JP2017025158A - Anticorrosion coating composition, anticorrosion coating film, substrate with anticorrosion coating film, and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anticorrosive coating material composition that does not need to remove a deteriorated coating layer on the surface of a deteriorated coating film, in particular, a deteriorated coating film formed from a tar epoxy resin coating material, a tar urethane resin coating material, a modified epoxy resin coating material, a modified urethane resin coating material, an epoxy resin coating material, an urethane resin coating material, an organic zinc coating material, an inorganic zinc coating material and the like, and can form a coating film having excellent anticorrosion properties and good adhesive properties even on a wet surface in which freed moisture adheres on the surface of the deteriorated coating film; an anticorrosive coating film; a base material with an anticorrosive coating film; and a method for producing the base material with the coating film.SOLUTION: An anticorrosive coating material composition capable of being coated onto a wet surface of a base material covered with a deteriorated coating film contains: an epoxy resin (A); at least one amine curing agent (B) selected from polyoxyalkylene polyamines, Mannich modified amines and ketimines; 1-15 pts.wt. of water (C) with respect to 100 pts.wt. of the coating material composition (nonvolatile content); and a flat pigment (D).SELECTED DRAWING: None

Description

  The present invention provides a coating film selected from a deteriorated coating film surface, particularly a tar epoxy resin paint, a tar urethane resin paint, a modified epoxy resin paint, a modified urethane resin paint, an epoxy resin paint, a urethane resin paint, an organic zinc paint, an inorganic zinc paint, etc. Without removing the deteriorated layer of the deteriorated coating film formed by the above, even on a wet surface where free moisture adheres to the surface of the deteriorated coating film, the anticorrosion property is excellent, and Anticorrosion coating composition capable of forming a coating film excellent in adhesion of the anticorrosion coating film, an anticorrosion coating film formed from the anticorrosion coating composition, a substrate with an anticorrosion coating film coated with the anticorrosion coating film, and the The present invention relates to a method for producing a substrate with an anticorrosion coating.

  For large steel structures such as ships, land structures, bridges, etc., to prevent corrosion, tar epoxy resin paint, tar urethane resin paint, modified epoxy resin paint, modified urethane resin paint, epoxy resin paint, urethane resin paint, It is coated with an anticorrosive coating with an anticorrosive paint such as an organic zinc paint or an inorganic zinc paint. However, since the surface of the anticorrosion coating film deteriorates due to aging, outdoor exposure, submersion, etc., periodic repair is required. If the deterioration coating is repaired with a general anticorrosion paint without pretreatment, sufficient adhesion cannot be obtained between the deterioration coating and the anticorrosion coating that has been repaired. There is a problem of causing cracks and peeling.

  Conventionally, as a countermeasure to the above-mentioned problems, when a repair paint is applied to the surface of the deteriorated paint film, the deteriorated layer of the deteriorated paint film is removed by blasting, electric tools, hand tools, water jets, etc. Paint is applied. However, since the removal of this deteriorated layer requires a great deal of labor and cost, a repair coating that can be applied by simple pretreatment with only water washing that does not require such removal treatment is desired. Furthermore, in order to reduce the drying process of the deteriorated coating film washed with water, even if repair coating is performed on the wet surface of the above deteriorated coating film, it is possible to form a coating film having excellent anticorrosion properties that does not cause problems such as cracking and peeling. If an anticorrosive coating composition can be developed, it is particularly difficult to completely dry the surface of a deteriorated coating film such as a ballast tank, or repair work where it is difficult to take sufficient drying time after water washing, It is also suitable for outdoor repair applications that are affected by the weather, and is effective in reducing labor and costs for such repairs.

  In Patent Document 1, 1 to 30 parts by weight per 100 parts by weight of organic solvent-type or solventless-type paint solids containing an epoxy resin having one or more epoxy groups in one molecule and an amine curing agent as resin components The coating composition characterized by containing the above-mentioned moisture, and the coating composition characterized in that the coating composition is applied to the surface of a deteriorated coating film formed from a highly anticorrosive coating such as a tar epoxy resin coating A method is disclosed.

  In Patent Document 2, a tar epoxy resin coating film, a tar urethane resin coating film, a modified epoxy resin coating film, a modified urethane resin coating film, an epoxy-polyamine resin coating film, and an epoxy urethane resin coating film are used. Epoxy-polyamine resin-based paint containing an epoxy resin having one or more epoxy groups in one molecule and an amine curing agent as a resin component on a deteriorated coating film having a water content of 0.3 to 5% by weight A repair coating method characterized by painting a coating is disclosed.

  In Patent Document 3, in a two-component reaction curable epoxy resin compound that does not contain an organic succinate, water is contained in at least one of the epoxy compound side and the curing agent side, thereby having thixotropy when mixed. A stop agent is disclosed.

  In patent document 1, the coating to the base material with a deterioration coating film is examined, and it is clarified that the composition currently disclosed is excellent in the initial adhesiveness with respect to a deterioration coating film. However, in general, it is known that the adhesion of a coating film is lowered by exposure to salt water and a high-temperature and high-humidity environment. In the coating film formed by the composition disclosed in Patent Document 1, Adhesion to deteriorated coatings for anticorrosion applications that are often exposed to the above environment is insufficient. Moreover, although the composition disclosed here has not been studied for coating on a substrate with a deteriorated coating film having a wet surface, adhesion to a substrate with a deteriorated coating film having a wet surface is also insufficient. .

  In Patent Document 2, a repair coating method for a deteriorated coating film having a predetermined moisture content in the coating film is examined, and in the [0016] paragraph, moisture may be condensed on the coating film surface. It is described that it is desirable that there is no free moisture on the surface of the coating film visually. In Examples of Patent Document 2, various moisture contents of the deteriorated coating film are measured by the Karl Fischer method. In paragraph [0017], there is free water on the surface of the coating film to be measured. In some cases, after removal, the moisture content is measured by the Karl Fischer method. Therefore, the application to the base material with a deteriorated coating film having a wet surface has not been studied. In addition, the epoxy-polyamine resin-based paint disclosed in Patent Document 2 does not have the technical idea of actively containing water in the paint composition, and has a substrate with a deteriorated coating film having a wet surface. Adhesion to is insufficient.

  Patent Document 3 does not discuss the coating on a substrate with a deteriorated coating film or its wet surface, but the composition disclosed here has insufficient adhesion to any substrate.

Japanese Patent Laid-Open No. 2001-2986 Japanese Patent Laid-Open No. 2001-300417 Japanese Patent Laid-Open No. 6-172697

  The present invention is intended to solve the above-mentioned problems in the prior art, and the surface of the deteriorated coating film, particularly tar epoxy resin paint, tar urethane resin paint, modified epoxy resin paint, modified urethane resin paint, epoxy resin paint, Without removing the deteriorated layer on the surface of the deteriorated coating formed by a paint selected from urethane resin paint, organic zinc paint, inorganic zinc paint, etc., the deteriorated paint film has a wet surface. Anti-corrosion coating composition, anti-corrosion coating film, base material with anti-corrosion coating film, and method for producing the base material with coating film The purpose is to provide.

  As a result of intensive studies on the method for solving the above problems, the present inventors have selected an amine curing agent having an affinity for water for the epoxy resin-based anticorrosion paint, and a predetermined amount in the anticorrosion paint. It has been found that the above object can be achieved by containing water and a flat pigment, and the present invention has been completed.

