The main component (A) as a component composing the high solid type anticorrosive coating composition of the present invention contains a semi-solid state bisphenol type epoxy resin having a specific epoxy equivalent weight. [0030]
From the viewpoint of obtaining a coating film excellent in the various properties, the epoxy equivalent weight as mentioned above is in the present invention normally in a range from 250 to 300 (g/equiv), preferably 260 to 280 (g/equiv). [0031]
The definition of "semi-solid state" of the bisphenol type epoxy resin (al) is that the viscosity at ordinary temperature (measured under the conditions of 23°C, 85% concentration in

xylene as solvent, using E-type FMD viscometer manufactured by TOKIMEC Co. , Ltd. ) is normally in the range of 4500 to 5500 mPa. s, and preferably 4000 to 5000 mPa.s. [0032]
In the present invention, bisphenol type (A type or F type) epoxy resin is used because it can provide a coating film having excellent adhesion to base material and anticorrosive properties, and bisphenol A type is particularly preferable among them. The "epoxy resin" includes a polymer or an oligomer having 2 or more epoxy groups in a molecule, as well as a polymer or an oligomer formed by ring-opening reaction of the epoxy group (collectively called "ring-opening reaction product"). [0033]
Examples of the bisphenol A type epoxy resin mentioned above include a polycondensate of bisphenol A type di-glycidyl ether such as bisphenol A di-glycidyl ether, bisphenol A propylene oxide di-glycidyl ether, bisphenol A ethylene oxide di-glycidyl ether, hydrogenated bisphenol A di-glycidyl ether, hydrogenated bisphenol A propylene oxide di-glycidyl ether, and the like. [0034]
Examples of the representative epoxy resin products which can be used in the present invention include "E-834-85X{PC)" produced by Ohtake-Meishin Chemical Co., Ltd. (epoxy eguivalent
weight: 260 to 280, viscosity: about 4000 mPa.s, property: semi-solid state), "Epicoat 834" produced by Japan Epoxy Resins Co., Ltd. (bisphenol A type epoxy resin, epoxy equivalent weight: 230 to 270, viscosity by Gardner/Holz method: P-U/25°C), and the like. [0035]
These bisphenol type epoxy resins can be used alone or in a combination of two or more kinds. When two or more kinds are used in combination, the molecular weight and the epoxy equivalent weight of the bisphenol A type epoxy resin (al) are defined to be the average of the resins used. [0036]
In the main component (A), a small amount of epoxy resin of a type other than bisphenol A such as glycidyl ester type, glycidyl amine type, phenol novolac type, cresol type, dimeric acid-modified type, aliphatic type, alicyclic type, epoxidized oil type and the like may be used together with the bisphenol A type as long as the effects of the present invention are not depressed. [0037]
Viscosity, epoxy equivalent weight, average molecular weight and the like of the bisphenol type epoxy resin (al) may be suitably adjusted within the predetermined range, considering
factors, in addition to the effect of the present invention, such as curing conditions (e.g., air-drying coating, baking finish coating), coating workability and the like of the coating composition. [0038]
In the present invention, in view of adhesion to a base material, water resistance and anticorrosive properties of the coating film obtained, the content of the bisphenol type epoxy resin (al) in the main component (A) (including volatile solvent) is normally 15 to 45 wt%, and preferably 20 to 40 wt%. [0039]
Based on the weight of the solid component excluding volatile solvent in the main component (A), the content of the bisphenol type epoxy resin (al) is, in the same sense of the term as above, normally 18 to 55 parts by weight, and preferably 25 to 45 parts by weight per 100 parts by weight of the solid component. [0040]

