry film thickness of each coating is 10 to 500 μm. In the case of coating multiple times, after forming a wet coating film by coating multiple layers, drying may be performed to obtain a dried coating film having a desired film thickness, or by forming a plurality of dry coating films. You may obtain the dried coating film which has a desired film thickness.

What is generally used in anticorrosion coating can be used as a top coat used for a top coat formed on an anticorrosion coat. Specific examples of the top coating include oil based paints, long oil based phthalate resin paints, silicone alkyd resin paints, phenol resin paints, chlorinated rubber based resin paints, epoxy resin paints, modified epoxy resin paints, tar epoxy resin paints, vinyl chloride resin Paints, polyurethane resin paints, fluorocarbon resin paints, silicon modified resin paints, antifouling paints for preventing biological adhesion, etc. Examples of the antifouling paint include acrylic resin antifouling paints and vinyl resin antifouling paints. The top coat is preferably an epoxy resin paint, a polyurethane resin paint, a fluorine resin paint, an acrylic resin antifouling paint, a vinyl resin antifouling paint or the like. The dry film thickness of the top coat film is usually about 10 to 300 μm.

The top coat may be the anticorrosion paint composition according to the present invention. In one embodiment where the anticorrosion paint composition of the present invention is a top coat, the anticorrosion paint composition according to the present invention, for example, for repair, on the old paint film formed from the anticorrosion paint composition according to the present invention It is a case of forming the coating film which consists of things. The anticorrosion paint composition according to the present invention can also be used exclusively for forming a top coat film, not a primer coat. The dry film thickness of the top coat film formed from the anticorrosive coating composition according to the present invention is usually about 10 to 300 μm.

The anticorrosion coating film formed from the anticorrosion coating composition according to the present invention can exhibit good anticorrosion properties and can exhibit good adhesion to the base and the top coat film.

<Color anticorrosion paint>
The colored anticorrosive paint (colored anticorrosive paint composition) according to the present invention can be used in the method for forming a coated film according to the present invention described in detail later. The coating film forming method according to the present invention is a method for forming a dry coating film on the surface of a substrate, and the following steps:
A step of setting a dry film thickness T (dry film thickness setting step),
Preparing or preparing a two-component colored anticorrosion paint comprising a first agent and a second agent and satisfying the conditions (a) to (e) described later (colorable anticorrosion paint preparation step);
A step (coating step) of applying a colored anticorrosion paint to the surface of the article to be coated until the surface of the substrate is covered with a paint anticorrosion paint (coating step) Step of drying) to obtain a dried coating (drying step)
including.

In the coating film forming method according to the present invention, a predetermined colored anticorrosive paint (colored anticorrosive paint composition) is used as a paint for forming a dried coating film. This colored anticorrosion paint is a paint having a "film thickness determination function" that can determine whether or not a predetermined film thickness has been reached by visually observing the hue of the coating (wet coating) during coating. . The colored anticorrosive paint according to the present invention will first be described in detail below.

The colored anticorrosion paint according to the present invention is a two-component anticorrosion paint composition comprising a first agent and a second agent. The colored anticorrosive paint according to the present invention contains a colored pigment [condition (c)]. The first agent of the colored anticorrosive paint contains a bisphenol A type epoxy resin (A), and the second agent contains an amine curing agent (B) and a monoepoxide compound (C) [condition (d)]. Each component will be described in detail below.

(1) Bisphenol A type epoxy resin (A)
The first agent (main agent) of the colored anticorrosive paint contains a bisphenol A epoxy resin (A). The description in "(1) Bisphenol A type epoxy resin (A)" of the above-mentioned <Anticorrosion paint composition> is cited about bisphenol A type epoxy resin (A) which the 1st agent of a coloring anticorrosion paint contains.

(2) Amine curing agent (B)
The second agent of the colored anticorrosive paint contains an amine curing agent (B). The amine curing agent (B) contains the alicyclic amine compound (B-1) represented by the above formula (B-1) [conditions (e)]. With respect to the amine curing agent (B) and the alicyclic amine compound (B-1) contained in the second agent, the description in "(2) Amine curing agent (B)" of the above-mentioned <Anticorrosion paint composition> Is quoted. As described in “(2) Amine-based curing agent (B)” of the above-mentioned <Anticorrosion paint composition>, the amine-based curing agent (B) has a surface represented by the above formula (b-1) from the viewpoint of pot life extension. It is preferred to include 2,4-di (4-aminocyclohexylmethyl) aniline.

(3) Monoepoxide compound (C)
The second agent of the colored anticorrosive paint contains a monoepoxide compound (C). As for the monoepoxide compound (C) contained in the second agent, the description in “(3) Monoepoxide compound (C)” of the above-mentioned <Anticorrosion paint composition> is cited. The first agent may further contain a monoepoxide compound (C). This is advantageous in reducing the viscosity of the first agent. The description in "(3) monoepoxide compound (C)" of the above-mentioned <anticorrosion paint composition> is cited also for the monoepoxide compound (C) contained in the first agent.

(4) Silane coupling agent (D)
The colored anticorrosive paint can contain a silane coupling agent (D), if necessary. The description in "(4) Silane coupling agent (D)" of the above-mentioned <anticorrosion paint composition> is quoted about a silane coupling agent (D).

(5) (meth) acrylate compound (E)
The colored anticorrosive paint can contain a (meth) acrylate compound (E) as needed. For the (meth) acrylate compound (E), the description in “(5) (Meth) acrylate compound (E)” of the above-mentioned <Anticorrosion paint composition> is cited.

(6) Colored Pigment As the colored pigment contained in the colored anticorrosive paint, various known colored pigments can be used, and colored anticorrosive paints of various hues can be realized by selecting the colored pigment. The type of the color pigment to be added to the color anticorrosive paint (the hue of the color anticorrosive paint) can be selected according to the color of the surface (surface to be coated) of the object to be coated. It is preferable to select the kind or combination of color pigments such that the color difference ΔE3 between the coating film formed from the above and the surface of the substrate is 20 or more. The hue of the coating formed from the colored anticorrosive paint having the dry coating thickness T is substantially the same as the hue of the colored anticorrosive paint itself, for example, in the case of a conventional solvent-based paint that does not cause color separation. is there.

Specific examples of the coloring pigment are not particularly limited. For example, carbon black, titanium dioxide, zircon oxide, basic lead sulfate, tin oxide, lead white, graphite, zinc sulfide, zinc oxide, chromium oxide, yellow nickel titanium, yellow chromium titanium Yellow iron oxide, red iron oxide, black iron oxide, chromium yellow, phthalocyanine blue, phthalocyanine green, ultramarine blue, quinacridones, azo red / yellow pigments and the like can be used. The color pigments may be used alone or in combination of two or more.

Among them, carbon black and titanium dioxide are preferably used because of high coloring power, and the color pigment preferably contains titanium dioxide. When only titanium dioxide is used as a color pigment, the coating film becomes light in color. To avoid this, it may be used in combination with other color pigments.

In particular, in the case of the colored anticorrosive paint according to the present invention for forming a thick film, it is preferable that the coloring pigment content is relatively small, since it is necessary to have relatively small background hiding ability. Specifically, the content of the color pigment is usually 0.01 to 3% by volume, preferably 0.1 to 2% by volume, in the film-forming component. If the content of the color pigment is too small, the substrate hiding power is too small, and the change in the hue of the wet coating during the coating is also too small, so it may be determined whether the specified film thickness has been reached. It will be difficult. On the other hand, if the content of the color pigment is too large, the surface hiding power is too large, and the coating film hides the surface of the object to be coated before reaching the target value T of the dry film thickness to be targeted. It becomes difficult to determine whether the film thickness has reached a prescribed value. In the present specification, "film-forming component" means all components other than the solvent contained in the colored anticorrosive paint.

(7) Pigments other than colored pigments The colored anticorrosive paint can contain pigments other than colored pigments, if necessary. As pigments other than color pigments, extender pigments, rust preventive pigments and the like can be mentioned. Specific examples of the extender pigment are talc, clay, calcium carbonate, magnesium carbonate, barium sulfate, silicic acid, silicate, alumina, calcium sulfate, mica-like iron oxide (MIO), glass flakes, mica (szolite mica, clarite)・ Including mica etc. Two or more extender pigments may be used.

Specific examples of the anti-corrosive pigment are calcium sulfate hemihydrate, zinc molybdate, aluminum molybdate, cyanamide lead, cyanamide calcium zinc, red lead, lead oxide, zinc chromate, strontium chromate, barium chromate, zinc powder ( Zn), zinc oxide (zinc flower), basic lead chromate, basic lead sulfate, calcium lead acid, aluminum tripolyphosphate, zinc phosphate, calcium phosphate, calcium phosphite, lead trioxide, lead oxide, aluminum powder ( Al), including hemihydrate gypsum and the like. Two or more rust preventive pigments may be used.