The configuration of the present invention is as follows.
A coating composition that can be applied to a wet surface of a substrate coated with a deteriorated coating film,
Epoxy resin (A),
At least one amine curing agent (B) selected from polyoxyalkylene polyamines, Mannich-modified amines and ketimines;
1 to 15 parts by weight of water (C) with respect to 100 parts by weight (nonvolatile content) of the coating composition,
A flat pigment (D);
An anticorrosive coating composition comprising:

  The deteriorated coating film is made of one kind of paint selected from tar epoxy resin paint, tar urethane resin paint, modified epoxy resin paint, modified urethane resin paint, epoxy resin paint, urethane resin paint, organic zinc paint, inorganic zinc paint, and the like. A formed coating film is preferred.

  The amine curing agent (B) preferably contains at least polyoxyalkylene polyamines among polyoxyalkylene polyamines, Mannich-modified amines and ketimines.

  It is preferable to contain at least 0.01 to 20 parts by weight (nonvolatile content) of polyoxyalkylene polyamines as the amine curing agent (B) with respect to 100 parts by weight (nonvolatile content) of the anticorrosive coating composition. .

It is preferable that the anticorrosion coating composition further contains at least one selected from the group consisting of a reactive diluent (E1) having an epoxy group and a modified epoxy resin (E2).
The anticorrosion coating film according to the present invention is formed from the anticorrosion coating composition.

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

  The method for producing a substrate with an anticorrosive coating film according to the present invention comprises the steps of coating the anticorrosive coating composition on the surface of the substrate with a deteriorated coating film, and curing the coated anticorrosive coating composition to prevent corrosion. A step of forming a coating film.

  The anticorrosion paint composition according to the present invention is an anticorrosion selected from tar epoxy resin paint, tar urethane resin paint, modified epoxy resin paint, modified urethane resin paint, epoxy resin paint, urethane resin paint, organic zinc paint, inorganic zinc paint, etc. Without removing the deteriorated layer of the deteriorated coating film formed by the paint, the surface of the deteriorated coating film (hereinafter referred to as the dried deteriorated coating film) to which free moisture is not adhered is used. Even if it is applied to the wet surface, it is possible to form an anticorrosion coating film having excellent anticorrosion properties and excellent adhesion.

FIG. 1 is a schematic view showing an example of the top coat adhesion test of the anticorrosive coating film.

  Hereinafter, the anticorrosion coating composition, the anticorrosion coating film, the substrate with the anticorrosion coating film, and the production method thereof according to the present invention will be described in detail including preferred embodiments.

<Anti-corrosion paint composition (also referred to as anti-corrosion paint)>
The anticorrosion coating composition according to the present invention comprises an epoxy resin (A), at least one amine curing agent (B) selected from polyoxyalkylene polyamines, Mannich-modified amines and ketimines, and the coating composition 100. It contains 1 to 15 parts by weight of water (C) and a flat pigment (D) with respect to parts by weight (nonvolatile content).

  The anticorrosion coating composition according to the present invention preferably further includes at least one selected from the group consisting of a reactive diluent (E1) having an epoxy group and a modified epoxy resin (E2).

<Base material with deteriorated coating film>
The base material with a deteriorated coating film according to the present invention is, for example, coated with a deteriorated coating film formed by a general anticorrosive paint composition or the like on the surface of a base material such as metal, wood, plastic, stone, slate, concrete, mortar, Has been. In particular, the surface of the substrate is one kind of paint selected from tar epoxy resin paint, tar urethane resin paint, modified epoxy resin paint, modified urethane resin paint, epoxy resin paint, urethane resin paint, organic zinc paint, inorganic zinc paint, etc. It is preferably coated with a deteriorated coating film formed by the above, and formed by one kind of paint selected from epoxy resin anticorrosion paints such as tar epoxy resin paint, modified epoxy resin paint, epoxy resin paint, epoxy zinc paint, etc. More preferably, the coated film is covered with a deteriorated coating film.

<Wet surface>
In the present invention, the moisture content of the wet surface is determined by spraying water on the surface of the dried deteriorated coating film by spraying water uniformly and measuring the weight (unit: g) of the sprayed moisture. The moisture adhesion amount (unit: g / m ² ) on the film surface was examined. In addition, when water has already adhered to the surface of a steel plate or a deteriorated coating film to form a wet surface, the moisture content (unit: g / m ² ) of the wet surface is, for example, the weight by drying the wet surface It can be measured by determining the decrease (unit: g).

The wet surface of the deteriorated coating film to which the anticorrosive coating composition according to the present invention is applied is, in its preferred embodiment, when the surface of a steel sheet or the like that is a non-water-absorbing substrate is coated with the deteriorated coating film. In general, 5 to 45 g / m ² of water adheres to the surface of the coating film, and the released moisture can usually be confirmed visually. For example, a wet surface is assumed to be attached to the surface of a deteriorated coating film of a large steel structure due to rain, washing with water, or dew condensation under high humidity. In particular, in a closed space such as a ballast tank, the humidity tends to be high due to the water used for cleaning the deteriorated coating film and the residual water of the ballast water. Often occurs.

<Epoxy resin (A)>
In the anticorrosion coating composition according to the present invention, the epoxy resin (A) is a polymer or oligomer containing two or more epoxy groups in the molecule, and a polymer or oligomer produced by a ring-opening reaction of the epoxy groups. Examples thereof include bisphenol type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin and the like. Among these, bisphenol-type epoxy resins are preferable from the viewpoint that an anticorrosion coating having excellent adhesion to a deteriorated coating film can be formed, and bisphenol A-type and bisphenol F-type bisphenol-type epoxy resins are more preferable. Bisphenol A epoxy resin is preferred, and particularly preferred. Moreover, the said epoxy resin (A) can be used individually by 1 type or in combination of 2 or more types.

  Examples of the bisphenol A-type epoxy resin include condensation polymers of bisphenol A-type diglycidyl ethers, and examples of bisphenol A-type diglycidyl ethers that form the condensation polymer include bisphenol A diglycidyl ether and bisphenol. A polypropylene oxide diglycidyl ether, bisphenol A ethylene oxide diglycidyl ether, and the like.

  The epoxy resin (A) is liquid at room temperature in the state before reaction curing with the amine curing agent (B), etc. from the viewpoint that it can form an anticorrosion coating film exhibiting excellent adhesion to a deteriorated coating film. Or a semi-solid thing is preferable.

  The epoxy equivalent of the epoxy resin (A) is preferably 150 to 1000, more preferably 150 to 800, and particularly preferably 180 to 700 from the viewpoint of corrosion resistance and the like. The epoxy equivalent is calculated based on JIS K 7236.

  The epoxy resin (A) may be synthesized by a conventionally known method or may be a commercially available product. Among the epoxy resins (A) used in the present invention, “E028” (manufactured by Otake Akira Shin Chemical Co., Ltd., bisphenol A type epoxy resin) is used as a liquid at room temperature (temperature of 15 to 25 ° C., the same shall apply hereinafter). , Epoxy equivalent 180-190, nonvolatile content 100%), “jER 807” (Mitsubishi Chemical Corporation, bisphenol F type epoxy resin, epoxy equivalent 160-175, nonvolatile content 100%), “E-028-90X” (Made by Otake Akira Shin Chemical Co., Ltd., xylene solution of bisphenol A type epoxy resin (828 type epoxy resin solution, epoxy equivalent 200-210, nonvolatile content 90%), etc. “JER 834” (manufactured by Mitsubishi Chemical Corporation, bisphenol A type epoxy resin, epoxy equivalent 230-270, nonvolatile content 100%), “E-8 34-85X "(manufactured by Otake Akira Shin Chemical Co., Ltd., xylene solution of bisphenol A type epoxy resin (834 type epoxy resin solution, epoxy equivalent of 270 to 320, non-volatile content of 85%), etc. As a thing, "jER 1001" (Mitsubishi Chemical Corporation make, bisphenol A type epoxy resin, epoxy equivalent 450-500, non-volatile content 100%), "E-001-75" (Otake Akira Shin Chemical Co., Ltd. make, Examples include xylene solutions of bisphenol A type epoxy resins (1001 type epoxy resin solutions), epoxy equivalents of 600 to 660, and non-volatile content of 75%.