The curing component (B) , which is another component composing the high solid type anticorrosive coating composition of the present invention, contains the epoxy adduct of xylylenediamine (b1) and the epoxy adduct of polyamide (b2) in
a specific ratio. [0041]
The epoxy adduct of xylylenediamine (b1) is obtained by reacting xylylenediamine with an epoxy resin such as a bisphenol A type epoxy resin. The epoxy resin used in this reaction has normally a lower molecular weight (for example, an epoxy equivalent weight of 184 to 194, and an average molecular weight of 368 to 388) than the epoxy resin in the main component (A) mentioned above. [0042]
The epoxy adduct of polyamide (b2) is obtained by reacting a polyamide with the same epoxy resin as used for (bl). [0043]
Examples of the epoxy adduct of xylylenediamine (bl) mentioned above include the commercial products such as "NAD 200P" (MXDA (methaxylylenediamine) epoxy adduct, viscosity: 1000 to 1500 mPa.s) produced by Ohtake-Meishin Chemical Co. , Ltd, and the example of the epoxy adduct of polyamide (b2) include "PA2 97P" (viscosity: 4000 to 7000 mPa.s) produced by Ohtake-Meishin Chemical Co., Ltd. [0044]
The coating composition of the present invention contains, from the viewpoint of physical properties, oil resistance,

solvent resistance, chemical resistance and water resistance of the obtained coating film, normally 50 to 200 parts by weight, and preferably 70 to 150 parts by weight of the epoxy adduct of polyamide (b2) per 100 parts by weight of the epoxy adduct of xylylenediamine (bl). If the content of the epoxy adduct of polyamide (b2) exceeds the above range, a relative content of the solvent increases, which makes it difficult to obtain a high solid type composition, and drying properties of the uncured coating film just after coating tends to be inferior. On the other hand, if the content is lower than above range, properties of the coating film, particularly oil resistance, solvent resistance and chemical resistance tend to be inferior. [0045]
In the coating composition of the present invention, in view of excellent crosslinking density, oil resistance, solvent resistance, chemical resistance and water resistance of the coating film obtained, the total amount of the bisphenol type epoxy resin (al), the epoxy adduct of xylylenediamine (bl) and the epoxy adduct of polyamide (b2), namely { (al) + (bl) + (b2) } is 15 to 45 wt%, and preferably 20 to 40 wt% of the paint composition. [0046]

In the present invention, addition of one or two or more kinds of silane coupling agent in the main component (A) and/or the curing component (B) is preferable to improve adhesion strength of the coating film to a base material, as well as water resistance. [0047]
As the silane coupling agent mentioned above, those compounds publicly known can be used. In the present invention, a silane coupling agent containing at least one reactive functional group selected from the group consisting of amino group, carboxyl group, hydroxyl group, epoxy group and glycidyl group, preferably that of containing an epoxy group is desirably used. [0048]
Specific examples of the above-mentioned silane coupling
agent containing epoxy group include those shown in (1) to (5)
in Table 1 below. Particularly, (3,4-epoxycyclohexyl)ethyl
trimethoxy silane as shown in (1), and -glycidoxypropyl
trimethoxy silane as shown in (2) (produced by Dow Corning Toray
Co., Ltd. "SH6040" etc.) are preferable. In addition,
y-glycidoxy propylmethyl dimethoxy silane as shown in (3) (produced by Dow Corning Toray Co., Ltd. "AY43-026"), and y-glycidoxy propylmethyl diethoxy silane as shown in (4) may be
(Table Removed)
When a silane coupling agent is used in the present invention, it is preferably added in the main component (A) . From the viewpoint of enhancing adhesion of coating film to a base material and water resistance, the amount to be added is normally 0.1 to 4 parts by weight, and preferably 0.2 to 2 parts by weight per 100 parts by weight of the main component (A). [0050]
Based on the total weight of the coating composition of the present invention, the amount of silane coupling agent to be added is normally 0.1 to 15 wt%, preferably 0.5 to 5 wt%, and more preferably 1 to 3 wt%. [0051]
By adding a silane coupling agent in the coating composition in the above-mentioned amount, adhesion of the coating film formed from the composition to a base material is enhanced without peeling of the film at all even immersed in water for a prolonged time, and effectively prevents a metal base material (particularly a stainless base material) from pitting corrosion, crevice corrosion, dissimilar metal contact corrosion and stress corrosion. These effects are markedly revealed when a silane coupling agent having an epoxy group is added. [0052]