When the dry coating thickness T set in the dry coating thickness setting step is selected from the range of 300 μm or more, the colored anticorrosive coating preferably has an average particle diameter of 10 to 300 μm and an average thickness of 2 to 50 μm, It is preferable to include a scale-like (flat) pigment (hereinafter, also simply referred to as a "scale-like pigment") (F) having an aspect ratio defined as an average particle size / average thickness of preferably 2 to 100. The definitions and measurement methods of the average particle size, the average thickness and the aspect ratio are as described in the Examples section. Hereinafter, scale-like pigment (F) and its function are demonstrated.

The film thickness determination paints described in Patent Documents 2 and 3 described above are all paints used for forming a coating film having a target dry film thickness (dry film thickness T) of 100 μm or more, and are included therein The paint is prepared so as to satisfy the following relationship with respect to color difference by adjusting the content of the color pigment to be produced.
(A) The color difference between the film thickness judgment paint and the substrate is 20 or more,
(B) The color difference between the coating film of the target dry film thickness and the coating film of the dry film thickness less than (target dry film thickness-50) m is 2 or more, and (c) the coating film of the target dry film thickness Film thickness + 50) Color difference of the coating film of dry film thickness more than μm is less than 1.

Among the above, (b) is particularly important, and if the difference between the hue of the coating film approaching the target film thickness and the hue of the coating film reaching the target film thickness is not clear, the coating operator It becomes difficult to visually determine whether the wet coating film during coating has reached the target film thickness as a dry coating film or is still insufficient.

Therefore, it can be said that the film thickness judgment is easier as the color difference between the coating film approaching the target film thickness and the coating film reaching the target film thickness is larger, but a thick coating film is formed by one application. In this case, it may be difficult to make the color difference sufficiently large. More specifically, if the target dry film thickness of the coating film formed by one-time application is up to about 250 μm (the target dry film thickness in the example of Patent Document 2 is 125 μm, the implementation of Patent Document 3) The target dry film thickness in the example is a maximum of 250 μm.) According to the preparation methods described in these patent documents, the above color difference is increased to some extent, and the film thickness is determined relatively easily in forming a coating film having a desired film thickness. It was possible to do.

Also in the prior art, it has been practiced to form a thick film having a thickness of more than 250 μm on a substrate. The anticorrosion coating (anticorrosion coating) formed on the surface of a marine structure such as a ship or a bridge, or a steel structure such as a plant is a typical example. However, conventionally, such a thick-film coating is not formed by single coating, but is formed by multiple coating (coating method in which a series of steps from coating to drying is performed multiple times to coat a dried coating). It was normal.

However, for example, when a coating method in which a thick film of 300 μm or more is formed not by multiple coating but by single coating is adopted in recent years, a coating film approaching a target film thickness and It is difficult to sufficiently increase the color difference from the coating film that has reached the target film thickness, and it is not always easy to determine whether the wet coating film has reached the target film thickness or is still insufficient in film thickness. It turned out not.

When the dry film thickness T set in the dry film thickness setting step is selected from the range of 300 μm or more, the significance of including the scale-like pigment (F) in the colored anticorrosive paint is as follows: . In paints (anticorrosion paints, etc.), it is a conventional technique to include an extender pigment to enhance the coating film strength or to enhance corrosion resistance if it is an anticorrosion paint, and it is a conventional technique and includes both an extender pigment and a color pigment Film thickness determination paints are also known (the above-mentioned patent documents 2 and 3). However, in the conventional film thickness judgment paint, as described above, when applied to a method of forming a thick film by single coating, the target film thickness (the set value T of the target dry film thickness) is obtained. It is difficult to sufficiently increase the color difference between the coating film that is getting very close and the coating film that has reached the target film thickness, and whether the wet coating film has reached the target film thickness or is still insufficient in film thickness It is not always easy to determine.

The above-mentioned conventional problems will be described in more detail. As the dry film thickness increases, ΔE (monotonously exponentially) decreases monotonously and the base region of the graph, that is, the set value T of the dry film thickness and its value In a front near region, there is almost no difference in ΔE (that is, a state in which the color difference between the coating film approaching the target film thickness and the coating film reaching the target film thickness is extremely small). This problem becomes more pronounced as the thickness of the coating film formed in a single application increases, but the larger the set value T of the thickness of the dried coating film, the wider the foot region where the difference ΔE hardly occurs. To spread out.

On the other hand, according to the colored anticorrosive paint containing the scaly pigment (F) and the method for forming a coating film using the same, for example, with reference to the graph of Example 14 shown in FIG. The graph is not exponentially rapid monotonous decrease, but a little ΔE is larger between the dry film thickness 0 μm and the setting value T of the dry film thickness compared with the shape of rapid monotonous decrease It will take on a shape that seems to swell. Even when the dry coating thickness T is selected from the range of 300 μm or more due to such a shape, the color difference between the coating having the dry coating thickness T and the coating having the dry coating thickness of 0.7 T It becomes possible to realize the condition [condition (b)] in which ΔE1 is 2.0 or more, that is, the coating film and the target which are approaching the target film thickness (the set value T of the target dry film thickness). It is possible to make the color difference with the coating film that has reached the film thickness sufficiently large, and it is easy to determine whether the wet coating film has reached the target film thickness or is still insufficient in film thickness. become able to.

The reason why the above graph shape is obtained is not clear, but in the first place, an extender pigment is a component that absorbs light and interferes with the transmission of light. It is considered that the light is likely to be oriented in the direction (the major axis of the scale-like pigment is oriented in the plane direction of the coating) and the light may easily transmit the scale-like pigment (F). It is thought that it is a cause which becomes such a graph shape.

The average particle diameter of the scale-like pigment (F) is preferably 10 to 300 μm, more preferably 10 to 200 μm, still more preferably 10 to 150 μm, from the viewpoint of the sufficiency of the condition (b) and the physical properties of the paint and coating film. It is. When the dry film thickness T set in the dry film thickness setting step is selected from the range of 300 μm or more when the average particle diameter is less than 10 μm, it may be difficult to realize the condition (b). . When the average particle size is less than 10 μm, the oil absorption of the scaly pigment (F) is increased, and the viscosity of the coating is increased accordingly, so that the coating workability tends to be lowered. Even when the average particle size exceeds 300 μm, when the dry coating thickness T is selected from the range of 300 μm or more, realization of the above condition (b) tends not to be easy, and the surface smoothness of the coating is It tends to be lost.

The aspect ratio of the scale-like pigment (F) is preferably 2 to 100 from the viewpoint of the sufficiency of the condition (b) and the physical properties of the paint and the coating film. If the aspect ratio is high to some extent, it is easy to increase the rise of the above-mentioned graph, and therefore the aspect ratio is more preferably 3 or more, further preferably 4 or more. When the dry film thickness T is selected from the range of 300 μm or more, the aspect ratio being less than 2 is disadvantageous for achieving the condition (b). On the other hand, when the aspect ratio is excessively large, the reinforcing effect of the coating film by the scaly pigment is insufficient, and the coating film strength and the corrosion resistance are easily reduced. Therefore, the aspect ratio is more preferably 20 or less.

The average thickness of the scaly pigment (F) is preferably 2 to 50 μm. The preferred range of the average thickness can be a range derived from the preferred range of the above average particle diameter and the preferred range of the above aspect ratio, and can be, for example, the range of 2 to 30 μm (for example, 2 to 20 μm).

The scaly pigment (F) preferably has a refractive index of 1.8 or less, more preferably 1.7 or less, and still more preferably 1.6 or less. The above condition (b) is realized by reducing the refractive index and suppressing light reflection at the interface between the binder resin (epoxy resin) and the scale-like pigment (F) in the coating film to increase the light transmission amount. It can be made easy. The method of measuring the refractive index is as described in the Example section.

The scaly pigment (F) can be an extender pigment, and specifically, it can be talc, mica (mica), clay, glass flakes, aluminum hydroxide and the like. Preferred are talc, mica (mica), clay and glass flakes, and more preferred are talc, mica (mica) and glass flakes. The colored anticorrosive paint can contain one or more flaky pigments (F).