  The epoxy resin (A) is preferably 5 to 40 parts by weight (nonvolatile content), more preferably 10 to 30 parts by weight (nonvolatile content) with respect to 100 parts by weight (nonvolatile content) of the anticorrosive coating composition of the present invention. It is desirable to be included in an amount of.

  When the anticorrosive coating composition of the present invention is a two-component coating composition comprising a main component and a curing agent component, the epoxy resin (A) is contained in the main component, and 100 parts by weight of the main component ( The non-volatile content is preferably 5 to 80 parts by weight (non-volatile content), more preferably 5 to 50 parts by weight (non-volatile content).

  In addition, the non-volatile content is a sufficiently reactive curing with respect to the anticorrosion coating composition in the anticorrosion coating composition according to the present invention containing a reactive component (eg, epoxy resin (A), amine curing agent (B), etc.). It means the percentage by weight of the coating film made of the paint. According to JIS K5601-1-2, the non-volatile content is obtained by heating a sample obtained by collecting 1 ± 0.1 g of the anticorrosive coating composition at a heating temperature of 125 ° C. for 1 hour (under normal pressure) to obtain a heating residue. , And calculated as a weight percentage of the heating residue with respect to the coating composition.

Similarly, the non-volatile content of each component of the anticorrosion coating composition according to the present invention can be calculated in accordance with JIS K5601-1-2.
<Amine curing agent (B)>
In the anticorrosion coating composition according to the present invention, as the amine curing agent (B), at least one amine curing agent selected from polyoxyalkylene polyamines having affinity with water, Mannich-modified amines, and ketimines is used. contains.

  In addition to the polyoxyalkylene polyamines, Mannich-modified amines, and ketimines that are amine curing agents (B), the curing agent component of the anticorrosion coating composition according to the present invention includes a conventional epoxy resin-based anticorrosion coating. Any amine curing agent other than the amine curing agent (B) used (eg, polyamidoamine, aliphatic amine, alicyclic amine, aromatic amine, aliphatic amine adduct, etc.) can be included.

In particular, the curing agent component contains a polyoxyalkylene polyamine alone as the amine curing agent (B) or a polyoxyalkylene polyamine and other amine curing agent (B), and if necessary, amine curing Any amine curing agent other than the agent (B) may be used in combination, and the formed anticorrosion coating is not only a dry deterioration coating but also a deterioration coating having a wet surface, in particular, moisture on the surface of the deterioration coating. Since there exists a tendency which shows the outstanding adhesiveness with respect to the deterioration coating film whose adhesion amount is 5-45 g / m < ² >, it is preferable.

  That is, as an aspect of the amine curing agent (B), (i) only polyoxyalkylene polyamines, (ii) polyoxyalkylene polyamines, Mannich modified amines, (iii) polyoxyalkylene polyamines, and ketimines (Iv) Four aspects of polyoxyalkylene polyamines, Mannich-modified amines and ketimines are excellent not only in adhesion to a dry deteriorated coating film but also in adhesion to a deteriorated coating film having a wet surface. Is preferable. Furthermore, as said hardening | curing agent component, in addition to said (i)-(iv), arbitrary amine hardening | curing agents other than an amine hardening | curing agent (B) can be included.

  When the polyoxyalkylene polyamine is used in combination with any amine curing agent other than the amine curing agent (B) or the amine curing agent (B), 100 parts by weight of the anticorrosive coating composition (non-volatile content) ), The polyoxyalkylene polyamines as the amine curing agent (B) are preferably 0.01 to 20 parts by weight (nonvolatile content), more preferably 1 to 10 parts by weight (nonvolatile content), particularly preferably. It is desirable to contain in an amount of 2 to 8 parts by weight (nonvolatile content).

  In the anticorrosion coating composition according to the present invention, the amine curing agent (B) and the epoxy resin (A) have an equivalent ratio (active hydrogen equivalent / epoxy equivalent), preferably 0.3 to 1.5, More preferably, the amount used is 0.4 to 1.0 in view of curing speed, anticorrosiveness and the like.

  As polyoxyalkylene polyamines used in the present invention, "Jeffamine D-230" (manufactured by Huntsman Japan Co., Ltd., polyoxypropylenediamine, active hydrogen equivalent 60, non-volatile content 100%), "Jeffamine D-400" (Manufactured by Huntsman Japan Co., Ltd., polyoxypropylene diamine, active hydrogen equivalent 115), “Jeffamine D-2000” (manufactured by Huntsman Japan Co., Ltd., polyoxypropylene diamine, active hydrogen equivalent 514) and “Jeffamine T- 403 "(manufactured by Huntsman Japan Co., Ltd., polyoxypropylene triamine, active hydrogen equivalent 81).

  As the Mannich modified amines used in the present invention, “MAD-204 (A)” (manufactured by Akira Ohtake Shin Chemical Co., Ltd., Mannich modified aliphatic polyamine, active hydrogen equivalent 202, nonvolatile content 65%), “Adeka Hardener EH-342W 3 "(manufactured by ADEKA, Mannich-modified polyamidoamine, active hydrogen equivalent 110)," Sunmide CX-1154 "(manufactured by Sanwa Chemical Co., Ltd., Mannich-modified aliphatic polyamine, active hydrogen equivalent 255), "Cardolite NX-4918" (manufactured by Cardlite, phenalkamine which is a Mannich-modified amine of cardanol and amine, active hydrogen equivalent 255, non-volatile content 80%), "Cardolite NC556X80" (manufactured by Cardlight, phenalkamine adduct, Active hydrogen equivalent 135), Fenalca Examples include phenalkamide, which is a reaction product of min and carboxylic acids.

Examples of the ketimines used in the present invention include “Ancamine 2459” (manufactured by Air Products Co., Ltd., active hydrogen equivalent 101, nonvolatile content 80%) and the like.
As an optional amine curing agent other than the amine curing agent (B), “PA-290 (A)” (manufactured by Akira Ohtake Shin Chemical Co., Ltd., polyamidoamine, active hydrogen equivalent 277, nonvolatile content 59%), “ Sunside P-1003 "(produced by Air Products Co., Ltd., aliphatic amine adduct, active hydrogen equivalent 125, nonvolatile content 60%)," AD-200P "(produced by Akira Otake Shin Chemical Co., Ltd., aliphatic amine adduct (Metal) Xylenediamine epoxy adduct), active hydrogen equivalent 155, non-volatile content 90%) and the like.

<Water (C)>
In the anticorrosive coating composition according to the present invention, the water (C) is 1 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 1 to 100 parts by weight (nonvolatile content) of the anticorrosive coating composition. It is desirable to be included in an amount of ˜7 parts by weight.