In the present invention, one or two or more kinds of extender pigments may be added to the main component (A) and/or the curing component (B). [0053]
As the extender pigment mentioned above, conventionally known compounds such as precipitated barium sulfate, potassium feldspar, kaolin, alumina white, clay, talc, bentonite, magnesium carbonate, barium carbonate, silica (particularly fine powder), mica powder, glass flake, stainless flake, aluminum flake, plastic flake and the like can be used. Among them talc, silica (particularly silica fine powder), mica and barium sulfate are preferably used in the present invention. [0054]
When such an extender pigment is added to the coating composition of the present invention, normally 5 to 80 parts by weight, preferably 20 to 70 parts by weight, and more preferably 40 to 60 parts by weight per 100 parts by weight of the main component (A) may be added. [0055]

In the present invention, one or two or more kinds of coloring pigments may be added to the main component (A) and/or

the curing component (B). [0056]
As the coloring pigment mentioned above, conventionally known inorganic pigments such as carbon black, titanium dioxide (titanium white), red iron oxide, iron oxide, iron hydroxide, ultramarine, or organic pigments such as cyanin blue, cyanin green, and the like may be used. Among them, titanium white, carbon black and red iron oxide may be preferably used in the present invention. [0057]
When such a coloring pigment is added to the paint composition of the present invention, normally 1 to 50 parts by weight, preferably 1 to 20 parts by weight, and more preferably 2 to 10 parts by weight per 100 parts by weight of the main component (A) may be added. [0058]
When at least one of the above-mentioned extender pigment and the coloring pigment is added to the anticorrosive coating composition of the present invention, the pigment volume content (PVC) of the total pigments including extender and coloring pigments is preferably 20 to 50 %, and more preferably 25 to 45 %, in order to maintain the effect of stress relaxation and water resistance of the coating film as well as coating workability at
an appropriate level. If PVC is lower than the above range, the effect of pigment addition on stress relaxation tends to be insufficient. On the other hand, if PVC exceeds the above range, water resistance of the coating film and coating workability tend to decrease. [0059]

In the main component (A) used in the present invention, various other components such as an anti-sagging agent (an anti-settling agent), a fibrous material, the surfactant described in JP-A-1990(H2)-298563, an anti-corrosive pigment, and the like may be suitably added. [0060]
Examples of the anti-sagging agent include conventionally known compounds such as organic clay-based wax such as a stearate, a lecithin salt, an alkyl sulfonate of Al, Ca, and Zn, polyethylene wax, amide wax, hydrogenated castor oil wax, polyamide wax, a mixture of hydrogenated castor oil wax with polyamide wax, synthetic fine powder silica, polyethylene oxide based wax, and the like. Among them, polyamide wax, synthetic fine powder silica, polyethylene oxide based wax and organic clay based wax are particularly preferable. [0061]
Examples of the commercial product of such anti-sagging agent include "DISPARLON 305", "DISPARLON 4200-20", "DISPARLON 6650" produced by Kusumoto Chemicals, Ltd. and "ASA T-250F" produced by Itoh Oil Chemicals Co., Ltd. [0062]
When using an antisagging agent in the present invention, 0.1 to 10 wt% of the antisagging agent may be added in the main component (A). [0063]
Production of the high solid type paint composition
The high solid type coating composition of the present invention can be produced by preparing separately the main component (A) and the curing component (B) in advance, and mixing and kneading them just before use. [0064]
The main component (A) can be prepared by mixing the resin, the pigment, the solvent and the additives composing thereof, followed by agitating and kneading the mixture. In this case, an SG mill or a high speed disperser may be used by keeping the mill base temperature at 55 to 60°C for about 30 minutes to disperse the components as homogeneously as possible. On the other hand, the curing component (B) can be prepared by mixing the resin, the solvent and the like composing thereof and dispersing them using
an agitator. [0065]
Use of the coating composition
By applying and curing the coating composition of the present invention on a base material surface, a coating film (layer) can be formed to provide the base material with various properties such as anticorrosive properties, oil resistance, solvent resistance, chemical resistance and water resistance. In other words, by coating the base material surface with the above-mentioned coating film, excellent oil resistance (particularly required for ship tanks) can be provided to the base material, and at the same time, pitting corrosion, crevice corrosion, dissimilar metal contact corrosion and stress corrosion of the base material can be prevented. [0066]
The paint composition of the present invention may be applied to the surface of a base material such as ship, steel structure, ship tank and the like, using the known methods such as airless spray, air spray, brushing, roller coating and the like. Examples of materials to which the coating composition of the present invention may be applied include steel, nonferrous metals (zinc, aluminum, stainless steel and the like) , and the like. It is preferable that mild steel (e.g., SS400) or the like is