The colored anticorrosive paint can contain other extender pigments other than the scaly pigment (F). The other extender pigment may be a flat-shaped extender pigment in which any one or more of the average particle diameter, the average thickness or the aspect ratio does not satisfy the above-mentioned predetermined range, or the particulate matter having an aspect ratio of 1 or about 1 It may be a pigment. The other extender pigment may be the same material as the scale-like pigment (F) or may be a different material, and specific examples thereof include calcium carbonate in addition to those described for the scale-like pigment (F). Including magnesium carbonate, barium sulfate, silica, alumina, bentonite, silicic acid, silicate, aluminum oxide hydrate and calcium sulfate. The colored anticorrosion paint can contain one or more other extender pigments.

The content of the scaly pigment (F) is preferably 5 to 45% by volume, more preferably 10 to 40% by volume (eg 15 to 35% by volume) in the film-forming component. If the content of the scaly pigment (F) is less than 5% by volume, it is difficult to obtain the above-mentioned effect by blending it, and if not using any other extender pigment, the coating film reinforcing effect And the coating film strength and corrosion resistance tend to be insufficient. Also, when it exceeds 45% by volume, the film forming property tends to be lowered.

When the scaly pigment (F) and the other extender pigment are used in combination, the total content thereof is preferably 45% by volume or less of the coating film-forming component. Moreover, when using scale-like pigment (F) and other extender pigments in combination, the content of scale-like pigment (F) in the total content of these is 10 from the viewpoint of the sufficiency of the condition (b). The volume ratio is preferably at least 20%, more preferably at least 20%, and still more preferably at least 30%.

When the dry film thickness T set in the dry film thickness setting step is selected from the range of less than 300 μm, the colored anticorrosive paint may or may not contain scale-like pigments (F). Good.

(8) Other Compounding Components The colored anticorrosive paint can contain one or more other compounding components, if necessary. Other components include, for example, thermoplastic resins, solvents, anti-sagging agents (anti-settling agents), anti-coloring agents, anti-foaming / anti-slip agents, film-forming assistants, UV absorbers, antioxidants, A leveling agent, a matting agent, a hardening accelerator, a dispersing agent, a viscosity regulator, a surface conditioner, a plasticizer, a preservative, a reactive diluent, a non-reactive diluent, etc. can be mentioned. As a thermoplastic resin, petroleum-based resin, (meth) acrylic resin, polyester resin etc. can be used, for example. By containing a thermoplastic resin, there are cases where the physical properties of the coating can be improved. It is preferable that the content of the other compounding components is such that it does not inhibit the clear hue and background hiding property of the color pigment and does not deteriorate the film thickness determination function of the color anticorrosive paint.

As the solvent, organic solvents can be suitably used. For example, aromatic hydrocarbons such as toluene, xylene and ethylbenzene; aliphatic or alicyclic hydrocarbons such as cyclopentane, octane, heptane, cyclohexane and white spirit Petroleum fractions mainly composed of aliphatic hydrocarbons and capable of exhibiting various boiling ranges having some aromatic hydrocarbons; dioxane, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol di Ethers such as butyl ether, diethylene glycol monomethyl ether and diethylene glycol monoethyl ether; butyl acetate, propyl acetate, benzyl acetate, ethylene glycol diacetate, 2- Esters such as xylethyl acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate; ketones such as methyl ethyl ketone, ethyl isobutyl ketone, methyl isobutyl ketone; n-butanol, i-butanol, t-butanol, n Mention may be made of alcohols such as -propanol, i-propanol, benzyl alcohol. A solvent may be used individually by 1 type, and may use 2 or more types together.

(9) Preparation of colored anticorrosive paint The colored anticorrosive paint according to the present invention can be prepared in the same manner as a general anticorrosive paint using an epoxy resin. The colored anticorrosive paint according to the present invention is a two-component type, and comprises a first agent (main agent) containing at least a bisphenol A epoxy resin (A), an alicyclic amine curing agent (B) and a monoepoxide compound (C). And a second agent (hardening agent) containing at least Both the first and second agents can contain a solvent. Usually, the first agent and the second agent are mixed and coated on a substrate just before use.

In the two-component type colored anticorrosion paint, the silane coupling agent (D), the (meth) acrylate compound (E), and the other compounding components including the pigment may be blended in any of the first agent and the second agent It may be blended with both or both. Usually, a silane coupling agent (D) and a (meth) acrylate compound (E) are mix | blended with a 1st agent.

The first agent and the second agent can be prepared by mixing the blending components using a mixer such as a ball mill, a pebble mill, a roll mill, a sand grind mill, or a high speed disper.

(10) Film Thickness Judgment Function of Colored Anticorrosion Paint The color corrosion preventive paint according to the present invention is excellent in film thickness judgment function, satisfying at least the following conditions (a) and (b), and preferably satisfying the following condition (f) Paint. The “dry film thickness T” under the following conditions is, for example, a thickness selected from the range of about 10 to 500 μm, and may be selected from the range of 300 μm or more.
(A) A coating film formed of a colored anticorrosion paint having a set dry film thickness T conceals the surface of the substrate,
(B) The color difference ΔE1 between the coating formed from the colored anticorrosive paint having the set dry coating thickness T and the coating formed from the colored anticorrosive coating having a dry coating thickness of 0.7 T is 2. Is 0 or more,
(F) The color difference ΔE2 between the coating formed from the colored anticorrosive paint having the set dry coating thickness T and the coating formed from the colored anticorrosive coating having the dry coating thickness of 1.3 T is less than 1 It is.

The color differences ΔE1 and ΔE2 and ΔE3 described later are generally recognized using a color difference meter (color meter) such as a tristimulus color meter SM color meter (type SM-T45, manufactured by Suga Test Instruments Co., Ltd.) It can be measured by a method. The color differences ΔE1, ΔE2 and ΔE3 are all absolute values.

The condition (a) is a coating formed from a colored anticorrosive paint having a dry coating thickness T (here, the coating is a dry coating, but the base concealability of the wet coating and the dry coating is The same is applied to the concealability of the surface of the object to be coated. When a colored anticorrosion paint is applied to the surface of a substrate, the degree of "show-through" on the surface of the substrate decreases as the thickness of the coating increases. When the hue on the surface of the object to be coated disappears and the hue on the coated surface becomes the same as the hue of the coating film made of the colored anticorrosive paint, the coating film formed of the colored anticorrosive paint hides the surface of the object It is judged that The colored anticorrosion paint according to the present invention can achieve such concealment of the surface of a substrate when forming a dry coating having a dry coating thickness T or more.

The hiding power of the dried coating film formed from the colored anticorrosive paint can also be evaluated by the hiding ratio in accordance with JIS K 5600-4-1: 1999. In order to satisfy the above condition (a), the coating film formed of the colored anticorrosive paint having a dry coating thickness T preferably has a hiding ratio of 0.90 to 0.98, 0.92 to 0 More preferably, .98 (eg, 0.92 to 0.96).

The above condition (b) specifies the color difference ΔE1 between when the film thickness is the dry film thickness T set as the target and when it is 0.7 T in the dried coating film formed from the colored anticorrosive paint. It is The coating having a dry coating thickness of 0.7 T is the coating before the completion of the coating. A large color difference ΔE1 of 2.0 or more means that the film thickness dependency of the coating film hue in the vicinity of the completion of coating [from dry coating film thickness T (0.7 T) to dry coating film thickness T] is large. Do. As a result, it is possible to sufficiently increase the color difference between the coating film approaching the dry film thickness T considerably and the coating film reaching the dry film thickness T, so that the wet film has a target film thickness. It is possible to easily determine whether the film thickness has been reached or the film thickness is still insufficient, and it is possible to form a dry film having a dry film thickness T extremely accurately, and even a slight film thickness deficiency It can be eliminated.

The color difference ΔE1 is preferably 2.1 or more, more preferably 2.5 or more, and still more preferably 3.0 or more. However, if the color difference ΔE1 is too large, color unevenness easily occurs due to a slight difference in film thickness, so the color difference ΔE1 is preferably 10 or less, more preferably 5 or less. As described above, in the case of forming a thick film of 300 μm or more, it is preferable to use a scaly pigment (F) in order to realize the color difference ΔE1 of “2.0 or more”.

If the color difference between the coating film approaching the dry film thickness T and the coating film reaching the dry film thickness T is sufficiently large, the wet film has reached the target film thickness or still the film thickness In order to be able to determine easily whether it is insufficient, the coating film formed from the colored anticorrosive paint having the set dry coating film thickness T, and the dry coating film thickness is 0.8T The color difference ΔE1 ′ with the coating film formed of the colored anticorrosive paint is preferably 1.0 or more, more preferably 1.1 or more, and 1.2 or more (eg, 1.5 or more). Is more preferred. For the same reason, the color difference ΔE1 ′ between the coating formed from the colored anticorrosive paint having the set dry coating thickness T and the coating formed from the colored anticorrosive coating having the dry coating thickness of 0.9 T 'Is preferably 0.5 or more, more preferably 0.6 or more, and still more preferably 0.7 or more.