  When the water (C) in the anticorrosion coating composition is less than 1 part by weight, the adhesion between the deteriorated coating film and the formed anticorrosion coating film is insufficient when coated on the deteriorated coating film having a wet surface. It becomes. On the other hand, when it exceeds 15 parts by weight, the anticorrosive property of the anticorrosive coating film tends to be lowered.

<Flat pigment (D)>
In the anticorrosive coating composition according to the present invention, the flat pigment (D) has a median diameter (D50) of 30 to 200 μm and an average aspect ratio (median diameter / average thickness) of 30 to 100. However, it is desirable in terms of improving the adhesion with a deteriorated coating film.

  The median diameter (D50) can be measured using a laser scattering diffraction type particle size distribution measuring device, for example, “SALD 2200” (manufactured by Shimadzu Corporation). The average thickness is observed from the horizontal direction with respect to the main surface of the flat pigment (D) using a scanning electron microscope (SEM), for example, “XL-30” (manufactured by Philips), and several tens to several hundreds The average value can be calculated by measuring the thickness of each pigment particle.

  Examples of the flat pigment (D) include mica, glass flakes, and the like, which are inexpensive and easy to obtain, and can more easily obtain an adhesion improving effect by relaxing the internal stress of the coating film. Mica is preferred. Examples of the mica include “Suzolite Mica 200-HK” (manufactured by West Japan Trading Co., Ltd., median diameter (D50): 65 μm, average aspect ratio: 54).

  Moreover, the said flat pigment (D) can be used individually by 1 type or in combination of 2 or more types.

  The flat pigment (D) is preferably 1 to 40 weights with respect to 100 parts by weight (nonvolatile content) of the anticorrosive coating composition of the present invention from the viewpoint that an excellent anticorrosive coating film can be formed due to the above effects. Parts, more preferably 3-20 parts by weight.

  As a reason why the anticorrosion coating film formed by the anticorrosion coating composition according to the present invention has excellent adhesion to the surface of the deteriorated coating film, the present inventors have adhered to the dry deteriorated coating film surface ( Reason 1) or adhesion to the surface of a deteriorated coating film having a wet surface (reason 2) is estimated as follows.

(Reason 1)
Regardless of the type of resin in the paint forming the deteriorated coating film, the deteriorated coating film changes its surface from hydrophobic to hydrophilic when immersed in seawater or exposed to sunlight. Tend. By adding a certain amount of water to the anticorrosive coating composition to be coated on the surface of the deteriorated coating, the coating becomes highly hydrophilic and easily adheres to the surface of the deteriorated coating. To do. Furthermore, the internal stress of the anticorrosion coating film formed is relieved by including a flat pigment in the anticorrosion coating composition. Therefore, the anticorrosion coating composition according to the present invention has excellent adhesion to a dried deteriorated coating film.

(Reason 2)
By adding a specific amine curing agent having an affinity for water to the anticorrosion coating composition, the anticorrosion coating composition becomes a factor that inhibits adhesion when the anticorrosion coating composition is applied to the wet surface of the deteriorated coating film. It shows the effect of incorporating part or all of the free water adhering to the surface of the deteriorated coating film into the anticorrosion paint instead of flipping it. Here, the amine curing agent having an affinity for water is at least one amine curing agent selected from polyoxyalkylene polyamines, Mannich-modified amines, and ketimines. Since the polyoxyalkylene polyamines have a highly polar ether bond in the molecule and the Mannich-modified amines have a hydroxyl group in the molecule, and thus have an affinity for water, Shows the effect of incorporating into anticorrosion paints. In addition, the ketimines react with moisture and produce an amine curing agent and a ketone, and thus exhibit the effect of incorporating the liberated moisture into the anticorrosion paint. Furthermore, since the hydrophilic property of the paint is increased by adding a predetermined amount of water to the anticorrosion paint composition, it becomes easy to get wet (easy to adapt) to the deteriorated coating film surface as in (Reason 1). In addition, the effect of taking in the released moisture is also improved. However, the effect of incorporating the liberated moisture into the anticorrosion paint only by containing only one of a specific amine curing agent having an affinity for water or a predetermined amount of water in the anticorrosion paint composition. It is not sufficient, and adhesion to the surface of a deteriorated coating film having a wet surface cannot be obtained.

  In order for the anticorrosion coating composition to exhibit excellent adhesion to the surface of a deteriorated coating film having a wet surface, the effect of incorporating the liberated moisture into the anticorrosion coating is not sufficient, and a specific amine curing agent and By incorporating a flat pigment in addition to a predetermined amount of water, the effect of improving the adhesion due to the relaxation of the internal stress of the anticorrosive coating film to be formed can be obtained as in (Reason 1). Therefore, the anticorrosive coating composition according to the present invention has the effect of incorporating the liberated moisture into the anticorrosive coating and the synergistic effect of the adhesion improving effect due to the relaxation of the internal stress on the surface of the deteriorated coating film having a wet surface. It has excellent adhesiveness.

<Other coating film forming components that can be added to the main component>
The main component of the anticorrosive coating composition according to the present invention is selected from the group consisting of a reactive diluent (E1) having an epoxy group and a modified epoxy resin (E2) as an additive in addition to the epoxy resin (A). At least one selected from the group consisting of

Examples of the reactive diluent (E1) having an epoxy group include phenyl glycidyl ether, alkyl glycidyl ether (alkyl group having 1 to 15 carbon atoms, preferably 11 to 15), versatic acid, and glycidyl ester. _{(R 1 R 2 R 3 C} -COO-Gly, alkyl group of _{R 1 + R 2 + R 3} = C8~C10, Gly: glycidyl group), alpha-olefin epoxide _{(CH 3 - (CH 2)} n-Gly, n = 11 to 13, Gly: the same as above), 1,6-hexanediol diglycidyl ether _{(Gly-O- (CH 2)} 6 -O-Gly, Gly: the same as above), neopentyl glycol diglycidyl ether (Gly-O- _{CH 2 -C (CH 3) 2} -CH 2 -O-Gly, Gly: the same as above), trimethylol Propane triglycidyl ether _{(CH 3 -CH 2 -C (CH} 2 -O-Gly) 3, Gly: the same as above), alkyl phenyl glycidyl ether (alkyl having a carbon number of groups 1-20, preferably 1-5, such as methyl Phenyl glycidyl ether, ethylphenyl glycidyl ether, propylphenyl glycidyl ether) and the like.

  Among these reactive diluents (E1) having an epoxy group, monofunctional phenyl glycidyl ether, alkyl glycidyl ether, and alkyl phenyl glycidyl ether have a low viscosity, so they are excellent in dilution effect (low viscosity of paint). , Which can contribute to high solidification of the paint (increasing the content of the film forming component contained in the paint composition can suppress the shrinkage of the paint film due to solvent evaporation), resulting in a wet surface. This is preferable because it improves the adhesion to the deteriorated coating film.

  The reactive diluent (E1) having an epoxy group can be used alone or in combination of two or more. As the reactive diluent (E1) having such an epoxy group, “Epodil 759” (manufactured by Air Products, alkyl (C12-C13) glycidyl ether, epoxy equivalent 285, nonvolatile content 100%), “Cardolite” 2513HP "(manufactured by Cardlight, alkylphenol glycidyl ether, epoxy equivalent 400, nonvolatile content 100%).

  The reactive diluent (E1) having an epoxy group is preferably 0 to 40 weights with respect to 100 parts by weight (nonvolatile content) of the epoxy resin (A) in the main component of the anticorrosive coating composition according to the present invention. Part (nonvolatile content), more preferably 0 to 20 parts by weight (nonvolatile content).