subjected in advance to surface preparation by polishing using such a tool as grit blasting. For coating work, the coating composition may be suitably diluted with a thinner or the like. [0067]
The thickness of the above coating film after curing
(drying) is not particularly limited. However, in order to
provide enough anticorrosive properties efficiently, the
thickness is normally 50 to 500 µm, and preferably 200 to 300 µm.
[0068]
The coating composition of the present invention, as mentioned above, can provide a coating film of excellent properties on the base material surface. Therefore, it can be suitably applied to, for example, a seawater desalination facility, a part of a marine structure where maintenance work is difficult to implement, around a dam and a water gate, piping in a plant using seawater, river water and industrial water for cooling, a water storage, a water tank, a storage pool for nuclear fuel waste, and the like. [0069]
It can also be used for repair coating of a corroded surface of a base material coated with an anticorrosive coating film. Namely, local corrosion of a stainless steel base material can be prevented by forming an anticorrosive coating film on a welded
part or a crevice, and by acting as an adhesive between the coating film surface and a stainless steel plate, it can prevent local corrosion stably for a long time and provide excellent anticorrosive properties. [0070]
Specifically, repairs of a stainless steel base material can be carried out, for example, by applying the epoxy resin composition of the present invention on the surface of a stainless steel base material having a welded part (weld line) or crevice, and bonding a stainless steel plate on the surface of the coating film before curing. The epoxy resin composition of the present invention may be further coated thereon. [0071]
Such a repair method can be applied without limitation to any structure made of stainless steel and is specifically applied to a water storage vessel, a water storage tank, a nuclear fuel waste storage pool and the like. As local corrosion tends to occur particularly if the nuclear fuel waste storage pool has a welded part (weld line) or a crevice on the surface of the base material inside the storage pool, application of the repair method using the epoxy resin composition of the present invention is effective. [0072]
When the coating composition of the present invention is
applied, dried and cured, for example, it is inferred that ring opening of an epoxy group in the epoxy resin contained in the main component (A) occurs, and that the epoxy oxygen (0) is converted into a hydroxyl group (-0H), while the terminal carbon atom of the molecule forming the epoxy group reacts with an amino group (-NH2) of the curing agent to form (-NH-) bond, or the like, thereby bonding to the curing agent.
EXAMPLES [0073]
The suitable embodiments of the present invention will be explained in further detail with reference to examples. However, the present invention is by no means restricted by these examples. [0074]
[Preparation of the main component, the curing component and the coating composition]
The coating compositions used in the Examples 1 to 2, and the Comparative Examples 1 to 6 were prepared as follows according to the compositions shown in Table 2. [0075]
First, all the constituents of the main component, that is, the resin, the pigment, the additives and the solvent were charged into a polyethylene container of 1 L volume and dispersed
for 1 to 2 hours using a paint shaker with glass Deads. Then the constituents of the curing component, namely the resin and the solvent were charged in a 1 Kg can and dispersed using a table agitator. Subsequently, the main component and the curing component were mixed, followed by addition of an appropriate amount of a thinner for epoxy compound (trade name: EPICON T-500 thinner) to prepare the coating composition. [0076]
[Preparation of a test plate]
A sand blasted steel plate of 2 . 3 mm x 70 mm x 150 mm in size made of SS400 (surface roughness: 40 to 75 µm) was prepared.
The coating composition prepared as described above was coated twice (once a day) on the surface of this steel plate using an air spray so that dry thickness of each coated film is 125 µm. After the plate was kept for drying at 23°C for 10 days, the painted steel plate obtained (test plate) was subjected to a test for evaluating various properties of the coating film.
The test results were shown in Table 2, the test methods and the details of evaluation criteria are shown in Table 3 (remarks 14 to 20 in Table 2). [0077]
Table 2-1