The above condition (f) specifies the color difference ΔE2 between when the film thickness is the dry film thickness T set as the target and when it is 1.3 T in the dried film formed from the colored anticorrosive paint. It is The coated film having a dry coating thickness of 1.3 T is a coated film after (or immediately after) the completion of the coating. When the color difference ΔE2 becomes 1 or more, the color difference between the coating having the dry coating thickness T and the coating exceeding the dry coating thickness T becomes large, and color unevenness easily occurs. The color difference ΔE2 is preferably 0.5 or less, more preferably 0.4 or less (for example, 0.2 or less).

The larger the color difference ΔE3 between the coating formed from the colored anticorrosion paint having the set dry coating thickness T and the surface of the substrate, the closer the coating thickness during coating approaches the target film thickness. Since it is easy to visually check how the color difference with the coating changes, it is easier to determine whether the wet coating film has reached the target film thickness or the film thickness is still insufficient. Accordingly, the color difference ΔE3 is preferably 20 or more [condition (g)], more preferably 25 or more, and still more preferably 30 or more. If the color difference ΔE3 is too small, it tends to be difficult to confirm whether the surface of the object to be coated is covered by the coating.

The colored anticorrosive paint satisfying the above conditions can be obtained by selecting the type (hue) of the colored pigment and adjusting the content thereof, or by adding a predetermined amount of scaly pigment (F). The set value of the dry film thickness T of the colored anticorrosive paint can be adjusted according to the content of the color pigment. That is, basically, by setting the content of the color pigment to be smaller, the set value of the dry film thickness T of the color anticorrosive paint can be made larger. In other words, since the set value of the dry coating thickness T is determined from the coating characteristics such as corrosion resistance required for the coating, the type of the object to be coated, etc. The color pigment content is adjusted to be compatible.

<Coating film formation method>
As described above, the coating film forming method according to the present invention is a method for forming a dried coating film on the surface of a substrate to be coated, and the following steps:
A step of setting a dry film thickness T (dry film thickness setting step),
A two-component colored anticorrosion paint comprising a first agent and a second agent, which is prepared to satisfy the above conditions (a) to (e) [preferably further conditions (f) and (g)] Or a step of preparing (coloring anticorrosive paint preparation step),
A step (coating step) of applying a colored anticorrosion paint to the surface of the article to be coated until the surface of the substrate is covered with a paint anticorrosion paint (coating step) Step of drying) to obtain a dried coating (drying step)
including.

The coating film forming method according to the present invention, as can be understood from the respective steps included in the present invention, defines the coating film forming method in single coating, but as long as it includes the coating film forming method in single coating All coating formation methods are included in the present invention. For example, a method of obtaining a dried coating film with a desired film thickness secured by multiple coating including the coating formation method by single coating according to the present invention is also included in the present invention. Each step will be described in detail below.

(1) Dry film thickness setting process This process is a process of setting dry film thickness T which is a film thickness of a target dry film formed by single application. In the present invention, the dry film thickness T is not particularly limited, but may be selected, for example, in the range of about 10 to 500 μm and may be selected in the range of 300 μm or more. In order to prepare or prepare a predetermined colored anticorrosive paint in the colored anticorrosive paint preparation step, the dry coating thickness T needs to be set in advance, so this step is carried out before the colored anticorrosive paint preparation step. Ru.

The dry film thickness T may be the film thickness of the dry film to be finally formed on the surface of the substrate, or may be the dry coating in the middle stage formed in forming the dry film. It may be the film thickness of the film. An example of the former is the case of forming a final dry coating film by a single coating on the surface of a substrate, and an example of the latter is a case of forming a final dry coating film by multiple coating. As a specific example of the latter, for example, after forming a dry coating film with a film thickness of 300 μm by one-time application, a dry coating film with a film thickness of 300 μm is further formed thereon, To form. The film thickness of the dried coating film to be finally formed on the surface of the substrate is usually such that the desired properties to be imparted to the surface of the substrate can be sufficiently obtained by film formation (for example, Film thickness that provides sufficient corrosion resistance).

(2) Colored Anticorrosion Paint Preparation Step This step is a two-component type colored anticorrosion paint comprising a first agent and a second agent, which comprises the conditions (a) to (e) [preferably further condition (f), (G) is a step of preparing or preparing a colored anticorrosive paint according to the present invention satisfying the above (g). The details of the colored anticorrosive paint including the preparation method are as described above, and thus are omitted here.

(3) Coating process This process is a process of applying a coloring anticorrosion paint on the surface until the surface of a to-be-coated-article is concealed by the coating film which consists of coloring anticorrosion paints. In this step, the colored anticorrosive paint is applied to the surface of the substrate while observing the change in color difference between the coating (wet film) during coating and the surface of the substrate. “To observe the change in color difference between the coating (wet coating) on the way of coating (wet coating) and the surface of the substrate” typically means that “the see-through” of the surface of the substrate has occurred on the coating surface That is, it is to observe how much the coating film (wet coating film) in the middle of coating conceals the surface of the object to be coated. More specifically, although the colored anticorrosive paint is applied to the surface of the object to be coated, since the thickness of the coating is small at the initial stage of application, the hue of the wet coating is the object to be the substrate. It largely reflects the hue of the surface (that is, the "see-through" is large). Thus, the change with respect to the hue of the to-be-coated-article surface of the hue of the coating film (wet coating film) in the middle of application is visually observed. As the thickness of the coating increases, this "see-through" decreases, and the color of the surface of the object is not reflected in the color of the wet layer, that is, when the wet layer hides the surface of the object. To reach. The base layer hiding property of the wet coating is almost the same as the base layer hiding property of the dried coating, so the coating thickness of the wet coating at this point (coating of the wet coating when the surface of the object is hidden) The film thickness) is a film thickness corresponding to the target dry film thickness T.

In the above-described coating method, it can be confirmed as follows whether or not the wet coating film has covered the surface of the object to be coated. For example, a color sample provided with a dry coating film having a target dry film thickness T is prepared in advance, and the wet coating film is coated when the hue of this color sample matches the hue of the wet coating film. It can be determined that the object surface has been hidden. In the case where a region where a coating film has been formed with a target film thickness already exists in the vicinity of the surface of the object to be coated, the hue of the coating film in this region and the wet coating film It can be judged that the wet coating film has concealed the surface of the object at the point when the color matches. In addition, since the hue of the dry coating film having the target dry coating thickness T and the wet coating film corresponding thereto is typically the same as the hue of the colored anticorrosive paint itself, the hue of the wet coating film is It can also be judged that the wet coating film has concealed the surface of the article at a point in time when it matches the color of the colored anticorrosive paint itself.

The coating method of the colored anticorrosive paint is not particularly limited, and for example, conventionally known methods such as immersion method, spray method, brush coating, roller, electrostatic coating and the like can be used. Specifically, the coating composition obtained by mixing the first agent and the second agent immediately before use is applied using the above method. Coating of the coating composition obtained by mixing the first agent and the second agent on a substrate is carried out within the pot life (useful time) after mixing the first agent and the second agent. . According to the colored anticorrosive paint of the present invention, since the pot life is long, coating workability can be improved.

The object to be coated (the object to which the colored anticorrosion paint is applied) is not particularly limited as long as it requires anticorrosion, but, for example, a ship (the inner surface of a ballast tank of a ship, the bottom of a ship, In addition to outer panels, etc.) Port facilities; Intake facilities such as power stations; Pipings such as water pipes for cooling; Bridges; Buoyancy; Industrial water systems; Submarine bases; Tanks; Marine structures such as plants (petroleum plants etc.) It can be a thing etc. The material of the surface of the article to which the colored anticorrosive paint is applied is, for example, iron-based metal such as steel (for example, steel such as untreated steel, blast-treated steel, acid-treated steel, galvanized steel, stainless steel); Non-ferrous metals such as aluminum (alloy) materials and copper (alloy) materials; concrete; plastics; and coatings such as old coatings. The old coating film refers to a coating film or a part thereof which has been previously formed and used.