Examples of the modified epoxy resin (E2) include fatty acid-modified epoxy resins and hydrogenated epoxy resins.
The fatty acid-modified epoxy resin used in the present invention is preferably obtained by dimer acid-modifying the epoxy resin (A) having an epoxy equivalent of preferably 150 to 1,000, more preferably 170 to 700, and particularly preferably 400 to 600. . When the epoxy equivalent of the epoxy resin (A) exceeds 1,000, the crosslinking density of the cured coating film made of the fatty acid-modified epoxy resin becomes low, and the corrosion resistance inherent in the epoxy resin tends to be impaired.

  The dimer acid is a dimer of unsaturated fatty acid and usually contains a small amount of monomer or trimer. As the unsaturated fatty acid, a carboxylic acid having 12 to 24, preferably 16 to 18, carbon atoms (including the carbon atom of the carboxyl group) and having one or more unsaturated bonds in one molecule. A compound is used. Examples of such unsaturated fatty acids include fatty acids having one unsaturated bond such as oleic acid, elaidic acid, and celetic acid; fatty acids having two unsaturated bonds such as sorbic acid and linoleic acid; linolenic acid and arachidone Examples include fatty acids having 3 or more unsaturated bonds such as acids. Furthermore, fatty acids obtained from animals and plants can also be used, and examples thereof include soybean oil fatty acid, tall oil fatty acid, linseed oil fatty acid and the like.

  The amount of modification by dimer acid in the fatty acid-modified epoxy resin is 4 to 30 parts by weight (nonvolatile content), preferably 5 to 20 parts by weight (nonvolatile content) with respect to 100 parts by weight (nonvolatile content) of the epoxy resin (A). It is desirable to be. If the amount of modification is less than 4 parts by weight (nonvolatile content), the resulting modified epoxy resin has low compatibility with the aromatic solvent, and the flexibility is not sufficient. On the other hand, when the amount of modification exceeds 30 parts by weight (nonvolatile content), the corrosion resistance and adhesion inherent in the epoxy resin tend to be impaired.

  The fatty acid-modified epoxy resin is obtained by reacting the epoxy resin (A) having the above-mentioned preferable epoxy equivalent with dimer acid. When the epoxy equivalent of the epoxy resin (A) used for the fatty acid-modified epoxy resin is less than 150, it tends to be difficult to synthesize a fatty acid-modified epoxy resin whose amount of modification by dimer acid is 4 parts by weight (nonvolatile content) or more. is there.

  A method for synthesizing the fatty acid-modified epoxy resin used in the present invention is not particularly limited, and a known method is used. For example, a method in which a solid or semi-solid epoxy resin is first synthesized at room temperature by a reaction between a liquid epoxy resin and bisphenol or a reaction between epichlorohydrin and bisphenol, and then a fatty acid is added and reacted (2 Step method), liquid epoxy resin, bisphenol, and fatty acid (one step method).

  In the two-stage method, an epoxy resin is first synthesized at a temperature of 50 to 250 ° C., preferably 100 to 200 ° C., using a catalyst used in a normal epoxidation reaction. Specific examples of the catalyst used in this synthesis include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide; alkali metal alcoholates such as sodium methylate; lithium chloride and lithium carbonate Alkali metal salts; tertiary amines such as dimethylbenzylamine, triethylamine and pyridine; quaternary ammonium salts such as tetramethylammonium chloride and benzyltrimethylammonium chloride; organophosphorus compounds such as triphenylphosphine, triethylphosphine and triphenylphosphine Lewis acids such as arsenic trifluoride, aluminum chloride, tin tetrachloride, diethyl ether complex of arsenic trifluoride; methyl iodide adducts and the like.

  Next, a predetermined amount of fatty acid is added to the epoxy resin obtained as described above, and an epoxy resin is added at 100 to 200 ° C. in the presence of a catalyst such as a tertiary amine, a quaternary ammonium salt, or a methyl iodide adduct. The resin and the fatty acid are reacted. In the one-step method in which the liquid epoxy resin, bisphenol, and fatty acid are reacted simultaneously, a catalyst such as a tertiary amine, a quaternary ammonium salt, or a methyl iodide adduct is added to these components at 100 to 200 ° C. Reaction is performed to synthesize a fatty acid-modified epoxy resin. The amount of catalyst used in these reactions is preferably about 0.01 to 10,000 ppm, more preferably about 0.1 to 1,000 ppm, based on the total weight of the reactants.

  Examples of the fatty acid-modified epoxy resin include “KE-8174X90” (manufactured by KOLON Chemical Co., Ltd., xylene cut product, epoxy equivalent 230 to 270, non-volatile content 90%), “DME-111” (manufactured by Otake Akira Shin Chemical Co., Ltd.) Xylene cut product, epoxy equivalent 260, non-volatile content 90%) and the like.

  The hydrogenated epoxy resin used in the present invention is an ordinary temperature obtained by selectively hydrogenating an epoxy resin having an aromatic ring with an epoxy equivalent of 150 to 1,000 under pressure in the presence of a catalyst. The liquid form is preferable.

  Examples of the epoxy resin having an aromatic ring include bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, and bisphenol S type epoxy resins; naphthalene type epoxy resins, phenol novolac epoxy resins, cresol novolac epoxy resins. Novolak type epoxy resins such as hydroxybenzaldehyde phenol novolac epoxy resin; polyfunctional type epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyvinylphenol.

  Among these epoxy resins having an aromatic ring, bisphenol A type epoxy resin, bisphenol F type epoxy resin, and phenol novolac type epoxy resin are preferable.

The hydrogenated epoxy resin can be produced by a conventionally known hydrogenation method. For example, the epoxy resin having an aromatic ring as a raw material is dissolved in an ether organic solvent such as tetrahydrofuran or dioxane, and reacted in the presence of a catalyst in which rhodium or ruthenium is supported on graphite (hexagonal crystal graphite). Thus, the aromatic ring can be selectively hydrogenated. As the graphite, surface area of ^{10 m} 2 / g or more, 400 meters ² / g following can be used. The above reaction is usually performed at a pressure of 1 to 30 MPa and a temperature of 30 to 150 ° C. over 1 to 20 hours. After completion of the reaction, the catalyst is removed by filtration, and the target hydrogenated epoxy resin is obtained by distilling off under reduced pressure until the ether organic solvent is substantially eliminated.

  Examples of the hydrogenated epoxy resin include “Licar Resin HBE-100” (manufactured by Shin Nippon Rikagaku Co., Ltd., diglycidyl ether of alicyclic diol, epoxy equivalent 215, nonvolatile content 100%) and the like.

  The modified epoxy resin (E2) can be used alone or in combination of two or more. Moreover, the modified epoxy resin (E2) is preferably 0 to 100 parts by weight (nonvolatile content) with respect to 100 parts by weight (nonvolatile content) of the epoxy resin (A) in the main component of the anticorrosive coating composition according to the present invention. ), More preferably 0 to 50 parts by weight (nonvolatile content), and particularly preferably 0 to 30 parts by weight (nonvolatile content).

<Other components that can be added to the curing agent component>
In addition to the amine curing agent (B), the curing agent component of the anticorrosion coating composition according to the present invention can optionally contain a curing accelerator that can contribute to adjustment of the curing rate, particularly acceleration. Examples of the curing accelerator include tertiary amines.