(Table Removed)
Notes
*1 Epoxy resin "E-834-85X": produced by Ohtake-Meishin Chemical Co., Ltd. Epoxy equivalent weight = 250. Non-volatile content = 85% (xylene 15%).
*2 Epoxy resin "E-834-8 5 (PC) ":produced by Ohtake-Meishin Chemical Co., Ltd. Epoxy equivalent weight = 270. Non-volatile content = 85% (xylene 15%).
*3 Epoxy resin "YD-128": produced by Tohto Kasei Co. , Ltd. Epoxy equivalent weight = 190, Non-volatile content = 100 %.
*4 Xylene resin "Nikanol L": produced by Mitsubishi Gas Chemical Co., Ltd.
*5 Anti-sagging agent (Amide wax) "ASAT-250F": produced by Itoh Oil Chemicals Co., Ltd.
*6 Silane coupling agent "KBM403": produced by Shin-Etsu Chemical Co., Ltd.
*1 MXDA epoxy adduct "NAD200P": produced by Ohtake-Meishin Chemical Co., Ltd. Active hydrogen equivalent weight = 136. Non-volatile content = 63% (solvent 37%).
*8 MXDA epoxy adduct "Sunmide X-2100": produced by Air Products Co., Ltd. Active hydrogen equivalent = 110. Non-volatile content = 100 %.
*9 Polyamide epoxy adduct "PA297P": produced by Ohtake-Meishin Chemical Co., Ltd. Active hydrogen equivalent =
239. Non-volatile content = 61%.
*10 Polyamide epoxy adduct "Ankamide 258 9": produced by
Air Products and Chemicals, Ltd. Active hydrogen equivalent =
100. Non-volatile content = 100%.
*11 Epoxy resin coating material 1 (used in Comparative
Example 3) : "Epicon T-500" produced by Chugoku Marine Paints Ltd.
Main component = bisphenol type solid epoxy resin (epoxy
equivalent weight = 475), extender pigment (talc, mica, barium
sulfate), coloring pigment (red iron oxide or titanium white and
carbon black), additives (anti-sagging agent, silane coupling
agent), solvent (toluene, MIBK (MEK)) are contained;
Curing component = DETA epoxy adduct resin, solvent (butanol, toluene) are contained;
Physical properties = good.
*12 Epoxy resin coating material 2 (used in Comparative Example 4) : "SIGMAGUARD EHB" produced by SIGMA COATINGS Co. , Ltd.;
Main component = bisphenol type semi-solid epoxy resin, extender pigment (talc, mica, barium sulfate), coloring pigment (titanium white or cyanine green) , additive (anti-sagging agent) , solvent (xylene, butanol, solvent naphtha);
Curing component - MXDA epoxy adduct resin, additives (tri-amino methylphenol, salicylic acid), solvent (methoxy propanol, isobutylmethyl ketone, xylene, butanol);
Physical properties: good.
*13 Epoxy resin coating material 3(used in Comparative Example 5): "Interline 604" produced by International Coatings Co., Ltd.;
Main component = bisphenol type semi-solid epoxy resin, extender pigment (tremolite, chrysotile, silica powder, barium sulfate), coloring pigment (titanium white), solvent (methyl n-ketone, solvesso);
Curing component = cardanol based modified polyamine (phenalkamine), solvent (butanol);
Physical properties = good. [0078]
*14 to *20 Test methods and evaluation criteria of the coating film are shown in the following Table 3. [0079]
Table 3
(Table Removed)