The surface of the substrate to which the colored anticorrosion paint is applied may be pretreated, if necessary, and may have a subbing layer (coated film). As the said coating film, the shop primer layer formed from the conventionally well-known rust-preventive-coating composition; Other anticorrosion coating films can be mentioned. To cite again the specific example used above, another anticorrosion coating is formed by, for example, forming a dry coating with a thickness of 300 μm by a single application, and further adding a dry coating with a thickness of 300 μm thereon. It can be a dry film of the first stage in the case of forming an anticorrosion coating having a film thickness of 600 μm, which is the final objective. When a subbing layer is formed on the surface of a substrate, the "surface of the substrate" in the above conditions (a) and (g) means the surface of the subbing layer.

The other anticorrosion coating may be formed according to the method of the present invention. When forming an anticorrosion coating further on the color anticorrosion coating according to the method of the present invention, in order to satisfy the above condition (g), a color anticorrosion paint for forming an anticorrosion coating of a substrate and It is preferable that it is a different color from the coloring anticorrosion paint for the anticorrosion coating film formed, and it is preferable that the color difference of two paints is 20 or more.

(4) Drying Step This step is a step of drying the coating film (wet coating film) obtained in the coating step to obtain a dried coating film. For drying (and curing) of the wet coating, conventionally known methods can be used. The drying temperature is usually normal temperature (about 20 to 35 ° C.), but may be performed at a lower temperature or a higher temperature.

(5) Other steps A top coat may be applied on the obtained dried coating to form a top coat. Alternatively, a binder coat may be formed on the obtained dried coating, and a top coating may be applied thereon to form a top coating. As the top coat, oil based paint, long oil based phthalate resin paint, epoxy resin based paint, modified epoxy resin paint, tar epoxy resin paint, chlorinated rubber resin based paint, vinyl chloride resin based paint, alkyd resin based paint, silicone alkyd Resin paint, acrylic resin paint, urethane resin paint, fluoro resin paint, polyester resin paint, epoxy acrylic resin paint, polysiloxane resin paint, phenol resin paint, etc. 1 or 2 selected More than species can be used. The top coat may be an antifouling paint applied to marine structures, ships and the like. As an antifouling paint, the antifouling paint which uses acrylic resin which has a hydrolysable group in a side chain as binder resin can be mentioned. The hydrolyzable group can be, for example, a metal ester group containing a metal atom such as divalent Cu or Zn, a trialkylsilyl ester group, or the like. The dry film thickness of the top coat film is usually about 10 to 300 μm.

The top coat may also be the colored anticorrosive paint according to the present invention. One embodiment in the case where the colored anticorrosive paint of the present invention is a top coat is formed of the colored anticorrosive paint according to the present invention on the old paint film formed from the colored anticorrosive paint according to the present invention, for example, for repair. It is a case of forming a coating film. The colored anticorrosive paint according to the present invention can also be used exclusively for forming a top coat, not a primer coat. The dry film thickness of the top coat film formed from the colored anticorrosive paint according to the present invention is usually about 10 to 500 μm.

The anticorrosive coating film formed from the colored anticorrosion paint according to the present invention can exhibit good anticorrosion and can exhibit good adhesion to a base or a topcoat film.

According to the method for forming a coating film using the colored anticorrosive paint according to the present invention, it can be easily determined whether or not the coating film during coating has reached a predetermined film thickness. The uniform coating film can be formed accurately. In this way, it is possible to effectively prevent the film thickness shortage that often occurs in the past. In addition, since excessive film thickness can be prevented, it is also possible to save paint.

In addition, according to the method for forming a coating film using the colored anticorrosive paint according to the present invention, it is possible to avoid the complicated work of sequentially measuring the thickness of the coating film and checking whether or not the predetermined film thickness is reached. While being able to aim at significant efficiency-ization of coating operation, the burden reduction of the coating operator can be aimed at. Furthermore, since the colored anticorrosive paint according to the present invention exhibits a good pot life, coating workability can be improved also in this respect.

The coating film forming method using the colored anticorrosive paint according to the present invention can be applied to the anticorrosion coating of various structures (in particular, ships and marine structures). According to the method of the present invention, in the case of applying anticorrosion coating to the outer surface of a large structure such as a ship or the like, even a structure or a portion thereof which is difficult to be coated has a predetermined dry film thickness. The coating film can be formed accurately and simply.

EXAMPLES The present invention will be more specifically described below by showing Examples and Comparative Examples, but the present invention is not limited by these examples. In addition, except for "PVC" in the table, parts and% are based on mass unless otherwise specified.

<Examples 1 to 13 and Comparative Example 1: Preparation of Colored Anticorrosion Paint>
According to the composition shown in Table 1 or Table 2, the respective components were mixed to prepare a first agent (main agent) and a second agent (hardener), respectively, to obtain a two-component type colored anticorrosive paint. The details of each compounding component shown in Tables 1 and 2 are as follows. In addition, the unit of the compounding quantity shown to a table | surface is the mass part converted into solid content.

Tables 1 and 2 also show the volume% indication (volume% in the film forming component) of the blending amount of the color pigment and the extender pigment. The film-forming component means all components other than the solvent contained in the colored anticorrosive paint. In addition, the setting value T of the dried coating thickness targeted by each colored anticorrosive coating, and the hiding ratio of the dried coating of each colored coating having the dried coating thickness T (“dried coating thickness T in Tables 1 and 2 It is indicated collectively as "the concealment rate in.

In Tables 1 and 2, "amine" in "amine / epoxy equivalent ratio (colored anticorrosive paint)" indicates the following component [17], and "epoxy" means the following components [1] and [2]. And [3]. In Tables 1 and 2, “(C) / (B) equivalent ratio (second agent)” means the monoepoxide compound (C) [solid content] contained in the second agent and the alicyclic amine curing The equivalent ratio to the agent (B-1) [solid content] is meant, and "(C) / (B) equivalent ratio (colored anticorrosion paint)" is a monoepoxide compound (C And the equivalent ratio of [solid content] to the alicyclic amine curing agent (B-1) [solid content].

[1] Bisphenol A (BFA) type epoxy resin (A): Bisphenol A type epoxy resin manufactured by Dow Chemical, trade name "DOW 331", epoxy equivalent weight: 189 g / eq, number average molecular weight (standard polystyrene conversion by GPC measurement) : 355, nonvolatile matter (solid content): 100% by mass,
[2] Bisphenol F (BFF) type epoxy resin: Bisphenol F type epoxy resin manufactured by DIC Corporation, trade name "EPICLON 830", epoxy equivalent: 180 g / eq, number average molecular weight (standard polystyrene conversion by GPC measurement): 290 Nonvolatile matter (solid content): 100% by mass, specific gravity: 1.1,
[3] Monoepoxide compound (C): 3-n-pentadecadienylphenyl glycidyl ether manufactured by Cardolite, trade name "Caldolite Lite 2513HP", epoxy equivalent weight: 413, nonvolatile matter (solid content): 100% by mass, Specific gravity: 1.1,
[4] Silane coupling agent (D): γ-glycidyloxypropyltrimethoxysilane manufactured by EVONIK DEGUSSA, trade name “DYNASYLAN GLYMO”, nonvolatile content (solid content): 100% by mass,
[5] Color pigment 1: Titanium oxide (white pigment) manufactured by Ishihara Sangyo Co., Ltd., trade name "CR50", nonvolatile content (solid content): 100% by mass, specific gravity: 4.1,
[6] Coloring pigment 2: Yellow iron oxide manufactured by Titan Kogyo Co., Ltd., trade name "TAROX synthetic iron oxide LL-XLO", nonvolatile matter (solid content): 100% by mass, specific gravity: 4.1,
[7] Constitutional pigment 1: Glass flakes manufactured by Nippon Sheet Glass Co., Ltd., trade name "RCF-140", average particle diameter: 149 μm, average thickness: 28 μm, aspect ratio: 5.3, refractive index: 1.5, non-volatile Minute: 100 mass%, specific gravity: 2.5,
[8] Constitutional pigment 2: Talc manufactured by Fuji Talc Industrial Co., Ltd., trade name "talc DS34-N", average particle diameter: 17 μm, average thickness: 4 μm, aspect ratio: 4.3, refractive index: 1.6, Nonvolatile content: 100% by mass, specific gravity: 2.7,
[9] Body pigment 3: Talc made by Fuji Talc Co., Ltd., trade name "talc SP 42", average particle diameter: 14 μm, average thickness: 4 μm, aspect ratio: 3.5, refractive index: 1.6, nonvolatile matter: 100 mass%, specific gravity: 2.7,
[10] Body pigment 4: Talc manufactured by Fuji Talc Co., Ltd., trade name "talc TPA-25", average particle diameter: 8 μm, average thickness: 3 μm, aspect ratio: 2.7, refractive index: 1.6, non-volatile Minutes: 100% by mass, specific gravity: 2.7,
[11] Constitution pigment 5: Mica manufactured by Kirara Co., Ltd., trade name "white mica 200M", average particle diameter: 78 μm, average thickness: 8 μm, aspect ratio: 9.8, refractive index: 1.6, nonvolatile matter: 100 mass%, specific gravity: 2.7,
[12] Body pigment 6: Mica manufactured by Mintech International, trade name "MT-MICA D325W", average particle size: 39 μm, average thickness: 7 μm, aspect ratio: 5.6, refractive index: 1.6, nonvolatile matter : 100 mass%, specific gravity: 2.8,
[13] Anticorrosion pigment: hemihydrate gypsum (β gypsum) manufactured by Noritake Co., Ltd .: trade name “TA-85N”, nonvolatile matter (solid content): 100% by mass,
[14] Solvent: benzyl alcohol,
[15] Anti-Dare agent: Anti-Dare agent manufactured by Enomoto Kasei Co., Ltd., trade name “Disparon 6700”, Non-volatile content (solid content): 100% by mass,
[16] Defoamer: Defoamer manufactured by Kushimoto Chemical Co., Ltd., trade name "Disparon # 1983", nonvolatile matter (solid content): 100% by mass,
[17] Alicyclic amine curing agent (B-1): Modified alicyclic polyamine manufactured by Air Products Co., Ltd., trade name "Ancamine 2280", amine equivalent: 110 mg KOH / g, nonvolatile matter (solid content): 54 mass%,
[18] Aliphatic polyamine curing agent: Modified aliphatic polyamine manufactured by Cardolite Chemical, trade name "CARDOLITE NX-5168", nonvolatile content: 64% by mass, specific gravity of nonvolatile content: 1.2.