Examples of the curing accelerator include triethanolamine (N (C ₂ H ₅ OH) ₃ ), dialkylaminomethanol ({CH ₃ (CH ₂ ) _n } ₂ NCH ₂ OH, n: number of repetitions), triethylenediamine (1 , 4-diazacyclo (2,2,2) octane), 2,4,6-tri (dimethylaminomethyl) phenol (C ₆ H ₅ —CH ₂ N (CH ₃ ) ₂ , specifically “Versamine EH30 ": Henkel Hakusui Co., Ltd.," Ancamine K-54 ": Air Products Co., Ltd.) and the like. These curing accelerators are contained in an amount of 0.1 to 2.0 parts by weight (non-volatile content) as necessary with respect to 100 parts by weight (non-volatile content) of the anticorrosive coating composition of the present invention.

<Other ingredients>
In addition to the various components described so far, the anticorrosive coating composition according to the present invention includes, as necessary, a pigment other than the flat pigment (D), a solvent, a silane coupling agent, a wetting and dispersing agent, a plasticizer. An agent, an anti-sagging / anti-settling agent, an inorganic dehydrating agent (stabilizer), an antifouling agent and the like can be included as long as the object of the present invention is not impaired.

<Pigments other than flat pigment (D)>
The pigment is not particularly limited as long as it is other than the flat pigment (D), and those generally used in coating compositions can be used. For example, barium sulfate, potassium feldspar, barite powder, Examples include extender pigments such as silica, calcium carbonate, and talc, and colored pigments such as titanium white, petiole, yellow petiole, and carbon black. The said pigment can be used individually by 1 type or in combination of 2 or more types.

<Solvent>
The solvent is not particularly limited by the boiling point as long as it can dissolve the epoxy resin (A), and may be appropriately selected and used depending on the coating workability of the anticorrosive coating composition according to the present invention. it can. Examples of the solvent include xylene, toluene, MIBK (methyl isobutyl ketone), 1-methoxy-2-propanol, MEK (methyl ethyl ketone), butyl acetate, n-butanol, iso-butanol, IPA (isopropyl alcohol) and the like. These solvents can be used singly or in combination of two or more.

  In the present invention, the amount of these solvents is usually not particularly limited, but in the case of using an aromatic solvent such as xylene or toluene from the viewpoint of adhesion to the wet surface of the deteriorated coating film, the anticorrosive paint of the present invention. It is preferably contained in an amount of 0 to 20 parts by weight, more preferably 0 to 10 parts by weight with respect to 100 parts by weight (nonvolatile content) of the composition.

<Silane coupling agent>
The silane coupling agent is not particularly limited, and a conventionally known silane coupling agent can be used. However, the silane coupling agent has at least two hydrolyzable groups in the same molecule. Preferably, it is a compound that can contribute to lowering, for example, the formula: X-SiMe _n Y _3-n [n is 0 or 1, X is a reactive group capable of reacting with an organic substance (eg, amino group, vinyl) A group, an epoxy group, a mercapto group, a halogen group, or a hydrocarbon group containing these groups, and a group formed by substituting an ether bond for a bond between carbon atoms of the hydrocarbon group. It is a methyl group, and Y represents a hydrolyzable group (eg, methoxy group, ethoxy group). ] It is more preferable that it is a compound represented by these. Examples of such silane coupling agents include “KBM403” (manufactured by Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane).

  When the silane coupling agent is used, it is preferably 0.1 to 10 parts by weight (nonvolatile content), more preferably 0.5 to 5 parts by weight with respect to 100 parts by weight (nonvolatile content) of the anticorrosive coating composition of the present invention. It is desirable to be included in the amount of parts (non-volatile content). When the silane coupling agent is used in such an amount in the anticorrosion coating composition according to the present invention, the coating performance such as adhesion of the resulting anticorrosion coating is improved, and particularly in the high solid anticorrosion coating composition, the coating viscosity is increased. Lowering improves paint workability.

<Wet dispersant>
The wetting and dispersing agent preferably has a polyalkyl ether structure. For example, “Plisurf A208B” (Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene lauryl ether phosphate, non-volatile content 98%), “ Plysurf A208F "(Daiichi Kogyo Seiyaku Co., Ltd., polyoxyethylene alkyl (C8) ether phosphate ester) and the like. These wetting and dispersing agents can be used alone or in combination of two or more.

<Plasticizer>
The plasticizer is not particularly limited, and a conventionally known plasticizer can be used, and the flexibility and weather resistance of the resulting anticorrosion coating film can be improved. In particular, it is desirable to use a plasticizer having a reactive group in terms of improving adhesion to a deteriorated coating film having a wet surface.

  Examples of the plasticizer include liquid hydrocarbon resins such as low-boiling fractions obtained by thermally decomposing naphtha that is liquid at room temperature, petroleum-based resins that are solid at room temperature, xylene resins, coumarone indene resins, and the like. It is done. Examples thereof include liquid hydrocarbon resins and flexibility imparting resins described in JP-A-2006-342360.

  Examples of commercially available liquid hydrocarbon resins include “Nesiles EPX-L”, “Nesiles EPX-L2” (manufactured by NEVCIN, phenol-modified hydrocarbon resin), “HILENOL PL-1000S” (manufactured by KOLON Chemical Co., Ltd., Phenol-modified hydrocarbon resins) and petroleum-based resins are commercially available as “Neopolymer E-100”, “Neopolymer K-2”, “Neopolymer K3” (above, Shin Nippon Petrochemical Co., Ltd., C9 Commercial hydrocarbon resin) and coumarone indene resin are “NOVARES CA 100” (Rutgers Chemicals AG), and xylene resin is “Nikanol Y-51” (Mitsubishi Gas Chemical Co., Ltd.). ) And the like.

<Use of the anticorrosion coating composition according to the present invention>
Large steel structures such as ships, land structures, bridges, etc. are covered with anticorrosion coatings intended to prevent corrosion, but the coatings deteriorate over time, exposure to the outdoors, submersion, etc. , Requires regular repair painting. The anticorrosion coating composition according to the present invention is an anticorrosion agent without removing a deteriorated layer on the surface of the deteriorated coating film, and even on a wet surface where free moisture adheres to the surface of the deteriorated coating film. It is possible to form a coating film having excellent properties and adhesion. Therefore, it is particularly affected by structures such as ballast tanks where it is difficult to completely dry the deteriorated paint film surface, repair work where it is difficult to take sufficient time to dry the deteriorated paint film surface after washing with water, and the weather. It is suitable for applications that apply to deteriorated coating films with wet surfaces such as outdoor repair applications.

When the anticorrosion coating composition according to the present invention is applied to the wet surface of the deteriorated coating film, when the moisture adhesion amount on the surface of the deteriorated coating film is 5 to 45 g / m ² , spray coating is suitable. When the amount of moisture attached to the surface of the deteriorated coating film is more than 45 g / m ² , painting with a brush, a roller, a spatula, or a trowel is suitable. The anticorrosion coating composition according to the present invention can be applied even in water by selecting an appropriate coating method depending on the moisture adhesion amount on the surface of the deteriorated coating film, and the anticorrosion coating formed from the anticorrosion coating. The film has good adhesion to the wet surface of the degraded coating.

  The spray coating conditions may be adjusted as appropriate according to the thickness of the anticorrosion coating film to be formed. At the time of airless spraying, for example, primary (air) pressure: about 0.4 to 0.8 MPa, secondary (paint ) Pressure: A pressure of about 10 to 26 MPa and a gun moving speed of about 50 to 120 cm / second are preferable.