CLAIMS
1. A high solid type anticorrosive coating composition
comprising:
(A) a main component containing a semi-solid state bisphenol type
epoxy resin (a1) having an epoxy equivalent weight of 250 to 300;
and
(B) a curing component containing an epoxy adduct of
xylylenediamine (b1) and an epoxy adduct of polyamide (b2),
the curing component (B) containing 50 to 200 parts by weight of
the epoxy adduct of polyamide (b2) per 100 parts by weight of the
epoxy adduct of xylylenediamine (bl).
2. The high solid type anticorrosive coating composition as set forth in claim 1, wherein the epoxy equivalent weight of the semi-solid state bisphenol type epoxy resin (al) contained in the main component (A) is 260 to 280.
3. The high solid type anticorrosive coating composition as set forth in claim 1 or 2, wherein the curing component (B) contains 70 to 150 parts by weight of the epoxy adduct of polyamide (b2) per 100 parts by weight of the epoxy adduct of xylylenediamine
(bl) .
4. The high solid type anticorrosive coating composition as set forth in any of claims 1 to 3, wherein the ratio of active hydrogen group in the curing component (B) to the epoxy group of the main component (A) is 0.8 to 1.0.
5. The high solid type anticorrosive coating composition as set forth in any of claims 1 to 4, wherein the main component (A) or the curing component (B) contains a silane coupling agent.
6. The high solid type anticorrosive coating composition as set forth in claim 5, wherein the silane coupling agent is contained at 0. 1 to 4 parts by weight per 100 parts by weight of the main component (A).
7. The high solid type anticorrosive coating composition as set forth in any of claims 1 to 6, wherein the main component (A) or the curing component (B) contains an extender pigment.
8. The high solid type anticorrosive coating composition as set forth in claim 7, wherein the extender pigment is at least one selected from the group consisting of silica, talc, mica and barium sulfate.The high solid type anticorrosive coating composition as set forth in claim 7 or 8, wherein the extender pigment is contained at 20 to 70 parts by weight per 100 parts by weight of the main component (A).
9. The high solid type anticorrosive coating composition as set forth in any of claims 1 to 9, wherein the main component (A) or the curing component (B) contains a coloring pigment.
10. The high solid type anticorrosive coating composition as set forth in claim 10, wherein the coloring pigment is at least one selected from the group consisting of titanium white, carbon black and red iron oxide.
11. The high solid type anticorrosive coating composition as set forth in claim 10 or 11, wherein the coloring pigment is contained at 1 to 20 parts by weight per 100 parts by weight of the main component (A).
12. The high solid type anticorrosive coating composition as set forth in any of claims 7 to 12, wherein the total pigment volume content (PVC) including the extender pigment and the coloring
pigment in the coating composition is in the range of 20 to 50 %.
14. The high solid type anticorrosive coating composition as set forth in claim 13, wherein the total pigment volume content (PVC) is in the range of 25 to 45 %.
15. The high solid type anticorrosive coating composition as set forth in any of claims 1 to 14, wherein the total amount of the bisphenol type epoxy resin (a1), the epoxy adduct of xylylenediamine (b1) and the epoxy adduct of polyamide (b2), {(al) + (bl) + (b2)}, in the coating composition is 15 to 45 wt%.
16. The high solid type anticorrosive coating composition as set forth in any of claims 1 to 15, wherein the total amount of the bisphenol type epoxy resin (al), the epoxy adduct of xylylenediamine (bl) and the epoxy adduct of polyamide (b2), {(al) + (bl) + (b2)}, in the coating composition is 20 to 40 wt%.
17. A coating film formed from the high solid type anticorrosive coating composition as set forth in any of claims 1 to 16.
18. An anticorrosive coating film formed from the high solid

type anticorrosive coating composition as set forth in any of claims 1 to 16.
19. An anticorrosive coating film for ships formed from the high solid type anticorrosive coating composition as set forth in any of claims 1 to 16.
20. An anticorrosive coating film for ship tanks formed from the high solid type anticorrosive coating composition as set forth in any of claims 1 to 16.
21. A base material coated with an anticorrosive coating film formed from the high solid type anticorrosive coating composition as set forth in any of claims 1 to 16.
22. A ship tank coated with an anticorrosive coating film formed from the high solid type anticorrosive coating composition as set forth in any of claims 1 to 16.
23. A method of preventing corrosion by coating with a coating film formed from the high solid type anticorrosive coating
composition as set forth in any of claims 1 to 16.