The alicyclic amine curing agent (B-1) contains 2,4-di (4-aminocyclohexylmethyl) aniline as a main component (60% by mass or more), and in addition, 2,4-di (4-) Aminocyclohexylmethyl) cyclohexylamine and a mixture of polyamines including partially hydrogenated trimethylenetetraaniline or an analogue thereof and the like.

The average particle size, average thickness, aspect ratio and refractive index of an extender pigment such as scale-like pigment, and the hiding ratio of the dried coating of each colored anticorrosive coating having the dried coating thickness T (the dried coating thickness of each colored anticorrosive coating The concealment rate at T) was measured according to the following method.

[A] Average particle diameter, average thickness and aspect ratio of an extender pigment: A particle image of the extender pigment is photographed using a powder image analyzer ("PITA-3" manufactured by Seishin Enterprise Co., Ltd.), and a photographed image obtained Among them, 50 particles taken in a direction perpendicular to the main surface of the particles were selected, and the major axis and the minor axis of each particle were measured. The average value of the major axes of the 50 particles was taken as the average particle size of the extender pigment, and the average value of the minor axes of the 50 particles was taken as the average thickness of the extender pigment. Also, the aspect ratio was calculated by dividing the average particle size by the average thickness. The measurement conditions of the above-mentioned powder image analysis device are as follows.

Dispersion medium of sample liquid and its flow rate: water, 0.42 μL / sec,
-Types of first and second carrier liquids and their flow rates: water, 500 μL / sec, both
-Observation magnification of photographed image: 10 times.

[B] Refractive index of extender pigment The refractive index of the extender pigment was measured according to JIS K 0062: 1992.

[C] Concealment ratio at dry coating thickness T of colored anticorrosion paint According to JIS K 5600-4-1: 1999, concealment of dry coated film of each colored anticorrosive paint whose film thickness is the set value T of dry coating thickness The rate was measured.

The amount ratio of the first agent (main agent) and the second agent (hardener) of the obtained two-component colored anticorrosion paint is shown in the "total" column in Table 1 or Table 2 (for example, in the case of Example 1) First agent: Second agent = 81.26 parts by mass: 19.90 parts by mass) The mixture was sufficiently stirred and homogenized to obtain a mixed paint (anticorrosion paint composition). The following evaluation test was done about the obtained mixed paint (anticorrosion paint composition). The test results are shown in Table 3.

[1] Pot Life Evaluation Test The pot life of the anticorrosion paint composition at 5 ° C., 10 ° C., and 25 ° C. was measured in accordance with JIS K 5600-2-6: 1999.

[2] Electric corrosion resistance evaluation test (cathode corrosion test)
First, an inorganic zinc shop primer (trade name "Ceramo") manufactured by Nippon Paint Marine Co., Ltd. was coated on a grid blasted steel plate (7 cm x 15 cm x 3.2 mm) so that its dry coating thickness would be about 15 m. By drying for 7 days, a primer-treated steel plate was produced. Subsequently, the above-mentioned anticorrosion paint composition immediately after preparation is applied to the primer-treated steel sheet with an air spray so as to have a dry coating thickness of about 250 μm, and it is performed for 7 days under an atmosphere of 23 ° C. × 65% RH. Each test board was obtained by drying. Using this test plate, it was tested and evaluated according to ASTM G8-90. That is, first, a 6.3 mm diameter drill blade was used at the center of the immersion portion of the test surface (painted surface) of the test coating plate to produce a plate having a 6.3 mm diameter base exposed portion. Next, this plate was immersed in an aqueous solution of 40 ° C. containing 1% by weight each of NaCl, Na ₂ SO ₄ , and Na ₂ CO ₃ to apply a potential of 1.5 V, and after 1 month, the coating from the exposed area was The length [creep width, mm] of the peeled portion of the film was measured. The numerical values (creep width) described in Table 3 are the average values of the results of immersion in the above three types of aqueous solutions. The smaller the creep width, the better the corrosion resistance.

[3] 40 ° C water resistance evaluation test (corrosion resistance evaluation test)
First, an inorganic zinc shop primer (trade name "Ceramo") manufactured by Nippon Paint Marine Co., Ltd. was coated on a grid blasted steel plate (7 cm x 15 cm x 3.2 mm) so that its dry coating thickness would be about 15 m. By drying for 7 days, a primer-treated steel plate was produced. Next, the above-mentioned anticorrosion coating composition immediately after preparation is applied to the primer-treated steel sheet with an air spray so as to have a dry coating thickness of about 250 μm, for 7 days under an atmosphere of 20 ° C. × 65% RH. Each test board was obtained by drying. Next, each of the test boards was immersed in pure water at 40 ° C. for 3 months. The adhesion (MPa) to a primer-treated steel plate of a coating film after immersion for 3 months was measured using an adhesion tester made by Elcometer.

[4] 40 ° C saltwater resistance evaluation test (corrosion resistance evaluation test)
First, an inorganic zinc shop primer (trade name "Ceramo") manufactured by Nippon Paint Marine Co., Ltd. was coated on a grid blasted steel plate (7 cm x 15 cm x 3.2 mm) so that its dry coating thickness would be about 15 m. By drying for 7 days, a primer-treated steel plate was produced. Next, the above-mentioned anticorrosion coating composition immediately after preparation is applied to the primer-treated steel sheet with an air spray so as to have a dry coating thickness of about 250 μm, for 7 days under an atmosphere of 20 ° C. × 65% RH. Each test board was obtained by drying. Next, each test board was immersed in 3% saline at 40 ° C. for 3 months. The adhesion (MPa) to a primer-treated steel plate of a coating film after immersion for 3 months was measured using an adhesion tester made by Elcometer.

[5] Moisture resistance evaluation test (corrosion resistance evaluation test)
First, an inorganic zinc shop primer (trade name "Ceramo") manufactured by Nippon Paint Marine Co., Ltd. was coated on a grid blasted steel plate (7 cm x 15 cm x 3.2 mm) so that its dry coating thickness would be about 15 m. By drying for 7 days, a primer-treated steel plate was produced. Next, the above-mentioned anticorrosion coating composition immediately after preparation is applied to the primer-treated steel sheet with an air spray so as to have a dry coating thickness of about 250 μm, for 7 days under an atmosphere of 20 ° C. × 65% RH. Each test board was obtained by drying. Next, each of the test coated plates was allowed to stand for 3 months in a wet environment at a temperature of 50 ° C. and a relative humidity of 95% using a wet testing machine CT-3 (JIS K 5600-7-2: 1999). The adhesion (MPa) of the coating film to the primer-treated steel plate after the 3-month wet resistance test was measured using an adhesion tester made by Elcometer.