  Although the film thickness of the anticorrosion coating film according to the present invention is not particularly limited as long as it exhibits a desired anticorrosion property, it is preferably 100 to 450 μm, more preferably 250 to 400 μm.

  When forming an anticorrosion coating film having such a film thickness, an anticorrosion coating film having a desired thickness may be formed by one coating, or twice (if necessary) depending on the required anticorrosion properties. The anticorrosive coating film having a desired thickness may be formed by coating. Since it is easy to form a more uniform coating film, it is preferable to form an anticorrosion coating film having a thickness in the above range by two coatings (or more if necessary).

  The method for curing (drying) the anticorrosion coating film formed from the anticorrosion paint according to the present invention is not particularly limited, and can be heated to about 50 to 60 ° C. in order to shorten the curing (drying) time. Usually, it is cured by allowing it to stand at room temperature and normal pressure for about 1 to 14 days.

  The method for producing a substrate with an anticorrosive coating film according to the present invention includes a step of applying the anticorrosion coating composition by an appropriate coating method to a substrate with a deteriorated coating film or a wet surface thereof, and the applied anticorrosion It comprises a step of curing the coating composition under the above-mentioned conditions to form an anticorrosion coating film.

  Furthermore, according to a desired application, a conventionally known top coating material such as an antifouling coating material may be applied and cured on the anticorrosion coating material of the substrate with the anticorrosion coating material.

  Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited thereto.

  Table 1 shows the main materials used in the examples of the present invention.

[Example 1]
As shown in Table 2 below, in a container, 26 parts by weight of epoxy resin “E-028” (Note 1), 5 parts by weight of reactive diluent “Epodil 759” (Note 3), 8.4 parts by weight of xylene, n -Butanol 3 parts by weight, MIBK (methyl isobutyl ketone) 2 parts by weight, silane coupling agent "KBM403" (Note 5) 1 part by weight, talc 25 parts by weight, mica "Suzolite Mica 200-HK" (Note 6) 5 Part by weight, 16 parts by weight of potassium feldspar, 5 parts by weight of titanium white, and 1.5 parts by weight of an anti-sagging agent were added, glass beads were added thereto, and these ingredients were mixed with a paint shaker. Next, remove the glass beads, add 2 parts by weight of water and 0.1 parts by weight of the wetting and dispersing agent “Plisurf A208B” (Note 7), and use a high-speed disper to disperse until uniform at room temperature (23 ° C.). And after heating to 56-60 degreeC after that, it cooled to 30 degrees C or less, and prepared the main ingredient component which comprises an anticorrosion coating composition.

Further, as shown in Table 2 below, polyoxyalkylene polyamine “Jeffamine D-230” (Note 8) 4 parts by weight, phenalkamine “Cardolite NX-4918” (Note 9) 9 parts by weight, tertiary amine “Ancamine K— 54 ”(Note 15) 0.2 parts by weight and 0.8 parts by weight of 1-methoxy-2-propanol were mixed using a high-speed disper (at normal temperature and normal pressure) to obtain an anticorrosive coating composition. A constituent hardener component was prepared.
The obtained main agent component and curing agent component were mixed before coating to prepare an anticorrosion coating composition.

[Examples 2 to 13 and Comparative Examples 1 to 6]
Each anticorrosion coating composition was prepared in the same manner as in Example 1 except that the components and blending amounts contained in the main component and the curing agent component of Example 1 were changed as shown in Table 2 below.

Preparation of Test Plate with Degraded Coating Tar Epoxy Resin Paint (Composition Composition: “jER 834” 2.9 parts by weight, “jER 1001” 6 parts by weight, “PA-66” (manufactured by Otake Akira Shin Chemical Co., Ltd., polyamide) Amine, active hydrogen equivalent 226, nonvolatile content 60%) 3.5 parts by weight, “Hytalon TC-77” (manufactured by SGS Chemical Co., Coal Tar Pitch) 31 parts by weight, talc 36 parts by weight, sagging inhibitor 3 parts by weight, tertiary amine “Ancamine K-54” (Note 15) 0.6 parts by weight, xylene 10.9 parts by weight, toluene 2.8 parts by weight, MIBK (methyl isobutyl ketone) 2.7 parts by weight, MEK (Methyl ethyl ketone) 0.9 parts by weight, IPA (isopropyl alcohol) 0.7 parts by weight, n-butanol 0.7 parts by weight) dimensions 150 mm × 70 mm × 1.6 mm (thickness) Airless spray (primary (air) pressure: 0.6 MPa, secondary (air) pressure: 18 Mpa) on a blasted steel plate (hereinafter also referred to as “test plate”) to a dry film thickness of 150 μm After coating for 7 days in a room with a temperature of 23 ° C. and humidity of 50% RH, it was exposed to the outdoors for 30 days and immersed in the sea for one year in 40 ° C. seawater. A test plate (Ab) was prepared.

  Further, instead of the tar epoxy resin paint, a modified epoxy resin paint (formulation composition: “E-028-90X” 16.5 parts by weight, “MAD-204 (A)” (Note 10) 8.1 parts by weight, "PA-290 (A)" (Note 12) 4.1 parts by weight, "Neopolymer E-100" 8.7 parts by weight, "HILENOL PL-1000S" 3.5 parts by weight, talc 20 parts by weight, mica " Suzolite Mica 200-HK "(Note 6) 5.2 parts by weight, Potassium feldspar 13 parts by weight, Titanium white 5.2 parts by weight, Yellow petrol 1.3 parts by weight, Silane coupling agent" KBM403 "(Note 5) ) 0.9 parts by weight, anti-sagging agent 1.3 parts by weight, tertiary amine "Ancamine K-54" (Note 15) 0.1 parts by weight, xylene 8.8 parts by weight, n-butanol 1.7 parts by weight 1-methoxy-2-propanol Except painted .6 parts by weight) was prepared outdoor exposure test plate in the same manner as described above and (B-a), the sea immersion test plate (B-b).

  It obtained in Examples 1-13 and Comparative Examples 1-6 using the said test board (Aa), (Ab), (Ba), (Bb) with a deteriorated coating film. The anticorrosion coating film formed from each anticorrosion coating composition was subjected to the following tests (1) to (6). The results are shown in Table 3 below.

(1) Anticorrosion test on substrate steel plate surface Each anticorrosion coating composition shown in Table 2 was sprayed with airless spray (primary (air) pressure: 0.00) so that the dry film thickness was about 250 μm. 6MPa, secondary (air) pressure: 18MPa), and in accordance with JIS K-5600 1-6, it is dried for 7 days in an atmosphere of 23 ° C and 50% RH. The corrosion resistance was evaluated by the following salt water resistance test, salt spray test, and high temperature and high humidity resistance test.

Salt water resistance test Corrosion protection coating after each test plate with anticorrosion coating prepared in (1) above was immersed in salt water (salt concentration 3%) at 40 ° C for 180 days in accordance with JIS K-56006-1. The appearance of the film was visually evaluated according to the following criteria.

Salt spray test Test plates with anticorrosion coating prepared in (1) above are placed in a 35 ± 2 ° C spray cabinet in accordance with JIS K-56007-1, and salt water (salt concentration 5%) is continuously added. The appearance of the anticorrosion coating after spraying for 180 days was visually evaluated according to the following criteria.

High temperature and high humidity resistance test Each test plate with anticorrosion coating film prepared in (1) above is placed in a high temperature and high humidity tester with a temperature of 50 ± 1 ° C and a humidity of 95% or more in accordance with JIS K-5600 7-2. The appearance of the anticorrosion coating after being held for 180 days was visually evaluated according to the following criteria.
(Evaluation criteria)
○: No change in swelling, cracking, rust, peeling, or hue.
Δ: Slight defects (changes) are observed in any of blisters, cracks, rust, peeling, and hue.
X: Obvious defects (changes) are observed in any of swelling, cracking, rust, peeling, and hue.

(2) Anticorrosion test on dried deteriorated coating film Before applying the anticorrosion coating composition on the surface of the test plate (Ab) with the deteriorated film, the test plate with the deteriorated film (Ab) From the surface of the film, foreign matters such as salt and dust were removed by washing with water, and dried at a temperature of 23 ° C. and a humidity of 50% for 1 hour, and it was visually confirmed that free moisture had not adhered to the surface of the deteriorated coating film. . Subsequently, each anticorrosion coating composition shown in Table 2 was coated and dried in the same manner as in (1) to prepare each anticorrosion test plate, and in the same manner as in (1), the salt water resistance test and the salt spray The corrosion resistance was evaluated by a test and a high temperature and high humidity resistance test.

(3) Anticorrosion test on a deteriorated coating film having a wet surface 0.2 g (19 g / m) immediately before coating the anticorrosion coating composition on the surface of the test plate (Ab) with the deteriorated coating film ² ) It sprayed water by spraying so that it might become ² ), it was made to adhere uniformly, and it checked visually that the moisture which was liberated on the deteriorated coating film surface adhered. Subsequently, each anticorrosion coating composition shown in Table 2 was coated and dried in the same manner as in (1) to prepare each anticorrosion test plate, and in the same manner as in (1), the salt water resistance test and the salt spray The corrosion resistance was evaluated by a test and a high temperature and high humidity resistance test.

(4) Topcoat adhesion test on the surface of the dried deteriorated coating film Each of the test plates with deteriorated coating films (A-a), (A-b), (B-a), and (B-b) is top-coated. Before painting, foreign matters such as salt and dust were removed by washing with water and dried at a temperature of 23 ° C. and a humidity of 50% for 1 hour, and it was visually confirmed that no free water adhered to the surface of the deteriorated coating film. . Then, each top-coat adhesion test board was created by applying and drying each anticorrosion coating composition shown in Table 2 in the same manner as in the above (1).

  Then, the top coat adhesion after each of the obtained top coat adhesion test plates was immersed in 40 ° C. salt water (salt concentration 3%) for 30 days was evaluated by the following method.

  On the surface of each of the above-mentioned top coat adhesion test plates (3-layer structure of test plate / deterioration coating film / anticorrosion coating film), as shown in FIG. The X-shaped notches 2 intersecting at 0 ° were made at least deep enough to reach the surface of the deteriorated coating film. Next, a cellophane adhesive tape was applied to the portion 3 where the X-shaped cut was made on the test plate, and one end of the tape was peeled off at an angle close to 90 ° with respect to the anticorrosive coating surface. The peeling state (peeling rate) between anticorrosion coating films was evaluated. Here, the peeling rate estimated the ratio of the area of the anticorrosion coating film which peeled from the deteriorated coating film with respect to the part 3 where the cut was made, and evaluated the top coat adhesion between the deteriorated coating film and the anticorrosion coating film.

The anticorrosive coating composition according to the present invention can be used without any practical problem as long as the peel rate in the result of the top coat adhesion test between the deteriorated coating film and the anticorrosive coating film is 20% or less.
(Evaluation criteria)
○: No peeling at all.
○ △: Less than 5% of the whole is peeled off.
(Triangle | delta): 5-20% of the whole has peeled.
X: The part which exceeds 20% of the whole has peeled.

(5) Adhesion of topcoat to deteriorated coating surface (I) having a wet surface Tests with deteriorated coatings (A-a), (A-b), (B-a) and (B-b) Immediately before coating the anticorrosive coating composition on the surface of the plate, water was sprayed uniformly with a spray so that the amount was 0.1 g (9.5 g / m ² ), and the moisture released on the surface of the deteriorated coating film It was visually confirmed that the adhering. Here, the deteriorated coating film surface in this state is referred to as “degraded coating film surface (I) having a wet surface”. Then, immediately (within 3 minutes after confirming the water content), each anti-corrosion coating composition shown in Table 2 was applied and dried in the same manner as in (1) above to obtain each topcoat adhesion test plate.
Thereafter, each of the obtained top coat adhesion test plates was immersed in 40 ° C. salt water (salt concentration 3%) for 30 days, and then the top coat adhesion was evaluated in the same manner as in (4) above.

(6) Adhesion of topcoat to deteriorated coating surface (II) having a wet surface Tests with deteriorated coatings (A-a), (A-b), (B-a) and (B-b) Immediately before coating the anticorrosive coating composition on the plate surface, spray water uniformly with a spray spray so that the amount is 0.2 g (19 g / m ² ), and free moisture adheres to the surface of the deteriorated coating film. It was confirmed visually. Here, the deteriorated coating film surface in this state is referred to as “degraded coating film surface (II) having a wet surface”.
Thereafter, the top coat adhesion was evaluated in the same manner as in (5) above.

  As is apparent from the test results in Table 3, by using a coating composition that satisfies the various conditions specified in the present invention, not only on the dried deteriorated coating film surface, but also on the deteriorated coating film surface having a wet surface, A coating film having excellent anti-corrosion properties and good adhesion can be formed.

1: Corrosion-resistant coating film 2: X-shaped cut 3: Site with cut

Claims (8)

A coating composition that can be applied to a wet surface of a substrate coated with a deteriorated coating film,
Epoxy resin (A),
At least one amine curing agent (B) selected from polyoxyalkylene polyamines, Mannich-modified amines and ketimines;
1 to 15 parts by weight of water (C) with respect to 100 parts by weight (nonvolatile content) of the coating composition,
A flat pigment (D);
An anticorrosive coating composition comprising:   The deteriorated coating film is formed of one kind of paint selected from tar epoxy resin paint, tar urethane resin paint, modified epoxy resin paint, modified urethane resin paint, epoxy resin paint, urethane resin paint, organic zinc paint and inorganic zinc paint. The anticorrosive coating composition according to claim 1, which is a coated film.   The anticorrosive coating composition according to claim 1 or 2, wherein the amine curing agent (B) contains at least polyoxyalkylene polyamines among polyoxyalkylene polyamines, Mannich-modified amines and ketimines. object.   It comprises at least 0.01 to 20 parts by weight (nonvolatile content) of polyoxyalkylene polyamines as the amine curing agent (B) with respect to 100 parts by weight (nonvolatile content) of the anticorrosion coating composition. The anticorrosion coating composition according to any one of claims 1 to 3.   The anticorrosion paint according to any one of claims 1 to 4, further comprising at least one selected from the group consisting of a reactive diluent having an epoxy group (E1) and a modified epoxy resin (E2). Composition.   The anticorrosion coating film formed from the anticorrosion coating composition of any one of Claims 1-5.   The base material with an anticorrosion coating film by which the surface of a base material with a deterioration coating film is coat | covered with the anticorrosion coating film formed from the anticorrosion coating composition of any one of Claims 1-5.   The process of coating the anticorrosion coating composition according to any one of claims 1 to 5 on the surface of a substrate with a deteriorated coating film, and the applied anticorrosion coating composition is cured to form an anticorrosion coating film. The manufacturing method of the base material with an anticorrosion coating film which has a process to carry out.

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