<Examples 14 to 28, Comparative Example 2: Formation of a dry film thickness using a colored anticorrosive paint>
Apply a shop primer ("Nippe Seramo Gray" or "Nippe Seramo Brown" manufactured by Nippon Paint Marine Co., Ltd.) to a 900 mm × 900 mm satin steel plate so that the dry film thickness is 15 μm, and allow 24 hours or more at room temperature. It dried and produced the test plate. In Tables 4 to 6, "Nippe Ceramo Gray" and "Nippe Ceramo Brown" are abbreviated as "Gray" and "Brown", respectively.

The amount ratio of the first agent (main agent) and the second agent (hardener) of the obtained two-component colored anticorrosion paint is shown in the "total" column in Table 1 or Table 2 (for example, in the case of Example 1) First agent: Second agent = 81.26 parts by mass: 19.90 parts by mass) The mixture was sufficiently stirred and homogenized to obtain a mixed paint (anticorrosion paint composition).

Next, on the shop primer surface of the test plate obtained, the mixed paint shown in Tables 4 to 6 prepared above by the airless spray method and mixed with the two solutions of the first agent and the second agent (anticorrosion paint The composition was applied and allowed to dry at room temperature for 24 hours to form an anticorrosive coating. Under the present circumstances, in each of each Example and a comparative example, several dry anti-corrosion coatings which have a dry film thickness shown in Table 4-Table 6 were formed. The dry film thickness of each coating was measured using an electromagnetic film thickness meter "COATING THICKNESS TESTER LE-900" manufactured by Ketto Co., Ltd.

Measurement according to JIS K 5600-4-5: 1999, using Suga Test Instruments Co., Ltd.'s tristimulus colorimeter SM color computer "SM-7CH" and calculation according to JIS K 5600-4-6: 1999 Thus, the color difference ΔE between the obtained anticorrosion coating film having each dried film thickness and the anticorrosion coating film having the set value T of the dried coating film thickness targeted by each colored anticorrosion paint was determined. The results are shown in Tables 4 to 6. Moreover, the base | substrate hiding property (hiding property of the shop primer coating film by the anticorrosion coating film) in the wet coating film state of the anticorrosion coating film which shows each dry film thickness was visually observed, and it evaluated based on the following judgment criteria. The results are shown together in Tables 4 to 6. For each example and comparative example, a graph with the dry film thickness (μm) shown in Tables 4 to 6 as the horizontal axis and the ΔE shown in Tables 4 to 6 as the vertical axis is shown in FIGS. Show.

A: I'm hiding
B: Slightly transparent,
C: It is totally transparent.

In Table 4 to Table 6, ΔE at a dry film thickness of 0 μm means the color difference between the anticorrosive coating film having a dry film thickness of T and the surface of the object to be coated (shop primer coating film surface). It is synonymous with color difference ΔE3.

Examples 29 to 35, Comparative Examples 3 to 6>
Each component is mixed according to the formulation shown in Table 7 to prepare a first agent (main agent) and a second agent (hardener), and a two-component type colored anticorrosion paint (anticorrosion paint composition) Obtained. The details of each ingredient shown in Table 7 are as follows. In addition, the unit of the compounding quantity shown to a table | surface is the mass part converted into solid content.

[1] Bisphenol A (BFA) type epoxy resin (A): Bisphenol A type epoxy resin manufactured by Dow Chemical, trade name "DOW 331", epoxy equivalent weight: 189 g / eq, number average molecular weight (standard polystyrene conversion by GPC measurement) : 355, nonvolatile matter (solid content): 100% by mass,
[2] Bisphenol F (BFF) type epoxy resin: Bisphenol F type epoxy resin manufactured by DIC Corporation, trade name "EPICLON 830", epoxy equivalent: 180 g / eq, number average molecular weight (standard polystyrene conversion by GPC measurement): 290 Non volatile matter (solid content): 100% by mass
[3] Curing agent (B-1): Modified alicyclic polyamine manufactured by Air Products, trade name "Ankamin 2280", amine equivalent: 110 mg KOH / g, nonvolatile matter (solid content): 54% by mass,
[4] Hardening agent (B-2): Aliphatic polyamine manufactured by Daito Sangyo Co., Ltd., trade name "Dytokraal D-6017", amine equivalent: 104 mg KOH / g, nonvolatile matter (solid content): 100% by mass,
[5] Monoepoxide compound (C-1): 3-n-pentadecadienylphenyl glycidyl ether manufactured by Cardolite, trade name "Caldolite Lite 2513HP", epoxy equivalent weight: 413, nonvolatile matter (solid content): 100 mass %,
[6] Monoepoxide compound (C-2): alkyl glycidyl ether compound manufactured by Air Products (with 12 to 14 carbon atoms in alkyl portion), trade name "Epodil 748", epoxy equivalent weight: 288, nonvolatile matter (solid content) : 100% by mass,
[7] Diepoxide compound: neopentyl glycol diglycidyl ether manufactured by Air Products, trade name "Epodil 749", epoxy equivalent: 137, nonvolatile matter (solid content): 100% by mass,
[8] Silane coupling agent (D): γ-glycidyloxypropyltrimethoxysilane manufactured by EVONIK DEGUSSA, trade name “DYNASYLAN GLYMO”, nonvolatile content (solid content): 100% by mass,
[9] Color pigment 1: Titanium oxide (white pigment) manufactured by Ishihara Sangyo Co., Ltd., trade name "CR50", nonvolatile content (solid content): 100% by mass,
[10] Coloring pigment 2: Yellow iron oxide manufactured by Titanium Industry Co., Ltd., trade name “TAROX Synthetic iron oxide LL-XLO”, nonvolatile matter (solid content): 100% by mass,
[11] Constitutional pigment 1: Glass flakes manufactured by Nippon Sheet Glass Co., Ltd., trade name "RCF-140", nonvolatile content (solid content): 100% by mass,
[12] Body pigment 2: Talc manufactured by Fuji Talc Industrial Co., Ltd., trade name "talc 34-N", nonvolatile matter (solid content): 100% by mass,
[13] Anticorrosion pigment: hemihydrate gypsum (β gypsum) manufactured by Noritake Co., Ltd .: trade name “TA-85N”, nonvolatile matter (solid content): 100% by mass,
[14] Anti-Dare agent: Anti-Dare agent manufactured by Enomoto Chemical Co., Ltd., trade name “Disparon 6700”, Non-volatile content (solid content): 100% by mass,
[15] Antifoaming agent: Antifoaming agent manufactured by Enomoto Chemical Co., Ltd., trade name "Disparon # 1983", nonvolatile matter (solid content): 100% by mass,
[16] Solvent: benzyl alcohol.

The curing agent (B-1) contains 2,4-di (4-aminocyclohexylmethyl) aniline as a main component (60% by mass or more), and in addition, 2,4-di (4-aminocyclohexylmethyl) cyclohexyl It is a mixture of amines and polyamines including partially hydrogenated trimethylene tetraaniline or its analogs and the like.

In Table 7, “amine” in “amine / epoxy equivalent ratio” is a generic name of the above components [3] to [4], and “epoxy” is the above components [1], [2], It is a generic term for [5] to [7]. In Table 7, “(C) / (B) equivalent ratio (second agent)” refers to the monoepoxide compound (C) [solid content] contained in the second agent and the amine curing agent (B) [B. "(C) / (B) equivalent ratio (anticorrosion coating composition)" means an equivalent ratio to the solid content], a monoepoxide compound (C) [solid content] contained in the entire anticorrosion coating composition It means the equivalent ratio of the amine curing agent (B) [solid content].

The amount ratio of the first agent (main agent) and the second agent (hardener) of the obtained two-pack anticorrosion paint composition is shown in the "total" column in Table 7 (for example, in the case of Example 29, the first agent : The second agent = 79.32 parts by mass: 18.26 parts by mass), and the mixture was sufficiently stirred and homogenized. The following evaluation test was done about the obtained mixed paint (anticorrosion paint composition). The test results are shown in Table 8. However, in Comparative Example 6, since the second agent (hardening agent) caused gelation, it was not possible to conduct an evaluation test on the pot life.

[2] Electric corrosion resistance evaluation test (cathode corrosion test)
First, an inorganic zinc shop primer (trade name "Ceramo") manufactured by Nippon Paint Marine Co., Ltd. was coated on a grid blasted steel plate (7 cm x 15 cm x 3.2 mm) so that its dry coating thickness would be about 15 m. By drying for 7 days, a primer-treated steel plate was produced. Subsequently, the above-mentioned anticorrosion paint composition immediately after preparation is applied to the primer-treated steel sheet with an air spray so as to have a dry coating thickness of about 250 μm, and it is performed for 7 days under an atmosphere of 23 ° C. × 65% RH. Each test board was obtained by drying. Using this test plate, it was tested and evaluated according to ASTM G8-90. That is, first, a 6.3 mm diameter drill blade was used at the center of the immersion portion of the test surface (painted surface) of the test coating plate to produce a plate having a 6.3 mm diameter base exposed portion. Next, this plate was immersed in an aqueous solution of 40 ° C. containing 1% by weight each of NaCl, Na ₂ SO ₄ , and Na ₂ CO ₃ to apply a potential of 1.5 V, and after 1 month, the coating from the exposed area was The length [creep width, mm] of the peeled portion of the film was measured. The numerical values (creep width) described in Table 8 are the average values of the results of immersion in the above three types of aqueous solutions.

Claims

A two-component anticorrosion paint composition comprising a first agent and a second agent, wherein
The first agent contains bisphenol A epoxy resin (A),
The second agent contains an amine curing agent (B) and a monoepoxide compound (C),
The amine curing agent (B) has the following formula (B-1):

[In formula (B-1), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a methyl group, x is 1 to 3 and y is 0 to 2, and x and y The total of is 2 to 4. ]
The anticorrosive coating composition containing the alicyclic amine compound (B-1) represented by these.
The amine curing agent (B) has the following formula (b-1):

The anticorrosion paint composition according to claim 1, comprising 2,4-di (4-aminocyclohexylmethyl) aniline represented by
The anticorrosive coating composition according to claim 1, wherein the content of the monoepoxide compound (C) in the second agent is 5 to 50 parts by mass with respect to 100 parts by mass of the amine curing agent (B).
The equivalent ratio of the monoepoxide compound (C) contained in the second agent and the amine curing agent (B) is 1/5 to 1/40 according to any one of claims 1 to 3. Anticorrosion paint composition.
The anticorrosive coating composition according to any one of claims 1 to 4, wherein the monoepoxide compound (C) comprises a phenyl glycidyl ether compound.
The anticorrosive coating composition according to any one of claims 1 to 5, further comprising a silane coupling agent (D).
A coating film formed from the anticorrosion paint composition according to any one of claims 1 to 6.
A ship or marine structure provided with the coating film according to claim 7.
A method for forming a dried coating on the surface of a substrate, comprising:
Following process:
[1] a step of setting a dry film thickness T;
[2] A two-component colored anticorrosion paint comprising a first agent and a second agent, which comprises the following conditions (a) to (e):
(A) The coating film formed from the colored anticorrosion paint having the dry coating thickness T conceals the surface of the object to be coated,
(B) A color difference ΔE1 between a coating formed of the colored anticorrosive paint having the dry coating thickness T and a coating formed of the colored anticorrosive coating having a dry coating thickness of 0.7 T is 2. Is 0 or more,
(C) containing a color pigment,
(D) The first agent contains a bisphenol A type epoxy resin (A), and the second agent contains an amine curing agent (B) and a monoepoxide compound (C).
(E) The amine curing agent (B) has the following formula (B-1):

[In formula (B-1), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a methyl group, x is 1 to 3 and y is 0 to 2, and x and y The total of is 2 to 4. ]
Containing an alicyclic amine compound (B-1) represented by
Preparing or preparing a colored anticorrosive paint satisfying
[3] a step of applying the colored anticorrosive paint to the surface until the surface of the object to be coated is covered with a coating film made of the colored anticorrosive paint;
[4] A step of drying the coated film obtained by the step of the above-mentioned [3] to obtain a dried coated film,
Method, including.
The colored anticorrosion paint is subjected to the following condition (f):
(F) The color difference ΔE2 between the coating formed of the colored anticorrosive paint having the dry coating thickness T and the coating formed of the colored anticorrosive coating having a dry coating thickness of 1.3 T is less than 1 Is
10. The method of claim 9, further satisfying
The said color anticorrosive paint is the following conditions (g):
(G) A color difference ΔE3 between the coating film formed from the colored anticorrosion paint having the dry coating thickness T and the surface of the article is 20 or more.
The method according to claim 9 or 10, further satisfying
The method according to any one of claims 9 to 11, wherein the coating film formed from the colored anticorrosive paint having the dry coating thickness T has a hiding factor of 0.90 to 0.98.
The method according to any one of claims 9 to 12, wherein the content of the color pigment is 0.01 to 3% by volume in the film-forming component.
The amine curing agent (B) has the following formula (b-1):

The method according to any one of claims 9 to 13, comprising 2,4-di (4-aminocyclohexylmethyl) aniline represented by
The content of the monoepoxide compound (C) in the second agent is 5 to 50 parts by mass with respect to 100 parts by mass of the amine curing agent (B). Method described.
The equivalent ratio of the monoepoxide compound (C) contained in the second agent and the amine curing agent (B) is 1/5 to 1/40, according to any one of claims 9 to 15. Method described.
The method according to any one of claims 9 to 16, wherein the monoepoxide compound (C) comprises a phenyl glycidyl ether compound.
The method according to any one of claims 9 to 17, wherein the colored anticorrosive paint further contains a silane coupling agent (D).
The colored anticorrosion paint further contains flake pigments (F) having an average particle size of 10 to 300 μm, an average thickness of 2 to 50 μm, and an aspect ratio of 2 to 100 defined as an average particle size / average thickness,
The method according to any one of claims 9 to 18, wherein the content of the scaly pigment (F) is 5 to 45% by volume in the film-forming component.
The method according to claim 19, wherein the scaly pigment (F) is at least one pigment selected from the group consisting of talc, mica and glass flakes.
It is a two-component colored anticorrosion paint comprising a first agent and a second agent, which is used to form a dry coating film having a dry coating thickness T on the surface of a substrate,
The following conditions (a) to (e):
(A) The coating film formed from the colored anticorrosion paint having the dry coating thickness T conceals the surface of the object to be coated,
(B) A color difference ΔE1 between a coating formed of the colored anticorrosive paint having the dry coating thickness T and a coating formed of the colored anticorrosive coating having a dry coating thickness of 0.7 T is 2. Is 0 or more,
(C) containing a color pigment,
(D) The first agent contains a bisphenol A type epoxy resin (A), and the second agent contains an amine curing agent (B) and a monoepoxide compound (C).
(E) The amine curing agent (B) has the following formula (B-1):

[In formula (B-1), R 1 , R 2 and R 3 each independently represent a hydrogen atom or a methyl group, x is 1 to 3 and y is 0 to 2, and x and y The total of is 2 to 4. ]
Containing an alicyclic amine compound (B-1) represented by
Meet the colored anticorrosive paint.
Following condition (f):
(F) The color difference ΔE2 between the coating formed of the colored anticorrosive paint having the dry coating thickness T and the coating formed of the colored anticorrosive coating having a dry coating thickness of 1.3 T is less than 1 Is
The colored anticorrosive paint according to claim 21, further satisfying
Following condition (g):
(G) A color difference ΔE3 between the coating film formed from the colored anticorrosion paint having the dry coating thickness T and the surface of the article is 20 or more.
The colored anticorrosive paint according to claim 21 or 22, further satisfying
The colored anticorrosive paint according to any one of claims 21 to 23, wherein a coating formed from the colored anticorrosive paint having the dry coating thickness T has a hiding ratio of 0.90 to 0.98.
The colored anticorrosive paint according to any one of claims 21 to 24, wherein the content of the color pigment is 0.01 to 3% by volume in the coating film-forming component.
The amine curing agent (B) has the following formula (b-1):

The colored anticorrosive paint according to any one of claims 21 to 25, which comprises 2,4-di (4-aminocyclohexylmethyl) aniline represented by
The content of the monoepoxide compound (C) in the second agent is 5 to 50 parts by mass with respect to 100 parts by mass of the amine curing agent (B). Colored anticorrosive paint as described.
The equivalent ratio of the monoepoxide compound (C) to the amine curing agent (B) contained in the second agent is 1/5 to 1/40, according to any one of claims 21 to 27. Colored anticorrosive paint as described.
The color and anticorrosive paint according to any one of claims 21 to 28, wherein the monoepoxide compound (C) comprises a phenyl glycidyl ether compound.
The colored anticorrosive paint according to any one of claims 21 to 29, further comprising a silane coupling agent (D).
It further contains a scale-like pigment (F) having an average particle size of 10 to 300 μm, an average thickness of 2 to 50 μm, and an aspect ratio of 2 to 100 defined as an average particle size / average thickness,
The colored anticorrosive paint according to any one of claims 21 to 30, wherein the content of the scaly pigment (F) is 5 to 45% by volume in the coating film-forming component.
The pigmented anticorrosion paint according to claim 31, wherein the scaly pigment (F) is at least one pigment selected from the group consisting of talc, mica and glass flakes.